ORCID Profile
0000-0003-2581-4986
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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)
Macromolecular and Materials Chemistry | Synthesis Of Macromolecules | Characterisation Of Macromolecules | Synthesis of Materials | Physical Chemistry Of Macromolecules | Nanotechnology | Nanobiotechnology | Nanochemistry and Supramolecular Chemistry | Polymerisation Mechanisms | Macromolecular Chemistry Not Elsewhere Classified | Biomaterials | Macromolecular and Materials Chemistry not elsewhere classified | Nanomaterials | Biochemistry and Cell Biology | Biomedical Engineering | Interdisciplinary Engineering Not Elsewhere Classified | Membrane And Separation Technologies | Nanotechnology | Pharmaceutical Sciences | Colloid And Surface Chemistry | Membrane and Separation Technologies | Medical Biotechnology | Therapies And Therapeutic Technology | Medical Physics | Instruments And Techniques | Medical Biotechnology | Functional Materials | Polymers and Plastics | Membrane Biology | Biosensor Technologies | Metals and Alloy Materials | Characterisation of Biological Macromolecules | Solid State Chemistry | Medical Biochemistry and Metabolomics not elsewhere classified | Nanomedicine | Other Physical Sciences | Photonics and Electro-Optical Engineering (excl. Communications) | Physical Organic Chemistry | Biological And Medical Chemistry | Organic Chemical Synthesis | Chemical Characterisation of Materials | Polymers | Biochemistry and Cell Biology not elsewhere classified | Structural Biology (incl. Macromolecular Modelling) | Organometallic Chemistry | Materials Engineering | Medicinal and Biomolecular Chemistry not elsewhere classified | Organic Chemistry | Biomaterials | Biomechanical Engineering | Biotechnology Not Elsewhere Classified | Electrochemistry | Industrial Chemistry | Cellular Interactions (incl. Adhesion, Matrix, Cell Wall) | Image Processing | Diagnostic Applications | Cell Neurochemistry
ANZSRC Socio-Economic Objective (SEO)
Paints | Expanding Knowledge in the Chemical Sciences | Polymeric materials (e.g. paints) | Treatments (e.g. chemicals, antibiotics) | Expanding Knowledge in the Biological Sciences | Prevention—biologicals (e.g. vaccines) | Human Pharmaceutical Treatments (e.g. Antibiotics) | Chemical sciences | Clinical health not specific to particular organs, diseases and conditions | Diagnostics | Plastics in primary forms | Expanding Knowledge in Technology | Other | Inherited Diseases (incl. Gene Therapy) | Human Diagnostics | Biological sciences | Other | Cancer and Related Disorders | Soaps and cosmetics | Synthetic resins and rubber | Expanding Knowledge in the Medical and Health Sciences | Expanding Knowledge in Engineering | Plant Production and Plant Primary Products not elsewhere classified | Health related to ageing | Health and support services not elsewhere classified | Health not elsewhere classified | Structural glass and glass products | Crop Protection Chemicals | Other (incl. production enhancement) | Inherited diseases (incl. gene therapy) | Integrated systems | Industrial chemicals and related products | Human pharmaceutical products | Human Pharmaceutical Products not elsewhere classified | Preventive medicine | Diagnostics | Materials performance and processes | Nervous System and Disorders | Physical sciences | Veterinary Pharmaceutical Treatments (e.g. Antibiotics) | Hearing, vision, speech and their disorders | Manufactured products not elsewhere classified | Organic industrial chemicals not classified elsewhere | Plastic products (incl. Construction materials) | Medical instrumentation | Diagnostic methods | Sheet metal products | Scientific instrumentation | Diagnostic Methods | Expanding Knowledge in the Physical Sciences |
Related Links
Publications
Reversible addition–fragmentation chain transfer polymerization initiated with γ-radiation at ambient temperature: an overview
Publisher: Elsevier BV
Date: 03-2003
Differential Roles of Plasma Protein Corona on Immune Cell Association and Cytokine Secretion of Oligomeric and Fibrillar Beta-Amyloid.
Publisher: American Chemical Society (ACS)
Date: 10-10-2019
Protein Release from Biodegradable PolyHPMA–Lysozyme Conjugates Resulting in Bioactivity Enhancement
Publisher: Wiley
Date: 17-03-2011
Abstract: A novel biodegradable thiazolidine-2-thione functional chain transfer agent was synthesized and employed as a reversible additional fragmentation chain transfer agent to prepare well-defined semitelechelic poly-N-(2-hydroxypropyl) methacrylamides (polyHPMAs) with predetermined molecular weights and narrow polydispersities. The protein reactive group, thiazolidine-2-thione, was located at the polymer chain ends fixed by biodegradable disulfide bonds. The functional polyHPMA chains were subsequently conjugated to protein (lysozyme) by exploiting reactions between the thiazolidine-2-thione functionality and amine residues on the protein surface to form covalent amide linkages. The in vitro bioactivities of the lysozyme-polyHPMA conjugates were assessed by using Micrococcus lysodeikticus cells as substrates. The lysozyme bioactivity was significantly reduced following the conjugation procedure. However, cleavage of the polymer chains from the bioconjugates (under reducing conditions) yielded free protein and a remarkable recovery of bioactivity. In vivo tests were performed by subcutaneous injection into mice and clearly demonstrated decreased proteolytic degradation for the protein-polymer conjugate when compared with native protein, indicating effective protein protection through a conjugation strategy. This bioreversible approach to conjugation allows for a balance to be made between protein protection and effective bioactivity maintenance.
Lipidated polymers for the stabilization of cubosomes: nanostructured drug delivery vehicles
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC05842J
Abstract: We report a straightforward approach for preparing polymers with lipidic chain ends, and show their application in stabilising nanostructured drug delivery vehicles.
Free-radical copolymerization of styrene and m-isopropenyl-alpha,alpha '-dimethylbenzyl isocyanate studied by H-1 NMR kinetic experiments
Publisher: Wiley
Date: 27-02-2002
DOI: 10.1002/POLA.10195
Long‐lived intermediates in reversible addition–fragmentation chain‐transfer (RAFT) polymerization generated by γ radiation
Publisher: Wiley
Date: 03-2002
DOI: 10.1002/POLA.10194
Implications of the Human Gut–Brain and Gut–Cancer Axes for Future Nanomedicine
Publisher: American Chemical Society (ACS)
Date: 02-11-2020
Synthesis, Characterization, and Bioactivity of Mid-Functional PolyHPMA−Lysozyme Bioconjugates
Publisher: American Chemical Society (ACS)
Date: 23-03-2010
DOI: 10.1021/MA100142W
PH-Responsive copolymer micelles to enhance itraconazole efficacy against: Candida albicans biofilms
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9TB02586C
Abstract: Candida albicans ( C. albicans ) is a common fungal pathogen causing both localised and systemic infections.
Amphiphilic Block Copolymers Based on Poly(2‐acryloyloxyethyl phosphorylcholine) Prepared via RAFT Polymerisation as Biocompatible Nanocontainers
Publisher: Wiley
Date: 13-04-2004
Abstract: Amphiphilic block copolymers composed of poly(butyl acrylate) and poly(2-acryloyloxyethyl phosphorylcholine) have been prepared using reversible addition fragmentation transfer (RAFT) polymerisation. The conversion of the polymerisation was determined using online FT NIR spectroscopy. NMR spectroscopy was used not only to support the results obtained from FT NIR spectroscopy but also prove the formation of micelles. Due to the strong aggregation tendency of these block copolymers and the resulting difficulties concerning the molecular weight analysis test experiments were carried out replacing poly(2-acryloyloxyethyl phosphorylcholine) with poly(2-hydroxyethyl acrylate). Micelle size and the aggregation behaviour were investigated using dynamic light scattering. The sizes of the nanocontainers obtained were found to be influenced by the block length as well as the solvent leading to micelles in the range between 40 and 160 nm. The toxicity of the RAFT agent used was then analysed by cell growth inhibition tests.
From influenza to COVID-19: Lipid nanoparticle mRNA vaccines at the frontiers of infectious diseases
Publisher: Elsevier BV
Date: 09-2021
Chain Length Dependent Termination in Butyl Acrylate Free-Radical Polymerization Studied via Stationary and Pulsed Laser Initiated RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 21-10-2005
DOI: 10.1021/MA051485K
Graphene quantum dots against human IAPP aggregation and toxicity in vivo
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8NR07180B
Abstract: Graphene quantum dots are biocompatible zero-dimensional nanostructures, which displayed a potency in rescuing zebrafish embryos from the toxicity of human islet amyloid polypeptide.
Synthesis of well-defined poly(acrylates) in ionic liquids via copper(II)-mediated photoinduced living radical polymerization
Publisher: American Chemical Society (ACS)
Date: 27-07-2015
Recent advances in magnetic nanoparticle-based molecular probes for hepatocellular carcinoma diagnosis and therapy.
Publisher: Bentham Science Publishers Ltd.
Date: 15-10-2018
DOI: 10.2174/1381612824666180516111939
Abstract: Hepatocellular carcinoma (HCC) is one of the most common cancers worldwide, leading to the second most likely cause of cancer-related deaths. Medical imaging is crucial in clinic for HCC screening and diagnosis. Due to the relatively high special resolution and excellent sensitivity, magnetic resonance imaging (MRI) by using magnetic nanoparticle-based contrast agents has been used so far in HCC imaging and staging, demonstrating great potential and promising in vivo applications. This review focuses on the use of different magnetic nanoparticles for construction of HCC nanoprobes for MR imaging and theranostic purpose.
Thiol-reactive (co)polymer scaffolds comprising organic arsenical acrylamides
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC03880A
Abstract: Well-defined polymeric arsenicals are synthesised for the first time and exploited as responsive and reactive polymer scaffolds.
Living free radical polymerisation under a constant source of gamma radiation - An example of reversible addition-fragmentation chain transfer or reversible termination?
Publisher: Wiley
Date: 08-2002
DOI: 10.1002/1521-3927(20020801)23:12<717::AID-MARC717>3.0.CO;2-I
Schwann cell endosome CGRP signals elicit periorbital mechanical allodynia in mice
Publisher: Springer Science and Business Media LLC
Date: 03-02-2022
DOI: 10.1038/S41467-022-28204-Z
Abstract: Efficacy of monoclonal antibodies against calcitonin gene-related peptide (CGRP) or its receptor (calcitonin receptor-like receptor/receptor activity modifying protein-1, CLR/RAMP1) implicates peripherally-released CGRP in migraine pain. However, the site and mechanism of CGRP-evoked peripheral pain remain unclear. By cell-selective RAMP1 gene deletion, we reveal that CGRP released from mouse cutaneous trigeminal fibers targets CLR/RAMP1 on surrounding Schwann cells to evoke periorbital mechanical allodynia. CLR/RAMP1 activation in human and mouse Schwann cells generates long-lasting signals from endosomes that evoke cAMP-dependent formation of NO. NO, by gating Schwann cell transient receptor potential ankyrin 1 (TRPA1), releases ROS, which in a feed-forward manner sustain allodynia via nociceptor TRPA1. When encapsulated into nanoparticles that release cargo in acidified endosomes, a CLR/RAMP1 antagonist provides superior inhibition of CGRP signaling and allodynia in mice. Our data suggest that the CGRP-mediated neuronal/Schwann cell pathway mediates allodynia associated with neurogenic inflammation, contributing to the algesic action of CGRP in mice.
Microgel stars via Reversible Addition Fragmentation Chain Transfer (RAFT) polymerisation - a facile route to macroporous membranes, honeycomb patterned thin films and inverse opal substrates
Publisher: Royal Society of Chemistry (RSC)
Date: 2003
DOI: 10.1039/B304208C
Copolymerization of styrene and methyl methacrylate in the presence of a catalytic chain transfer agent
Publisher: American Chemical Society (ACS)
Date: 07-04-1998
DOI: 10.1021/MA971541K
Core‐shell microspheres with surface grafted poly(vinyl alcohol) as drug carriers for the treatment of hepatocellular carcinoma
Publisher: Wiley
Date: 11-06-2007
DOI: 10.1002/POLA.22074
Glycopolymer Decoration of Gold Nanoparticles Using a LbL Approach
Publisher: American Chemical Society (ACS)
Date: 10-03-2010
DOI: 10.1021/MA100250X
Bioapplications of RAFT polymerization
Publisher: American Chemical Society (ACS)
Date: 18-09-2009
DOI: 10.1021/CR9001403
Direct Synthesis of Pyridyl Disulfide‐Terminated Polymers by RAFT Polymerization
Publisher: Wiley
Date: 30-01-2007
The Membrane Axis of Alzheimer's Nanomedicine
Publisher: Wiley
Date: 08-12-2021
Origin of inhibition effects in the reversible addition fragmentation chain transfer (RAFT) polymerization of methyl acrylate
Publisher: American Chemical Society (ACS)
Date: 21-09-2002
DOI: 10.1021/MA0203445
A New Chemo‐Enzymatic Route to Side‐Chain Liquid‐Crystalline Polymers: The Synthesis and Polymerization of 6‐(4‐Methoxybiphenyl‐4′‐oxy)hexyl Vinyl Hexanedioate
Publisher: Wiley
Date: 11-2003
Critically evaluated rate coefficients for free-radical polymerization, 3. Propagation rate coefficients for alkyl methacrylates
Publisher: Wiley
Date: 08-2000
DOI: 10.1002/1521-3935(20000801)201:12<1355::AID-MACP1355>3.0.CO;2-Q
Water-Soluble, Thermoresponsive, Hyperbranched Copolymers Based on PEG-Methacrylates: Synthesis, Characterization, and LCST Behavior
Publisher: Wiley
Date: 24-05-2010
DOI: 10.1002/POLA.24027
Mapping Free Radical Reactivity: A High-Resolution Electrospray Ionization−Mass Spectrometry Study of Photoinitiation Processes in Methyl Methacrylate Free Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 14-11-2006
DOI: 10.1021/MA0616559
Amyloid Self‐Assembly of hIAPP8‐20 via the Accumulation of Helical Oligomers, α‐Helix to β‐Sheet Transition, and Formation of β‐Barrel Intermediates
Publisher: Wiley
Date: 25-03-2019
Arginine-Rich Manganese Silicate Nanobubbles as a Ferroptosis-Inducing Agent for Tumor-Targeted Theranostics.
Publisher: American Chemical Society (ACS)
Date: 29-11-2018
One-Pot Conversion of RAFT-Generated Multifunctional Block Copolymers of HPMA to Doxorubicin Conjugated Acid- and Reductant-Sensitive Crosslinked Micelles
Publisher: American Chemical Society (ACS)
Date: 10-10-2008
DOI: 10.1021/BM800657E
Abstract: N-(2-Hydroxypropyl)methacrylamide (HPMA) containing polymers that are widely used as anticancer drug carriers. We have synthesized new hiphilic block copolymers of HPMA with a functional monomer 2-(2-pyridyldisulfide)ethylmethacrylate (PDSM) via reversible addition-fragmentation chain transfer (RAFT) polymerization. In a one-pot reaction, the versatility of PDS groups on poly(PDSM)- b-poly(HPMA) was used to conjugate an anticancer drug, doxorubicin (DOX), and also simultaneously crosslink the micellar assemblies via acid-cleavable hydrazone bonds and reducible disulfide bonds. DOX-conjugated crosslinked micelles with an average diameter of approximately 60 nm were observed to be formed in aqueous medium. Disintegration of the micelles into unimers in the presence of a disulfide reducing agent confirmed the crosslinking via disulfide bonds. While the release of DOX from the crosslinked micelles at pH 5.0 was faster compared to the release at pH 7.4, a high proportion of released DOX was found to retain the original active structure. Overall results demonstrate the simplicity and the versatility of the poly(PDSM)- b-poly(HPMA) system, which are potentially important in the design of new generation of polymer therapeutics.
Synthesis and Thermoresponsive Solution Properties of Poly[oligo(ethylene glycol) (meth)acrylamide]s: Biocompatible PEG Analogues
Publisher: American Chemical Society (ACS)
Date: 02-2012
DOI: 10.1021/MA202700Y
Nano‐ and Micro‐Engineering of Ordered Porous Blue‐Light‐Emitting Films by Templating Well‐Defined Organic Polymers Around Condensing Water Droplets
Publisher: Wiley
Date: 07-08-2003
Functional Disulfide-Stabilized Polymer−Protein Particles
Publisher: American Chemical Society (ACS)
Date: 30-09-2009
DOI: 10.1021/BM900817A
Abstract: Polymer-protein hybrid particles (PPHPs) have a significant potential in drug delivery, diagnosis, and biomedical imaging applications. Herein, we describe a simple route to disulfide cross-linked, poly(ethylene glycol)-streptavidin hybrid particles with tunable diameters. These particles have great versatility and potential for a number of reasons. First, they possess free biotin binding sites on their streptavidin (SAv) coated surface, enabling the conjugation of any biotinylated-molecule such as biotinylated antibodies. Second, core-stabilization can easily be controlled using reversible disulfide cross-links, and third, thiol- and ene-reactive functionalities in the core are available for the conjugation of drugs and labels. In detail, micelles having a biotinylated poly(ethylene glycol) corona and a disulfide cross-linked, reactive core were formed using alpha-biotin PEG-b-poly(pyridyldisulfide ethylmethacrylate) block copolymers synthesized via RAFT polymerization. Functionalization of the micelle core was performed in a one-pot reaction concurrent with the micellization and cross-linking processes by using a thiol-reactive model compound (a maleimide derivative of a green fluorophore). The resultant micelles displayed spherical morphology with a diameter of 54 +/- 4 nm. Biotin functionality was largely exposed on the micelle corona (75 mol % availability), as determined by a streptavidin/HABA assay. The micelles were subsequently decorated with (red fluorophore-labeled) streptavidin (SAv) through the accessible biotins on the surface, yielding SAv-linked micelle aggregates with tunable dimensions (in the range between 350 nm and 2 microm), as determined by transmission electron microscopy. Fluorescent-labels on the particles were monitored using confocal microscopy, revealing that the SAv coats the periphery of the PPHPs.
Engineering Polymers via Understanding the Effect of Anchoring Groups for Highly Stable Liquid Metal Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 14-02-2022
The importance of nanoparticle shape in cancer drug delivery
Publisher: Informa UK Limited
Date: 20-08-2015
DOI: 10.1517/17425247.2014.950564
Abstract: Nanoparticles have been successfully used for cancer drug delivery since 1995. In the design of commercial nanoparticles, size and surface characteristics have been exploited to achieve efficacious delivery. However, the design of optimized drug delivery platforms for efficient delivery to disease sites with minimal off-target effects remains a major research goal. One crucial element of nanoparticle design influencing both pharmacokinetics and cell uptake is nanoparticle morphology (both size and shape). In this succinct review, the authors collate the recent literature to assess the current state of understanding of the influence of nanoparticle shape on the effectiveness of drug delivery with a special emphasis on cancer therapy. This review draws on studies that have focused on the role of nonspherical nanoparticles used for cancer drug delivery. In particular, the authors summarize the influence of nanoparticle shape on biocirculation, biodistribution, cellular uptake and overall drug efficacy. By comparing spherical and nonspherical nanoparticles, they establish some general design principles to serve as guidelines for developing the next generation of nanocarriers for drug delivery. Pioneering studies on nanoparticles show that nonspherical shapes show great promise as cancer drug delivery vectors. Filamentous or worm-like micelles together with other rare morphologies such as needles or disks may become the norm for next-generation drug carriers, though at present, traditional spherical micelles remain the dominant shape of nanocarriers described in the literature due to synthesis and testing difficulties. The few reports that do exist describing nonspherical nanoparticles show a number of favorable properties that should encourage more efforts to develop facile and versatile nanoparticle synthesis methodologies with the flexibility to create different shapes, tunable sizes and adaptable surface chemistries. In addition, the authors note that there is a current lack of understanding into the factors governing (and optimizing) the inter-relationships of size, surface characteristics and shapes of many nanoparticles proposed for use in cancer therapy.
Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate: Detailed Structural Investigation via Coupled Size Exclusion Chromatography−Electrospray Ionization Mass Spe
Publisher: American Chemical Society (ACS)
Date: 03-01-2004
DOI: 10.1021/MA035244T
An approach to biodegradable star polymeric architectures using disulfide coupling
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B817037A
Abstract: The straightforward synthesis of biodegradable star polymers via both in situ polymerization from a trifunctional RAFT agent and post-polymerization conjugation of pyridyldisulfide-ended linear polymers to a trithiol precursor is described.
Polymers with Dithiobenzoate End Groups Constitutively Release Hydrogen Sulfide upon Exposure to Cysteine and Homocysteine
Publisher: American Chemical Society (ACS)
Date: 26-03-2020
RAFT polymerization with phthalimidomethyl trithiocarbonates or xanthates. On the origin of bimodal molecular weight distributions in living radical polymerization
Publisher: American Chemical Society (ACS)
Date: 11-07-2006
DOI: 10.1021/MA0604338
Shell-Cross-Linked Vesicles Synthesized from Block Copolymers of Poly(d ,l -lactide) and Poly(N-isopropyl acrylamide) as Thermoresponsive Nanocontainers
Publisher: American Chemical Society (ACS)
Date: 03-11-2004
DOI: 10.1021/LA0484016
Abstract: A polylactide (D,L-PLA) macroRAFT agent was prepared by utilizing a hydroxyl-functional trithiocarbonate as a coinitiator for the ring-opening polymerization. The length of the resultant polymer was controlled by the concentration of the coinitiator leading to the formation of two PLA polymers with M(n) = 12500 g mol(-)(1) (PDI = 1.46) and M(n) = 20500 g mol(-)(1) (PDI = 1.38) each with omega-trithiocarbonate functionality. Chain extension of PLA via the RAFT (free radical) polymerization of N-isopropyl acrylamide (NIPAAm) resulted in the formation of hiphilic block copolymers with the PNIPAAm block increasing in size with conversion. TEM measurements of the aggregates obtained by self-organization of the block copolymers in aqueous solutions indicated the formation of vesicles. The sizes of these aggregates were influenced by the ratio of both blocks and the molecular weight of each block. The lower critical solution temperature (LCST) of the block copolymer was largely unaffected by the size of each block. UV turbidity measurements indicated a higher LCST for the block copolymers than for the corresponding PNIPAAm homopolymers. Stabilization of the vesicles was attained by a cross-linking chain extension of the PNIPAAm block using hexamethylene diacrylate. As the trithiocarbonate group was located between the PLA and PNIPAAm blocks, the chain extension resulted in a cross-linked layer between the core and corona of the vesicles.
Hydrolyzable Poly[Poly(Ethylene Glycol) Methyl Ether Acrylate]-Colistin Prodrugs through Copper-Mediated Photoinduced Living Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 07-07-2017
Propagation and termination rate coefficients in N-vinylcarbazole free radical polymerization obtained via 440 nm pulsed laser and online H-1 NMR kinetic experiments
Publisher: Wiley
Date: 04-2003
Abstract: Propagation rate coefficients, k p , of N ‐vinylcarbazole in solution have been determined via visible light pulsed‐laser polymerization over a wide temperature range ( E A = 25.3 ± 5 kJ · mol −1 , A = 1.0 × 10 8 L · mol −1 · s −1 ). The k p data set was used to deduce (average) termination rate coefficients via 1 H NMR spectroscopic kinetic experiments and the corresponding Arrhenius parameters ( E A = −8.5 kJ · mol −1 ± 8 kJ · mol −1 ). Temperature dependence of the propagation rate coefficient, k p , in the free radical solution polymerization of NVC. The graph shows the data from 355 and 440 nm initiation as well as data previously obtained by Yamamoto et al. 5 The three sets of data have been analyzed separately (for details see text). magnified image Temperature dependence of the propagation rate coefficient, k p , in the free radical solution polymerization of NVC. The graph shows the data from 355 and 440 nm initiation as well as data previously obtained by Yamamoto et al. 5 The three sets of data have been analyzed separately (for details see text).
Cancer-Associated Fibroblasts in Pancreatic Ductal Adenocarcinoma Determine Response to SLC7A11 Inhibition
Publisher: American Association for Cancer Research (AACR)
Date: 12-05-2021
DOI: 10.1158/0008-5472.CAN-20-2496
Abstract: This study demonstrates that SLC7A11 in PDAC stromal cells is important for the tumor-promoting activity of CAFs and validates a clinically translatable nanomedicine for therapeutic SLC7A11 inhibition in PDAC.
Rapid Photochromic Switching in a Rigid Polymer Matrix Using Living Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 21-01-2006
DOI: 10.1021/MA052002F
Photochromic Spirooxazines Functionalized with Oligomers: Investigation of Core−Oligomer Interactions and Photomerocyanine Isomer Interconversion Using NMR Spectroscopy and DFT
Publisher: American Chemical Society (ACS)
Date: 12-04-2010
DOI: 10.1021/JO100081G
Abstract: Photochromic spirooxazines functionalized with poly(ethylene glycol) (PEG) and poly(dimethylsiloxane) (PDMS) oligomers were monitored using NMR spectroscopy at temperatures between 193 and 233 K before and after in situ exposure to UV irradiation. NOESY and ROESY experiments reveal the TTC (trans-s-trans-cis) isomer to be the dominant merocyanine isomer formed on photolysis, with some CTC (cis-s-trans-cis) isomer also present. Significant ROE cross peaks were observed between the "bulk" of the oligomeric units and protons across the entire photochromic core of the molecule, the intensity of these cross peaks suggesting that the interaction of the oligomer side chain and core of the molecule is significantly enhanced by the permanent attachment, especially with the PDMS side chain. The 2D NMR spectra indicate that there is exchange between the TTC and CTC isomers even at 193 K. This isomerization of the parent spirooxazine compounds, lacking the oligomeric side chains, was found to be acid-catalyzed, and DFT calculations support the strong possibility that it is the protonated merocyanine form that undergoes the facile isomerization process. Interconversion of the different merocyanine isomers is suggested to be fast on the NMR time scale under many experimental conditions, precluding the observation of different isomers using NMR spectroscopy at room temperature.
