ORCID Profile
0000-0002-0197-497X
Current Organisation
University of Melbourne
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Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Nanotechnology | Nanotechnology | Colloid And Surface Chemistry | Nanobiotechnology | Nanomaterials | Nanomedicine | Synthesis of Materials | Biomaterials | Synthesis Of Macromolecules | Polymers | Functional Materials | Macromolecular and Materials Chemistry | Physical Chemistry (Incl. Structural) | Biosensor Technologies | Biomedical Engineering | Cellular Interactions (incl. Adhesion, Matrix, Cell Wall) | Cellular Immunology | Structural Chemistry | Organic Chemical Synthesis | Physiology | Analytical Spectrometry | Membrane and Separation Technologies | Characterisation Of Macromolecules | Physical Chemistry Of Macromolecules | Composite Materials | Pharmaceutical Sciences | Sociology and Social Studies of Science and Technology | Optical Physics Not Elsewhere Classified | Polymers and Plastics | Membrane Biology | Biomedical Engineering Not Elsewhere Classified | Optics And Opto-Electronic Physics | Organic Chemistry | Biomaterials | Biomechanical Engineering | Biotechnology Not Elsewhere Classified | Nanoscale Characterisation | Soil Biology | Animal Physiology—Systems | Diagnostic Applications |
ANZSRC Socio-Economic Objective (SEO)
Chemical sciences | Expanding Knowledge in the Chemical Sciences | Expanding Knowledge in the Biological Sciences | Biological sciences | Physical sciences | Expanding Knowledge in Technology | Other | Polymeric materials (e.g. paints) | Expanding Knowledge in the Physical Sciences | Cancer and Related Disorders | Prevention—biologicals (e.g. vaccines) | Diagnostics | Expanding Knowledge in Engineering | Agricultural and Environmental Standards | Inherited Diseases (incl. Gene Therapy) | Organic Industrial Chemicals (excl. Resins, Rubber and Plastics) | Manufactured products not elsewhere classified | Organs, diseases and abnormal conditions not elsewhere classified | Immune System and Allergy | Workforce Transition and Employment | Chemical Fertilisers | Cardiovascular system and diseases | Diagnostic methods | Integrated circuits and devices | Expanding Knowledge in the Medical and Health Sciences | Scientific instrumentation | Farmland, Arable Cropland and Permanent Cropland Soils | Human Pharmaceutical Treatments (e.g. Antibiotics) | Diagnostic Methods | Public health not elsewhere classified | Diagnostics
Related Links
Publications
Modular Assembly of Host–Guest Metal–Phenolic Networks Using Macrocyclic Building Blocks
Publisher: Wiley
Date: 13-11-2020
Abstract: The manipulation of interfacial properties has broad implications for the development of high-performance coatings. Metal-phenolic networks (MPNs) are an emerging class of responsive, adherent materials. Herein, host-guest chemistry is integrated with MPNs to modulate their surface chemistry and interfacial properties. Macrocyclic cyclodextrins (host) are conjugated to catechol or galloyl groups and subsequently used as components for the assembly of functional MPNs. The assembled cyclodextrin-based MPNs are highly permeable (even to high molecular weight polymers: 250-500 kDa), yet they specifically and noncovalently interact with various functional guests (including small molecules, polymers, and carbon nanomaterials), allowing for modular and reversible control over interfacial properties. Specifically, by using either hydrophobic or hydrophilic guest molecules, the wettability of the MPNs can be readily tuned between superrepellency (>150°) and superwetting (ca. 0°).
Bioresponsive Polyphenol-Based Nanoparticles as Thrombolytic Drug Carriers
Publisher: American Chemical Society (ACS)
Date: 12-01-2022
Abstract: Thrombolytic (clot-busting) therapies with plasminogen activators (PAs) are first-line treatments against acute thrombosis and ischemic stroke. However, limitations such as narrow therapeutic windows, low success rates, and bleeding complications hinder their clinical use. Drug-loaded polyphenol-based nanoparticles (NPs) could address these shortfalls by delivering a more targeted and safer thrombolysis, coupled with advantages such as improved biocompatibility and higher stability in vivo. Herein, a template-mediated polyphenol-based supramolecular assembly strategy is used to prepare nanocarriers of thrombolytic drugs. A thrombin-dependent drug release mechanism is integrated using tannic acid (TA) to cross-link urokinase-type PA (uPA) and a thrombin-cleavable peptide on a sacrificial mesoporous silica template via noncovalent interactions. Following drug loading and template removal, the resulting NPs retain active uPA and demonstrate enhanced plasminogen activation in the presence of thrombin (1.14-fold
A few clarifications on MIRIBEL.
Publisher: Springer Science and Business Media LLC
Date: 2020
Degradable polyelectrolyte capsules filled with oligonucleotide sequences
Publisher: Wiley
Date: 20-11-2006
Particle engineering enabled by polyphenol-mediated supramolecular networks
Publisher: Springer Science and Business Media LLC
Date: 23-09-2020
DOI: 10.1038/S41467-020-18589-0
Abstract: We report a facile strategy for engineering erse particles based on the supramolecular assembly of natural polyphenols and a self-polymerizable aromatic dithiol. In aqueous conditions, uniform and size-tunable supramolecular particles are assembled through π–π interactions as mediated by polyphenols. Owing to the high binding affinity of phenolic motifs present at the surface, these particles allow for the subsequent deposition of various materials (i.e., organic, inorganic, and hybrid components), producing a variety of monodisperse functional particles. Moreover, the solvent-dependent disassembly of the supramolecular networks enables their removal, generating a wide range of corresponding hollow structures including capsules and yolk–shell structures. The versatility of these supramolecular networks, combined with their negligible cytotoxicity provides a pathway for the rational design of a range of particle systems (including core–shell, hollow, and yolk–shell) with potential in biomedical and environmental applications.
Overcoming the Blood-Brain Barrier: The Role of Nanomaterials in Treating Neurological Diseases.
Publisher: Wiley
Date: 31-07-2018
Abstract: Therapies directed toward the central nervous system remain difficult to translate into improved clinical outcomes. This is largely due to the blood-brain barrier (BBB), arguably the most tightly regulated interface in the human body, which routinely excludes most therapeutics. Advances in the engineering of nanomaterials and their application in biomedicine (i.e., nanomedicine) are enabling new strategies that have the potential to help improve our understanding and treatment of neurological diseases. Herein, the various mechanisms by which therapeutics can be delivered to the brain are examined and key challenges facing translation of this research from benchtop to bedside are highlighted. Following a contextual overview of the BBB anatomy and physiology in both healthy and diseased states, relevant therapeutic strategies for bypassing and crossing the BBB are discussed. The focus here is especially on nanomaterial-based drug delivery systems and the potential of these to overcome the biological challenges imposed by the BBB. Finally, disease-targeting strategies and clearance mechanisms are explored. The objective is to provide the erse range of researchers active in the field (e.g., material scientists, chemists, engineers, neuroscientists, and clinicians) with an easily accessible guide to the key opportunities and challenges currently facing the nanomaterial-mediated treatment of neurological diseases.
Nanoengineering of particle surfaces
Publisher: Wiley
Date: 2001
DOI: 10.1002/1521-4095(200101)13:1<11::AID-ADMA11>3.0.CO;2-N
Nano- and microengineering: Three-dimensional colloidal photonic crystals prepared from submicrometer-sized polystyrene latex spheres pre-coated with luminescent polyelectrolyte/nanocrystal shells
Publisher: Wiley
Date: 03-2000
DOI: 10.1002/(SICI)1521-4095(200003)12:5<333::AID-ADMA333>3.0.CO;2-X
Probing the permeability of polyelectrolyte multilayer capsules via a molecular beacon approach
Publisher: American Chemical Society (ACS)
Date: 06-03-2007
DOI: 10.1021/LA063674H
Abstract: Application of polyelectrolyte multilayer (PEM) capsules as vehicles for the controlled delivery of substances, such as drugs, genes, pesticides, cosmetics, and foodstuffs, requires a sound understanding of the permeability of the capsules. We report the results of a detailed investigation into probing capsule permeability via a molecular beacon (MB) approach. This method involves preparing MB-functionalized bimodal mesoporous silica (BMSMB) particles, encapsulating the BMSMB particles within the PEM film to be probed, and then incubating the encapsulated BMSMB particles with DNA target sequences of different lengths. Permeation of the DNA targets through the capsule shell causes the immobilized MBs to open due to hybridization of the DNA targets with the complementary loop region of the MBs, resulting in an increase in the MB fluorescence. The assay conditions (BMSMB particle concentration, MB loading within the BMS particles, DNA target concentration, DNA target size, pH, sodium chloride concentration) where the MB-DNA sensing process is effective were first examined. The permeability of DNA through poly(sodium 4-styrenesulfonate) (PSS) oly(allylamine hydrochloride) (PAH) multilayer films, with and without a poly(ethyleneimine) (PEI) precursor layer, was then investigated. The permeation of the DNA targets decreases considerably as the thickness of the PEM film encapsulating the BMSMB particles increases. Furthermore, the presence of a PEI precursor layer gives rise to less permeable PSS/PAH multilayers. The diffusion coefficients calculated for the DNA targets through the PEM capsules range from 10-19 to 10-18 m2 s-1. This investigation demonstrates that the MB approach to measuring permeability is an important new tool for the characterization of PEM capsules and is expected to be applicable for probing the permeability of other systems, such as membranes, liposomes, and emulsions.
Nanoporous colloids: building blocks for a new generation of structured materials
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B901742A
Surface interactions during polyelectrolyte multilayer buildup. 1. Interactions and layer structure in dilute electrolyte solutions
Publisher: American Chemical Society (ACS)
Date: 18-05-2004
DOI: 10.1021/LA049636K
Abstract: We report the investigation of surface forces between polyelectrolyte multilayers of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) assembled on mica surfaces during film buildup using a surface force apparatus. Up to four polyelectrolyte layers were prepared on each surface ex situ, and the surface interactions were measured in 10(-4) M KBr solutions. The film thickness under high compressive loads (above 2000 microN/m) increased linearly with the number of deposited layers. In all cases, the interaction between identical surfaces at large separations (>100 A from contact) was dominated by electrostatic double-layer repulsion. By fitting DLVO theory to the experimental force curves, the apparent double-layer potential of the interacting surfaces was calculated. At shorter separations, an additional non-DLVO repulsion was present due to polyelectrolyte chains extending some distance from the surface into solution, thus generating an electrosteric type of repulsion. Forces between dissimilar multilayers (i.e., one of the multilayers terminated with PSS and the other with PAH) were attractive at large separations (30-400 A) owing to a combination of electrostatic attraction and polyelectrolyte bridging.
Multilayered polymer nanocapsules derived from gold nanoparticle templates
Publisher: Wiley
Date: 12-2000
DOI: 10.1002/1521-4095(200012)12:24<1947::AID-ADMA1947>3.0.CO;2-8
Peptide-functionalized, low-biofouling click multilayers for promoting cell adhesion and growth
Publisher: Wiley
Date: 19-02-2009
Formation and Degradation of Layer-by-Layer-Assembled Polyelectrolyte Polyrotaxane Capsules
Publisher: American Chemical Society (ACS)
Date: 31-01-2013
DOI: 10.1021/LA304580X
Abstract: We report the preparation of degradable capsules via layer-by-layer assembly using polyelectrolyte (PE) polyrotaxanes (PRXs). The PRX capsules were prepared by the sequential deposition of PRXs onto silica particles followed by the dissolution of the silica cores. The colloidal stability of the PRX capsules that are formed depends on the salt/buffer solution used in the assembly process. Various salt/buffer combinations were examined to avoid aggregation of the core-shell particles during PRX assembly and core dissolution. Using appropriate assembly conditions, we prepared colloidally stable, robust capsules. PRX capsules consisting of eight layers of PE PRXs had a wall thickness of ~15 nm. The degradation of the PRX capsules was demonstrated through the disassembly of the PE PRXs using glutathione, which cleaves the disulfide bonds linking the end-capping groups of the PE PRXs. Given the supramolecular noncovalent structure of PRXs and their adjustable properties, it is expected that PRXs will be used as building blocks for assembling advanced capsules with unique and tailored properties.
Investigation of immuno-reactions in a flow-injection system using surface plasmon resonance
Publisher: Elsevier BV
Date: 10-1995
Tuning particle biodegradation through polymer-peptide blend composition
Publisher: American Chemical Society (ACS)
Date: 31-10-2014
DOI: 10.1021/BM5012272
Abstract: We report the preparation of polymer-peptide blend replica particles via the mesoporous silica (MS) templated assembly of poly(ethylene glycol)-block-poly(2-diisopropylaminoethyl methacrylate-co-2-(2-(2-(prop-2-ynyloxy)ethoxy)ethoxy)ethyl methacrylate) (PEG45-b-P(DPA55-co-PgTEGMA4)) and poly(l-histidine) (PHis). PEG45-b-P(DPA55-co-PgTEGMA4) was synthesized by atom transfer radical polymerization (ATRP), and was coinfiltrated with PHis into poly(methacrylic acid) (PMA)-coated MS particles assembled from different peptide-to-polymer ratios (1:1, 1:5, 1:10, or 1:15). Subsequent removal of the sacrificial templates and PMA resulted in monodisperse, colloidally stable, noncovalently cross-linked polymer-peptide blend replica particles that were stabilized by a combination of hydrophobic interactions between the PDPA and the PHis, hydrogen bonding between the PEG and PHis backbone, and π-π stacking of the imidazole rings of PHis side chains at physiological pH (pH ∼ 7.4). The synergistic charge-switchable properties of PDPA and PHis, and the enzymatic degradability of PHis, make these particles responsive to pH and enzymes. In vitro studies, in simulated endosomal conditions and inside cells, demonstrated that particle degradation kinetics could be engineered (from 2 to 8 h inside dendritic cells) based on simple adjustment of the peptide-to-polymer ratio used.
Nanoparticles assembled via pH-responsive reversible segregation of cyclodextrins in polyrotaxanes
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6NR04841B
Abstract: Supramolecular polymers with monomers bound together by secondary interactions, such as polyrotaxanes (PRXs), consisting of alpha cyclodextrin (αCD) threaded onto poly(ethylene glycol) (PEG), have attracted interest as a result of their ability to overcome physical limitations present in conventional, covalently structured polymers. Herein, we describe the formation of pH-responsive supramolecular assemblies from carboxyethylester bearing αCD and PEG PRXs. These PRXs were formed using PEG of Mw 20 kDa and a threading degree of 28%. Upon charge neutralisation the threaded αCDs co-localise, resulting in aggregation of the PRXs and the formation of a suspension by self-assembly. This process is shown to be reversible and possible via the mobility of CDs along the PEG guest chain. As a result of the inherent properties of PRXs, such as enhanced multivalent interactions and degradation, these responsive supramolecular polymers are expected to be of interest in fields where PRX-based materials have already found application, including paints, self-healing materials, surface coatings, and polymer therapeutics.
Semiconductor and metal nanoparticle formation on polymer spheres coated with weak polyelectrolyte multilayers
Publisher: American Chemical Society (ACS)
Date: 15-07-2004
DOI: 10.1021/CM049957H
Role of Molecular Interactions in Supramolecular Polypeptide–Polyphenol Networks for Engineering Functional Materials
Publisher: American Chemical Society (ACS)
Date: 07-2022
DOI: 10.1021/JACS.2C05052
Abstract: Supramolecular assembly affords the development of a wide range of polypeptide-based biomaterials for drug delivery and nanomedicine. However, there remains a need to develop a platform for the rapid synthesis and study of erse polypeptide-based materials without the need for employing complex chemistries. Herein, we develop a versatile strategy for creating polypeptide-based materials using polyphenols that display multiple synergistic cross-linking interactions with different polypeptide side groups. We evaluated the erse interactions operating within these polypeptide-polyphenol networks via binding affinity, thermodynamics, and molecular docking studies and found that positively charged polypeptides (
Probing the conformation of polyelectrolytes in mesoporous silica spheres
Publisher: American Chemical Society (ACS)
Date: 05-03-2008
DOI: 10.1021/LA703647Y
Abstract: We report a fluorescence-based approach to probing the conformation of a macromolecule, poly(allylamine hydrochloride) (PAH), in bimodal mesoporous silica (BMS) particles. The method involves monitoring the fluorescent properties of the probe, 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (4-PSA), upon electrostatic binding to PAH molecules adsorbed in the nanopores of the BMS particles. PAH infiltration into the BMS particles, quantified by thermogravimetric analysis and visualized by confocal laser scanning microscopy, was examined as a function of PAH adsorption time, PAH molecular weight, and the sodium chloride (NaCl) concentration and pH of the PAH adsorption solution. The conformation of PAH molecules in the nanopores was investigated by incubating the PAH-loaded BMS particles in 4-PSA and using the ratio of the excimer to monomer emission intensity to discern differences in the PAH conformation in the nanopores. Control experiments involving nonporous silica (NS) particles were also conducted to determine the extent to which the nanopores within the BMS particles influence the degree of PAH adsorption and the conformation of the adsorbed PAH molecules. The data indicate that PAH molecules adsorbed in the nanopores adopt a more coiled conformation than PAH molecules adsorbed on NS particles over a wide range of conditions. Further, the conformation of PAH molecules in the nanopores can be tuned by adjusting the NaCl concentration and/or pH of the PAH adsorption solution. 4-PSA titration experiments revealed that at saturation binding there are ca. 3.8 PAH monomer units per 4-PSA molecule. This study provides insights into macromolecule infiltration and conformation in nanopores, which are important for the application of mesoporous materials in the fields of adsorption/immobilization, catalysis, delivery, sensing, separations, and synthesis.
Novel Engineered Ion Channel Provides Controllable Ion Permeability for Polyelectrolyte Microcapsules Coated with a Lipid Membrane
Publisher: Wiley
Date: 08-01-2009
Surface chemical activation of quartz crystal microbalance gold electrodes — analysis by frequency changes, contact angle measurements and grazing angle FTIR
Publisher: Elsevier BV
Date: 05-1995
Self-assembling influenza nanoparticle vaccines drive extended germinal center activity and memory B cell maturation
Publisher: American Society for Clinical Investigation
Date: 21-05-2020
Click poly(ethylene glycol) multilayers on RO membranes: Fouling reduction and membrane characterization
Publisher: Elsevier BV
Date: 08-2012
Engineering Metal–Phenolic Networks for Solar Desalination with Directional Salt Crystallization
Publisher: Wiley
Date: 08-12-2023
Abstract: Solar desalination is one of the most promising strategies to address the global freshwater shortage crisis. However, the residual salt accumulated on the top surface of solar evaporators severely reduces light absorption and steam evaporation efficiency, thus impeding the further industrialization of this technology. Herein, a metal–phenolic network (MPN)‐engineered 3D evaporator composed of photothermal superhydrophilic/superhydrophobic sponges and side‐twining hydrophilic threads for efficient desalination with directional salt crystallization and zero liquid discharge is reported. The MPN coatings afford the engineering of alternating photothermal superhydrophilic/superhydrophobic sponges with high heating efficiency and defined vapor escape channels, while the side‐twining threads induce site‐selective salt crystallization. The 3D evaporator exhibits a high and stable indoor desalination rate (≈2.3 kg m −2 h −1 ) of concentrated seawater (20 wt%) under simulated sun irradiation for over 21 days without the need for salt crystallization inhibitors. This direct desalination is also achieved in outdoor field operations with a production rate of clean water up to ≈1.82 kg m −2 h −1 from concentrated seawater (10 wt%). Together with the high affinity and multiple functions of MPNs, this work is expected to facilitate the rational design of solar desalination devices and boost the research translation of MPN materials in broader applications.
Engineered Metal-Phenolic Capsules Show Tunable Targeted Delivery to Cancer Cells.
Publisher: American Chemical Society (ACS)
Date: 06-2016
DOI: 10.1021/ACS.BIOMAC.6B00537
Abstract: We engineered metal-phenolic capsules with both high targeting and low nonspecific cell binding properties. The capsules were prepared by coating phenolic-functionalized hyaluronic acid (HA) and poly(ethylene glycol) (PEG) on calcium carbonate templates, followed by cross-linking the phenolic groups with metal ions and removing the templates. The incorporation of HA significantly enhanced binding and association with a CD44 overexpressing (CD44+) cancer cell line, while the incorporation of PEG reduced nonspecific interactions with a CD44 minimal-expressing (CD44-) cell line. Moreover, high specific targeting to CD44+ cells can be balanced with low nonspecific binding to CD44- cells simply by using an optimized feed-ratio of HA and PEG to vary the content of HA and PEG incorporated into the capsules. Loading an anticancer drug (i.e., doxorubicin) into the obtained capsules resulted in significantly higher cytotoxicity to CD44+ cells but lower cytotoxicity to CD44- cells.
Nanoporous polyelectrolyte spheres prepared by sequentially coating sacrificial mesoporous silica spheres
Publisher: Wiley
Date: 03-05-2005
Optical properties of nanoparticle-based metallodielectric inverse opals
Publisher: Wiley
Date: 03-11-2005
Abstract: Metallodielectric inverse opals were prepared by co-crystallizing silica-coated gold nanoparticles and polymer spheres, followed by removal of the crystal template. The inverse opals exhibit a distinct reflectance peak, which results from Bragg diffraction due to the highly ordered 3D macroporous structure. Photonic band-structure calculations indicate that the characteristic reflectance peaks observed are signatures of the directional gap at the L point. It is demonstrated that the optical properties (the position and magnitude of the electromagnetic bandgaps) of the gold-silica nanocomposite inverse opals can be engineered by varying the nanoparticle morphology (core size and shell thickness) and/or the nanoparticle volume-filling ratio of the composite. The use of metallodielectric nanoparticles to form inverse opals offers a versatile approach to prepare photonic materials that may exhibit absolute bandgaps.
Biodegradable Click Capsules with Engineered Drug-Loaded Multilayers
Publisher: American Chemical Society (ACS)
Date: 04-03-2010
DOI: 10.1021/NN9014278
Abstract: We report the modular assembly of a polymer-drug conjugate into covalently stabilized, responsive, biodegradable, and drug-loaded capsules with control over drug dose and position in the multilayer film. The cancer therapeutic, doxorubicin hydrochloride (DOX), was conjugated to alkyne-functionalized poly(l-glutamic acid) (PGA(Alk)) via amide bond formation. PGA(Alk) and PGA(Alk+DOX) were assembled via hydrogen bonding with poly(N-vinyl pyrrolidone) (PVPON) on planar and colloidal silica templates. The films were subsequently covalently stabilized using diazide cross-linkers, and PVPON was released from the multilayers by altering the solution pH to disrupt hydrogen bonding. After removal of the sacrificial template, single-component PGA(Alk) capsules were obtained and analyzed by optical microscopy, transmission electron microscopy, and atomic force microscopy. The PGA(Alk) capsules were stable in the pH range between 2 and 11 and exhibited reversible swelling/shrinking behavior. PGA(Alk+DOX) was assembled to form drug-loaded polymer capsules with control over drug dose and position in the multilayer system (e.g., DOX in every layer or exclusively in layer 3). The drug-loaded capsules could be degraded enzymatically, resulting in the sustained release of active DOX over approximately 2 h. Cellular uptake studies demonstrate that the viability of cells incubated with DOX-loaded PGA(Alk) capsules significantly decreased. The general applicability of this modular approach, in terms of incorporation of polymer-drug conjugates in other click multilayer systems, was also demonstrated. Biodegradable click capsules with drug-loaded multilayers are promising candidates as carrier systems for biomedical applications.
Spontaneous phase transfer of nanoparticulate metals from organic to aqueous media
Publisher: Wiley
Date: 17-08-2001
DOI: 10.1002/1521-3773(20010817)40:16<3001::AID-ANIE3001>3.0.CO;2-5
Glycogen-nucleic acid constructs for gene silencing in multicellular tumor spheroids
Publisher: Elsevier BV
Date: 09-2018
DOI: 10.1016/J.BIOMATERIALS.2018.05.024
Abstract: The poor penetration of nanocarrier-siRNA constructs into tumor tissue is a major hurdle for the in vivo efficacy of siRNA therapeutics, where the ability of the constructs to permeate the 3D multicellular matrix is determined by their physicochemical properties. Herein, we optimized the use of soft glycogen nanoparticles for the engineering of glycogen-siRNA constructs that can efficiently penetrate multicellular tumor spheroids and exert a significant gene silencing effect. Glycogen nanoparticles from different bio-sources and with different structural features were investigated. We show that larger glycogen nanoparticles ranging from 50 to 80 nm are suboptimal systems for complexation of nucleic acids if fine control of the size of constructs is required. Our studies suggest that 20 nm glycogen nanoparticles are optimal for complexation and efficient delivery of siRNA. The chemical composition, surface charge, and size of glycogen-siRNA constructs were finely controlled to minimize interactions with serum proteins and allow penetration into 3D multicellular spheroids of human kidney epithelial cells and human prostate cancer cells. We introduced pH sensitive moieties within the construct to enhance early endosome escape and efficiently improve the silencing effect in vitro. Glycogen-siRNA constructs were found to mediate gene silencing in 3D multicellular spheroids causing ∼60% specific gene silencing. The optimized construct exhibited an in vivo circulation lifetime of 8 h in mice, with preferential accumulation in the liver. No accumulation in the kidney, lung, spleen, heart or brain, or signs of toxicity in mice were observed. Our results highlight the potential for screening siRNA nanocarriers in 3D cultured prostate tumor models, thereby improving the predictive therapeutic efficacy of glycogen-based platforms in human physiological conditions.
Characterization of Polyelectrolyte−Protein Multilayer Films by Atomic Force Microscopy, Scanning Electron Microscopy, and Fourier Transform Infrared Reflection−Absorption Spectroscopy
Publisher: American Chemical Society (ACS)
Date: 15-07-1998
DOI: 10.1021/LA971288H
Engineering and evaluating drug delivery particles in microfluidic devices
Publisher: Elsevier BV
Date: 09-2014
DOI: 10.1016/J.JCONREL.2014.04.030
Abstract: The development of new and improved particle-based drug delivery is underpinned by an enhanced ability to engineer particles with high fidelity and integrity, as well as increased knowledge of their biological performance. Microfluidics can facilitate these processes through the engineering of spatiotemporally highly controlled environments using designed microstructures in combination with physical phenomena present at the microscale. In this review, we discuss microfluidics in the context of addressing key challenges in particle-based drug delivery. We provide an overview of how microfluidic devices can: (i) be employed to engineer particles, by providing highly controlled interfaces, and (ii) be used to establish dynamic in vitro models that mimic in vivo environments for studying the biological behavior of engineered particles. Finally, we discuss how the flexible and modular nature of microfluidic devices provides opportunities to create increasingly realistic models of the in vivo milieu (including multi-cell, multi-tissue and even multi-organ devices), and how ongoing developments toward commercialization of microfluidic tools are opening up new opportunities for the engineering and evaluation of drug delivery particles.
Distribution of Particles in Human Stem Cell-Derived 3D Neuronal Cell Models: Effect of Particle Size, Charge, and Density
Publisher: American Chemical Society (ACS)
Date: 29-07-2020
Mechanics of pH-Responsive Hydrogel Capsules
Publisher: American Chemical Society (ACS)
Date: 25-07-2013
DOI: 10.1021/LA402111V
Abstract: While soft hydrogel nano- and microstructures hold great potential for therapeutic treatments and in vivo applications, their nanomechanical characterization remains a challenge. In this paper, soft, single-component, supported hydrogel films were fabricated using pendant-thiol-modified poly(methacrylic acid) (PMASH). The influence of hydrogel architecture on deformation properties was studied by fabricating films on particle supports and producing free-standing capsules. The influence of the degree of thiol-based cross-linking on the mechanical properties of the soft hydrogel systems (core-shell and capsules) was studied using a colloidal-probe (CP) AFM technique. It was found that film mechanical properties, stability, and capsule swelling could be finely tuned by controlling the extent of poly(methacrylic acid) thiol modification. Furthermore, switching the pH from 7.4 to 4.0 led to film densification due to increased hydrogen bonding. Hydrogel capsule systems were found to have stiffness values ranging from 0.9 to 16.9 mN m(-1) over a thiol modification range of 5 to 20 mol %. These values are significantly greater than those for previously reported PMASH planar films of 0.7-5.7 mN m(-1) over the same thiol modification range (Best et al., Soft Matter 2013, 9, 4580-4584). Films on particle substrates had comparable mechanical properties to planar films, demonstrating that while substrate geometry has a negligible effect, membrane and tension effects may play an important role in capsule force resistance. Further, when transitioning from solid-supported films to free-standing capsules, simple predictions of shell stiffness based on modulus changes found for supported films are not valid. Rather, additional effects like diameter increases (geometrical changes) as well as tension buildup need to be taken into account. These results are important for research related to the characterization of soft hydrogel materials and control over their mechanical properties.
Nanoencapsulated microcrystalline particles for superamplified biochemical assays
Publisher: American Chemical Society (ACS)
Date: 25-09-2002
DOI: 10.1021/AC0200522
Abstract: We report on the preparation and utilization of a novel class of particulate labels based on nanoencapsulated organic microcrystals with the potential to create highly lified biochemical assays. Labels were constructed by encapsulating microcrystalline fluorescein diacetate (FDA average size of 500 nm) within ultrathin polyelectrolyte layers of poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) via the layer-by-layer technique. Subsequently, the polyelectrolyte coating was used as an "interface" for the attachment of anti-mouse antibodies through adsorption. A high molar ratio of fluorescent molecules present in the microcrystal core to biomolecules on the particle surface was achieved. The applicability of the microcrystal-based label system was demonstrated in a model sandwich immunoassay for mouse immunoglobulin G detection. Following the immunoreaction, the FDA core was dissolved by exposure to organic solvent, leading to the release of the FDA molecules into the surrounding medium. Amplification rates of 70-2000-fold (expressed as an increase in assay sensitivity) of the microcrystal label-based assay compared with the corresponding immunoassay performed with direct fluorescently labeled antibodies are reported. Our approach provides a general and facile means to prepare a novel class of biochemical assay labeling systems. The technology has the potential to compete with enzyme-based labels as it does not require long incubation times, thus speeding up bioaffinity tests.
Template-Assisted Antibody Assembly: A Versatile Approach for Engineering Functional Antibody Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 07-04-2022
Light-responsive polyelectrolyte/gold nanoparticle microcapsules
Publisher: American Chemical Society (ACS)
Date: 26-01-2005
DOI: 10.1021/JP045070X
Abstract: We report the preparation and characterization of light-responsive delivery vehicles, microcapsules composed of multiple polyelectrolyte layers and light-absorbing gold nanoparticles. The nanostructured capsules were loaded with macromolecules (fluorescein isothiocyanate-labeled dextran) by exploiting the pH-dependence of the shell permeability, and the encapsulated material was released on demand upon irradiation with short (10 ns) laser pulses in the near-infrared (1064 nm). In addition, the polyelectrolyte multilayer shell was modified with lipids (dilauroylphosphatidylethanolamine) and then functionalized with ligands (monoclonal immunoglobulin G antibodies) for the purposes of enhanced stability and targeted delivery, respectively. We anticipate that these capsules will find application in a range of areas where controlled delivery is desirable.
Enzyme multilayer-modified porous membranes as biocatalysts
Publisher: American Chemical Society (ACS)
Date: 12-2005
DOI: 10.1021/CM048659H
2-DIMENSIONAL DIFFUSION OF AMPHIPHILES IN PHOSPHOLIPID MONOLAYERS AT THE AIR-WATER-INTERFACE
Publisher: Elsevier BV
Date: 12-1993
Stiffness-mediated adhesion of cervical cancer cells to soft hydrogel films
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3SM50587A
Coated colloids with tailored optical properties
Publisher: American Chemical Society (ACS)
Date: 11-09-2003
DOI: 10.1021/JP034302+
Hierarchical Assembly of Zeolite Nanoparticles into Ordered Macroporous Monoliths Using Core−Shell Building Blocks
Publisher: American Chemical Society (ACS)
Date: 23-09-2000
DOI: 10.1021/CM000438Y
Preparation and Characterization of Ordered Nanoparticle and Polymer Composite Multilayers on Colloids
Publisher: American Chemical Society (ACS)
Date: 16-09-1999
DOI: 10.1021/LA990426V
Protein Component of Oyster Glycogen Nanoparticles: An Anchor Point for Functionalization
Publisher: American Chemical Society (ACS)
Date: 06-08-2020
Modulating the Pattern Quality of Micropatterned Multilayer Films Prepared by Layer-by-Layer Self-Assembly
Publisher: American Chemical Society (ACS)
Date: 21-12-2005
DOI: 10.1021/LA052057A
Abstract: Patterned multilayer films composed of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate) (PSS) were prepared using dip and spin self-assembly (SA) methods. A silicon substrate was patterned with a photoresist thin film using conventional photolithography, and PAH/PSS multilayers were then deposited onto the substrate surface using dip or spin SA. For spin SA, the photoresist on the substrate was retained, despite the high centrifugal forces involved in depositing the polyelectrolytes (PEs). The patterned multilayer films were formed by immersing the PE-coated substrates in acetone for 10 min. The effect of ionic strength on the pattern quality in dip and spin multilayer patterns (line-edge definition and surface roughness of the patterned region) was investigated by increasing the salt concentration in the PE solution (range 0-1 M). In dip multilayer patterns, the presence of salt increased the film surface roughness and pattern thickness without any deformation of pattern shape. The spin multilayer patterns formed without salt induced a height profile of about 130 nm at the pattern edge, whereas the patterns formed with high salt content (1 M) were extensively washed off the substrates. Well-defined pattern shapes of spin SA multilayers were obtained at an ionic strength of 0.4 M NaCl. Multilayer patterns prepared using spin SA and lift-off methods at the same ionic strength had a surface roughness of about 2 nm, and those prepared using the dip SA and lift-off method had a surface roughness of about 5 nm. The same process was used to prepare well-defined patterns of organic/metallic multilayer films consisting of PE and gold nanoparticles. The spin SA process yielded patterned multilayer films with various lengths and shapes.
YAP signaling regulates the cellular uptake and therapeutic effect of nanoparticles
Publisher: Cold Spring Harbor Laboratory
Date: 10-03-2023
DOI: 10.1101/2023.03.10.532035
Abstract: Interactions between living cells and nanoparticles have been extensively studied to enhance the delivery of therapeutics. Nanoparticles size, shape, stiffness and surface charge have been regarded as the main features able to control the fate of cell-nanoparticle interactions. However, the clinical translation of nanotherapies has so far been limited, and there is a need to better understand the biology of cell-nanoparticle interactions. This study investigated the role of cellular mechanosensitive components in cell-nanoparticle interactions. We demonstrate that the genetic and pharmacologic inhibition of yes-associated protein (YAP), a key component of cancer cell mechanosensing apparatus and Hippo pathway effector, improves nanoparticle internalization in triple-negative breast cancer cells regardless of nanoparticle properties or substrate characteristics. This process occurs through YAP-dependent regulation of endocytic pathways, cell mechanics, and membrane organization. Hence, we propose targeting YAP may sensitize triple negative breast cancer cells to chemotherapy and increase the selectivity of nanotherapy.
Thermally Induced Charge Reversal of Layer-by-Layer Assembled Single-Component Polymer Films
Publisher: American Chemical Society (ACS)
Date: 08-03-2016
Abstract: Temperature can be harnessed to engineer unique properties for materials useful in various contexts and has been shown to affect the layer-by-layer (LbL) assembly of polymer thin films and cause physical changes in preassembled polymer thin films. Herein we demonstrate that exposure to relatively low temperatures (≤ 100 °C) can induce physicochemical changes in cationic polymer thin films. The surface charge of polymer films containing primary and secondary amines reverses after heating (from positive to negative), and different characterization techniques are used to show that the change in surface charge is related to oxidation of the polymer that specifically occurs in the thin film state. This charge reversal allows for single-polymer LbL assembly to be performed with poly(allylamine) hydrochloride (PAH) through alternating heat/deposition steps. Furthermore, the negative charge induced by heating reduces the fouling and cell-association of PAH-coated planar and particulate substrates, respectively. This study highlights a unique property of thin films which is relevant to LbL assembly and biofouling and is of interest for the future development of thin polymer films for biomedical systems.
Achieving HIV-1 control through RNA-directed gene regulation
Publisher: MDPI AG
Date: 07-12-2016
DOI: 10.3390/GENES7120119
Direct synthesis of amorphous coordination polymers and metal–organic frameworks
Publisher: Springer Science and Business Media LLC
Date: 06-03-2023
Targeting cancer cells: Controlling the binding and internalization of antibody-functionalized capsules
Publisher: American Chemical Society (ACS)
Date: 07-08-2012
DOI: 10.1021/NN3010476
Abstract: The development of nanoengineered particles, such as polymersomes, liposomes, and polymer capsules, has the potential to offer significant advances in vaccine and cancer therapy. However, the effectiveness of these carriers has the potential to be greatly improved if they can be specifically delivered to target cells. We describe a general method for functionalizing nanoengineered polymer capsules with antibodies using click chemistry and investigate their interaction with cancer cells in vitro. The binding efficiency to cells was found to be dependent on both the capsule-to-cell ratio and the density of antibody on the capsule surface. In mixed cell populations, more than 90% of target cells bound capsules when the capsule-to-target cell ratio was 1:1. Strikingly, greater than 50% of target cells exhibited capsules on the cell surface even when the target cells were present as less than 0.1% of the total cell population. Imaging flow cytometry was used to quantify the internalization of the capsules, and the target cells were found to internalize capsules efficiently. However, the role of the antibody in this process was determined to enhance accumulation of capsules on the cell surface rather than promote endocytosis. This represents a significant finding, as this is the first study into the role antibodies play in internalization of such capsules. It also opens up the possibility of targeting these capsules to cancer cells using targeting molecules that do not trigger an endocytic pathway. We envisage that this approach will be generally applicable to the specific targeting of a variety of nanoengineered materials to cells.
Catalytically Active Copper Phosphate–Dextran Sulfate Microparticle Coatings for Bioanalyte Sensing
Publisher: Wiley
Date: 28-09-2020
Magnetic core-shell particles: Preparation of magnetite multilayers on polymer latex microspheres
Publisher: Wiley
Date: 08-1999
DOI: 10.1002/(SICI)1521-4095(199908)11:11<950::AID-ADMA950>3.0.CO;2-T
Layer-by-layer assembly of nanoblended thin films: Poly(allylamine hydrochloride) and a binary mixture of a synthetic and natural polyelectrolyte
Publisher: American Chemical Society (ACS)
Date: 31-07-2004
DOI: 10.1021/MA0490698
Nanoporous Metal–Phenolic Particles as Ultrasound Imaging Probes for Hydrogen Peroxide
Publisher: Wiley
Date: 09-2015
Abstract: Nanoporous metal-phenolic particles are fabricated through the nanostructural replication of dense Fe
Optically addressable nanostructured capsules
Publisher: Wiley
Date: 16-12-2004
Assembly of multilayer films from polyelectrolytes containing weak and strong acid moieties
Publisher: American Chemical Society (ACS)
Date: 19-08-2005
DOI: 10.1021/LA051197H
Abstract: Multilayer films were assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA), deposited in alternation with poly(allylamine hydrochloride) (PAH). The strongly charged groups (styrene sulfonate, SS) are expected to form electrostatic linkages (to enhance film stability), while the weakly charged groups (maleic acid, MA) can alter multilayer film properties because they are responsive to external pH changes. In this study, we varied several assembly conditions such as pH, SS/MA ratio in PSSMA, and the ionic strength of the polyelectrolyte solutions. The multilayer films were also treated by immersion into pH 2 and 11 solutions after assembly. Quartz crystal microgravimetry and UV-visible spectrophotometry showed that the thickness of PSSMA/PAH multilayers decreases with increasing assembly pH regardless of whether salt was present in the polyelectrolyte solutions. When no salt was added, the multilayers are thinner, smoother, and grow less regularly. Atomic force microscopy images indicate that the presence of salt in polyelectrolyte solutions results in rougher surface morphologies, and this effect is especially significant in multilayers assembled at pH 2 and pH 11. When both polyelectrolytes are adsorbed at conditions where they are highly charged, salt was necessary to promote regular multilayer growth. Fourier transform infrared spectroscopy studies show that the carboxylic acids in the multilayers are essentially ionized when assembled from different pHs in 0.5 M sodium chloride solutions, whereas some carboxylic acids remain protonated in the multilayers assembled from solutions with no added salt. This resulted in different pH stability regimes when the multilayers were exposed to different pH solutions, post assembly.
Flake-Shell Capsules: Adjustable Inorganic Structures
Publisher: Wiley
Date: 07-05-2012
Abstract: Structure-adjustable capsules are fabricated from inorganic components by using a self-template dissolution-regrowth mechanism to give flake-shell silica microcapsules. The capsules shrink under thermal stimulus and their structures can be adjusted by treatment at different pH values. Tuning of shell pore diameters leads to tailored drug release over prolonged periods.
Lateral diffusion of lipoidal spectroscopic probes in Langmuir-Blodgett films at the solid/liquid interface
Publisher: American Chemical Society (ACS)
Date: 10-1994
DOI: 10.1021/LA00022A001
Polyelectrolyte-coated colloid spheres as templates for sol-gel reactions
Publisher: American Chemical Society (ACS)
Date: 17-04-2002
DOI: 10.1021/CM0211251
Polyphenol-Based Nanoparticles for Intracellular Protein Delivery via Competing Supramolecular Interactions
Publisher: American Chemical Society (ACS)
Date: 30-09-2020
Binding, internalization, and antigen presentation of vaccine-loaded nanoengineered capsules in blood
Publisher: Wiley
Date: 16-12-2008
Polymersome-loaded capsules for controlled release of DNA
Publisher: Wiley
Date: 04-07-2011
Abstract: The formation of a novel drug-delivery carrier for the controlled release of plasmid DNA that comprises layer-by-layer polymer capsules subcompartmentalized with pH-sensitive nanometer-sized polymersomes is reported. The hiphilic diblock copolymer poly(oligoethylene glycol methacrylate)-block-poly(2-(diisopropylamino)ethyl methacrylate) forms polymersomes at physiological pH, but transitions to unimeric polymer chains upon acidification to cellular endocytic pH. These polymersomes can thus release an encapsulated payload in response to a change in pH from physiological to endocytic conditions. Multicomponent layer-by-layer capsules are formed by exploiting the ability of tannic acid to act as an efficient hydrogen-bond donor for both the polymersomes and poly(N-vinyl pyrrolidone) at physiological pH. These capsules show release of a plasmid DNA payload encapsulated within the polymersome subcompartments in response to changes in pH between physiological and endocytic conditions.
Tutorials and Articles on Best Practices
Publisher: American Chemical Society (ACS)
Date: 22-09-2020
Nanoporous block copolymer micelle/micelle multilayer films with dual optical properties
Publisher: American Chemical Society (ACS)
Date: 12-07-2006
DOI: 10.1021/JA062437Y
Abstract: We introduce a novel and versatile approach for preparing self-assembled nanoporous multilayered films with tunable optical properties. Protonated polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and anionic polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer micelles (BCM) were used as building blocks for the layer-by-layer assembly of BCM multilayer films. BCM film growth is governed by electrostatic and hydrogen-bonding interactions between the opposite BCMs. Both film porosity and film thickness are dependent upon the charge density of the micelles, with the porosity of the film controlled by the solution pH and the molecular weight (M(w)) of the constituents. PS(7K)-b-P4VP(28K)/PS(2K)-b-PAA(8K) films prepared at pH 4 (for PS(7K)-b-P4VP(28K)) and pH 6 (for PS(2K)-b-PAA(8K)) are highly nanoporous and antireflective. In contrast, PS(7K)-b-P4VP(28K)/PS(2K)-b-PAA(8K) films assembled at pH 4/4 show a relatively dense surface morphology due to the decreased charge density of PS(2K)-b-PAA(8K). Films formed from BCMs with increased PS block and decreased hydrophilic block (P4VP or PAA) size (e.g., PS(36K)-b-P4VP(12K)/PS(16K)-b-PAA(4K) at pH 4/4) were also nanoporous. This is attributed to a decrease in interdigitation between the adjacent corona shells of the low M(w) BCMs, thus creating more void space between the micelles. Multilayer films with antireflective and photochromic properties were obtained by incorporating a water-insoluble photochromic dye (spiropyran) into the hydrophobic PS core of the BCMs assembled in the films. The optical properties of these films can be modulated by UV irradiation to selectively and reversibly control the transmission of light. Light transmission of higher than 99% was observed with accompanying photochromism in the (PS(7K)-b-P4VP(28K)/PS(2K)-b-PAA(8K)) multilayer films assembled at pH 4/6. Our approach highlights the potential to incorporate a range of materials, ranging from conventional hydrophilic materials with specific interactions to hydrophobic compounds, into the assembled BCMs to yield multifunctional nanoporous films.
