ORCID Profile
0000-0001-5055-9046
Current Organisations
University of Warwick
,
Monash University
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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 Materials | Nanochemistry and Supramolecular Chemistry | Synthesis Of Macromolecules | Characterisation Of Macromolecules | Pharmaceutical Sciences | Structural Biology (incl. Macromolecular Modelling) | Functional Materials | Polymers and Plastics | Materials Engineering | Macromolecular and Materials Chemistry not elsewhere classified | Nanobiotechnology | Photonics and Electro-Optical Engineering (excl. Communications) | Materials engineering | Physical Chemistry of Materials | Catalytic Process Engineering | Biochemistry and Cell Biology | Organic Chemical Synthesis | Polymerisation Mechanisms | Carbon Capture Engineering (excl. Sequestration) | Membrane and Separation Technologies | Chemical Characterisation of Materials | Polymers and plastics | Nanotechnology | Pharmacology and Pharmaceutical Sciences | Polymerisation mechanisms | Characterisation of Biological Macromolecules | Biomaterials | Electrochemistry | Nanomaterials | Nanomedicine |
ANZSRC Socio-Economic Objective (SEO)
Expanding Knowledge in the Chemical Sciences | Plastics in Primary Forms | Chemical sciences | Expanding Knowledge in Technology | Plastic Products (incl. Construction Materials) | Expanding Knowledge in the Biological Sciences | Cotton | Management of Solid Waste from Energy Activities | Management of Greenhouse Gas Emissions from Energy Activities (excl. Electricity Generation) | Management of Greenhouse Gas Emissions from Electricity Generation | Respiratory System and Diseases (incl. Asthma) | Neurodegenerative Disorders Related to Ageing | Human Diagnostics | Biological sciences | Endocrine Organs and Diseases (excl. Diabetes) | Cancer and Related Disorders | Prevention—biologicals (e.g. vaccines) | Health not elsewhere classified | Treatments (e.g. chemicals, antibiotics) | Hearing, Vision, Speech and Their Disorders | Hydrogen Storage | Expanding Knowledge in the Medical and Health Sciences | Hydrogen Production from Renewable Energy | Biofuel (Biomass) Energy | Industrial Chemicals and Related Products not elsewhere classified | Expanding Knowledge in Engineering | Human Pharmaceutical Products not elsewhere classified
Related Links
Publications
Temperature- and pH-responsive micelles with collapsible poly(n -isopropylacrylamide) headgroups
Publisher: American Chemical Society (ACS)
Date: 07-2014
DOI: 10.1021/LA501861T
Abstract: We have studied the micelle formation and phase behavior of a series of temperature- and pH-responsive surfactants prepared by controlled radical (RAFT) polymerization. These C12NIPAMm surfactants consist of a dodecyl tail, a poly(N-isopropylacrylamide) (polyNIPAM) headgroup with average degrees of polymerization of between 7 and 96, and an ionizable carboxylate group. In the un-ionized state, these surfactants phase separate on warming toward a lower critical solution temperature (LCST), which decreases as the length of the NIPAM group is decreased. This is in agreement with the behavior of conventional nonionic poly(ethylene oxide)-based surfactants but is very different from that of polyNIPAM oligomer solutions. Small angle neutron scattering (SANS) shows that these surfactants self-assemble into micelles consisting of a nearly spherical hydrophobic core surrounded by a "hairy" polyNIPAM shell far below their LCST. Upon warming, the micelles undergo a sphere-to-rod transition induced by the collapse of the polyNIPAM shell, causing a reduction in the headgroup area. In the un-ionized state the demixing follows at the LCST, but a single charge on the free polymer end completely suppresses phase separation, allowing micelles to undergo a shape change but remain dissolved.