Facile production of nanoaggregates with tuneable morphologies from thermoresponsive P(DEGMA-co-HPMA)
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5PY01467K
Abstract: RAFT-mediated emulsion polymerization of styrene and subsequent morphological transition produces nanoaggregates with tuneable morphologies.
Synthesis and postfunctionalization of well-defined star polymers via double click chemistry
Publisher: Wiley
Date: 04-10-2011
DOI: 10.1002/POLA.25001
RAFT polymerization and thiol-ene modification of 2-vinyloxyethyl methacrylate: Towards functional branched polymers
Publisher: Elsevier BV
Date: 11-2009
Ambient temperature reversible addition–fragmentation chain transfer polymerisation
Publisher: Royal Society of Chemistry (RSC)
Date: 2001
DOI: 10.1039/B101794M
Design and Synthesis of Dual Thermoresponsive and Antifouling Hybrid Polymer/Gold Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 10-07-2009
DOI: 10.1021/MA9013127
Dynamic Protein Corona of Gold Nanoparticles with an Evolving Morphology
Publisher: American Chemical Society (ACS)
Date: 19-11-2021
Single-Molecular Heteroamyloidosis of Human Islet Amyloid Polypeptide
Publisher: American Chemical Society (ACS)
Date: 28-08-2019
Copolymerization propagation kinetics of dimethyl itaconate and styrene: Strong entropic contributions to the penultimate unit effect
Publisher: American Chemical Society (ACS)
Date: 28-04-2001
DOI: 10.1021/MA001952S
A lipid-anchored neurokinin 1 receptor antagonist prolongs pain relief by a three-pronged mechanism of action targeting the receptor at the plasma membrane and in endosomes
Publisher: Elsevier BV
Date: 2021
RAFT Synthesis and Aqueous Solution Behavior of Novel pH- and Thermo-Responsive (Co)Polymers Derived from Reactive Poly(2-vinyl-4,4-dimethylazlactone) Scaffolds
Publisher: American Chemical Society (ACS)
Date: 12-09-2013
DOI: 10.1021/MA4013187
A traceless reversible polymeric colistin prodrug to combat multidrug-resistant (MDR) gram-negative bacteria.
Publisher: Elsevier BV
Date: 08-2017
DOI: 10.1016/J.JCONREL.2017.02.005
Abstract: Colistin methanesulfonate (CMS) is the only prodrug of colistin available for clinical use for the treatment of infections caused by multidrug-resistant (MDR) Gram-negative bacteria. Owing to its slow and variable release, an alternative is urgently required to improve effectiveness. Herein we describe a PEGylated colistin prodrug whereby the PEG is attached via a cleavable linker (col-aaPEG) introducing an acetic acid terminated poly (ethylene glycol) methyl ether (aaPEG) onto the Thr residue of colistin. Due to the labile ester containing link, this prodrug is converted back into active colistin in vitro within 24h. Compared to CMS, it showed a similar or better antimicrobial performance against two MDR isolates of Pseudomonas aeruginosa and Acinetobacter baumannii through in vitro disk diffusion, broth dilution and time-kill studies. In a mouse infection model, col-aaPEG displayed acceptable bacterial killing against P. aeruginosa ATCC 27853 and no nephrotoxicity was found after systemic administration, suggesting it to be a potential alternative for CMS.
The Use of Novel F-RAFT Agents in High Temperature and High Pressure Ethene Polymerization: Can Control be Achieved?
Publisher: CSIRO Publishing
Date: 2007
DOI: 10.1071/CH07200
Abstract: Simulations are employed to establish the feasibility of achieving controlled/living ethene polymerizations. Such simulations indicate that reversible addition–fragmentation chain transfer (RAFT) agents carrying a fluorine Z group may be suitable to establish control in high-pressure high-temperature ethene polymerizations. Based on these simulations, specific fluorine (F-RAFT) agents have been designed and tested. The initial results are promising and indicate that it may indeed be possible to achieve molecular weight distributions with a polydispersity being significantly lower than that observed in the conventional free radical process. In our initial trials presented here (using the F-RAFT agent isopropylfluorodithioformate), a correlation between the degree of polymerization and conversion can indeed be observed. Both the lowered polydispersity and the linear correlation between molecular weight and conversion indicate that control may in principle be possible.
Functionalization of NaGdF4 nanoparticles with a dibromomaleimide-terminated polymer for MR/optical imaging of thrombosis
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9PY01568J
Abstract: A thrombosis-targeted molecular imaging probe with magnetic resonance (MR) and optical dual-modality capacity using dibromomaleimide (DBM)-bearing polymer-grafted NaGdF 4 nanoparticles.
Cellular Interactions of Liposomes and PISA Nanoparticles during Human Blood Flow in a Microvascular Network
Publisher: Wiley
Date: 25-06-2020
Functional, star polymeric molecular carriers, built from biodegradable microgel/nanogel cores
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CC04532B
Abstract: Acid and disulfide biodegradable cross-linkers have been employed to generate microgel star polymers, using RAFT-polymer arms. RAFT end-groups were then exploited to attach functional compounds via both thiol-ene and thiol-pyridyl disulfide exchange reactions.
Elucidating the effect of sequence and degree of polymerization on antimicrobial properties for block copolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9PY01435G
Abstract: Sequence-controlled copolymers have recently attracted great interest in a variety of applications, including antimicrobial materials.
Determination of propagation rate coefficients for an α-substituted acrylic ester: Pulsed laser polymerization of dimethyl itaconate
Publisher: Wiley
Date: 15-06-2000
DOI: 10.1002/(SICI)1099-0518(20000615)38:12<2192::AID-POLA80>3.0.CO;2-G
Implementing the reversible addition–fragmentation chain transfer process in PREDICI
Publisher: Wiley
Date: 02-02-2004
DOI: 10.1002/POLA.11089
Synthesis, Characterization, and Multilayer Assembly of pH Sensitive Graphene-Polymer Nanocomposites
Publisher: American Chemical Society (ACS)
Date: 27-04-2010
DOI: 10.1021/LA1001978
Abstract: pH sensitive graphene-polymer composites have been prepared by the modification of graphene basal planes with pyrene-terminated poly(2-N,N'-(dimethyl amino ethyl acrylate) (PDMAEA) and poly(acrylic acid) (PAA) via pi-pi stacking. The pyrene-terminal PDMAEA and PAA were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization with a pyrene-functional RAFT agent. The graphene-polymer composites were found to demonstrate phase transfer behavior between aqueous and organic media at different pH values. Atomic force microscopy (AFM) analysis revealed that the thicknesses of the graphene-polymer sheets were approximately 3.0 nm when prepared using PDMAEA (M(n): 6800 and PDI: 1.12). The surface coverage of polymer chains on the graphene basal plane was calculated to be 5.3 x 10(-11) mol cm(-2) for PDMAEA and 1.3 x 10(-10) mol cm(-2) for PAA. The graphene-polymer composites were successfully characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, and thermogravimetric analysis (TGA). Self-assembly of the two oppositely charged graphene-polymer composites afforded layer-by-layer (LbL) structures as evidenced by high-resolution scanning electron microscopy (SEM) and quartz crystal microbalance (QCM) measurements.
Interactions of core cross-linked poly(2-oxazoline) and poly(2-oxazine) micelles with immune cells in human blood
Publisher: Elsevier BV
Date: 07-2021
Elucidating the Influences of Size, Surface Chemistry, and Dynamic Flow on Cellular Association of Nanoparticles Made by Polymerization-Induced Self-Assembly
Publisher: Wiley
Date: 25-07-2018
Abstract: The size and surface chemistry of nanoparticles dictate their interactions with biological systems. However, it remains unclear how these key physicochemical properties affect the cellular association of nanoparticles under dynamic flow conditions encountered in human vascular networks. Here, the facile synthesis of novel fluorescent nanoparticles with tunable sizes and surface chemistries and their association with primary human umbilical vein endothelial cells (HUVECs) is reported. First, a one-pot polymerization-induced self-assembly (PISA) methodology is developed to covalently incorporate a commercially available fluorescent dye into the nanoparticle core and tune nanoparticle size and surface chemistry. To characterize cellular association under flow, HUVECs are cultured onto the surface of a synthetic microvascular network embedded in a microfluidic device (SynVivo, INC). Interestingly, increasing the size of carboxylic acid-functionalized nanoparticles leads to higher cellular association under static conditions but lower cellular association under flow conditions, whereas increasing the size of tertiary amine-decorated nanoparticles results in a higher level of cellular association, under both static and flow conditions. These findings provide new insights into the interactions between polymeric nanomaterials and endothelial cells. Altogether, this work establishes innovative methods for the facile synthesis and biological characterization of polymeric nanomaterials for various potential applications.
RAFT controlled synthesis of six-armed biodegradable star polymeric architectures via a ‘core-first’ methodology
Publisher: Elsevier BV
Date: 09-2009
Accessing Chain Length Dependent Termination Rate Coefficients of Methyl Methacrylate (MMA) via the Reversible Addition Fragmentation Chain Transfer (RAFT) Process
Publisher: Wiley
Date: 14-10-2005
Direct Synthesis of Well-Defined Heterotelechelic Polymers for Bioconjugations
Publisher: American Chemical Society (ACS)
Date: 19-07-2008
DOI: 10.1021/MA800289U
Studies on the propagation reaction in the free radical polymerization of ethylα-hydroxymethacrylate
Publisher: Wiley
Date: 11-2000
DOI: 10.1002/1521-3935(20001101)201:16<2128::AID-MACP2128>3.0.CO;2-3
Thioketone‐Mediated Polymerization of Butyl Acrylate: Controlling Free‐Radical Polymerization via a Dormant Radical Species
Publisher: Wiley
Date: 16-03-2007
Stimuli-responsive nano-assemblies for remotely controlled drug delivery
Publisher: Elsevier BV
Date: 06-2020
Well-defined PDMAEA stars via Cu(0)-mediated reversible deactivation radical polymerization
Publisher: American Chemical Society (ACS)
Date: 15-11-2016
Rapid synthesis of ultrahigh molecular weight and low polydispersity polystyrene diblock copolymers by RAFT-mediated emulsion polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5PY00166H
Abstract: An environmentally friendly emulsion technique produces uniform nanoparticles with precise control over molecular weight and particle size.
Molecular composite materials formed from block copolymers containing a side-chain liquid crystalline segment and an amorphous styrene/maleic anhydride segment
Publisher: Elsevier BV
Date: 10-2004
Polymerization-Induced Self-Assembly: The Effect of End Group and Initiator Concentration on Morphology of Nanoparticles Prepared via RAFT Aqueous Emulsion Polymerization
Publisher: American Chemical Society (ACS)
Date: 31-08-2017
Synthesis of biodegradable hydrogel nanoparticles for bioapplications using inverse miniemulsion RAFT polymerization
Publisher: American Chemical Society (ACS)
Date: 18-08-2011
DOI: 10.1021/MA201531W
Reversible addition fragmentation chain transfer polymerization of sterically hindered monomers: Toward well‐defined rod/coil architectures
Publisher: Wiley
Date: 06-04-2004
DOI: 10.1002/POLA.20098
A Detailed On‐Line FT/NIR and 1H NMR Spectroscopic Investigation into Factors Causing Inhibition in Xanthate‐Mediated Vinyl Acetate Polymerization
Publisher: Wiley
Date: 26-04-2004
Proteins Conjugated with Sulfoxide-Containing Polymers Show Reduced Macrophage Cellular Uptake and Improved Pharmacokinetics
Publisher: American Chemical Society (ACS)
Date: 19-05-2020
pH-Responsive Polymers for Improving the Signal-to-Noise Ratio of Hypoxia PET Imaging with [18F]Fluoromisonidazole
Publisher: Wiley
Date: 06-04-2020
Synthesis of macromonomers via catalytic chain transfer (CCT) polymerization and their characterization via NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS)
Publisher: Wiley
Date: 04-2004
Synthesis of dendritic carbohydrate end‐functional polymers via RAFT: Versatile multi‐functional precursors for bioconjugations
Publisher: Wiley
Date: 21-07-2009
DOI: 10.1002/POLA.23482
Synthesis of functional core, star polymers via RAFT polymerization for drug delivery applications
Publisher: Wiley
Date: 12-04-2012
Abstract: Poly(oligoethylene glycol) methyl ether acrylate was polymerized via reversible addition fragmentation transfer polymerization (RAFT), and then chain extended in the presence of both a cross-linker and vinyl benzaldehyde (VBA), yielding monodisperse star polymers. The presence of aldehyde groups in the core was exploited to attach doxorubicin. The drug loading was controlled by the amount of VBA incorporated (until 28 wt% in drug). The doxorubicin release was studied at pH = 5.5 and 7.4 conditions representative of endosomal and extra cellular environments. In vitro studies revealed that the doxorubicin-conjugated star polymers had a level of cytotoxicity comparable to that found for free doxorubicin. Confocal microscopy and flow cytometry studies confirmed efficient cell uptake of the star polymers.
Kinetic Analysis of Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerizations: Conditions for Inhibition, Retardation, and Optimum Living Polymerization
Publisher: Wiley
Date: 11-2002
DOI: 10.1002/1521-3919(20021101)11:8<823::AID-MATS823>3.0.CO;2-R
Chain Length Dependent Termination Rate Coefficients of Methyl Methacrylate (MMA) in the Gel Regime: Accessing kti,i Using Reversible Addition-Fragmentation Chain
Publisher: American Chemical Society (ACS)
Date: 20-03-2007
DOI: 10.1021/MA062405V
Accelerated Amyloid Beta Pathogenesis by Bacterial Amyloid FapC
Publisher: Wiley
Date: 16-07-2020
Abstract: The gut–brain axis has attracted increasing attention in recent years, fueled by accumulating symptomatic, physiological, and pathological findings. In this study, the aggregation and toxicity of amyloid beta (A β ), the pathogenic peptide associated with Alzheimer's disease (AD), seeded by FapC amyloid fragments (FapCS) of Pseudomonas aeruginosa that colonizes the gut microbiome through infections are examined. FapCS display favorable binding with A β and a catalytic capacity in seeding the peptide amyloidosis. Upon seeding, twisted A β fibrils assume a much‐shortened periodicity approximating that of FapC fibrils, accompanied by a 37% sharp rise in the fibrillar diameter, compared with the control. The robust seeding capacity for A β by FapCS and the biofilm fragments derived from P. aeruginosa entail abnormal behavior pathology and immunohistology, as well as impaired cognitive function of zebrafish. Together, the data offer the first concrete evidence of structural integration and inheritance in peptide cross‐seeding, a crucial knowledge gap in understanding the pathological correlations between different amyloid diseases. The catalytic role of infectious bacteria in promoting A β amyloidosis may be exploited as a potential therapeutic target, while the altered mesoscopic signatures of A β fibrils may serve as a prototype for molecular assembly and a biomarker for screening bacterial infections in AD.
Polymer-Assisted Magnetic Nanoparticle Assemblies for Biomedical Applications
Publisher: American Chemical Society (ACS)
Date: 08-11-2020
Pulsed Laser Copolymerization of Ring-Opening Cyclic Allylic Sulfide Monomers with Methyl Methacrylate and Styrene
Publisher: American Chemical Society (ACS)
Date: 21-02-2002
DOI: 10.1021/MA0111663
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
Functionalizing Biodegradable Dextran Scaffolds Using Living Radical Polymerization: New Versatile Nanoparticles for the Delivery of Therapeutic Molecules
Publisher: American Chemical Society (ACS)
Date: 18-10-2012
DOI: 10.1021/MP300144Y
Abstract: Conferring biodegradability to nanoparticles is vitally important when nanomedicine applications are being targeted, as this prevents potential problems with bioaccumulation of byproducts after delivery. In this work, dextran has been modified (and rendered hydrophobic) by partial acetalation. A solid state NMR method was first developed to fully characterize the acetalated polymers. In a subsequent synthetic step, RAFT functionality was attached via residual unmodified hydroxyl groups. The RAFT groups were then used in a living free radical polymerization reaction to control the growth of hydrophilic PEG-methacrylate chains, thereby generating hiphilic comblike polymers. The hiphilic polymers were then self-assembled in water to form various morphologies, including small vesicles, wormlike rods, and micellar structures, with PEG at the periphery acting as a nonfouling biocompatible polymer layer. The acetalated dextran nanoparticles were designed for potential doxorubicin (DOX) delivery application based on the premise that in the cell compartments (endosome, lysozome) the acetalated dextran would hydrolyze, destroying the nanoparticle structure, releasing the encapsulated DOX. In-vitro studies confirmed minimal cytotoxicity of the (unloaded) nanoparticles, even after 3 days, proving that the hydrolysis products from the acetal groups (methanol and acetone) had no observable cytotoxic effect. An intriguing initial result is reported that in vitro studies of DOX-loaded dextran-nanoparticles (compared to free DOX) revealed an increased differential toxicity toward a cancer cell line when compared to a normal cell line. Efficient accumulation of DOX in a human neuroblastoma cell line (SY-5Y) was confirmed by both confocal microscopy and flow cytometry measurements. Furthermore, the time dependent release of DOX was monitored using fluorescence lifetime imaging microscopy (FLIM) in SY-5Y live cells. FLIM revealed bimodal lifetime distributions, showing the accumulation of both DOX-loaded dextran-nanoparticles and subsequent release of DOX in the living cells. From FLIM data analysis, the amount of DOX released in SY-5Y cells was found to increase from 35% to 55% when the incubation time increased from 3 h to 24 h.
Molecular weight (hydrodynamic volume) dictates the systemic pharmacokinetics and tumour disposition of PolyPEG star polymers
Publisher: Elsevier BV
Date: 11-2015
DOI: 10.1016/J.NANO.2015.08.001
Abstract: Herein we report for the first time the biological fate of poly[(oligoethylene glycol) acrylate] (POEGA) star polymers synthesised via a versatile arm-first reversible addition-fragmentation chain transfer (RAFT) polymerisation approach. The biopharmaceutical behaviour of three different molecular weight (49, 64 and 94kDa) POEGA stars was evaluated in rats and nude mice bearing human MDA MB-231 tumours after intravenous administration. The 94kDa star polymer exhibited a longer plasma exposure time than the 49kDa or 64kDa star polymer an observation attributable to differences in the rates of both polymer biodegradation and urinary excretion. Tumour biodistribution also correlated with molecular weight and was greatest for the longest circulating 94kDa star. Different patterns of liver and spleen biodistribution were observed between mice and rats for the different sized polymers. The polymers were also well-tolerated in vivo and in vitro at therapeutic concentrations. Advances in nanotechnology has enabled scientists to produce nanoparticle as drug carriers in cancer therapeutics. In this article, the authors studied the biological fate of poly[(oligoethylene glycol) acrylate] (POEGA) star polymers of different size, after intravenous injections. This would allow the subsequent comparison to other drug delivery systems for better drug delivery.
Polymers with acyl-protected perthiol chain termini as convenient building blocks for doubly responsive H2S-donating nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY01484H
Abstract: H 2 S-releasing polymers with an acyl-protected perthiol chain terminus were prepared using a simple, high yielding end-group modification process.
Degradation of Poly(methyl methacrylate) Model Compounds Under Extreme Environmental Conditions
Publisher: Wiley
Date: 17-05-2010
Comparison of the Mayo and chain length distribution procedures for the measurement of chain transfer constants
Publisher: American Chemical Society (ACS)
Date: 20-08-1999
DOI: 10.1021/MA990076J
Gadolinium-functionalized nanoparticles for application as magnetic resonance imaging contrast agents
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6PY01797E
Abstract: Polymerization-induced self-assembly (PISA) is an easily applied synthetic technique for the preparation of polymer nanoparticles with various shapes and at high concentrations.
Human plasma proteome association and cytotoxicity of nano-graphene oxide grafted with stealth polyethylene glycol and poly(2-ethyl-2-oxazoline)
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8NR00835C
Abstract: Human plasma proteome associations with nGO grafted with stealth polymers PEG and PEtOx.
Dendrimers as Scaffolds for Reversible Addition Fragmentation Chain Transfer (RAFT) Agents: a Route to Star-Shaped Block Copolymers
Publisher: CSIRO Publishing
Date: 2005
DOI: 10.1071/CH05036
Abstract: Star-shaped block copolymers of styrene and n-butyl acrylate having three, six, and twelve pendent arms were successfully synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization. Dendritic cores (based on 1,1,1-trimethylolpropane) of generation 0, 1, and 2 have been functionalized with 3-benzylsulfanylthiocarbonylsulfanylpropionic ester groups and have subsequently been employed to mediate the polymerization of styrene and n-butyl acrylate to generate macro-star-RAFT agents as starting materials for chain extension. The chain extension of the macro-star-RAFT agents with either styrene or n-butyl acrylate by bulk free radical polymerization at 60°C gives narrowly distributed polymer (final polydispersities close to 1.2) increasing linearly in molecular weight with increasing monomer-to-polymer conversion. However, with an increasing number of arms (i.e., when going from three- to twelve-armed star polymers), the chain extension becomes significantly less efficient. The molecular weight of the generated block copolymers was assessed using 1H NMR spectroscopy as well as size exclusion chromatography calibrated with linear polystyrene standards. The hydrodynamic radius, Rh, of the star block copolymers as well as the precursor star polymers was determined in tetrahydrofuran by dynamic light scattering (90°) at 25°C. Interestingly, the observed Rh–Mn relationships indicate a stronger dependence of Rh on Mn for poly(butyl acrylate) stars than for the corresponding styrene polymers. Rh increases significantly when the macro-star-RAFT agent is chain extended with either styrene or n-butyl acrylate.
Synthesis of star polymers by RAFT polymerization as versatile nanoparticles for biomedical applications
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH17391
Abstract: The precise control of polymer chain architecture has been made possible by developments in polymer synthesis and conjugation chemistry. In particular, the synthesis of polymers in which at least three linear polymeric chains (or arms) are tethered to a central core has yielded a useful category of branched architecture, so-called star polymers. Fabrication of star polymers has traditionally been achieved using either a core-first technique or an arm-first approach. Recently, the ability to couple polymeric chain precursors onto a functionalized core via highly efficient coupling chemistry has provided a powerful new methodology for star synthesis. Star syntheses can be implemented using any of the living polymerization techniques using ionic or living radical intermediates. Consequently, there are innumerable routes to fabricate star polymers with varying chemical composition and arm numbers. In comparison with their linear counterparts, star polymers have unique characteristics such as low viscosity in solution, prolonged blood circulation, and high accumulation in tumour regions. These advantages mean that, far beyond their traditional application as rheology control agents, star polymers may also be useful in the medical and pharmaceutical sciences. In this account, we discuss recent advances made in our laboratory focused on star polymer research ranging from improvements in synthesis through to novel applications of the product materials. Specifically, we examine the core-first and arm-first preparation of stars using reversible addition–fragmentation chain transfer (RAFT) polymerization. Further, we also discuss several biomedical applications of the resulting star polymers, particularly those made by the arm-first protocol. Emphasis is given to applications in the emerging area of nanomedicine, in particular to the use of star polymers for controlled delivery of chemotherapeutic agents, protein inhibitors, signalling molecules, and siRNA. Finally, we examine possible future developments for the technology and suggest the further work required to enable clinical applications of these interesting materials.
Direct esterification of a hydroxyl functional polyester resin with p-hydroxybenzoic acid
Publisher: Elsevier BV
Date: 11-2000
Consistent experimental and theoretical evidence for long-lived intermediate radicals in living free radical polymerization
Publisher: American Chemical Society (ACS)
Date: 12-11-2004
DOI: 10.1021/JA046292B
Abstract: The cumyl dithiobenzoate (CDB)-mediated reversible addition fragmentation chain transfer (RAFT) polymerization of styrene at 30 degrees C is studied via both kinetic experiments and high-level ab initio molecular orbital calculations. The kinetic data clearly indicate the delayed onset of steady-state behavior. Such an observation is consistent with the slow fragmentation model for the RAFT process, but cannot be reconciled with the cross-termination model. The comprehensive failure of the cross-termination model is quantitatively demonstrated in a detailed kinetic analysis, in which the independent influences of the pre-equilibria and main equilibria and the possible chain length dependence of cross-termination are fully taken into account. In contrast, the slow fragmentation model can describe the data, provided the main equilibrium has a large fragmentation constant of at least 8.9 x 10(6) L mol(-1). Such a high equilibrium constant (for both equilibria) is consistent with high-level ab initio quantum chemical calculations (K = 7.3 x 10(6) L mol(-1)) and thus appears to be physically realistic. Given that the addition rate coefficient for macroradicals to (polymeric) RAFT agent is 4 x 10(6) L mol(-1) s(-1), this implies that the lifetime of the RAFT adduct radicals is close to 2.5 s. Since the radical is also kinetically stable to termination, it can thus function as a radical sink in its own right.