Revisiting cell–particle association in vitro: A quantitative method to compare particle performance
Publisher: Elsevier BV
Date: 08-2019
DOI: 10.1016/J.JCONREL.2019.06.027
Abstract: Nanoengineering has the potential to revolutionize medicine by designing drug delivery systems that are both efficacious and highly selective. Determination of the affinity between cell lines and nanoparticles is thus of central importance, both to enable comparison of particles and to facilitate prediction of in vivo response. Attempts to compare particle performance can be dominated by experimental artifacts (including settling effects) or variability in experimental protocol. Instead, qualitative methods are generally used, limiting the reusability of many studies. Herein, we introduce a mathematical model-based approach to quantify the affinity between a cell-particle pairing, independent of the aforementioned confounding artifacts. The analysis presented can serve as a quantitative metric of the stealth, fouling, and targeting performance of nanoengineered particles in vitro. We validate this approach using a newly created in vitro dataset, consisting of seven different disulfide-stabilized poly(methacrylic acid) particles ranging from ~100 to 1000 nm in diameter that were incubated with three different cell lines (HeLa, THP-1, and RAW 264.7). We further expanded this dataset through the inclusion of previously published data and use it to determine which of five mathematical models best describe cell-particle association. We subsequently use this model to perform a quantitative comparison of cell-particle association for cell-particle pairings in our dataset. This analysis reveals a more complex cell-particle association relationship than a simplistic interpretation of the data, which erroneously assigns high affinity for all cell lines examined to large particles. Finally, we provide an online tool (bionano.xyz/estimator), which allows other researchers to easily apply this modeling approach to their experimental results.
A Biomolecular Ship-in-a-Bottle: Continuous RNA Synthesis Within Hollow Polymer Hydrogel Assemblies
Publisher: Wiley
Date: 04-02-2010
Capsosomes with Multilayered Subcompartments: Assembly and Loading with Hydrophobic Cargo
Publisher: Wiley
Date: 28-12-2010
Modular Metal‐Quinone Networks with Tunable Architecture and Functionality
Publisher: Wiley
Date: 20-02-2023
Abstract: Nanostructured materials with tunable structures and functionality are of interest in erse areas. Herein, metal ions are coordinated with quinones through metal‐acetylacetone coordination bonds to generate a class of structurally tunable, universally adhesive, hydrophilic, and pH‐degradable materials. A library of metal‐quinone networks (MQNs) is produced from five model quinone ligands paired with nine metal ions, leading to the assembly of particles, tubes, capsules, and films. Importantly, MQNs show bidirectional pH‐responsive disassembly in acidic and alkaline solutions, where the quinone ligands mediate the disassembly kinetics, enabling temporal and spatial control over the release of multiple components using multilayered MQNs. Leveraging this tunable release and the inherent medicinal properties of quinones, MQN prodrugs with a high drug loading ( wt %) are engineered using doxorubicin for anti‐cancer therapy and shikonin for the inhibition of the main protease in the SARS‐CoV‐2 virus.
Reflectivity behavior of opals of gold nanoparticle coated spheres
Publisher: AIP Publishing
Date: 03-05-2004
DOI: 10.1063/1.1739512
Abstract: The light reflectance in three-dimensional metallodielectric photonic crystals assembled from polyelectrolyte-coated latex spheres infiltrated with gold nanoparticles has been studied. Strong deviation of the optical reflectance of Au opals from bare opals has been observed, including flattening of the diffraction resonance dispersion and nondispersive surface plasmon bands.
Site‐Selective Coordination Assembly of Dynamic Metal‐Phenolic Networks
Publisher: Wiley
Date: 13-07-2022
Abstract: Coordination states of metal‐organic materials are known to dictate their physicochemical properties and applications in various fields. However, understanding and controlling coordination sites in metal‐organic systems is challenging. Herein, we report the synthesis of site‐selective coordinated metal‐phenolic networks (MPNs) using flavonoids as coordination modulators. The site‐selective coordination was systematically investigated experimentally and computationally using ligands with one, two, and multiple different coordination sites. Tuning the multimodal Fe coordination with catechol, carbonyl, and hydroxyl groups within the MPNs enabled the facile engineering of erse physicochemical properties including size, selective permeability (20–2000 kDa), and pH‐dependent degradability. This study expands our understanding of metal‐phenolic chemistry and provides new routes for the rational design of structurally tailorable coordination‐based materials.
Robust and Versatile Coatings Engineered via Simultaneous Covalent and Noncovalent Interactions
Publisher: Wiley
Date: 06-08-2021
Abstract: Interfacial modular assembly has emerged as an adaptable strategy for engineering the surface properties of substrates in biomedicine, photonics, and catalysis. Herein, we report a versatile and robust coating (pBDT‐TA), self‐assembled from tannic acid (TA) and a self‐polymerizing aromatic dithiol (i.e., benzene‐1,4‐dithiol, BDT), that can be engineered on erse substrates with a precisely tuned thickness (5–40 nm) by varying the concentration of BDT used. The pBDT‐TA coating is stabilized by covalent (disulfide) bonds and supramolecular (π‐π) interactions, endowing the coating with high stability in various harsh aqueous environments across ionic strength, pH, temperature (e.g., 100 mM NaCl, HCl (pH 1) or NaOH (pH 13), and water at 100 °C), as well as surfactant solution (e.g., 100 mM Triton X‐100) and biological buffer (e.g., Dulbecco's phosphate‐buffered saline), as validated by experiments and simulations. Moreover, the reported pBDT‐TA coating enables secondary reactions on the coating for engineering hybrid adlayers (e.g., ZIF‐8 shells) via phenolic‐mediated adhesion, and the facile integration of aromatic fluorescent dyes (e.g., rhodamine B) via π interactions without requiring elaborate synthetic processes.
Preparation of enzyme multilayers on colloids for biocatalysis
Publisher: Wiley
Date: 07-2000
DOI: 10.1002/1521-3927(20000701)21:11<750::AID-MARC750>3.0.CO;2-3
Functionalization of colloids with robust inorganic-based lipid coatings
Publisher: American Chemical Society (ACS)
Date: 12-2004
DOI: 10.1021/MA048706R
Electrostatically assembled fluorescent thin films of rare-earth-doped lanthanum phosphate nanoparticles
Publisher: American Chemical Society (ACS)
Date: 21-09-2002
DOI: 10.1021/CM0212257
Metal-phenolic networks as a versatile platform to engineer nanomaterials and biointerfaces
Publisher: Elsevier BV
Date: 02-2017
An Enzyme‐Coated Metal–Organic Framework Shell for Synthetically Adaptive Cell Survival
Publisher: Wiley
Date: 05-06-2017
Challenges facing colloidal delivery systems: From synthesis to the clinic
Publisher: Elsevier BV
Date: 06-2011
Generalizable Strategy for Engineering Protein Particles with pH-Triggered Disassembly and Recoverable Protein Functionality
Publisher: American Chemical Society (ACS)
Date: 13-01-2015
DOI: 10.1021/MZ5007443
pH-Responsive Poly(acrylic acid) Core Cross-Linked Star Polymers: Morphology Transitions in Solution and Multilayer Thin Films
Publisher: American Chemical Society (ACS)
Date: 13-03-2008
DOI: 10.1021/MA7019557
Modular Assembly of Layer-by-Layer Capsules with Tailored Degradation Profiles †
Publisher: American Chemical Society (ACS)
Date: 03-12-2011
DOI: 10.1021/LA104232R
Abstract: Herein we report the preparation of layer-by-layer (LbL) assembled, biodegradable, covalently stabilized capsules with tunable degradation properties. Poly(L-glutamic acid) modified with alkyne moieties (PGA(Alk)) was alternately assembled with poly(N-vinyl pyrrolidone) (PVPON) on silica particles via hydrogen-bonding. The films were cross-linked with a bis-azide linker, followed by removal of the sacrificial template and PVPON at physiological pH through hydrogen bond disruption, yielding one-component PGA(Alk) capsules. To control the kinetics and location of capsule degradation, a number of approaches were investigated. First, a degradable bis-azide cross-linker was incorporated into the inherently enzymatically degradable capsules. Second, we assembled low-fouling capsules composed of nondegradable poly(N-vinyl pyrrolidone-ran-propargyl acrylate) (PVPON(Alk)) via hydrogen bonding with poly(methacrylic acid) (PMA) and combined this with the aforementioned system (PGA(Alk)/PVPON) to produce stratified hybrid capsules. The degradation profiles of these stratified capsules can be closely controlled by the number as well as the position of nondegradable barrier layers in the systems. The facile tailoring of the degradation kinetics makes this stratified LbL approach promising for the design of tailored drug-delivery vehicles.
Fabrication of polymer-nanoparticle composite inverse opals by a one-step electrochemical co-deposition process
Publisher: American Chemical Society (ACS)
Date: 26-11-2004
DOI: 10.1021/NL0348443
Template-Mediated Assembly of DNA into Microcapsules for Immunological Modulation
Publisher: Wiley
Date: 06-08-2020
Dense nanoparticulate thin films via gold nanoparticle self-assembly
Publisher: Wiley
Date: 04-04-2002
DOI: 10.1002/1521-4095(20020404)14:7<508::AID-ADMA508>3.0.CO;2-T
Super-Soft Hydrogel Particles with Tunable Elasticity in a Microfluidic Blood Capillary Model
Publisher: Wiley
Date: 10-09-2014
Abstract: Super-soft PEG hydrogel particles with tunable elasticity are prepared via a mesoporous silica templating method. The deformability behavior of these particles, in a microfluidic blood-capillary model, can be tailored to be similar to that of human red blood cells. These results provide a new platform for the design and development of soft hydrogel particles for investigating bio-nano interactions.
Exploiting Supramolecular Dynamics in Metal–Phenolic Networks to Generate Metal–Oxide and Metal–Carbon Networks
Publisher: Wiley
Date: 17-05-2021
Abstract: Supramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal–phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their erse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal–oxide networks (MONs) and metal–carbon networks, respectively. Furthermore, by integrating photo‐responsive motifs (i.e., TiO 2 ) and silanization, the MONs are endowed with reversible superhydrophobic ( °) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into erse materials, this work offers a versatile pathway for advanced materials engineering.
Adsorption and desorption behavior of an anionic pyrene chromophore in sequentially deposited polyelectrolyte-dye thin films
Publisher: American Chemical Society (ACS)
Date: 31-05-2000
DOI: 10.1021/JA994029I
Multifunctional Thrombin‐Activatable Polymer Capsules for Specific Targeting to Activated Platelets
Publisher: Wiley
Date: 03-08-2015
Abstract: Smart poly(2-oxazoline) (POx)-based multifunctional polymer capsules that specifically target glycoprotein (GP) IIb/IIIa on the surface of activated platelets are degraded by the serine protease thrombin and release the urokinase plasminogen activator loaded into the polymer capsules, only in the area of acute thrombosis.
Electrostatic Self-Assembly of Silica Nanoparticle−Polyelectrolyte Multilayers on Polystyrene Latex Particles
Publisher: American Chemical Society (ACS)
Date: 08-1998
DOI: 10.1021/JA9815024
Shape-dependent cellular processing of polyelectrolyte capsules
Publisher: American Chemical Society (ACS)
Date: 12-12-2013
DOI: 10.1021/NN3046117
Abstract: Particle shape is emerging as a key design parameter for tailoring the interactions between particles and cells. Herein, we report the preparation of rod-shaped layer-by-layer (LbL)-assembled polymer hydrogel capsules with tunable aspect ratios (ARs). By templating spherical and rodlike silica particles, disulfide-stabilized poly(methacrylic acid) hydrogel capsules (PMA HCs) with different ARs (from 1 to 4) are generated. The influence of capsule AR on cellular internalization and intracellular fate was quantitatively investigated by flow cytometry, imaging flow cytometry, and fluorescence deconvolution microscopy. These experiments reveal that the cellular internalization kinetics of PMA HCs are dependent on the AR, with spherical capsules being internalized more rapidly and to a greater extent compared with rod-shaped capsules. In contrast, the capsules with different ARs are colocalized with the lysosomal marker LAMP1, suggesting that the lysosomal compartmentalization is independent of shape for these soft polymer capsules.
Ultrasonic synthesis of stable, functional lysozyme microbubbles
Publisher: American Chemical Society (ACS)
Date: 19-08-2008
DOI: 10.1021/LA801093Q
Abstract: High-intensity ultrasound induces emulsification and cross-linking of protein molecules in aqueous medium. The stability and the functionality of the resultant protein-coated microbubbles are crucial in many of their applications. For ex le, the stability of drug-loaded microbubbles should be sufficiently long enough, in vivo, so that they can be ruptured only at specific sites for release of the drugs. In this study, we report the synthesis of stable and functional microbubbles, coated with chemically reduced lysozyme, using high-intensity ultrasound in aqueous solution. In the absence of chemical reduction, stable microbubbles were not produced with native lysozyme, indicating the importance of free -SH functional groups for protein cross-linking. The degree of cross-linking between lysozyme molecules was controlled by manipulating both the extent of chemical reduction of the intramolecular disulfide bonds and sonication time. The lysozyme-coated microbubbles are stable for several months and retain the enzymatic (antimicrobial) activity of lysozyme. The layer-by-layer (LbL) deposition of polyelectrolytes onto the protein-shell air-core template has been used as a versatile procedure to modify the surface properties of the microbubbles, indicating the possibility of adsorbing potential drugs and/or biolabels on the surface of these microbubbles for therapeutic and diagnostic applications.
Nanoengineering multifunctional hybrid interfaces using adhesive glycogen nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0TB00299B
Abstract: Amphiphilic phytoglycogen nanoparticles are used as building blocks for engineering multifunctional hybrid films with catalytic and sensing properties.
Phototriggered, metal-free continuous assembly of polymers for the fabrication of ultrathin films
Publisher: American Chemical Society (ACS)
Date: 26-07-2012
DOI: 10.1021/MZ300307E
Abstract: A facile and metal-free thin film fabrication technology based on the photoinduced continuous assembly of polymers (photoCAP) is described. The efficiency and versatility of this method is demonstrated by the formation of crosslinked and surface-confined nanoengineered thin films, in the form of surface coatings and hollow polymer capsules.
Nanomedicine toward 2040
Publisher: American Chemical Society (ACS)
Date: 02-03-2020
The use of carbonic anhydrase to accelerate carbon dioxide capture processes
Publisher: Wiley
Date: 14-08-2015
DOI: 10.1002/JCTB.4502
Next-generation enhanced-efficiency fertilizers for sustained food security
Publisher: Springer Science and Business Media LLC
Date: 21-07-2022
A Framework to Account for Sedimentation and Diffusion in Particle-Cell Interactions
Publisher: American Chemical Society (ACS)
Date: 06-07-2016
DOI: 10.1021/ACS.LANGMUIR.6B01634
Abstract: In vitro experiments provide a solid basis for understanding the interactions between particles and biological systems. An important confounding variable for these studies is the difference between the amount of particles administered and that which reaches the surface of cells. Here, we engineer a hydrogel-based nanoparticle system and combine in situ characterization techniques, 3D-printed cell cultures, and computational modeling to evaluate and study particle-cell interactions of advanced particle systems. The framework presented demonstrates how sedimentation and diffusion can explain differences in particle-cell association, and provides a means to account for these effects. Finally, using in silico modeling, we predict the proportion of particles that reaches the cell surface using common experimental conditions for a wide range of inorganic and organic micro- and nanoparticles. This work can assist in the understanding and control of sedimentation and diffusion when investigating cellular interactions of engineered particles.
Super-resolution Imaging of Proton Sponge-Triggered Rupture of Endosomes and Cytosolic Release of Small Interfering RNA
Publisher: American Chemical Society (ACS)
Date: 19-12-2019
Abstract: The intracellular delivery of nucleic acids and proteins remains a key challenge in the development of biological therapeutics. In gene therapy, the inefficient delivery of small interfering RNA (siRNA) to the cytosol by lipoplexes or polyplexes is often ascribed to the entrapment and degradation of siRNA payload in the endosomal compartments. A possible mechanism by which polyplexes rupture the endosomal membrane and release their nucleic acid cargo is commonly defined as the "proton sponge effect". This is an osmosis-driven process triggered by the proton buffering capacity of polyplexes. Herein, we investigate the molecular basis of the "proton sponge effect" through direct visualization of the siRNA trafficking process, including analysis of in idual polyplexes and endosomes, using stochastic optical reconstruction microscopy. We probe the sequential siRNA trafficking steps through single molecule super-resolution analysis of subcellular structures, polyplexes, and silencing RNA molecules. Specifically, in idual intact polyplexes released in the cytosol upon rupture of the endosomes, the damaged endosomal vesicles, and the disassembly of the polyplexes in the cytosol are examined. We find that the architecture of the polyplex and the rigidity of the cationic polymer chains are crucial parameters that control the mechanism of endosomal escape driven by the proton sponge effect. We provide evidence that in highly branched and rigid cationic polymers, such as glycogen or polyethylenimine, immobilized on silica nanoparticles, the proton sponge effect is effective in inducing osmotic swelling and rupture of endosomes.
Effect of UV-irradiation on polyelectrolyte multilayered films and hollow capsules prepared by layer-by-layer assembly
Publisher: American Chemical Society (ACS)
Date: 24-10-2006
DOI: 10.1021/MA0615598
Low-Fouling, Biofunctionalized, and Biodegradable Click Capsules
Publisher: American Chemical Society (ACS)
Date: 08-11-2008
DOI: 10.1021/BM800794W
Abstract: We report the synthesis of covalently stabilized hollow capsules from biodegradable materials using a combination of click chemistry and layer-by-layer (LbL) assembly. The biodegradable polymers poly(L-lysine) (PLL) and poly(L-glutamic acid) (PGA) were modified with alkyne and azide moieties. Linear film buildup was observed for both materials on planar surfaces and colloidal silica templates. A variation of the assembly conditions, such as an increase in the salt concentration and variations in pH, was shown to increase the in idual layer thickness by almost 200%. The biodegradable click capsules were analyzed with optical microscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Capsules were uniform in size and had a regular, spherical shape. They were found to be stable between pH 2 and 11 and showed reversible, pH-responsive shrinking/swelling behavior. We also show that covalently stabilized PLL films can be postfunctionalized by depositing a monolayer of heterobifunctional poly(ethylene glycol) (PEG), which provides low-fouling properties and simultaneously enhances specific protein binding. The responsive, biodegradable click films reported herein are promising for a range of applications in the biomedical field.
Biofunctional metal–phenolic films from dietary flavonoids.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6CC08607A
Abstract: Flavonoid films: dietary flavonoids assemble into biofunctional films and capsules in a one-step process via metal coordination. The antioxidant property of the parent flavonoid is enhanced when assembled into a film and can be reused over multiple cycles.
Supramolecular Polyphenol‐DNA Microparticles for In Vivo Adjuvant and Antigen Co‐Delivery and Immune Stimulation
Publisher: Wiley
Date: 10-02-2023
Abstract: DNA‐based materials have attracted interest due to the tunable structure and encoded biological functionality of nucleic acids. A simple and general approach to synthesize DNA‐based materials with fine control over morphology and bioactivity is important to expand their applications. Here, we report the synthesis of DNA‐based particles via the supramolecular assembly of tannic acid (TA) and DNA. Uniform particles with different morphologies are obtained using a variety of DNA building blocks. The particles enable the co‐delivery of cytosine‐guanine adjuvant sequences and the antigen ovalbumin in model cells. Intramuscular injection of the particles in mice induces antigen‐specific antibody production and T cell responses with no apparent toxicity. Protein expression in cells is shown using capsules assembled from TA and plasmid DNA. This work highlights the potential of TA as a universal material for directing the supramolecular assembly of DNA into gene and vaccine delivery platforms.
Protein Adsorption and Coordination-Based End-Tethering of Functional Polymers on Metal–Phenolic Network Films
Publisher: American Chemical Society (ACS)
Date: 22-02-2019
DOI: 10.1021/ACS.BIOMAC.9B00006
Abstract: Metal-phenolic network (MPN) coatings have generated increasing interest owing to their biologically inspired nature, facile fabrication, and near-universal adherence, especially for biomedical applications. However, a key issue in biomedicine is protein fouling, and the adsorption of proteins on tannic acid-based MPNs remains to be comprehensively studied. Herein, we investigate the interaction of specific biomedically relevant proteins in solution (e.g., bovine serum albumin (BSA), immunoglobulin G (IgG), fibrinogen) and complex biological media (serum) using layer-by-layer-assembled tannic acid/Fe
Nanotubes prepared by layer-by-layer coating of porous membrane templates
Publisher: Wiley
Date: 04-11-2003
Engineered hydrogen-bonded glycopolymer capsules and their interactions with antigen presenting cells
Publisher: American Chemical Society (ACS)
Date: 10-02-2017
Abstract: Hollow glycopolymer microcapsules were fabricated by hydrogen-bonded layer-by-layer (LbL) assembly, and their interactions with a set of antigen presenting cells (APCs), including dendritic cells (DCs), macrophages (MACs), and myeloid derived suppressor cells (MDSCs), were investigated. The glycopolymers were obtained by cascade postpolymerization modifications of poly(oligo(2-ethyl-2-oxazoline methacrylate)-stat-glycidyl methacrylate) involving the modification of the glycidyl groups with propargylamine and the subsequent attachment of mannose azide by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). Multilayer assembly of the hydrogen-bonding pair (glycopolymer oly(methacrylic acid) (PMA)) onto planar and particulate supports (SiO
Expanding the Toolbox of Metal–Phenolic Networks via Enzyme‐Mediated Assembly
Publisher: Wiley
Date: 04-12-2019
Self-Assembled Stimuli-Responsive Polyrotaxane Core-Shell Particles
Publisher: American Chemical Society (ACS)
Date: 13-12-2014
DOI: 10.1021/BM401244A
Abstract: Thermodynamically assembled core-shell nanocarriers are potential candidates for drug delivery applications due to their submicrometer size and the ability to load drugs into their hydrophobic core. Herein, we describe the formation of core-shell particles that consist of noncovalent polymers, that is, polyrotaxanes (PRXs), that form an α-cyclodextrin (αCD) core surrounded by a corona of low-fouling poly(ethylene glycol) (PEG). The PRX core-shell particles are able to sequester small organic molecules, such as pyrene and calcein, releasing these small molecules during degradation. The small, cellular peptide, glutathione, was used to degrade the particles through the reductive cleavage of disulfide bonds that stabilize the in idual PRX polymers. Cleavage of a single bond allows for the degradation of the supramolecular-polymer, making these PRX core-shell particles highly responsive. Furthermore, these particles demonstrate negligible cytotoxicity in mammalian cells, making them promising carriers for future drug delivery research.
Layer-by-Layer Polymer Coating on Discrete Particles of Cubic Lyotropic Liquid Crystalline Dispersions (Cubosomes)
Publisher: American Chemical Society (ACS)
Date: 08-10-2013
DOI: 10.1021/LA401660H
Abstract: Cubic phase lyotropic liquid crystalline colloidal dispersions (cubosomes) were surface-modified with seven polyelectrolyte layers using a layer-by-layer (LbL) approach. The first layer consisted of a copolymer synthesized from methacrylic acid and oleoyl methacrylate for enhanced incorporation within the bilayer of the cubic nanostructure. Six additional layers of poly(L-lysine) and poly(methacrylic acid) were then sequentially added, followed by a washing procedure to remove polymer aggregates from the soft matter particles. Polymer buildup was monitored via microelectrophoresis, dynamic light scattering, and small-angle X-ray scattering. Polymer-coated cubosomes were observed with cryo-transmission electron microscopy. A potential application of the modified nanostructured particles presented in this study is to reduce the burst-release effect associated with drug-loaded cubosomes. The effectiveness of this approach was demonstrated through loading and release results from a model hydrophilic small molecule (fluorescein).
Encapsulation of Water-Insoluble Drugs in Polymer Capsules Prepared Using Mesoporous Silica Templates for Intracellular Drug Delivery
Publisher: Wiley
Date: 18-06-2010
Nanoporous polymer thin films via polyelectrolyte templating
Publisher: Wiley
Date: 05-09-2005
Synthesis of Chemically Asymmetric Silica Nanobottles and Their Application for Cargo Loading and as Nanoreactors and Nanomotors
Publisher: Wiley
Date: 20-10-2016
Abstract: We report the synthesis of chemically asymmetric silica nanobottles (NBs) with a hydrophobic exterior surface (capped with 3‐chloropropyl groups) and a hydrophilic interior surface for spatially selective cargo loading, and for application as nanoreactors and nanomotors. The silica NBs, which have a “flask bottle” shape with an average diameter of 350 nm and an opening of ca. 100 nm, are prepared by anisotropic sol–gel growth in a water/n‐pentanol emulsion. Due to their chemically asymmetric properties, nanoparticles (NPs) with hydrophilic or hydrophobic surface properties can be selectively loaded inside the NBs or on the outside of the NBs, respectively. A high‐performance nanomotor is constructed by selectively loading catalytically active hydrophilic Pt NPs inside the NBs. It is also demonstrated that these NBs can be used as vessels for various reactions, such as the in situ synthesis of Au NPs, and using Au NP‐loaded NBs as nanoreactors for catalytic reactions.
Preparation of J-aggregate liposome dispersions and their chromic transformation
Publisher: American Chemical Society (ACS)
Date: 10-06-2004
DOI: 10.1021/LA049569U
Abstract: We report the preparation of aqueous liposome dispersions of J-aggregates formed by the hiphilic merocyanine dye (MD). A series of liposome-forming lipids were dispersed together with MD J-aggregates at different molar ratios of MD to lipid. The MD J-aggregate dispersions prepared with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) at the MD to DMPC ratio of 0.16 exhibit good dispersibility that is, they can be readily redispersed without any flocculation even after their precipitation. By use of different counterions for the MD molecules, two types of J-aggregate dispersions, one that exhibits an absorption band (J-band) at 635 nm (type I) and the other at 600 nm (type II), were obtained. As an ex le of the use of MD J-aggregates liposome dispersions, the thermochromic transformation of MD J-aggregates was demonstrated. When the dispersions are heated, J-aggregates of type I transformed into type II at a certain temperature (T(disp)). The parameters that control the speed of the transformation and the value of T(disp) were determined.
Interactions between circulating nanoengineered polymer particles and extracellular matrix components in vitro
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6BM00726K
Abstract: A simple and modular flow-based system is used to rapidly screen fundamental interactions of soft polymer particles with biologically relevant microenvironments under flow-conditions.
Assembly of β-glucosidase multilayers on spherical colloidal particles and their use as active catalysts
Publisher: Elsevier BV
Date: 09-2000
An Engineered Nanosugar Enables Rapid and Sustained Glucose‐Responsive Insulin Delivery in Diabetic Mice
Publisher: Wiley
Date: 12-03-2023
Abstract: Glucose‐responsive insulin‐delivery platforms that are sensitive to dynamic glucose concentration fluctuations and provide both rapid and prolonged insulin release have great potential to control hyperglycemia and avoid hypoglycemia diabetes. Here, biodegradable and charge‐switchable phytoglycogen nanoparticles capable of glucose‐stimulated insulin release are engineered. The nanoparticles are “nanosugars” bearing glucose‐sensitive phenylboronic acid groups and amine moieties that allow effective complexation with insulin (≈95% loading capacity) to form nanocomplexes. A single subcutaneous injection of nanocomplexes shows a rapid and efficient response to a glucose challenge in two distinct diabetic mouse models, resulting in optimal blood glucose levels (below 200 mg dL –1 ) for up to 13 h. The morphology of the nanocomplexes is found to be key to controlling rapid and extended glucose‐regulated insulin delivery in vivo. These studies reveal that the injected nanocomplexes enabled efficient insulin release in the mouse, with optimal bioavailability, pharmacokinetics, and safety profiles. These results highlight a promising strategy for the development of a glucose‐responsive insulin delivery system based on a natural and biodegradable nanosugar.
Cobalt Phosphate Nanostructures for Non-Enzymatic Glucose Sensing at Physiological pH
Publisher: American Chemical Society (ACS)
Date: 13-11-2018
Abstract: Nanostructured materials have potential as platforms for analytical assays and catalytic reactions. Herein, we report the synthesis of electrocatalytically active cobalt phosphate nanostructures (CPNs) using a simple, low-cost, and scalable preparation method. The electrocatalytic properties of CPNs toward the electrooxidation of glucose (Glu) were studied by cyclic voltammetry and chrono erometry in relevant biological electrolytes, such as phosphate-buffered saline (PBS), at physiological pH (7.4). Using CPNs, Glu detection could be achieved over a wide range of biologically relevant concentrations, from 1 to 30 mM Glu in PBS, with a sensitivity of 7.90 nA/mM cm
Synthesis of Discrete Alkyl‐Silica Hybrid Nanowires and Their Assembly into Nanostructured Superhydrophobic Membranes
Publisher: Wiley
Date: 09-06-2016
Fabrication of chiral stationary phases via continuous assembly of polymers for resolution of enantiomers by liquid chromatography
Publisher: Wiley
Date: 07-07-2014
Polyelectrolyte blend multilayer films: Surface morphology, wettability, and protein adsorption characteristics
Publisher: American Chemical Society (ACS)
Date: 31-03-2007
DOI: 10.1021/LA0634746
Abstract: We report the influence of polyelectrolyte (PE) multilayer films prepared from poly(styrene sulfonate)-poly(acrylic acid) (PSS-PAA) blends, deposited in alternation with poly(allylamine hydrochloride) (PAH), on film wettability and the adsorption behavior of the protein immunoglobulin G (IgG). Variations in the chemical composition of the PAH/(PSS-PAA) multilayer films, controlled by the PSS/PAA blend ratio in the dipping solutions, were used to systematically control film thickness, surface morphology, surface wettability, and IgG adsorption. Spectroscopic ellipsometry measurements indicate that increasing the PSS content in the blend solutions results in a systematic decrease in film thickness. Increasing the PSS content in the blend solutions also leads to a reduction in film surface roughness (as measured by atomic force microscopy), with a corresponding increase in surface hydrophobicity. Advancing contact angles (theta) range from 7 degrees for PAH/PAA films through to 53 degrees for PAH/PSS films. X-ray photoelectron spectroscopy measurements indicate that the increase in film hydrophobicity is due to an increase in PSS concentration at the film surface. In addition, the influence of added electrolyte in the PE solutions was investigated. Adsorption from PE solutions containing added salt favors PSS adsorption and results in more hydrophobic films. The amount of IgG adsorbed on the multilayer films systematically increased on films assembled from blends with increasing PSS content, suggesting strong interactions between PSS in the multilayer films and IgG. Hence, multilayer films prepared from blended PE solutions can be used to tune film thickness and composition, as well as wetting and protein adsorption characteristics.
Tuning the Properties of Polymer Capsules for Cellular Interactions
Publisher: American Chemical Society (ACS)
Date: 26-05-2017
DOI: 10.1021/ACS.BIOCONJCHEM.7B00168
Abstract: Particle-cell interactions are governed by, among other factors, the composition and surface properties of the particles. Herein, we report the preparation of various polymer capsules with different compositions and properties via atom transfer radical polymerization mediated continuous assembly of polymers (CAP
Compositional and structural engineering of DNA multilayer films
Publisher: American Chemical Society (ACS)
Date: 03-02-2006
DOI: 10.1021/LA052581H
Abstract: We report the layer-by-layer (LbL) preparation of multilayered thin films that consist solely of DNA. The properties of the films were varied by assembling the layers from different oligonucleotide building blocks, which are composed of repeating homopolymeric units of nucleotides [adenosine (A), cytosine (C), guanine (G), and thymidine (T)] or "random" sequences. Films assembled from oligonucleotides with a single complementary unit did not show continual layer buildup. To form a repeating multilayer system, it was necessary for single-stranded DNA to be available for subsequent layers to hybridize. By using oligonucleotides with multiple nucleotide units, multilayer films were successfully assembled. We demonstrate that the thickness and swellability of the films can be controlled by the extent of hydrogen bonding (the G/C content of the oligonucleotide) and orientation of the oligomers. We have examined the stability and swellability of the films in solutions of varying salt concentration as well as in a denaturing urea solution. Stable, hollow DNA capsules were also formed by preparing the films on sacrificial colloidal templates, followed by removal of the core. The assembly of propagating structures through DNA hybridization paves the way for the engineering of DNA films with tailored composition, structure, and permeability, making them likely to find application in drug/gene delivery and biomolecular sensing.
A Focus on “Bio” in Bio–Nanoscience: The Impact of Biological Factors on Nanomaterial Interactions
Publisher: Wiley
Date: 25-06-2021
Abstract: Bio–nanoscience research encompasses studies on the interactions of nanomaterials with biological structures or what is commonly referred to as the biointerface. Fundamental studies on the influence of nanomaterial properties, including size, shape, composition, and charge, on the interaction with the biointerface have been central in bio–nanoscience to assess nanomaterial efficacy and safety for a range of biomedical applications. However, the state of the cells, tissues, or biological models can also influence the behavior of nanomaterials at the biointerface and their intracellular processing. Focusing on the “bio” in bio–nano, this review discusses the impact of biological properties at the cellular, tissue, and whole organism level that influences nanomaterial behavior, including cell type, cell cycle, tumor physiology, and disease states. Understanding how the biological factors can be addressed or exploited to enhance nanomaterial accumulation and uptake can guide the design of better and suitable models to improve the outcomes of materials in nanomedicine.
Stabilization of hydrogen-bonded poly(N-isopropylacrylamide) multilayers by a dual electrostatic/hydrogen bonding copolymer
Publisher: CSIRO Publishing
Date: 2005
DOI: 10.1071/CH05052
Abstract: Multilayer thin films were prepared based on hydrogen bonding between poly(N-isopropylacrylamide) (PNiPAAm), and poly(styrene sulfonate-co-maleic acid) (PSSMA). Since PSSMA is capable of associating with other polymers through both hydrogen bonding and electrostatic interactions, multilayer assemblies incorporating PSSMA, PNiPAAm, and intercalated poly(allylamine hydrochloride) (PAH) layers were also prepared. Intercalated PAH layers were included to improve the pH stability of the film by introducing electrostatic linkages into the assembly. Film construction was studied as a function of pH of the deposition solution and the number of inserted PAH layers. Film morphology varied significantly with incorporation of PAH into the film. It was also demonstrated that by intercalating several PAH layers within the PNiPAAm/PSSMA assembly, the pH stability of the films at pH 5.8 could be substantially improved.
Fabrication of polyelectrolyte multilayer films comprising nanoblended layers
Publisher: American Chemical Society (ACS)
Date: 04-02-2004
DOI: 10.1021/JA039830D
Abstract: Polyelectrolyte multilayer thin films were prepared via the alternate deposition of poly(allylamine hydrochloride) (PAH) and a blend of poly(acrylic acid) (PAA) and poly(styrenesulfonate) (PSS). When the pH of the blend solution was 3.5, the presence of PAA in this solution significantly increased the total film thickness. With only 10 wt % PAA in the blend adsorption solution, a large increase in film thickness was observed (92 nm cf. 18 nm). It was also demonstrated that the total amount of PSS adsorbed was enhanced by the presence of PAA in the blend solution, showing that the blend solution composition influenced that of the multilayer films. Thin films prepared with nanoblended layers also showed improved pH stability, because they exhibited reduced film rearrangement upon exposure to acidic conditions (pH = 2.5).
X-ray-Based Techniques to Study the Nano–Bio Interface
Publisher: American Chemical Society (ACS)
Date: 02-03-2021
Layer-by-layer assembly of weak-strong copolymer polyelectrolytes: A route to morphological control of thin films
Publisher: Wiley
Date: 03-08-2007
DOI: 10.1002/POLA.22179
Spray Assembled, Cross-Linked Polyelectrolyte Multilayer Membranes for Salt Removal
Publisher: American Chemical Society (ACS)
Date: 18-07-2014
DOI: 10.1021/LA501855K
Abstract: The present study reports the synthesis of spray-coated cross-linked polyelectrolyte multilayer membranes. Membrane cross-linking was performed using alkyne-azide "click" chemistry, where alkyne and azide functional groups were used to modify the poly(acrylic acid) (PAA) and the poly(allylamine) hydrochloride (PAH) polyelectrolytes. The results demonstrate that deposition at lower ionic strength produced smoother and denser membrane structures. Pore size analysis using neutral poly(ethylene glycol) revealed a decrease in the membrane pore size as the degree of cross-linking was increased, resulting in the membrane rejecting alent CaCl2 at levels of up to 80%, and 50% rejection of monovalent NaCl. When poly(sodium-4-styrenesulfonate) (PSS) was combined with small amounts of cross-linkable PAA, significant flux increases were observed in the multilayer membranes with no observable reduction in ion rejection.
Versatile Loading of Diverse Cargo into Functional Polymer Capsules
Publisher: Wiley
Date: 29-01-2015
Robust and Versatile Coatings Engineered via Simultaneous Covalent and Noncovalent Interactions
Publisher: Wiley
Date: 06-08-2021
Abstract: Interfacial modular assembly has emerged as an adaptable strategy for engineering the surface properties of substrates in biomedicine, photonics, and catalysis. Herein, we report a versatile and robust coating (pBDT‐TA), self‐assembled from tannic acid (TA) and a self‐polymerizing aromatic dithiol (i.e., benzene‐1,4‐dithiol, BDT), that can be engineered on erse substrates with a precisely tuned thickness (5–40 nm) by varying the concentration of BDT used. The pBDT‐TA coating is stabilized by covalent (disulfide) bonds and supramolecular (π‐π) interactions, endowing the coating with high stability in various harsh aqueous environments across ionic strength, pH, temperature (e.g., 100 mM NaCl, HCl (pH 1) or NaOH (pH 13), and water at 100 °C), as well as surfactant solution (e.g., 100 mM Triton X‐100) and biological buffer (e.g., Dulbecco's phosphate‐buffered saline), as validated by experiments and simulations. Moreover, the reported pBDT‐TA coating enables secondary reactions on the coating for engineering hybrid adlayers (e.g., ZIF‐8 shells) via phenolic‐mediated adhesion, and the facile integration of aromatic fluorescent dyes (e.g., rhodamine B) via π interactions without requiring elaborate synthetic processes.
Targeting dendritic cells: The role of specific receptors in the internalization of polymer capsules
Publisher: Wiley
Date: 20-01-2013
Metal-Phenolic Supramolecular Gelation
Publisher: Wiley
Date: 30-09-2016
Abstract: Materials assembled by coordination interactions between naturally abundant polyphenols and metals are of interest for a wide range of applications, including crystallization, catalysis, and drug delivery. Such an interest has led to the development of thin films with tunable, dynamic properties, however, creating bulk materials remains a challenge. Reported here is a class of metallogels formed by direct gelation between inexpensive, naturally abundant tannic acid and group(IV) metal ions. The metallogels exhibit erse properties, including self-healing and transparency, and can be doped with various materials by in situ co-gelation. The robustness and flexibility, combined with the ease, low cost, and scalability of the coordination-driven assembly process make these metallogels potential candidates for chemical, biomedical, and environmental applications.
Structure Governs the Deformability of Polymer Particles in a Microfluidic Blood Capillary Model
Publisher: American Chemical Society (ACS)
Date: 19-10-2015
Exploiting Supramolecular Dynamics in Metal–Phenolic Networks to Generate Metal–Oxide and Metal–Carbon Networks
Publisher: Wiley
Date: 17-05-2021
Abstract: Supramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal–phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their erse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal–oxide networks (MONs) and metal–carbon networks, respectively. Furthermore, by integrating photo‐responsive motifs (i.e., TiO 2 ) and silanization, the MONs are endowed with reversible superhydrophobic ( °) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into erse materials, this work offers a versatile pathway for advanced materials engineering.
Bridging Bio-Nano Science and Cancer Nanomedicine
Publisher: American Chemical Society (ACS)
Date: 19-09-2017
Abstract: The interface of bio-nano science and cancer medicine is an area experiencing much progress but also beset with controversy. Core concepts of the field-e.g., the enhanced permeability and retention (EPR) effect, tumor targeting and accumulation, and even the purpose of "nano" in cancer medicine-are hotly debated. In parallel, considerable advances in neighboring fields are occurring rapidly, including the recent progress of "immuno-oncology" and the fundamental impact it is having on our understanding and the clinical treatment of the group of diseases collectively known as cancer. Herein, we (i) revisit how cancer is commonly treated in the clinic and how this relates to nanomedicine (ii) examine the ongoing debate on the relevance of the EPR effect and tumor targeting (iii) highlight ways to improve the next-generation of nanomedicines and (iv) discuss the emerging concept of working with (and not against) biology. While discussing these controversies, challenges, emerging concepts, and opportunities, we explore new directions for the field of cancer nanomedicine.
The Biomolecular Corona in 2D and Reverse: Patterning Metal-Phenolic Networks on Proteins, Lipids, Nucleic Acids, Polysaccharides, and Fingerprints
Publisher: Wiley
Date: 31-10-2020
Polyelectrolyte functionalization of electrospun fibers
Publisher: American Chemical Society (ACS)
Date: 29-03-2006
DOI: 10.1021/CM052760K
Size and Rigidity of Cylindrical Polymer Brushes Dictate Long Circulating Properties In Vivo
Publisher: American Chemical Society (ACS)
Date: 29-01-2015
DOI: 10.1021/NN505125F
Abstract: Studies of spherical nanoengineered drug delivery systems have suggested that particle size and mechanical properties are key determinants of in vivo behavior however, for more complex structures, detailed analysis of correlations between in vitro characterization and in vivo disposition is lacking. Anisotropic materials in particular bear unknowns in terms of size tolerances for in vivo clearance and the impact of shape and rigidity. Herein, we employed cylindrical polymer brushes (CPBs) to answer questions related to the impact of size, length and rigidity on the in vivo behavior of PEGylated anisotropic structures, in particular their pharmacokinetics and biodistribution. The modular grafting assembly of CPBs allowed for the systematic tailoring of parameters such as aspect ratio or rigidity while keeping the overall chemical composition the same. CPBs with altered length were produced from polyinitiator backbones with different degrees of polymerization. The side chain grafts consisted of a random copolymer of poly[(ethylene glycol) methyl ether methacrylate] (PEGMA) and poly(glycidyl methacrylate) (PGMA), and rendered the CPBs water-soluble. The epoxy groups of PGMA were subsequently reacted with propargylamine to introduce alkyne groups, which in turn were used to attach radiolabels via copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC). Radiolabeling allowed the pharmacokinetics of intravenously injected CPBs to be followed as well as their deposition into major organs post dosing to rats. To alter the rigidity of the CPBs, core-shell-structured CPBs with polycaprolactone (PCL) as a water-insoluble and crystalline core and PEGMA-co-PGMA as the hydrophilic shell were synthesized. This modular buildup of CPBs allowed their shape and rigidity to be altered, which in turn could be used to influence the in vivo circulation behavior of these anisotropic polymer particles. Increasing the aspect ratio or altering the rigidity of the CPBs led to reduced exposure, higher clearance rates, and increased mononuclear phagocytic system (MPS) organ deposition.