One-pot RAFT/click chemistry via isocyanates: Efficient synthesis of α-end-functionalized polymers
Publisher: American Chemical Society (ACS)
Date: 19-07-2012
DOI: 10.1021/JA3030643
Abstract: A new methodology has been developed for preparing α-functional polymers in a one-pot simultaneous polymerization/isocyanate "click" reaction. Our original synthetic strategy is based on the preparation of a carbonyl-azide chain transfer agent (CTA) precursor that undergoes the Curtius rearrangement in situ during reversible addition-fragmentation chain transfer (RAFT) polymerization yielding well-controlled α-isocyanate modified polymers. This strategy overcomes numerous difficulties associated with the synthesis of a polymerization mediator bearing an isocyanate at the R group and with the handling of such a reactive functionality. This new carbonyl-azide CTA can control the polymerization of a wide range of monomers, including (meth)acrylates, acrylamides, and styrenes (M(n) = 2-30 kDa Đ = 1.16-1.38). We also show that this carbonyl-azide CTA can be used as a universal platform for the synthesis of α-end-functionalized polymers in a one-pot RAFT polymerization/isocyanate "click" procedure.
Sequence Control as a Powerful Tool for Improving the Selectivity of Antimicrobial Polymers
Publisher: American Chemical Society (ACS)
Date: 09-11-2017
Abstract: Antimicrobial polymers appear as a promising alternative to tackle the current development of bacterial resistance against conventional antibiotics as they rely on bacterial membrane disruption. This study investigates the effect of segmentation of hydrophobic and cationic functionalities on antimicrobial polymers over their selectivity between bacteria and mammalian cells. Using RAFT technology, statistical, diblock, and highly segmented multiblock copolymers were synthesized in a controlled manner. Polymers were analyzed by HPLC, and the segmentation was found to have a significant influence on their overall hydrophobicity. In addition, the amount of incorporated cationic comonomer was varied to yield a small library of bioactive macromolecules. The antimicrobial properties of these compounds were probed against pathogenic bacteria (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Staphylococcus epidermidis), and their biocompatibility was tested using hemolysis and erythrocyte aggregation assays, as well as mammalian cell viability assays. In all cases, diblock and multiblock copolymers were found to outperform statistical copolymers, and for polymers with a low content of cationic comonomer, the multiblock showed a tremendously increased selectivity for P. aeruginosa and S. epidermidis compared to its statistical and diblock analogue. This work highlights the remarkable effect of segmentation on both the physical properties of the materials as well as their interaction with biological systems. Due to the outstanding selectivity of multiblock copolymers toward certain bacteria strains, the presented materials are a promising platform for the treatment of infections and a valuable tool to combat antimicrobial resistance.
Selective Patterning of Gold Surfaces by Core/Shell, Semisoft Hybrid Nanoparticles
Publisher: Wiley
Date: 15-09-2014
Abstract: The generation of patterned surfaces with well-defined nano- and microdomains is demonstrated by attaching core/shell, semisoft nanoparticles with narrow size distribution to microdomains of a gold-coated silicon wafer. Near monodisperse nanoparticles are prepared using reversible addition-fragmentation chain transfer (RAFT) polymerization, initiated from a silica surface, to prepare a polystyrene shell around a silica core. The particles are then used as-prepared, or after aminolysis of the terminal thiocarbonyl group of the polystyrene shell, to give thiol-terminated nanoparticles. When gold-coated silicon wafers are immersed into very dilute suspensions of these particles (as low as 0.004 wt%), both types of particles are shown to adhere to the gold domains. The thiolated particles adhere selectively to the gold microdomains, allowing for microdomain patterning, while particles that contain the trithiocarbonate functionality lead to a much more even coverage of the gold surface with fewer particle aggregations.
Targeting intracellular, multi-drug resistant Staphylococcus aureus with guanidinium polymers by elucidating the structure-activity relationship
Publisher: Elsevier BV
Date: 10-2019
DOI: 10.1016/J.BIOMATERIALS.2019.119249
Abstract: Intracellular persistence of bacteria represents a clinical challenge as bacteria can thrive in an environment protected from antibiotics and immune responses. Novel targeting strategies are critical in tackling antibiotic resistant infections. Synthetic antimicrobial peptides (SAMPs) are interesting candidates as they exhibit a very high antimicrobial activity. We first compared the activity of a library of ammonium and guanidinium polymers with different sequences (statistical, tetrablock and diblock) synthesized by RAFT polymerization against methicillin-resistant S. aureus (MRSA) and methicillin-sensitive strains (MSSA). As the guanidinium SAMPs were the most potent, they were used to treat intracellular S. aureus in keratinocytes. The diblock structure was the most active, reducing the amount of intracellular MSSA and MRSA by two-fold. We present here a potential treatment for intracellular, multi-drug resistant bacteria, using a simple and scalable strategy.
Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding-Chain Extension-Folding Process
Publisher: American Chemical Society (ACS)
Date: 18-11-2016
Thermoresponsive behavior of amphiphilic diblock co-oligomers of ethylene glycol and styrene in aqueous solution
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3SM50245G
Synthesis and immunological evaluation of self-assembling and self-adjuvanting tricomponent glycopeptide cancer-vaccine candidates
Publisher: Wiley
Date: 22-10-2012
Abstract: Self-adjuvanting tricomponent vaccines were prepared and assessed for their self-assembly and immunological activity in mouse models. The vaccines each consisted of a peptide or glycopeptide antigen that corresponds to a complete copy of the variable-number tandem repeat (VNTR) of the tumor-associated mucin 1 (MUC1) glycoprotein, the universal T-cell helper peptide epitope PADRE, and the immunoadjuvant Pam(3)CysSer. The vaccines were shown to spontaneously self-assemble in water to form isotropic particles varying in size from 17 to 25 nm and elicited robust humoral responses in murine models without the addition of an external adjuvant. The serum antibodies could recognize tumor-associated MUC1 epitopes on the surface of MCF7 breast-cancer cells and B16 melanoma cells, which overexpress this tumor-associated glycoprotein.
Tunable self-assembly of triazole-linked porphyrin-polymer conjugates
Publisher: Wiley
Date: 12-08-2013
Abstract: The convergence of supramolecular chemistry and polymer science offers many powerful approaches for building functional nanostructures with well-defined dynamic behaviour. Herein we report the efficient "click" synthesis and self-assembly of AB2 - and AB4 -type multitopic porphyrin-polymer conjugates (PPCs). PPCs were prepared using the copper(I)-catalysed azide-alkyne cycloaddition (CuAAC) reaction, and consisted of linear polystyrene, poly(butyl acrylate), or poly(tert-butyl acrylate) arms attached to a zinc(II) porphyrin core via triazole linkages. We exploit the presence of the triazole groups obtained from CuAAC coupling to direct the self-assembly of the PPCs into short oligomers (2-6 units in length) via intermolecular porphyrinatozinc-triazole coordination. By altering the length and grafting density of the polymer arms, we demonstrate that the association constant of the porphyrinatozinc-triazole complex can be systematically tuned over two orders of magnitude. Self-assembly of the PPCs also resulted in a 6 K increase in the glass transition temperature of the bulk material compared to a non-assembling PPC. The modular synthesis and tunable self-assembly of the triazole-linked PPCs thus represents a powerful supramolecular platform for building functional nanostructured materials.
Visible light induced controlled cationic polymerization by: In situ generated catalyst from manganese carbonyl
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CC03317C
Abstract: Controlled cationic polymerization of various vinyl ethers is achieved under light radiation, utilizing commercially available reagents, under mild conditions and the molecular weight distributions can be modulated by simply regulating the irradiation time.
The future of reversible addition fragmentation chain transfer polymerization
Publisher: Wiley
Date: 25-07-2008
DOI: 10.1002/POLA.22866
Stimuli-responsive membrane activity of cyclic-peptide-polymer conjugates
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9SC00756C
Abstract: Cyclic peptide nanotubes were coupled to poly(oxazoline)s using a cleavable connection. Upon stimuli responsive detachment of the polymer an on-demand membrane activity could be achieved.
Tubular supramolecular alternating copolymers fabricated by cyclic peptide–polymer conjugates
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1SC02389F
Abstract: Tubular supramolecular alternating copolymers using cyclic peptide–polymer conjugates are synthesized by the introduction of an extra complementary noncovalent interaction.
A New Methodology for Assessing Macromolecular Click Reactions and Its Application to Amine-Tertiary Isocyanate Coupling for Polymer Ligation
Publisher: American Chemical Society (ACS)
Date: 21-03-2016
DOI: 10.1021/JACS.5B11831
SO2 Uptake on Oleic Acid: A New Formation Pathway of Organosulfur Compounds in the Atmosphere
Publisher: American Chemical Society (ACS)
Date: 29-01-2016
Control of block copolymer morphology: An example of selective morphology induced by self‐assembly formation condition
Publisher: Wiley
Date: 05-11-2009
DOI: 10.1002/POLA.23718
Multiblock copolymer synthesis via RAFT emulsion polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2CS00115B
Abstract: Emulsion polymerization mediated by RAFT confers a plenty of advantages for the synthesis of multiblock copolymers, including but not limited to control over particle morphology, molecular weight, livingness, composition, and time.