Approaches to phthalimido and amino end-functional polystyrene by atom transfer radical polymerisation (ATRP)
Publisher: Elsevier BV
Date: 2006
Influences of the Structural Design of RAFT Agents on Living Radical Polymerization Kinetics
Publisher: American Chemical Society
Date: 26-06-2003
Determination of the propagation rate coefficient for 3-[tris(trimethylsilyloxy)silyl] propyl methacrylate by pulsed-laser polymerization
Publisher: Elsevier BV
Date: 02-2000
Copolymerization Propagation Kinetics of Para-Substituted Styrenes: A Critical Test of the Implicit Penultimate Model
Publisher: American Chemical Society (ACS)
Date: 06-05-1999
DOI: 10.1021/MA990077B
Amidine functionality as a stimulus-responsive building block
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CS60065C
Abstract: This mini-review describes basic features and applications of small molecules and macromolecules containing amidine, and to a lesser extent, guanidine functional groups. The emphasis in this article is on the exploitation of such functionality as species that are capable of reversibly binding carbon dioxide in the presence of water, a process that also commonly involves a hydrophobic-to-hydrophilic transition. The review is not intended to be exhaustive but rather serves to highlight this one particular feature and demonstrate its application in areas ranging from reversible emulsion stabilization, purification and reversible self-assembly of polymeric nanoparticles.
Living free-radical polymerization of styrene under a constant source of γ radiation
Publisher: Wiley
Date: 06-11-2002
DOI: 10.1002/POLA.10086
Reversible Addition Fragmentation Chain Transfer (RAFT) and Hetero-Diels−Alder Chemistry as a Convenient Conjugation Tool for Access to Complex Macromolecular Designs
Publisher: American Chemical Society (ACS)
Date: 20-05-2008
DOI: 10.1021/MA8002328
Cofibrillization of Pathogenic and Functional Amyloid Proteins with Gold Nanoparticles against Amyloidogenesis.
Publisher: American Chemical Society (ACS)
Date: 14-11-2017
Mitigating Human IAPP Amyloidogenesis In Vivo with Chiral Silica Nanoribbons
Publisher: Wiley
Date: 07-10-2018
Synthesis of Poly(styrene) Star Polymers Grown from Sucrose, Glucose, and Cyclodextrin Cores via Living Radical Polymerization Mediated by a Half-Metallocene Iron Carbonyl Complex
Publisher: American Chemical Society (ACS)
Date: 07-2001
DOI: 10.1021/MA0021803
Enhanced Ionization in Electrospray Ionization Mass Spectrometry of Labile End-Group-Containing Polystyrenes Using Silver(I) Tetrafluoroborate as Doping Salt
Publisher: American Chemical Society (ACS)
Date: 21-02-2008
DOI: 10.1021/MA702163V
Reproducible Access to Tunable Morphologies via the Self-Assembly of an Amphiphilic Diblock Copolymer in Water
Publisher: American Chemical Society (ACS)
Date: 19-03-2015
A Mechanistic Perspective on Solvent Effects in Free-Radical Copolymerization
Publisher: Informa UK Limited
Date: 1998
Functional gold nanoparticles for the storage and controlled release of nitric oxide: Applications in biofilm dispersal and intracellular delivery
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4TB00632A
Abstract: Gold nanoparticles (size 10 nm) were designed to store and release nitric oxide (NO), by functionalizing their surfaces with functional polymers modified with NO-donor molecules.
Transfer and propagation reactions in free-radical copolymerization
Publisher: Wiley
Date: 06-2002
DOI: 10.1002/1521-3900(200206)182:1<131::AID-MASY131>3.0.CO;2-C
Zinc-coordination and C-peptide complexation: a potential mechanism for the endogenous inhibition of IAPP aggregation
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC04291D
Abstract: Zinc-coordination and C-peptide complexation stabilize IAPP and inhibit its amyloid aggregation.
Thermoresponsive silver/polymer nanohybrids with switchable metal enhanced fluorescence
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CC18069C
Abstract: In this communication we describe a new approach to the fabrication of fluorescent silver olymer nanohybrids with thermo-switchable metal enhanced fluorescence (MEF). By manipulating a soft polymer spacer between the silver nanoparticles and the fluorophores a tunable MEF was achieved.
Polystyrene comb polymers built on cellulose or poly(styrene-co-2-hydroxyethylmethacrylate) backbones as substrates for the preparation of structured honeycomb films
Publisher: Elsevier BV
Date: 10-2005
The precise molecular location of gadolinium atoms has a significant influence on the efficacy of nanoparticulate MRI positive contrast agents
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3PY01676E
Facile one-pot/one-step synthesis of heterotelechelic N-acylated poly(aminoester) macromonomers for carboxylic acid decorated comb polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6PY01553K
Abstract: Optimal monomer ratios in the spontaneous zwitterionic copolymerisation yield defined telechelic macromonomers with near quantitative ω-carboxylic acid end groups.
One-Pot Synthesis of ABCDE Multiblock Copolymers with Hydrophobic, Hydrophilic, and Semi-Fluorinated Segments
Publisher: Wiley
Date: 24-10-2017
Abstract: The scope and accessibility of sequence-controlled multiblock copolymers is demonstrated by direct "in situ" polymerization of hydrophobic, hydrophilic and fluorinated monomers. Key to the success of this strategy is the ability to synthesize ABCDE, EDCBA and EDCBABCDE sequences with high monomer conversions (>98 %) through iterative monomer additions, yielding excellent block purity and low overall molar mass dispersities (Ð<1.16). Small-angle X-ray scattering showed that certain sequences can form well-ordered mesostructures. This synthetic approach constitutes a simple and versatile platform for expanding the availability of tailored polymeric materials from readily available monomers.
Modular photo-induced RAFT polymerised hydrogels via thiol-ene click chemistry for 3D cell culturing
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY01038A
Abstract: Visible-light induced thiol–ene click gelation of RAFT polymers, creating a modular hydrogel system for 3D cell culture assays.
An atom-efficient conjugation approach to well-defined block copolymers using RAFT chemistry and hetero Diels–Alder cycloaddition
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B718180A
Abstract: The tendency of electron-deficient dithioesters to undergo hetero Diels-Alder cycloadditions is successfully used to generate polymer conjugates between a RAFT-polymerized poly(styrene) and a diene-terminated poly(epsilon-caprolactone).
Direct esterification of a hydroxyl functional polyester resin with p-hydroxybenzoic acid
Publisher: Elsevier BV
Date: 11-2000
NanoEHS beyond toxicity – focusing on biocorona
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6EN00579A
Abstract: We believe continued development of the field of environmental health and safety of nanomaterials (nanoEHS) hinges on a critical extension from reporting macroscopic and microscopic phenomena to understanding nano-biomolecular interactions.
End-Group Analysis of Polymers by Electrospray Ionization Mass Spectrometry: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one Initiated Free-Radical Photopolymerization
Publisher: CSIRO Publishing
Date: 2002
DOI: 10.1071/CH02107
Abstract: End-group analysis of poly(methyl acrylate) and poly(dicyclohexyl itaconate) initiated by 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (MMMP) has been performed by electrospray ionization mass spectrometry (ESI-MS). MMMP has been found to fragment into two radicals that are near-equally capable of initiating free-radical polymerization processes. The present study indicates the occurrence of significant termination by disproportionation in the polymerization of methyl acrylate. Additionally, it has been demonstrated that dicyclohexyl itaconate undergoes termination by disproportionation almost exclusively.
Nanotoxicology and nanomedicine: The Yin and Yang of nano-bio interactions for the new decade
Publisher: Elsevier BV
Date: 08-2021
Monomer substituent effects in catalytic chain transfer polymerization: tert-butyl methacrylate and dimethyl itaconate
Publisher: American Chemical Society (ACS)
Date: 12-2002
DOI: 10.1021/MA020719M
Well-Defined Protein−Polymer Conjugates via in Situ RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 15-05-2007
DOI: 10.1021/JA070956A
Abstract: Biotechnology, biomedicine, and nanotechnology applications would benefit from methods generating well-defined, monodisperse protein-polymer conjugates, avoiding time-consuming and difficult purification steps. Herein, we report the in situ synthesis of protein-polymer conjugates via reversible addition-fragmentation chain transfer polymerization (RAFT) as an efficient method to generate well-defined, homogeneous protein-polymer conjugates in one step, eliminating major postpolymerization purification steps. A water soluble RAFT agent was conjugated to a model protein, bovine serum albumin (BSA), via its free thiol group at Cys-34 residue. The conjugation of the RAFT agent to BSA was confirmed by UV-visible spectroscopy, matrix-assisted laser desorption ionization--time of flight (MALDI-TOF), and 1H NMR. BSA-macroRAFT agent was then used to control the polymerization of two different water soluble monomers, N-isopropylacrylamide (NIPAAm) and hydroxyethyl acrylate (HEA), in aqueous medium at 25 degrees C. The growth of the polymer chains from BSA-macroRAFT agent was characterized by size exclusion chromatography (SEC), 1H NMR, MALDI-TOF, and polyacrylamide gel electrophoresis (PAGE) analyses. The controlled character of the RAFT polymerizations was confirmed by the linear evolution of molecular weight with monomer conversion. The SEC analyses showed no detectable free, nonconjugated polymer formation during the in situ polymerization. The efficiency of BSA-macroRAFT agent to generate BSA-polymer conjugates was found to be ca. 1 by deconvolution of the SEC traces of the polymerization mixtures. The structural integrity and the conformation-related esterase activity of BSA were found to be unaffected by the polymerization conditions and the conjugation of the polymer chain. BSA-poly(NIPAAm) conjugates showed hybrid temperature-dependent phase separation and aggregation behavior. The lower critical solution temperature values of the conjugates were found to increase with the decrease in molecular weight of poly(NIPAAm) block conjugated to BSA.
Bio-reversible polyPEGylation
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B915512K
Abstract: Protein conjugation with biodegradable polyPEGMA and subsequent release is described.
Targeting endosomal receptors, a new direction for polymers in nanomedicine
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3TB00156C
Abstract: In this perspective, we outline a new opportunity for exploiting nanoparticle delivery of antagonists to target G-protein coupled receptors localized in intracellular compartments.
Reducing the cytotoxicity of ZnO nanoparticles by a pre-formed protein corona in a supplemented cell culture medium
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5RA14870G
Abstract: The safety of zinc oxide (ZnO) nanoparticles (NPs) remains a critical concern considering that they are a common constituent in cosmetics and sunscreen formulation.
Reversible addition-fragmentation chain transfer synthesis of amidine-based, CO2-responsive homo and AB diblock (Co)polymers comprised of histamine and their gas-triggered self-assembly in water
Publisher: Wiley
Date: 29-10-2013
DOI: 10.1002/POLA.26397
Recent advances in molecular imaging of atherosclerotic plaques and thrombosis
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0NR00599A
Abstract: Recent advances in emerging molecular imaging techniques bring new opportunities in the diagnosis of atherosclerosis plaques and thrombosis.
PEGylated gold nanoparticles functionalized with β-cyclodextrin inclusion complexes: Towards metal nanoparticle-polymer-carbohydrate cluster biohybrid materials
Publisher: CSIRO Publishing
Date: 2010
DOI: 10.1071/CH10091
Abstract: A cholesterol-functional trithiocarbonate reversible addition–fragmentation chain transfer (RAFT) agent was synthesized and employed to generate well-defined poly(polyethylene glycol) acrylate with cholesterol chain termini using RAFT polymerization. Subsequently, the polymers were grafted onto the surface of gold nanoparticles using the trithiocarbonate functionality to bind to the gold surface. The cholesterol moieties were then modified via complexation with β-cyclodextrin. The step-by-step modification of gold nanoparticles was characterized by dynamic light scattering, attenuated total reflection infrared spectroscopy and surface plasmon resonance analysis.
Engineering macromolecular nanocarriers for local delivery of gaseous signaling molecules
Publisher: Elsevier BV
Date: 12-2021
A Novel Method for the Measurement of Chain Transfer to Monomer Constants in Styrene Homopolymerizations: The Pulsed Laser Rotating Reactor Assembly
Publisher: American Chemical Society (ACS)
Date: 28-03-2001
DOI: 10.1021/MA001871W
A novel small molecule that kills a subset of MLL-rearranged leukemia cells by inducing mitochondrial dysfunction
Publisher: Springer Science and Business Media LLC
Date: 22-01-2019
Understanding Effects of PAMAM Dendrimer Size and Surface Chemistry on Serum Protein Binding with Discrete Molecular Dynamics Simulations
Publisher: American Chemical Society (ACS)
Date: 31-07-2018
Star Polymers
Publisher: American Chemical Society (ACS)
Date: 14-06-2016
DOI: 10.1021/ACS.CHEMREV.6B00008
Abstract: Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an ex le, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.
Well-Defined Diblock Glycopolymers from RAFT Polymerization in Homogeneous Aqueous Medium
Publisher: American Chemical Society (ACS)
Date: 08-10-2005
DOI: 10.1021/MA051310A
RAFT and click chemistry: A versatile approach to well-defined block copolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B611224B
Abstract: The combination of reversible chain transfer chemistry with highly orthogonal [2 + 3] cycloadditions ('click chemistry') allows for the synthesis of well-defined block copolymers of monomers with extremely disparate reactivities.
Cationic acrylate oligomers comprising amino acid mimic moieties demonstrate improved antibacterial killing efficiency
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6TB02787C
Abstract: A new class of oligomeric cationic polymers with lipophilic tails were developed as antibacterial lipopeptide mimics, and revealed structurally dependent bacterial killing.
Advanced Computational Strategies for Modelling the Evolution of Full Molecular Weight Distributions Formed During Multiarmed (Star) Polymerisations
Publisher: Wiley
Date: 30-03-2005
Depolymerization kinetics of di(4‐tert‐butyl cyclohexyl) itaconate and Mark‐Houwink‐Kuhn‐Sakurada parameters of di(4‐tert‐butyl cyclohexyl) itaconate and di‐n‐butyl itaconate
Publisher: Wiley
Date: 09-04-2007
DOI: 10.1002/POLA.21957
The application of a photochromic probe to monitor the self-assembly of thermosensitive block copolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0SM00746C
Accessing the Chain Length Dependence of the Termination Rate Coefficient for Disparate Length Radicals via Reversible Addition Fragmentation Chain Transfer Chemistry: A Theoretical Study
Publisher: American Chemical Society (ACS)
Date: 27-06-2006
DOI: 10.1021/MA060646X
Multipulse Initiation in Pulsed Laser and Quenched Instationary Polymerization: Determination of the Propagation and Termination Rate Coefficients for Dicyclohexyl Itaconate Polymerization
Publisher: American Chemical Society (ACS)
Date: 13-03-2002
DOI: 10.1021/MA0118264
A simple methodology for the synthesis of heterotelechelic protein–polymer–biomolecule conjugates
Publisher: Wiley
Date: 03-02-2010
DOI: 10.1002/POLA.23902
Physical and toxicological profiles of human IAPP amyloids and plaques
Publisher: Elsevier BV
Date: 2019
Comprehensive Modulation of Naphthopyran Photochromism in a Rigid Host Matrix by Applying Polymer Conjugation
Publisher: American Chemical Society (ACS)
Date: 10-02-2009
DOI: 10.1021/MA801947D
Stability Enhancing N-Terminal PEGylation of Oxytocin Exploiting Different Polymer Architectures and Conjugation Approaches
Publisher: American Chemical Society (ACS)
Date: 15-07-2016
DOI: 10.1021/ACS.BIOMAC.6B00919
Abstract: Oxytocin, a cyclic nine amino acid neurohypophyseal hormone therapeutic, is effectively used in the control of postpartum hemorrhaging (PPH) and is on the WHO List of Essential Medicines. However, oxytocin has limited shelf life stability in aqueous solutions, particularly at temperatures in excess of 25 °C and injectable aqueous oxytocin formulations require refrigeration (<8 °C). This is particularly problematic in the hot climates often found in many developing countries where daytime temperatures can exceed 40 °C and where reliable cold-chain storage is not always achievable. The purpose of this study was to develop N-terminal amine targeted PEGylation strategies utilizing both linear PEG and polyPEG "comb" polymers as an effective method for stabilizing solution formulations of this peptide for prolonged storage in the absence of efficient cold-chain storage. The conjugation chemistries investigated herein include irreversible amine targeted conjugation methods utilizing NHS ester and aldehyde reductive amination chemistry. Additionally, one reversible conjugation method using a Schiff base approach was explored to allow for the release of the native peptide, thus, ensuring that biological activity remains unaffected. The reversibility of this approach was investigated for the different polymer architectures, alongside a nonpolymer oxytocin analogue to monitor how pH can tune native peptide release. Elevated temperature degradation studies of the polymer conjugates were evaluated to assess the stability of the PEGylated analogues in comparison to the native peptide in aqueous formulations to mimic storage conditions in developing nations and regions where storage under appropriate conditions is challenging.
Transesterification of poly(ethyl‐α‐hydroxymethacrylate) prepared via reversible addition–fragmentation chain transfer polymerization
Publisher: Wiley
Date: 04-10-2005
DOI: 10.1002/POLA.20991
Surfactant-free RAFT emulsion polymerization using a novel biocompatible thermoresponsive polymer
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6PY02158A
Abstract: A facile, high-scale, and versatile technique to prepare biocompatible nanoparticles with tailorable properties from thermoresponsive macro-CTAs and macro-stabilizers.
Ex vivo culture of intact human patient derived pancreatic tumour tissue.
Publisher: Springer Science and Business Media LLC
Date: 21-01-2021
DOI: 10.1038/S41598-021-81299-0
Abstract: The poor prognosis of pancreatic ductal adenocarcinoma (PDAC) is attributed to the highly fibrotic stroma and complex multi-cellular microenvironment that is difficult to fully recapitulate in pre-clinical models. To fast-track translation of therapies and to inform personalised medicine, we aimed to develop a whole-tissue ex vivo explant model that maintains viability, 3D multicellular architecture, and microenvironmental cues of human pancreatic tumours. Patient-derived surgically-resected PDAC tissue was cut into 1–2 mm explants and cultured on gelatin sponges for 12 days. Immunohistochemistry revealed that human PDAC explants were viable for 12 days and maintained their original tumour, stromal and extracellular matrix architecture. As proof-of-principle, human PDAC explants were treated with Abraxane and we observed different levels of response between patients. PDAC explants were also transfected with polymeric nanoparticles + Cy5-siRNA and we observed abundant cytoplasmic distribution of Cy5-siRNA throughout the PDAC explants. Overall, our novel model retains the 3D architecture of human PDAC and has advantages over standard organoids: presence of functional multi-cellular stroma and fibrosis, and no tissue manipulation, digestion, or artificial propagation of organoids. This provides unprecedented opportunity to study PDAC biology including tumour-stromal interactions and rapidly assess therapeutic response to drive personalised treatment.
Engineering Organic/Inorganic Nanohybrids through RAFT Polymerization for Biomedical Applications
Publisher: American Chemical Society (ACS)
Date: 22-10-2019
DOI: 10.1021/ACS.BIOMAC.9B01158
Abstract: Despite many early accomplishments in nanomaterial design and synthesis, there remains a significant requirement for novel inorganic and organic nanohybrids with the potential to act as efficacious molecular imaging agents and theranostic vectors. The functionalization of surfactant-coated inorganic nanoparticles with polymer shells represents one of the most suitable and popular methods to synthesize polymer/inorganic nanohybrids for theranostic applications. Key requirements for effective imaging agent design include water dispersibility, biocompatibility and functionality to enable enhanced contrast magnetic resonance imaging (MRI), positron-emission tomography (PET), computed tomography (CT), or ultrasound modalities. In this Perspective, we highlight recent advances in the fabrication of organic/inorganic nanohybrids exploiting functionalized polymers prepared using reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymer shells can imbue favorable traits to the nanoparticles such as stealth, image enhancement, storage (and release) of therapeutics, and sensitivity to biological stimuli. In this Perspective, we discuss the design and synthesis of hybrid nanoparticles and discuss current trends and future opportunities.
Synthesis of biscarboxylic acid functionalised EDTA mimicking polymers and their ability to form Zr(iv ) chelation mediated nanostructures
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY00304B
Abstract: We present a new biscarboxylic acid acrylate, which is used for the synthesis of double hydrophilic EDTA-mimicking block copolymers capable of self-assembly upon zirconium complexation.
An in-depth analytical approach to the mechanism of the RAFT process in acrylate free radical polymerizations via coupled size exclusion chromatography–electrospray ionization mass spectrometry (SEC–E
Publisher: Elsevier BV
Date: 09-2005
RAFT Polymerization of N‐Isopropylacrylamide and Acrylic Acid under γ‐Irradiation in Aqueous Media
Publisher: Wiley
Date: 22-05-2006
Intra-articular Treatment of Osteoarthritis with Diclofenac-Conjugated Polymer Reduces Inflammation and Pain
Publisher: American Chemical Society (ACS)
Date: 24-05-2019
Abstract: The most common treatment for osteoarthritis is daily oral administration of a nonsteroidal anti-inflammatory drug such as diclofenac. This daily dosage regime is often associated with severe side effects. In this study, we explored the potential of utilizing a high molecular weight cross-linked polyurethane polymer covalently linked to diclofenac (
Honeycomb structured porous films from amphiphilic block copolymers prepared via RAFT polymerization
Publisher: Elsevier BV
Date: 08-2007
Reversible addition fragmentation chain transfer polymerization of 3-[tris(trimethylsilyloxy) silyl] propyl methacrylate
Publisher: Elsevier BV
Date: 08-2003
The generic enhancement of photochromic dye switching speeds in a rigid polymer matrix
Publisher: Springer Science and Business Media LLC
Date: 06-02-2005
DOI: 10.1038/NMAT1326
Abstract: The switching or isomerization speed of photochromic dyes in a rigid polymeric matrix (such as an ophthalmic lens) is generally significantly slower than that observed in the mobile environment of a solution. Here we describe that the attachment of flexible oligomers having a low glass-transition temperature-such as poly(dimethylsiloxane)-to photochromic dyes greatly increases their switching speeds in a rigid polymer matrix. The greatest impact was observed in the thermal fade parameters T(1/2) and T(3/4)-the times it takes for the optical density to reduce by half and three quarters of the initial optical density of the coloured state-which were reduced by 40-95% and 60-99% respectively for spirooxazines, chromenes and an azo dye in a host polymer with a glass-transition temperature of 120 degrees C. The method does not alter the electronic nature of the dyes but simply protects them from the host matrix and provides greater molecular mobility for the switching process. In addition to ophthalmic lenses, the generic nature of the method may find further utility in data recording or optical switching.
Effect of the Ester Side-Chain on the Propagation Kinetics of Alkyl MethacrylatesAn Entropic or Enthalpic Effect?
Publisher: American Chemical Society (ACS)
Date: 02-1998
DOI: 10.1021/MA9707291
Catalytic Chain Transfer Isomerization Reactions Involving 2-Phenylallyl Alcohol
Publisher: American Chemical Society (ACS)
Date: 09-10-2001
DOI: 10.1021/MA0109727
Depropagation kinetics of sterically demanding monomers: A pulsed laser size exclusion chromatography study
Publisher: American Chemical Society (ACS)
Date: 15-06-2005
DOI: 10.1021/MA050444L
Electrospray Ionization Mass Spectrometry Investigation of Reversible Addition Fragmentation Chain Transfer Mediated Acrylate Polymerizations Initiated via 60Co γ-Irradiation: Mapping Reac
Publisher: American Chemical Society (ACS)
Date: 18-05-2007
DOI: 10.1021/MA0701484
Combining thio-bromo Click chemistry and raft polymerization: a powerful tool for preparing functionalized multiblock and hyperbranched polymers
Publisher: American Chemical Society (ACS)
Date: 07-12-2010
DOI: 10.1021/MA902154H
Nitric oxide-sensing actuators for modulating structure in lipid-based liquid crystalline drug delivery systems
Publisher: Elsevier BV
Date: 12-2017
DOI: 10.1016/J.JCIS.2017.08.079
Abstract: Herein we report on the development of a nitric oxide-sensing lipid-based liquid crystalline (LLC) system specifically designed to release encapsulated drugs on exposure to NO through a stimulated phase change. A series of nitric oxide (NO)-sensing lipids compatible with phytantriol and GMO cubic phases were designed and synthesized, and utilized in enabling nitric oxide-sensing LLC systems. The nitric oxide (NO)-sensing lipids react with nitric oxide, resulting in hydrolysis of these lipids and phase transition of the LLC system. Specifically, the N-3-aminopyridinyl myristylamine (NAPyM)+phytantriol mixture formed a lamellar phase in excess aqueous environment. The NAPyM+phytantriol LLC responded to the nitric oxide gas as a chemical stimulus which triggers a phase transition from lamellar phase to inverse cubic and hexagonal phase. The nitric oxide-triggered phase transition of the LLC accelerated the release of encapsulated model drug from the LLC bulk phase, resulting in a 15-fold increase in the diffusion coefficient compared to the starting lamellar structure. The nitric oxide-sensing LLC system has potential application in the development of smart medicines to treat nitric oxide implicated diseases.