Engineering Flexible Metal‐Phenolic Networks with Guest Responsiveness via Intermolecular Interactions
Publisher: Wiley
Date: 24-03-2023
Abstract: Flexible metal‐organic materials are of growing interest owing to their ability to undergo reversible structural transformations under external stimuli. Here, we report flexible metal‐phenolic networks (MPNs) featuring stimuli‐responsive behavior to erse solute guests. The competitive coordination of metal ions to phenolic ligands of multiple coordination sites and solute guests (e.g., glucose) primarily determines the responsive behavior of the MPNs, as revealed experimentally and computationally. Glucose molecules can be embedded into the dynamic MPNs upon mixing, leading to the reconfiguration of the metal‐organic networks and thus changes in their physicochemical properties for targeting applications. This study expands the library of stimuli‐responsive flexible metal‐organic materials and the understanding of intermolecular interactions between metal‐organic materials and solute guests, which is essential for the rational design of responsive materials for various applications.
Conjugated Polymer Inverse Opals for Potentiometric Biosensing
Publisher: Wiley
Date: 17-12-2002
Assembling DNA into advanced materials: From nanostructured films to biosensing and delivery systems
Publisher: Wiley
Date: 16-10-2007
Polymer Capsules for Plaque-Targeted In Vivo Delivery
Publisher: Wiley
Date: 30-06-2016
Abstract: Targeted polymer capsules can selectively bind to unstable plaques in mice after intravenous injection. Different formulations of the capsules are explored with a synthetic/biopolymer hybrid capsule showing the best stability and small-molecule drug retention. The synthetic polymer is composed of pH-sensitive blocks (PDPA), low-binding blocks (PEG), and click-groups for postfunctionalization with targeting peptides specific to plaques.
Protein precoating modulates biomolecular coronas and nanocapsule–immune cell interactions in human blood
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2TB00672C
Abstract: We demonstrate the effects of protein precoating on biomolecular corona formation and immune cell interactions of metal–phenolic network nanocapsules using proteomics analyses and human blood assays.
Sono‐Fenton Chemistry Converts Phenol and Phenyl Derivatives into Polyphenols for Engineering Surface Coatings
Publisher: Wiley
Date: 25-08-2021
Abstract: We report a sono‐Fenton strategy to mediate the supramolecular assembly of metal–phenolic networks (MPNs) as substrate‐independent coatings using phenol and phenyl derivatives as building blocks. The assembly process is initiated from the generation of hydroxyl radicals ( . OH) using high‐frequency ultrasound (412 kHz), while the metal ions synergistically participate in the production of additional . OH for hydroxylation henolation of phenol and phenyl derivatives via the Fenton reaction and also coordinate with the phenolic compounds for film formation. The coating strategy is applicable to various phenol and phenyl derivatives and different metal ions including Fe II , Fe III , Cu II , and Co II . In addition, the sono‐Fenton strategy allows real‐time control over the assembly process by turning the high‐frequency ultrasound on or off. The properties of the building blocks are maintained in the formed films. This work provides an environmentally friendly and controllable method to expand the application of phenolic coatings for surface engineering.
Bromoisobutyramide as an Intermolecular Surface Binder for the Preparation of Free-standing Biopolymer Assemblies
Publisher: Wiley
Date: 07-11-2011
Abstract: Bromoisobutyramide (BrIBAM)-modified silica templates facilitate the formation of bio-functional thin films made of a range of biopolymers (e.g., polypeptides, nucleic acids or polysaccharides). Upon template removal, non-covalent free-standing biopolymeric assemblies (e.g., hollow capsules or replicated spheres and fibers) are formed without the need for covalent cross-linking.
Dynamic Electrophoretic Assembly of Metal-Phenolic Films: Accelerated Formation and Cytocompatible Detachment
Publisher: American Chemical Society (ACS)
Date: 02-09-2020
Chlorine Resistant Glutaraldehyde Crosslinked Polyelectrolyte Multilayer Membranes for Desalination
Publisher: Wiley
Date: 16-03-2015
Abstract: Crosslinked polyelectrolyte multilayer membranes are synthesized with salt rejection values approaching those of commercial desalination membranes, but with increased chlorine resistance. The membranes are fabricated directly onto porous commercial substrates. Subsequent crosslinking of the polycation layers with glutaraldehyde leads to NaCl rejections of up to 97%, while the incorporation of a highly sulfonated polysulfone polyanion leads to high chlorine resistance.
Self-Assembly and Characterization of Polyaniline and Sulfonated Polystyrene Multilayer-Coated Colloidal Particles and Hollow Shells
Publisher: American Chemical Society (ACS)
Date: 21-08-2003
DOI: 10.1021/LA034827T
Stereoselective Growth of Small Molecule Patches on Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 16-07-2021
DOI: 10.1021/JACS.1C04272
Abstract: Patchy nanoparticles featuring tunable surface domains with spatial and chemical specificity are of fundamental interest, especially for creating three-dimensional (3D) colloidal structures. Guided assembly and regioselective conjugation of polymers have been widely used to manipulate such topography on nanoparticles however, the processes require presynthesized specialized polymer chains and elaborate assembly conditions. Here, we show how small molecules can form 3D patches in aqueous environments in a single step. The patch features (e.g., size, number, conformation, and stereoselectivity) are modulated by a self-polymerizable aromatic dithiol and comixed ligands, which indicates an autonomous assembly mechanism involving covalent polymerization and supramolecular assembly. Moreover, this method is independent of the underlying nanoparticle material and dimension, offering a streamlined and powerful toolset to design heterogeneous patches on the nanoscale.
mRNA Treatment Rescues Niemann–Pick Disease Type C1 in Patient Fibroblasts
Publisher: American Chemical Society (ACS)
Date: 20-09-2022
DOI: 10.1021/ACS.MOLPHARMACEUT.2C00463
Abstract: Messenger RNA (mRNA) holds great potential as a disease-modifying treatment for a wide array of monogenic disorders. Niemann-Pick disease type C1 (NP-C1) is an ultrarare monogenic disease that arises due to loss-of-function mutations in the
Fluorinated Metal–Organic Coatings with Selective Wettability
Publisher: American Chemical Society (ACS)
Date: 25-06-2021
DOI: 10.1021/JACS.1C04396
An Electrifying Choice for the 2019 Chemistry Nobel Prize: Goodenough, Whittingham, and Yoshino
Publisher: American Chemical Society (ACS)
Date: 12-11-2019
Ordered Mesoporous Metal–Phenolic Network Particles
Publisher: American Chemical Society (ACS)
Date: 18-12-2020
DOI: 10.1021/JACS.9B10835
Abstract: Mesoporous metal-organic networks have attracted widespread interest owing to their potential applications in erse fields including gas storage, separations, catalysis, and drug delivery. Despite recent advances, the synthesis of metal-organic networks with large and ordered mesochannels (>20 nm), which are important for loading, separating, and releasing macromolecules, remains a challenge. Herein, we report a templating strategy using sacrificial double cubic network polymer cubosomes (
Gel-Mediated Electrospray Assembly of Silica Supraparticles for Sustained Drug Delivery
Publisher: American Chemical Society (ACS)
Date: 07-09-2018
Abstract: Supraparticles (SPs) composed of smaller colloidal particles provide a platform for the long-term, controlled release of therapeutics in biomedical applications. However, current synthesis methods used to achieve high drug loading and those involving biocompatible materials are often tedious and low throughput, thereby limiting the translation of SPs to erse applications. Herein, we present a simple, effective, and automatable alginate-mediated electrospray technique for the assembly of robust spherical silica SPs (Si-SPs) for long-term (>4 months) drug delivery. The Si-SPs are composed of either porous or nonporous primary Si particles within a decomposable alginate matrix. The size and shape of the Si-SPs can be tailored by controlling the concentrations of alginate and silica primary particles used and key electrospraying parameters, such as flow rate, voltage, and collector distance. Furthermore, the performance (including drug loading kinetics, loading capacity, loading efficiency, and drug release) of the Si-SPs can be tuned by changing the porosity of the primary particles and through the retention or removal (via calcination) of the alginate matrix. The structure and morphology of the Si-SPs were characterized by electron microscopy, dynamic light scattering, N
Improved Auditory Nerve Survival with Nanoengineered Supraparticles for Neurotrophin Delivery into the Deafened Cochlea
Publisher: Public Library of Science (PLoS)
Date: 27-10-2016
Supramolecular Polyphenol‐DNA Microparticles for In Vivo Adjuvant and Antigen Co‐Delivery and Immune Stimulation
Publisher: Wiley
Date: 2030
Abstract: DNA‐based materials have attracted interest due to the tunable structure and encoded biological functionality of nucleic acids. A simple and general approach to synthesize DNA‐based materials with fine control over morphology and bioactivity is important to expand their applications. Here, we report the synthesis of DNA‐based particles via the supramolecular assembly of tannic acid (TA) and DNA. Uniform particles with different morphologies are obtained using a variety of DNA building blocks. The particles enable the co‐delivery of cytosine‐guanine adjuvant sequences and the antigen ovalbumin in model cells. Intramuscular injection of the particles in mice induces antigen‐specific antibody production and T cell responses with no apparent toxicity. Protein expression in cells is shown using capsules assembled from TA and plasmid DNA. This work highlights the potential of TA as a universal material for directing the supramolecular assembly of DNA into gene and vaccine delivery platforms.
Ultrathin, responsive polymer click capsules
Publisher: American Chemical Society (ACS)
Date: 26-05-2007
DOI: 10.1021/NL070698F
Abstract: We report a general click chemistry approach for the layer-by-layer assembly of ultrathin, polymer films on particles and the subsequent formation of polymer click capsules (CCs). Poly(acrylic acid) copolymers, synthesized with a minor component of either alkyne (PAA-Alk) or azide (PAA-Az) functionality, were alternately assembled on silica particles. The (PAA-Az/PAA-Alk)-coated particles were subsequently functionalized by exploiting the free alkyne click moieties present in the film upon exposure to an azide-modified rhodamine dye. Further, PAA CCs, obtained following removal of the silica particle template, were shown to exhibit pH-responsive behavior. This was demonstrated by reversible size changes of the CCs upon cycling between basic and acidic solutions. Polymer CCs are anticipated to find applications in various fields, including drug delivery and sensing.
Uptake and intracellular fate of disulfide-bonded polymer hydrogel capsules for doxorubicin delivery to colorectal cancer cells
Publisher: American Chemical Society (ACS)
Date: 26-04-2010
DOI: 10.1021/NN100173H
Abstract: Understanding the interactions between drug carriers and cells is of importance to enhance the delivery of therapeutics. The release of therapeutics into different intracellular environments, such as the lysosomes or the cell cytoplasm, will impact their pharmacological activity. Herein, we investigate the intracellular fate of layer-by-layer (LbL)-assembled, submicrometer-sized polymer hydrogel capsules in a human colon cancer derived cell line, LIM1899. The cellular uptake of the disulfide-stabilized poly(methacrylic acid) (PMA(SH)) capsules by colon cancer cells is a time-dependent process. Confocal laser scanning microscopy and transmission electron microscopy reveal that the internalized capsules are deformed in membrane-enclosed compartments, which further mature to late endosomes or lysosomes. We further demonstrate the utility of these redox-responsive PMA(SH) capsules for the delivery of doxorubicin (DOX) to colon cancer cells. The DOX-loaded PMA(SH) capsules demonstrate a 5000-fold enhanced cytotoxicity in cell viability studies compared to free DOX.
Nanostructured particles assembled from natural building blocks for advanced therapies
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1CS00343G
Abstract: Bio-derived components are natural and abundant, often with inherent biocompatibility, natural bioactivity, and erse chemical properties, which makes them promising building blocks to assemble nanoparticles for advanced therapeutic applications.
Degradation of liposomal subcompartments in PEGylated capsosomes
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1SM05623A
Immobilized Particle Imaging for Quantification of Nano- and Microparticles
Publisher: American Chemical Society (ACS)
Date: 31-03-2016
DOI: 10.1021/ACS.LANGMUIR.6B00229
Abstract: The quantification of nano- and microparticles is critical for erse applications relying on the exact knowledge of the particle concentration. Although many techniques are available for counting particles, there are some limitations in regards to counting with low-scattering materials and facile counting in harsh organic solvents. Herein, we introduce an easy and rapid particle counting technique, termed "immobilized particle imaging" (IPI), to quantify fluorescent particles with different compositions (i.e., inorganic or organic), structures (i.e., solid, porous, or hollow), and sizes (50-1000 nm) dispersed in either aqueous or organic solutions. IPI is achieved by immobilizing particles of interest in a cell matrix-like scaffold (e.g., agarose) and imaging using standard microscopy techniques. Imaging a defined volume of the immobilized particles allows for the particle concentration to be calculated from the count numbers in a fixed volume. IPI provides a general and facile approach to quantify advanced nano- and microparticles, which may be helpful to researchers to obtain new insights for different applications (e.g., nanomedicine).
Injectable and Sprayable Polyphenol-Based Hydrogels for Controlling Hemostasis
Publisher: American Chemical Society (ACS)
Date: 23-01-2020
Abstract: Injectable and sprayable hydrogels have attracted considerable attention for application in the biomedical field owing to their high moldability and efficiency in encapsulating therapeutics and cells. Herein, we report the spontaneous assembly of injectable and sprayable hydrogels via a one-step mixing of solutions of tannic acid (TA) and
An Enzyme-Coated Metal–Organic Framework Shell for Synthetically Adaptive Cell Survival
Publisher: Wiley
Date: 05-06-2017
Abstract: A bioactive synthetic porous shell was engineered to enable cells to survive in an oligotrophic environment. Eukaryotic cells (yeast) were firstly coated with a β-galactosidase (β-gal), before crystallization of a metal-organic framework (MOF) film on the enzyme coating thereby producing a bioactive porous synthetic shell. The β-gal was an essential component of the bioactive shell as it generated nutrients (that is, glucose and galactose) required for cell viability in nutrient-deficient media (lactose-based). Additionally, the porous MOF coating carried out other vital functions, such as 1) shielding the cells from cytotoxic compounds and radiation, 2) protecting the non-native enzymes (β-gal in this instance) from degradation and internalization, and 3) allowing for the diffusion of molecules essential for the survival of the cells. Indeed, this bioactive porous shell enabled the survival of cells in simulated extreme oligotrophic environments for more than 7 days, leading to a decrease in cell viability less than 30 %, versus a 99 % decrease for naked yeast. When returned to optimal growth conditions the bioactive porous exoskeleton could be removed and the cells regained full growth immediately. The construction of bioactive coatings represents a conceptually new and promising approach for the next-generation of cell-based research and application, and is an alternative to synthetic biology or genetic modification.
Photoinitiated Alkyne-Azide Click and Radical Cross-Linking Reactions for the Patterning of PEG Hydrogels
Publisher: American Chemical Society (ACS)
Date: 14-02-2012
DOI: 10.1021/BM201802W
Abstract: The photolithographical patterning of hydrogels based solely on the surface immobilization and cross-linking of alkyne-functionalized poly(ethylene glycol) (PEG-tetraalkyne) is described. Photogenerated radicals as well as UV absorption by a copper chelating ligand result in the photochemical redox reduction of Cu(II) to Cu(I). This catalyzes the alkyne-azide click reaction to graft the hydrogels onto an azide-functionalized plasma polymer (N(3)PP) film. The photogenerated radicals were also able to abstract hydrogen atoms from PEG-tetraalkyne to form poly(α-alkoxy) radicals. These radicals can initiate cross-linking by addition to the alkynes and intermolecular recombination to form the PEG hydrogels. Spatially controlling the two photoinitiated reactions by UV exposure through a photomask leads to surface patterned hydrogels, with thicknesses that were tunable from tens to several hundreds of nanometers. The patterned PEG hydrogels (ca. 60 μm wide lines) were capable of resisting the attachment of L929 mouse fibroblast cells, resulting in surfaces with spatially controlled cell attachment. The patterned hydrogel surface also demonstrated spatially resolved chemical functionality, as postsynthetic modification of the hydrogels was successfully carried out with azide-functionalized fluorescent dyes via subsequent alkyne-azide click reactions.
Mesoporous silica particles as templates for preparing enzyme-loaded biocompatible microcapsules
Publisher: Wiley
Date: 18-07-2005
Stabilization of DNA multilayer films through oligonucleotide crosslinking
Publisher: Wiley
Date: 05-2008
Abstract: Multilayer films and capsules synthesized from DNA are of interest because they are biodegradable, biocompatible, and the structure of the films can be finely controlled by base pairing of the nucleotides. As DNA films are held together through a balance between the attractive hydrogen bonding and the aromatic stacking of the base pairs and the electrostatic repulsion of the negatively charged phosphate backbones, the films can be subject to disintegration at low salt concentrations (<200 mM). Enhancement of the stability of the films is essential if they are to be used in bioapplications. Herein, we describe an approach to form DNA films and capsules that are stable under a variety of buffer conditions, including low salt concentrations (down to 25 mM NaCl). The films are assembled using a triblock oligonucleotide system, in which the two outer blocks facilitate the assembly of the film and the middle block can be used to stabilize the films by hybridizing oligonucleotide sequences that crosslink the films. Additionally, crosslinked DNA capsules are shown to exhibit significantly different shrinkage properties to those of noncrosslinked capsules, thus demonstrating further control over the capsule properties. These DNA capsules are envisaged to find applications as drug-delivery vehicles, in diagnostics, and as microreactors.
Person-Specific Biomolecular Coronas Modulate Nanoparticle Interactions with Immune Cells in Human Blood
Publisher: American Chemical Society (ACS)
Date: 28-10-2020
Synthesis of Metal Nanoparticles in Metal-Phenolic Networks: Catalytic and Antimicrobial Applications of Coated Textiles
Publisher: Wiley
Date: 12-10-2017
Abstract: The synthesis of metal nanoparticle (NP)-coated textiles (nanotextiles) is achieved by a dipping process in water without toxic chemicals or complicated synthetic procedures. By taking advantage of the unique nature of tannic acid, metal-phenolic network-coated textiles serve as reducing and stabilizing sites for the generation of metal nanoparticles of controllable size. The textiles can be decorated with various metal nanoparticles, including palladium, silver, or gold, and exhibit properties derived from the presence of the metal nanoparticles, for ex le, catalytic activity in water (>96% over five cycles using palladium nanoparticles) and antibacterial activity against Gram-negative bacteria (inhibition of Escherichia coli using silver nanoparticles) that outperforms a commercial bandage. The reported strategy offers opportunities for the development of hybrid nanomaterials that may have application in fields outside of catalysis and antimicrobials, such as sensing and smart clothing.
Ultrathin molybdenum polyoxometalate-polyelectrolyte multilayer films
Publisher: American Chemical Society (ACS)
Date: 29-05-1998
DOI: 10.1021/LA980177V
RNAi therapeutics: an antiviral strategy for human infections
Publisher: Elsevier BV
Date: 10-2020
Polyphenol-Mediated Assembly of Proteins for Engineering Functional Materials
Publisher: Wiley
Date: 20-03-2020
Targeting and uptake of multilayered particles to colorectal cancer cells
Publisher: Wiley
Date: 06-07-2006
Thin multilayer films of weak polyelectrolytes on colloid particles
Publisher: American Chemical Society (ACS)
Date: 21-11-2002
DOI: 10.1021/MA0209388
Metal-dependent inhibition of amyloid fibril formation: synergistic effects of cobalt–tannic acid networks
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8NR09221D
Abstract: Cobalt–tannic acid-coated gold nanoparticles are found to better inhibit amyloid fibril formation than other metal-based tannic acid-coated particles.
Charge-Shifting Click Capsules with Dual-Responsive Cargo Release Mechanisms
Publisher: Wiley
Date: 09-08-2011
New Insights into the Substrate-Plasma Polymer Interface
Publisher: American Chemical Society (ACS)
Date: 04-05-2011
DOI: 10.1021/JP200864K
Abstract: We describe a new method to characterize the underside (substrate interface) of plasma polymer (PP) thin films via their simple delamination from a sodium chloride single crystal substrate. By depositing the PP film onto an ionic bonded surface such as a sodium chloride crystal, the PP films investigated were easily delaminated from the substrate. Two plasma polymer films deposited from 1-bromopropane (BrPP) and allylamine (AAPP) were used to exemplify this new technique. The top- and underside (substrate-plasma polymer interface) of the films were examined by X-ray photoelectron spectroscopy (XPS) and synchrotron-based near edge X-ray adsorption fine structure (NEXAFS) spectroscopy. The results demonstrate that both films exhibit heterogeneous film structures with their chemical composition and levels of unsaturated species. The underside of both the BrPP and the AAPP films exhibited higher concentrations of oxygen, while their topsides contained higher levels of unsaturated species. These results provide useful insights into the BrPP and AAPP film formation and the chemistry. The delamination technique provides a simple method to analyze the early stages of film chemistry for plasma polymer thin films. Furthermore, this approach opens new opportunities for additional studies on the mechanisms and fundamentals of plasma polymer thin film formation with various monomers.
Construction and Degradation of Polyrotaxane Multilayers
Publisher: Wiley
Date: 13-05-2011
One-pot ultrasonic synthesis of multifunctional microbubbles and microcapsules using synthetic thiolated macromolecules
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CC05095D
Abstract: A one-pot ultrasonic procedure has been developed as a versatile route for synthesizing polymer-coated microspheres that have potential application as drug delivery vehicles. The use of synthetic thiolated poly(methacrylic acid) macromolecules as the shell material offers control over size, morphology and functionality of the microspheres.
Lysine functionalised amyloid fibrils: the design and assembly of a TTR1-based peptide
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3SM27244C
Noncovalent Liposome Linkage and Miniaturization of Capsosomes for Drug Delivery
Publisher: American Chemical Society (ACS)
Date: 19-11-2010
DOI: 10.1021/BM101020E
Abstract: We report the synthesis of poly(methacrylic acid)-co-(oleyl methacrylate) with three different amounts of oleyl methacrylate and compare the ability of these polymers with that of poly(methacrylic acid)-co-(cholesteryl methacrylate) (PMA(c)) to noncovalently anchor liposomes to polymer layers. We subsequently assembled ∼1 μm diameter PMA(c)-based capsosomes, polymer hydrogel capsules that contain up to ∼2000 liposomal subcompartments, and investigate the potential of these carriers to deliver water-insoluble drugs by encapsulating two different antitumor compounds, thiocoraline or paclitaxel, into the liposomes. The viability of lung cancer cells is used to substantiate the cargo concentration-dependent activity of the capsosomes. These findings cover several crucial aspects for the application of capsosomes as potential drug delivery vehicles.
Engineered Coatings via the Assembly of Amino‐Quinone Networks
Publisher: Wiley
Date: 30-11-2020
Peptide-Tunable Drug Cytotoxicity via One-Step Assembled Polymer Nanoparticles
Publisher: Wiley
Date: 27-12-2014
Abstract: A novel class of nanoparticles is developed for the co-delivery of a short cell penetrating peptide and a chemotherapeutic drug to achieve enhanced cytotoxicity. Tunable cytotoxicity is achieved through non-toxic peptide-facilitated gating. The strategy relies on a one-step blending process from polymer building blocks to form monodisperse, PEGylated particles that are sensitive to cellular pH variations. By varying the amount of peptide loading, the chemotherapeutic effects can be enhanced by up to 30-fold.
Templated synthesis of single-component polymer capsules and their application in drug delivery
Publisher: American Chemical Society (ACS)
Date: 20-05-2008
DOI: 10.1021/NL080877C
Abstract: We report a general and facile approach for the fabrication of a new class of monodispersed, single-component and thick-walled polymer nanocapsules via the single-step assembly of macromolecules in solid core/mesoporous shell (SC/MS) silica particle templates, followed by cross-linking of the macromolecules and removal of the SC/MS templates. The general applicability of this approach is demonstrated by the preparation of nanocapsules using various polymers, including synthetic polyelectrolytes, polypeptides, and polypeptide-drug conjugates. The potential of doxorubicin (Dox)-loaded poly(L-glutamic acid) nanocapsules in tumor therapy applications is demonstrated via in vitro degradation experiments, which show a near-linear release of the Dox in the presence of a lysosomal hydrolase, nanocapsule uptake by human colorectal tumor cells, and delivery of the anticancer drug into the tumor cells, leading to tumor cell death.
Towards 3D metal-dielectric photonic crystal. Optical characterization
Publisher: Informa UK Limited
Date: 2004
Lateral diffusion study of amphiphiles in air-water monolayer films of polymerizable surfactants
Publisher: American Chemical Society (ACS)
Date: 1994
DOI: 10.1021/MA00079A013
Tuning the Permeability of Polymer Hydrogel Capsules: An Investigation of Cross-Linking Density, Membrane Thickness, and Cross-Linkers
Publisher: American Chemical Society (ACS)
Date: 18-01-2011
DOI: 10.1021/LA104510E
Abstract: Nanoengineered poly(methacrylic acid) hydrogel capsules (PMA HCs) are promising candidate carriers for biomedical applications, especially in the areas of drug delivery, encapsulated catalysis, and cell mimicry. The assembly, stability, and degradation of these carriers, as well as their use for the encapsulation of therapeutics, have received considerable attention. However, tailoring the permeability properties of PMA HCs to various types of cargo remains largely unexplored. Herein, we investigate fundamental parameters that govern the structural integrity and the capability of PMA HCs to encapsulate macromolecular cargo. The thiol content of the constituent polymers and the number of deposited polymer layers are shown to be key factors in controlling cargo retention within the PMA HCs. We further introduce a new strategy to achieve disulfide cross-linking for PMA HCs via a thiol-disulfide exchange in order to obtain capsules with superior cargo retention characteristics. Finally, we provide evidence for the semipermeable nature of PMA HCs based on the charge of the solutes and demonstrate that rational design of these systems can yield capsules with specific cargo retention properties. This work contributes toward the development of multilayered polymer capsules and PMA HCs and associated applications in biomedicine.
The Future of Healthcare Materials
Publisher: American Chemical Society (ACS)
Date: 24-01-2023
NFAT signaling in human mesenchymal stromal cells affects extracellular matrix remodeling and antifungal immune responses
Publisher: Elsevier BV
Date: 06-2021
Biomimetic Liposome- and Polymersome-Based Multicompartmentalized Assemblies
Publisher: American Chemical Society (ACS)
Date: 25-07-2012
DOI: 10.1021/LA301958V
Abstract: Liposomes and polymersomes have attracted significant attention and have emerged as versatile materials for therapeutic delivery and in the design of artificial cells and organelles. Through the judicious choice of building blocks, these synthetic carriers can be readily engineered with tailored interfacial properties, offering new possibilities for the design of advanced assemblies with specific permeability, stability, stimuli response, and targeting capabilities. In this feature article, we highlight recent studies on biomimetic liposome- and polymersome-based multicompartmentalized assemblies en route toward the development of artificial cells, microreactors, and therapeutic delivery carriers. The strategies employed to produce these carriers are outlined, and the properties that contribute to their performance are discussed. Applications of these biomimetic assemblies are highlighted, and finally, areas that require additional investigation for the future development of these assemblies as next-generation therapeutic systems are outlined.
Semiconductor quantum dot-labeled microsphere bioconjugates prepared by stepwise self-assembly
Publisher: American Chemical Society (ACS)
Date: 26-07-2002
DOI: 10.1021/NL025624C
Stepwise polyelectrolyte assembly on particle surfaces: a novel approach to colloid design
Publisher: Wiley
Date: 10-1998
DOI: 10.1002/(SICI)1099-1581(1998100)9:10/11<759::AID-PAT846>3.0.CO;2-Q
Peptide-Based Coacervate Protocells with Cytoprotective Metal–Phenolic Network Membranes
Publisher: American Chemical Society (ACS)
Date: 03-10-2023
DOI: 10.1021/JACS.3C07748
Selective Metal–Phenolic Assembly from Complex Multicomponent Mixtures
Publisher: American Chemical Society (ACS)
Date: 30-04-2019
Abstract: Selective self-assembly in multicomponent mixtures offers a method for isolating desired components from complex systems for the rapid production of functional materials. Developing approaches capable of selective assembly of "target" components into intended three-dimensional structures is challenging because of the intrinsically high complexity of multicomponent systems. Herein, we report the selective coordination-driven self-assembly of metal-phenolic networks (MPNs) from a series of complex multicomponent systems (including crude plant extracts) into thin films via metal chelation with phenolic ligands. The metal (Fe
Engineering Polymer Hydrogel Nanoparticles for Lymph Node-Targeted Delivery
Publisher: Wiley
Date: 15-12-2016
Abstract: The induction of antigen-specific adaptive immunity exclusively occurs in lymphoid organs. As a consequence, the efficacy by which vaccines reach these tissues strongly affects the efficacy of the vaccine. Here, we report the design of polymer hydrogel nanoparticles that efficiently target multiple immune cell subsets in the draining lymph nodes. Nanoparticles are fabricated by infiltrating mesoporous silica particles (ca. 200 nm) with poly(methacrylic acid) followed by disulfide-based crosslinking and template removal. PEGylation of these nanoparticles does not affect their cellular association in vitro, but dramatically improves their lymphatic drainage in vivo. The functional relevance of these observations is further illustrated by the increased priming of antigen-specific T cells. Our findings highlight the potential of engineered hydrogel nanoparticles for the lymphatic delivery of antigens and immune-modulating compounds.
Multilayer assemblies of silica-encapsulated gold nanoparticles on decomposable colloid templates
Publisher: Wiley
Date: 07-2001
DOI: 10.1002/1521-4095(200107)13:14<1090::AID-ADMA1090>3.0.CO;2-H
Protease-Responsive Hydrogel Microparticles for Intradermal Drug Delivery
Publisher: American Chemical Society (ACS)
Date: 12-06-2023
Programmable Permeability of Metal–Phenolic Network Microcapsules
Publisher: American Chemical Society (ACS)
Date: 04-08-2020
Layer-by-layer assembled charge-trap memory devices with adjustable electronic properties
Publisher: Springer Science and Business Media LLC
Date: 12-2007
Abstract: We describe a versatile approach for preparing flash memory devices composed of polyelectrolyte/gold nanoparticle multilayer films. Anionic gold nanoparticles were used as the charge storage elements, and poly(allylamine) oly(styrenesulfonate) multilayers deposited onto hafnium oxide (HfO2)-coated silicon substrates formed the insulating layers. The top contact was formed by depositing HfO2 and platinum. In this study, we investigated the effect of increasing the number of polyelectrolyte and gold nanoparticle layers on memory performance, including the size of the memory window (the critical voltage difference between the 'programmed' and 'erased' states of the devices) and programming speed. We observed a maximum memory window of about 1.8 V, with a stored electron density of 4.2 x 1012 cm-2 in the gold nanoparticle layers, when the devices consist of three polyelectrolyte/gold nanoparticle layers. The reported approach offers new opportunities to prepare nanostructured polyelectrolyte/gold nanoparticle-based memory devices with tailored performance.
The Role of Particle Geometry and Mechanics in the Biological Domain
Publisher: Wiley
Date: 14-12-2012
Abstract: Nanostructured particulate materials are expected to revolutionize diagnostics and the delivery of therapeutics for healthcare. To date, chemistry-derived solutions have been the major focus in the design of materials to control interactions with biological systems. Only recently has control over a new set of physical parameters, including size, shape, and rigidity, been explored to optimize the biological response and the in vivo performance of nanoengineered delivery vectors. This Review highlights the methods used to manipulate the physical properties of particles and the relevance of these physical properties to cellular and circulatory interactions. Finally, the importance of future work to synergistically tailor both physical and chemical properties of particulate materials is discussed, with the aim of improving control over particle interactions in the biological domain.
Release Behavior of Thin-Walled Microcapsules Composed of Polyelectrolyte Multilayers
Publisher: American Chemical Society (ACS)
Date: 24-02-2001
DOI: 10.1021/LA001550D
Tailoring the interfaces between nematic liquid crystal emulsions and aqueous phases via layer-by-layer assembly
Publisher: American Chemical Society (ACS)
Date: 12-09-2006
DOI: 10.1021/NL061604P
Abstract: We report the assembly of polyelectrolyte multilayer (PEM) films at the interfaces of thermotropic liquid crystal (LC) droplets dispersed in an aqueous phase. Exposure of PEM-coated droplets to surfactant slowed the bipolar-to-radial ordering transition of the LCs by 2 orders of magnitude relative to naked droplets. This shows that PEMs can be used to influence the interactions of analytes with the LC cores of the droplets, allowing tuning of the LC emulsion sensing properties.
Semiconducting polymer inverse opals prepared by electropolymerization
Publisher: Wiley
Date: 04-01-2002
DOI: 10.1002/1521-4095(20020104)14:1<34::AID-ADMA34>3.0.CO;2-M
Orientational Aspects of Antibody Immobilization and Immunological Activity on Quartz Crystal Microbalance Electrodes
Publisher: Elsevier BV
Date: 03-1996
Glycogen as a Building Block for Advanced Biological Materials
Publisher: Wiley
Date: 16-10-2020
Abstract: Biological nanoparticles found in living systems possess distinct molecular architectures and erse functions. Glycogen is a unique biological polysaccharide nanoparticle fabricated by nature through a bottom-up approach. The biocatalytic synthesis of glycogen has evolved over time to form a nanometer-sized dendrimer-like structure (20-150 nm) with a highly branched surface and a dense core. This makes glycogen markedly different from other natural linear or branched polysaccharides and particularly attractive as a platform for biomedical applications. Glycogen is inherently biodegradable, nontoxic, and can be functionalized with erse surface and internal motifs for enhanced biofunctional properties. Recently, there has been growing interest in glycogen as a natural alternative to synthetic polymers and nanoparticles in a range of applications. Herein, the recent literature on glycogen in the material-based sciences, including its use as a constituent in biodegradable hydrogels and fibers, drug delivery vectors, tumor targeting and penetrating nanoparticles, immunomodulators, vaccine adjuvants, and contrast agents, is reviewed. The various methods of chemical functionalization and physical assembly of glycogen nanoparticles into multicomponent nanodevices, which advance glycogen toward a functional therapeutic nanoparticle from nature and back again, are discussed in detail.
Advanced Subcompartmentalized Microreactors:
Publisher: Wiley
Date: 18-04-2013
Abstract: The design of compartmentalized carriers for advanced drug delivery systems or artificial cells and organelles is of interest for biomedical applications. Herein, a polymer carrier microreactor that contains two different classes of subcompartments, multilayered polymer capsules and liposomes, is presented. 50 nm-diameter liposomes and 300 nm-diameter polymer capsules are encapsulated into a larger polymer carrier capsule, demonstrating control over the spatial positioning of the subcompartments, which are either 'membrane-associated' or 'free-floating' in the aqueous interior. Selective and spatially dependent degradation of the 300 nm-diameter subcompartments (without destroying the structural integrity of the enzyme-loaded liposomes) is also shown, by performing an encapsulated enzymatic reaction using the liposomal subcompartments. These findings cover several important aspects toward the development of engineered compartmentalized carrier vessels for the creation of artificial cell mimics or advanced therapeutic delivery systems.
Interfacial Assembly of Metal-Phenolic Networks for Hair Dyeing
Publisher: American Chemical Society (ACS)
Date: 16-06-2020
Modular assembly of superstructures from polyphenol-functionalized building blocks
Publisher: Springer Science and Business Media LLC
Date: 10-10-2016
Abstract: The organized assembly of particles into superstructures is typically governed by specific molecular interactions or external directing factors associated with the particle building blocks, both of which are particle-dependent. These superstructures are of interest to a variety of fields because of their distinct mechanical, electronic, magnetic and optical properties. Here, we establish a facile route to a erse range of superstructures based on the polyphenol surface-functionalization of micro- and nanoparticles, nanowires, nanosheets, nanocubes and even cells. This strategy can be used to access a large number of modularly assembled superstructures, including core-satellite, hollow and hierarchically organized supraparticles. Colloidal-probe atomic force microscopy and molecular dynamics simulations provide detailed insights into the role of surface functionalization and how this facilitates superstructure construction. Our work provides a platform for the rapid generation of superstructured assemblies across a wide range of length scales, from nanometres to centimetres.
Modulated Fragmentation of Proapoptotic Peptide Nanoparticles Regulates Cytotoxicity
Publisher: American Chemical Society (ACS)
Date: 13-03-2017
DOI: 10.1021/JACS.6B11302
Abstract: Peptides perform a erse range of physiologically important functions. The formulation of nanoparticles directly from functional peptides would therefore offer a versatile and robust platform to produce highly functional therapeutics. Herein, we engineered proapoptotic peptide nanoparticles from mitochondria-disrupting KLAK peptides using a template-assisted approach. The nanoparticles were designed to disassemble into free native peptides via the traceless cleavage of disulfide-based cross-linkers. Furthermore, the cytotoxicity of the nanoparticles was tuned by controlling the kinetics of disulfide bond cleavage, and the rate of regeneration of the native peptide from the precursor species. In addition, a small molecule drug (i.e., doxorubicin hydrochloride) was loaded into the nanoparticles to confer synergistic cytotoxic activity, further highlighting the potential application of KLAK particles in therapeutic delivery.
Supramolecular Assembly of Polyphenols and Nucleic Acids by Thermal Cycling for Immune Cell Activation
Publisher: American Chemical Society (ACS)
Date: 24-08-2023
Investigation of Electrostatic Interactions in Polyelectrolyte Multilayer Films: Binding of Anionic Fluorescent Probes to Layers Assembled onto Colloids
Publisher: American Chemical Society (ACS)
Date: 09-03-1999
DOI: 10.1021/MA980674I
Investigation of the factors influencing the formation of dendrimer/polyanion multilayer films
Publisher: American Chemical Society (ACS)
Date: 29-08-2002
DOI: 10.1021/LA020251G
The resilience of carbonic anhydrase enzyme for membrane-based carbon capture applications
Publisher: Elsevier BV
Date: 07-2017
Template synthesis of nanostructured materials via layer-by-layer assembly
Publisher: American Chemical Society (ACS)
Date: 11-12-2008
DOI: 10.1021/CM7024813
pH-Responsive Capsules Engineered from Metal-Phenolic Networks for Anticancer Drug Delivery
Publisher: Wiley
Date: 03-01-2015
Abstract: A new class of pH-responsive capsules based on metal-phenolic networks (MPNs) for anticancer drug loading, delivery and release is reported. The fabrication of drug-loaded MPN capsules, which is based on the formation of coordination complexes between natural polyphenols and metal ions over a drug-coated template, represents a rapid strategy to engineer robust and versatile drug delivery carriers.
Detection of atomic spin labels in a lipid bilayer using a single-spin nanodiamond probe
Publisher: Proceedings of the National Academy of Sciences
Date: 17-06-2013
Abstract: Magnetic field fluctuations arising from fundamental spins are ubiquitous in nanoscale biology, and are a rich source of information about the processes that generate them. However, the ability to detect the few spins involved without averaging over large ensembles has remained elusive. Here, we demonstrate the detection of gadolinium spin labels in an artificial cell membrane under ambient conditions using a single-spin nanodiamond sensor. Changes in the spin relaxation time of the sensor located in the lipid bilayer were optically detected and found to be sensitive to near-in idual (4 ± 2) proximal gadolinium atomic labels. The detection of such small numbers of spins in a model biological setting, with projected detection times of 1 s [corresponding to a sensitivity of ∼5 Gd spins per Hz 1/2 ], opens a pathway for in situ nanoscale detection of dynamical processes in biology.
Bio-nano Science: Better Metrics Would Accelerate Progress
Publisher: American Chemical Society (ACS)
Date: 23-09-2021
Endocytic pH-triggered degradation of nanoengineered multilayer capsules
Publisher: Wiley
Date: 27-12-2014
Abstract: The synthesis of cross-linker free layer-by-layer (LbL) capsules that solely utilize cellular pH variations as a trigger to specifically deconstruct and subsequently release cargo in cells is reported. These capsules demonstrate retention of water-soluble therapeutic molecules as small as 500 Da at extracellular pH. Triggered capsule degradation and release of cargo is observed within 30 min of cell uptake.
Link between Low-Fouling and Stealth: A Whole Blood Biomolecular Corona and Cellular Association Analysis on Nanoengineered Particles.
Publisher: American Chemical Society (ACS)
Date: 18-04-2019
Abstract: Upon exposure to human blood, nanoengineered particles interact with a multitude of plasma components, resulting in the formation of a biomolecular corona. This corona modulates downstream biological responses, including recognition by and association with human immune cells. Considerable research effort has been directed toward the design of materials that can demonstrate a low affinity for various proteins (low-fouling materials) and materials that can exhibit low association with human immune cells (stealth materials). An implicit assumption common to bio-nano research is that nanoengineered particles that are low-fouling will also exhibit stealth. Herein, we investigated the link between the low-fouling properties of a particle and its propensity for stealth in whole human blood. High-fouling mesoporous silica (MS) particles and low-fouling zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) particles were synthesized, and their interaction with blood components was assessed before and after precoating with serum albumin, immunoglobulin G, or complement protein C1q. We performed an in-depth proteomics characterization of the biomolecular corona that both identifies specific proteins and measures their relative abundance. This was compared with observations from a whole blood association assay that identified with which cell type each particle system associates. PMPC-based particles displayed reduced association both with cells and with serum proteins compared with MS-based particles. Furthermore, the enrichment of specific proteins within the biomolecular corona was found to correlate with association with specific cell types. This study demonstrates how the low-fouling properties of a material are indicative of its stealth with respect to immune cell association.
Fluidized Bed Layer-by-Layer Microcapsule Formation
Publisher: American Chemical Society (ACS)
Date: 12-08-2014
DOI: 10.1021/LA502176G
Abstract: Polymer microcapsules can be used as bioreactors and artificial cells however, preparation methods for cell-like microcapsules are typically time-consuming, low yielding, and/or involve custom microfluidics. Here, we introduce a rapid (∼30 min per batch, eight layers), scalable (up to 500 mg of templates), and efficient (98% yield) microcapsule preparation technique utilizing a fluidized bed for the layer-by-layer (LbL) assembly of polymers, and we investigate the parameters that govern the formation of robust capsules. Fluidization in water was possible for particles of comparable diameter to mammalian cells (>5 μm), with the experimental flow rates necessary for fluidization matching well with the theoretical values. Important variables for polymer film deposition and capsule formation were the concentration of polymer solution and the molecular weight of the polymer, while the volume of the polymer solution had a negligible impact. In combination, increasing the polymer molecular weight and polymer solution concentration resulted in improved film deposition and the formation of robust microcapsules. The resultant polymer microcapsules had a thickness of ∼5.5 nm per bilayer, which is in close agreement with conventionally prepared (quiescent (nonflow) adsorption/centrifugation/wash) LbL capsules. The technique reported herein provides a new way to rapidly generate microcapsules (approximately 8 times quicker than the conventional means), while being also amenable to scale-up and mass production.
Thermoresponsive nanoassemblies: Layer-by-layer assembly of hydrophilic-hydrophobic alternating copolymers
Publisher: American Chemical Society (ACS)
Date: 11-03-2005
DOI: 10.1021/MA047414N
Real time monitoring of the detergency process by using a quartz crystal microbalance
Publisher: American Chemical Society (ACS)
Date: 07-01-1998
DOI: 10.1021/LA971076K
Patterned Poly(dopamine) Films for Enhanced Cell Adhesion
Publisher: American Chemical Society (ACS)
Date: 18-11-2017
DOI: 10.1021/ACS.BIOCONJCHEM.6B00544
Abstract: Engineered materials that promote cell adhesion and cell growth are important in tissue engineering and regenerative medicine. In this work, we produced poly(dopamine) (PDA) films with engineered patterns for improved cell adhesion. The patterned films were synthesized via the polymerization of dopamine at the air-water interface of a floating bed of spherical particles. Subsequent dissolution of the particles yielded free-standing PDA films with tunable geometrical patterns. Our results show that these patterned PDA films significantly enhance the adhesion of both cancer cells and stem cells, thus showing promise as substrates for cell attachment for various biomedical applications.