Complex molecular architecture polymers via RAFT
Publisher: CSIRO Publishing
Date: 2004
DOI: 10.1071/CH03232
Trisulfide-Bearing PEG Brush Polymers Donate Hydrogen Sulfide and Ameliorate Cellular Oxidative Stress
Publisher: American Chemical Society (ACS)
Date: 19-11-2020
Photoinduced sequence-control via one pot living radical polymerization of acrylates
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4SC01374C
Abstract: A versatile and inexpensive photochemical platform for the preparation of high-order multiblock functional materials.
Radical ring-opening copolymerization of 2-methylene 1,3-dioxepane and methyl methacrylate: Experiments originally designed to probe the origin of the penultimate unit effect
Publisher: American Chemical Society (ACS)
Date: 19-02-1999
DOI: 10.1021/MA9813587
Stealth nanorods via the aqueous living crystallisation-driven self-assembly of poly(2-oxazoline)s
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1SC00938A
Abstract: Triggered by heating, a poly(2-alkyl-2-oxazoline) block copolymer undergoes seeded growth in water forming length tuneable nanorods. Morphology and composition combine to impart low immune cell association and promising blood circulation lifetimes.
Garlic-inspired trisulfide linkers for thiol-stimulated H2S release
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC03820H
Abstract: Garlic-inspired cholesterol-mPEG conjugates incorporating a trisulfide linkage have the ability to cleave upon exposure to thiols with a concomitant release of H 2 S.
Nanoscale inhibition of polymorphic and ambidextrous IAPP amyloid aggregation with small molecules
Publisher: Springer Science and Business Media LLC
Date: 07-2018
Transformation of RAFT Polymer End Groups into Nitric Oxide Donor Moieties: En Route to Biochemically Active Nanostructures
Publisher: American Chemical Society (ACS)
Date: 03-11-2015
Nitroxide-functional PEGylated nanostars arrest cellular oxidative stress and exhibit preferential accumulation in co-cultured breast cancer cells
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1TB00812A
Abstract: Conjugation to nanostars enhances the biological performance of TEMPO.
Synthesis and in vitro properties of iron oxide nanoparticles grafted with brushed phosphorylcholine and polyethylene glycol
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5PY02024G
Abstract: A new and facile strategy for grafting IONPs by phosphonic acic terminated PC brushes has been demonstrated and characterized in vitro .
Nitric oxide (NO) cleavable biomimetic thermoresponsive double hydrophilic diblock copolymer with tunable LCST
Publisher: American Chemical Society (ACS)
Date: 11-06-2015
RAFT Polymerization and Thiol Chemistry: A Complementary Pairing for Implementing Modern Macromolecular Design
Publisher: Wiley
Date: 12-05-2011
Abstract: Reversible addition fragmentation chain transfer (RAFT) polymerization is one of the most extensively studied reversible deactivation radical polymerization methods for the production of well-defined polymers. After polymerization, the RAFT agent end-group can easily be converted into a thiol, opening manifold opportunities for thiol modification reactions. This review is focused both on the introduction of functional end-groups using well-established methods, such as thiol-ene chemistry, as well as on creating bio-cleavable disulfide linkages via disulfide exchange reactions. We demonstrate that thiol modification is a highly attractive and efficient chemistry for modifying RAFT polymers.
Macromolecular thiolysis of oxiranes: end-group modification of RAFT prepared homopolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1PY00046B
Shell-Cross-Linked Micelles Containing Cationic Polymers Synthesized via the RAFT Process: Toward a More Biocompatible Gene Delivery System
Publisher: American Chemical Society (ACS)
Date: 11-08-2007
DOI: 10.1021/BM070370G
Abstract: Block copolymers poly(2-(dimethylamino) ethyl methacrylate)-b-poly(polyethylene glycol methacrylate) (PDMAEMA-b-P(PEGMA)) were prepared via reversible addition fragmentation chain transfer polymerization (RAFT). The polymerization was found to proceed with the expected living behavior resulting in block copolymers with varying block sizes of low polydispersity (PDI <1.3). The resulting block copolymer was self-assembled in an aqueous environment, leading to the formation of pH-responsive micelles. Further stabilization of the micellar system was performed in water using ethylene glycol dimethacrylate and the RAFT process to cross-link the shell. The cross-linked micelle was found to have properties significantly different from those of the uncross-linked block copolymer micelle. While a distinct critical micelle concentration (CMC) was observed using block copolymers, the CMC was absent in the cross-linked system. In addition, a better stability against disintegration was observed when altering the ionic strength such as the absence of changes of the hydrodynamic diameter with increasing NaCl concentration. Both cross-linked and uncross-linked micelles displayed good binding ability for genes. However, the cross-linked system exhibited a slightly superior tendency to bind oligonucleotides. Cytotoxicity tests confirmed a significant improvement of the biocompatibility of the synthesized cross-linked micelle compared to that of the highly toxic PDMAEMA. The cross-linked micelles were taken up by cells without causing any signs of cell damage, while the PDMAEMA homopolymer clearly led to cell death.
Biologically Targeted Magnetic Hyperthermia: Potential and Limitations
Publisher: Frontiers Media SA
Date: 02-08-2018
Remarkable Solvent Effects of Oxygen- and Sulfur-Containing Compounds on the Propagation Rate of Methyl Methacrylate
Publisher: Walter de Gruyter GmbH
Date: 03-2005
DOI: 10.1524/ZPCH.219.3.267.59184
Abstract: The propagation kinetics of methyl methacrylate (MMA) in the presence of a number of oxygen- and sulfur-containing compounds have been investigated. Solvents used were 2-methyl-1,3-dioxepane (MDOP), 2,6-dithiaheptane (DTHP) and 1,5-dithiacyclooctane (DTCO). In the presence of DTHP and DTCO, the propagation rate coefficient, k p , of MMA was found to be 25% to 100% higher compared to bulk polymerisations under the same conditions. The significant increase of k p was explained by electron donation from the sulfur-containing solvents, which increased the reactivity of the macroradicals. MDOP had no observable effect on k p . The solvent influence on polymer tacticity was also studied using both 1 H and 13 C NMR spectroscopy. No significant influence of the solvent on polymer tacticity was found.
In Situ Formation of Protein–Polymer Conjugates through Reversible Addition Fragmentation Chain Transfer Polymerization
Publisher: Wiley
Date: 12-04-2007
Poly(2-isopropenyl-2-oxazoline)-a structural analogue to poly(vinyl azlactone) with Orthogonal Reactivity
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY00861C
Abstract: A modular copolymer platform based on two oxazole derivatives is presented. Post-polymerisation modifications revealed the potential to selectively modify the in idual side groups, providing access to functional copolymer libraries in the future.
Probing mechanistic features of conventional, catalytic and living free radical polymerizations using soft ionization mass spectrometric techniques
Publisher: Elsevier BV
Date: 10-2004
Design Criteria for Star Polymer Formation Processes via Living Free Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 19-08-2006
DOI: 10.1021/MA060964W
Delivery of polymeric nanostars for molecular imaging and endoradiotherapy through the enhanced permeability and retention (EPR) effect
Publisher: Ivyspring International Publisher
Date: 2020
DOI: 10.7150/THNO.36777
Sequence-controlled methacrylic multiblock copolymers via sulfur-free RAFT emulsion polymerization
Publisher: Springer Science and Business Media LLC
Date: 17-10-2017
DOI: 10.1038/NCHEM.2634
Abstract: Translating the precise monomer sequence control achieved in nature over macromolecular structure (for ex le, DNA) to whole synthetic systems has been limited due to the lack of efficient synthetic methodologies. So far, chemists have only been able to synthesize monomer sequence-controlled macromolecules by means of complex, time-consuming and iterative chemical strategies such as solid-state Merrifield-type approaches or molecularly dissolved solution-phase systems. Here, we report a rapid and quantitative synthesis of sequence-controlled multiblock polymers in discrete stable nanoscale compartments via an emulsion polymerization approach in which a vinyl-terminated macromolecule is used as an efficient chain-transfer agent. This approach is environmentally friendly, fully translatable to industry and thus represents a significant advance in the development of complex macromolecule synthesis, where a high level of molecular precision or monomer sequence control confers potential for molecular targeting, recognition and biocatalysis, as well as molecular information storage.
In vitro and in vivo models for anti-amyloidosis nanomedicines
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0NH00548G
Abstract: Impactful research in nanomedicine depends upon the adequate use of cellular and animal models. Here we systematically review and evaluate the in vitro and in vivo models which have enabled the development of anti-amyloidosis nanomedicines.
Critically Evaluated Rate Coefficients for Free‐Radical Polymerization, 4
Publisher: Wiley
Date: 30-06-2003
Biomimetic surface modification of honeycomb films via a grafting from approach
Publisher: American Chemical Society (ACS)
Date: 02-07-2010
DOI: 10.1021/LA1011567
Abstract: Hydrophobic isoporous membranes were fabricated using the "breath figure" method from polystyrene stars synthesized via ATRP. The living polymer chain ends at the surface of the films were then used, without further modification, in a "grafting-from" approach to grow surface-linked polyglycidyl methacrylate chains under conditions that maintained the regular honeycomb structure. This versatile functional surface was then used as a platform to build a small library of surfaces using a variety of simple chemistries: (i) the acid hydrolysis of the epoxide to form bis-alcohol groups and (ii) utilizing the "click-like" epoxide-amine reaction to functionalize the surface with a model biomolecule-(biotinamido)pentylamine. The successful modifications were confirmed by a combination of spectroscopic and biological means. Changes in the growth characteristics of nonmotile Psychrobacter sp. strain, SW5, on the honeycomb films, provided further evidence confirming changes in the hydrophobicity of the surface upon grafting.
Tailoring Photochromic Performance of Polymer-Dye Conjugates Using Living Radical Polymerization (ATRP)
Publisher: Informa UK Limited
Date: 05-2005
Conventional and catalytic chain transfer in the free-radical polymerization of 2-phenoxyethyl methacrylate
Publisher: Elsevier BV
Date: 02-2000
Novel α,α-Bischolesteryl Functional (Co)Polymers: RAFT Radical Polymerization Synthesis and Preliminary Solution Characterization
Publisher: Wiley
Date: 03-02-2014
Abstract: Well-defined poly[pentafluorophenyl (meth)acrylate] (PPFP(M)A) homopolymers are prepared by RAFT radical polymerization mediated by a novel chain transfer agent containing two cholesteryl groups in the R-group fragment. Subsequent reaction with a series of small-molecule amines in the presence of an appropriate Michael acceptor for ω-group end-capping yields a library of novel bischolesteryl functional hydrophilic homopolymers. Two ex les of statistical copolymers are also prepared including a biologically relevant sugar derivative. Specific ex les of these homopolymers are examined with respect to their ability to self assemble in aqueous media-a process driven entirely by the cholesteryl end groups. In all instances evaluated, and under the preparation conditions examined, the homopolymers aggregate clearly forming polymersomes spanning an impressive size range.
Nanoparticle–proteome in vitro and in vivo
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8TB01634H
Abstract: The protein corona is a concept central to a range of disciplines exploiting the bio–nano interface.
A hydrogel-based localized release of colistin for antimicrobial treatment of burn wound infection
Publisher: Wiley
Date: 13-09-2017
Abstract: There is an urgent unmet medical need for new treatments for wound and burn infections caused by multidrug-resistant Gram-negative "superbugs," especially the problematic Pseudomonas aeruginosa. In this work, the incorporation of colistin, a potent lipopeptide into a self-healable hydrogel (via dynamic imine bond formation) following the chemical reaction between the amine groups present in glycol chitosan and an aldehyde-modified poly(ethylene glycol), is reported. The storage module (G') of the colistin-loaded hydrogel ranges from 1.3 to 5.3 kPa by varying the amount of the cross-linker and colistin loading providing different options for topical wound healing. The majority of the colistin is released from the hydrogel within 24 h and remains active as demonstrated by both antibacterial in vitro disk diffusion and time-kill assays. Moreover and pleasingly, the colistin-loaded hydrogel performs almost equally well as native colistin against both the colistin-sensitive and also colistin-resistant P. aeruginosa strain in the in vivo animal "burn" infection model despite exhibiting a slower killing profile in vitro. Based on this antibiotic performance along with the biodegradability of the product, it is believed the colistin-loaded hydrogel to be a potential localized wound-healing formulation to treat burn wounds against microbial infection.
Biodegradable Star Polymers Functionalized With β-Cyclodextrin Inclusion Complexes
Publisher: American Chemical Society (ACS)
Date: 07-08-2009
DOI: 10.1021/BM900646G
Abstract: Three-armed biodegradable star polymers made from polystyrene (polySt) and poly (polyethylene glycol) acrylate (polyPEG-A) were synthesized via a "core first" methodology using a trifunctional RAFT agent, created by attaching RAFT agents to a core via their R-groups. The resultant three-armed polymeric structures were well-defined, with polydispersity indices less than 1.2. Upon aminolysis and further reaction with dithiodipyridine (DTDP), these three-armed polymers could be tailored with sulfhydryl and pyridyldisulfide (PDS) end functionalities, available for further reaction with any free-sulfhydryl group containing precursors to form disulfide linkages. Nuclear magnetic resonance (NMR) confirmed that more than 98% of the polymer arms retained integral trithiocarbonate active sites after polymerization. Intradisulfide linkages between the core and the arms conferred biodegradability on the star architectures. Subsequently, the arm-termini were attached to cholesterol also via disulfide linkages. The cholesterol terminated arms were then used to form supramolecular structures via inclusion complex formation with beta-cyclodextrin (beta-CD). The star architectures were found to degrade rapidly on treatment with DL-dithiothereitol (DTT). The star polymers and supramolecular structures were characterized using gel permation chromatography (GPC), static light scattering (SLS), 2D NMR, and fluorescence spectroscopy.
Control of Photochromism through Local Environment Effects Using Living Radical Polymerization (ATRP)
Publisher: American Chemical Society (ACS)
Date: 25-11-2004
DOI: 10.1021/MA048627F
Recent Advances in the Kinetics of Reversible Addition Fragmentation Chain-Transfer Polymerization
Publisher: CSIRO Publishing
Date: 2002
DOI: 10.1071/CH02042
Overcoming Surfactant-Induced Morphology Instability of Noncrosslinked Diblock Copolymer Nano-Objects Obtained by RAFT Emulsion Polymerization
Publisher: American Chemical Society (ACS)
Date: 10-01-2018
DOI: 10.1021/ACSMACROLETT.7B00978
Abstract: RAFT emulsion polymerization techniques including polymerization-induced self-assembly (PISA) and temperature-induced morphological transformation (TIMT) are widely used to produce noncrosslinked nano-objects with various morphologies. However, the worm, vesicle and lamellar morphologies produced by these techniques typically cannot tolerate the presence of added surfactants, thus limiting their potential applications. Herein we report the surfactant tolerance of noncrosslinked worms, vesicles, and lamellae prepared by RAFT emulsion polymerizations using poly(di(ethylene glycol) ethyl ether methacrylate-
Visible light pulsed-OPO-laser polymerization at 450 nm employing a bis(acylphosphine oxide) photoinitiator
Publisher: American Chemical Society (ACS)
Date: 26-02-1998
DOI: 10.1021/MA971370J
Heat-Induced Living Crystallization-Driven Self-Assembly: The Effect of Temperature and Polymer Composition on the Assembly and Disassembly of Poly(2-oxazoline) Nanorods
Publisher: American Chemical Society (ACS)
Date: 19-04-2022
Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis
Publisher: American Chemical Society (ACS)
Date: 30-07-2016
Microfluidic Mass Production of Stabilized and Stealthy Liquid Metal Nanoparticles
Publisher: Wiley
Date: 22-04-2018
Abstract: Functional nanoparticles comprised of liquid metals, such as eutectic gallium indium (EGaIn) and Galinstan, present exciting opportunities in the fields of flexible electronics, sensors, catalysts, and drug delivery systems. Methods used currently for producing liquid metal nanoparticles have significant disadvantages as they rely on both bulky and expensive high-power sonication probe systems, and also generally require the use of small molecules bearing thiol groups to stabilize the nanoparticles. Herein, an innovative microfluidics-enabled platform is described as an inexpensive, easily accessible method for the on-chip mass production of EGaIn nanoparticles with tunable size distributions in an aqueous medium. A novel nanoparticle-stabilization approach is reported using brushed polyethylene glycol chains with trithiocarbonate end-groups negating the requirements for thiol additives while imparting a "stealth" surface layer. Furthermore, a surface modification of the nanoparticles is demonstrated using galvanic replacement and conjugation with antibodies. It is envisioned that the demonstrated microfluidic technique can be used as an economic and versatile platform for the rapid production of liquid metal-based nanoparticles for a range of biomedical applications.
Controlling Nanomaterial Size and Shape for Biomedical Applications via Polymerization-Induced Self-Assembly.
Publisher: Wiley
Date: 09-08-2018
Abstract: Rapid developments in the polymerization-induced self-assembly (PISA) technique have paved the way for the environmentally friendly production of nanoparticles with tunable size and shape for a erse range of applications. In this feature article, the biomedical applications of PISA nanoparticles and the substantial progress made in controlling their size and shape are highlighted. In addition to early investigations into drug delivery, applications such as medical imaging, tissue culture, and blood cryopreservation are also described. Various parameters for controlling the morphology of PISA nanoparticles are discussed, including the degree of polymerization of the macro-CTA and core-forming polymers, the concentration of macro-CTA and core-forming monomers, the solid content of the final products, the solution pH, the thermoresponsitivity of the macro-CTA, the macro-CTA end group, and the initiator concentration. Finally, several limitations and challenges for the PISA technique that have been recently addressed, along with those that will require further efforts into the future, will be highlighted.
pH-Detachable Polymer Brushes Formed Using Titanium-Diol Coordination Chemistry and Living Radical Polymerization (RAFT)
Publisher: American Chemical Society (ACS)
Date: 30-03-2009
DOI: 10.1021/MA802256G
Glutathione responsive polymers and their application in drug delivery systems
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6PY01365A
Abstract: Materials which respond to biological cues are the subject of intense research interest due to their possible application in smart drug delivery vehicles.
Comparison between the LCST and UCST Transitions of Double Thermoresponsive Diblock Copolymers: Insights into the Behavior of POEGMA in Alcohols
Publisher: American Chemical Society (ACS)
Date: 02-04-2012
DOI: 10.1021/MA300374Y
Pancreatic β-Cell Membrane Fluidity and Toxicity Induced by Human Islet Amyloid Polypeptide Species
Publisher: Springer Science and Business Media LLC
Date: 16-02-2016
DOI: 10.1038/SREP21274
Abstract: Aggregation of human islet amyloid polypeptide (hIAPP) into fibrils and plaques is associated with pancreatic β-cell loss in type 2 diabetes (T2D). However, due to the rapidness of hIAPP conversion in aqueous phase, exactly which hIAPP species is responsible for the observed toxicity and through what mechanisms remains ambiguous. In light of the importance of understanding hIAPP toxicity for T2D here we show a biophysical scheme based on the use of a lipophilic Laurdan dye for examining MIN6 cell membranes upon exposure to fresh and oligomeric hIAPP as well as mature amyloid. It has been found that all three hIAPP species, especially fresh hIAPP, enhanced membrane fluidity and caused losses in cell viability. The cell generation of reactive oxygen species (ROS), however, was the most pronounced with mature amyloid hIAPP. The correlation between changes in membrane fluidity and cell viability and their lack of correlation with ROS production suggest hIAPP toxicity is elicited through both physical and biochemical means. This study offers a new insight into β-cell toxicity induced by controlled hIAPP species, as well as new biophysical methodologies that may prove beneficial for the studies of T2D as well as neurological disorders.
A block copolymer-stabilized co-precipitation approach to magnetic iron oxide nanoparticles for potential use as MRI contrast agents
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3PY01778H
Abstract: A library of magnetic nanoparticles was generated using in situ co-precipitation of ferrous (Fe 2+ ) and ferric (Fe 3+ ) ions from aqueous solutions in the presence of functional block copolymers.
Polymerization-Induced Self-Assembly (PISA) – control over the morphology of nanoparticles for drug delivery applications
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3PY01306E
Nanosilver Mitigates Biofilm Formation via FapC Amyloidosis Inhibition
Publisher: Wiley
Date: 27-01-2020
Application of Heterocyclic Polymers in the Ratiometric Spectrophotometric Determination of Fluoride
Publisher: American Chemical Society (ACS)
Date: 10-06-2015
DOI: 10.1021/MZ500782R
Solvent and oxygen effects on the free radical polymerization of 6-O-vinyladipoyl-d-glucopyranose
Publisher: Elsevier BV
Date: 04-2005
Tuning Cellular Interactions of Carboxylic Acid-Side-Chain-Containing Polyacrylates: The Role of Cyanine Dye Label and Side-Chain Type
Publisher: American Chemical Society (ACS)
Date: 29-06-2020
Applications of Lawesson's reagent in organic and organometallic syntheses
Publisher: Georg Thieme Verlag KG
Date: 2003
DOI: 10.1055/S-2003-41447
Thiol-responsive lyotropic liquid crystals exhibit triggered phase re-arrangement and hydrogen sulfide (H2S) release
Publisher: Elsevier BV
Date: 05-2022
DOI: 10.1016/J.JCIS.2021.12.180
Abstract: Hydrogen sulfide (H
Spontaneous formation of β-sheet nano-barrels during the early aggregation of Alzheimer’s amyloid beta
Publisher: Elsevier BV
Date: 06-2021
Stabilization of Polymer-Hydrogel Capsules via Thiol-Disulfide Exchange
Publisher: Wiley
Date: 11-11-2009
Polymeric micelles with anti-virulence activity against Candida albicans in a single- and dual-species biofilm
Publisher: Springer Science and Business Media LLC
Date: 13-03-2021
Electrochemical impedance immunosensor based on gold nanoparticles and aryl diazonium salt functionalized gold electrodes for the detection of antibody
Publisher: Elsevier BV
Date: 04-2011
Termination Rate Coefficient of Dimethyl Itaconate: Comparison of Modeling and Experimental Results
Publisher: American Chemical Society (ACS)
Date: 02-2002
DOI: 10.1021/MA011535V
Facile Access to Chain Length Dependent Termination Rate Coefficients via Reversible Addition−Fragmentation Chain Transfer (RAFT) Polymerization: Influence of the RAFT Agent Structure
Publisher: American Chemical Society (ACS)
Date: 09-03-2004
DOI: 10.1021/MA0358428
Reversible addition-fragmentation chain-transfer graft polymerization of styrene
Publisher: Wiley
Date: 15-10-2002
DOI: 10.1002/POLA.10513
Kinetic investigations of reversible addition fragmentation chain transfer polymerizations: Cumyl phenyldithioacetate mediated homopolymerizations of styrene and methyl methacrylate
Publisher: American Chemical Society (ACS)
Date: 29-09-2001
DOI: 10.1021/MA010349M
Biomimetic polymers responsive to a biological signaling molecule: Nitric oxide triggered reversible self-assembly of single macromolecular chains into nanoparticles
Publisher: Wiley
Date: 04-06-2014
Abstract: Novel nitric oxide (NO) responsive monomers (NAPMA and APUEMA) containing o-phenylenediamine functional groups have been polymerized to form NO-responsive macromolecular chains as truly biomimetic polymers. Upon exposure to NO--a ubiquitous cellular signaling molecule--the NAPMA- and APUEMA-labeled thermoresponsive copolymers exhibited substantial changes in solubility, clearly characterized by tuneable LCST behavior, thereby inducing self-assembly into nanoparticulate structures. Moreover, the NO-triggered self-assembly process in combination with environmentally sensitive fluorescence dyes could be employed to detect and image endogenous NO.
Thioketone spin traps as mediating agents for free radical polymerization processes
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B515561D
Abstract: Thioketones are demonstrated to be suitable agents for controlling free radical polymerization processes: the polymerizations carry (pseudo) living characteristics indicating that the control process is induced by a persistent radical effect.
Influence of Size and Shape on the Biodistribution of Nanoparticles Prepared by Polymerization-Induced Self-Assembly
Publisher: American Chemical Society (ACS)
Date: 29-09-2017
DOI: 10.1021/ACS.BIOMAC.7B00995
Abstract: Polymerization-induced self-assembly (PISA) is a facile one-pot synthetic technique for preparing polymeric nanoparticles with different sizes and shapes for application in a variety of fields including nanomedicine. However, the in vivo biodistribution of nanoparticles obtained by PISA still remains unclear. To address this knowledge gap, we report the synthesis, cytotoxicity, and biodistribution in an in vivo tumor-bearing mouse model of polystyrene micelles with various sizes and polystyrene filomicelles with different lengths prepared by PISA. First, a library of nanoparticles was prepared comprised of poly(glycidyl methacrylate)-b-poly(oligo(ethylene glycol) methyl ether methacrylate)-b-polystyrene polymers, and their size and morphology were tuned by varying the polystyrene block length without affecting the surface chemistry. The
The use of endogenous gaseous molecules (NO and CO2) to regulate the self-assembly of a dual-responsive triblock copolymer
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4PY01678E
Abstract: A nitric oxide (NO) and carbon dioxide (CO 2 ) dual-responsive block copolymer was self-assembled in aqueous solution upon gas stimuli to form nanostructures.
A Thermodynamics Model for the Emergence of a Stripe‐like Binary SAM on a Nanoparticle Surface
Publisher: Wiley
Date: 20-07-2015
Initiator efficiency of 2,2′‐azobis(isobutyronitrile) in bulk dodecyl acrylate free‐radical polymerizations over a wide conversion and molecular weight range
Publisher: Wiley
Date: 09-09-2004
DOI: 10.1002/POLA.20322
Modulating protein amyloid aggregation with nanomaterials
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7EN00436B
Abstract: Understanding nanoparticle-mediated protein amyloid aggregation is essential for sustainable nanotechnology and safe nanomedicines.
Polymer-gold nanohybrids with potential use in bimodal MRI/CT: enhancing the relaxometric properties of Gd(III) complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2JM34999J
Development of a shape-controlled H2S delivery system using epoxide-functional nanoparticles
Publisher: Wiley
Date: 23-04-2019
DOI: 10.1002/POLA.29382
Magnetic nanoparticles with diblock glycopolymer shells give lectin concentration-dependent MRI signals and selective cell uptake
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3SC52838C
H2S-Donating trisulfide linkers confer unexpected biological behaviour to poly(ethylene glycol)-cholesteryl conjugates
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9TB02614B
Abstract: A comprehensive in vitro study into trisulfide-bearing PEG-conjugates was conducted. For these materials the combination of a cholesteryl group and an H 2 S donating moiety is required to confer cytoprotective and ROS-mitigating effects.
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.
Reversible addition–fragmentation chain‐transfer polymerization: Unambiguous end‐group assignment via electrospray ionization mass spectrometry
Publisher: Wiley
Date: 03-10-2002
DOI: 10.1002/POLA.10500
Synthesis of poly(vinyl alcohol) combs via MADIX/RAFT polymerization
Publisher: Elsevier BV
Date: 02-2006
Access to Chain Length Dependent Termination Rate Coefficients of Methyl Acrylate via Reversible Addition−Fragmentation Chain Transfer Polymerization
Publisher: American Chemical Society (ACS)
Date: 25-02-2005
DOI: 10.1021/MA047476D
Synthesis of core-shell poly(divinylbenzene) microspheres via reversible addition fragmentation chain transfer graft polymerization of styrene
Publisher: Wiley
Date: 07-09-2004
DOI: 10.1002/POLA.20328
Copolymerization of styrene and alpha-methylstyrene in the presence of a catalytic chain transfer agent
Publisher: American Chemical Society (ACS)
Date: 15-08-1998
DOI: 10.1021/MA9802531
Copolymerization Propagation Kinetics of Styrene and Methyl MethacrylateRevisited. 1. Pulsed Laser Polymerization Study
Publisher: American Chemical Society (ACS)
Date: 12-1997
DOI: 10.1021/MA971051S
Laser induced marking of polymer chains with radical spin traps
Publisher: Wiley
Date: 19-03-2008
Copolymerization Propagation Kinetics of Styrene and Methyl Methacrylate-Revisited. 2. Kinetic Analysis
Publisher: American Chemical Society (ACS)
Date: 12-1997
DOI: 10.1021/MA971052K
Tuning the Structure, Stability, and Responsivity of Polymeric Arsenical Nanoparticles Using Polythiol Cross-Linkers
Publisher: American Chemical Society (ACS)
Date: 24-01-2019
A Framework of Paracellular Transport via Nanoparticles‐Induced Endothelial Leakiness
Publisher: Wiley
Date: 08-09-2021
Abstract: Nanomaterial‐induced endothelial leakiness (NanoEL) is an interfacial phenomenon denoting the paracellular transport of nanoparticles that is pertinent to nanotoxicology, nanomedicine and biomedical engineering. While the NanoEL phenomenon is complementary to the enhanced permeability and retention effect in terms of their common applicability to delineating the permeability and behavior of nanoparticles in tumoral environments, these two effects significantly differ in scope, origin, and manifestation. In the current study, the descriptors are fully examined of the NanoEL phenomenon elicited by generic citrate‐coated gold nanoparticles (AuNPs) of changing size and concentration, from microscopic gap formation and actin reorganization down to molecular signaling pathways and nanoscale interactions of AuNPs with VE‐cadherin and its intra/extracellular cofactors. Employing synergistic in silico methodologies, for the first time the molecular and statistical mechanics of cadherin pair disruption, especially in response to AuNPs of the smallest size and highest concentration are revealed. This study marks a major advancement toward establishing a comprehensive NanoEL framework for complementing the understanding of the transcytotic pathway and for guiding the design and application of future nanomedicines harnessing the myriad functions of the mammalian vasculature.
Stathmin mediates neuroblastoma metastasis in a tubulin-independent manner via RhoA/ROCK signaling and enhanced transendothelial migration
Publisher: Springer Science and Business Media LLC
Date: 20-06-2016
DOI: 10.1038/ONC.2016.220
Abstract: Neuroblastoma, the most common solid tumor of young children, frequently presents with aggressive metastatic disease and for these children the 5-year survival rates are dismal. Metastasis, the movement of cancer cells from one site to another, involves remodeling of the cytoskeleton including altered microtubule dynamics. The microtubule-destabilizing protein, stathmin, has recently been shown to mediate neuroblastoma metastasis although precise functions remain poorly defined. In this study we investigated stathmin's contribution to the metastatic process and potential mechanism(s) by which it exerts these effects. Stathmin suppression significantly reduced neuroblastoma cell invasion of 3D tumor spheroids into an extracellular matrix. Moreover, inhibiting stathmin expression significantly reduced transendothelial migration in two different neuroblastoma cell lines in vitro. Inhibition of ROCK, a key regulator of cell migration, in neuroblastoma cells highlighted that stathmin regulates transendothelial migration through ROCK signaling. Reduced stathmin expression in neuroblastoma cells significantly increased the activation of the RhoA small GTPase. Notably, re-expression of either wild type or a phospho-mimetic stathmin mutant (4E) made defective in tubulin binding returned cell migration and transendothelial migration back to control levels, indicating that stathmin may influence these processes in neuroblastoma cells independent of tubulin binding. Finally, stathmin suppression in neuroblastoma cells significantly reduced whole body, lung, kidney and liver metastases in an experimental metastases mouse model. In conclusion, stathmin suppression interferes with the metastatic process via RhoA/ROCK signaling in neuroblastoma cells. These findings highlight the importance of stathmin to the metastatic process and its potential as a therapeutic target for the treatment of neuroblastoma.
Catalytic chain transfer polymerization of methyl methacrylate in supercritical carbon dioxide: Evidence for a diffusion-controlled transfer process
Publisher: American Chemical Society (ACS)
Date: 08-1999
DOI: 10.1021/MA990467Y
A tunable one-pot three-component synthesis of an125I and Gd-labelled star polymer nanoparticle for hybrid imaging with MRI and nuclear medicine
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8PY00621K
Abstract: Bimodal radioiodine/Gd labelled polymeric nanoparticles prepared using a versatile one-step three-component click reaction.
Probing the Aggregation and Immune Response of Human Islet Amyloid Polypeptides with Ligand-Stabilized Gold Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 21-01-2019
Abstract: The use of nanomaterials has recently become an emerging strategy against protein amyloidosis associated with a range of metabolic and brain diseases. To facilitate research in this area, here we first demonstrated the use of hyperspectral imaging (HSI) and COMSOL simulations for reporting the aggregation of human islet amyloid polypeptides (IAPPs), a hallmark of type 2 diabetes, as well as the physical interactions between the peptide and gold nanoparticles (AuNPs) grafted with citrate and poly(ethylene glycol) (PEG
In Vivo Mitigation of Amyloidogenesis through Functional–Pathogenic Double-Protein Coronae
Publisher: American Chemical Society (ACS)
Date: 08-08-2018
DOI: 10.1021/ACS.NANOLETT.8B02446
Abstract: Amyloid diseases are global epidemics with no cure available. Herein, we report a first demonstration of in vivo mitigation of amyloidogenesis using biomimetic nanotechnology. Specifically, the amyloid fragments (b
Free radical polymerization with catalytic chain transfer: Using NMR to probe the strength of the cobalt-carbon bond in small molecule model reactions
Publisher: Wiley
Date: 20-09-2006
DOI: 10.1002/POLA.21662
Assessment of errors in the determination of Mark-Houwink-Sakurada and Stockmayer-Fixman constants using size-exclusion chromatography with on-line viscometric detection: Analyses of poly(p-substitute
Publisher: Wiley
Date: 15-09-1999
DOI: 10.1002/(SICI)1099-0488(19990915)37:18<2557::AID-POLB2>3.0.CO;2-O
Effective Delivery of siRNA into Cancer Cells and Tumors Using Well-Defined Biodegradable Cationic Star Polymers
Publisher: American Chemical Society (ACS)
Date: 06-05-2013
DOI: 10.1021/MP400049E
Abstract: Cancer is one of the most common causes of death worldwide. Two types of cancer that have high mortality rates are pancreatic and lung cancer. Despite improvements in treatment strategies, resistance to chemotherapy and the presence of metastases are common. Therefore, novel therapies which target and silence genes involved in regulating these processes are required. Short-interfering RNA (siRNA) holds great promise as a therapeutic to silence disease-causing genes. However, siRNA requires a delivery vehicle to enter the cell to allow it to silence its target gene. Herein, we report on the design and synthesis of cationic star polymers as novel delivery vehicles for siRNA to silence genes in pancreatic and lung cancer cells. Dimethylaminoethyl methacrylate (DMAEMA) was polymerized via reversible addition-fragmentation transfer polymerization (RAFT) and then chain extended in the presence of both cross-linkers N,N-bis(acryloyl)cistamine and DMAEMA, yielding biodegradable well-defined star polymers. The star polymers were characterized by transmission electron microscopy, dynamic light scattering, ζ potential, and gel permeation chromatography. Importantly, the star polymers were able to self-assemble with siRNA and form small uniform nanoparticle complexes. Moreover, the ratios of star polymer required to complex siRNA were nontoxic in both pancreatic and lung cancer cells. Treatment with star polymer-siRNA complexes resulted in uptake of siRNA into both cell lines and a significant decrease in target gene mRNA and protein levels. In addition, delivery of clinically relevant amounts of siRNA complexed to the star polymer were able to silence target gene expression by 50% in an in vivo tumor setting. Collectively, these results provide the first evidence of well-defined small cationic star polymers to deliver active siRNA to both pancreatic and lung cancer cells and may be a valuable tool to inhibit key genes involved in promoting chemotherapy drug resistance and metastases.
Profiling the Serum Protein Corona of Fibrillar Human Islet Amyloid Polypeptide
Publisher: American Chemical Society (ACS)
Date: 10-05-2018
Synthesis, self-assembly and stimuli responsive properties of cholesterol conjugated polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2PY20112G
Effect of the copolymer composition on the K and α constants of the Mark–Houwink equation: Comments on a recent article by Songkhla and Wootthikanokkhan
Publisher: Wiley
Date: 05-02-2003
DOI: 10.1002/POLB.10389
The reversible addition‐fragmentation chain transfer process and the strength and limitations of modeling: Comment on “the magnitude of the fragmentation rate coefficient”
Publisher: Wiley
Date: 08-2003
DOI: 10.1002/POLA.10854
Bioconjugation and Fluorescence Labeling of Iron Oxide Nanoparticles Grafted with Bromomaleimide-Terminal Polymers
Publisher: American Chemical Society (ACS)
Date: 11-10-2018
DOI: 10.1021/ACS.BIOMAC.8B01282
Abstract: Iron oxide nanoparticles have been widely applied in biomedical applications for their unique physical properties. Despite the relatively mature synthetic approaches for iron oxide nanoparticles, surface modification strategies for obtaining particles with satisfactory biofunctionality are still urgently needed to meet the challenge of nanomedicine. Herein, we report a surface modification and biofunctionalization strategy for iron oxide-based magnetic nanoparticles based on a dibromomaleimide (DBM)-terminated polymer with brushed polyethylene glycol (PEG) chains. PEG acrylate and phosphonate monomers, serving as antibiofouling and surface anchoring compartments for iron oxide nanoparticles, were incorporated utilizing a novel DBM containing reversible addition-fragmentation chain transfer (RAFT) agent. The particles prepared through this new surface architecture possessed high colloidal stability in a physiological buffer and the capacity of covalent conjugation with biomolecules for targeting. Cell tracking of the molecular probes was achieved concomitantly by exploiting DBM conjugation-induced fluorescence of the nanoparticles.
Functional Liquid Metal Nanoparticles Produced by Liquid-Based Nebulization
Publisher: Wiley
Date: 26-10-2019
Mapping Formation Pathways and End Group Patterns of Stimuli-Responsive Polymer Systems via High-Resolution Electrospray Ionization Mass Spectrometry
Publisher: American Chemical Society (ACS)
Date: 26-07-2007
DOI: 10.1021/BM700526J
Abstract: "Smart" polymers and polymer-protein conjugates find a vast array of biomedical applications. Ambient temperature reversible addition fragmentation chain transfer (RAFT) polymerizations conducted in an aqueous environment are a favorable method of choice for the synthesis of these materials however, information regarding the initiation mechanisms behind these polymerizations-and thus the critical polymer end groups-is lacking. In the current study, high-resolution soft ionization mass spectrometry techniques were used to map the product species generated during ambient temperature gamma-radiation induced RAFT polymerizations of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA) in aqueous media, allowing the generated end groups to be unambiguously established. It was found that trithiocarbonate and *R radicals produced from the radiolysis of the RAFT agent, *OH and *OOH radicals produced from the radiolysis of water, and *H radicals produced from the radiolysis of water, RAFT agent, or monomer were capable of initiating polymerizations and thus contribute toward the generated chain ends. Additionally, thiol terminated chains were formed via degradation of trithiocarbonate end groups. The current study is the first to provide comprehensive mapping of the formation pathways and end group patterns of stimuli-responsive polymers, thus allowing the design and implementation of these materials to proceed in a more tailored fashion.
Catalytic-chain-transfer polymerization of styrene revisited: The importance of monomer purification and polymerization conditions
Publisher: Wiley
Date: 23-01-2003
DOI: 10.1002/POLA.10613
Intracellular nitric oxide delivery from stable NO-polymeric nanoparticle carriers
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2CC37181B
Abstract: The encapsulation of S-nitrosoglutathione into polymeric nanoparticles substantially improves NO stability in aqueous media without affecting the efficacy of intracellular delivery. The combination of nano-NO delivery and chemotherapy has been found to enhance antitumour activity of chemotherapeutics, as demonstrated using preliminary in vitro experiments with neuroblastoma cells.
Synthesis of semi-biodegradable crosslinked microspheres for the delivery of 1,25 dihydroxyvitamin D3 for the treatment of hepatocellular carcinoma
Publisher: Elsevier BV
Date: 05-2007
Hyperbranched polymers as scaffolds for multifunctional reversible addition-fragmentation chain-transfer agents
Publisher: Wiley
Date: 23-10-2003
DOI: 10.1002/POLA.10976
Complications in the 355 nm Pulsed-Laser Polymerization ofN-Vinylcarbazole
Publisher: Wiley
Date: 09-2001
DOI: 10.1002/1521-3927(20010901)22:13<1035::AID-MARC1035>3.0.CO;2-Y
RAFT-prepared α-difunctional poly(2-vinyl-4,4-dimethylazlactone)s and their derivatives: synthesis and effect of end-groups on aqueous inverse temperature solubility
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4PY01108B
Abstract: Five R-group di-functional dithiobenzoates have been prepared and used in the reversible addition–fragmentation chain transfer polymerization of 2-vinyl-4,4-dimethylazlactone.
An optimised Cu(0)-RDRP approach for the synthesis of lipidated oligomeric vinyl azlactone: Toward a versatile antimicrobial materials screening platform
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9TB01624D
Abstract: For the first time Cu(0)-RDRP conditions were optimised to allow for the fast and controlled polymerisation of vinyl azlactone with tuneable lipid elements: a versatile platform material for the high-throughput synthesis of antimicrobial materials.
Simultaneous reversible addition fragmentation chain transfer and ring‐opening polymerization
Publisher: Wiley
Date: 27-03-2008
DOI: 10.1002/POLA.22647
Organic arsenicals as efficient and highly specific linkers for protein/peptide-polymer conjugation
Publisher: American Chemical Society (ACS)
Date: 20-03-2015
DOI: 10.1021/JACS.5B01140
Abstract: The entropy-driven affinity of trivalent (in)organic arsenicals for closely spaced dithiols has been exploited to develop a novel route to peptide rotein-polymer conjugation. A trivalent arsenous acid (As(III)) derivative (1) obtained from p-arsanilic acid (As(V)) was shown to readily undergo conjugation to the therapeutic peptide salmon calcitonin (sCT) via bridging of the Cys(1)-Cys(7) disulfide, which was verified by RP-HPLC and MALDI-ToF-MS. Conjugation was shown to proceed rapidly (t < 2 min) in situ and stoichiometrically through sequential reduction-conjugation protocols, therefore exhibiting conjugation efficiencies equivalent to those reported for the current leading disulfide-bond targeting strategies. Furthermore, using bovine serum albumin as a model protein, the trivalent organic arsenical 1 was found to demonstrate enhanced specificity for disulfide-bond bridging in the presence of free cysteine residues relative to established maleimide functional reagents. This specificity represents a shift toward potential orthogonality, by clearly distinguishing between the reactivity of mono- and disulfide-derived (vicinal or neighbors-through-space) dithiols. Finally, p-arsanilic acid was transformed into an initiator for aqueous single electron-transfer living radical polymerization, allowing the synthesis of hydrophilic arsenic-functional polymers which were shown to exhibit negligible cytotoxicity relative to a small molecule organic arsenical, and an unfunctionalized polymer control. Poly(poly[ethylene glycol] methyl ether acrylate) (PPEGA480, DPn = 10, Mn,NMR = 4900 g·mol(-1), Đ = 1.07) possessing a pentavalent arsenic acid (As(V)) α-chain end was transformed into trivalent As(III) post-polymerization via initial reduction by biological reducing agent glutathione (GSH), followed by binding of GSH. Conjugation of the resulting As(III)-functional polymer to sCT was realized within 35 min as indicated by RP-HPLC and verified later by thermodynamically driven release of sCT, from the conjugate, in the presence of strong chelating reagent ethanedithiol.
Direct observation of cobalt-carbon bond formation in the catalytic chain transfer polymerization of methyl acrylate using matrix-assisted laser desorption ionization time-of-flight mass spectrometry
Publisher: American Chemical Society (ACS)
Date: 29-09-2000
DOI: 10.1021/MA0003506
DNA Polyplexes Formed Using PEGylated Biodegradable Hyperbranched Polymers
Publisher: Wiley
Date: 09-06-2010
Abstract: A novel PEGylated biodegradable hyperbranched PEG-b-PDMAEMA has been synthesized. The low toxicity, small molecular weight PDMAEMA chains were crosslinked using a biodegradable disulfide-based dimethacrylate (DSDMA) agent to yield higher molecular weight hyperbranched polymers. PEG chains were linked onto the polymer surface, masking the positive charge (as shown by Zeta potential measurements) and reducing the toxicity of the polymer. The hyperbranched structures were also cleaved under reducing conditions and analyzed, confirming the expected component structures. The hyperbranched polymer was mixed with DNA and efficient binding was shown to occur through electrostatic interactions. The hyperbranched structures could be reduced easily, generating lower toxicity oligomer chains.
An overview of protein–polymer particles
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0SM00412J
Macromolecular Ligands for Gadolinium MRI Contrast Agents
Publisher: American Chemical Society (ACS)
Date: 09-05-2012
DOI: 10.1021/MA300521C
Implications of peptide assemblies in amyloid diseases
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CS00372B
Abstract: We highlight the role of molecular self-assembly in eliciting the mesoscopic and pathological properties of amyloid proteins. This knowledge is pivotal for the development of theranostics against amyloid diseases.
Selective Postmodification of Copolymer Backbones Bearing Different Activated Esters with Disparate Reactivities
Publisher: American Chemical Society (ACS)
Date: 25-09-2013
DOI: 10.1021/MZ4004375
Abstract: In this communication, we report an easy method for introducing functional groups into polymer structures by successively reacting two different activated ester functionalities (pentafluorophenyl (PFP) ester and azlactone (AZ)) with different functional amine compounds. By exploiting the difference in reactivity of the two activated esters (PFP and AZ) toward different amino compounds, we demonstrate, for the first time, a selective modification of the different activated ester groups, thereby introducing functional groups to the polymer backbone in a controlled manner. Statistical and block copolymers of vinyl dimethyl azlactone (VDM) and pentafluorophenyl acrylate (PFPA), i.e.,(p(VDM-
Journey to the centre of the cell: Virtual reality immersion into scientific data
Publisher: Wiley
Date: 21-11-2018
DOI: 10.1111/TRA.12538
Abstract: Visualization of scientific data is crucial not only for scientific discovery but also to communicate science and medicine to both experts and a general audience. Until recently, we have been limited to visualizing the three-dimensional (3D) world of biology in 2 dimensions. Renderings of 3D cells are still traditionally displayed using two-dimensional (2D) media, such as on a computer screen or paper. However, the advent of consumer grade virtual reality (VR) headsets such as Oculus Rift and HTC Vive means it is now possible to visualize and interact with scientific data in a 3D virtual world. In addition, new microscopic methods provide an unprecedented opportunity to obtain new 3D data sets. In this perspective article, we highlight how we have used cutting edge imaging techniques to build a 3D virtual model of a cell from serial block-face scanning electron microscope (SBEM) imaging data. This model allows scientists, students and members of the public to explore and interact with a "real" cell. Early testing of this immersive environment indicates a significant improvement in students' understanding of cellular processes and points to a new future of learning and public engagement. In addition, we speculate that VR can become a new tool for researchers studying cellular architecture and processes by populating VR models with molecular data.
Branched Polymer−Protein Conjugates Made From Mid-Chain-Functional P(HPMA)
Publisher: American Chemical Society (ACS)
Date: 04-09-2009
DOI: 10.1021/BM900678R
Abstract: A novel midchain-functional chain transfer agent was synthesized and used as a reversible addition-fragmentation chain transfer polymerization agent to prepare branched poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA). The P(HPMA) contained a thio-reactive group, namely, pyridyldisulfide midchain. The synthesized polymers were fully analyzed by (1)H NMR, GPC, and hydrolysis, confirming well-defined structures (predesigned molecular weights, narrow polydispersities, and high functionalization efficiencies). These midfunctionalized polymers were incubated with bovine serum albumin to generate protein-polymer conjugates. This straightforward methodology for the synthesis of branched midfunctionalized polymers for protein conjugation has the potential to enhance the properties of polymer-protein conjugates by improving biomolecule stability and enhancing circulation time.
Nanotechnology in Medical Research
Publisher: Elsevier
Date: 2017
Using the reversible addition–fragmentation chain transfer process to synthesize core‐crosslinked micelles
Publisher: Wiley
Date: 10-02-2006
DOI: 10.1002/POLA.21328
The effects of particle size, shape, density and flow characteristics on particle margination to vascular walls in cardiovascular diseases
Publisher: Informa UK Limited
Date: 13-04-2018
DOI: 10.1080/17425247.2017.1316262
Abstract: Vascular-targeted drug delivery is a promising approach for the treatment of atherosclerosis, due to the vast involvement of endothelium in the initiation and growth of plaque, a characteristic of atherosclerosis. One of the major challenges in carrier design for targeting cardiovascular diseases (CVD) is that carriers must be able to navigate the circulation system and efficiently marginate to the endothelium in order to interact with the target receptors. This review draws on studies that have focused on the role of particle size, shape, and density (along with flow hemodynamics and hemorheology) on the localization of the particles to activated endothelial cell surfaces and vascular walls under different flow conditions, especially those relevant to atherosclerosis. Generally, the size, shape, and density of a particle affect its adhesion to vascular walls synergistically, and these three factors should be considered simultaneously when designing an optimal carrier for targeting CVD. Available preliminary data should encourage more studies to be conducted to investigate the use of nano-constructs, characterized by a sub-micrometer size, a non-spherical shape, and a high material density to maximize vascular wall margination and minimize capillary entrapment, as carriers for targeting CVD.