Biomimetic Replication of Microscopic Metal-Organic Framework Patterns Using Printed Protein Patterns
Publisher: Wiley
Date: 19-10-2015
Abstract: It is demonstrated that metal-organic frameworks (MOFs) can be replicated in a biomimetic fashion from protein patterns. Bendable, fluorescent MOF patterns are formed with micrometer resolution under ambient conditions. Furthermore, this technique is used to grow MOF patterns from fingerprint residue in 30 s with high fidelity. This technique is not only relevant for crime-scene investigation, but also for biomedical applications.
Protein Capsules Assembled via Isobutyramide Grafts: Sequential Growth, Biofunctionalization, and Cellular Uptake
Publisher: American Chemical Society (ACS)
Date: 05-09-2012
DOI: 10.1021/NN302024T
Abstract: We report the sequential assembly of proteins via the alternating physical adsorption of human serum albumin (HSA) and chemical grafting with isobutyramide (IBAM) or bromoisobutyramide (BrIBAM) groups. This approach, performed on silica template particles, leads to the formation of noncovalent protein films with controlled growth at the nanometer scale. Further, after template removal, hollow protein capsules with tunable wall thicknesses and high mechanical stability are obtained. The use of BrIBAM, compared to IBAM grafts, leads to significantly thicker capsule walls, highlighting the influence of the bromine atoms in the assembly process, which is discussed in terms of a theoretical model of noncovalent interactions. Another feature of the process is the possibility to functionalize the HSA capsules with other biologically active macromolecules, including enzymes, polysaccharides, or DNA plasmids, demonstrating the versatility of this approach. We also report that BrIBAM-HSA and IBAM-HSA capsules display negligible cytotoxicity in vitro with HeLa cells and that their cellular uptake is dependent on the thickness of the capsule walls. These findings support the potential use of these protein capsules in tailored biological applications such as drug delivery.
Stabilization and Functionalization of Polymer Multilayers and Capsules via Thiol−Ene Click Chemistry
Publisher: American Chemical Society (ACS)
Date: 23-01-2009
DOI: 10.1021/CM803011W
Metal-Organic Frameworks for Cell and Virus Biology: A Perspective
Publisher: American Chemical Society (ACS)
Date: 08-01-2018
Abstract: Metal-organic frameworks (MOFs) are a class of coordination polymers, consisting of metal ions or clusters linked together by chemically mutable organic groups. In contrast to zeolites and porous carbons, MOFs are constructed from a building block strategy that enables molecular level control of pore size/shape and functionality. An area of growing interest in MOF chemistry is the synthesis of MOF-based composite materials. Recent studies have shown that MOFs can be combined with biomacromolecules to generate novel biocomposites. In such materials, the MOF acts as a porous matrix that can encapsulate enzymes, oligonucleotides, or even more complex structures that are capable of replication/reproduction (i.e., viruses, bacteria, and eukaryotic cells). The synthetic approach for the preparation of these materials has been termed "biomimetic mineralization", as it mimics natural biomineralization processes that afford protective shells around living systems. In this Perspective, we focus on the preparation of MOF biocomposites that are composed of complex biological moieties such as viruses and cells and canvass the potential applications of this encapsulation strategy to cell biology and biotechnology.
Engineering Low-Fouling and pH-Degradable Capsules through the Assembly of Metal-Phenolic Networks
Publisher: American Chemical Society (ACS)
Date: 05-02-2015
DOI: 10.1021/BM5017139
Abstract: Metal-phenolic coordination chemistry provides a simple and rapid way to fabricate ultrathin films. Here, we report a facile strategy for the preparation of low-fouling and pH-degradable metal-phenolic network (MPN) capsules using a synthetic polyphenol derivative, poly(ethylene glycol) (PEG)-polyphenol, as a building block. PEG-MPN capsules exhibit reduced nonspecific protein adsorption and cell association compared with tannic acid (TA)-MPN capsules. In addition, they show faster disassembly at a biologically relevant pH (5) than TA-MPN capsules (80% in 5 h vs 30% in 10 days). PEG-MPN capsules combine both the low fouling properties of PEG and the advantages of the MPN-driven assembly process (e.g., fast assembly and pH-degradability).
Engineered bacterially expressed polypeptides: Assembly into polymer particles with tailored degradation profiles
Publisher: Wiley
Date: 23-11-2012
Abstract: In nature, the sequence of amino acids in a protein is determined by the genetic code. Biosynthesis of polypeptides by bacteria can be used to exploit this natural process to afford exact control over properties such as molecular weight, chemical functionality, and structure. It is demonstrated how control over the positioning of functional groups can be used to tune the degradation of assembled polypeptide particles (see scheme).
Role of the Protein Corona Derived from Human Plasma in Cellular Interactions between Nanoporous Human Serum Albumin Particles and Endothelial Cells
Publisher: American Chemical Society (ACS)
Date: 14-07-2017
DOI: 10.1021/ACS.BIOCONJCHEM.7B00231
Abstract: The presence of a protein corona on various synthetic nanomaterials has been shown to strongly influence how they interact with cells. However, it is unclear if the protein corona also exists on protein particles, and if so, its role in particle-cell interactions. In this study, pure human serum albumin (HSA) particles were fabricated via mesoporous silica particle templating. Our data reveal that various serum proteins adsorbed on the particles, when exposed to human blood plasma, forming a corona. In human umbilical vein endothelial cells (HUVECs), the corona was shown to decrease particle binding to the cell membrane, increase the residence time of particles in early endosomes, and reduce the amount of internalized particles within the first hours of exposure to particles. These findings reveal important information regarding the mechanisms used by vascular endothelial cells to internalize protein-based particulate materials exposed to blood plasma. The ability to control the cellular recognition of these organic particles is expected to aid the advancement of HSA-based materials for intravenous drug delivery.
Influence of size, surface, cell line, and kinetic properties on the specific binding of A33 antigen-targeted multilayered particles and capsules to colorectal cancer cells
Publisher: American Chemical Society (ACS)
Date: 14-08-2007
DOI: 10.1021/NN700060M
Abstract: There has been increased interest in the use of polymer capsules formed by the layer-by-layer (LbL) technique as therapeutic carriers to cancer cells due to their versatility and ease of surface modification. We have investigated the influence of size, surface properties, cell line, and kinetic parameters such as dosage (particle concentration) and incubation time on the specific binding of humanized A33 monoclonal antibody (huA33 mAb)-coated LbL particles and capsules to colorectal cancer cells. HuA33 mAb binds to the A33 antigen present on almost all colorectal cancer cells and has demonstrated great promise in clinical trials as an immunotherapeutic agent for cancer therapy. Flow cytometry experiments showed the cell binding specificity of huA33 mAb-coated particles to be size-dependent, with the optimal size for enhanced selectivity at approximately 500 nm. The specific binding was improved by increasing the dosage of particles incubated with the cells. The level of specific versus nonspecific binding was compared for particles terminated with various polyelectrolytes to examine the surface dependency of antibody attachment and subsequent cell binding ability. The specific binding of huA33 mAb-coated particles is also reported for two colorectal cancer cell lines, with an enhanced binding ratio between 4 and 10 obtained for the huA33 mAb-functionalized particles. This investigation aims to improve the level of specific targeting of LbL particles, which is important in targeted drug and gene delivery applications.
Templated assembly of albumin-based nanoparticles for simultaneous gene silencing and magnetic resonance imaging
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4NR02623C
Abstract: We report the preparation of albumin-based nanoparticles assembled via isobutyramide groups providing simultaneous magnetic resonance imaging and cellular gene silencing.
Electrochemical Behavior and Redox-Dependent Disassembly of Gallic Acid/FeIII Metal-Phenolic Networks
Publisher: American Chemical Society (ACS)
Date: 30-01-2018
Abstract: Metal-phenolic networks (MPNs) are a versatile class of organic-inorganic hybrid systems that are generating interest for applications in catalysis, bioimaging, and drug delivery. These self-assembled MPNs possess metal-coordinated structures and may potentially serve as redox-responsive platforms for triggered disassembly or drug release. Therefore, a comprehensive study of the reduction and oxidation behavior of MPNs for evaluating their redox responsiveness, specific conditions required for their disassembly, and the kinetics of metal ion release, is necessary. Using a representative MPN gallic acid-iron (GA/Fe
Immobilization and Intracellular Delivery of Structurally Nanoengineered Antimicrobial Peptide Polymers Using Polyphenol-Based Capsules
Publisher: Wiley
Date: 14-11-2022
Abstract: Structurally nanoengineered antimicrobial peptide polymers (SNAPPs) are an emerging class of antimicrobials against multidrug‐resistant bacteria. Their encapsulation in particle carriers can improve their therapeutic efficacy by preventing peptide degradation, reducing clearance, and enhancing intracellular delivery and dosage to bacteria‐infected host cells. Herein, two template‐mediated strategies are reported for immobilizing SNAPPs in microcapsules through 1) complexation of SNAPPs with tannic acid (TA) onto porous CaCO 3 templates and subsequent removal of the templates (SNAPP–TA capsules) and 2) adsorption of SNAPPs onto CaCO 3 templates and subsequent encapsulation within a metal–phenolic (Fe III –TA) coating and template removal (SNAPP–Fe III –TA capsules). The loading amounts of SNAPPs are 0.8 and 4.4 pg per SNAPP–TA and SNAPP–Fe III –TA capsule, respectively. At pH 7.4, there is sustained release of SNAPPs, which retain high antimicrobial activity with minimum inhibitory concentration values of ≈30 µg mL −1 in Escherichia coli . Both capsule systems are internalized by alveolar macrophages in vitro, with negligible cytotoxicity and are amenable to nebulization, remaining stable in nebulized droplets. This study demonstrates the potential of engineered polyphenol‐based capsules for peptide drug immobilization and intracellular delivery, which have prospective application in the pulmonary delivery of antimicrobials against respiratory bacterial infections (e.g., pneumonia, tuberculosis).
Acousto-optic surface-plasmon resonance measurements of thin films on gold
Publisher: AIP Publishing
Date: 15-01-1998
DOI: 10.1063/1.366792
Abstract: In this work a highly sensitive optical technique was used to study the adsorption of thin organic layers onto a gold film from water, in situ and in real-time. Optical excitation of a surface-plasmon resonance (SPR) was used to probe the gold/water interface. The use of an acousto-optic tunable filter then provides a differential technique for monitoring the SPR position in optical wavelength. This allows optical changes at the metal/liquid interface to be measured as the adsorption of thin organic layers occurs. Adsorption of a poly(ethylene glycol) monododecyl ether surfactant (C12E8) and a 30-mer DNA oligonucleotide with a mercaptohexyl group at the 5′-phosphate end (DNA-SH) onto gold from water were examined. Conventional, angle-dependent reflectivity measurements taken on the same system provided complementary SPR data, allowing the sensitivity of the two techniques to be compared.
Modular Metal‐Quinone Networks with Tunable Architecture and Functionality
Publisher: Wiley
Date: 20-02-2023
Abstract: Nanostructured materials with tunable structures and functionality are of interest in erse areas. Herein, metal ions are coordinated with quinones through metal‐acetylacetone coordination bonds to generate a class of structurally tunable, universally adhesive, hydrophilic, and pH‐degradable materials. A library of metal‐quinone networks (MQNs) is produced from five model quinone ligands paired with nine metal ions, leading to the assembly of particles, tubes, capsules, and films. Importantly, MQNs show bidirectional pH‐responsive disassembly in acidic and alkaline solutions, where the quinone ligands mediate the disassembly kinetics, enabling temporal and spatial control over the release of multiple components using multilayered MQNs. Leveraging this tunable release and the inherent medicinal properties of quinones, MQN prodrugs with a high drug loading ( wt %) are engineered using doxorubicin for anti‐cancer therapy and shikonin for the inhibition of the main protease in the SARS‐CoV‐2 virus.
Multilayer assembly. Technology-driven layer-by-layer assembly of nanofilms.
Publisher: American Association for the Advancement of Science (AAAS)
Date: 24-04-2015
Abstract: The deposition of thin films from multiple materials is essential to a range of materials fabrication processes. Layer-by-layer processes involve the sequential deposition of two or more materials that physically bond together. Richardson et al. review some of the techniques and materials that are used to make thin films, including sequential dip coating, spraying, and electrochemical deposition. Despite the versatility of the methods and the range of materials that can be deposited, the techniques remain mostly confined to the lab because of challenges in industrial scaling. But because there is tremendous scope for fine-tuning the structure and properties of the multilayers, there is interest in broadening the use of these techniques. Science , this issue 10.1126/science.aaa2491
In Vivo T Cell-Targeting Nanoparticle Drug Delivery Systems: Considerations for Rational Design
Publisher: American Chemical Society (ACS)
Date: 18-02-2021
Microemulsion-Assisted Templating of Metal-Stabilized Poly(ethylene glycol) Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 18-12-2020
Nanostructured polymer assemblies formed at interfaces: applications from immobilization and encapsulation to stimuli-responsive release
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CP02287J
Abstract: In recent years, interfacial properties have been tailored with nanostructured polymer assemblies to generate materials with specific properties and functions for application in erse fields, including biomaterials, drug delivery, catalysis, sensing, optics and corrosion. This perspective begins with a brief introduction of the assembly techniques that are commonly employed for the synthesis of nanostructured polymer materials, followed by discussions on how the interfaces influence the properties and thus the functionalities of the polymer materials prepared. Applications of the interfacial polymer nanostructures, particularly for the immobilization and encapsulation of cargo, are then reviewed, focusing on stimuli-responsive cargo release from the polymer nanostructured assemblies for controlled delivery applications. Finally, future research directions in these areas are briefly discussed.
Unravelling off-target effects of redox-active polymers and polymer multilayered capsules in prostate cancer cells
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4NR07240E
Abstract: Redox-active polymers and carriers are oxidizing nanoagents that can potentially trigger intracellular off-target effects. In the present study, we investigated the occurrence of off-target effects in prostate cancer cells following exposure to redox-active polymer and thin multilayer capsules with different chemical properties. We show that, depending on the intracellular antioxidant capacity, thiol-functionalized poly(methacrylic acid), PMA(SH) triggers cell defense responses erturbations that result in off-target effects (i.e., induction of autophagy and down-regulation of survivin). Importantly, the conversion of the carboxyl groups of PMA(SH) into the neutral amides of poly(hydroxypropylmetacrylamide) (pHPMA(SH)) nullified the off-target effects and cytotoxicity in tested cell lines. This suggests that the simultaneous action of carboxyl and disulfide groups in PMA(SH) polymer or capsules may play a role in mediating the intracellular off-target effects. Our work provides evidence that the rational design of redox-active carriers for therapeutic-related application should be guided by a careful investigation on potential disturbance of the cellular machineries related to the carrier association.
Surface Click Chemistry on Brominated Plasma Polymer Thin Films
Publisher: American Chemical Society (ACS)
Date: 10-11-2010
DOI: 10.1021/LA9031688
Abstract: A brominated plasma polymer (BrPP) thin film was fabricated on a variety of substrate surfaces (silicon wafers, glass, gold, and polymers) via the radio frequency glow discharge of 1-bromopropane. This BrPP thin film was highly adherent and stable and was found to be a useful platform for secondary reactions, leading to surfaces with specific chemical functionalities. Following nucleophilic exchange, an azide-functionalized PP thin film was prepared that was reactive toward two different alkynes via the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, a paradigm of "click" chemistry. "Click" microcontact printing (microCP) of a fluorescent alkyne was also successfully carried out, demonstrating the versatility and functionality of this new class of reactive thin film plasma polymer coatings.
Emerging Techniques in Proteomics for Probing Nano-Bio Interactions
Publisher: American Chemical Society (ACS)
Date: 07-12-2012
DOI: 10.1021/NN3052499
Abstract: Nanoengineered particles that can facilitate drug formulation and improve specificity of delivery afford exciting opportunities for improved lesion-specific therapy. Understanding and controlling the nano-bio interactions of these materials is central to future developments in this area. Mass-spectrometry-based proteomics techniques, in conjunction with other emerging technologies, are enabling novel insights into the modulation of particle surfaces by biological fluids (formation of the protein corona) and subsequent particle-induced cellular responses. In this Perspective, we summarize important recent developments using proteomics-based techniques to understand nano-bio interactions and discuss the impact of such knowledge on improving particle design.
Immobilization and Intracellular Delivery of an Anticancer Drug Using Mussel-Inspired Polydopamine Capsules
Publisher: American Chemical Society (ACS)
Date: 13-07-2012
DOI: 10.1021/BM300835R
Abstract: We report a facile approach to immobilize pH-cleavable polymer-drug conjugates in mussel-inspired polydopamine (PDA) capsules for intracellular drug delivery. Our design takes advantage of the facile PDA coating to form capsules, the chemical reactivity of PDA films, and the acid-labile groups in polymer side chains for sustained pH-induced drug release. The anticancer drug doxorubicin (Dox) was conjugated to thiolated poly(methacrylic acid) (PMA(SH)) with a pH-cleavable hydrazone bond, and then immobilized in PDA capsules via robust thiol-catechol reactions between the polymer-drug conjugate and capsule walls. The loaded Dox showed limited release at physiological pH but significant release (over 85%) at endosomal/lysosomal pH. Cell viability assays showed that Dox-loaded PDA capsules enhanced the efficacy of eradicating HeLa cancer cells compared with free drug under the same assay conditions. The reported method provides a new platform for the application of stimuli-responsive PDA capsules as drug delivery systems.
Engineering Advanced Capsosomes: Maximizing the Number of Subcompartments, Cargo Retention, and Temperature-Triggered Reaction
Publisher: American Chemical Society (ACS)
Date: 03-2010
DOI: 10.1021/NN901843J
Abstract: Advanced mimics of cells require a large yet controllable number of subcompartments encapsulated within a scaffold, equipped with a trigger to initiate, terminate, and potentially restart an enzymatic reaction. Recently introduced capsosomes, polymer capsules containing thousands of liposomes, are a promising platform for the creation of artificial cells. Capsosomes are formed by sequentially layering liposomes and polymers onto particle templates, followed by removal of the template cores. Herein, we engineer advanced capsosomes and demonstrate the ability to control the number of subcompartments and hence the degree of cargo loading. To achieve this, we employ a range of polymer separation layers and liposomes to form functional capsosomes comprising multiple layers of enzyme-loaded liposomes. Differences in conversion rates of an enzymatic assay are used to verify that multilayers of intact enzyme-loaded liposomes are assembled within a polymer hydrogel capsule. The size-dependent retention of the cargo encapsulated within the liposomal subcompartments during capsosome assembly and its dependence on environmental pH changes are also examined. We further show that temperature can be used to trigger an enzymatic reaction at the phase transition temperature of the liposomal subcompartments, and that the encapsulated enzymes can be utilized repeatedly in several subsequent conversions. These engineered capsosomes with tailored properties present new opportunities en route to the development of functional artificial cells.
A quartz crystal microbalance study of the removal of solid organic soils from a hard surface in aqueous surfactant solution
Publisher: Elsevier BV
Date: 1999
Boronate–Phenolic Network Capsules with Dual Response to Acidic pH and cis‐Diols
Publisher: Wiley
Date: 18-06-2015
Abstract: Dual-responsive boronate-phenolic network (BPN) capsules are fabricated by the complexation of phenylborate and phenolic materials. The BPN capsules are stable in the presence of competing carbohydrates, but dissociate at acidic pH or in the presence of competing cis-diols at physiological pH. This engineered capsule system provides a platform for a wide range of biological and biomedical applications.
Macroporous zeolitic membrane bioreactors
Publisher: Wiley
Date: 10-2004
Hollow capsule processing through colloidal templating and self-assembly
Publisher: Wiley
Date: 04-02-2000
DOI: 10.1002/(SICI)1521-3765(20000204)6:3<413::AID-CHEM413>3.0.CO;2-9
Abstract: Hollow capsules of nanometer to micrometer dimensions constitute an important class of materials that are employed in erse technological applications, ranging from the delivery of encapsulated products for cosmetic and medicinal purposes to their use as light-weight composite materials and as fillers with low dielectric constant in electronic components. Hollow capsules comprising polymer, glass, metal, and ceramic are nowadays routinely produced by using various chemical and physicochemical methods. The current article focuses on a recent novel and versatile technique, based on a combination of colloidal templating and self-assembly processes, developed for synthesizing uniform hollow capsules of a broad range of materials. The strategy outlined readily affords control over the size, shape, composition, and wall thickness of the hollow capsules.
Particles on the Move: Intracellular Trafficking and Asymmetric Mitotic Partitioning of Nanoporous Polymer Particles
Publisher: American Chemical Society (ACS)
Date: 28-05-2013
DOI: 10.1021/NN401800U
Abstract: Nanoporous polymer particles (NPPs) prepared by mesoporous silica templating show promise as a new class of versatile drug/gene delivery vehicles owning to their high payload capacity, functionality, and responsiveness. Understanding the cellular dynamics of such particles, including uptake, intracellular trafficking, and distribution, is an important requirement for their development as therapeutic carriers. Herein, we examine the spatiotemporal map of the cellular processing of submicrometer-sized disulfide-bonded poly(methacrylic acid) (PMASH) NPPs in HeLa cells using both flow cytometry and fluorescence microscopy. The data show that the PMASH NPPs are transported from the early endosomes to the lysosomes within a few minutes. Upon cell ision, the lysosome-enclosed PMASH NPPs are distributed asymmetrically between two daughter cells. Statistical analysis of cells during cytokinesis suggests that partitioning of particles is biased with an average segregation deviation of 60%. Further, two-dimensional difference gel electrophoresis (2D-DIGE) analysis reveals that 127 out of 3059 identified spots are differentially regulated upon exposure to the PMASH NPPs. Pathway analysis of the proteomics data suggests that ubiquitylation, a reversible modification of cellular proteins with ubiquitin, plays a central role in overall cellular responses to the particles. These results provide important insights into the cellular dynamics and heterogeneity of NPPs, as well as the mechanisms that regulate the motility of these particles within cells, all of which have important implications for drug susceptibility characteristics in cancer cells using particle-based carriers.
Stepwise self-assembled poly(amidoamine) dendrimer and poly(styrenesulfonate) microcapsules as sustained delivery vehicles
Publisher: American Chemical Society (ACS)
Date: 07-09-2002
DOI: 10.1021/BM025562K
Abstract: Hollow microcapsules comprised of poly(styrenesulfonate) (PSS) and a fourth generation poly(amidoamine) dendrimer (4G PAMAM) were prepared by depositing PSS/4G PAMAM multilayers on melamine formaldehyde (MF) colloid particles by the layer-by-layer self-assembly technique and subsequently dissolving the templated cores. The PSS/4G PAMAM layers were unstable toward the core removal procedure (pH approximately 1), resulting in a low yield of intact hollow capsules (<10% for 3.5 microm diameter MF templates). Stretching of the multilayer film due to core swelling during MF core dissolution leads to partial or complete destruction of capsules, giving discrete PSS-4G PAMAM complexes. Yields were increased by increasing inter- and intramolecular attractive forces between the PSS chains in the capsules through electrostatic, hydrophobic, and a combination of these interactions. The yields, however, were practically unaffected by enhancing such effects between dendrimer molecules. Transmission electron microscopy and scanning force microscopy measurements show no deformation for 3.5 microm capsules stabilized through the various interactions stated above. Further, capsules were filled with low molecular weight dextran sulfate and subsequently loaded with a model, therapeutically active molecule, doxorubicin hydrochloride (DOX). Release of DOX from the capsules was also studied to highlight the drug delivery potential of the dendrimer-based microcapsules.
Tuning the Mechanical Properties of Nanoporous Hydrogel Particles via Polymer Cross-Linking
Publisher: American Chemical Society (ACS)
Date: 25-07-2013
DOI: 10.1021/LA402146T
Abstract: Soft hydrogel particles with tunable mechanical properties are promising for next-generation therapeutic applications. This is due to the increasingly proven role that physicochemical properties play in particulate-based delivery vectors, both in vitro and in vivo. The ability to understand and quantify the mechanical properties of such systems is therefore essential to optimize function and performance. We report control over the mechanical properties of poly(methacrylic acid) (PMA) hydrogel particles based on a mesoporous silica templating method. The mechanical properties of the obtained particles can be finely tuned through variation of the cross-linker concentration, which is hereby quantified using a cross-linking polymer with a fluorescent tag. We demonstrate that the mechanical properties of the particles can be elucidated using an atomic force microscopy (AFM) force spectroscopy method, which additionally allows for the study of hydrogel material properties at the nanoscale through high-resolution force mapping. Young's modulus and stiffness of the particles were tuned between 0.04 and 2.53 MPa and between 1.6 and 28.4 mN m(-1), respectively, through control over the cross-linker concentration. The relationship between the concentration of the cross-linker added and the amount of adsorbed polymer was observed to follow a Langmuir isotherm, and this relationship was found to correlate linearly with the particle mechanical properties.
Surface-modification of polyelectrolyte multilayer-coated particles for biological applications
Publisher: American Chemical Society (ACS)
Date: 27-06-2003
DOI: 10.1021/LA030016D
Assembly of Layer-by-Layer Particles and Their Interactions with Biological Systems
Publisher: American Chemical Society (ACS)
Date: 22-08-2014
DOI: 10.1021/CM402126N
Factors influencing the growth and topography of nanoscale films fabricated by ROMP-mediated continuous assembly of polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2PY20692G
Template-Directed Mild Synthesis of Anatase Hybrid Nanotubes within Cylindrical Core–Shell–Corona Polymer Brushes
Publisher: American Chemical Society (ACS)
Date: 23-08-2012
DOI: 10.1021/MA301232M
Luminescent Metal‐Phenolic Networks for Multicolor Particle Labeling
Publisher: Wiley
Date: 18-10-2021
Abstract: The development of fluorescence labeling techniques has attracted widespread interest in various fields, including biomedical science as it can facilitate high‐resolution imaging and the spatiotemporal understanding of various biological processes. We report a supramolecular fluorescence labeling strategy using luminescent metal‐phenolic networks (MPNs) constructed from metal ions, phenolic ligands, and common and commercially available dyes. The rapid labeling process ( min) produces ultrathin coatings (≈10 nm) on erse particles (e.g., organic, inorganic, and biological entities) with customized luminescence (e.g., red, blue, multichromatic, and white light) simply through the selection of fluorophores. The fluorescent coatings are stable at pH values from 1 to 8 and in complex biological media owing to the dominant π interactions between the dyes and MPNs. These coatings exhibit negligible cytotoxicity and their strong fluorescence is retained even when internalized into intracellular compartments. This strategy is expected to provide a versatile approach for fluorescence labeling with potential in erse fields across the physical and life sciences.
Modular Click Assembly of Degradable Capsules Using Polyrotaxanes
Publisher: American Chemical Society (ACS)
Date: 31-05-2012
DOI: 10.1021/NN301045Z
Abstract: A modular approach for the formation of degradable capsules using polyrotaxanes (PRXs) is described. The PRXs consist of α-cyclodextrin (αCD) and poly(ethylene glycol) (PEG), which are both biologically benign and the main degradation products of the capsules. The PRXs were equipped with three alkyne groups at their ends and could be successfully grafted to azide-functionalized silica particles (2.76 μm diameter) using azide-alkyne click chemistry. The assembled PRXs were then cross-linked using a degradable linker. The cross-linked structure was sufficiently robust to allow the formation of capsules after dissolving the template silica particles. The formation of capsules of ca. 2 μm diameter was verified by optical microscopy, TEM, and AFM imaging. The capsules were loaded with the chemotherapy drug doxorubicin (DOX) by conjugating it to the threaded αCDs via their free OH groups, while maintaining degradability of the capsules. Alkyne moieties at the surface of the cross-linked PRX architecture were available for further functionalization of the capsules, as is demonstrated by clicking on fluorescent PEG moieties. The DOX-loaded capsules were degraded within 90 min at 37 °C upon exposure to a 5 mM solution of glutathione in water.
Preparation of Nano- and Microcapsules by Electrophoretic Polymer Assembly
Publisher: Wiley
Date: 09-05-2013
Targeting Ability of Affibody-Functionalized Particles Is Enhanced by Albumin but Inhibited by Serum Coronas
Publisher: American Chemical Society (ACS)
Date: 30-10-2015
Fabrication of nanopatterned polymeric microparticles using a diatom as a sacrificial template
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4RA06728B
Abstract: Diatoms serve as sacrificial templates to fabricate polymeric microparticles with elaborate nano-scale architecture.
Influence of Polyelectrolyte Multilayer Coatings on Förster Resonance Energy Transfer between 6-Carboxyfluorescein and Rhodamine B-Labeled Particles in Aqueous Solution
Publisher: American Chemical Society (ACS)
Date: 24-02-1998
DOI: 10.1021/JP980198Y
Infiltration of macromolecules into nanoporous silica particles
Publisher: American Chemical Society (ACS)
Date: 20-09-2007
DOI: 10.1021/MA071125S
Giant self-contained metallosupramolecular entities
Publisher: Royal Society of Chemistry (RSC)
Date: 1999
DOI: 10.1039/A905115E
Best Practices for New Polymers and Nanoparticulate Systems How Not To Be Soft with Reporting Standards
Publisher: American Chemical Society (ACS)
Date: 09-10-2018
Preparation of nanoporous polyelectrolyte multilayer films via nanoparticle templating
Publisher: American Chemical Society (ACS)
Date: 21-10-2006
DOI: 10.1021/CM061626C
Supramolecular Metal-Phenolic Gels for the Crystallization of Active Pharmaceutical Ingredients
Publisher: Wiley
Date: 28-05-2018
Abstract: The use of supramolecular gel media for the crystallization of active pharmaceutical ingredients (APIs) is of interest for controlling crystal size, morphology, and polymorphism, as these features determine the performance of pharmaceutical formulations. In contrast to supramolecular systems prepared from synthetic gelators, herein, supramolecular metallogels based on a natural polyphenol (tannic acid) are used for the crystallization of APIs. The gel-grown API crystals exhibit considerable differences in size, morphology, and polymorphism when compared with those formed in solutions. These physical features can also be tailored by varying the gel composition and additives, suggesting an influence of the gel medium on the crystallization outcomes. Furthermore, these gel-API crystal composites can be used for sustained drug release, indicating their potential as drug delivery systems. The facile preparation of these supramolecular gels and the use of naturally abundant components in their synthesis provide a generic platform for studying gel-mediated crystallization of erse APIs.
Mechanically tunable, self-adjuvanting nanoengineered polypeptide particles
Publisher: Wiley
Date: 10-05-2013
Abstract: DNA-loaded polypeptide particles are prepared via templated assembly of mesoporous silica for the delivery of adjuvants. The elasticity and cargo-loading capacity of the obtained particles can be tuned by the amount of cross-linker used to stabilize the polypeptide particles. The use of polypeptide particles as biocarriers provides a promising method for vaccine delivery.
Analysing intracellular deformation of polymer capsules using structured illumination microscopy.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6NR02151D
Abstract: Understanding the behaviour of therapeutic carriers is important in elucidating their mechanism of action and how they are processed inside cells. Herein we examine the intracellular deformation of layer-by-layer assembled polymer capsules using super-resolution structured illumination microscopy (SIM). Spherical- and cylindrical-shaped capsules were studied in three different cell lines, namely HeLa (human epithelial cell line), RAW264.7 (mouse macrophage cell line) and differentiated THP-1 (human monocyte-derived macrophage cell line). We observed that the deformation of capsules was dependent on cell line, but independent of capsule shape. This suggests that the mechanical forces, which induce capsule deformation during cell uptake, vary between cell lines, indicating that the capsules are exposed to higher mechanical forces in HeLa cells, followed by RAW264.7 and then differentiated THP-1 cells. Our study demonstrates the use of super-resolution SIM in analysing intracellular capsule deformation, offering important insights into the cellular processing of drug carriers in cells and providing fundamental knowledge of intracellular mechanobiology. Furthermore, this study may aid in the design of novel drug carriers that are sensitive to deformation for enhanced drug release properties.
Liquid Crystal Emulsions as the Basis of Biological Sensors for the Optical Detection of Bacteria and Viruses
Publisher: Wiley
Date: 16-07-2009
Fabrication of asymmetric Janus'' particles via plasma polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0CC00474J
Abstract: A versatile approach has been developed using plasma polymerization to fabricate functional Janus particles. A brominated plasma polymer is toposelectively deposited on a monolayer of silica microparticles, endowing the particles with a chemically reactive polymeric and silica hemisphere.
Polymeric Multilayer Films Comprising Deconstructible Hydrogen-Bonded Stacks Confined between Electrostatically Assembled Layers
Publisher: American Chemical Society (ACS)
Date: 29-03-2003
DOI: 10.1021/MA021049N
Facile tailoring of film morphology and release properties using layer-by-layer assembly of thermoresponsive materials
Publisher: American Chemical Society (ACS)
Date: 09-12-2004
DOI: 10.1021/LA0360310
Abstract: Layer-by-layer self-assembly was used to prepare thermoresponsive thin films of poly(N-isopropylacrylamide) (PNIPAAm) and poly(acrylic acid) (PAA) based on hydrogen bonding. The temperature of PNIPAAm adsorption was shown to significantly affect both the mass proportion of PNIPAAm in the film and the film surface morphology. When the adsorption was conducted at temperatures close to the lower critical solubility temperature of PNIPAAm, the amount of PNIPAAm in the film increased significantly (from 51 to 59%), and the total film mass increased by 30-40%. The films prepared at 30 degrees C also exhibited a lower surface roughness (1-2 nm) compared with 5-8 nm when prepared at 10 or 21 degrees C. The resulting multilayer films ([PAA/PNIPAAm]10) were capable of being reversibly loaded and unloaded with dye (Rhodamine B) by exposure to solutions at elevated temperatures. The rate of loading and release was shown to depend on both the solution temperature and film preparation temperature, leading to tunable loading/release properties.
Production of Hollow Microspheres from Nanostructured Composite Particles
Publisher: American Chemical Society (ACS)
Date: 13-10-1999
DOI: 10.1021/CM991083P
A Cytoprotective and Degradable Metal-Polyphenol Nanoshell for Single-Cell Encapsulation
Publisher: Wiley
Date: 19-08-2014
Abstract: Single-cell encapsulation promises the cytoprotection of the encased cells against lethal stressors, reminiscent of the sporulation process in nature. However, the development of a cytocompatible method for chemically mimicking the germination process (i.e., shell degradation on-demand) has been elusive, despite the shell degradation being pivotal for the practical use of functional cells as well as for single cell-based biology. We report that an artificial shell, composed of tannic acid (TA) and Fe(III) , on in idual Saccharomyces cerevisiae controllably degrades on-demand, while protecting the yeast from multiple external aggressors, including UV-C irradiation, lytic enzymes, and silver nanoparticles. Cell ision is suppressed by the TA-Fe(III) shell, but restored fully upon shell degradation. The formation of a TA-Fe(III) shell would provide a versatile tool for achieving the chemical version of "sporulation and germination".
Template synthesis of stimuli-responsive nanoporous polymer-based spheres via sequential assembly
Publisher: American Chemical Society (ACS)
Date: 28-07-2006
DOI: 10.1021/CM060866P
Solid-State Encapsulation of Urea via Mechanochemistry-Driven Engineering of Metal–Phenolic Networks
Publisher: American Chemical Society (ACS)
Date: 07-09-2023
Advancing Metal-Phenolic Networks for Visual Information Storage
Publisher: American Chemical Society (ACS)
Date: 19-07-2019
Abstract: We report a facile inking strategy for visual information storage (e.g., writing, printing, and beyond) via surface modification of substrates with polyphenols and subsequent in situ formation of metal-phenolic networks (MPNs) on the substrates. The reported technique has several advantages compared with current printing techniques. Diverse substrates can be used to fulfill the requirements for different applications (e.g., printing, writing, painting, and st ing). A range of colors (e.g., yellow, blue, and green) can be realized using different polyphenols (e.g., tannic acid, gallic acid, and pyrogallol) and metal ions (e.g., Cu
A Microreactor with Thousands of Subcompartments: Enzyme-Loaded Liposomes within Polymer Capsules
Publisher: Wiley
Date: 26-05-2009
Abstract: Fully loaded: Noncovalent anchoring of liposomes into polymer multilayered films with cholesterol-modified polymers allows the preparation of capsosomes-liposome-compartmentalized polymer capsules (see picture). A quantitative enzymatic reaction confirmed the presence of active cargo within the capsosomes and was used to determine the number of subcompartments within this novel biomedical carrier system.
Engineering Poly(ethylene glycol) Nanoparticles for Accelerated Blood Clearance Inhibition and Targeted Drug Delivery
Publisher: American Chemical Society (ACS)
Date: 27-09-2022
DOI: 10.1021/JACS.2C06877
Abstract: Surface modification with poly(ethylene glycol) (PEGylation) is an effective strategy to improve the colloidal stability of nanoparticles (NPs) and is often used to minimize cellular uptake and clearance of NPs by the immune system. However, PEGylation can also trigger the accelerated blood clearance (ABC) phenomenon, which is known to reduce the circulation time of PEGylated NPs. Herein, we report the engineering of stealth PEG NPs that can avoid the ABC phenomenon and, when modified with hyaluronic acid (HA), show specific cancer cell targeting and drug delivery. PEG NPs cross-linked with disulfide bonds are prepared by using zeolitic imidazolate framework-8 NPs as templates. The reported templating strategy enables the simultaneous removal of the template and formation of PEG NPs under mild conditions (pH 5.5 buffer). Compared to PEGylated liposomes, PEG NPs avoid the secretion of anti-PEG antibodies and the presence of anti-PEG IgM and IgG did not significantly accelerate the blood clearance of PEG NPs, indicating the inhibition of the ABC effect for the PEG NPs. Functionalization of the PEG NPs with HA affords PEG NPs that retain their stealth properties against macrophages, target CD44-expressed cancer cells and, when loaded with the anticancer drug doxorubicin, effectively inhibit tumor growth. The innovation of this study lies in the engineering of PEG NPs that can circumvent the ABC phenomenon and that can be functionalized for the improved and targeted delivery of drugs.
Influence of Ionic Strength on the Deposition of Metal-Phenolic Networks
Publisher: American Chemical Society (ACS)
Date: 27-09-2017
DOI: 10.1021/ACS.LANGMUIR.7B02692
Abstract: Metal-phenolic networks (MPNs) are a versatile class of self-assembled materials that are able to form functional thin films on various substrates with potential applications in areas including drug delivery and catalysis. Different metal ions (e.g., Fe
Biofunctionalization of fluorescent rare-earth-doped lanthanum phosphate colloidal nanoparticles
Publisher: Wiley
Date: 10-11-2004
Layer-by-layer engineered capsules and their applications
Publisher: Elsevier BV
Date: 10-2006
Nanoporous protein particles through templating mesoporous silica spheres
Publisher: Wiley
Date: 17-03-2006
Phenolische Bausteine für die Assemblierung von Funktionsmaterialien
Publisher: Wiley
Date: 11-12-2018
Electrostatically Assembled Polyelectrolyte/Dendrimer Multilayer Films as Ultrathin Nanoreservoirs
Publisher: American Chemical Society (ACS)
Date: 08-02-2002
DOI: 10.1021/NL015696O
Protocols for Reproducible, Increased-Scale Synthesis of Engineered Particles—Bridging the “Upscaling Gap”
Publisher: American Chemical Society (ACS)
Date: 05-02-2021
Continuous assembly of polymers via solid phase reactions
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4SC01240B
Abstract: The formation of cross-linked polymer films, with tunable thickness, proceeds directionally from the substrate surface by controlled polymerization in the solid state.
Stabilization of Polymer-Hydrogel Capsules via Thiol-Disulfide Exchange
Publisher: Wiley
Date: 11-11-2009
Bypassing Multidrug Resistance in Cancer Cells with Biodegradable Polymer Capsules
Publisher: Wiley
Date: 25-10-2010
Experimental Quantification of Interactions Between Drug Delivery Systems and Cells In Vitro: A Guide for Preclinical Nanomedicine Evaluation
Publisher: MyJove Corporation
Date: 28-09-2022
DOI: 10.3791/64259
Abstract: A major component of designing drug delivery systems concerns how to lify or attenuate interactions with specific cell types. For instance, a chemotherapeutic might be functionalized with an antibody to enhance binding to cancer cells ("targeting") or functionalized with polyethylene glycol to help evade immune cell recognition ("stealth"). Even at a cellular level, optimizing the binding and uptake of a drug carrier is a complex biological design problem. Thus, it is valuable to separate how strongly a new carrier interacts with a cell from the functional efficacy of a carrier's cargo once delivered to that cell. To continue the chemotherapeutic ex le, "how well it binds to a cancer cell" is a separate problem from "how well it kills a cancer cell". Quantitative in vitro assays for the latter are well established and usually rely on measuring viability. However, most published research on cell-carrier interactions is qualitative or semiquantitative. Generally, these measurements rely on fluorescent labeling of the carrier and, consequently, report interactions with cells in relative or arbitrary units. However, this work can be standardized and be made absolutely quantitative with a small number of characterization experiments. Such absolute quantification is valuable, as it facilitates rational, inter- and intra-class comparisons of various drug delivery systems-nanoparticles, microparticles, viruses, antibody-drug conjugates, engineered therapeutic cells, or extracellular vesicles. Furthermore, quantification is a prerequisite for subsequent meta-analyses or in silico modeling approaches. In this article, video guides, as well as a decision tree for how to achieve in vitro quantification for carrier drug delivery systems, are presented, which take into account differences in carrier size and labeling modality. Additionally, further considerations for the quantitative assessment of advanced drug delivery systems are discussed. This is intended to serve as a valuable resource to improve rational evaluation and design for the next generation of medicine.
Surface Engineering of Polypropylene Membranes with Carbonic Anhydrase-Loaded Mesoporous Silica Nanoparticles for Improved Carbon Dioxide Hydration
Publisher: American Chemical Society (ACS)
Date: 28-05-2015
DOI: 10.1021/ACS.LANGMUIR.5B01020
Abstract: Carbonic anhydrase (CA) is a native enzyme that facilitates the hydration of carbon dioxide into bicarbonate ions. This study reports the fabrication of thin films of active CA enzyme onto a porous membrane substrate using layer-by-layer (LbL) assembly. Deposition of multilayer films consisting of polyelectrolytes and CA was monitored by quartz crystal microgravimetry, while the enzymatic activity was assayed according to the rates of p-nitrophenylacetate (p-NPA) hydrolysis and CO2 hydration. The fabrication of the films onto a nonporous glass substrate showed CO2 hydration rates of 0.52 ± 0.09 μmol cm(-2) min(-1) per layer of bovine CA and 2.6 ± 0.7 μmol cm(-2) min(-1) per layer of a thermostable microbial CA. The fabrication of a multilayer film containing the microbial CA on a porous polypropylene membrane increased the hydration rate to 5.3 ± 0.8 μmol cm(-2) min(-1) per layer of microbial CA. The addition of mesoporous silica nanoparticles as a film layer prior to enzyme adsorption was found to increase the activity on the polypropylene membranes even further to a rate of 19 ± 4 μmol cm(-2) min(-1) per layer of microbial CA. The LbL treatment of these membranes increased the mass transfer resistance of the membrane but decreased the likelihood of membrane pore wetting. These results have potential application in the absorption of carbon dioxide from combustion flue gases into aqueous solvents using gas-liquid membrane contactors.