Zwitterionic Amino Acid-Derived Polyacrylates as Smart Materials Exhibiting Cellular Specificity and Therapeutic Activity
Publisher: American Chemical Society (ACS)
Date: 04-05-2022
DOI: 10.1021/ACS.BIOMAC.2C00143
Abstract: The synthesis of new amino acid-containing, cell-specific, therapeutically active polymers is presented. Amino acids served as starting material for the preparation of tailored polymers with different amino acids in the side chain. The reversible addition-fragmentation chain-transfer (RAFT) polymerization of acrylate monomers yielded polymers of narrow size distribution (
Impact of heavy rainfall events and shading on the temperature of sea turtle nests
Publisher: Springer Science and Business Media LLC
Date: 24-11-2020
Serotonin-induced vascular permeability is mediated by transient receptor potential vanilloid 4 in the airways and upper gastrointestinal tract of mice
Publisher: Elsevier BV
Date: 07-2021
Cobalt(II)-mediated catalytic chain transfer polymerization of styrene: Estimating individual rate coefficients via kinetic modeling
Publisher: American Chemical Society (ACS)
Date: 28-01-2003
DOI: 10.1021/MA021152C
Using Kinetics and Thermodynamics in the Controlled Synthesis of Low Molecular Weight Polymers in Free-Radical Polymerization
Publisher: Wiley
Date: 04-2001
DOI: 10.1002/1521-3919(20010401)10:4<255::AID-MATS255>3.0.CO;2-V
N. Charton, A. Feldermann, A. Theis, M. H. Stenzel, T. P. Davis, C. Barner‐Kowollik, Initiator efficiency of 2,2′‐azobis(isobutyronitrile) in bulk dodecyl acrylate free‐radical polymerizations over
Publisher: Wiley
Date: 24-09-2004
DOI: 10.1002/POLA.20518
Mapping Poly(butyl acrylate) Product Distributions by Mass Spectrometry in a Wide Temperature Range: Suppression of Midchain Radical Side Reactions
Publisher: American Chemical Society (ACS)
Date: 09-11-2007
DOI: 10.1021/MA071471+
Amphiphilic surface chemistry of fullerenols is necessary for inhibiting the amyloid aggregation of alpha-synuclein NACore
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9NR02407G
Abstract: Featuring small sizes, caged structures, low cytotoxicity and the capability to cross biological barriers, fullerene hydroxy derivatives named fullerenols have been explored as nanomedicinal candidates for amyloid inhibition.
Free-radical copolymerization of styrene and itaconic acid studied by1H NMR kinetic experiments
Publisher: Wiley
Date: 2001
DOI: 10.1002/1099-0518(20010301)39:5<656::AID-POLA1037>3.0.CO;2-9
Mitigation of Amyloidosis with Nanomaterials
Publisher: Wiley
Date: 11-06-2019
Aerosol delivery of star polymer-siRNA nanoparticles as a therapeutic strategy to inhibit lung tumor growth
Publisher: Elsevier BV
Date: 06-2022
DOI: 10.1016/J.BIOMATERIALS.2022.121539
Abstract: Lung cancer is a major contributor to cancer-related death worldwide. siRNA nanomedicines are powerful tools for cancer therapeutics. However, there are challenges to overcome to increase siRNA delivery to solid tumors, including penetration of nanoparticles into a complex microenvironment following systemic delivery while avoiding rapid clearance by the reticuloendothelial system, and limited siRNA release from endosomes once inside the cell. Here we characterized cell uptake, intracellular trafficking, and gene silencing activity of miktoarm star polymer (PDMAEMA-POEGMA) nanoparticles (star nanoparticles) complexed to siRNA in lung cancer cells. We investigated the potential of nebulized star-siRNA nanoparticles to accumulate into orthotopic mouse lung tumors to inhibit expression of two genes [βIII-tubulin, Polo-Like Kinase 1 (PLK1)] which: 1) are upregulated in lung cancer cells 2) promote tumor growth and 3) are difficult to inhibit using chemical drugs. Star-siRNA nanoparticles internalized into lung cancer cells and escaped the endo-lysosomal pathway to inhibit target gene expression in lung cancer cells in vitro. Nebulized star-siRNA nanoparticles accumulated into lungs and silenced the expression of βIII-tubulin and PLK1 in mouse lung tumors, delaying aggressive tumor growth. These results demonstrate a proof-of-concept for aerosol delivery of star-siRNA nanoparticles as a novel therapeutic strategy to inhibit lung tumor growth.
Delivering nitric oxide with nanoparticles
Publisher: Elsevier BV
Date: 05-2015
DOI: 10.1016/J.JCONREL.2015.02.007
Abstract: While best known for its important signalling functions in human physiology, nitric oxide is also of considerable therapeutic interest. As such, nanoparticle-based systems which enable the sustained exogenous delivery of nitric oxide have been the subject of considerable investigation in recent years. Herein we review the various nanoparticle systems that have been used to date for nitric oxide delivery, and explore the array of potential therapeutic applications that have been reported. Specifically, we discuss the modification of sol-gel based silica particles, functionalised metal/metal oxide nanoparticles, polymer-coated metal nanoparticles, dendrimers, micelles and star polymers to impart nitric oxide release capability. We also consider the various areas in which therapeutic applications are envisaged: wound healing, antimicrobial applications, cardiovascular treatments, sexual medicine and cancer treatment. Finally, we discuss possible future directions for this versatile and potentially important technology.
Macromolecular Hydrogen Sulfide Donors Trigger Spatiotemporally Confined Changes in Cell Signaling
Publisher: American Chemical Society (ACS)
Date: 23-12-2016
DOI: 10.1021/ACS.BIOMAC.5B01469
Abstract: Hydrogen sulfide (H2S) is involved in a myriad of cell signaling processes that trigger physiological events ranging from vasodilation to cell proliferation. Moreover, disturbances to H2S signaling have been associated with numerous pathologies. As such, the ability to release H2S in a cellular environment and stimulate signaling events is of considerable interest. Herein we report the synthesis of macromolecular H2S donors capable of stimulating cell signaling pathways in both the cytosol and at the cell membrane. Specifically, copolymers having pendent oligo(ethylene glycol) and benzonitrile groups were synthesized, and the benzonitrile groups were subsequently transformed into primary aryl thioamide groups via thionation using sodium hydrosulfide. These thioamide moieties could be incorporated into a hydrophilic copolymer or a block copolymer (i.e., into either the hydrophilic or hydrophobic domain). An electrochemical sensor was used to demonstrate release of H2S under simulated physiological conditions. Subsequent treatment of HEK293 cells with a macromolecular H2S donor elicited a slow and sustained increase in cytosolic ERK signaling, as monitored using a FRET-based biosensor. The macromolecular donor was also shown to induce a small, fast and sustained increase in plasma membrane-localized PKC activity immediately following addition to cells. Studies using an H2S-selective fluorescent probe in live cells confirmed release of H2S from the macromolecular donor over physiologically relevant time scales consistent with the signaling observations. Taken together, these results demonstrate that by using macromolecular H2S donors it is possible to trigger spatiotemporally confined cell signaling events. Moreover, the localized nature of the observed signaling suggests that macromolecular donor design may provide an approach for selectively stimulating certain cellular biochemical pathways.
Uptake and transcytosis of functionalized superparamagnetic iron oxide nanoparticles in an in vitro blood brain barrier model
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7BM01012E
Abstract: Phosphoryl choline grafting secured high cellular uptake and increased transcytosis of superparamagnetic iron oxide nanoparticles through a model blood brain barrier.
Synthesis of Versatile Thiol-Reactive Polymer Scaffolds via RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 20-06-2008
DOI: 10.1021/BM800197V
Abstract: Well-defined polymer scaffolds convertible to (multi)functional polymer structures via selective and efficient modifications potentially provide an easy, versatile, and useful approach for a wide variety of applications. Considering this, a homopolymer scaffold, poly(pyridyldisulfide ethylmethacrylate) (poly(PDSM)), having pendant groups selectively reactive with thiols, was synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. Soluble polymers with controlled molecular weights and narrow PDIs were generated efficiently. The versatility of the scaffold to generate random co- and ter-polymers combining multiple functionalities with controlled-composition was shown by separate and simultaneous conjugation of different mercapto-compounds, including a tripeptide in one-step. Conversion of water-insoluble scaffold to peptide-containing water-soluble copolymers was observed to yield nanometer-size particles with narrow polydispersity. The overall results suggest that the well-defined PDSM homopolymer scaffold generated via RAFT polymerization can be a versatile building block for generation of new structures having potential for drug delivery applications via a straightforward synthetic approach.
Optimizing the generation of narrow polydispersity ‘arm-first’ star polymers made using RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1PY00102G
Functional iron oxide magnetic nanoparticles with hyperthermia-induced drug release ability by using a combination of orthogonal click reactions
Publisher: Wiley
Date: 19-11-2013
Effect of the Penultimate Unit on Radical Stability and Reactivity in Free-Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 13-04-1999
DOI: 10.1021/MA9818073
Plasma Proteome Association and Catalytic Activity of Stealth Polymer‐Grafted Iron Oxide Nanoparticles
Publisher: Wiley
Date: 07-08-2017
Abstract: Polyethylene glycol (PEG) is widely used as an antifouling and stealth polymer in surface engineering and nanomedicine. However, recent research has revealed adverse effects of bioaccumulation and immunogenicity following the administration of PEG, prompting this proteomic examination of the plasma protein coronae association with superparamagnetic iron oxide nanoparticles (IONPs) grafted with brushed PEG (bPEG) and an alternative, brushed phosphorylcholine (bPC). Using label-free quantitation by liquid chromatography tandem-mass spectrometry, this study determines protein abundances for the in vitro hard coronae of bare, bPC-, and bPEG-grafted IONPs in human plasma. This study also shows unique protein compositions in the plasma coronae of each IONP, including enrichment of coagulation factors and immunogenic complement proteins with bPEG, and enhanced binding of apolipoproteins with bPC. Functional analysis reveals that plasma protein coronae elevate the horseradish peroxidase-like activities of the bPC- and bPEG-IONPs by approximately twofold, an effect likely mediated by the erse composition and physicochemical properties of the polymers as well as their associated plasma proteins. Taken together, these observations support the rational design of stealth polymers based on a quantitative understanding of the interplay between IONPs and the plasma proteome, and should prove beneficial for the development of materials for nanomedicine, biosensing, and catalysis.
Sustained endosomal release of a neurokinin-1 receptor antagonist from nanostars provides long-lasting relief of chronic pain
Publisher: Elsevier BV
Date: 06-2022
DOI: 10.1016/J.BIOMATERIALS.2022.121536
Abstract: Soft polymer nanoparticles designed to disassemble and release an antagonist of the neurokinin 1 receptor (NK
Serum albumin impedes the amyloid aggregation and hemolysis of human islet amyloid polypeptide and alpha synuclein
Publisher: Elsevier BV
Date: 09-2018
DOI: 10.1016/J.BBAMEM.2018.01.015
Abstract: Protein aggregation is a ubiquitous phenomenon underpinning the origins of a range of human diseases. The amyloid aggregation of human islet amyloid polypeptide (IAPP) and alpha synuclein (αS), specifically, is a hallmark of type 2 diabetes (T2D) and Parkinson's disease impacting millions of people worldwide. Although IAPP and αS are strongly associated with pancreatic β-cell islets and presynaptic terminals, they have also been found in blood circulation and the gut. While extensive biophysical and biochemical studies have been focused on IAPP and αS interacting with cell membranes or model lipid vesicles, the roles of plasma proteins on the amyloidosis and membrane association of these two major types of amyloid proteins have rarely been examined. Using a thioflavin T kinetic assay, transmission electron microscopy and a hemolysis assay here we show that human serum albumin, the most abundant protein in the plasma, impeded the fibrillization and mitigated membrane damage of both IAPP and αS. This study offers a new insight on the native inhibition of amyloidosis.
Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates: Facile Access to Functional Materials
Publisher: American Chemical Society (ACS)
Date: 13-04-2017
DOI: 10.1021/JACS.7B01694
Abstract: A highly efficient photomediated atom transfer radical polymerization protocol is reported for semi-fluorinated acrylates and methacrylates. Use of the commercially available solvent, 2-trifluoromethyl-2-propanol, optimally balances monomer, polymer, and catalyst solubility while eliminating transesterification as a detrimental side reaction. In the presence of UV irradiation and ppm concentrations of copper(II) bromide and Me
UCST-driven self-assembly and crosslinking of diblock copolymer micelles
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2PY20204B
Trisulfide linked cholesteryl PEG conjugate attenuates intracellular ROS and collagen-1 production in a breast cancer co-culture model
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0BM01544J
Abstract: Treatment of cancer cell-fibroblast co-cultures with H 2 S-releasing trisulfide conjugate causes restoration of ROS levels in the cancer cells and normalisation of collagen-1 expression in the fibroblasts.
Modulation of the Surface Charge on Polymer-Stabilized Gold Nanoparticles by the Application of an External Stimulus
Publisher: American Chemical Society (ACS)
Date: 06-11-2021
DOI: 10.1021/LA902746V
Abstract: A new approach to controlling the charge on gold nanoparticle surfaces is described. The method exploits the simultaneous coattachment of both charged and neutral polymers onto gold surfaces. The charged and neutral polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, and the RAFT end-group functionality was used as the anchor for attachment to gold. The approach described is general and can be applied to a wide range of monomers those exemplified in the paper are poly(2-aminoethyl methacrylamide) (P(AEA)), poly(acrylic acid) (PAA), and poly(N,N-diemthylaminoethyl acrylate) (P(DMAEA)) together with neutral polymers based on poly(oligoethylene oxide) acrylate (P(OEG-A)). The hybrid polymer-stabilized GNPs thus formed were characterized in solution using dynamic light scattering and zeta potential measurements, transmission electron microscopy, UV-visible spectroscopy, X-ray photoelectron spectroscopy, and attenuated total reflection-Fourier-transform IR spectroscopy. The grafting densities of the polymers on GNPs were measured using thermal gravimetric analyses (TGA), as 0.4 chains/nm(2) (for PAA), 0.9 chains/nm(2) (for neutral polymers, such as P(NIPAAm), and 0.6 chain/nm(2) for the positive charged polymers P(AEA) and P(DMAEA). The directed coassembly of two different polymers (one charged and one noncharged) on the gold nanoparticle surfaces provided a mechanism (dependent on molecular weight) for shielding the surface charge imparted by the charged polymer component, allowing for a range of surface charges on the GNPs from -30 to +39 mV. In further work, the surface-charges were modulated by an external stimulus (temperature). The charge-modulation was controlled by the use of thermosensitive neutral polymers coassembled with charged polymers. The thermosensitive polymers exemplified in this paper are P(oligoethylene oxide acrylate-co-diethylene oxide acrylate) (P(OEG-A-co-DEG-A)) and P(N-isopropyl acrylamide) (P(NIPAAm). The temperature of the aqueous phase (from 15 to 70 degrees C) was then adjusted to tune the zeta potentials of the hybrid GNPs from +39 or -30 to approximately 0 mV. Finally, by manipulating the solution pH, reversible aggregation behavior of the hybrid GNPs could be induced.
Nanoparticles Based on Star Polymers as Theranostic Vectors: Endosomal-Triggered Drug Release Combined with MRI Sensitivity
Publisher: Wiley
Date: 07-2015
Abstract: Dual-functional star polymers (diameters 15 nm) are synthesized producing nanoparticles with excellent colloidal stability in both water and serum. The nanoparticles are built with aldehyde groups in the core and activated esters in the arms. The different reactivity of the two functional groups to sequentially react with different amino compounds is exploited doxorubicin (DOX) and 1-(5-amino-3-aza-2-oxypentyl)-4,7,10-tris(tert-butoxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane (DO3A-tBu-NH2 )-a chelating agent effective for the complexation of Gadolinium ions (Gd). The activated ester group is employed to attach the DO3A chelating agent, while the aldehyde groups are exploited for DOX conjugation, providing a controlled release mechanism for DOX in acidic environments. DOX/Gd-loaded nanoparticles are rapidly taken up by MCF-7 breast cancer cells, subsequently releasing DOX as demonstrated using in vitro fluorescence lifetime imaging microscopy (FLIM). Endosomal, DOX release is observed, using a phasor plot representation of the fluorescence lifetime data, showing an increase of native DOX with time. The MRI properties of the stars are assessed and the relaxivity of Gd loaded in stars is three times higher than conventional organic Gd/DO3A complexes. The DOX/Gd-conjugated nanoparticles yield a similar IC50 to native DOX for breast cancer cell lines, confirming that DOX integrity is conserved during nanoparticle attachment and release.
Nanomaterial synthesis, an enabler of amyloidosis inhibition against human diseases
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0NR04273K
Abstract: We summarize current strategies for the synthesis and construction of nanoparticle inhibitors and probes against pathogenic amyloidosis.
Biodegradable PEG hydrogels cross-linked using biotin-avidin interactions
Publisher: CSIRO Publishing
Date: 2010
DOI: 10.1071/CH10168
Abstract: Poly(ethylene glycol) (PEG) hydrogels are water-swellable, non-toxic, non-immunogenic, and biocompatible. In this paper, we describe the generation of biodegradable PEG hydrogels by cross-linking biotinylated PEG oligomers containing intrinsic disulfide bonds via biotin-avidin interactions. The biotinylated PEG oligomers were synthesized by the condensation reaction between PEG and 3,3′-dithiodipropionic acid, followed by the reaction with biotin. This methodology obviates the need for potentially toxic chemical cross-linking agents that are usually used in the common preparation of hydrogels. Therefore it may be particularly useful in biomedical or pharmaceutical applications.
Dextran-Based Doxorubicin Nanocarriers with Improved Tumor Penetration
Publisher: American Chemical Society (ACS)
Date: 18-12-2013
DOI: 10.1021/BM401526D
Abstract: Drug delivery systems with improved tumor penetration are valuable assets as anticancer agents. A dextran-based nanocarrier system with aldehyde functionalities capable of forming an acid labile linkage with the chemotherapy drug doxorubicin was developed. Aldehyde dextran nanocarriers (ald-dex-dox) demonstrated efficacy as delivery vehicles with an IC50 of ∼300 nM against two-dimensional (2D) SK-N-BE(2) monolayers. Confocal imaging showed that the ald-dex-dox nanocarriers were rapidly internalized by SK-N-BE(2) cells. Fluorescence lifetime imaging microscopy (FLIM) analysis indicated that ald-dex-dox particles were internalized as intact complexes with the majority of the doxorubicin released from the particle four hours post uptake. Accumulation of the ald-dex-dox particles was significantly enhanced by ∼30% in the absence of glucose indicating a role for glucose and its receptors in their endocytosis. However, inhibition of clathrin dependent and independent endocytosis and macropinocytosis as well as membrane cholesterol depletion had no effect on ald-dex-dox particle accumulation. In three-dimensional (3D) SK-N-BE(2) tumor spheroids, which more closely resemble a solid tumor, the ald-dex-dox nanoparticles showed a significant improvement in efficacy over free doxorubicin, as evidenced by decreased spheroid outgrowth. Drug penetration studies in 3D demonstrated the ability of the ald-dex-dox nanocarriers to fully penetrate into a SK-N-BE(2) tumor spheroids, while doxorubicin only penetrates to a maximum distance of 50 μM. The ald-dex-dox nanocarriers represent a promising therapeutic delivery system for the treatment of solid tumors due to their unique enhanced penetration ability combined with their improved efficacy over the parent drug in 3D.
Synthesis, aggregation and responsivity of block copolymers containing organic arsenicals
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7PY01852E
Abstract: Block copolymers containing an organic arsenical (AsAm) have been synthesised by aqueous SET-LRP.
RAFT-mediated polymerization and grafting of sodium 4-styrenesulfonate from cellulose initiated via gamma-radiation
Publisher: Elsevier BV
Date: 02-2009
The application of ionizing radiation in reversible addition-fragmentation chain transfer (RAFT) polymerization: Renaissance of a key synthetic and kinetic tool
Publisher: Elsevier BV
Date: 10-2007
Synthesis of Various Glycopolymer Architectures via RAFT Polymerization: From Block Copolymers to Stars
Publisher: American Chemical Society (ACS)
Date: 13-12-2005
DOI: 10.1021/BM0506086
Abstract: Well-defined linear poly(acryloyl glucosamine) (PAGA) exhibiting molar masses ranging from 3 to 120 K and low polydispersities have been prepared via reversible addition-fragmentation chain transfer polymerization (RAFT) in aqueous solution without recourse to protecting group chemistry. The livingness of the process was further demonstrated by successfully chain-extending one of these polymers with N-isopropylacrylamide affording narrow dispersed thermosensitive diblocks. This strategy of polymerization was finally extended to the preparation of glycopolymer stars from Z designed non-water-soluble trifunctional RAFT agent. After the growth of very short blocks of poly(hydroxyethyl acrylate) ((-)DP(n)(branch) = 10), AGA was polymerized in aqueous solution in a controlled manner affording well-defined 3-arm glycopolymer stars.
A Rationally Optimized Nanoparticle System for the Delivery of RNA Interference Therapeutics into Pancreatic Tumors in Vivo
Publisher: American Chemical Society (ACS)
Date: 28-06-2016
DOI: 10.1021/ACS.BIOMAC.6B00185
Abstract: Pancreatic cancer is a devastating disease with a dismal prognosis. Short-interfering RNA (siRNA)-based therapeutics hold promise for the treatment of cancer. However, development of efficient and safe delivery vehicles for siRNA remains a challenge. Here, we describe the synthesis and physicochemical characterization of star polymers (star 1, star 2, star 3) using reversible addition-fragmentation chain transfer polymerization (RAFT) for the delivery of siRNA to pancreatic cancer cells. These star polymers were designed to contain different lengths of cationic poly(dimethylaminoethyl methacrylate) (PDMAEMA) side-arms and varied amounts of poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA). We showed that star-POEGMA polymers could readily self-assemble with siRNA to form nanoparticles. The star-POEGMA polymers were nontoxic to normal cells and delivered siRNA with high efficiency to pancreatic cancer cells to silence a gene (TUBB3/βIII-tubulin) which is currently undruggable using chemical agents, and is involved in regulating tumor growth and metastases. Notably, systemic administration of star-POEGMA-siRNA resulted in high accumulation of siRNA to orthotopic pancreatic tumors in mice and silenced βIII-tubulin expression by 80% at the gene and protein levels in pancreatic tumors. Together, these novel findings provide strong rationale for the use of star-POEGMA polymers as delivery vehicles for siRNA to pancreatic tumors.
Antifouling Surfaces Enabled by Surface Grafting of Highly Hydrophilic Sulfoxide Polymer Brushes
Publisher: American Chemical Society (ACS)
Date: 11-12-2020
Poly(vinyl alcohol) star polymers prepared via MADIX/RAFT polymerisationElectronic Supplementary Information (ESI) available: synthesis and NMR data of MADIX agents, polymerisation and analysis techni
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B404763J
Abstract: Poly(vinyl acetate) stars were prepared using MADIX/RAFT polymerisation mediated by xanthates. The polymerisation shows living characteristics with molecular weight increasing with conversion. The subsequent hydrolysis of these three and four arm stars led to the formation of poly(vinyl alcohol) stars.
miR-99b-5p, miR-380-3p, and miR-485-3p are novel chemosensitizing miRNAs in high-risk neuroblastoma
Publisher: Elsevier BV
Date: 03-2022
Synthesis of amphiphilic block copolymers based on poly(dimethylsiloxane) via fragmentation chain transfer (RAFT) polymerization
Publisher: Elsevier BV
Date: 06-2004
Optimizing the photochromic performance of naphthopyrans in a rigid host matrix using poly(dimethylsiloxane) conjugation
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B904345D
Nano-assemblies of cationic mPEG brush block copolymers with gadolinium polyoxotungstate [Gd(W5O18)2]9− form stable, high relaxivity MRI contrast agents
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8NR01544A
Abstract: Nano-assemblies of gadolinium polyoxotungstate and cationic mPEG brush block copolymer demonstrated good stability and enhanced relaxivity at physiological pH.
Thermosensitive Graphene Nanocomposites Formed Using Pyrene-Terminal Polymers Made by RAFT Polymerization
Publisher: Wiley
Date: 07-12-2010
DOI: 10.1002/POLA.23802
Assessment of Cholesterol-Derived Ionic Copolymers as Potential Vectors for Gene Delivery
Publisher: American Chemical Society (ACS)
Date: 30-10-2013
DOI: 10.1021/BM4013088
Abstract: A library of cholesterol-derived ionic copolymers were previously synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization as 'smart' gene delivery vehicles that hold erse surface charges. Polyplex systems formed with anionic poly(methacrylic acid-co-cholesteryl methacrylate) (P(MAA-co-CMA)) and cationic poly(dimethylamino ethyl methacrylate-co-cholesteryl methacrylate) (Q-P(DMAEMA-co-CMA)) copolymer series were evaluated for their therapeutic efficiency. Cell viability assays, conducted on SHEP, HepG2, H460, and MRC5 cell lines, revealed that alterations in the copolymer composition (CMA mol %) affected the cytotoxicity profile. Increasing the number of cholesterol moieties in Q-P(DMAEMA-co-CMA) copolymers reduced the overall toxicity (in H460 and HepG2 cells) while P(MAA-co-CMA) series displayed no significant toxicity regardless of the CMA content. Agarose gel electrophoresis was employed to investigate the formation of stable polyplexes and determine their complete conjugation ratios. P(MAA-co-CMA) copolymer series were conjugated to DNA through a cationic linker, oligolysine, while Q-P(DMAEMA-co-CMA)-siRNA complexes were readily formed via electrostatic interactions at conjugation ratios beginning from 6:1:1 (oligolysine-P(MAA-co-CMA)-DNA) and 20:1 (Q-P(DMAEMA-co-CMA)-siRNA), respectively. The hydrodynamic diameter, ζ potential and complex stability of the polyplexes were evaluated in accordance to complexation ratios and copolymer composition by dynamic light scattering (DLS). The therapeutic efficiency of the conjugates was assessed in SHEP cells via transfection and imaging assays using RT-qPCR, Western blotting, flow cytometry, and confocal microscopy. DNA transfection studies revealed P(MAA-co-CMA)-oligolysine-DNA ternary complexes to be ineffective transfection vehicles that mostly adhere to the cell surface as opposed to internalizing and partaking in endosomal disrupting activity. The transfection efficiency of Q-P(DMAEMA-co-CMA)-GFP siRNA complexes were found to be polymer composition and N/P ratio dependent, with Q-2% CMA-GFP siRNA polyplexes at N/P ratio 20:1 showing the highest gene suppression in GFP expressing SHEP cells. Cellular internalization studies suggested that Q-P(DMAEMA-co-CMA)-siRNA conjugates efficiently escaped the endolysosomal pathway and released siRNA into the cytoplasm. The gene delivery profile, reported herein, illuminates the positive and negative attributes of each therapeutic design and strongly suggests Q-P(DMAEMA-co-CMA)-siRNA particles are extremely promising candidates for in vivo applications of siRNA therapy.
The stabilization and bio-functionalization of iron oxide nanoparticles using heterotelechelic polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B815202K
Living free-radical polymerization (reversible addition-fragmentation chain transfer) of 6-[4-(4 '-methoxyphenyl)phenoxy]hexyl methacrylate: A route to architectural control of side-chain liquid-crystal line polymers
Publisher: Wiley
Date: 08-08-2003
DOI: 10.1002/POLA.10894
Thiol-reactive star polymers functionalized with short ethoxy-containing moieties exhibit enhanced uptake in acute lymphoblastic leukemia cells
Publisher: Informa UK Limited
Date: 12-2019
DOI: 10.2147/IJN.S220326
Grafting of P(OEGA) Onto Magnetic Nanoparticles Using Cu(0) Mediated Polymerization: Comparing Grafting "from" and "to" Approaches in the Search for the Optimal Material, Design of Nanoparticle MRI Contrast Agents
Publisher: American Chemical Society (ACS)
Date: 02-08-2013
DOI: 10.1021/MA401250F
Graphene oxide inhibits hIAPP amyloid fibrillation and toxicity in insulin-producing NIT-1 cells
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CP05924K
Abstract: Using a multidisciplinary approach combining computational modeling, biophysical characterization, and in vitro toxicity studies, the anti-amyloid effect of graphene oxide and its molecular mechanism is investigated.
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.
Sulfoxide-Containing Polymer-Coated Nanoparticles Demonstrate Minimal Protein Fouling and Improved Blood Circulation
Publisher: Wiley
Date: 17-05-2020
Factors influencing the synthesis and the post-modification of PEGylated pentafluorophenyl acrylate containing copolymers
Publisher: Elsevier BV
Date: 10-2013
Thermolysis of RAFT-synthesized polymers. A convenient method for trithiocarbonate group elimination
Publisher: American Chemical Society (ACS)
Date: 28-05-2005
DOI: 10.1021/MA050402X
The transient receptor potential vanilloid 4 (TRPV4) ion channel mediates protease activated receptor 1 (PAR1)-induced vascular hyperpermeability.
Publisher: Elsevier BV
Date: 08-2020
Substituent effects on the chain‐transfer behavior of 7‐methylene‐2‐methyl‐1,5‐dithiacyclooctane in the presence of disulfides and thiols
Publisher: Wiley
Date: 29-10-2002
DOI: 10.1002/POLA.10528
Efficient Binding, Protection, and Self-Release of dsRNA in Soil by Linear and Star Cationic Polymers
Publisher: American Chemical Society (ACS)
Date: 12-07-2018
Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX)
Publisher: Elsevier BV
Date: 02-2006
Conformational Dependence of the Penultimate Unit Effect in Free-Radical Copolymerization
Publisher: American Chemical Society (ACS)
Date: 22-07-1999
DOI: 10.1021/MA990468Q
Copolyampholytes Produced from RAFT Polymerization of Protic Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 10-11-2017
RAFT Synthesis and DNA Binding of Biodegradable, Hyperbranched Poly(2-(dimethylamino)ethyl Methacrylate
Publisher: American Chemical Society (ACS)
Date: 26-06-2009
DOI: 10.1021/MA900865C
End Group Reactions of RAFT-Prepared (Co)Polymers
Publisher: CSIRO Publishing
Date: 2011
DOI: 10.1071/CH11152
Abstract: This review highlights the chemistry of thiocarbonylthio groups with an emphasis on chemistry conducted at ω or α and ω chain-ends in copolymers prepared by reversible addition–fragmentation chain-transfer (RAFT) radical polymerization. We begin by giving a general overview of reactions associated with the thiocarbonylthio groups, followed by ex les associated with macromolecular thiols.
Graphene quantum dots obstruct the membrane axis of Alzheimer's amyloid beta
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1CP04246G
Abstract: Graphene quantum dots bind with Aβ, thereby blocking the membrane axis of the peptide and averting downstream pathogenic effects.
Verification of controlled grafting of styrene from cellulose via radiation-induced RAFT polymerization
Publisher: American Chemical Society (ACS)
Date: 08-09-2007
DOI: 10.1021/MA070825U
Investigation of the influence of the architectures of poly(vinyl pyrrolidone) polymers made via the reversible addition–fragmentation chain transfer/macromolecular design via the interchange of xanth
Publisher: Wiley
Date: 20-06-2006
DOI: 10.1002/POLA.21518
Graphene quantum dots rescue protein dysregulation of pancreatic β-cells exposed to human islet amyloid polypeptide
Publisher: Springer Science and Business Media LLC
Date: 26-09-2019
Effect of an added base on (4-cyanopentanoic acid)-4-dithiobenzoate mediated RAFT polymerization in water
Publisher: Elsevier BV
Date: 02-2006
Nonionic Water-Soluble and Cytocompatible Poly(amide acrylate)s
Publisher: American Chemical Society (ACS)
Date: 06-01-2020
Reversible addition-fragmentation chain transfer polymerization of methacrylate, acrylate and styrene monomers in 1-alkyl-3-methylimidazolium hexfluorophosphate
Publisher: Elsevier BV
Date: 03-2003
Polymeric filomicelles and nanoworms: two decades of synthesis and application
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6PY00639F
Abstract: This review highlights the substantial progress in the syntheses and applications of filomicelles, an emerging nanomaterial with distinct and useful properties.
Elevated amyloidoses of human IAPP and amyloid beta by lipopolysaccharide and their mitigation by carbon quantum dots
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0NR02710C
Abstract: CQDs were potent in inhibiting IAPP and Aβ amyloidosis, allowing hatching of zebrafish embryos into healthy larvae.
Polymeric arsenicals as scaffolds for functional and responsive hydrogels
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8TB02569J
Abstract: Here arsenohydrogels are introduced for the first time as functional, tuneable and responsive hydrogels.
Amyloidosis inhibition, a new frontier of the protein corona
Publisher: Elsevier BV
Date: 12-2020
Dendrimers as scaffolds for multifunctional reversible addition–fragmentation chain transfer agents: Syntheses and polymerization
Publisher: Wiley
Date: 13-10-2004
DOI: 10.1002/POLA.20434
Protected amine-functional initiators for the synthesis of α-amine homo- and heterotelechelic poly(2-ethyl-2-oxazoline)s
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2PY00649A
Abstract: Screening a series of protected amine cationic ring-opening polymerization initiators revealed the commercially available N -(3-bromopropyl)phthalimide as the most suitable to achieve defined polymers with high degree of amine functionalization.
Reversible addition-fragmentation chain transfer polymerization of methyl methacrylate in suspension
Publisher: Wiley
Date: 06-04-2005
DOI: 10.1002/POLA.20673
Nucleation of β-rich oligomers and β-barrels in the early aggregation of human islet amyloid polypeptide
Publisher: Elsevier BV
Date: 02-2019
Facile access to polymeric vesicular nanostructures: Remarkable ω-end group effects in cholesterol and pyrene functional (Co)polymers
Publisher: American Chemical Society (ACS)
Date: 23-12-2011
DOI: 10.1021/MA102386J
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.
Synthesis and identification of novel pyridazinylpyrazolone based diazo compounds as inhibitors of human islet amyloid polypeptide aggregation
Publisher: Elsevier BV
Date: 03-2019
DOI: 10.1016/J.BIOORG.2018.11.039
Abstract: We have carried out a docking inspired synthesis and screening of a library of diazenyl-derivatives of pyridazinylpyrazolone molecules for their ability to modulate the amyloidogenic self-assembly of human islet amyloid polypeptide (hIAPP). hIAPP is a 37-residue peptide which is involved in glycemic control along with insulin. Its extracellular fibrillar assemblies in pancreatic β-cells are responsible for type 2 diabetes. A three-step synthetic scheme was used to prepare these novel compounds using 2-(6-chloropyridazin-3-yl)-5-methyl-2,4-dihydro-3H-pyrazol-3-one as a key intermediate that was reacted with various diazo electrophiles to generate a library of compounds with yields ranging from 64 to 85%. The effect of the compounds on hIAPP amyloid fibril formation was evaluated with a thioflavin T (ThT) fluorescence-based kinetic assay. Furthermore, TEM imaging was carried out to corroborate the interactions of the compounds with hIAPP and subsequent hIAPP inhibition at the different level of fibrillization. The CD spectroscopy showed that upon incubation with SSE15314 for 12 h, the percentage of α-helices was maintained to a level of hIAPP at 0 h. The current study presents identification and characterization of SSE15314 as the hit, which completely inhibited the fibril formation and can be further optimized into a lead compound.
Photo-responsive systems and biomaterials: photochromic polymers, light-triggered self-assembly, surface modification, fluorescence modulation and beyond
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B9PY00300B
Synthesis of Functionalized and Biodegradable Hyperbranched Polymers from Novel AB2 Macromonomers Prepared by RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 19-08-2009
DOI: 10.1021/MA901290A
Stabilizing Off-pathway Oligomers by Polyphenol Nanoassemblies for IAPP Aggregation Inhibition
Publisher: Springer Science and Business Media LLC
Date: 14-01-2016
DOI: 10.1038/SREP19463
Abstract: Experimental studies have shown that many naturally occurring polyphenols have inhibitory effect on the aggregation of several proteins. Here, we use discrete molecular dynamics (DMD) simulations and high-throughput dynamic light scattering (DLS) experiments to study the anti-aggregation effects of two polyphenols, curcumin and resveratrol, on the aggregation of islet amyloid polypeptide (IAPP or amylin). Our DMD simulations suggest that the aggregation inhibition is caused by stabilization of small molecular weight IAPP off-pathway oligomers by the polyphenols. Our analysis indicates that IAPP-polyphenol hydrogen bonds and π-π stacking combined with hydrophobic interactions are responsible for the stabilization of oligomers. The presence of small oligomers is confirmed with DLS measurements in which nanometer-sized oligomers are found to be stable for up to 7.5 hours, the time frame within which IAPP aggregates in the absence of polyphenols. Our study offers a general anti-aggregation mechanism for polyphenols and further provides a computational framework for the future design of anti-amyloid aggregation therapeutics.
A Simple Approach to Micro-Patterned Surfaces by Breath Figures with Internal Structure Using Thermoresponsive Amphiphilic Block Copolymers
Publisher: CSIRO Publishing
Date: 2005
DOI: 10.1071/CH05186
Abstract: Employing hiphilic block copolymers in a casting process to obtain honeycomb-structured films via breath figures leads to a suborder of these porous films. A thermoresponsive block copolymer, polystyrene-block-poly(N-isopropyl acrylamide), was synthesized and used to test the arrangement of both blocks within the honeycomb-structured films. Contact angle measurements reveal that the surface of these films has a different composition compared to the structure of the pores. The pores were found to be enriched in hydrophilic sequences showing stimuli-responsive behavior, whereas the surface reacts like a typical hydrophobic porous film.
Living free radical polymerization (RAFT) of dodecyl acrylate: Chain length dependent termination, mid-chain radicals and monomer reaction order
Publisher: Elsevier BV
Date: 08-2005
Honeycomb-structured porous films from polypyrrole-containing block copolymers prepared via RAFT polymerization as a scaffold for cell growth
Publisher: American Chemical Society (ACS)
Date: 25-03-2006
DOI: 10.1021/BM050858M
Abstract: Honeycomb-structured porous films were prepared using customized hiphilic block copolymers, synthesized by RAFT polymerization. Pyrrole was templated along an hiphilic block copolymer, composed of polystyrene and poly(acrylic acid). Subsequent oxidation of pyrrol to polypyrrole, resulted in the formation of a soluble polypyrrole-containing polymer. Gel permeation chromatography and dynamic light scattering studies confirmed the solubility of the resulting customized hiphilic block copolymer, in both water and organic solvent, forming either micelles or inverse aggregates. Porous films with a hexagonal array of micron-sized pores were generated with the polymer, using the breath figures templating technique. The resulting films were found to be non-cytotoxic and hence suitable as scaffolds for tissue engineering. Initial fibroblast cell culture studies on these scaffolds demonstrated a dependency of cell attachment on the pore size of scaffolds.
Ultrasmall Molybdenum Disulfide Quantum Dots Cage Alzheimer’s Amyloid Beta to Restore Membrane Fluidity
Publisher: American Chemical Society (ACS)
Date: 18-06-2021
Grafting of n-butyl acrylate and N,N '-dimethyl acrylamide from poly(divinylbenzene) microspheres by RAFT polymerization
Publisher: CSIRO Publishing
Date: 2005
DOI: 10.1071/CH05057
Abstract: N,N´-Dimethyl acrylamide and n-butyl acrylate have been grafted from crosslinked poly( inylbenzene) core microspheres by both reversible addition–fragmentation chain transfer (RAFT) polymerization and conventional free radical polymerization. The microspheres were prepared by precipitation polymerization utilizing 55 and 80 wt. % inylbenzene (DVB), respectively. The RAFT agent cumyl dithiobenzoate (CDB) was utilized and grafting was performed in toluene at 80°C with 2,2´-azoisobutyronitrile (AIBN) as thermal initiator. Particle weights increased up to 6% for poly(n-butyl acrylate) and up to 15% for poly(N,N´-dimethyl acrylamide). Grafting from poly(DVB-55) microspheres results in a higher particle weight increase than grafting from poly(DVB-80) microspheres while using the same RAFT agent concentrations. The particle weight increase is approximately higher by a factor of two. The grafted microspheres were characterized by attenuated total reflection (ATR) IR spectroscopy and scanning electron microscopy.
Xanthate Mediated Living Polymerization of Vinyl Acetate: A Systematic Variation in MADIX/RAFT Agent Structure
Publisher: Wiley
Date: 06-2003
Effects of Protein Corona on IAPP Amyloid Aggregation, Fibril Remodelling, and Cytotoxicity
Publisher: Springer Science and Business Media LLC
Date: 26-05-2017
DOI: 10.1038/S41598-017-02597-0
Abstract: Aggregation of islet amyloid polypeptide (IAPP), a peptide hormone co-synthesized and co-stored with insulin in pancreatic cells and also co-secreted to the circulation, is associated with beta-cell death in type-2 diabetes (T2D). In T2D patients IAPP is found aggregating in the extracellular space of the islets of Langerhans. Although the physiological environments of these intra- and extra-cellular compartments and vascular systems significantly differ, the presence of proteins is ubiquitous but the effects of protein binding on IAPP aggregation are largely unknown. Here we examined the binding of freshly-dissolved IAPP as well as pre-formed fibrils with two homologous proteins, namely cationic lysozyme (Lys) and anionic alpha-lactalbumin (aLac), both of which can be found in the circulation. Biophysical characterizations and a cell viability assay revealed distinct effects of Lys and aLac on IAPP amyloid aggregation, fibril remodelling and cytotoxicity, pointing to the role of protein “corona” in conferring the biological impact of amyloidogenic peptides. Systematic molecular dynamics simulations further provided molecular and structural details for the observed differential effects of proteins on IAPP amyloidosis. This study facilitates our understanding of the fate and transformation of IAPP in vivo , which are expected to have consequential bearings on IAPP glycemic control and T2D pathology.
Prediction and Measurement of Propagation Rate Coefficients in Terpolymerization Reactions. Part I. Derivation of Equations
Publisher: Informa UK Limited
Date: 03-1999
Prediction and Measurement of Propagation Rate Coefficients in Terpolymerization Reactions. Part II. Experimental Study
Publisher: Informa UK Limited
Date: 03-1999
Critically evaluated rate coefficients for free‐radical polymerization, 2.. Propagation rate coefficients for methyl methacrylate
Publisher: Wiley
Date: 05-1997
Synthesis of Hollow Polymer Nanocapsules Exploiting Gold Nanoparticles as Sacrificial Templates
Publisher: American Chemical Society (ACS)
Date: 25-01-2010
DOI: 10.1021/MA902663N
The mechanism of the propagation step in free-radical copolymerisation
Publisher: Elsevier BV
Date: 11-1999
Half a century of amyloids: past, present and future
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9CS00199A
Abstract: Amyloid diseases are global epidemics with profound health, social and economic implications and yet remain without a cure.
Acid‐Degradable Core‐Crosslinked Micelles Prepared from Thermosensitive Glycopolymers Synthesized via RAFT Polymerization
Publisher: Wiley
Date: 11-01-2008
Modeling the reversible addition-fragmentation chain transfer process in cumyl dithiobenzoate-mediated styrene homopolymerizations: Assessing rate coefficients for the addition-fragmentation equilibrium
Publisher: Wiley
Date: 14-03-2001
DOI: 10.1002/POLA.1112
A Synthetic Approach to a Novel Class of Fluorine-Bearing Reversible Addition - Fragmentation Chain Transfer (RAFT) Agents: F-RAFT
Publisher: CSIRO Publishing
Date: 2005
DOI: 10.1071/CH05069
Abstract: A synthetic route is described to a novel class of reversible addition–fragmentation chain transfer (RAFT) agents bearing a fluorine Z-group. Such F-RAFT agents are theoretically predicted to allow living free radical polymerization of various monomers without affecting the rate of polymerization, and should also facilitate the construction of block copolymers from monomers with disparate reactivity. The class of F-RAFT agents is exemplified by the ex le of benzyl fluoro dithioformate (BFDF) in styrene free-radical polymerizations and the process is shown to induce living polymerization.
Using Fluorescence Lifetime Imaging Microscopy to Monitor Theranostic Nanoparticle Uptake and Intracellular Doxorubicin Release
Publisher: American Chemical Society (ACS)
Date: 16-10-2013
DOI: 10.1021/NN404407G
Abstract: We describe the synthesis of iron oxide nanoparticles (IONPs) with excellent colloidal stability in both water and serum, imparted by carefully designed grafted polymer shells. The polymer shells were built with attached aldehyde functionality to enable the reversible attachment of doxorubicin (DOX) via imine bonds, providing a controlled release mechanism for DOX in acidic environments. The IONPs were shown to be readily taken up by cell lines (MCF-7 breast cancer cells and H1299 lung cancer cells), and intracellular release of DOX was proven using in vitro fluorescence lifetime imaging microscopy (FLIM) measurements. Using the fluorescence lifetime difference exhibited by native DOX (~1 ns) compared to conjugated DOX (~4.6 ns), the intracellular release of conjugated DOX was in situ monitored in H1299 and was estimated using phasor plot representation, showing a clear increase of native DOX with time. The results obtained from FLIM were corroborated using confocal microscopy, clearly showing DOX accumulation in the nuclei. The IONPs were also assessed as MRI negative contrast agents. We observed a significant change in the transverse relaxivity properties of the IONPs, going from 220 to 390 mM(-1) s(-1), in the presence or absence of conjugated DOX. This dependence of MRI signal on IONP-DOX/water interactions may be exploited in future theranostic applications. The in vitro studies were then extended to monitor cell uptake of the DOX loaded IONPs (IONP@P(HBA)-b-P(OEGA) + DOX) into two 3D multicellular tumor spheroids (MCS) grown from two independent cell lines (MCF-7 and H1299) using multiphoton excitation microscopy.
Precise control of drug loading and release of an NSAID–polymer conjugate for long term osteoarthritis intra-articular drug delivery
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7TB01518F
Abstract: The synthesis of biocompatible polymer diclofenac conjugates (PDCs) that have a high drug loading and high degree of control over diclofenac (DCF) release is described.
A pH-responsive nanoparticle targets the neurokinin 1 receptor in endosomes to prevent chronic pain
Publisher: Springer Science and Business Media LLC
Date: 04-11-2019
A novel route to the preparation of aldehyde end-functionalised oligomers via catalytic chain transfer polymerisation
Publisher: Royal Society of Chemistry (RSC)
Date: 1998
DOI: 10.1039/A807177B
Structure Dependent Differential Modulation of Aβ Fibrillization by Selenadiazole-Based Inhibitors
Publisher: American Chemical Society (ACS)
Date: 10-2021
Synthesis of Star Polymers using RAFT Polymerization: What is Possible?
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06297
Abstract: Various pathways to generate star polymers using reversible addition–fragmentation transfer (RAFT) are discussed. Similar to other polymerization techniques, star polymers can be generated using arm-first and core-first approaches. Unique to the RAFT process is the sub ision of the core-first approach into the R-group and Z-group approaches, depending on the attachment of the RAFT agent to the multifunctional core. The mechanism of the R- and Z-group approaches are discussed in detail and it is shown that both techniques have to overcome difficulties arising from termination reactions. Termination reactions were found to broaden the molecular weight. However, these side reactions can be limited by careful design of the synthesis. Considerations include RAFT and radical concentration, number of arms, type of RAFT agent and monomer. Despite obvious challenges, the RAFT process is highly versatile, allowing the synthesis of novel polymer architectures such as poly(vinyl acetate) and poly(vinyl pyrrolidone) star polymers.
Reversible addition fragmentation chain transfer copolymerization: influence of the RAFT process on the copolymer composition
Publisher: Elsevier BV
Date: 05-2004
Photochromic Polymer Conjugates: The Importance of Macromolecular Architecture in Controlling Switching Speed within a Polymer Matrix
Publisher: American Chemical Society (ACS)
Date: 02-11-2009
DOI: 10.1021/MA901830B
Biomedical Applications of Liquid Metal Nanoparticles: A Critical Review
Publisher: MDPI AG
Date: 30-11-2020
DOI: 10.3390/BIOS10120196
Abstract: This review is focused on the basic properties, production, functionalization, cytotoxicity, and biomedical applications of liquid metal nanoparticles (LMNPs), with a focus on particles of the size ranging from tens to hundreds of nanometers. Applications, including cancer therapy, medical imaging, and pathogen treatment are discussed. LMNPs share similar properties to other metals, such as photothermal conversion ability and a propensity to form surface oxides. Compared to many other metals, especially mercury, the cytotoxicity of gallium is low and is considered by many reports to be safe when applied in vivo. Recent advances in exploring different grafting molecules are reported herein, as surface functionalization is essential to enhance photothermal therapeutic effects of LMNPs or to facilitate drug delivery. This review also outlines properties of LMNPs that can be exploited in making medical imaging contrast agents, ion channel regulators, and anti-pathogenic agents. Finally, a foresight is offered, exemplifying underexplored knowledge and highlighting the research challenges faced by LMNP science and technology in expanding into applications potentially yielding clinical advances.
Gold-Loaded Organic/Inorganic Nanocomposite Honeycomb Membranes
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06173
Abstract: RAFT polymerization was used to prepare polystyrene – poly(4-vinyl pyridine) block copolymers, PSn-b-P(4VP)m. Well-defined block copolymers were obtained despite some indications of hydrolysis of the RAFT endgroup during synthesis. The block copolymer PS70-b-P(4VP)55 was self-assembled into micellar structures in dichloromethane, leading to nanoparticles with hydrodynamic diameters of 70 nm. The micelles were loaded with HAuCl4 and, upon reduction, micellar gold-containing nanoparticles with hydrodynamic diameters of 240 nm were obtained. These nanoparticles were employed in the preparation of honeycomb-structured porous films by means of the breath figures technique to yield gold nanocomposites with a hexagonal porous array.