Engineering Programmable DNA Particles and Capsules Using Catechol-Functionalized DNA Block Copolymers
Publisher: American Chemical Society (ACS)
Date: 03-08-2022
II-VI semiconductor nanocrystals in thin films and colloidal crystals
Publisher: Elsevier BV
Date: 04-2002
Two-Component, Ultrathin Microcapsules Prepared by a Core-Mediated Layer-by-Layer Approach
Publisher: American Chemical Society (ACS)
Date: 28-04-2004
DOI: 10.1021/CM049891Q
Functional Ligand-Enabled Particle Assembly for Bio–Nano Interactions
Publisher: American Chemical Society (ACS)
Date: 24-05-2023
Engineering cellular degradation of multilayered capsules through controlled cross-linking
Publisher: American Chemical Society (ACS)
Date: 02-11-2012
DOI: 10.1021/NN3039353
Abstract: We report a versatile approach for controlling the intracellular degradation of polymer capsules by tailoring the degree of cross-linking in the capsules. Poly(2-diisopropylaminoethyl methacrylate) capsules were assembled by the layer-by-layer technique and covalently stabilized with a redox-responsive bisazide cross-linker using click chemistry. The degree of cross-linking, determined using radiation scintillation counting, was tuned from 65% to 98% by adjusting the amount of cross-linker used to stabilize the polymer films. Transmission electron microscopy and fluorescence microscopy studies showed that the pH responsiveness of the capsules was maintained, regardless of the degree of cross-linking. Atomic force microscopy measurements on planar surfaces revealed that increasing the degree of cross-linking decreased the film roughness (from 8.7 to 1.7 nm), hence forming smoother films however the film thicknesses were not significantly altered. Cellular studies showed that the rate of intracellular degradation of the capsules could be controlled between 0 and 6 h by altering the degree of cross-linking in the polymer capsules. These studies also demonstrated that the cellular degradation of highly cross-linked capsules (>90%) was significantly retarded compared to degradation in simulated cellular conditions. This suggests that the naturally occurring cellular reducing environment is rapidly depleted, and there is a significant delay before the cells can replenish the reducing environment. The modular and versatile nature of this approach lends itself to application to a wide range of polymer carriers and thus offers significant potential for the design of polymer-based systems for drug and gene delivery.
Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating
Publisher: American Association for the Advancement of Science (AAAS)
Date: 06-11-1998
DOI: 10.1126/SCIENCE.282.5391.1111
Abstract: Hollow silica and silica-polymer spheres with diameters between 720 and 1000 nanometers were fabricated by consecutively assembling silica nanoparticles and polymer onto colloids and subsequently removing the templated colloid either by calcination or decomposition upon exposure to solvents. Scanning and transmission electron microscopy images demonstrate that the wall thickness of the hollow spheres can be readily controlled by varying the number of nanoparticle-polymer deposition cycles, and the size and shape are determined by the morphology of the templating colloid. The hollow spheres produced are envisioned to have applications in areas ranging from medicine to pharmaceutics to materials science.
Thin films of polyelectrolyte-encapsulated catalase microcrystals for biosensing
Publisher: American Chemical Society (ACS)
Date: 10-05-2003
DOI: 10.1021/AC0340049
Abstract: Polyelectrolyte (PE)-encapsulated catalase microcrystals were assembled onto gold electrodes by their sequential deposition with oppositely charged PEs, utilizing electrostatic interactions to form enzyme thin films for biosensing. The PE coating around the microcrystals provided a regular surface charge, thus facilitating the stepwise film growth, and it effectively prevented catalase leakage from the assembled films. The encapsulated catalase was shown to retain both its biological and its electrochemical activity. Direct electron transfer between catalase molecules and the gold electrode was achieved without the aid of any electron mediator. In pH 5.0 phosphate buffer solution, the apparent formal potential (E(o)') of catalase was -0.131 V (vs Ag/AgCl). As a H2O2 biosensor, films consisting of one layer of the encapsulated catalase displayed considerably higher (approximately 5-fold) and more stable electrocatalytic responses to the reduction of H2O2 than did corresponding films made of one layer of nonencapsulated catalase or solubilized catalase. An increase in either the number of "precursor" PE layers between the gold electrodes and the catalase microcrystal layers in the film or the number of PE layers encapsulating the catalase microcrystals was found to decrease the electrocatalytic activity of the electrode. At low precursor PE layer numbers (approximately 2) and PE encapsulating layers (approximately 4), the current response was proportional to the H2O2 concentration in the range 3.0 x 10(-6) to 1.0 x 10(-2) M. The overall electroactivity of the multilayer film increased for the first two layers of encapsulated catalase, after which a plateau was observed. This was attributed to the increasing difficulty of electron transfer and substrate diffusion limitations. The current approach of using immobilized PE-encapsulated enzyme microcrystals for biosensing provides a versatile method to prepare high enzyme content films with high and tailored enzyme activities.
Endocytic Capsule Sensors for Probing Cellular Internalization
Publisher: Wiley
Date: 04-04-2014
Abstract: A new class of polymer capsules with an in-built endocytic pH-coupled fluorescence switch is reported. These capsules display reversible "on/off" fluorescence in response to cellular pH variations. Using this system, the high-throughput quantification between surface-bound and internalized capsules is demonstrated. This system allows a fundamental study of the interaction between nanoengineered materials and biological systems at a cellular level.
Metal–Phenolic Networks as Tunable Buffering Systems
Publisher: American Chemical Society (ACS)
Date: 22-03-2021
Templated Assembly of pH-Labile Polymer-Drug Particles for Intracellular Drug Delivery
Publisher: Wiley
Date: 12-07-2012
Characterization of the growth of polyelectrolyte multilayers formed at interfaces between aqueous phases and thermotropic liquid crystals
Publisher: American Chemical Society (ACS)
Date: 18-04-2008
DOI: 10.1021/LA800013F
Abstract: Polyelectrolyte multilayers (PEMs) formed at interfaces between aqueous solutions and thermotropic (water-immiscible) liquid crystals (LCs) offer the basis of a new method to tailor the nanometer-scale structure and chemical functionality of these interfaces. Toward this end, we report a study that compares the growth of PEMs formed at mobile and deformable interfaces defined by LCs relative to growth observed at model (rigid) solid surfaces. Experiments aimed at determining if polyelectrolytes such as poly(sodium-4-styrenesulfonate) (PSS) can partition from the aqueous phase into the bulk of the LC yielded no evidence of such partitioning. Whereas measurements of the growth of PEMs formed from poly(allylamine hydrochloride) (PAH) and PSS at the aqueous-LC interface revealed growth characteristics similar to those measured at both hydrophobic and hydrophilic interfaces of solids, the growth of PEMs from PAH and poly(acrylic acid) (PAA) at the aqueous-LC interface was found to differ substantially from the solids investigated: (i) the linear growth of PEMs of PAH/PAA that was measured at the aqueous-LC interface under conditions that did not lead to the growth of PEMs at the interface of octadecyltrichlorosilane (OTS)-treated glass (a hydrophobic solid surface), and (ii) in comparison to the growth of PEMs of PAH/PAA at the surface of glass (a hydrophilic charged surface), a higher rate of growth was observed at the aqueous-LC interface. The finding that the growth rate of PEMs of PAH/PAA at aqueous-LC interfaces is greater than on solid surfaces is supported by additional measurements of growth as a function of pH. Finally, the pH-triggered reorganization of PAH/PAA PEMs supported at the aqueous-LC interface led to changes in the order and optical properties of the LC. These data are discussed in light of the nature of aqueous-LC interfaces, including the mobility and deformability of the interface and recent measurements of the zeta-potentials of aqueous-LC interfaces.
Monodisperse emulsions through templating polyelectrolyte multilayer capsules
Publisher: American Chemical Society (ACS)
Date: 22-02-2008
DOI: 10.1021/CM703237A
Layer-by-Layer Particles Deliver Epigenetic Silencing siRNA to HIV-1 Latent Reservoir Cell Types
Publisher: American Chemical Society (ACS)
Date: 27-02-2023
Nanoengineered Films via Surface‐Confined Continuous Assembly of Polymers
Publisher: Wiley
Date: 24-08-2011
Self-Polymerization of Dopamine as a Versatile and Robust Technique to Prepare Polymer Capsules
Publisher: American Chemical Society (ACS)
Date: 29-06-2009
DOI: 10.1021/CM901293E
Bioconjugate Materials in Vaccines and Immunotherapies
Publisher: American Chemical Society (ACS)
Date: 21-03-2018
Coordination-Driven Multistep Assembly of Metal–Polyphenol Films and Capsules
Publisher: American Chemical Society (ACS)
Date: 10-02-2014
DOI: 10.1021/CM403903M
A Decade of the Protein Corona
Publisher: American Chemical Society (ACS)
Date: 05-12-2017
Abstract: In this Perspective, we reflect on a decade of research on the protein corona and contemplate its broad implications for future science and engineering at the bio-nano interface. Specifically, we focus on the physical origins and time evolution of the protein corona, differences in the nanoparticle-protein entity in in vitro and in vivo environments, the role of stealth polymers to minimize the formation of the protein corona, relevant computational and theoretical developments, and the "biocorona", a concept extrapolated from the field of nanomedicine. We conclude the Perspective by outlining future directions and opportunities concerning the protein corona in the coming decade.
Probing transcription factor binding activity and downstream gene silencing in living cells with a DNA nanoswitch
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7NR07814E
Abstract: A dynamic DNA nanoswitch is used to probe NF-κB binding activity and its expression level directly in living cells.
Multivalent Directed Assembly of Colloidal Particles
Publisher: Wiley
Date: 18-02-2013
Integrated catalytic activity of patterned multilayer films based on pH-induced electrostatic properties of enzymes
Publisher: Wiley
Date: 19-05-2008
Fabrication of polyaniline inverse opals via templating ordered colloidal assemblies
Publisher: Wiley
Date: 03-2001
DOI: 10.1002/1521-4095(200103)13:5<350::AID-ADMA350>3.0.CO;2-X
In-situ measurement of DNA immobilization and hybridization using a 27MHz quartz crystal microbalance
Publisher: Elsevier BV
Date: 03-1998
In situ layer-by-layer assembled carbonic anhydrase-coated hollow fiber membrane contactor for rapid CO2 absorption
Publisher: Elsevier BV
Date: 09-2016
Cellular Association and Cargo Release of Redox-Responsive Polymer Capsules Mediated by Exofacial Thiols
Publisher: Wiley
Date: 02-08-2011
Dynamic Flow Impacts Cell-Particle Interactions: Sedimentation and Particle Shape Effects
Publisher: American Chemical Society (ACS)
Date: 17-10-2016
DOI: 10.1021/ACS.LANGMUIR.6B03216
Abstract: The interaction of engineered particles with biological systems determines their performance in biomedical applications. Although standard static cell cultures remain the norm for in vitro studies, modern models mimicking aspects of the dynamic in vivo environment have been developed. Herein, we investigate fundamental cell-particle interactions under dynamic flow conditions using a simple and self-contained device together with standard multiwell cell culture plates. We engineer two particle systems and evaluate their cell interactions under dynamic flow, and we compare the results to standard static cell cultures. We find substantial differences between static and dynamic flow conditions and attribute these to particle shape and sedimentation effects. These results demonstrate how standard static assays can be complemented by dynamic flow assays for a more comprehensive understanding of fundamental cell-particle interactions.
Engineering enzyme-cleavable hybrid click capsules with a pH-sheddable coating for intracellular degradation
Publisher: Wiley
Date: 10-07-2014
Abstract: The engineering of layer-by-layer (LbL) hybrid click capsules that are responsive to biological stimuli is reported. The capsules comprise a pH-sheddable, non cross-linked outer coating that protects enzyme-cleavable inner layers. Upon cellular uptake, the outer coating is released and the capsules are enzymatically degraded. In vitro cell degradation results in rapid capsule degradation (10 min) upon cellular internalization.
Metal–Organic Framework Coatings as Cytoprotective Exoskeletons for Living Cells
Publisher: Wiley
Date: 14-07-2016
Abstract: The biomimetic mineralization of metal-organic framework (MOF) material on living cells is reported. ZIF-8 can be crystallized on a living cell surface as an exoskeleton that offers physical protection while allowing transport of essential nutrients, thus maintaining cell viability. The MOF shell prevents cell ision, leading to an artificially induced pseudo-hibernation state. Cellular functions can be fully restored upon MOF removal.
Exploiting the directionality of DNA: Controlled shrinkage of engineered oligonucleotide capsules
Publisher: Wiley
Date: 23-03-2007
Tuning the Mechanical Behavior of Metal-Phenolic Networks through Building Block Composition.
Publisher: American Chemical Society (ACS)
Date: 05-02-2019
Abstract: Metal-phenolic networks (MPNs) are an emerging class of functional metal-organic materials with a high degree of modularity in terms of the choice of metal ion, phenolic ligand, and assembly method. Although various applications, including drug delivery, imaging, and catalysis, have been studied with MPNs, in the form of films and capsules, the influence of metals and organic building blocks on their mechanical properties is poorly understood. Herein, we demonstrate that the mechanical properties of MPNs can be tuned through choice of the metal ion and/or phenolic ligand. Specifically, the pH of the metal ion solution and/or size of phenolic ligand influence the Young's modulus ( E
Synthesis of Thermoresponsive, Catechol-Rich Poly(ethylene glycol) Brush Polymers for Attenuating Cellular Oxidative Stress
Publisher: American Chemical Society (ACS)
Date: 05-12-2022
Nanostructured electrochemical sensor based on dense gold nanoparticle films
Publisher: American Chemical Society (ACS)
Date: 12-08-2003
DOI: 10.1021/NL034363J
Characterization of Ferritin Adsorption onto Gold
Publisher: Elsevier BV
Date: 02-1997
Abstract: The adsorption of ferritin from phosphate-buffered saline (PBS) onto gold has been examined using a quartz crystal microbalance (QCM), surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Application of these techniques allows elucidation of the surface coverage and layer thickness of ferritin on gold. The kinetics of ferritin adsorption onto gold were investigated by monitoring the resonant frequency shift of a QCM. Adsorption isotherms for ferritin in PBS and in air have been measured by QCM. These isotherms suggest less than monolayer coverage of ferritin on gold. A layer thickness of 4.8 ± 0.2 nm was calculated for the dry ferritin film from QCM data. Measurements of the shift in the reflectivity of light at a fixed angle close to the SPR plasmon resonance were also used to follow the kinetics of ferritin adsorption. Full SPR curves were measured in PBS solution and air and were used to determine the effective thickness of the ferritin layer in both environments. The ferritin layer on gold from SPR data was found to be twice as thick when measured in PBS as it was for a dry film. This difference in thickness is attributed to shrinkage of ferritin with drying. Angle-resolved XPS measurements on a dry ferritin film (preadsorbed on gold) yield a ferritin thickness of 4.7 ± 0.5 nm, a value in good agreement with those determined from QCM and SPR. QCM, SPR, and XPS all yield a surface coverage of 6.3 ± 0.7 mg m-2 for dry ferritin layers on gold. AFM enabled examination of the topography of ferritin adsorbed on gold on the nanometer scale and confirmed that ferritin forms an incomplete monolayer. In all cases, ferritin was found to be irreversibly adsorbed to gold and to form a stable protein layer, thus making it well suited as a biological receptor layer for immunosensing applications.
Particle Carriers for Combating Multidrug-Resistant Cancer
Publisher: American Chemical Society (ACS)
Date: 11-11-2013
DOI: 10.1021/NN405632S
Abstract: Multidrug resistance (MDR) in tumors accounts for significant treatment failure. Particle carriers offer potential benefits for treating cancer, including the ability to target tumors and to deliver multiple cargo, providing opportunities to overcome drug resistance. In this Perspective, we provide a brief introduction to the MDR mechanisms and implications of tumor heterogeneity that contribute to drug resistance. We also highlight recent advances in the design of particles aimed at treating resistant tumors through particle-based codelivery of therapeutics. Finally, we discuss future directions, where an increased understanding of the tumor biology can be leveraged to develop new and improved particle-based cancer therapies.
Chemistry of materials - 20 years on and on the rise
Publisher: American Chemical Society (ACS)
Date: 08-12-2008
DOI: 10.1021/CM703223U
Photocontrolled Cargo Release from Dual Cross-Linked Polymer Particles
Publisher: American Chemical Society (ACS)
Date: 23-02-2016
Abstract: Burst release of a payload from polymeric particles upon photoirradiation was engineered by altering the cross-linking density. This was achieved via a dual cross-linking concept whereby noncovalent cross-linking was provided by cyclodextrin host-guest interactions, and irreversible covalent cross-linking was mediated by continuous assembly of polymers (CAP). The dual cross-linked particles (DCPs) were efficiently infiltrated (∼80-93%) by the biomacromolecule dextran (molecular weight up to 500 kDa) to provide high loadings (70-75%). Upon short exposure (5 s) to UV light, the noncovalent cross-links were disrupted resulting in increased permeability and burst release of the cargo (50 mol % within 1 s) as visualized by time-lapse fluorescence microscopy. As sunlight contains UV light at low intensities, the particles can potentially be incorporated into systems used in agriculture, environmental control, and food packaging, whereby sunlight could control the release of nutrients and antimicrobial agents.
Microfluidic Examination of the “Hard” Biomolecular Corona Formed on Engineered Particles in Different Biological Milieu
Publisher: American Chemical Society (ACS)
Date: 18-02-2018
DOI: 10.1021/ACS.BIOMAC.8B00196
Abstract: The formation of a biomolecular corona around engineered particles determines, in large part, their biological behavior in vitro and in vivo. To gain a fundamental understanding of how particle design and the biological milieu influence the formation of the "hard" biomolecular corona, we conduct a series of in vitro studies using microfluidics. This setup allows the generation of a dynamic incubation environment with precise control over the applied flow rate, stream orientation, and channel dimensions, thus allowing accurate control of the fluid flow and the shear applied to the proteins and particles. We used mesoporous silica particles, poly(2-methacryloyloxyethylphosphorylcholine) (PMPC)-coated silica hybrid particles, and PMPC replica particles (obtained by removal of the silica particle templates), representing high-, intermediate-, and low-fouling particle systems, respectively. The protein source used in the experiments was either human serum or human full blood. The effects of flow, particle surface properties, incubation medium, and incubation time on the formation of the biomolecular corona formation are examined. Our data show that protein adhesion on particles is enhanced after incubation in human blood compared to human serum and that dynamic incubation leads to a more complex corona. By varying the incubation time from 2 s to 15 min, we demonstrate that the "hard" biomolecular corona is kinetically sub ided into two phases comprising a tightly bound layer of proteins interacting directly with the particle surface and a loosely associated protein layer. Understanding the influence of particle design parameters and biological factors on the corona composition, as well as its dynamic assembly, may facilitate more accurate prediction of corona formation and therefore assist in the design of advanced drug delivery vehicles.
Low-Fouling and Biodegradable Protein-Based Particles for Thrombus Imaging
Publisher: American Chemical Society (ACS)
Date: 07-06-2018
Photoelectrochemical behaviour of CdS Q-state semiconductor particles in 10,12-nonacosadiynoic acid polymer langmuir-blodgett films
Publisher: Springer Science and Business Media LLC
Date: 1999
Particle-mediated delivery of frataxin plasmid to a human sensory neuronal model of Friedreich's ataxia
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9BM01757G
Abstract: Multilayered particles in gene therapy for Friedreich's ataxia induce a 27 000-fold increase in frataxin gene expression in a patient-derived cell model.
Multivalent-ion-mediated stabilization of hydrogen-bonded multilayers
Publisher: Wiley
Date: 06-06-2006
Assembly of Metal–Phenolic Networks on Water‐Soluble Substrates in Nonaqueous Media
Publisher: Wiley
Date: 10-03-2022
Abstract: Interfacial modular assemblies of eco‐friendly metal–phenolic networks (MPNs) are of interest for surface and materials engineering. To date, most MPNs are assembled on water‐stable substrates however, the self‐assembly of MPNs on highly water‐soluble substrates remains unexplored. Herein, a versatile approach is reported to engineer thickness‐tunable coatings (2–25 µm) on a water‐soluble substrate (i.e., urea) via the self‐assembly of MPNs in a nonaqueous solvent (i.e., acetonitrile). The coordination‐driven assembly of the MPN coatings in the nonaqueous solvent is distinct from that in aqueous systems, as the assembly is only achieved following the addition of urea granules into the iron–tannin solution. The coating occurs relatively rapidly (5–60 min), generating micrometer‐thick coatings from the adsorption of Fe III –TA complexes and micrometer‐sized Fe III –TA particles formed in solution. The straightforward nature of the present fabrication method in generating thick and robust coatings with high stability in nonaqueous environments (including at 60 °C) coupled with the broad range of available naturally abundant polyphenol–metal ion combinations expand the applicability of MPNs as coatings for water‐soluble materials, thus providing new opportunities for their broader application in a range of industrial processes and applications.
Fabrication of heterogeneous macroporous materials based on a sequential electrostatic deposition process
Publisher: Royal Society of Chemistry (RSC)
Date: 2001
DOI: 10.1039/B009897N
Protein Multilayer Formation on Colloids through a Stepwise Self-Assembly Technique
Publisher: American Chemical Society (ACS)
Date: 06-1999
DOI: 10.1021/JA990441M
SupraCells: Living Mammalian Cells Protected within Functional Modular Nanoparticle-Based Exoskeletons
Publisher: Wiley
Date: 29-04-2019
Abstract: Creating a synthetic exoskeleton from abiotic materials to protect delicate mammalian cells and impart them with new functionalities could revolutionize fields like cell-based sensing and create erse new cellular phenotypes. Herein, the concept of "SupraCells," which are living mammalian cells encapsulated and protected within functional modular nanoparticle-based exoskeletons, is introduced. Exoskeletons are generated within seconds through immediate interparticle and cell article complexation that abolishes the macropinocytotic and endocytotic nanoparticle internalization pathways that occur without complexation. SupraCell formation is shown to be generalizable to wide classes of nanoparticles and various types of cells. It induces a spore-like state, wherein cells do not replicate or spread on surfaces but are endowed with extremophile properties, for ex le, resistance to osmotic stress, reactive oxygen species, pH, and UV exposure, along with abiotic properties like magnetism, conductivity, and multifluorescence. Upon decomplexation cells return to their normal replicative states. SupraCells represent a new class of living hybrid materials with a broad range of functionalities.
Core−Shell Particles and Hollow Shells Containing Metallo-Supramolecular Components
Publisher: American Chemical Society (ACS)
Date: 27-10-1999
DOI: 10.1021/CM9911058
Polyphenol‐Mediated Assembly of Proteins for Engineering Functional Materials
Publisher: Wiley
Date: 20-03-2020
Mold-Templated Inorganic–Organic Hybrid Supraparticles for Codelivery of Drugs
Publisher: American Chemical Society (ACS)
Date: 16-10-2014
DOI: 10.1021/BM501171J
Abstract: This paper reports a facile and robust mold-templated technique for the assembly of mesoporous silica (MS) supraparticles and demonstrates their potential as vehicles for codelivery of brain-derived neurotrophic factor (BDNF) and dexamethasone (DEX). The MS supraparticles are assembled using gelatin as a biodegradable adhesive to bind and cross-link the particles. Microfabricated molds made of polydimethylsiloxane are used to control the size and shape of the supraparticles. The obtained mesoporous silica-gelatin hybrid supraparticles (MSG-SPs) are stable in water as well as in organic solvents, such as dimethyl sulfoxide, and efficiently coencapsulate both BDNF and DEX. The MSG-SPs also exhibit sustained release kinetics in simulated physiological conditions (>30 days), making them potential candidates for long-term delivery of therapeutics to the inner ear.
Oxidation‐Mediated Kinetic Strategies for Engineering Metal–Phenolic Networks
Publisher: Wiley
Date: 05-08-2019
Direct Assembly of Metal‐Phenolic Network Nanoparticles for Biomedical Applications
Publisher: Wiley
Date: 06-10-2023
Gold−Titania Core−Shell Nanoparticles by Polyelectrolyte Complexation with a Titania Precursor
Publisher: American Chemical Society (ACS)
Date: 12-09-2001
DOI: 10.1021/CM011128Y
Size-Dependent Ordering of Liquid Crystals Observed in Polymeric Capsules with Micrometer and Smaller Diameter
Publisher: Wiley
Date: 10-02-2009
Abstract: Made to order: Aqueous dispersions of polymer-encapsulated liquid crystal (LC) droplets were synthesized with precise interfacial chemistry and sizes in the micrometer-to-sub-micrometer range. Size-dependent changes in LC ordering could be observed. Study of the competition between size and interfacial chemistry on LC ordering enables size-dependent properties of LC droplets to be exploited in applications such as photonics and sensing.
Fabrication of ultra-thin polyrotaxane-based films via solid-state continuous assembly of polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4CC08759C
Abstract: Surface-confined ultra-thin polyrotaxane (PRX)-based films with tunable composition, surface topology and swelling characteristics were prepared by solid-state continuous assembly of polymers (ssCAP).
A molecular beacon approach to measuring the DNA permeability of thin films
Publisher: American Chemical Society (ACS)
Date: 23-06-2005
DOI: 10.1021/JA0527166
Abstract: A new method for determining the permeability of thin films has been developed. A molecular beacon immobilized inside a porous silica particle that is subsequently encapsulated within a thin film can be used to determine the size of DNA that can permeate through the film. Using this technique, it has been determined that over 3 h, molecules larger than 4.7 nm do not permeate 15-nm thick polyelectrolyte multilayers and after 75 h molecules larger than 6 nm were excluded. This technique has applications for determining the permeability of films used for controlled drug and gene delivery.
One-Step Assembly of Coordination Complexes for Versatile Film and Particle Engineering
Publisher: American Association for the Advancement of Science (AAAS)
Date: 12-07-2013
Abstract: Thin adherent films formed from ferric ions and a natural polyphenol, tannic acid, can coat a wide variety of surfaces. [Also see Perspective by Bentley and Payne ]
Monoclonal Antibody-Functionalized Multilayered Particles: Targeting Cancer Cells in the Presence of Protein Coronas
Publisher: American Chemical Society (ACS)
Date: 25-02-2015
DOI: 10.1021/NN506929E
Abstract: Engineered particles adsorb biomolecules (e.g., proteins) when introduced in a biological medium to form a layer called a "corona". Coronas, in particular the protein corona, play an important role in determining the surface properties of particles and their targeting abilities. This study examines the influence of protein coronas on the targeting ability of layer-by-layer (LbL)-assembled polymer capsules and core-shell particles functionalized with monoclonal antibodies. Upon exposure of humanized A33 monoclonal antibody (huA33 mAb)-functionalized poly(methacrylic acid) (PMA) capsules or huA33 mAb-PMA particles to human serum, a total of 83 or 65 proteins were identified in the protein coronas, respectively. Human serum of varying concentrations altered the composition of the protein corona. The antibody-driven specific cell membrane binding was qualitatively and quantitatively assessed by flow cytometry and fluorescence microscopy in both the absence and presence of a protein corona. The findings show that although different protein coronas formed in human serum (at different concentrations), the targeting ability of both the huA33 mAb-functionalized PMA capsules and particles toward human colon cancer cells was retained, demonstrating no significant difference compared with capsules and particles in the absence of protein coronas: ∼70% and ∼90% A33-expressing cells were targeted by the huA33 mAb-PMA capsules and particles, respectively, in a mixed cell population. This result demonstrates that the formation of protein coronas did not significantly influence the targeting ability of antibody-functionalized LbL-polymer carriers, indicating that the surface functionality of engineered particles in the presence of protein coronas can be preserved.
Templated Polymer Replica Nanoparticles to Facilitate Assessment of Material-Dependent Pharmacokinetics and Biodistribution
Publisher: American Chemical Society (ACS)
Date: 25-09-2017
Abstract: Surface modification is frequently used to tailor the interactions of nanoparticles with biological systems. In many cases, the chemical nature of the treatments employed to modify the biological interface (for ex le attachment of hydrophilic polymers or targeting groups) is the focus of attention. However, isolation of the fundamental effects of the materials employed to modify the interface are often confounded by secondary effects imparted by the underlying substrate. Herein, we demonstrate that polymer replica particles templated from degradable mesoporous silica provide a facile means to evaluate the impact of surface modification on the biological interactions of nanomaterials, independent of the substrate. Poly(ethylene glycol) (PEG), poly(N-(2 hydroxypropyl)methacrylamide) (PHPMA), and poly(methacrylic acid) (PMA) were templated onto mesoporous silica and cross-linked and the residual particles were removed. The resulting nanoparticles, comprising interfacial polymer alone, were then investigated using a range of in vitro and in vivo tests. As expected, the PEG particles showed the best stealth properties, and these trends were consistent in both in vitro and in vivo studies. PMA particles showed the highest cell association in cell lines in vitro and were rapidly taken up by monocytes in ex vivo whole blood, properties consistent with the very high in vivo clearance subsequently seen in rats. In contrast, PHPMA particles showed rapid association with both granulocytes and monocytes in ex vivo whole blood, even though in vivo clearance was less rapid than the PMA particles. Rat studies confirmed better systemic exposure for PEG and PHPMA particles when compared to PMA particles. This study provides a new avenue for investigating material-dependent biological behaviors of polymer particles, irrespective of the properties of the underlying core, and provides insights for the selection of polymer particles for future biological applications.
Engineering Poly(ethylene glycol) Particles for Improved Biodistribution
Publisher: American Chemical Society (ACS)
Date: 21-01-2015
DOI: 10.1021/NN5061578
Abstract: We report the engineering of poly(ethylene glycol) (PEG) hydrogel particles using a mesoporous silica (MS) templating method via tuning the PEG molecular weight, particle size, and the presence or absence of the template and investigate the cell association and biodistribution of these particles. An ex vivo assay based on human whole blood that is more sensitive and relevant than traditional cell-line based assays for predicting in vivo circulation behavior is introduced. The association of MS@PEG particles (template present) with granulocytes and monocytes is higher compared with PEG particles (template absent). Increasing the PEG molecular weight (from 10 to 40 kDa) or decreasing the PEG particle size (from 1400 to 150 nm) reduces phagocytic blood cell association of the PEG particles. Mice biodistribution studies show that the PEG particles exhibit extended circulation times (>12 h) compared with the MS@PEG particles and that the retention of smaller PEG particles (150 nm) in blood, when compared with larger PEG particles (>400 nm), is increased at least 4-fold at 12 h after injection. Our findings highlight the influence of unique aspects of polymer hydrogel particles on biological interactions. The reported PEG hydrogel particles represent a new class of polymer carriers with potential biomedical applications.
Engineering Biocoatings To Prolong Drug Release from Supraparticles
Publisher: American Chemical Society (ACS)
Date: 14-08-2019
DOI: 10.1021/ACS.BIOMAC.9B00710
Abstract: Supraparticles (SPs) assembled from smaller colloidal nanoparticles can serve as depots of therapeutic compounds and are of interest for long-term, sustained drug release in biomedical applications. However, a key challenge to achieving temporal control of drug release from SPs is the occurrence of an initial rapid release of the loaded drug (i.e., "burst" release) that limits sustained release and potentially causes burst release-associated drug toxicity. Herein, a biocoating strategy is presented for silica-SPs (Si-SPs) to reduce the extent of burst release of the loaded model protein lysozyme. Specifically, Si-SPs were coated with a fibrin film, formed by enzymatic conversion of fibrinogen into fibrin. The fibrin-coated Si-SPs,
Poly(ethylene glycol) Cross-Linked Antibody Nanoparticles for Tunable Biointeractions
Publisher: American Chemical Society (ACS)
Date: 21-06-2023
Increasing the Impact of Materials in and beyond Bio-Nano Science
Publisher: American Chemical Society (ACS)
Date: 27-09-2016
DOI: 10.1021/JACS.6B08673
Abstract: This is an exciting time for the field of bio-nano science: enormous progress has been made in recent years, especially in academic research, and materials developed and studied in this area are poised to make a substantial impact in real-world applications. Herein, we discuss ways to leverage the strengths of the field, current limitations, and valuable lessons learned from neighboring fields that can be adopted to accelerate scientific discovery and translational research in bio-nano science. We identify and discuss five interconnected topics: (i) the advantages of cumulative research (ii) the necessity of aligning projects with research priorities (iii) the value of transparent science (iv) the opportunities presented by "dark data" and (v) the importance of establishing bio-nano standards.
Triggering release of encapsulated cargo
Publisher: Wiley
Date: 26-03-2010
Nanoengineering Particles through Template Assembly
Publisher: American Chemical Society (ACS)
Date: 06-10-2017
Understanding the Uptake of Nanomedicines at Different Stages of Brain Cancer Using a Modular Nanocarrier Platform and Precision Bispecific Antibodies
Publisher: American Chemical Society (ACS)
Date: 28-04-2020
BEHAVIOR OF A PYRENE-LABELED PHOSPHOLIPID IN MONOLAYERS OF DIMYRISTOYL-ALPHA-PHOSPHATIDYLCHOLINE AT THE GAS WATER INTERFACE - A FLUORESCENCE QUENCHING STUDY
Publisher: American Chemical Society (ACS)
Date: 07-1993
DOI: 10.1021/J100130A040
Ricocheting Droplets Moving on Super‐Repellent Surfaces
Publisher: Wiley
Date: 12-09-2019
Nanoengineering of Poly(ethylene glycol) Particles for Stealth and Targeting
Publisher: American Chemical Society (ACS)
Date: 22-08-2018
DOI: 10.1021/ACS.LANGMUIR.8B02117
Abstract: The assembly of particles composed solely or mainly of poly(ethylene glycol) (PEG) is an emerging area that is gaining increasing interest within bio-nano science. PEG, widely considered to be the "gold standard" among polymers for drug delivery, is providing a platform for exploring fundamental questions and phenomena at the interface between particle engineering and biomedicine. These include the targeting and stealth behaviors of synthetic nanomaterials in biological environments. In this feature article, we discuss recent work in the nanoengineering of PEG particles and explore how they are enabling improved targeting and stealth performance. Specific ex les include PEG particles prepared through surface-initiated polymerization, mesoporous silica replication via postinfiltration, and particle assembly through metal-phenolic coordination. This particle class exhibits unique in vivo behavior (e.g., biodistribution and immune cell interactions) and has recently been explored for drug delivery applications.
From polymeric films to nanoreactors
Publisher: Wiley
Date: 10-1999
Polyelectrolyte multilayer films of different charge density copolymers with synergistic nonelectrostatic interactions prepared by the layer-by-layer technique
Publisher: American Chemical Society (ACS)
Date: 03-2004
DOI: 10.1021/LA035909K
Abstract: Random copolymers composed of diallyldimethylammonium chloride (DADMAC) and acrylamide with varying contents (8-100 mol %) of the cationic DADMAC component were alternated with polyanionic, fully charged poly(styrenesulfonate) to form multilayer thin films. UV-vis spectrophotometry, FTIR spectroscopy, and quartz-crystal microgravimetry (QCM) were employed to follow multilayer buildup. Atomic force microscopy was used to obtain structural information. Layer thicknesses have been determined with small-angle X-ray scattering and ellipsometry, in addition to values calculated from QCM. While in previous work, a critical charge density limit could be observed, below which no layer growth is possible in this system, multilayer formation takes place with copolymers with charge densities as low as 8 mol %. Instead of a continuous increase of adsorbed amounts with decreasing charge density above the critical charge density, as found in previous work, similar layer thicknesses for films with 100 and 8 mol % charged polyelectrolytes and maximally adsorbed amounts for copolymers in an intermediate charge density region have been found. This adsorption behavior is explained in terms of synergistic nonelectrostatic interactions between the polyelectrolytes used.
Degradable, Surfactant-Free, Monodisperse Polymer-Encapsulated Emulsions as Anticancer Drug Carriers
Publisher: Wiley
Date: 04-05-2009
Gravimetric Monitoring of Nonionic Surfactant Adsorption from Nonaqueous Media onto Quartz Crystal Microbalance Electrodes and Colloidal Silica
Publisher: American Chemical Society (ACS)
Date: 1996
DOI: 10.1021/LA9510588
Monitoring ion-channel function in real time through quantum decoherence
Publisher: Proceedings of the National Academy of Sciences
Date: 11-10-2010
Abstract: In drug discovery, there is a clear and urgent need for detection of cell-membrane ion-channel operation with wide-field capability. Existing techniques are generally invasive or require specialized nanostructures. We show that quantum nanotechnology could provide a solution. The nitrogen-vacancy (NV) center in nanodiamond is of great interest as a single-atom quantum probe for nanoscale processes. However, until now nothing was known about the quantum behavior of a NV probe in a complex biological environment. We explore the quantum dynamics of a NV probe in proximity to the ion channel, lipid bilayer, and surrounding aqueous environment. Our theoretical results indicate that real-time detection of ion-channel operation at millisecond resolution is possible by directly monitoring the quantum decoherence of the NV probe. With the potential to scan and scale up to an array-based system, this conclusion may have wide-ranging implications for nanoscale biology and drug discovery.
Self-Assembled Metal–Phenolic Networks on Emulsions as Low-Fouling and pH-Responsive Particles
Publisher: Wiley
Date: 29-08-2018
Abstract: Interfacial self-assembly is a powerful organizational force for fabricating functional nanomaterials, including nanocarriers, for imaging and drug delivery. Herein, the interfacial self-assembly of pH-responsive metal-phenolic networks (MPNs) on the liquid-liquid interface of oil-in-water emulsions is reported. Oleic acid emulsions of 100-250 nm in diameter are generated by ultrasonication, to which poly(ethylene glycol) (PEG)-based polyphenolic ligands are assembled with simultaneous crosslinking by metal ions, thus forming an interfacial MPN. PEG provides a protective barrier on the emulsion phase and renders the emulsion low fouling. The MPN-coated emulsions have a similar size and dispersity, but an enhanced stability when compared with the uncoated emulsions, and exhibit a low cell association in vitro, a blood circulation half-life of ≈50 min in vivo, and are nontoxic to healthy mice. Furthermore, a model anticancer drug, doxorubicin, can be encapsulated within the emulsion phase at a high loading capacity (≈5 fg of doxorubicin per emulsion particle). The MPN coating imparts pH-responsiveness to the drug-loaded emulsions, leading to drug release at cell internalization pH and a potent cell cytotoxicity. The results highlight a straightforward strategy for the interfacial nanofabrication of pH-responsive emulsion-MPN systems with potential use in biomedical applications.
Programmable Phototaxis of Metal–Phenolic Particle Microswimmers
Publisher: Wiley
Date: 26-02-2202
Cholesterol-mediated anchoring of enzyme-loaded liposomes within disulfide-stabilized polymer carrier capsules
Publisher: Elsevier BV
Date: 10-2009
DOI: 10.1016/J.BIOMATERIALS.2009.07.040
Abstract: Polymer capsules containing multiple liposomes, termed capsosomes, are a promising new concept toward the design of artificial cells. Herein, we report on the fundamental aspects underpinning the assembly of capsosomes. A stable and high loading of intact liposomal cargo into a polymer film was achieved by non-covalently sandwiching the liposomes between a tailor-made cholesterol-modified poly(L-lysine) (PLL(c)) precursor layer and a poly(methacrylic acid)-co-(cholesteryl methacrylate) (PMA(c)) capping layer. The film assembly, optimized on planar surfaces, was successfully transferred onto colloidal substrates, and a polymer membrane was subsequently assembled by the alternating adsorption of poly(N-vinyl pyrrolidone) (PVP) and thiol-modified poly(methacrylic acid) (PMA(SH)) onto the pre-adsorbed layer of liposomes. Upon removal of the silica template, stable capsosomes encapsulating the enzyme luciferase or beta-lactamase within their liposomal sub-compartments were obtained at both assembly (pH 4) and physiological conditions (pH 7.4). Excellent retention of the liposomes and the enzymatic cargo within the polymer carrier capsules was observed for up to 14 days. These engineered capsosomes are particularly attractive as autonomous microreactors, which can be utilized to repetitively add smaller reactants to cause successive distinct reactions within the capsosomes and simultaneously release the products to the surrounding environment, bringing these systems one step closer toward constructing artificial cells.
Investigation of the Influence of Polyelectrolyte Charge Density on the Growth of Multilayer Thin Films Prepared by the Layer-by-Layer Technique
Publisher: American Chemical Society (ACS)
Date: 20-12-2001
DOI: 10.1021/MA011349P
Confinement of acoustic cavitation for the synthesis of protein-shelled nanobubbles for diagnostics and nucleic acid delivery
Publisher: American Chemical Society (ACS)
Date: 21-06-2012
DOI: 10.1021/MZ3002534
Abstract: We report a novel flow-through sonication technique for synthesizing stable and monodispersed nano- and micrometer-sized bubbles that have potential applications in diagnostics and gene therapy. The size and size distribution of the bubbles are controlled by the active cavitation zone generated by ultrasound. These bubbles are shown to possess echogenic properties and can be used for loading oligonucleotides.
Monodisperse polyelectrolyte-supported asymmetric lipid-bilayer vesicles
Publisher: Wiley
Date: 22-03-2005
Engineering Metal–Phenolic Network Nanoparticles via Microfluidics
Publisher: American Chemical Society (ACS)
Date: 09-10-2023
Bio-click chemistry: enzymatic functionalization of PEGylated capsules for targeting applications
Publisher: Wiley
Date: 28-06-2012
Abstract: All sorted: The enzyme Sortase A was used to catalyze functionalization of PEGylated capsules with an activation-specific anti-platelet single-chain antibody (scFv). This enzymatic method allows fast, covalent, and site-directed functionalization of delivery vehicles under mild conditions. Activation-specific anti-platelet scFv-coated PEGylated capsules exhibited a high level of selective binding to thrombi, thus suggesting their potential for thrombosis therapy.
Novel hollow polymer shells by colloid-templated assembly of polyelectrolytes
Publisher: Wiley
Date: 04-09-1998
DOI: 10.1002/(SICI)1521-3773(19980904)37:16<2201::AID-ANIE2201>3.0.CO;2-E
Engineered Coatings via the Assembly of Amino‐Quinone Networks
Publisher: Wiley
Date: 30-11-2020
Expanding the Toolbox of Metal-Phenolic Networks via Enzyme-Mediated Assembly.
Publisher: Wiley
Date: 04-12-2020
Abstract: Functional coatings are of considerable interest because of their fundamental implications for interfacial assembly and promise for numerous applications. Universally adherent materials have recently emerged as versatile functional coatings however, such coatings are generally limited to catechol, (ortho-diphenol)-containing molecules, as building blocks. Here, we report a facile, biofriendly enzyme-mediated strategy for assembling a wide range of molecules (e.g., 14 representative molecules in this study) that do not natively have catechol moieties, including small molecules, peptides, and proteins, on various surfaces, while preserving the molecule's inherent function, such as catalysis (≈80 % retention of enzymatic activity for trypsin). Assembly is achieved by in situ conversion of monophenols into catechols via tyrosinase, where films form on surfaces via covalent and coordination cross-linking. The resulting coatings are robust, functional (e.g., in protective coatings, biological imaging, and enzymatic catalysis), and versatile for erse secondary surface-confined reactions (e.g., biomineralization, metal ion chelation, and N-hydroxysuccinimide conjugation).