Graft block copolymers of propargyl methacrylate and vinyl acetate via a combination of RAFT/MADIX and click chemistry: Reaction analysis
Publisher: Wiley
Date: 21-11-2008
DOI: 10.1002/POLA.22367
Reversible cobalt-carbon bond formation in catalytic chain transfer polymerization
Publisher: American Chemical Society (ACS)
Date: 31-03-1999
DOI: 10.1021/MA981707X
Minimum information reporting in bio-nano experimental literature
Publisher: Springer Science and Business Media LLC
Date: 09-2018
Degradation of Poly(methyl methacrylate) Model Compounds at Constant Elevated Temperature Studied via High Resolution Electrospray Ionization Mass Spectrometry (ESI‐MS)
Publisher: Wiley
Date: 10-08-2007
Practical Chain-End Reduction of Polymers Obtained with ATRP
Publisher: Wiley
Date: 18-05-2017
Star Polymers Reduce Islet Amyloid Polypeptide Toxicity via Accelerated Amyloid Aggregation
Publisher: American Chemical Society (ACS)
Date: 31-10-2017
Nanoparticle (Star Polymer) Delivery of Nitric Oxide Effectively Negates Pseudomonas aeruginosa Biofilm Formation
Publisher: American Chemical Society (ACS)
Date: 10-06-2014
DOI: 10.1021/BM500422V
Abstract: Biofilms are increasingly recognized as playing a major role in human infectious diseases, as they can form on both living tissues and abiotic surfaces, with serious implications for applications that rely on prolonged exposure to the body such as implantable biomedical devices or catheters. Therefore, there is an urgent need to develop improved therapeutics to effectively eradicate unwanted biofilms. Recently, the biological signaling molecule nitric oxide (NO) was identified as a key regulator of dispersal events in biofilms. In this paper, we report a new class of core cross-linked star polymers designed to store and release nitric oxide, in a controlled way, for the dispersion of biofilms. First, core cross-linked star polymers were prepared by reversible addition-fragmentation chain transfer polymerization (RAFT) via an arm first approach. Poly(oligoethylene methoxy acrylate) chains were synthesized by RAFT polymerization, and then chain extended in the presence of 2-vinyl-4,4-dimethyl-5-oxazolone monomer (VDM) with N,N-methylenebis(acrylamide) employed as a cross-linker to yield functional core cross-linked star polymers. Spermine was successfully attached to the star core by reaction with VDM. Finally, the secondary amine groups were reacted with NO gas to yield NO-core cross-linked star polymers. The core cross-linked star polymers were found to release NO in a controlled, slow delivery in bacterial cultures showing great efficacy in preventing both cell attachment and biofilm formation in Pseudomonas aeruginosa over time via a nontoxic mechanism, confining bacterial growth to the suspended liquid.
Functional Brush Poly(2‐ethyl‐2‐oxazine)s: Synthesis by CROP and RAFT, Thermoresponsiveness and Grafting onto Iron Oxide Nanoparticles
Publisher: Wiley
Date: 12-02-2019
Abstract: Brush polymers are highly functional polymeric materials combining the properties of different polymer classes and have found numerous applications, for ex le, in nanomedicine. Here, the synthesis of functional phosphonate-ester-bearing brush polymers based on poly(2-oxazine)s is reported through a combination of cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazine and reversible addition-fragmentation chain transfer (RAFT) polymerization. In this way, a small library of well-defined (Đ ≤ 1.17) poly(oligo(2-ethyl-2-oxazine) methacrylate) P(OEtOzMA)
Inhibition of amyloid beta toxicity in zebrafish with a chaperone-gold nanoparticle dual strategy
Publisher: Springer Science and Business Media LLC
Date: 22-08-2019
DOI: 10.1038/S41467-019-11762-0
Abstract: Alzheimer’s disease (AD) is the most prevalent form of neurodegenerative disorders, yet no major breakthroughs have been made in AD human trials and the disease remains a paramount challenge and a stigma in medicine. Here we eliminate the toxicity of amyloid beta (Aβ) in a facile, high-throughput zebrafish ( Danio rerio ) model using casein coated-gold nanoparticles (βCas AuNPs). βCas AuNPs in systemic circulation translocate across the blood brain barrier of zebrafish larvae and sequester intracerebral Aβ 42 and its elicited toxicity in a nonspecific, chaperone-like manner. This is evidenced by behavioral pathology, reactive oxygen species and neuronal dysfunction biomarkers assays, complemented by brain histology and inductively coupled plasma-mass spectroscopy. We further demonstrate the capacity of βCas AuNPs in recovering the mobility and cognitive function of adult zebrafish exposed to Aβ. This potent, safe-to-use, and easy-to-apply nanomedicine may find broad use for eradicating toxic amyloid proteins implicated in a range of human diseases.
Exploiting Macromolecular Design to Optimize the Antibacterial Activity of Alkylated Cationic Oligomers
Publisher: American Chemical Society (ACS)
Date: 25-10-2018
DOI: 10.1021/ACS.BIOMAC.8B01317
Abstract: There is growing interest in synthetic polymers which co-opt the structural features of naturally occurring antimicrobial peptides. However, our understanding of how macromolecular architecture affects antibacterial activity remains limited. To address this, we investigated whether varying architectures of a series of block and statistical co-oligomers influenced antibacterial and hemolytic activity. Cu(0)-mediated polymerization was used to synthesize oligomers constituting 2-(Boc-amino)ethyl acrylate units and either diethylene glycol ethyl ether acrylate (DEGEEA) or poly(ethylene glycol) methyl ether acrylate units with varying macromolecular architecture subsequent deprotection produced primary amine functional oligomers. Further guanylation provided an additional series of antimicrobial candidates. Both chemical composition and macromolecular architecture were shown to affect antimicrobial activity. A broad spectrum antibacterial oligomer (containing guanidine moieties and DEGEEA units) was identified that possessed promising activity (MIC = 2 μg mL
Thiol-Reactive Star Polymers Display Enhanced Association with Distinct Human Blood Components
Publisher: American Chemical Society (ACS)
Date: 03-04-2017
Abstract: Directing nanoparticles to specific cell types using nonantibody-based methods is of increasing interest. Thiol-reactive nanoparticles can enhance the efficiency of cargo delivery into specific cells through interactions with cell-surface proteins. However, studies to date using this technique have been largely limited to immortalized cell lines or rodents, and the utility of this technology on primary human cells is unknown. Herein, we used RAFT polymerization to prepare pyridyl disulfide (PDS)-functionalized star polymers with a methoxy-poly(ethylene glycol) brush corona and a fluorescently labeled cross-linked core using an arm-first method. PDS star polymers were examined for their interaction with primary human blood components: six separate white blood cell subsets, as well as red blood cells and platelets. Compared with control star polymers, thiol-reactive nanoparticles displayed enhanced association with white blood cells at 37 °C, particularly the phagocytic monocyte, granulocyte, and dendritic cell subsets. Platelets associated with more PDS than control nanoparticles at both 37 °C and on ice, but they were not activated in the duration examined. Association with red blood cells was minor but still enhanced with PDS nanoparticles. Thiol-reactive nanoparticles represent a useful strategy to target primary human immune cell subsets for improved nanoparticle delivery.
Facile access to thermoresponsive filomicelles with tuneable cores
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CC00900J
Abstract: Thermoresponsive nanoworms with tuneable cores prepared via aqueous RAFT-mediated emulsion polymerizations and temperature-induced morphological transformation (TIMT) technique.
Antibacterial low molecular weight cationic polymers: dissecting the contribution of hydrophobicity, chain length and charge to activity
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5RA24361K
Abstract: We report the antibacterial activity of a novel class of low molecular weight cationic polymers synthesised using Cu(0) mediated polymerisation.
Intrinsic Green Fluorescent Cross-Linked Poly(ester amide)s by Spontaneous Zwitterionic Copolymerization
Publisher: American Chemical Society (ACS)
Date: 08-10-2021
Specific and Differential Binding of N-Acetylgalactosamine Glycopolymers to the Human Macrophage Galactose Lectin and Asialoglycoprotein Receptor
Publisher: American Chemical Society (ACS)
Date: 18-04-2017
DOI: 10.1021/ACS.BIOMAC.7B00228
Abstract: A range of glycopolymers composed of N-acetylgalactosamine were prepared via sequential Cu(I)-mediated polymerization and alkyne-azide click (CuAAC). The resulting polymers were shown, via multichannel surface plasmon resonance, to interact specifically with human macrophage galactose lectin (MGL CD301) with high affinity (K
Star‐polymer synthesis via radical reversible addition–fragmentation chain‐transfer polymerization
Publisher: Wiley
Date: 27-06-2001
DOI: 10.1002/POLA.1256
Easy Access to Chain-Length-Dependent Termination Rate Coefficients Using RAFT Polymerization
Publisher: Wiley
Date: 11-2002
DOI: 10.1002/1521-3927(200211)23:16<952::AID-MARC952>3.0.CO;2-F
Human Plasma Protein Corona of Aβ Amyloid and Its Impact on Islet Amyloid Polypeptide Cross-Seeding
Publisher: American Chemical Society (ACS)
Date: 07-01-2020
Ambient temperature synthesis of well-defined microspheres via precipitation polymerization initiated by UV-irradiation
Publisher: Wiley
Date: 19-06-2007
DOI: 10.1002/POLA.22132
Molecular weight fractionation of poly(methyl methacrylate) using Gas Anti-Solvent techniques
Publisher: Elsevier BV
Date: 06-2003
Polymer-grafted, nonfouling, magnetic nanoparticles designed to selectively store and release molecules via ionic interactions
Publisher: American Chemical Society (ACS)
Date: 22-08-2013
DOI: 10.1021/MA401171D
Recent advances in the delivery of hydrogen sulfide via a macromolecular approach
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8PY00938D
Abstract: This mini review highlights recent advances in the design of macromolecular materials that can deliver hydrogen sulfide either spontaneously or in response to chemical and physical triggers.
Laser‐induced decomposition of 2,2‐dimethoxy‐2‐phenylacetophenone and benzoin in methyl methacrylate homopolymerization studied via matrix‐assisted laser desorption/ionization time‐of‐flight mass spec
Publisher: Wiley
Date: 15-01-2002
DOI: 10.1002/POLA.10150
Viscosity effects in cobaloxime-mediated catalytic chain-transfer polymerization of methacrylates
Publisher: Wiley
Date: 31-01-2002
DOI: 10.1002/POLA.10152
Pulsed-laser polymerization-gel permeation chromatographic determination of the propagation-rate coefficient for the methyl acrylate dimer: A sterically hindered monomer
Publisher: Wiley
Date: 02-10-2001
DOI: 10.1002/POLA.10034
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.
An Efficient and Highly Versatile Synthetic Route to Prepare Iron Oxide Nanoparticles/Nanocomposites with Tunable Morphologies
Publisher: American Chemical Society (ACS)
Date: 19-08-2014
DOI: 10.1021/LA502656U
Abstract: We report a versatile synthetic method for the in situ self-assembly of magnetic-nanoparticle-functionalized polymeric nanomorphologies, including spherical micelles and rod-like and worm-like micelles and vesicles. Poly(oligoethylene glycol methacrylate)-block-(methacrylic acid)-block-poly(styrene) (POEGMA-b-PMAA-b-PST) triblock copolymer chains were simultaneously propagated and self-assembled via a polymerization-induced self-assembly (PISA) approach. Subsequently, the carboxylic acid groups in the copolymers were used to complex an iron ion (Fe(II)/Fe(III)) mixture. Iron oxide nanoparticles were then formed in the central block, within the polymeric nanoparticles, via alkaline coprecipitation of the iron(II) and (III) salts. Nanoparticle morphologies, particle sizes, molecular weights, and chemical structures were then characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), size exclusion chromatography (SEC), and (1)H NMR measurements. TEM micrographs showed that the average size of the magnetic nanoparticles was ∼7 nm at the hydrophobic/hydrophilic nexus contained within the nanoparticles. In addition, XRD was used to confirm the formation of iron oxide nanoparticles. Importantly, the polymeric nanoparticle morphologies were not affected by the coprecipitation of the magnetic nanoparticles. The hybrid nanoparticles were then evaluated as negative MRI contrast agents, displaying remarkably high transverse relaxivities (r2, greater than 550 mM(-1) s(-1) at 9.4 T) a result, that we hypothesize, ensues from iron oxide nanoparticle clustering at the hydrophobic-hydrophilic interface. This simple synthetic procedure is highly versatile and produces nanocarriers of tunable size and shape with high efficacy as MRI contrast agents and potential utility as theranostic delivery vectors.
Carboxylated Cy5-Labeled Comb Polymers Passively Diffuse the Cell Membrane and Target Mitochondria
Publisher: American Chemical Society (ACS)
Date: 08-2019
Abstract: A detailed understanding of the cellular uptake and trafficking of nanomaterials is essential for the design of "smart" intracellular drug delivery vehicles. Typically, cellular interactions can be tailored by endowing materials with specific properties, for ex le, through the introduction of charges or targeting groups. In this study, water-soluble carboxylated
Inhibition of Amyloid Aggregation and Toxicity with Janus Iron Oxide Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 03-08-2021
Reversible addition-fragmentation chain transfer graft copolymerization of styrene and m-isopropenyl-alpha,alpha '-dimethylbenzyl isocyanate from polypropylene lanterns: Solid phases for scavenging applications
Publisher: Wiley
Date: 02-12-2006
DOI: 10.1002/POLA.21216
Living polymerization: Rationale for uniform terminology
Publisher: Wiley
Date: 15-05-2000
DOI: 10.1002/(SICI)1099-0518(20000515)38:10<1706::AID-POLA20>3.0.CO;2-5
Formation of honeycomb‐structured, porous films via breath figures with different polymer architectures
Publisher: Wiley
Date: 02-03-2006
DOI: 10.1002/POLA.21334
Lysophosphatidylcholine modulates the aggregation of human islet amyloid polypeptide
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CP06670H
Abstract: Micellar lysophosphatidylcholine inhibits the aggregation of human islet amyloid polypeptide (IAPP).
Poly(2-oxazoline)-based micro- and nanoparticles: A review
Publisher: Elsevier BV
Date: 03-2017
Complex macromolecular architectures by reversible addition fragmentation chain transfer chemistry: Theory and practice
Publisher: Wiley
Date: 03-2007
The endocytic pathway and therapeutic efficiency of doxorubicin conjugated cholesterol-derived polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4BM00224E
Abstract: Previously synthesized poly(methacrylic acid- co -cholesteryl methacrylate) P(MAA- co -CMA) copolymers were examined as potential drug delivery vehicles.
Synthesis and bioactivity of poly(HPMA)–lysozyme conjugates: the use of novel thiazolidine-2-thione coupling chemistry
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B907061C
Abstract: A novel thiazolidine-2-thione functionalized chain transfer agent (CTA) was synthesized and used as a reversible addition-fragmentation chain transfer (RAFT) polymerization agent to prepare well-defined poly-N-(2-hydroxypropyl) methacrylamide (PHPMA). The polymer chains had pre-designed molecular weights, narrow polydispersities and were chain-end functionalized. On incubation with protein (lysozyme) under different pH conditions, PHPMA was conjugated to the protein surface via covalent amide bonding. The bioactivity of the lysozyme-PHPMA conjugates was assessed using Micrococcus lysodeikticus (Ml) cells as substrates. The number of polymer chains attached to the protein could be controlled by both the pH of the conjugation reaction and the molecular weights of the polymers, thereby influencing significantly the bioactivity of the protein-polymer conjugates.
Cholesterol modified self-assemblies and their application to nanomedicine
Publisher: American Chemical Society (ACS)
Date: 22-06-2015
DOI: 10.1021/ACS.BIOMAC.5B00550
Abstract: Cholesterol is a ubiquitous molecule in biological systems, and in particular plays various important roles in mammalian cellular processes. The presence of cholesterol is integral to the structure and behavior of biological membranes, and profoundly influences membrane involvement in cellular mechanisms. This review focuses on the incorporation of cholesterol into synthetic nanomaterials and assemblies, focusing on LC phase behavior, morphology/self-organization and hydrophobic interactions, all important factors in the design of nanomedicines. We highlight cholesteryl conjugates, liposomes and polymeric micelles, focusing on self-assembly capabilities, drug encapsulation and intracellular delivery. An area of considerable interest identified in this review is the use of cholesteryl-functional vectors to deliver drugs or nucleic acids. Such applications depend on the ability of the nanoparticle carrier to associate with both the cellular and endosomal membrane.
Mapping Photolysis Product Radical Reactivities via Soft Ionization Mass Spectrometry in Acrylate, Methacrylate, and Itaconate Systems
Publisher: American Chemical Society (ACS)
Date: 16-08-2007
DOI: 10.1021/MA070626A
Well-Defined Glycopolymers from RAFT Polymerization: Poly(methyl 6-O-methacryloyl-α-d -glucoside) and Its Block Copolymer with 2-Hydroxyethyl Methacrylate
Publisher: American Chemical Society (ACS)
Date: 08-09-2004
DOI: 10.1021/MA049129+
Spatio-temporal analysis of nanoparticles in live tumor spheroids impacted by cell origin and density
Publisher: Elsevier BV
Date: 2022
DOI: 10.1016/J.JCONREL.2021.12.014
Abstract: Nanoparticles hold great preclinical promise in cancer therapy but continue to suffer attrition through clinical trials. Advanced, three dimensional (3D) cellular models such as tumor spheroids can recapitulate elements of the tumor environment and are considered the superior model to evaluate nanoparticle designs. However, there is an important need to better understand nanoparticle penetration kinetics and determine how different cell characteristics may influence this nanoparticle uptake. A key challenge with current approaches for measuring nanoparticle accumulation in spheroids is that they are often static, losing spatial and temporal information which may be necessary for effective nanoparticle evaluation in 3D cell models. To overcome this challenge, we developed an analysis platform, termed the Determination of Nanoparticle Uptake in Tumor Spheroids (DONUTS), which retains spatial and temporal information during quantification, enabling evaluation of nanoparticle uptake in 3D tumor spheroids. Outperforming linear profiling methods, DONUTS was able to measure silica nanoparticle uptake to 10 μm accuracy in both isotropic and irregularly shaped cancer cell spheroids. This was then extended to determine penetration kinetics, first by a forward-in-time, center-in-space model, and then by mathematical modelling, which enabled the direct evaluation of nanoparticle penetration kinetics in different spheroid models. Nanoparticle uptake was shown to inversely relate to particle size and varied depending on the cell type, cell stiffness and density of the spheroid model. The automated analysis method we have developed can be applied to live spheroids in situ, for the advanced evaluation of nanoparticles as delivery agents in cancer therapy.
A simple method for determining protic end-groups of synthetic polymers by H-1 NMR spectroscopy
Publisher: Elsevier BV
Date: 03-2006
Multimodal Nanoprobe for Pancreatic Beta Cell Detection and Amyloidosis Mitigation
Publisher: American Chemical Society (ACS)
Date: 16-01-2020
Access to cyclic polystyrenes via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization and click chemistry
Publisher: Elsevier BV
Date: 04-2008
Poly(vinyl ester) Star Polymers via Xanthate-Mediated Living Radical Polymerization: From Poly(vinyl alcohol) to Glycopolymer Stars
Publisher: American Chemical Society (ACS)
Date: 27-05-2005
DOI: 10.1021/MA050050U
Acid degradable and biocompatible polymeric nanoparticles for the potential codelivery of therapeutic agents
Publisher: American Chemical Society (ACS)
Date: 16-09-2011
DOI: 10.1021/MA201085Z
The Use of Block Copolymers to Systematically Modify Photochromic Behavior
Publisher: American Chemical Society (ACS)
Date: 12-2006
DOI: 10.1021/MA061674I
Contrasting effects of nanoparticle–protein attraction on amyloid aggregation
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5RA20182A
Abstract: Nanoparticles (NPs) have been experimentally found to either promote or inhibit amyloid aggregation of proteins, but the molecular mechanisms for such complex behaviors remain unknown.
Reversible addition - Fragmentation chain transfer polymerization initiated with ultraviolet radiation
Publisher: American Chemical Society (ACS)
Date: 27-08-2002
DOI: 10.1021/MA0204296
Amyloid Aggregation under the Lens of Liquid–Liquid Phase Separation
Publisher: American Chemical Society (ACS)
Date: 24-12-2020
Nitric Oxide (NO) Endows Arylamine-Containing Block Copolymers with Unique Photoresponsive and Switchable LCST Properties
Publisher: American Chemical Society (ACS)
Date: 15-03-2016
Living free‐radical polymerization of sterically hindered monomers: Improving the understanding of 1,1‐disubstituted monomer systems
Publisher: Wiley
Date: 24-04-2006
DOI: 10.1002/POLA.21470
Rapid Assessment of Nanoparticle Extravasation in a Microfluidic Tumor Model
Publisher: American Chemical Society (ACS)
Date: 29-03-2019
Synthesis of well-defined polystyrene with primary amine end groups through the use of phthalimido-functional RAFT agents
Publisher: American Chemical Society (ACS)
Date: 08-07-2006
DOI: 10.1021/MA060245H
Mapping Chain Length and Conversion Dependent Termination Rate Coefficients in Methyl Acrylate Free Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 11-2005
DOI: 10.1021/MA051370G
The design and utility of polymer-stabilized iron-oxide nanoparticles for nanomedicine applications
Publisher: Springer Science and Business Media LLC
Date: 3
The effects of ester chain length and temperature on the catalytic chain transfer polymerization of methacrylates
Publisher: American Chemical Society (ACS)
Date: 27-05-1999
DOI: 10.1021/MA9901341
Propagation rate coefficients for styrene solution polymerization in dimethyl formamide and acetonitrile
Publisher: Elsevier BV
Date: 11-2000
The Pharmacokinetics and Biodistribution of a 64 kDa PolyPEG Star Polymer After Subcutaneous and Pulmonary Administration to Rats
Publisher: Elsevier BV
Date: 2016
DOI: 10.1016/J.XPHS.2015.11.038
Abstract: PolyPEG star polymers have potential utility as cost-effective polymeric drug delivery vehicles, and as such, it is important to develop an understanding of their biopharmaceutical behavior. Moreover, although a number of studies have evaluated the utility of PolyPEG stars in vitro, investigation of these novel materials in vivo has been limited. Herein, we evaluated the pharmacokinetics of a 64 kDa tritiated PEG-based star polymer after subcutaneous and pulmonary administration in rats. After subcutaneous administration, the star polymer showed near complete bioavailability (∼80%) and a similar organ biodistribution profile to the polymer after intravenous administration. After intratracheal instillation to the lungs, the star polymer showed limited bioavailability (∼3%), and most of the administered radiolabel was recovered in lung tissue and feces after 6 d. The data reported here suggest that star polymers display similar pharmaceutical behavior to PEGylated dendrimers after subcutaneous and inhaled delivery and may therefore be used as similar, but more cost-effective drug delivery vehicles.
Facile synthesis of comb, star, and graft polymers via reversible addition–fragmentation chain transfer (RAFT) polymerization
Publisher: Wiley
Date: 15-07-2002
DOI: 10.1002/POLA.10369
PolyPEGylation of Protein using Semitelechelic and Mid-functional Poly(PEGMA)s synthesized by RAFT polymerization
Publisher: CSIRO Publishing
Date: 2011
DOI: 10.1071/CH11312
Abstract: A series of well defined semitelechelic and mid-functionalized poly(poly(ethylene glycol) methyl ether methacrylate)s (poly(PEGMA)s) were synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerization using thiazolidine-2-thione-functionalized chain transfer agents (CTAs). The thiazolidine-2-thione group was located either at the end or in the middle of polymer chains depending on the different structural CTAs. All polymers were fully analyzed by 1H NMR spectroscopy and GPC, confirming their well-defined structures, such as predesigned molecular weights, narrow polydispersity indices, and high yield chain-end or chain-middle functionalization. The thiazolidine-2-thione functionality located at the end of or at the middle of the polymer chains can react with amine residues on protein surfaces, forming protein-polymer conjugates via amide linkages. The bioactivity of protein conjugates were subsequently tested using micrococcus lysodeikticus cell as substitute. The protein conjugations from the mid-functionalized polymer remained much more protein bioactivity comparing to their semitelechelic counterpart with similar molecular weights, indicating the steric hindrance of the mid-functionalized poly(PEGMA)s lead to the better selective conjugation to protein. The number of polymer chains on the protein surface was additionally evaluated by TNBS analysis, exhibiting that there are less mid-functionalized poly(PEGMA)s linked on the protein surface than the semitelechelic polymers, also supporting the hypothesis that the steric hindrance from branch-structural polymers results in the better reaction selectivity. This synthetic methodology is suitable for universal proteins, seeking a balance between the protein bioactivity and the protein protection by the covalent linkage with polymer, and exhibits promising potential for pharmaceutical protein conjugation.
The effect of remote substituents in free radical addition reactions: new evidence for the penultimate unit effect
Publisher: Elsevier BV
Date: 04-1999
Ambient temperature RAFT polymerization of acrylic acid initiated with ultraviolet radiation in aqueous solution
Publisher: American Chemical Society (ACS)
Date: 03-04-2007
DOI: 10.1021/MA0703094
Propagation Kinetics of Para-Substituted Styrenes: A Test of the Applicability of the Hammett Relationship to Free-Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 06-1999
DOI: 10.1021/MA990146M
Factors Influencing Photochromism of Spiro-Compounds Within Polymeric Matrices
Publisher: Informa UK Limited
Date: 31-12-2003
DOI: 10.1081/MC-120025978
RAFT Miniemulsion Polymerization: Influence of the Structure of the RAFT Agent
Publisher: American Chemical Society (ACS)
Date: 29-08-2002
DOI: 10.1021/MA012214M
Linker chemistry dictates the delivery of a phototoxic organometallic rhenium(i) complex to human cervical cancer cells from core crosslinked star polymer nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8TB02464B
Abstract: Release of a photoactive Re( i ) complex from a polymer star via ketimine linkages gives improved phototoxicity.
Hemagglutinin Functionalized Liposomal Vaccines Enhance Germinal Center and Follicular Helper T Cell Immunity
Publisher: Wiley
Date: 09-03-2021
Related Organisations
University Of Salford
Location: United Kingdom of Great Britain and Northern Ireland
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