Template-Directed Synthesis of Silica Nanowires and Nanotubes from Cylindrical Core–Shell Polymer Brushes
Publisher: American Chemical Society (ACS)
Date: 04-05-2012
DOI: 10.1021/CM300312G
Dopamine-Mediated Continuous Assembly of Biodegradable Capsules
Publisher: American Chemical Society (ACS)
Date: 17-06-2011
DOI: 10.1021/CM201390E
Phenolic film engineering for template-mediated microcapsule preparation
Publisher: Springer Science and Business Media LLC
Date: 14-05-2014
DOI: 10.1038/PJ.2014.32
Self-Assembled Nanoparticles from Phenolic Derivatives for Cancer Therapy
Publisher: Wiley
Date: 16-05-2017
Abstract: Therapeutic nanoparticles hold clinical promise for cancer treatment by avoiding limitations of conventional pharmaceuticals. Herein, a facile and rapid method is introduced to assemble poly(ethylene glycol) (PEG)-modified Pt prodrug nanocomplexes through metal-polyphenol complexation and combined with emulsification, which results in ≈100 nm diameter nanoparticles (PtP NPs) that exhibit high drug loading (0.15 fg Pt per nanoparticle) and low fouling properties. The PtP NPs are characterized for potential use as cancer therapeutics. Mass cytometry is used to quantify uptake of the nanoparticles and the drug concentration in in idual cells in vitro. The PtP NPs have long circulation times, with an elimination half-life of ≈18 h in healthy mice. The in vivo antitumor activity of the PtP NPs is systematically investigated in a human prostate cancer xenograft mouse model. Mice treated with the PtP NPs demonstrate four times better inhibition of tumor growth than either free prodrug or cisplatin. This study presents a promising strategy to prepare therapeutic nanoparticles for biomedical applications.
Conductive core-shell particles: An approach to self-assembled mesoscopic wires
Publisher: Wiley
Date: 04-07-2003
Surface Modification of Spider Silk Particles to Direct Biomolecular Corona Formation
Publisher: American Chemical Society (ACS)
Date: 05-05-2020
Multiligand Metal-Phenolic Assembly from Green Tea Infusions.
Publisher: American Chemical Society (ACS)
Date: 19-07-2018
Abstract: The synthesis of hybrid functional materials using the coordination-driven assembly of metal-phenolic networks (MPNs) is of interest in erse areas of materials science. To date, MPN assembly has been explored as monoligand systems (i.e., containing a single type of phenolic ligand) where the phenolic components are primarily obtained from natural sources via extraction, isolation, and purification processes. Herein, we demonstrate the fabrication of MPNs from a readily available, crude phenolic source-green tea (GT) infusions. We employ our recently introduced rust-mediated continuous assembly strategy to prepare these GT MPN systems. The resulting hollow MPN capsules contain multiple phenolic ligands and have a shell thickness that can be controlled through the reaction time. These multiligand MPN systems have different properties compared to the analogous MPN systems reported previously. For ex le, the Young's modulus (as determined using colloidal-probe atomic force microscopy) of the GT MPN system presented herein is less than half that of MPN systems prepared using tannic acid and iron salt solutions, and the disassembly kinetics are faster (∼50%) than other, comparable MPN systems under identical disassembly conditions. Additionally, the use of rust-mediated assembly enables the formation of stable capsules under conditions where the conventional approach (i.e., using iron salt solutions) results in colloidally unstable dispersions. These differences highlight how the choice of phenolic ligand and its source, as well as the assembly protocol (e.g., using solution-based or solid-state iron sources), can be used to tune the properties of MPNs. The strategy presented herein expands the toolbox of MPN assembly while also providing new insights into the nature and robustness of metal-phenolic interfacial assembly when using solution-based or solid-state metal sources.
Nanoassembly of biocompatible microcapsules for urease encapsulation and their use as biomimetic reactors
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B601490A
Abstract: Biocompatible polypeptide capsules with high enzyme loading and activity prepared by templating mesoporous silica spheres were used as biomimetic reactors for performing CaCO3 synthesis exclusively inside the capsule interior via urease-catalyzed urea hydrolysis.
Magnetically directed self-assembly of submicron spheres with a Fe3O4 nanoparticle shell
Publisher: Elsevier BV
Date: 02-2002
IMMOBILIZATION OF IGG ONTO GOLD SURFACES AND ITS INTERACTION WITH ANTI-IGG STUDIED BY SURFACE-PLASMON RESONANCE
Publisher: Elsevier BV
Date: 10-1994
DOI: 10.1016/0022-1759(94)90358-1
Abstract: The optical excitation of surface plasmon resonance (SPR) at a metal dielectric interface has been used to study the binding of immunoglobulin G (IgG) to gold and anti-IgG to immobilised IgG layers. In these studies both a monoclonal mouse and polyclonal sheep IgG were used as receptor layers for anti-IgG. The kinetics of binding were investigated by monitoring the reflectivity of light at an angle close to plasmon resonance. Both the initial rate of change and final reflectivity were measured during and after protein binding. The amount of protein bound to the surface was found to be less for the monoclonal mouse IgG compared to the polyclonal sheep IgG, these two IgG nominally being of the same dimensions and molecular weight. Further, anti-IgG binding produced greater changes in reflectivity than the initial IgG layers. By fitting the full angle-dependent reflectivity data to the Fresnel equation the effective protein layer thicknesses of IgG and anti-IgG as a function of concentration were determined. Differences in the effective thickness of the bound layer for the two IgG was observed, the mouse IgG having a thinner effective thickness compared with the sheep IgG. The limitations of direct binding of protein to metal surfaces in SPR biosensor applications are discussed.
Nanotubes Prepared by Templating Sacrificial Nickel Nanorods
Publisher: American Chemical Society (ACS)
Date: 27-10-2001
DOI: 10.1021/NL015622C
Engineering particles for therapeutic delivery: Prospects and challenges
Publisher: American Chemical Society (ACS)
Date: 30-04-2012
DOI: 10.1021/NN3016162
Abstract: Nanoengineered particles that can facilitate drug formulation and passively target tumors have reached the clinic in recent years. These early successes have driven a new wave of significant innovation in the generation of advanced particles. Recent developments in enabling technologies and chemistries have led to control over key particle properties, including surface functionality, size, shape, and rigidity. Combining these advances with the rapid developments in the discovery of many disease-related characteristics now offers new opportunities for improving particle specificity for targeted therapy. In this Perspective, we summarize recent progress in particle-based therapeutic delivery and discuss important concepts in particle design and biological barriers for developing the next generation of particles.
Toward therapeutic delivery with layer-by-layer engineered particles
Publisher: American Chemical Society (ACS)
Date: 25-05-2011
DOI: 10.1021/NN201793F
Abstract: Layer-by-layer (LbL)-engineered particles have recently emerged as a promising class of materials for applications in biomedicine, with studies progressing from in vitro to in vivo. The versatility of LbL assembly coupled with particle templating has led to engineered particles with specific properties (e.g., stimuli-responsive, high cargo encapsulation efficiency, targeting), thus offering new opportunities in targeted and triggered therapeutic release. This Perspective highlights an important development by Poon et al. on tumor targeting in vivo using LbL-engineered nanoparticles containing a pH-responsive poly(ethylene glycol) (PEG) surface layer. Further, we summarize recent progress in the application of LbL particles in the fields of drug, gene, and vaccine delivery and cancer imaging. Finally, we explore future directions in this field, focusing on the biological processing of LbL-assembled particles.
Formation of polyelectrolyte multilayer films at interfaces between thermotropic liquid crystals and aqueous phases
Publisher: Wiley
Date: 04-04-2006
LATERAL DIFFUSION OF AMPHIPHILES IN FATTY-ACID MONOLAYERS AT THE AIR-WATER-INTERFACE - A STEADY-STATE AND TIME-RESOLVED FLUORESCENCE QUENCHING STUDY
Publisher: American Chemical Society (ACS)
Date: 11-1993
DOI: 10.1021/LA00035A065
Photonic Materials from Self-Assembly of “Tolerant” Core−Shell Coated Colloids
Publisher: American Chemical Society (ACS)
Date: 19-04-2002
DOI: 10.1021/LA011772R
Nanoscale engineering of low-fouling surfaces through polydopamine immobilisation of zwitterionic peptides
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3SM53056F
Abstract: We report a versatile approach for the design of substrate-independent low-fouling surfaces via mussel-inspired immobilisation of zwitterionic peptides. Using mussel-inspired polydopamine (PDA) coatings, zwitterionic glutamic acid- and lysine-based peptides were immobilised on various substrates, including noble metals, metal oxides, polymers, and semiconductors. The variation of surface chemistry and surface wettability upon surface treatment was monitored with X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. Following peptide immobilisation, the surfaces became more hydrophilic due to the strong surface hydration compared with PDA-coated surfaces. The peptide-functionalised surfaces showed resistance to human blood serum adsorption and also effectively prevented the adhesion of gram-negative and gram-positive bacteria (i.e., Escherichia coli and Staphylococcus epidermidis) and mammalian cells (i.e., NIH 3T3 mouse embryonic fibroblast cells). The versatility of mussel-inspired chemistry combined with the unique biological nature and tunability of peptides allows for the design of low-fouling surfaces, making this a promising coating technique for various applications.
Polyphenol-Mediated Assembly for Particle Engineering
Publisher: American Chemical Society (ACS)
Date: 22-06-2020
Core-shell colloids and hollow polyelectrolyte capsules based on diazoresins
Publisher: Wiley
Date: 04-2001
DOI: 10.1002/1616-3028(200104)11:2<122::AID-ADFM122>3.0.CO;2-N
Robuste Chemie: die Bedeutung des Teilens von Daten und Methoden
Publisher: Wiley
Date: 12-2017
Particle Targeting in Complex Biological Media
Publisher: Wiley
Date: 15-08-2018
Abstract: Over the past few decades, nanoengineered particles have gained increasing interest for applications in the biomedical realm, including diagnosis, imaging, and therapy. When functionalized with targeting ligands, these particles have the potential to interact with specific cells and tissues, and accumulate at desired target sites, reducing side effects and improve overall efficacy in applications such as vaccination and drug delivery. However, when targeted particles enter a complex biological environment, the adsorption of biomolecules and the formation of a surface coating (e.g., a protein corona) changes the properties of the carriers and can render their behavior unpredictable. For this reason, it is of importance to consider the potential challenges imposed by the biological environment at the early stages of particle design. This review describes parameters that affect the targeting ability of particulate drug carriers, with an emphasis on the effect of the protein corona. We highlight strategies for exploiting the protein corona to improve the targeting ability of particles. Finally, we provide suggestions for complementing current in vitro assays used for the evaluation of targeting and carrier efficacy with new and emerging techniques (e.g., 3D models and flow-based technologies) to advance fundamental understanding in bio-nano science and to accelerate the development of targeted particles for biomedical applications.
Generation of complex colloids by polyelectrolyte-assisted electrostatic self-assembly
Publisher: CSIRO Publishing
Date: 2001
DOI: 10.1071/CH01109
Self-assembly and magnetism in core-shell microspheres
Publisher: American Vacuum Society
Date: 07-2003
DOI: 10.1116/1.1564031
Abstract: We report on the fabrication and characterization of magnetic composite colloids with a defined shape, composition and multilayer shell thickness. They consist of a core of a polystyrene microsphere (640 nm diameter) coated with consecutive shells of Fe3O4 nanoparticles (12 nm diameter), polyelectrolytes and Au nanoparticles (15 nm). The homogeneity of the coating was confirmed by transmission electron microscopy. Composite core-shell microspheres were self-assembled into periodically ordered chains up to 2 mm in length by magnetophoretic deposition. The self-organization was visualized by optical and atomic force microscopy. Magnetic properties were determined by angular dependent ferromagnetic resonance (FMR) and superconducting quantum interference device magnetometry between 5 and 300 K. The FMR reveals long-range magnetic order at 300 K due to dipolar coupling and an easy axis in plane along the chains. We find a magnetic moment that is reduced in comparison with the magnetite bulk value.
(Super)hydrophobic and multilayered amphiphilic films prepared by continuous assembly of polymers
Publisher: Wiley
Date: 16-05-2013
Copper-assisted weak polyelectrolyte multilayer formation on microspheres and subsequent film crosslinking
Publisher: Wiley
Date: 03-12-2003
Subcompartmentalized polymer hydrogel capsules with selectively degradable carriers and subunits
Publisher: Wiley
Date: 09-07-2010
Abstract: Subcompartmentalized hydrogel capsules (SHCs) with selectively degradable carriers and subunits are designed for potential applications in drug delivery and microencapsulated biocatalysis. Thiolated poly(methacrylic acid) and poly(N-vinyl pyrrolidone) are used to assemble 3-microm-diameter carrier capsules and 300-nm-diameter subunits, independently stabilized by a erse range of covalent linkages. This paper presents ex les of SHCs with tens of subcompartments and their successful drug loading, as well as selective degradation of the SHC carrier and/or subunits in response to multiple chemical stimuli.
Multilayer Buildup and Biofouling Characteristics of PSS-b-PEG Containing Films
Publisher: American Chemical Society (ACS)
Date: 05-03-2010
DOI: 10.1021/LA100430G
Abstract: Thin films exhibiting protein resistance are of interest in erse areas, ranging from low fouling surfaces in biomedicine to marine applications. Herein, we report the preparation of low protein and cell binding multilayer thin films, formed by the alternate deposition of a block copolymer comprising polystyrene sulfonate and poly(poly(ethylene glycol) methyl ether acrylate) (PSS-b-PEG), and polyallylamine hydrochloride (PAH). Film buildup was followed by quartz crystal microgravimetry (QCM), which showed linear growth and a high degree of hydration of the PSS-b-PEG/PAH films. Protein adsorption studies with bovine serum albumin using QCM demonstrated that multilayer films of PSS/PAH with a terminal layer of PSS-b-PEG were up to 5-fold more protein resistant than PSS-terminated films. Protein binding was dependent on the ionic strength at which the terminal layer of PSS-b-PEG was adsorbed, as well as the pH of the protein solution. It was also possible to control the protein resistance of the films by coadsorption of the final layer with another component (PSS), which showed an increase in protein resistance as the proportion of PSS-b-PEG in the adsorption solution was increased. In addition, protein resistance could also be controlled by the location of a single PSS-b-PEG layer within a PSS/PAH film. Finally, the buildup of PSS-b-PEG/PAH films on colloidal particles was demonstrated. PSS-b-PEG-terminated particles exhibited a 6.5-fold enhancement in cell binding resistance compared with PSS-terminated particles. The stability of PSS-b-PEG films combined with their low protein and cell binding characteristics provide opportunities for the use of the films as low fouling coatings in devices and other surfaces requiring limited interaction with biological interfaces.
Tunable superhydrophobic and optical properties of colloidal films coated with block-copolymer-micelles/micelle-multilayers
Publisher: Wiley
Date: 17-12-2007
Ligand-Functionalized Poly(ethylene glycol) Particles for Tumor Targeting and Intracellular Uptake
Publisher: American Chemical Society (ACS)
Date: 26-08-2019
DOI: 10.1021/ACS.BIOMAC.9B00925
Abstract: Drug carriers typically require both stealth and targeting properties to minimize nonspecific interactions with healthy cells and increase specific interaction with diseased cells. Herein, the assembly of targeted poly(ethylene glycol) (PEG) particles functionalized with cyclic peptides containing Arg-Gly-Asp (RGD) (ligand) using a mesoporous silica templating method is reported. The influence of PEG molecular weight, ligand-to-PEG molecule ratio, and particle size on cancer cell targeting to balance stealth and targeting of the engineered PEG particles is investigated. RGD-functionalized PEG particles (PEG-RGD particles) efficiently target U-87 MG cancer cells under static and flow conditions in vitro, whereas PEG and cyclic peptides containing Arg-Asp-Gly (RDG)-functionalized PEG (PEG-RDG) particles display negligible interaction with the same cells. Increasing the ligand-to-PEG molecule ratio improves cell targeting. In addition, the targeted PEG-RGD particles improve cell uptake via receptor-mediated endocytosis, which is desirable for intracellular drug delivery. The PEG-RGD particles show improved tumor targeting (14% ID g
Sulfoxide-Containing Polymer-Coated Nanoparticles Demonstrate Minimal Protein Fouling and Improved Blood Circulation
Publisher: Wiley
Date: 17-05-2020
Influence of solvent quality on the growth of polyelectrolyte multilayers
Publisher: American Chemical Society (ACS)
Date: 07-01-2004
DOI: 10.1021/LA035485U
Abstract: The effect of solvent conditions on the growth of polyelectrolyte (PE) multilayer films comprising poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) on planar substrates was investigated by means of surface plasmon resonance spectroscopy (SPRS), quartz crystal microbalance (QCM), and atomic force microscopy techniques. The solvent quality was varied by the addition of ethanol to the PE solutions used for deposition of the layers, thus tuning the relative strength of electrostatic and secondary intermolecular and intramolecular interactions. Experiments were performed with PE solutions both without added electrolyte and containing 0.5 M NaCl. Decreasing the solvent quality (i.e., increasing the amount of ethanol in the adsorption solution) resulted in a marked increase of both the multilayer film thickness and mass loading, as determined from the SPRS spectra and QCM frequency shifts, respectively. With the solution composition approaching the precipitation point, thick PAH/PSS films were formed due to the screening of the electrostatic intra- and interchain repulsions and enhanced hydrophobic interactions between the polyelectrolyte chains. However, the films formed from water/ethanol mixtures remained stable upon subsequent exposure to water or salt-containing solutions: no significant film desorption occurred after up to 24 h of exposure to water or 0.5 M NaCl solutions. In addition, the effect of postdeposition exposure to water/ethanol mixtures was investigated for PE multilayers assembled from aqueous solutions. In this case, the optical thickness of the films was determined during exposure to water/ethanol mixtures, and instead of swelling, the polyelectrolyte films collapse to the surface as a result of the unfavorable segment-solvent interactions.
Particle generation, functionalization and sortase A-mediated modification with targeting of single-chain antibodies for diagnostic and therapeutic use
Publisher: Springer Science and Business Media LLC
Date: 11-12-2015
Abstract: Antibody fusion to nonprotein materials such as contrast agents or radio-tracers, nano- or microparticles or small-molecule drugs is attracting major interest for molecular imaging and drug delivery. Nondirected bioconjugation techniques may impair antibody affinity, result in lower amounts of functional antibodies and generate multicomponent mixtures. We present a detailed protocol for the enzymatic bioconjugation of small recombinant antibodies to imaging particles, and we also describe the generation of and conjugation to a low-fouling capsule assembled for drug delivery from PEG and PVPON (poly(N-vinylpyrrolidone) by a layer-by-layer (LbL) technique. The single-chain variable fragment (scFv) is equipped with a short C-terminal LPETG tag and the fusion partners are functionalized with an N-terminal GGG nucleophilic group for sortase A conjugation. The LbL capsules are assembled through hydrogen bonding by depositing alkyne-modified poly(vinylpyrrolidone) and poly(methacrylic acid) layers on silica particles, followed by depositing alkyne-modified PEG. The generation of the antibodies and LbL capsules takes ∼1-2 weeks each. The conjugation and functional testing takes another 3-4 d.
Low-fouling poly(N-vinyl pyrrolidone) capsules with engineered degradable properties
Publisher: American Chemical Society (ACS)
Date: 09-2009
DOI: 10.1021/BM900673M
Abstract: We report the assembly of low-fouling polymer capsules with engineered deconstruction properties by using a combination of layer-by-layer (LbL) assembly and click chemistry. Preformed, hydrogen-bonded multilayers of alkyne-functionalized poly(N-vinyl pyrrolidone) (PVPON(Alk)) and poly(methacrylic acid) (PMA) assembled at pH 4 on silica particles were cross-linked with a bisazide linker (containing a disulfide link) through alkyne-azide click chemistry. Following dissolution of the silica template particles, and altering the solution pH to 7.2 to disrupt hydrogen bonding between PVPON(Alk) and PMA to effect removal of PMA, stable, cross-linked PVPON capsules were obtained. The presence of the disulfide bond in the bisazide linker endowed the PVPON capsules with degradable characteristics under model intracellular conditions. The capsules deconstructed within 4 h in the presence of 5 mM glutathione. The cross-linked PVPON(Alk) multilayers (assembled on silica particles) were low-fouling to a range of proteins, including fibrinogen, lysozyme, immunoglobulin G, and bovine serum albumin. Further, MTT assays showed that the PVPON capsules had no effect on the proliferation of cells from a human colon cancer cell line (LIM1899), indicating negligible cytotoxicity toward the LIM1899 cells. The low-fouling, degradable, and low cytotoxicity characteristics of the PVPON capsules makes them attractive as a platform for the development of advanced therapeutic delivery systems.
Cobalt-Directed Assembly of Antibodies onto Metal–Phenolic Networks for Enhanced Particle Targeting
Publisher: American Chemical Society (ACS)
Date: 10-03-2020
Metal–Phenolic Supramolecular Gelation
Publisher: Wiley
Date: 30-09-2016
Dissecting the intracellular signalling and fate of a DNA nanosensor by super-resolution and quantitative microscopy
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0NR03087B
Abstract: The intracellular interactions and fate of a DNA nanosensor were investigated by combining quantitative microscopy and stochastic optical reconstruction microscopy.
Enzyme Multilayers on Colloid Particles: Assembly, Stability, and Enzymatic Activity
Publisher: American Chemical Society (ACS)
Date: 31-10-2000
DOI: 10.1021/LA000942H
Anti-PEG Antibodies Boosted in Humans by SARS-CoV-2 Lipid Nanoparticle mRNA Vaccine
Publisher: American Chemical Society (ACS)
Date: 27-06-2022
Cross-linked, luminescent spherical colloidal and hollow-shell particles
Publisher: American Chemical Society (ACS)
Date: 11-2001
DOI: 10.1021/LA011006K
Formation of luminescent spherical core-shell particles by the consecutive adsorption of polyelectrolyte and CdTe(S) nanocrystals on latex colloids
Publisher: Elsevier BV
Date: 31-03-2000
Immunological Principles Guiding the Rational Design of Particles for Vaccine Delivery
Publisher: American Chemical Society (ACS)
Date: 11-01-2017
Abstract: Despite the immense public health successes of immunization over the past century, effective vaccines are still lacking for globally important pathogens such as human immunodeficiency virus, malaria, and tuberculosis. Exciting recent advances in immunology and biotechnology over the past few decades have facilitated a shift from empirical to rational vaccine design, opening possibilities for improved vaccines. Some of the most important advancements include (i) the purification of subunit antigens with high safety profiles, (ii) the identification of innate pattern recognition receptors (PRRs) and cognate agonists responsible for inducing immune responses, and (iii) developments in nano- and microparticle fabrication and characterization techniques. Advances in particle engineering now allow highly tunable physicochemical properties of particle-based vaccines, including composition, size, shape, surface characteristics, and degradability. Enhanced collaborative efforts between researchers in immunology and materials science are expected to rise to next-generation vaccines. This process will be significantly aided by a greater understanding of the immunological principles guiding vaccine antigenicity, immunogenicity, and efficacy. With specific emphasis on PRR-targeted adjuvants and particle physicochemical properties, this review aims to provide an overview of the current literature to guide and focus rational particle-based vaccine design efforts.
A protective vaccine delivery system for in vivo T cell stimulation using nanoengineered polymer hydrogel capsules
Publisher: American Chemical Society (ACS)
Date: 13-10-2009
DOI: 10.1021/NN900715G
Abstract: Successful delivery of labile vaccine antigens, such as peptides and proteins, to stimulate CD4 and CD8 T cell immunity could improve vaccine strategies against chronic infections such as HIV and Hepatitis C. Layer-by-layer (LbL)-assembled nanoengineered hydrogel capsules represent a novel and promising technology for the protection and delivery of labile vaccine candidates to antigen-presenting cells (APCs). Here we report on the in vitro and in vivo immunostimulatory capabilities of LbL-assembled disulfide cross-linked poly(methacrylic acid) (PMA(SH)) hydrogel capsules as a delivery strategy for protein and peptide vaccines using robust transgenic mice models and ovalbumin (OVA) as a model vaccine. We demonstrate that OVA protein as well as multiple OVA peptides can be successfully encapsulated within nanoengineered PMA(SH) hydrogel capsules. OVA-containing PMA(SH) capsules are internalized by mouse APCs, resulting in presentation of OVA epitopes and subsequent activation of OVA-specific CD4 and CD8 T cells in vitro. OVA-specific CD4 and CD8 T cells are also activated to proliferate in vivo following intravenous vaccination of mice with OVA protein- and OVA peptide-loaded PMA(SH) hydrogel capsules. Furthermore, we show that OVA encapsulated within the PMA(SH) capsules resulted in at least 6-fold greater proliferation of OVA-specific CD8 T cells and 70-fold greater proliferation of OVA-specific CD4 T cells in vivo compared to the equivalent amount of OVA protein administered alone. These results highlight the potential of nanoengineered hydrogel capsules for vaccine delivery.
Characterization of Adsorbate-Induced Ordering Transitions of Liquid Crystals within Monodisperse Droplets
Publisher: American Chemical Society (ACS)
Date: 06-07-2009
DOI: 10.1021/LA900786B
Abstract: The ordering of liquid crystals (LCs) within micrometer-sized droplets is known to depend strongly on the presence of interfacial adsorbates, although the exact sequence of ordered equilibrium states that accompany a change in interfacial anchoring from tangential to perpendicular has not been established. In this paper, we report use of a methodology that permits the preparation of monodisperse LC droplets in aqueous phases to investigate ordering transitions in the LC droplets that accompany the adsorption of hiphiles at the aqueous-LC droplet interface. By using an hiphile that undergoes reversible adsorption at the aqueous-LC interface (sodium dodecylsulfate, SDS), we identified six distinct topologically ordered states of the LC droplets as a function of increasing concentration of SDS. We exploited the reversible adsorption of the SDS to LC droplets with diameters of 8.0+/-0.2 microm to confirm that these topological states are equilibrium ones. We also exposed LC droplets to a continuous gradient in concentration of SDS to document the continuous transitions between topological states and to confirm the absence of additional, intermediate topological states. The formation of the LC droplets as aqueous dispersions also enabled an investigation of ordering transitions in LC droplets driven by biomolecular interactions. Surprisingly, enzymatic hydrolysis of the phospholipid L-dipalmitoyl phosphatidylcholine (L-DLPC) by phospholipase A2 at the interfaces of the LC droplets was observed to trigger the same progression of topologically ordered states of the LC as was observed with SDS. Overall, the results presented in this paper resolve prior conflicting data in the literature by providing an unambiguous set of observations regarding topologically ordered states encountered in LC droplets. This paper provides a data set against which future theories and simulations of LCs can be compared to develop a fundamental understanding of the competition between volumetric and interfacial effects in droplets. The results also suggest that topological ordering transitions in LC droplets can be exploited to report interfacial enzymatic reactions.
Highly Stable and Active Flexible Electrocatalysts Derived from Lotus Fibers
Publisher: Wiley
Date: 29-01-2023
Abstract: The stability and activity of electrocatalysts are fundamental in energy‐related applications (e.g., hydrogen generation and energy storage). Electrocatalysts degrade over time when the active centers are not strongly anchored to the support. However, if the active centers are too strongly anchored, the activity of the electrocatalysts decreases due to reduced accessibility to reactants. Herein, a strategy is presented to balance the stability and activity of different active materials using a natural and flexible support material that can be woven and carbonized. Lotus fibers, which have surface hydroxyl and phenolic groups, high mechanical strength, and a mesoscale porosity post‐pyrolysis, are used to load erse functional metal‐containing materials such as metal–organic frameworks, 2D materials, metal sulfide nanoparticles, metal ions, and high‐entropy alloys. After pyrolysis, the electrocatalysts display flexibility, high catalytic performance, and long‐term stability, outperforming commercial benchmarks (e.g., Pt/C) in specific scenarios for water splitting, liquid batteries, and flexible electronics.
Compositional engineering of polyelectrolyte blend capsules
Publisher: American Chemical Society (ACS)
Date: 14-09-2007
DOI: 10.1021/MA071372W
Site‐Selective Coordination Assembly of Dynamic Metal‐Phenolic Networks
Publisher: Wiley
Date: 13-07-2022
Abstract: Coordination states of metal‐organic materials are known to dictate their physicochemical properties and applications in various fields. However, understanding and controlling coordination sites in metal‐organic systems is challenging. Herein, we report the synthesis of site‐selective coordinated metal‐phenolic networks (MPNs) using flavonoids as coordination modulators. The site‐selective coordination was systematically investigated experimentally and computationally using ligands with one, two, and multiple different coordination sites. Tuning the multimodal Fe coordination with catechol, carbonyl, and hydroxyl groups within the MPNs enabled the facile engineering of erse physicochemical properties including size, selective permeability (20–2000 kDa), and pH‐dependent degradability. This study expands our understanding of metal‐phenolic chemistry and provides new routes for the rational design of structurally tailorable coordination‐based materials.
Macromolecular Engineering of Thermoresponsive Metal-Phenolic Networks.
Publisher: American Chemical Society (ACS)
Date: 27-12-2022
DOI: 10.1021/JACS.1C10979
Abstract: Dynamic nanostructured materials that can react to physical and chemical stimuli have attracted interest in the biomedical and materials science fields. Metal-phenolic networks (MPNs) represent a modular class of such materials: these networks form via coordination of phenolic molecules with metal ions and can be used for surface and particle engineering. To broaden the range of accessible MPN properties, we report the fabrication of thermoresponsive MPN capsules using Fe
Rust-Mediated Continuous Assembly of Metal-Phenolic Networks
Publisher: Wiley
Date: 07-04-2017
Abstract: The use of natural compounds for preparing hybrid molecular films-such as surface coatings made from metal-phenolic networks (MPNs)-is of interest in areas ranging from catalysis and separations to biomedicine. However, to date, the film growth of MPNs has been observed to proceed in discrete steps (≈10 nm per step) where the coordination-driven interfacial assembly ceases beyond a finite time (≈1 min). Here, it is demonstrated that the assembly process for MPNs can be modulated from discrete to continuous by utilizing solid-state reactants (i.e., rusted iron objects). Gallic acid etches iron from rust and produces chelate complexes in solution that continuously assemble at the interface of solid substrates dispersed in the system. The result is stable, continuous growth of MPN films. The presented double dynamic process-that is, etching and self-assembly-provides new insights into the chemistry of MPN assembly while enabling control over the MPN film thickness by simply varying the reaction time.
Improving Targeting of Metal-Phenolic Capsules by the Presence of Protein Coronas
Publisher: American Chemical Society (ACS)
Date: 25-08-2016
Abstract: Particles adsorb proteins when they enter a physiological environment this results in a surface coating termed a "protein corona". A protein corona can affect both the properties and functionalities of engineered particles. Here, we prepared hyaluronic acid (HA)-based capsules through the assembly of metal-phenolic networks (MPNs) and engineered their targeting ability in the absence and presence of protein coronas by varying the HA molecular weight. The targeting ability of the capsules was HA molecular weight dependent, and a high HA molecular weight (>50 kDa) was required for efficient targeting. The specific interactions between high molecular weight HA capsules and receptor-expressing cancer cells were negligibly affected by the presence of protein coronas, whereas nonspecific capsule-cell interactions were significantly reduced in the presence of a protein corona derived from human serum. Consequently, the targeting specificity of HA-based MPN capsules was enhanced due to the formation of a protein corona. This study highlights the significant and complex roles of a protein corona in biointeractions and demonstrates how protein coronas can be used to improve the targeting specificity of engineered particles.
Probing cell internalisation mechanics with polymer capsules
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6NR06657G
Abstract: We report polymer capsule-based probes for quantifying the pressure exerted by cells during capsule internalisation (P
Capsosomes as Long-Term Delivery Vehicles for Protein Therapeutics
Publisher: American Chemical Society (ACS)
Date: 09-07-2015
DOI: 10.1021/ACS.LANGMUIR.5B01667
Abstract: We report the preparation of polymer capsules containing liposomal subcompartments, termed capsosomes, and their ability for the sustained delivery of protein therapeutics. Capsosomes were formed through the layer-by-layer (LbL) assembly of polymers and protein-loaded liposomes, followed by the formation of a capsule membrane based on disulfide cross-linked poly(methacrylic acid). The loading capacities of a model cargo (lysozyme) and brain-derived neurotrophic factor (BDNF), an important neurotrophin that has significant physiological functions on the nervous system, were determined, and the long-term release kinetics of the proteins was investigated in simulated physiological conditions. The capsosomes exhibited protein loading and release behavior that can be tuned by the lipid composition of the liposomal compartments, where inclusion of anionic lipids resulted in enhanced protein loading and slower release over the course of 80 days. These findings highlight the potential of capsosomes for the long-term delivery of protein therapeutics.
Macromolecule Functionalization of Disulfide-Bonded Polymer Hydrogel Capsules and Cancer Cell Targeting
Publisher: American Chemical Society (ACS)
Date: 19-01-2012
DOI: 10.1021/NN204319B
Abstract: We present a generic and versatile method for functionalization of disulfide-stabilized PMA hydrogel capsules (HCs) with macromolecules, including a number of specific antibodies to cancer cells. Functionalization was achieved by reversible addition-fragmentation chain transfer (RAFT) polymerization of poly(N-vinyl pyrrolidone) (PVPON), which introduced biorelevant heterotelechelic end groups (thiol and amine) to the polymer chain. The PVPON with heterotelechelic end groups was conjugated to the outermost layer of PMA HCs through the thiol groups and reacted with biotin via the amine groups to generate PMA/PVPON(biotin) HCs. On the basis of the high specific interaction and high affinity between biotin and avidin, and its derivates, such as NeutrAvidin (NAv), we functionalized the PMA HCs with biotinylated antibodies. We demonstrate significantly enhanced cellular binding and internalization of the antibody (Ab)-functionalized capsules compared with control human immunoglobulin (IgG)-functionalized capsules, suggesting these capsules can specifically interact with cells through antibody/antigen recognition. We anticipate that the versatility of the functionalization approach reported in this study will assist in targeted therapeutic delivery applications.
Synthesis of Chemically Asymmetric Silica Nanobottles and Their Application for Cargo Loading and as Nanoreactors and Nanomotors
Publisher: Wiley
Date: 20-10-2016
Quartz crystal microbalance study of DNA immobilization and hybridization for nucleic acid sensor development
Publisher: American Chemical Society (ACS)
Date: 06-1997
DOI: 10.1021/AC961220R
Abstract: The immobilization of two 30-mer oligonucleotides, one biotinylated (biotin-DNA) and the other having a mercaptohexyl group at the 5'-phosphate end (BS1-SH), onto modified gold surfaces has been examined using a quartz crystal microbalance (QCM). Both single-layer and multilayer DNA films were prepared. The single-layer films of biotin-DNA were constructed by binding to a precursor layer of avidin, which had been attached to the QCM either covalently using a water-soluble carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) or via electrostatic interaction with poly(allylamine hydrochloride) (PAH). Single-layer films of BS1-SH were also formed on PAH via the electrostatic attraction between the amine groups on PAH and the negatively charged phosphate backbone of DNA. Multilayer films of DNA were fabricated by the successive deposition of avidin and poly(styrenesulfonate) (PSS), up to a total of nine avidin/PSS layers, followed by DNA adsorption. DNA immobilization and hybridization of the immobilized DNAs was monitored in situ from QCM frequency changes. Hybridization was induced by exposure of the DNA-containing films to complementary DNA in solution. Equal frequency changes were observed for the DNA immobilization and hybridization steps for the single-layer films, indicating a DNA probe-to-hybridized DNA target ratio of 1:1. The multilayer DNA films also exhibited DNA hybridization, with a greater quantity of DNA hybridized compared with the single-layer films. The multilayer films provide a novel means for the fabrication of DNA-based thin films with increased capacity for nucleic acid detection.
Electrostatic Interactions between Polyelectrolytes and a Titania Precursor: Thin Film and Solution Studies
Publisher: American Chemical Society (ACS)
Date: 11-01-2002
DOI: 10.1021/LA011310D
Effect of dendrimer on entrapment and release of bioactive from liposomes
Publisher: Elsevier BV
Date: 2002
DOI: 10.1016/S0378-5173(01)00901-2
Abstract: An active encapsulation method to obtain high entrapment in liposomes is described. The method harnesses the ability of dendrimer to interact with oppositely charged phospholipid and solubilize acidic drugs in their interior. The high drug entrapment in liposomes is due to the enhanced entrapment of dendrimer, which creates sink in the liposomal aqueous compartment where the methotrexate (MTX) molecules are fluxed in. The encapsulation increases with dendrimer generation. The release of bioactive was also decreased by this method. The method may be useful to entrap drugs with relatively high therapeutic dose.
Cellular Targeting of Bispecific Antibody-Functionalized Poly(ethylene glycol) Capsules: Do Shape and Size Matter?
Publisher: American Chemical Society (ACS)
Date: 08-2019
Abstract: In the present study, a capsule system that consists of a stealth carrier based on poly(ethylene glycol) (PEG) and functionalized with bispecific antibodies (BsAbs) is introduced to examine the influence of the capsule shape and size on cellular targeting. Hollow spherical and rod-shaped PEG capsules with tunable aspect ratios (ARs) of 1, 7, and 18 were synthesized and subsequently functionalized with BsAbs that exhibit dual specificities to PEG and epidermal growth factor receptor (EGFR). Dosimetry (variation between the concentrations of capsules present and capsules that reach the cell surface) was controlled through "dynamic" incubation (i.e., continuously mixing the incubation medium). The results obtained were compared with those obtained from the "static" incubation experiments. Regardless of the incubation method and the capsule shape and size studied, BsAb-functionalized PEG capsules showed >90% specific cellular association to EGFR-positive human breast cancer cells MDA-MB-468 and negligible association with both control cell lines (EGFR negative Chinese hamster ovary cells CHO-K1 and murine macrophages RAW 264.7) after incubation for 5 h. When dosimetry was controlled and the dose concentration was normalized to the capsule surface area, the size or shape had a minimal influence on the cell association behavior of the capsules. However, different cellular internalization behaviors were observed, and the capsules with ARs 7 and 18 were, respectively, the least and most optimal shape for achieving high cell internalization under both dynamic and static conditions. Dynamic incubation showed a greater impact on the internalization of rod-shaped capsules (∼58-67% change) than on the spherical capsules (∼24-29% change). The BsAb-functionalized PEG capsules reported provide a versatile particle platform for the evaluation and comparison of cellular targeting performance of capsules with different sizes and shapes in vitro.
Synthesis of Discrete Alkyl-Silica Hybrid Nanowires and Their Assembly into Nanostructured Superhydrophobic Membranes
Publisher: Wiley
Date: 09-06-2016
Abstract: We report the synthesis of highly flexible and mechanically robust hybrid silica nanowires (NWs) which can be used as novel building blocks to construct superhydrophobic functional materials with three-dimensional macroporous networks. The hybrid silica NWs, with an average diameter of 80 nm and tunable length of up to 12 μm, are prepared by anisotropic deposition of the hydrolyzed tetraethylorthosilicate in water/n-pentanol emulsions. A mechanistic investigation reveals that the trimethoxy(octadecyl)silane introduced to the water-oil interface in the synthesis plays key roles in stabilizing the water droplets to sub-100 nm and also growing a layer of octadecyl groups on the NW surface. This work opens a solution-based route for the one-pot preparation of monodisperse, hydrophobic silica NWs and represents an important step toward the bottom-up construction of 3D superhydrophobic materials and macroporous membranes.
Inverse opals for optical affinity biosensing
Publisher: Wiley
Date: 18-11-2002
DOI: 10.1002/1521-4095(20021118)14:22<1629::AID-ADMA1629>3.0.CO;2-2
Liquid Crystal Chemical Sensors That Cells Can Wear
Publisher: Wiley
Date: 29-11-2013
Biocolloids with ordered urease multilayer shells as enzymatic reactors
Publisher: American Chemical Society (ACS)
Date: 08-08-2001
DOI: 10.1021/AC010118D
Abstract: The preparation of biocolloids with organized enzyme-containing multilayer shells for exploitation as colloidal enzymatic nanoreactors is described. Urease multilayers were assembled onto submicrometer-sized polystyrene spheres by the sequential adsorption of urease and polyelectrolyte, in a predetermined order, utilizing electrostatic interactions for layer growth. The catalytic activity of the biocolloids increased proportionally with the number of urease layers deposited on the particles, demonstrating that biocolloid particles with tailored enzymatic activities can be produced. It was further found that precoating the latex spheres with nanoparticles (40-nm silica or 12-nm magnetite) enhanced both the stability (with respect to adsorption) and enzymatic activity of the urease multilayers. The presence of the magnetite nanoparticle coating also provided a magnetic function that allowed the biocolloids to be easily and rapidly separated with a permanent magnet. The fabrication of such colloids opens new avenues for the application of bioparticles and represents a promising route for the creation of complex catalytic particles.
Thin multilayer films and microcapsules containing DNA quadruplex motifs
Publisher: Wiley
Date: 23-11-2011
Abstract: The assembly of multifunctional nanostructures bearing G-quadruplex motifs broadens the prospects of using G-quadruplexes as therapeutic carriers. Herein, we report the synthesis and characterization of an oligodeoxyguanosine, G15-mer polymer conjugate. We demonstrate that G15-mer oligonucleotides grafted to a polymer chain preserve the ability to self-assemble into ordered structures. The G-quadruplex-polymer conjugates were assembled onto a surface via hybridization with 30-mer cytosine strands, C30-mer, using a layer-by-layer approach to form microcapsules. A mechanism for the sequential assembly of the multilayer films and microcapsules is presented. We further investigate the photophysical behavior of porphyrin TMPyP4 bound to multilayer-coated particles. This study shows that the multilayer films bear residual and functional quadruplex moieties that can be used to effectively bind therapeutic agents.
Engineering of Nebulized Metal–Phenolic Capsules for Controlled Pulmonary Deposition
Publisher: Wiley
Date: 10-01-2020
Modular Metal–Organic Polyhedra Superassembly: From Molecular-Level Design to Targeted Drug Delivery
Publisher: Wiley
Date: 31-01-2019
Coatings super-repellent to ultralow surface tension liquids.
Publisher: Springer Science and Business Media LLC
Date: 15-10-2018
DOI: 10.1038/S41563-018-0178-2
Abstract: High-performance coatings that durably and fully repel liquids are of interest for fundamental research and practical applications. Such coatings should allow for droplet beading, roll off and bouncing, which is difficult to achieve for ultralow surface tension liquids. Here we report a bottom-up approach to prepare super-repellent coatings using a mixture of fluorosilanes and cyanoacrylate. On application to surfaces, the coatings assemble into thin films of locally multi-re-entrant hierarchical structures with very low surface energies. The resulting materials are super-repellent to solvents, acids and bases, polymer solutions and ultralow surface tension liquids, characterized by ultrahigh liquid contact angles (>150°) and negligible roll-off angles (~0°). Furthermore, the coatings are transparent, durable and demonstrate universal liquid bouncing, tailored responsiveness and anti-freezing properties, and are thus a promising alternative to existing synthetic super-repellent coatings.
Controlled release of DNA from poly(vinylpyrrolidone) capsules using cleavable linkers
Publisher: Elsevier BV
Date: 09-2011
DOI: 10.1016/J.BIOMATERIALS.2011.05.011
Abstract: The design of polymer carriers with tunable degradation and cargo release is fundamental for applications in drug and gene delivery. In this study, we report low-fouling poly(N-vinyl pyrrolidone) (PVPON) capsules assembled via hydrogen bonding and stabilized using covalent cross-linking. We first investigated the effects of pH and ionic strength to optimize the assembly conditions. A model therapeutic cargo (plasmid DNA) was then loaded in the capsules and used for encapsulation and release studies. Two bisazide cross-linkers that contain a disulfide bond, termed PEG₈ (poly(ethylene glycol)) and PEG(16), were employed to stabilize the multilayer films, and used to tune the degradation and cargo release behavior of the capsules in simulated cytoplasmic conditions. The results suggest that PEG₈-stabilized capsules were more efficiently cross-linked, and hence displayed higher plasmid encapsulation. Consequently, the capsules cross-linked with PEG₈ also showed a two-fold reduction in degradation rate. This ability to achieve controlled carrier degradation and cargo release makes these capsules of potential interest for drug and gene delivery.
Capsosomes with Free-Floating Liposomal Subcompartments
Publisher: Wiley
Date: 27-07-2011
A paradigm for peptide vaccine delivery using viral epitopes encapsulated in degradable polymer hydrogel capsules
Publisher: Elsevier BV
Date: 10-2009
DOI: 10.1016/J.BIOMATERIALS.2009.05.078
Abstract: We report on the use of degradable polymer capsules as carriers for the delivery of oligopeptide antigens to professional antigen presenting cells (APCs). To achieve encapsulation, oligopeptide sequences were covalently linked to a negatively charged carrier polymer via biodegradable linkages and the resulting conjugate was then adsorbed onto amine-functionalized silica particles. These peptide-coated particles were then used as templates for the layer-by-layer (LbL) deposition of thiolated poly(methacrylic acid) (PMA(SH)) and poly(vinylpyrrolidone) (PVPON) multilayers. Removal of the silica core and disruption of the hydrogen bonding between PMA(SH) and PVPON by altering the solution pH yielded disulfide-stabilized PMA capsules that retain the encapsulated cargo in an oxidative environment. In the presence of a natural reducing agent, glutathione, cleavage of the disulfide bonds causes release of the peptide from the capsules. The developed strategy provides control over peptide loading into polymer capsules and yields colloidally stable micron- and submicron-sized carriers with uniform size and peptide loading. The conjugation and encapsulation procedures were proven to be non-degrading to the peptide vaccines. The peptide-loaded capsules were successfully used to deliver their cargo to APCs and activate CD8 T lymphocytes in a non-human primate model of SIV infection ex vivo. The reported approach represents a novel paradigm in the delivery of peptide vaccines and other therapeutic agents.
Mesoporous Silica-Templated Assembly of Luminescent Polyester Particles
Publisher: American Chemical Society (ACS)
Date: 27-08-2009
DOI: 10.1021/CM901621Y
Enzyme Encapsulation in Layer-by-Layer Engineered Polymer Multilayer Capsules
Publisher: American Chemical Society (ACS)
Date: 29-01-2000
DOI: 10.1021/LA991161N
Surface plasmon resonance in gold nanoparticle infiltrated dielectric opals
Publisher: AIP Publishing
Date: 04-04-2005
DOI: 10.1063/1.1875735
Abstract: Light reflectance in three-dimensional metallo-dielectric photonic crystals of polyelectrolyte-coated latex spheres infiltrated with gold nanoparticles has been studied. Broad directional reflectance bands associated with the surface plasmon resonance in the lattice of the gold nanoparticle shells are observed in a wavelength range well separated from the diffraction resonance of the opal lattice. Dependence of surface plasmon resonance spectra on the Au nanoparticle distribution has been demonstrated.
Shape-Dependent Activation of Cytokine Secretion by Polymer Capsules in Human Monocyte-Derived Macrophages
Publisher: American Chemical Society (ACS)
Date: 26-02-2016
DOI: 10.1021/ACS.BIOMAC.6B00027
Abstract: Particles with tailored geometries have received significant attention due to their specific interactions with biological systems. In this work, we examine the effect of polymer capsule shape on cytokine secretion by human monocyte-derived macrophages. Thiolated poly(methacrylic acid) (PMASH) polymer capsules with different shapes (spherical, short rod-shaped, and long rod-shaped) were prepared by layer-by-layer assembly. The effect of PMASH capsule shape on cellular uptake and cytokine secretion by macrophages differentiated from THP-1 monocytes (dTHP-1) was investigated. PMASH capsules with different shapes were internalized to a similar extent in dTHP-1 cells. However, cytokine secretion was influenced by capsule geometry: short rod-shaped PMASH capsules promoted a stronger increase in TNF-α and IL-8 secretion compared with spherical (1.7-fold in TNF-α and 2.1-fold in IL-8) and long rod-shaped (2.8-fold in TNF-α and 2.0-fold in IL-8) PMASH capsules in dTHP-1 cells (capsule-to-cell ratio of 100:1). Our results indicate that the immunological response based on the release of cytokines is influenced by the shape of the polymer capsules, which could be potentially exploited in the rational design of particle carriers for vaccine delivery.
Robust Chemistry: The Importance of Data and Methods Sharing
Publisher: Wiley
Date: 12-2018
Abstract: "… Robustness in chemistry can be enhanced by increasing the adoption of best data-sharing practices and the use of photos and videos for sharing methods and practical knowledge. Journals are an integral part of the foundation of scientific endeavor, and methods and data sharing are complementary practices that could lead to a step change in how we conduct and report research …" Read more in the Editorial by Mattias Björnmalm and Frank Caruso.
Multilayered Titania, Silica, and Laponite Nanoparticle Coatings on Polystyrene Colloidal Templates and Resulting Inorganic Hollow Spheres
Publisher: American Chemical Society (ACS)
Date: 16-01-2001
DOI: 10.1021/CM001175A
A radiolabeled drug tracing method to study neurotrophin-3 retention and distribution in the cochlea after nano-based local delivery
Publisher: Elsevier BV
Date: 2020
Biological and physical applications of water-based metal nanoparticles synthesised in organic solution
Publisher: Wiley
Date: 18-01-2002
DOI: 10.1002/1439-7641(20020118)3:1<110::AID-CPHC110>3.0.CO;2-Q
Influence of protein corona on the interaction of glycogen–siRNA constructs with ex vivo human blood immune cells
Publisher: Elsevier BV
Date: 09-2022
DOI: 10.1016/J.BIOADV.2022.213083
Abstract: Glycogen-nucleic acid constructs i.e., glycoplexes are emerging promising platforms for the alteration of gene expression and transcription. Understanding the interaction of glycoplexes with human blood components, such as serum proteins and peripheral blood mononuclear cells (PBMCs), is important to overcome immune cell activation and control biodistribution upon administration of the glycoplexes in vivo. Herein, we investigated the interactions of polyethylene glycol (PEG)ylated and non-PEGylated glycoplexes carrying siRNA molecules with PBMCs isolated from the blood of healthy donors. We found that both types of glycoplexes were non-toxic and were primarily phagocytosed by monocytes without triggering a pro-inflammatory interleukin 6 cytokine production. Furthermore, we investigated the role of the protein corona on controlling the internalization efficiency in immune cells - we found that the adsorption of serum proteins, in particular haptoglobin, alpha-1-antitrypsin and apolipoprotein A-II, onto the non-PEGylated glycoplexes, significantly reduced the uptake of the glycoplexes by PBMCs. Moreover, the non-PEGylated glycoplexes were efficient in the nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) knockdown in monocytic THP-1 cell line. This study provides an insight into the rational design of glycogen-based nanocarriers for the safe delivery of siRNA without eliciting unwanted immune cell activation and efficient siRNA activity upon its delivery.
In vivo imaging and tracking of individual nanodiamonds in drosophila melanogaster embryos
Publisher: The Optical Society
Date: 20-03-2014
DOI: 10.1364/BOE.5.001250
Influence of Poly(ethylene glycol) Molecular Architecture on Particle Assembly and Ex Vivo Particle–Immune Cell Interactions in Human Blood
Publisher: American Chemical Society (ACS)
Date: 19-05-2021
Self-Assembly of Nano- to Macroscopic Metal-Phenolic Materials
Publisher: American Chemical Society (ACS)
Date: 09-08-2018
Ultrathin, bioresponsive and drug-functionalized protein capsules
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2JM33737A
Tuning the Properties of Layer-by-Layer Assembled Poly(acrylic acid) Click Films and Capsules
Publisher: American Chemical Society (ACS)
Date: 04-02-2011
DOI: 10.1021/MA102593K
Developing the supraparticle technology for round window-mediated drug administration into the cochlea
Publisher: Elsevier BV
Date: 09-2023
Quartz Crystal Microbalance and Surface Plasmon Resonance Study of Surfactant Adsorption onto Gold and Chromium Oxide Surfaces
Publisher: American Chemical Society (ACS)
Date: 05-1995
DOI: 10.1021/LA00005A023
Phenolic Building Blocks for the Assembly of Functional Materials.
Publisher: Wiley
Date: 11-12-2019
Abstract: Phenolic materials have long been known for their use in inks, wood coatings, and leather tanning. However, there has recently been a renewed interest in engineering advanced materials from phenolic building blocks. The intrinsic properties of phenolic compounds, such as metal chelation, hydrogen bonding, pH responsiveness, redox potentials, radical scavenging, polymerization, and light absorbance, have made them a distinct class of structural motifs for the synthesis of functional materials. Materials prepared from phenolic compounds often retain many of these useful properties with synergistic effects in applications ranging from catalysis to biomedicine. This Review provides an overview of the erse functional materials that can be prepared from natural and synthetic phenolic building blocks, as well as their applications.
Stimuli-Responsive Delivery of Antimicrobial Peptides Using Polyelectrolyte Complexes
Publisher: Wiley
Date: 24-07-2023
Abstract: Antimicrobial peptides (AMPs) are antibiotics with the potential to address antimicrobial resistance. However, their translation to the clinic is h ered by issues such as off‐target toxicity and low stability in biological media. Stimuli‐responsive delivery from polyelectrolyte complexes offers a simple avenue to address these limitations, wherein delivery is triggered by changes occurring during microbial infection. The review first provides an overview of pH‐responsive delivery, which exploits the intrinsic pH‐responsive nature of polyelectrolytes as a mechanism to deliver these antimicrobials. The ex les included illustrate the challenges faced when developing these systems, in particular balancing antimicrobial efficacy and stability, and the potential of this approach to prepare switchable surfaces or nanoparticles for intracellular delivery. The review subsequently highlights the use of other stimuli associated with microbial infection, such as the expression of degrading enzymes or changes in temperature. Polyelectrolyte complexes with dual stimuli‐response based on pH and temperature are also discussed. Finally, the review presents a summary and an outlook of the challenges and opportunities faced by this field. This review is expected to encourage researchers to develop stimuli‐responsive polyelectrolyte complexes that increase the stability of AMPs while providing targeted delivery, and thereby facilitate the translation of these antimicrobials.
Polyelectrolyte blend multilayers: A versatile route to engineering interfaces and films
Publisher: Wiley
Date: 11-12-2008
Direct Assembly of Metal‐Phenolic Network Nanoparticles for Biomedical Applications
Publisher: Wiley
Date: 06-10-2023
Mesoporous silica spheres as supports for enzyme immobilization and encapsulation
Publisher: American Chemical Society (ACS)
Date: 04-02-2005
DOI: 10.1021/CM0483137
Layer-by-Layer Construction of Novel Biofunctional Fluorescent Microparticles for Immunoassay Applications
Publisher: Elsevier BV
Date: 02-2001
Oxidation-Mediated Kinetic Strategies for Engineering Metal-Phenolic Networks.
Publisher: Wiley
Date: 05-08-2019
Abstract: The tunable growth of metal-organic materials has implications for engineering particles and surfaces for erse applications. Specifically, controlling the self-assembly of metal-phenolic networks (MPNs), an emerging class of metal-organic materials, is challenging, as previous studies suggest that growth often terminates through kinetic trapping. Herein, kinetic strategies were used to temporally and spatially control MPN growth by promoting self-correction of the coordinating building blocks through oxidation-mediated MPN assembly. The formation and growth mechanisms were investigated and used to engineer films with microporous structures and continuous gradients. Moreover, reactive oxygen species generated by ultrasonication expedite oxidation and result in faster (ca. 30 times) film growth than that achieved by other MPN assembly methods. This study expands our understanding of metal-phenolic chemistry towards engineering metal-phenolic materials for various applications.
Modulating the Selectivity and Stealth Properties of Ellipsoidal Polymersomes through a Multivalent Peptide Ligand Display
Publisher: Wiley
Date: 19-05-2020
Magnetic nanocomposite particles and hollow spheres constructed by a sequential layering approach
Publisher: American Chemical Society (ACS)
Date: 09-12-2001
DOI: 10.1021/CM001164H
Metallodielectric opals of layer-by-layer processed coated colloids
Publisher: Wiley
Date: 16-08-2002
DOI: 10.1002/1521-4095(20020816)14:16<1160::AID-ADMA1160>3.0.CO;2-1
Composite photonic crystals from semiconductor nanocrystal/polyelectrolyte-coated colloidal spheres
Publisher: American Chemical Society (ACS)
Date: 19-06-2003
DOI: 10.1021/CM031003O
Synthesis and functionalization of nanoengineered materials using click chemistry
Publisher: Elsevier BV
Date: 07-2012
Disulfide cross-linked polymer capsules: En route to biodeconstructible systems
Publisher: American Chemical Society (ACS)
Date: 10-12-2006
DOI: 10.1021/BM050832V
Abstract: Hydrogen-bonded multilayer thin films were constructed using poly(vinylpyrrolidone) and poly(methacrylic acid) functionalized with cysteamine. The resulting films included thiol moieties that were cross-linked to render the films stable at physiological pH. Film buildup was followed using quartz crystal microgravimetry, which was also used to demonstrate the improved stability imparted by reacting the thiol moieties to form disulfide bonds. Films without disulfide bonds were readily deconstructed at physiological pH, while those with disulfide bonds were swollen upon exposure to this pH (7) but remained intact. Addition of a common thiol-disulfide exchange reagent, dithiothreitol (DTT) at pH 7 led to disassembly of the multilayer films. The films were also prepared on colloidal substrates (as demonstrated using confocal microscopy) and were used to retain a model drug (fluorescently labeled transferrin) and release this molecule when triggered by the addition of DTT. This approach has potential for the in vivo applications of hollow capsules, as thiol-disulfide exchange leading to deconstruction of the capsules can occur with the assistance of intracellular proteins.
Synthesis of Macroporous Titania and Inorganic Composite Materials from Coated Colloidal SpheresA Novel Route to Tune Pore Morphology
Publisher: American Chemical Society (ACS)
Date: 12-01-2001
DOI: 10.1021/CM001184J
Targeting of cancer cells using click-functionalized polymer capsules
Publisher: American Chemical Society (ACS)
Date: 26-10-2010
DOI: 10.1021/JA106405C
Abstract: Targeted delivery of drugs to specific cells allows a high therapeutic dose to be delivered to the target site with minimal harmful side effects. Combining targeting molecules with nanoengineered drug carriers, such as polymer capsules, micelles and polymersomes, has significant potential to improve the therapeutic delivery and index of a range of drugs. We present a general approach for functionalization of low-fouling, nanoengineered polymer capsules with antibodies using click chemistry. We demonstrate that antibody (Ab)-functionalized capsules specifically bind to colorectal cancer cells even when the target cells constitute less than 0.1% of the total cell population. This precise targeting offers promise for drug delivery applications.
Interfacing materials science and biology for drug carrier design
Publisher: Wiley
Date: 26-02-2015
Abstract: Over the last ten years, there has been considerable research interest in the development of polymeric carriers for biomedicine. Such delivery systems have the potential to significantly reduce side effects and increase the bioavailability of poorly soluble therapeutics. The design of carriers has relied on harnessing specific variations in biological conditions, such as pH or redox potential, and more recently, by incorporating specific peptide cleavage sites for enzymatic hydrolysis. Although much progress has been made in this field, the specificity of polymeric carriers is still limited when compared with their biological counterparts. To synthesize the next generation of carriers, it is important to consider the biological rationale for materials design. This requires a detailed understanding of the cellular microenvironments and how these can be harnessed for specific applications. In this review, several important physiological cues in the cellular microenvironments are outlined, with a focus on changes in pH, redox potential, and the types of enzymes present in specific regions. Furthermore, recent studies that use such biologically inspired triggers to design polymeric carriers are highlighted, focusing on applications in the field of therapeutic delivery.
Investigation of the interactions between ligand-stabilized gold nanoparticles and polyelectrolyte multilayer films
Publisher: American Chemical Society (ACS)
Date: 29-07-2005
DOI: 10.1021/CM050972B
Multicompartment Particle Assemblies for Bioinspired Encapsulated Reactions
Publisher: American Chemical Society (ACS)
Date: 06-10-2011
DOI: 10.1021/JZ200994N
Low-fouling, biospecific films prepared by the continuous assembly of polymers
Publisher: American Chemical Society (ACS)
Date: 10-07-2013
DOI: 10.1021/BM400680D
Abstract: We report that the continuous assembly of polymers (CAP) approach, mediated by ring-opening metathesis polymerization (ROMP), is a facile and versatile technology to prepare engineered nanocoatings for various biomedical applications. Low-fouling coatings on particles were obtained by the formation of multicompositional, layered films via simple and efficient tandem CAP(ROMP) processes that are analogous to chain extension reactions. In addition, the CAP(ROMP) approach allows for the efficient postfunctionalization of the CAP films with bioactive moieties via cross-metathesis reactions between the surface-immobilized catalysts and symmetrical alkene derivatives. The combined features of the CAP(ROMP) approach (i.e., versatile polymer selection and facile functionalization) allow for the fabrication and surface modification of various types of polymer films, including those with intrinsic protein-repellent properties and selective protein recognition capabilities. This study highlights the various types of advanced coatings and materials that the CAP approach can be used to generate, which may be useful for biomedical applications.
Quantitatively Tracking Bio–Nano Interactions of Metal–Phenolic Nanocapsules by Mass Cytometry
Publisher: American Chemical Society (ACS)
Date: 21-07-2021
Luminescent Metal‐Phenolic Networks for Multicolor Particle Labeling
Publisher: Wiley
Date: 18-10-2021
Abstract: The development of fluorescence labeling techniques has attracted widespread interest in various fields, including biomedical science as it can facilitate high‐resolution imaging and the spatiotemporal understanding of various biological processes. We report a supramolecular fluorescence labeling strategy using luminescent metal‐phenolic networks (MPNs) constructed from metal ions, phenolic ligands, and common and commercially available dyes. The rapid labeling process ( min) produces ultrathin coatings (≈10 nm) on erse particles (e.g., organic, inorganic, and biological entities) with customized luminescence (e.g., red, blue, multichromatic, and white light) simply through the selection of fluorophores. The fluorescent coatings are stable at pH values from 1 to 8 and in complex biological media owing to the dominant π interactions between the dyes and MPNs. These coatings exhibit negligible cytotoxicity and their strong fluorescence is retained even when internalized into intracellular compartments. This strategy is expected to provide a versatile approach for fluorescence labeling with potential in erse fields across the physical and life sciences.
Minimum information reporting in bio-nano experimental literature
Publisher: Springer Science and Business Media LLC
Date: 09-2018
Gold nanoparticle-based core-shell and hollow spheres and ordered assemblies thereof
Publisher: American Chemical Society (ACS)
Date: 09-07-2003
DOI: 10.1021/CM031014H
Assembly of Bioactive Nanoparticles via Metal–Phenolic Complexation
Publisher: Wiley
Date: 30-01-2022
Abstract: The integration of bioactive materials (e.g., proteins and genes) into nanoparticles holds promise in fields ranging from catalysis to biomedicine. However, it is challenging to develop a simple and broadly applicable nanoparticle platform that can readily incorporate distinct biomacromolecules without affecting their intrinsic activity. Herein, a metal–phenolic assembly approach is presented whereby erse functional nanoparticles can be readily assembled in water by combining various synthetic and natural building blocks, including poly(ethylene glycol), phenolic ligands, metal ions, and bioactive macromolecules. The assembly process is primarily mediated by metal–phenolic complexes through coordination and hydrophobic interactions, which yields uniform and spherical nanoparticles (mostly nm), while preserving the function of the incorporated biomacromolecules (siRNA and five different proteins used). The functionality of the assembled nanoparticles is demonstrated through cancer cell apoptosis, RNA degradation, catalysis, and gene downregulation studies. Furthermore, the resulting nanoparticles can be used as building blocks for the secondary engineering of superstructures via templating and cross‐linking with metal ions. The bioactivity and versatility of the platform can potentially be used for the streamlined and rational design of future bioactive materials.
Fundamental studies of hybrid poly(2-(diisopropylamino)ethyl methacrylate)/poly(N-vinylpyrrolidone) films and capsules
Publisher: American Chemical Society (ACS)
Date: 27-06-2014
DOI: 10.1021/BM500640T
Abstract: Hybrid and multicompartment carriers are of significant interest for the development of next-generation therapeutic drug carriers. Herein, fundamental investigations on layer-by-layer (LbL) capsules consisting of two different polymers are presented. The hybrid systems were designed to have pH-responsive, charge-shifting poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) inner layers and low-fouling poly(N-vinylpyrrolidone) (PVPON) outer layers. Planar hybrid films with different layer ratios were studied by quartz crystal microgravimetry (QCM) and atomic force microscopy (AFM). The information obtained was translated to particulate templates to prepare hybrid capsules, which were stabilized by click chemistry. The charge-shifting behavior of PDPA improved the cargo encapsulation and initial retention of a model CpG cargo, while outer layers of PVPON improved biofouling properties compared to single-component PDPA capsules. The results demonstrate the need to understand and design multifunctional systems that can successfully embody different functionalities in a single, stable construct for the fabrication of next-generation drug and gene delivery carriers aimed at overcoming the challenges encountered in biological systems.
Polyphenol-Functionalized Cubosomes as Thrombolytic Drug Carriers.
Publisher: Wiley
Date: 13-09-2022
Abstract: The safe administration of thrombolytic agents is a challenge for the treatment of acute thrombosis. Lipid-based nanoparticle drug delivery technologies present opportunities to overcome the existing clinical limitations and deliver thrombolytic therapy with enhanced therapeutic outcomes and safety. Herein, lipid cubosomes are examined as nanocarriers for the encapsulation of thrombolytic drugs. The lipid cubosomes are loaded with the thrombolytic drug urokinase-type plasminogen activator (uPA) and coated with a low-fouling peptide that is incorporated within a metal-phenolic network (MPN). The peptide-containing MPN (pep-MPN) coating inhibits the direct contact of uPA with the surrounding environment, as assessed by an in vitro plasminogen activation assay and an ex vivo whole blood clot degradation assay. The pep-MPN-coated cubosomes prepared with 22 wt% peptide demonstrate a cell membrane-dependent thrombolytic activity, which is attributed to their fusogenic lipid behavior. Moreover, compared with the uncoated lipid cubosomes, the uPA-loaded pep-MPN-coated cubosomes demonstrate significantly reduced nonspecific cell association (<10% of the uncoated cubosomes) in the whole blood assay, a prolonged circulating half-life, and reduced splenic uPA accumulation in mice. These studies confirm the preserved bioactivity and cell membrane-dependent release of uPA within pep-MPN-coated lipid cubosomes, highlighting their potential as a delivery vehicle for thrombolytic drugs.
Triggering the nanophase separation of albumin through multivalent binding to glycogen for drug delivery in 2D and 3D multicellular constructs
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1NR08429A
Abstract: Nanocomplexes of glycogen nanoparticles with serum albumin were formed by triggering the nanophase separation of albumin. The nanocomplexes enabled the delivery of chemotherapeutics in complex multicellular 3D tumour-like structures.
Modular Assembly of Host–Guest Metal–Phenolic Networks Using Macrocyclic Building Blocks
Publisher: Wiley
Date: 13-11-2020
In Situ Characterization of Protein Corona Formation on Silica Microparticles Using Confocal Laser Scanning Microscopy Combined with Microfluidics
Publisher: American Chemical Society (ACS)
Date: 02-01-0008
Abstract: In biological fluids, proteins bind to particles, forming so-called protein coronas. Such adsorbed protein layers significantly influence the biological interactions of particles, both in vitro and in vivo. The adsorbed protein layer is generally described as a two-component system comprising "hard" and "soft" protein coronas. However, a comprehensive picture regarding the protein corona structure is lacking. Herein, we introduce an experimental approach that allows for in situ monitoring of protein adsorption onto silica microparticles. The technique, which mimics flow in vascularized tumors, combines confocal laser scanning microscopy with microfluidics and allows the study of the time-evolution of protein corona formation. Our results show that protein corona formation is kinetically ided into three different phases: phase 1, proteins irreversibly and directly bound (under physiologically relevant conditions) to the particle surface phase 2, irreversibly bound proteins interacting with preadsorbed proteins, and phase 3, reversibly bound "soft" protein corona proteins. Additionally, we investigate particle-protein interactions on low-fouling zwitterionic-coated particles where the adsorption of irreversibly bound proteins does not occur, and on such particles, only a "soft" protein corona is formed. The reported approach offers the potential to define new state-of-the art procedures for kinetics and protein fouling experiments.
Colloid surface engineering via deposition of multilayered thin films from polyelectrolyte blend solutions
Publisher: American Chemical Society (ACS)
Date: 16-04-2005
DOI: 10.1021/LA047156N
Abstract: Multilayer thin films were constructed on polystyrene colloidal particles by depositing alternating layers of poly(allylamine hydrochloride) (PAH) at pH 7.5 and varying composition blends of poly(acrylic acid) (PAA) and poly(styrenesulfonate) (PSS) at pH 3.5. Following the deposition of each layer, microelectrophoresis experiments showed alternating zeta-potentials, suggesting the formation of multilayered films on the particles. Scanning and transmission electron microscopy were used to examine the surface morphology of the colloidal particles, with homogeneous surface coatings apparent for films deposited from PAA/PSS blend solutions containing up to 90 wt % PAA. The colloidal stability of these particles is greater than those coated with in idual PAH and PAA layers. In the case of the blend PAA/PSS = 25:75 wt %, up to 20 layers were assembled without compromising the colloidal stability of the dispersion. The results demonstrate that the deposition of layers from PE blend solutions containing a strong and weak PE can be used as a facile method for controlling the surface properties and hence the colloidal stability of core-shell particles, as well as the thickness and morphology of the coatings. Control of these parameters is important for subsequent processing and application of these particles in controlled delivery, photonics, catalytic, and separation applications.
Assembly of ultrathin polymer multilayer films by click chemistry
Publisher: American Chemical Society (ACS)
Date: 28-06-2006
DOI: 10.1021/JA063043+
Abstract: Layer-by-layer (LbL) assembly is a versatile and robust technique for fabricating tailored thin films of erse composition. Herein we report a new method of covalent coupling, click chemistry, to facilitate the LbL assembly of thin films. Linear film growth was observed using both UV-vis and FTIR spectroscopy, and film thicknesses were determined by ellipsometry and atomic force microscopy. The assembled films are shown to be stable in a wide pH range. This technique offers the potential to enable the synthesis of new types of stable and responsive LbL films from a variety of polymers.
Growth of multilayer films of fixed and variable charge density polyelectrolytes: Effect of mutual charge and secondary interactions
Publisher: American Chemical Society (ACS)
Date: 20-06-2003
DOI: 10.1021/MA034018G
DETERMINATION OF LATERAL DIFFUSION-COEFFICIENTS IN AIR WATER MONOLAYERS BY FLUORESCENCE QUENCHING MEASUREMENTS
Publisher: American Chemical Society (ACS)
Date: 06-1991
DOI: 10.1021/JA00013A019
Capsosomes: Subcompartmentalizing Polyelectrolyte Capsules Using Liposomes
Publisher: American Chemical Society (ACS)
Date: 16-06-2009
DOI: 10.1021/LA900213A
Abstract: Next-generation therapeutic approaches are expected to rely on the engineering of multifunctional particle carriers that can mimic specific cellular functions. The key features of such particles are the semipermeable nature of the shell for communication with the external environment and multiple nanosized in idual subcompartments confined within a micron-sized structurally stable scaffold for conducting specific reactions. Herein, we report the formation of capsosomes, a new class of polyelectrolyte capsules containing structurally intact liposomes as cargo. The multilayer film assembly of polyelectrolytes (poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH)) and liposomes (50 nm 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC)) was characterized on planar substrates using quartz crystal microbalance with dissipation monitoring, and these findings were then correlated to the film growth of the polyelectrolytes and structurally intact liposomes on silica particles. Upon removal of the silica template core, stable capsosomes, containing one or two layers of intact liposomes as cargo, were obtained. This novel platform, capsosomes, which combines the advantages of two systems, liposomes and polyelectrolyte capsules, is expected to find erse applications in biomedicine, in particular for the creation of artificial cells or organelles where the performance of reactions within a confined environment is a prerequisite.
Disulfide-stabilized poly(methacrylic acid) capsules: Formation, cross-linking, and degradation behavior
Publisher: American Chemical Society (ACS)
Date: 15-03-2008
DOI: 10.1021/CM703403P
Advancing Research Using Action Cameras
Publisher: American Chemical Society (ACS)
Date: 13-12-2016
Triggered Cargo Release by Encapsulated Enzymatic Catalysis in Capsosomes
Publisher: American Chemical Society (ACS)
Date: 12-10-2011
DOI: 10.1021/NL202906J
Abstract: We report the coencapsulation of glutathione reductase and disulfide-linked polymer-oligopeptide conjugates into capsosomes, polymer carrier capsules containing liposomal subcompartments. The architecture of the capsosomes enables a temperature-triggered conversion of oxidized glutathione to its reduced sulfhydryl form by the encapsulated glutathione reductase. The reduced glutathione subsequently induces the release of the encapsulated oligopeptides from the capsosomes by reducing the disulfide linkages of the conjugates. This study highlights the potential of capsosomes to continuously generate a potent antioxidant while simultaneously releasing small molecule therapeutics.
Enzyme encapsulation in nanoporous silica spherest
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B403871A
Abstract: Encapsulating enzymes in mesoporous silica spheres via immobilization, followed by assembling an organic/inorganic nanocomposite shell on the particle surface leads to high loadings, high enzymatic activity and stability, and protection from proteolysis.
Click-engineered, bioresponsive, drug-loaded PEG spheres
Publisher: Wiley
Date: 20-11-2009
Abstract: A click-chemistry approach to synthesize bioresponsive poly(ethylene glycol acrylate) particles is described. The particles are loaded with a model anticancer drug (doxorubicin, DOX), and undergo simultaneous particle deconstruction and DOX release upon specific activation by the simulated environment of the cellular cytoplasm.
Spray Assembly of Metal-Phenolic Networks: Formation, Growth, and Applications
Publisher: American Chemical Society (ACS)
Date: 21-09-2018
Abstract: Hybrid conformal coatings, such as metal-phenolic networks (MPNs) that are constructed from the coordination-driven assembly of natural phenolic ligands, are of interest in areas including biomedicine, separations, and energy. To date, most MPN coatings have been prepared by immersing substrates in solutions containing the phenolic ligands and metal ions, which is a suitable method for coating small or flexible objects. In contrast, more industrially relevant methods for coating and patterning large substrates, such as spray assembly, have been explored to a lesser extent toward the fabrication of MPNs, particularly regarding the effect of process variables on MPN growth. Herein, a spray assembly method was used to fabricate MPN coatings with various phenolic building blocks and metal ions and their formation and patterning were explored for different applications. Different process parameters including solvent, pH, and metal-ligand pair allowed for control over the film properties such as thickness and roughness. On the basis of these investigations, a potential route for the formation of spray-assembled MPN films was proposed. Conditions favoring the formation of bis complexes could produce thicker coatings than those favoring the formation of mono or tris complexes. Finally, the spray-assembled MPNs were used to generate superhydrophilic membranes for oil-water separation and colorless films for UV shielding. The present study provides insights into the chemistry of MPN assembly and holds promise for advancing the fabrication of multifunctional hybrid materials.
Hollow titania spheres from layered precursor deposition on sacrificial colloidal core particles
Publisher: Wiley
Date: 05-2001
DOI: 10.1002/1521-4095(200105)13:10<740::AID-ADMA740>3.0.CO;2-6
Nanoscale probing and imaging of HIV-1 RNA in cells with a chimeric LNA–DNA sensor
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1NR08418F
Abstract: A chimeric locked nucleic acid (LNA)–DNA sensor enables hybridization chain reaction (HCR) for the efficient detection and nanoscale imaging of HIV-1 RNA transcripts in cell lysates, and fixed and live cells.
Innovation in Layer-by-Layer Assembly
Publisher: American Chemical Society (ACS)
Date: 23-11-2016
DOI: 10.1021/ACS.CHEMREV.6B00627
Abstract: Methods for depositing thin films are important in generating functional materials for erse applications in a wide variety of fields. Over the last half-century, the layer-by-layer assembly of nanoscale films has received intense and growing interest. This has been fueled by innovation in the available materials and assembly technologies, as well as the film-characterization techniques. In this Review, we explore, discuss, and detail innovation in layer-by-layer assembly in terms of past and present developments, and we highlight how these might guide future advances. A particular focus is on conventional and early developments that have only recently regained interest in the layer-by-layer assembly field. We then review unconventional assemblies and approaches that have been gaining popularity, which include inorganic/organic hybrid materials, cells and tissues, and the use of stereocomplexation, patterning, and dip-pen lithography, to name a few. A relatively recent development is the use of layer-by-layer assembly materials and techniques to assemble films in a single continuous step. We name this "quasi"-layer-by-layer assembly and discuss the impacts and innovations surrounding this approach. Finally, the application of characterization methods to monitor and evaluate layer-by-layer assembly is discussed, as innovation in this area is often overlooked but is essential for development of the field. While we intend for this Review to be easily accessible and act as a guide to researchers new to layer-by-layer assembly, we also believe it will provide insight to current researchers in the field and help guide future developments and innovation.
Surface-Initiated Polymerization within Mesoporous Silica Spheres for the Modular Design of Charge-Neutral Polymer Particles
Publisher: American Chemical Society (ACS)
Date: 16-05-2014
DOI: 10.1021/LA501324R
Abstract: We report a templating approach for the preparation of functional polymer replica particles via surface-initiated polymerization in mesoporous silica templates. Subsequent removal of the template resulted in discrete polymer particles. Furthermore, redox-responsive replica particles could be engineered to disassemble in a reducing environment. Particles, made of poly(methacryloyloxyethyl phosphorylcholine) (PMPC) or poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA), exhibited very low association to human cancer cells (below 5%), which renders the reported charge-neutral polymer particles a modular and versatile class of highly functional carriers with potential applications in drug delivery.
Assembly and degradation of low-fouling click-functionalized poly(ethylene glycol)-based multilayer films and capsules
Publisher: Wiley
Date: 21-03-2011
Abstract: Nano-/micrometer-scaled films and capsules made of low-fouling materials such as poly(ethylene glycol) (PEG) are of interest for drug delivery and tissue engineering applications. Herein, the assembly and degradation of low-fouling, alkyne-functionalized PEG (PEG(Alk) ) multilayer films and capsules, which are prepared by combining layer-by-layer (LbL) assembly and click chemistry, are reported. A nonlinear, temperature-responsive PEG(Alk) is synthesized, and is then used to form hydrogen-bonded multilayers with poly(methacrylic acid) (PMA) at pH 5. The thermoresponsive behavior of PEG(Alk) is exploited to tailor film buildup by adjusting the assembly conditions. Using alkyne-azide click chemistry, PEG(Alk)/PMA multilayers are crosslinked with a bisazide linker that contains a disulfide bond, rendering these films and capsules redox-responsive. At pH 7, by disrupting the hydrogen bonding between the polymers, PEG(Alk) LbL films and PEG(Alk) -based capsules are obtained. These films exhibit specific deconstruction properties under simulated intracellular reducing conditions, but remain stable at physiological pH, suggesting potential applications in controlled drug release. The low-fouling properties of the PEG films are confirmed by incubation with human serum and a blood clot. Additionally, these capsules showed negligible toxicity to human cells.
Quantum measurement and orientation tracking of fluorescent nanodiamonds inside living cells
Publisher: Springer Science and Business Media LLC
Date: 08-05-2011
Abstract: Fluorescent particles are routinely used to probe biological processes. The quantum properties of single spins within fluorescent particles have been explored in the field of nanoscale magnetometry, but not yet in biological environments. Here, we demonstrate optically detected magnetic resonance of in idual fluorescent nanodiamond nitrogen-vacancy centres inside living human HeLa cells, and measure their location, orientation, spin levels and spin coherence times with nanoscale precision. Quantum coherence was measured through Rabi and spin-echo sequences over long (>10 h) periods, and orientation was tracked with effective 1° angular precision over acquisition times of 89 ms. The quantum spin levels served as fingerprints, allowing in idual centres with identical fluorescence to be identified and tracked simultaneously. Furthermore, monitoring decoherence rates in response to changes in the local environment may provide new information about intracellular processes. The experiments reported here demonstrate the viability of controlled single spin probes for nanomagnetometry in biological systems, opening up a host of new possibilities for quantum-based imaging in the life sciences.
Modulating Targeting of Poly(ethylene glycol) Particles to Tumor Cells Using Bispecific Antibodies
Publisher: Wiley
Date: 14-03-2019
Abstract: Low-fouling or "stealth" particles composed of poly(ethylene glycol) (PEG) display a striking ability to evade phagocytic cell uptake. However, functionalizing them for specific targeting is challenging. To address this challenge, stealth PEG particles prepared by a mesoporous silica templating method are functionalized with bispecific antibodies (BsAbs) to obtain PEG-BsAb particles via a one-step binding strategy for cell and tumor targeting. The dual specificity of the BsAbs-one arm binds to the PEG particles while the other targets a cell antigen (epidermal growth factor receptor, EGFR)-is exploited to modulate the number of targeting ligands per particle. Increasing the BsAb incubation concentration increases the amount of BsAb tethered to the PEG particles and enhances targeting and internalization into breast cancer cells overexpressing EGFR. The degree of BsAb functionalization does not significantly reduce the stealth properties of the PEG particles ex vivo, as assessed by their interactions with primary human blood granulocytes and monocytes. Although increasing the BsAb amount on PEG particles does not lead to the expected improvement in tumor accumulation in vivo, BsAb functionalization facilitates tumor cell uptake of PEG particles. This work highlights strategies to balance evading nonspecific clearance pathways, while improving tumor targeting and accumulation.
The mechanical regulation of RNA binding protein hnRNPC in the failing heart
Publisher: Cold Spring Harbor Laboratory
Date: 28-08-2021
DOI: 10.1101/2021.08.27.457906
Abstract: Cardiac pathologies are characterized by intense remodeling of the extracellular matrix (ECM) that eventually leads to heart failure. Cardiomyocytes respond to the ensuing biomechanical stress by re-expressing fetal contractile proteins via transcriptional and post-transcriptional processes, like alternative splicing (AS). Here, we demonstrate that the heterogeneous nuclear ribonucleoprotein C (hnRNPC) is upregulated and relocates to the sarcomeric Z-disk upon ECM pathological remodeling. We show that this is an active site of localized translation, where the ribonucleoprotein associates to the translation machinery. Alterations in hnRNPC expression and localization can be mechanically determined and affect the AS of numerous mRNAs involved in mechanotransduction and cardiovascular diseases, like Hippo pathway effector YAP1. We propose that cardiac ECM remodeling serves as a switch in RNA metabolism by impacting an associated regulatory protein of the spliceosome apparatus. These findings offer new insights on the mechanism of mRNAs homeostasis mechanoregulation in pathological conditions.
Converging layer-by-layer polyelectrolyte microcapsule and cubic lyotropic liquid crystalline nanoparticle approaches for molecular encapsulation
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0SM01410A
Nanoengineered Templated Polymer Particles: Navigating the Biological Realm
Publisher: American Chemical Society (ACS)
Date: 20-05-2016
DOI: 10.1021/ACS.ACCOUNTS.6B00088
Abstract: Nanoengineered materials offer tremendous promise for developing the next generation of therapeutics. We are transitioning from simple research questions, such as "can this particle eradicate cancer cells?" to more sophisticated ones like "can we design a particle to preferentially deliver cargo to a specific cancer cell type?" These developments are poised to usher in a new era of nanoengineered drug delivery systems. We primarily work with templating methods for engineering polymer particles and investigate their biological interactions. Templates are scaffolds that facilitate the formation of particles with well-controlled size, shape, structure, stiffness, stability, and surface chemistry. In the past decade, breakthroughs in engineering new templates, combined with advances in coating techniques, including layer-by-layer (LbL) assembly, surface polymerization, and metal-phenolic network (MPN) coordination chemistry, have enabled particles with specific physicochemical properties to be engineered. While materials science offers an ever-growing number of new synthesis techniques, a central challenge of therapeutic delivery has become understanding how nanoengineered materials interact with biological systems. Increased collaboration between chemists, biologists, and clinicians has resulted in a vast research output on bio-nano interactions. Our understanding of cell-particle interactions has grown considerably, but conventional in vitro experimentation provides limited information, and understanding how to bridge the in vitro/in vivo gap is a continuing challenge. As has been demonstrated in other fields, there is now a growing interest in applying computational approaches to advance this area. A considerable knowledge base is now emerging, and with it comes new and exciting opportunities that are already being capitalized on through the translation of materials into the clinic. In this Account, we outline our perspectives gained from a decade of work at the interface between polymer particle engineering and bio-nano interactions. We ide our research into three areas: (i) biotrafficking, including cellular association, intracellular transport, and biodistribution (ii) biodegradation and how to achieve controlled, responsive release of therapeutics and (iii) applications, including drug delivery, controlling immunostimulatory responses, biosensing, and microreactors. There are common challenges in these areas for groups developing nanoengineered therapeutics. A key "lesson-learned" has been the considerable challenge of staying informed about the developments relevant to this field. There are a number of reasons for this, most notably the interdisciplinary nature of the work, the large numbers of researchers and research outputs, and the limited standardization in technique nomenclature. Additionally, a large body of work is being generated with limited central archiving, other than vast general databases. To help address these points, we have created a web-based tool to organize our past, present, and future work [Bio-nano research knowledgebase, bionano.eng.unimelb.edu.au/knowledge_base/ (accessed May 2, 2016)]. This tool is intended to serve as a first step toward organizing results in this large, complex area. We hope that this will inspire researchers, both in generating new ideas and also in collecting, collating, and sharing their experiences to guide future research.
Origins of Structural Elasticity in Metal-Phenolic Networks Probed by Super-Resolution Microscopy and Multiscale Simulations
Publisher: American Chemical Society (ACS)
Date: 29-11-2022
Abstract: Metal-phenolic networks (MPNs) are amorphous materials that can be used to engineer functional films and particles. A fundamental understanding of the heat-driven structural reorganization of MPNs can offer opportunities to rationally tune their properties ( e . g ., size, permeability, wettability, hydrophobicity) for applications such as drug delivery, sensing, and tissue engineering. Herein, we use a combination of single-molecule localization microscopy, theoretical electronic structure calculations, and all-atom molecular dynamics simulations to demonstrate that MPN plasticity is governed by both the inherent flexibility of the metal (Fe III )-phenolic coordination center and the conformational elasticity of the phenolic building blocks (tannic acid, TA) that make up the metal-organic coordination complex. Thermal treatment (heating to 150 °C) of the flexible TA/Fe III networks induces a considerable increase in the number of aromatic π-π interactions formed among TA moieties and leads to the formation of hydrophobic domains. In the case of MPN capsules, 15 min of heating induces structural rearrangements that cause the capsules to shrink (from ∼4 to ∼3 μm), resulting in a thicker (3-fold), less porous, and higher protein ( e.g. , bovine serum albumin) affinity MPN shell. In contrast, when a simple polyphenol such as gallic acid is complexed with Fe III to form MPNs, rigid materials that are insensitive to temperature changes are obtained, and negligible structural rearrangement is observed upon heating. These findings are expected to facilitate the rational engineering of versatile TA-based MPN materials with tunable physiochemical properties for erse applications.
Synthesis, multilayer film assembly, and capsule formation of macromolecularly engineered acrylic acid and styrene sulfonate block copolymers
Publisher: American Chemical Society (ACS)
Date: 19-07-2008
DOI: 10.1021/LA8011074
Abstract: We report the use of copolymers synthesized with specific block ratios of weakly and strongly charged groups for the preparation of stable, pH-responsive multilayers. In this study, we utilized reversible addition-fragmentation chain transfer (RAFT) polymerization in the synthesis of novel pH-sensitive copolymers comprising block domains of acrylic acid (AA) and styrene sulfonate (SS) groups. The PAA x- b-SS y copolymers, containing 37%, 55%, and 73% of AA groups by mass (denoted as PAA 37- b-SS 63, PAA 55- b-SS 45, and PAA 73- b-SS 27, respectively), were utilized to perform stepwise multilayer assembly in alternation with poly(allylamine hydrochloride), PAH. The ratio of AA to SS groups, and the effect of the pH of both anionic and cationic adsorption solutions, on multilayer properties, were investigated using ellipsometry and atomic force microscopy. The presence of SS moieties in the PAA x- b-SS y copolymers, regardless of the precise composition, lead to films with a relatively consistent thickness. Exposure of these multilayers to acidic conditions postassembly revealed that these multilayers do not exhibit the characteristic large swelling that occurs with PAA/PAH films. The film stability was attributed to the presence of strongly charged SS groups. PAA x- b-SS y/PAH films were also formed on particle substrates under various adsorption conditions. Microelectrophoresis measurements revealed that the surface charge and isoelectric point of these core-shell particles are dependent on assembly pH and the proportion of AA groups in PAA x- b-SS y. These core-shell particles can be used as precursors to hollow capsules that incorporate weak polyelectrolyte functionality. The role of AA groups in determining the growth profile of these capsules was also examined. The multilayer films prepared may find applications in areas where pH-responsive films are required but large film swelling is unfavorable.
Fluorescence Studies of the Binding of Anionic Derivatives of Pyrene and Fluorescein to Cationic Polyelectrolytes in Aqueous Solution
Publisher: American Chemical Society (ACS)
Date: 10-1998
DOI: 10.1021/MA980538D
Gold-silica inverse opals by colloidal crystal templating
Publisher: Wiley
Date: 18-06-2002
DOI: 10.1002/1521-4095(20020618)14:12<908::AID-ADMA908>3.0.CO;2-1
Poly(L-lysine) nanostructured particles for gene delivery and hormone stimulation
Publisher: Elsevier BV
Date: 03-2010
DOI: 10.1016/J.BIOMATERIALS.2009.11.032
Abstract: In this work, we designed replica particles based on poly (L-lysine) (PLL) polymers crosslinked via a homobifunctional linker to support coadsorption of a plasmid DNA and a peptide hormone for concurrent transfection and induction of a cellular function. PLL replica particles (PLL(RP)) were prepared by infiltrating polymer into mesoporous silica (MS) particles, crosslinking the adsorbed chains by using a homobifunctional crosslinker and finally removing the template particles. Moreover, we verified their cytotoxicity. Furthermore, based on this PLL(RP) gene delivery system, we simultaneously evaluated the melanin stimulation and gene expression in these cells by fluorescence microscopy. To further understand the bi-functionality, we labeled the SPT7pTL and PGA-alpha-MSH with YOYO-1 and Rhodamine, respectively, to follow its intracellular pathway by confocal microscopy. Our data suggests that the PLL(RP) is a promising vector for gene therapy and hormone stimulation.
Tailoring the Polyelectrolyte Coating of Metal Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 27-06-2001
DOI: 10.1021/JP0111665
Preparation and Organization of Nanoscale Polyelectrolyte-Coated Gold Nanoparticles
Publisher: Wiley
Date: 04-03-2003
Surface-Confined Amorphous Films from Metal-Coordinated Simple Phenolic Ligands.
Publisher: American Chemical Society (ACS)
Date: 06-08-2015
Assembly of free-standing polypeptide films via the synergistic combination of hyperbranched macroinitiators, the grafting-from approach, and cross-chain termination
Publisher: Wiley
Date: 31-05-2013
Abstract: Cross-linked polypeptide-based films are fabricated via a novel and robust method employing surface-initiated ring opening polymerization of α-amino acid N-carboxyanhydrides (NCA-ROP). The judicious combination of amine-based hyperbranched macroinitiators and benzyl ester-protected NCA derivatives promotes network formation by cross-chain terminations, which allows the formation of stable cross-linked peptide-based capsules in a one-pot system.
Triggered Enzymatic Degradation of DNA within Selectively Permeable Polymer Capsule Microreactors
Publisher: Wiley
Date: 22-12-2009
Poly(vinylpyrrolidone) for bioconjugation and surface ligand immobilization
Publisher: American Chemical Society (ACS)
Date: 23-08-2007
DOI: 10.1021/BM700498J
Abstract: Poly(vinylpyrrolidone) (PVP), a nonionic and nontoxic polymer with antifouling properties, has been synthesized via RAFT polymerization to obtain thiol-terminated PVP. We demonstrate that when the polymer is adsorbed onto the surface of colloidal silica particles, the terminal thiol groups of PVP remain accessible for chemical modification and lend themselves to the immobilization of ligands. We show that ligand attachment onto the surface via conjugation to PVP is reversible, as the polymer can be desorbed from the surface for conjugate and surface recovery. We present the conjugation of a model peptide and an oligonucleotide to PVP via the polymer terminal thiol and demonstrate that conjugates remain functional in molecular recognition assay. The developed technique offers a novel method to functionalize low-fouling surfaces for a variety of biomedical applications and presents opportunities to use PVP as a macromolecular drug carrier.
Synthesis of Customizable Macromolecular Conjugates as Building Blocks for Engineering Metal–Phenolic Network Capsules with Tailorable Properties
Publisher: American Chemical Society (ACS)
Date: 29-10-2021
Emerging methods for the fabrication of polymer capsules
Publisher: Elsevier BV
Date: 05-2014
DOI: 10.1016/J.CIS.2013.10.012
Abstract: Hollow polymer capsules are attracting increasing research interest due to their potential application as drug delivery vectors, sensors, biomimetic nano- or multi-compartment reactors and catalysts. Thus, significant effort has been directed toward tuning their size, composition, morphology, and functionality to further their application. In this review, we provide an overview of emerging techniques for the fabrication of polymer capsules, encompassing: self-assembly, layer-by-layer assembly, single-step polymer adsorption, bio-inspired assembly, surface polymerization, and ultrasound assembly. These techniques can be applied to prepare polymer capsules with erse functionality and physicochemical properties, which may fulfill specific requirements in various areas. In addition, we critically evaluate the challenges associated with the application of polymer capsules in drug delivery systems.
Multilayer thin films based on polyelectrolyte-complex nanoparticles
Publisher: Elsevier BV
Date: 07-2002
Bioinspired colloidal systems via layer-by-layer assembly
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B511930H
Formation of Polyrotaxane Particles via Template Assembly
Publisher: American Chemical Society (ACS)
Date: 15-06-2017
DOI: 10.1021/ACS.BIOMAC.7B00450
Abstract: In this study, we report a versatile method to assemble tunable poly(ethylene glycol) (PEG)-based polyrotaxane (PRX) particles and capsules. By threading α-cyclodextrins (αCDs) onto PEG chains physically adsorbed onto template particles and subsequently dissolving the templates, PRX replica particles and hollow capsules are formed. This approach overcomes issues related to CD steric hindrance, and also reduces the multiple processing steps often associated with PRX-based particle formation. By simple variation of the molecular weight and end-group functionality of the PEG, we show that the rate of particle degradation as well as the stability of the particles can be tuned. We also demonstrate the loading and release of model (drug) compounds, achieving burst and controlled release of the compounds. It is envisaged that this approach will provide a flexible platform for the engineering of a erse range of PRX-based particles, enabling PRX materials to be further explored in various applications.
Engineering Flexible Metal‐Phenolic Networks with Guest Responsiveness via Intermolecular Interactions
Publisher: Wiley
Date: 24-03-2023
Abstract: Flexible metal‐organic materials are of growing interest owing to their ability to undergo reversible structural transformations under external stimuli. Here, we report flexible metal‐phenolic networks (MPNs) featuring stimuli‐responsive behavior to erse solute guests. The competitive coordination of metal ions to phenolic ligands of multiple coordination sites and solute guests (e.g., glucose) primarily determines the responsive behavior of the MPNs, as revealed experimentally and computationally. Glucose molecules can be embedded into the dynamic MPNs upon mixing, leading to the reconfiguration of the metal‐organic networks and thus changes in their physicochemical properties for targeting applications. This study expands the library of stimuli‐responsive flexible metal‐organic materials and the understanding of intermolecular interactions between metal‐organic materials and solute guests, which is essential for the rational design of responsive materials for various applications.
High activity enzyme microcrystal multilayer films
Publisher: American Chemical Society (ACS)
Date: 27-07-2001
DOI: 10.1021/JA015807L
1. Ultrathin Multilayer Polyelectrolyte Films on Gold: Construction and Thickness Determination
Publisher: American Chemical Society (ACS)
Date: 06-1997
DOI: 10.1021/LA960821A
Homogeneous, competitive fluorescence quenching immunoassay based on gold nanoparticle/polyelectrolyte coated latex particles
Publisher: American Chemical Society (ACS)
Date: 10-2005
DOI: 10.1021/JP052748F
Abstract: This study reports a homogeneous and competitive fluorescence quenching immunoassay based on gold nanoparticle olyelectrolyte (Au(NP)/PE) coated latex particles prepared by the layer-by-layer (LbL) technique. First, the resonant energy transfer from a layer of fluorescent PEs to Au(NP) in LbL assembled films on planar substrates was investigated. The quenching efficiency (QE) for the planar films depended on the cube of the distance between the two layers. A QE of 50% was achieved at a distance of ca. 15 nm, indicating that the Au(NP)/PE system is suitable for detecting binding/release events for antibodies. A homogeneous, competitive binding immunoassay for biotin was designed based on Au(NP)/PE-coated polystyrene particles of 488 nm diameter as quenching agents for a fluorescein isothiocyanate labeled anti-biotin immunoglobulin (FITC-anti-biotin IgG). Biotin molecules were localized on the Au(NP)/PE-coated latexes by depositing a layer of biotinylated poly(allylamine hydrochloride) (B-PAH), and FITC-anti-biotin IgGs were subsequently bound to the particles through interaction with the biotin on B-PAH. Transmission electron microscopy and quartz crystal microgravimetry confirmed the multilayer formation on latex particles and planar gold surfaces, respectively. The biotin-functionalized Au(NP)/PE-coated latexes terminated by FITC-anti-biotin IgG exhibited a dynamic sensing range of 1-50 nmol. These results indicate that Au(NP)/PE-coated latexes can be readily used as dynamic range tunable sensors.
Cell-Conditioned Protein Coronas on Engineered Particles Influence Immune Responses
Publisher: American Chemical Society (ACS)
Date: 11-01-2017
DOI: 10.1021/ACS.BIOMAC.6B01545
Abstract: A protein corona, which forms on engineered particles as soon as they are introduced into biological environments, is known to provide particles with a "biological identity". Protein coronas derived from various biological environments have been demonstrated to alter the cell internalization mechanism, to diminish targeting ability and to induce nanoparticle aggregation. So far, most of these studies have challenged engineered particles with a static biological environment. However, the extracellular environment is highly dynamic due to the process termed "cell-conditioning", in which cells deplete and secrete biomolecules. In this work, we demonstrate that protein coronas formed on engineered particles from such cell-conditioned media affect the biophysical particle properties and protein adsorption differently to protein coronas derived from an unconditioned environment. When investigating particles with protein coronas formed in various biologically relevant environments for their interaction with immune cells, we observed differences in pro-inflammatory cytokine secretion and immune cell apoptosis. We found that the particles either increased or mitigated the secretion of a specific cytokine, depending on the environment where the protein corona was formed. Our study suggests that the use of protein coronas could be useful to engineer drug carriers for elongated circulation, enhanced biocompatibility, and lower toxicity by triggering a specific immune response.
Tailoring the Chain Packing in Ultrathin Polyelectrolyte Films Formed by Sequential Adsorption: Nanoscale Probing by Positron Annihilation Spectroscopy
Publisher: American Chemical Society (ACS)
Date: 21-11-2012
DOI: 10.1021/JA308716V
Abstract: Depth profiling experiments by positron annihilation spectroscopy have been used to investigate the free volume element size and concentration in films assembled using the layer-by-layer (LbL) adsorption method. Films prepared from strong polyelectrolytes, weak polyelectrolytes, hydrogen-bonding polymers, and blended polyelectrolyte multilayers have different chain packing that is reflected in the free volume characteristics. The influence of various parameters on free volume, such as number of bilayers, salt concentration, solution pH, and molecular weight, has been systematically studied. The free volume cavity diameters vary from 4 to 6 Å, and the free volume concentrations vary from (1.1-4.3) × 10(20) cm(-3), depending on the choice of assembly polymers and conditions. Films assembled from strong polyelectrolytes have fewer free volume cavities with a larger average size than films prepared from weak polyelectrolytes. Blending the weak polyanion poly(acrylic acid), PAA, with the strong polyanion poly(styrene sulfonate), PSS, to layer alternately with the polycation poly(allyamine hydrochloride), PAH, is shown to be a viable method to achieve intermediate free volume characteristics in these LbL films. An increase in salt concentration of the adsorption solutions for films prepared from strong polyelectrolytes makes these films tend toward weaker polyelectrolyte free volume characteristics. Hydrogen-bonded layered films show larger free volume element size and concentration than do their electrostatically bonded counterparts, while reducing the molecular weight of these hydrogen-bonded polymers results in slightly reduced free volume size and concentration. A study of the effect of solution pH on films prepared from weak polyelectrolytes shows that when both polyelectrolytes are substantially charged in solution (assembly pH = 7.5), the chains pack similarly to strong polyelectrolytes (i.e., lower free volume concentration), but with smaller average cavity sizes. These results give, for the first time, a clear indication of how the free volume profile develops in LbL thin films, offering numerous methods to tailor the Ångström-scale free volume properties by judicious selection of the assembly polymers and conditions. These findings can be potentially exploited to tailor the properties of thin polymer films for applications spanning membranes, sensing, and drug delivery.
Monodisperse Polymer Capsules: Tailoring Size, Shell Thickness, and Hydrophobic Cargo Loading via Emulsion Templating
Publisher: Wiley
Date: 25-05-2010
Immersive Polymer Assembly on Immobilized Particles for Automated Capsule Preparation
Publisher: Wiley
Date: 07-10-2013
Abstract: We report a versatile approach for polymer capsule preparation using immobilized particles, which are immersed into polymer solutions either manually or by using an automated robotic dipping machine. This technique produces polyelectrolyte capsules with improved retention over conventionally prepared capsules. Additionally, responsive hydrogel capsules of different diameter can be prepared simultaneously.
Ag Nanoparticle/Polydopamine-Coated Inverse Opals as Highly Efficient Catalytic Membranes
Publisher: American Chemical Society (ACS)
Date: 27-01-2016
Abstract: Polymeric three-dimensional inverse-opal (IO) structures provide unique structural properties useful for various applications ranging from optics to separation technologies. Despite vast needs for IO functionalization to impart additional chemical properties, this task has been seriously challenged by the intrinsic limitation of polymeric porous materials that do not allow for the easy penetration of waterborne moieties or precursors. To overcome this restriction, we present a robust and straightforward method of employing a dipping-based surface modification with polydopamine (PDA) inside the IO structures, and demonstrate their application to catalytic membranes via synthetic incorporation of Ag nanoparticles. The PDA coating offers simultaneous advantages of achieving the improved hydrophilicity required for the facilitated infiltration of aqueous precursors and successful creation of nucleation sites for a reduction of growth of the Ag nanoparticles. The resulting Ag nanoparticle-incorporated IO structures are utilized as catalytic membranes for the reduction of 4-nitrophenol to its amino derivatives in the presence of NaBH4. Synergistically combined characteristics of high reactivity of Ag nanoparticles along with a greatly enhanced internal surface area of IO structures enable the implementation of remarkably improved catalytic performance, exhibiting a good conversion efficiency greater than 99% while minimizing loss in the membrane permeability.
2. Assembly of Alternating Polyelectrolyte and Protein Multilayer Films for Immunosensing
Publisher: American Chemical Society (ACS)
Date: 06-1997
DOI: 10.1021/LA9608223
Surface interactions during polyelectrolyte multilayer build-up. 2. The effect of ionic strength on the structure of preformed multilayers
Publisher: American Chemical Society (ACS)
Date: 31-03-2006
DOI: 10.1021/LA052946Y
Abstract: Interactions between surfaces bearing multilayer films of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) were investigated across a range of aqueous KBr solutions. Three layer films (PAH/PSS/PAH) were preassembled on mica surfaces, and the resulting interactions were measured with the interferometric surface force apparatus (SFA). Increasing the ionic strength of the medium resulted in a progressive swelling of the multilayer films. Interactions in solutions containing more than 10(-3) M KBr were dominated by a long-ranged steric repulsion originating from compression of polyelectrolyte segments extending into solution. In 10(-1) M KBr, repeated measurements at the same contact position showed a considerable reduction of the range and the strength of the steric force, indicating a flattening of the film during initial approach. Furthermore, this flattening was irreversible on the time scale of the experiments, and measurements performed up to 72 h after the initial compression showed no signs of relaxation. These studies aid in understanding the dominant interactions between polyelectrolyte multilayers, including polyelectrolyte films deposited on colloidal particles, which is important for the preparation of colloidally stable nanoengineered particles.
Self-Assembly of a Metal-Phenolic Sorbent for Broad-Spectrum Metal Sequestration
Publisher: American Chemical Society (ACS)
Date: 08-01-2020
Abstract: Metal contamination of water bodies from industrial effluents presents a global threat to the aquatic ecosystem. To address this challenge, metal sequestration via adsorption onto solid media has been explored extensively. However, existing sorbent systems typically involve energy-intensive syntheses and are applicable to a limited range of metals. Herein, a sorbent system derived from physically cross-linked polyphenolic networks using tannic acid and Zr
The Future of Layer-by-Layer Assembly: A Tribute to ACS Nano Associate Editor Helmuth Möhwald
Publisher: American Chemical Society (ACS)
Date: 24-05-2019
Abstract: Layer-by-layer (LbL) assembly is a widely used tool for engineering materials and coatings. In this Perspective, dedicated to the memory of ACS Nano associate editor Prof. Dr. Helmuth Möhwald, we discuss the developments and applications that are to come in LbL assembly, focusing on coatings, bulk materials, membranes, nanocomposites, and delivery vehicles.
Lithium Niobate Inverse Opals Prepared by Templating Colloidal Crystals of Polyelectrolyte-Coated Spheres
Publisher: Wiley
Date: 05-02-2003
Microencapsulation of Uncharged Low Molecular Weight Organic Materials by Polyelectrolyte Multilayer Self-Assembly †
Publisher: American Chemical Society (ACS)
Date: 17-08-2000
DOI: 10.1021/LA000401S
Tunable UV-Responsive Organic−Inorganic Hybrid Capsules
Publisher: American Chemical Society (ACS)
Date: 30-12-2009
DOI: 10.1021/CM802873F
Phase transfer of surface-modified gold nanoparticles by hydrophobization with alkylamines
Publisher: American Chemical Society (ACS)
Date: 21-06-2003
DOI: 10.1021/LA034018+
A Partially Graphitic Mesoporous Carbon Membrane with Three-Dimensionally Networked Nanotunnels for Ultrasensitive Electrochemical Detection
Publisher: American Chemical Society (ACS)
Date: 08-06-2017
Metal Ion-Directed Functional Metal–Phenolic Materials
Publisher: American Chemical Society (ACS)
Date: 10-05-2022
DOI: 10.1021/ACS.CHEMREV.1C01042
Abstract: Metal ions are ubiquitous in nature and play significant roles in assembling functional materials in fields spanning chemistry, biology, and materials science. Metal-phenolic materials are assembled from phenolic components in the presence of metal ions through the formation of metal-organic complexes. Alkali, alkali-earth, transition, and noble metal ions as well as metalloids interacting with phenolic building blocks have been widely exploited to generate erse hybrid materials. Despite extensive studies on the synthesis of metal-phenolic materials, a comprehensive summary of how metal ions guide the assembly of phenolic compounds is lacking. A fundamental understanding of the roles of metal ions in metal-phenolic materials engineering will facilitate the assembly of materials with specific and functional properties. In this review, we focus on the ersity and function of metal ions in metal-phenolic material engineering and emerging applications. Specifically, we discuss the range of underlying interactions, including (i) cation-π, (ii) coordination, (iii) redox, and (iv) dynamic covalent interactions, and highlight the wide range of material properties resulting from these interactions. Applications (e.g., biological, catalytic, and environmental) and perspectives of metal-phenolic materials are also highlighted.
Microfluidic polymer multilayer adsorption on liquid crystal droplets for microcapsule synthesis
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B808826H
Abstract: Exploiting microfluidic principles, the potential for chip-based multilayer assembly for the synthesis of polymer microcapsules was investigated. We demonstrate that continuous flow microfluidic multilayer synthesis is a fast, efficient, automated alternative to conventional batch synthesis. In this work, we dispersed liquid crystal (LC) molecules (organic phase) as monodisperse droplets in an aqueous continuous phase containing the primary polymer and a suitable surfactant. The primary polymer was coadsorbed with the surfactant at the organic/aqueous interface, stabilizing the LC droplets against coalescence and providing a template for subsequent polymer adsorption. As the droplet templates are transported through the microfluidic channel, the polymer-containing aqueous continuous phase is selectively withdrawn and replaced with rinse solution, and then with an alternative polymer solution. This selective withdrawal and infusion cycle was repeated to assemble polymer multilayers onto the emulsion droplets. The process was followed using fluorescence microscopy of the fluorescently-labelled polymers at the LC interface and of the flowing polymer solutions during the sequential rinse stages. Cross-linking of the multilayers and removal of the dispersed LC phase resulted in polymer capsules retaining the high monodispersity of the droplet templates. This microfluidic approach significantly reduces the multilayer formation time (to <2 min for 3-layer capsules) of well-defined capsules that are envisaged to have benefits in biomedical applications, including drug delivery and encapsulated biochemical reactions.
Biosensors: recent advances
Publisher: IOP Publishing
Date: 11-1997
Engineered hydrogen-bonded polymer multilayers: From assembly to biomedical applications
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CS00001A
Abstract: In this tutorial review , developments in hydrogen-bonded LbL materials are discussed, with an emphasis on loading and release of cargo for biomedical applications.
Oligosilsesquioxanes as versatile building blocks for the preparation of self-assembled thin films
Publisher: American Chemical Society (ACS)
Date: 14-06-2002
DOI: 10.1021/JA0127382
Abstract: A self-assembly approach to the preparation of nanocomposite siliceous thin films by using oligosilsesquioxanes as building blocks is presented. Poly(styrene-4-sulfonate), PSS, and octa(3-aminopropyl)silsesquioxane, NSi8, were layer-by-layer (LbL) assembled onto planar substrates and polystyrene (PS) particles, thus forming composite multilayers. We have clarified the binding properties of NSi8 to PSS by examining the pH influence on film buildup by microelectrophoresis (zeta-potential) and quartz crystal microgravimetry (QCM). The regular growth of PSS/NSi8 multilayers on planar supports was confirmed by surface plasmon resonance (SPR) spectroscopy and QCM. By applying the LbL coating procedure to spherical templates, we prepared compact, microporous hollow silica spheres by calcining PS spheres coated with (poly(allylamine hydrochloride) (PAH)/PSS)(2)/(NSi8/PSS)(n) (n varying from 3 to 12), at 750 degrees C, because of sintering of the octameric clusters (NSi8). Hollow spheres derived from coatings with n = 3 drastically altered in size (relative to the template core), depending on the size of the PS particles used. The novelty of this method for the nanofabrication of siliceous films stems from the use of well-defined and discrete building blocks, such as NSi8, leading to homogeneous organic-silica composite films as well as in idual siliceous particles of variable size and shape.
Redox-sensitive PEG-polypeptide nanoporous particles for survivin silencing in prostate cancer cells
Publisher: American Chemical Society (ACS)
Date: 29-06-2015
DOI: 10.1021/ACS.BIOMAC.5B00562
Abstract: We report the engineering of intracellular redox-responsive nanoporous poly(ethylene glycol)-poly(l-lysine) particles (NPEG-PLLs). The obtained particles exhibit no toxicity while maintaining the capability to deliver a small interfering RNA sequence (siRNA) targeting the anti-apoptotic factor, survivin, in prostate cancer cells. The redox-mediated cleavage of the disulfide bonds stabilizing the NPEG-PLL-siRNA complex results in the release of bioactive siRNA into the cytosol of prostate cancer PC-3 cells, which, in turn, leads to the effective silencing (∼59 ± 8%) of the target gene. These findings, obtained under optimal conditions, indicate that NPEG-PLLs may protect the therapeutic nucleic acid in the extracellular and intracellular environments, thus preventing the occurrence of competitive interactions with serum and cytosolic proteins as well as degradation by RNase. The intracellular trafficking and final fate of the NPEG-PLLs were investigated by a combination of deconvolution microscopy, fluorescence lifetime imaging microscopy, and super-resolution structured illumination microscopy. A significant impairment of cell survival was observed in cells concomitantly exposed to paclitaxel and siRNA-loaded NPEG-PLLs. Overall, our findings indicate that NPEG-PLLs represent a highly loaded depot for the delivery of therapeutic nucleic acids to cancer cells.
Mesoporous Silica Supraparticles for Sustained Inner‐Ear Drug Delivery
Publisher: Wiley
Date: 05-08-2014
Abstract: Mesoporous silica supraparticles (MS-SPs) are prepared via self-assembly of mesoporous silica nanoparticles under capillary force action in confined droplets. The MS-SPs are effective carriers for sustained drug delivery. Animal studies show that these particles are suitable for chronic intracochlear implantation, and neurotrophins released from the MS-SPs can efficiently rescue primary auditory neurons in an in vivo sensorineural hearing loss model.
Nanoporous Thin Films Formed by Salt-Induced Structural Changes in Multilayers of Poly(acrylic acid) and Poly(allylamine)
Publisher: American Chemical Society (ACS)
Date: 25-05-2001
DOI: 10.1021/LA0102612
Template-Free Synthesis of Chemically Asymmetric Silica Nanotubes for Selective Cargo Loading and Sustained Drug Release
Publisher: American Chemical Society (ACS)
Date: 22-05-2019
The mechanical regulation of RNA binding protein hnRNPC in the failing heart
Publisher: American Association for the Advancement of Science (AAAS)
Date: 23-11-2022
DOI: 10.1126/SCITRANSLMED.ABO5715
Abstract: Cardiac pathologies are characterized by intense remodeling of the extracellular matrix (ECM) that eventually leads to heart failure. Cardiomyocytes respond to the ensuing biomechanical stress by reexpressing fetal contractile proteins via transcriptional and posttranscriptional processes, such as alternative splicing (AS). Here, we demonstrate that the heterogeneous nuclear ribonucleoprotein C (hnRNPC) is up-regulated and relocates to the sarcomeric Z-disc upon ECM pathological remodeling. We show that this is an active site of localized translation, where the ribonucleoprotein associates with the translation machinery. Alterations in hnRNPC expression, phosphorylation, and localization can be mechanically determined and affect the AS of mRNAs involved in mechanotransduction and cardiovascular diseases, including Hippo pathway effector Yes-associated protein 1. We propose that cardiac ECM remodeling serves as a switch in RNA metabolism by affecting an associated regulatory protein of the spliceosome apparatus. These findings offer new insights on the mechanism of mRNA homeostatic mechanoregulation in pathological conditions.
DNA multilayer films on planar and colloidal supports: Sequential assembly of like-charged polyelectrolytes
Publisher: American Chemical Society (ACS)
Date: 20-04-2005
DOI: 10.1021/NL050608B
Abstract: Multilayer films comprising solely negatively charged polyelectrolytes were sequentially assembled based on DNA hybridization. Films prepared from alternating layers of two-block homopolymeric nucleotides (polyA(20)G(20) olyT(20)C(20)) grew linearly with increasing layer number, as verified by quartz crystal microgravimetry, UV-vis spectrophotometry and optical microscopy. Urea treatment of the films induced morphological changes, while exposure to low ionic strength solutions resulted in film disassembly. DNA multilayer films were also formed on silica particles, and DNA hollow capsules were obtained following dissolution of the template core.
Assembly of nanostructured films with hydrophobic subcompartments via continuous assembly of polymers
Publisher: American Chemical Society (ACS)
Date: 27-09-2013
DOI: 10.1021/MA4017357
Contiguous silver nanoparticle coatings on dielectric spheres
Publisher: Wiley
Date: 17-05-2002
DOI: 10.1002/1521-4095(20020517)14:10<732::AID-ADMA732>3.0.CO;2-P
Void Engineering in Metal-Organic Frameworks via Synergistic Etching and Surface Functionalization
Publisher: Wiley
Date: 09-06-2016
Design of Degradable Click Delivery Systems
Publisher: Wiley
Date: 06-05-2013
Abstract: Click chemistry has had a significant impact in the field of materials science over the last 10 years, as it has enabled the design of new hybrid building blocks, leading to multifunctional and responsive materials. One key application for such materials is in the biomedical field, such as gene or drug delivery. However, to meet the functional requirements of such applications, tailored degradability of these materials under biological conditions is critical. There has been an increasing interest in combining click chemistry techniques with a range of degradable or responsive building blocks as well as investigating new or milder chemistries to design click delivery systems that are capable of physiologically relevant degradation. This Feature Article will cover some of the different approaches to synthesize degradable click delivery systems and their investigation for therapeutic release.
Polymer hydrogel capsules: en route toward synthetic cellular systems
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B9NR00143C
Abstract: Engineered synthetic cellular systems are expected to become a powerful biomedical platform for the development of next-generation therapeutic carrier vehicles. In this mini-review, we discuss the potential of polymer capsules derived by the layer-by-layer assembly as a platform system for the construction of artificial cells and organelles. We outline the characteristics of polymer capsules that make them unique for these applications, and we describe several successful ex les of microencapsulated catalysis, including biologically relevant enzymatic reactions. We also provide ex les of subcompartmentalized polymer capsules, which represent a major step toward the creation of synthetic cells.
Decomposable hollow biopolymer-based capsules
Publisher: American Chemical Society (ACS)
Date: 26-07-2001
DOI: 10.1021/BM010052W
Abstract: Decomposable hollow capsules based on deoxyribonucleic acid (DNA) and a low molecular weight organic molecule, a naturally occurring polyamine, spermidine (SP), were formed by applying the layer-by-layer adsorption strategy to colloid particles, viz., assembling DNA/SP multilayers on colloids and subsequently removing the templated core. For comparison, hollow capsules from the higher molecular weight biopolymers, alginate (ALG) and poly(lysine) (PL), were also prepared. The multilayers were first formed on polystyrene spheres, and their growth was followed by microelectrophoresis. The preparation of hollow capsules, derived from multilayer coating melamine formaldehyde core particles and then decomposing the core by acid treatment, was verified by atomic force microscopy and transmission electron microscopy. In contrast to the hollow ALG/PL capsules, the hollow DNA/SP capsules displayed a high sensitivity to salt solutions: Decomposition of the DNA/SP multilayers occurred after exposure to sodium chloride solutions. The hollow capsules prepared are attractive for the encapsulation and release of various substances for ex le, the release of encapsulated compounds, such as dyes or drugs, can occur when loaded DNA/SP capsules are exposed to environmental (salt) conditions that decompose them, e.g., in the bloodstream.
Engineering Multifunctional Capsules through the Assembly of Metal-Phenolic Networks
Publisher: Wiley
Date: 02-04-2014
Abstract: Metal-organic coordination materials are of widespread interest because of the coupled benefits of inorganic and organic building blocks. These materials can be assembled into hollow capsules with a range of properties, which include selective permeability, enhanced mechanical/thermal stability, and stimuli-responsiveness. Previous studies have primarily focused on the assembly aspects of metal-coordination capsules however, the engineering of metal-specific functionality for capsule design has not been explored. A library of functional metal-phenolic network (MPN) capsules prepared from a phenolic ligand (tannic acid) and a range of metals is reported. The properties of the MPN capsules are determined by the coordinated metals, allowing for control over film thickness, disassembly characteristics, and fluorescence behavior. Furthermore, the functional properties of the MPN capsules were tailored for drug delivery, positron emission tomography (PET), magnetic resonance imaging (MRI), and catalysis. The ability to incorporate multiple metals into MPN capsules demonstrates that a erse range of functional materials can be generated.
Standardizing Nanomaterials
Publisher: American Chemical Society (ACS)
Date: 22-11-2016
The role of capsule stiffness on cellular processing
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5SC00416K
Abstract: A systematic and quantitative study on the role of capsule stiffness in cellular processing was performed using hyaluronic acid capsules with tunable stiffness constructed via continuous assembly of polymers.
Transforming the Chemical Structure and Bio‐Nano Activity of Doxorubicin by Ultrasound for Selective Killing of Cancer Cells
Publisher: Wiley
Date: 18-02-2022
Abstract: Reconfiguring the structure and selectivity of existing chemotherapeutics represents an opportunity for developing novel tumor‐selective drugs. Here, as a proof‐of‐concept, the use of high‐frequency sound waves is demonstrated to transform the nonselective anthracycline doxorubicin into a tumor selective drug molecule. The transformed drug self‐aggregates in water to form ≈200 nm nanodrugs without requiring organic solvents, chemical agents, or surfactants. The nanodrugs preferentially interact with lipid rafts in the mitochondria of cancer cells. The mitochondrial localization of the nanodrugs plays a key role in inducing reactive oxygen species mediated selective death of breast cancer, colorectal carcinoma, ovarian carcinoma, and drug‐resistant cell lines. Only marginal cytotoxicity (80–100% cell viability) toward fibroblasts and cardiomyocytes is observed, even after administration of high doses of the nanodrug (25–40 µg mL −1 ). Penetration, cytotoxicity, and selectivity of the nanodrugs in tumor‐mimicking tissues are validated by using a 3D coculture of cancer and healthy cells and 3D cell‐collagen constructs in a perfusion bioreactor. The nanodrugs exhibit tropism for lung and limited accumulation in the liver and spleen, as suggested by in vivo biodistribution studies. The results highlight the potential of this approach to transform the structure and bioactivity of anticancer drugs and antibiotics bearing sono‐active moieties.
Lactosylated Glycogen Nanoparticles for Targeting Prostate Cancer Cells
Publisher: American Chemical Society (ACS)
Date: 10-05-2017
Abstract: Glyconanoparticles that exhibit multivalent binding to lectins are desirable for molecular recognition and therapeutic applications. Herein we explore the use of glycogen nanoparticles as a biosourced glycoscaffold for engineering multivalent glyconanoparticles. Glycogen nanoparticles, a naturally occurring highly branched polymer of glucose, was functionalized with lactose, achieved through copper(I)-catalyzed alkyne-azide cycloaddition chemistry, for targeted interaction with lectins ex situ and on prostate cancer cells. The lactosylated glycogen, which contains terminal β-galactoside moieties, is termed galacto-glycogen (GG), and is found to interact strongly with peanut agglutinin (PNA), a β-galactoside-specific lectin, as observed by optical waveguide lightmode spectroscopy, dynamic light scattering, and quartz crystal microbalance measurements. The GG nanoparticles exhibit multivalent binding to PNA with an affinity constant of 3.4 × 10
Sono‐Fenton Chemistry Converts Phenol and Phenyl Derivatives into Polyphenols for Engineering Surface Coatings
Publisher: Wiley
Date: 24-08-2021
Abstract: We report a sono‐Fenton strategy to mediate the supramolecular assembly of metal–phenolic networks (MPNs) as substrate‐independent coatings using phenol and phenyl derivatives as building blocks. The assembly process is initiated from the generation of hydroxyl radicals ( . OH) using high‐frequency ultrasound (412 kHz), while the metal ions synergistically participate in the production of additional . OH for hydroxylation henolation of phenol and phenyl derivatives via the Fenton reaction and also coordinate with the phenolic compounds for film formation. The coating strategy is applicable to various phenol and phenyl derivatives and different metal ions including Fe II , Fe III , Cu II , and Co II . In addition, the sono‐Fenton strategy allows real‐time control over the assembly process by turning the high‐frequency ultrasound on or off. The properties of the building blocks are maintained in the formed films. This work provides an environmentally friendly and controllable method to expand the application of phenolic coatings for surface engineering.
Nanoporous Peptide Particles for Encapsulating and Releasing Neurotrophic Factors in an Animal Model of Neurodegeneration
Publisher: Wiley
Date: 21-05-2012
Mechanical characterization of ultrasonically synthesized microbubble shells by flow cytometry and AFM
Publisher: American Chemical Society (ACS)
Date: 29-10-2013
DOI: 10.1021/AM403108Y
Abstract: The mechanical properties of the shell of ultrasonically synthesized lysozyme microbubbles, LSMBs, were evaluated by acoustic interrogation and nanoindentation techniques. The Young's modulus of LSMBs was found to be 1.0 ± 0.3 MPa and 0.6 ± 0.1 MPa when analyzed by flow cytometry and AFM, respectively. The shell elasticity and Young's modulus were not affected by the size of the microbubbles (MBs). The hydrogel-like protein shell of LSMBs offers a softer, more elastic and viscous interface compared to lipid-shelled MBs. We show that the acoustic interrogation technique is a real-time, fast, and high-throughput method to characterize the mechanical characteristics of air-filled microbubbles coated by a variety of materials.
Metal–Phenolic Coatings as a Platform to Trigger Endosomal Escape of Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 10-2019
Abstract: The intracellular delivery of functional nanoparticles (NPs) and the release of therapeutic payloads at a target site are central issues for biomedical applications. However, the endosomal entrapment of NPs typically results in the degradation of active cargo, leading to poor therapeutic outcomes. Current advances to promote the endosomal escape of NPs largely involve the use of polycationic polymers and cell-penetrating peptides (CPPs), which both can suffer from potential toxicity and convoluted synthesis/conjugation processes. Herein, we report the use of metal-phenolic networks (MPNs) as versatile and nontoxic coatings to facilitate the escape of NPs from endo/lysosomal compartments. The MPNs, which were engineered from the polyphenol tannic acid and Fe
Pharmacokinetics and biodistribution of supraparticle-delivered neurotrophin 3 in the guinea pig cochlea
Publisher: Elsevier BV
Date: 02-2022
DOI: 10.1016/J.JCONREL.2021.12.037
Abstract: Hearing loss is the most prevalent sensory disorder affecting nearly half a billion people worldwide. Aside from devices to assist hearing, such as hearing aids and cochlear implants, a drug treatment for hearing loss has yet to be developed. The neurotrophin family of growth factors has long been established as a potential therapy, however delivery of these factors into the inner ear at therapeutic levels over a sustained period of time has remained a challenge restricting clinical translation. We previously demonstrated that direct delivery of exogenous neurotrophin-3 (NT3) in the guinea pig cochleae via a bolus injection was rapidly cleared from the inner ear, with almost complete elimination 3 days post-treatment. Here, we explored the potential of suprapaticles (SPs) for NT3 delivery to the inner ear to achieve sustained delivery over time. SPs are porous spheroid structures comprised of smaller colloidal silica nanoparticles that provide a platform for long-term controlled release of therapeutics. This study aimed to assess the pharmacokinetics and biodistribution of SP-delivered NT3. We used a radioactive tracer (iodine 125:
Next generation, sequentially assembled ultrathin films: Beyond electrostatics
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B610778H
Abstract: Over the last 15 years, the layer-by-layer (LbL) assembly technology has proven to be a versatile method for surface modification. This approach is likely to find widespread application because of its simplicity and versatility however, the conventional use of highly charged materials with limited responsive behaviour presents some key limitations. In this tutorial review, the formation of multilayer thin films prepared through non-electrostatic interactions is reviewed. We discuss the assembly of films via a number of different methodologies, with particular emphasis on those that provide enhanced orientational control, stimuli-responsive behaviour, and improved film stability.
mRNA Treatment Rescues Niemann-Pick Disease Type C1 in Patient Fibroblasts
Publisher: Cold Spring Harbor Laboratory
Date: 24-02-2022
DOI: 10.1101/2022.02.21.479058
Abstract: Messenger RNA (mRNA) holds great potential as a disease-modifying treatment for a wide array of monogenic disorders. Niemann-Pick disease type C1 (NP-C1) is an ultra-rare monogenic disease that arises due to loss-of-function mutations in the NPC1 gene, resulting in the entrapment of unesterified cholesterol in the lysosomes of affected cells and a subsequent reduction in their capacity for cholesterol esterification. This causes severe damage to various organs including the brain, liver, and spleen. In this work, we describe the use of NPC1-encoded mRNA to rescue the protein insufficiency and pathogenic phenotype caused by biallelic NPC1 mutations in cultured fibroblasts derived from an NP-C1 patient. We first evaluated engineering strategies for the generation of potent mRNAs capable of eliciting high protein expression across multiple cell types. We observed that “GC3” codon optimization, coupled with N1-methylpseudouridine base modification, yielded an mRNA that was approximately a thousand-fold more potent than wildtype, unmodified mRNA in a luciferase reporter assay, and consistently superior to other mRNA variants. Our data suggest that the improved expression associated with this design strategy was due in large part to the increased secondary structure of the designed mRNAs. Both codon optimization and base modification appear to contribute to increased secondary structure. Applying these principles to the engineering of NPC1-encoded mRNA, we observed a normalization in NPC1 protein levels after mRNA treatment, as well as a rescue of the mutant phenotype. Specifically, mRNA treatment restored the cholesterol esterification capacity of patient cells to wildtype levels, and induced a significant reduction in both unesterified cholesterol levels ( % reduction compared to Lipofectamine-treated control in a cholesterol esterification assay) and lysosome size (157 μm 2 reduction compared to lipofectamine-treated control). These findings show that engineered mRNA can correct the deficit caused by NPC1 mutations. More broadly, they also serve to further validate the potential of this technology to correct diseases associated with loss-of-function mutations in genes coding for large, complex, intracellular proteins.
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ARC Centre Of Excellence In Convergent Bio-Nano Science And Technology
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Amount: $440,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE0775562
Start Date: 2007
End Date: 06-2008
Amount: $500,000.00
Funder: Australian Research Council
View Funded ActivitySpecial Research Initiatives - Grant ID: SR0354588
Start Date: 01-2004
End Date: 12-2003
Amount: $10,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE120100131
Start Date: 02-2012
End Date: 02-2013
Amount: $150,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE0560679
Start Date: 2005
End Date: 12-2005
Amount: $932,870.00
Funder: Australian Research Council
View Funded ActivityAustralian Laureate Fellowships - Grant ID: FL120100030
Start Date: 10-2012
End Date: 10-2017
Amount: $2,779,572.00
Funder: Australian Research Council
View Funded ActivityIndustrial Transformation Research Hubs - Grant ID: IH200100023
Start Date: 08-2021
End Date: 08-2026
Amount: $4,950,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP200100713
Start Date: 02-2020
End Date: 02-2023
Amount: $700,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP170103331
Start Date: 2017
End Date: 12-2019
Amount: $423,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP0343840
Start Date: 2003
End Date: 12-2008
Amount: $1,090,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE200100163
Start Date: 06-2020
End Date: 05-2022
Amount: $700,000.00
Funder: Australian Research Council
View Funded ActivityARC Centres Of Excellence - Grant ID: CE140100036
Start Date: 06-2014
End Date: 06-2021
Amount: $26,000,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE0882576
Start Date: 05-2008
End Date: 12-2009
Amount: $588,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE110100125
Start Date: 10-2011
End Date: 10-2012
Amount: $500,000.00
Funder: Australian Research Council
View Funded ActivityLinkage - International - Grant ID: LX0668851
Start Date: 2006
End Date: 12-2009
Amount: $300,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE0668435
Start Date: 2006
End Date: 03-2007
Amount: $1,300,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE0989341
Start Date: 10-2009
End Date: 12-2010
Amount: $690,000.00
Funder: Australian Research Council
View Funded Activity