Sequence‐Controlled Multiblock Copolymers via RAFT Polymerization: Modeling and Simulations
Publisher: Wiley
Date: 20-02-2014
Copper(0)-mediated living radical polymerization of methyl methacrylate in a non-polar solvent
Publisher: Wiley
Date: 13-07-2010
Abstract: The metal catalyzed polymerization of methyl methacrylate using Cu(0) as the catalyst source has been investigated in toluene. This work looks at polymerizations in a non-polar medium allowing control over the molecular weight and polydispersity with a 4-fold reduction in catalyst concentration versus conventional ATRP, while the use of an active ligand allows the reaction to proceed at room temperature. The use of an excess of PMDETA ligand allows for high conversions, and the addition of a small amount of CuBr(2) enhances living characteristics, enabling efficient chain extension.
Smart hybrid materials by conjugation of responsive polymers to biomacromolecules
Publisher: Springer Science and Business Media LLC
Date: 17-11-2015
DOI: 10.1038/NMAT4106
Abstract: The chemical structure and function of biomacromolecules has evolved to fill many essential roles in biological systems. More specifically, proteins, peptides, nucleic acids and polysaccharides serve as vital structural components, and mediate chemical transformations and energy/information storage processes required to sustain life. In many cases, the properties and applications of biological macromolecules can be further expanded by attaching synthetic macromolecules. The modification of biomacromolecules by attaching a polymer that changes its properties in response to environmental variations, thus affecting the properties of the biomacromolecule, has led to the emergence of a new family of polymeric biomaterials. Here, we summarize techniques for conjugating responsive polymers to biomacromolecules and highlight applications of these bioconjugates reported so far. In doing so, we aim to show how advances in synthetic tools could lead to rapid expansion in the variety and uses of responsive bioconjugates.
Synthesis of self-assembling cyclic peptide-polymer conjugates using click chemistry
Publisher: CSIRO Publishing
Date: 2010
DOI: 10.1071/CH10128
Abstract: Self-assembling cyclic peptide-polymer conjugates were prepared by ‘clicking’ polymers (prepared by RAFT polymerization) to an azide functionalized d-alt-l cyclic octapeptide via the Huisgen 1,3-dipolar cycloaddition reaction. Due to the high graft density, the efficiency of the click chemistry conjugation reaction was found to be highly dependent on the size of the polymer. At relatively low molecular weights, as many as four polymer chains could be grafted to each 8 residue cyclic peptide ring. Evidence for the self assembly of the conjugates into peptide-polymer nanotubes was observed by TEM and IR.
Exploring precision polymers to fine-tune magnetic resonance imaging properties of iron oxide nanoparticles
Publisher: Elsevier BV
Date: 11-2020
Tuning the Structure, Stability, and Responsivity of Polymeric Arsenical Nanoparticles Using Polythiol Cross-Linkers
Publisher: American Chemical Society (ACS)
Date: 24-01-2019
Spatially controlled photochemical peptide and polymer conjugation on biosurfaces
Publisher: American Chemical Society (ACS)
Date: 12-11-2013
DOI: 10.1021/BM401274V
Abstract: An efficient phototriggered Diels-Alder conjugation is utilized to graft in an effective and straightforward approach poly(trifluoro ethyl methacrylate) (Mn = 3700 Da, Đ = 1.27) and a model peptide (GIGKFLHS) onto thin hyaluronan films and cellulose surfaces. The surfaces were functionalized with an o-quinodimethane moiety - capable of releasing a caged diene - via carbodiimide mediated coupling. The o-quinodimethane group is employed as a photoactive linker to tether predefined peptide olymer strands in a spatially controlled manner onto the biosurface by photoenol ligation. An in-depth characterization employing XPS, ToF-SIMS, SPR, ellipsometry, and AFM was conducted to evidence the effectiveness of the presented approach.
Optimization of energy transfer in a polymer composite with perylene chromophores
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8TC02457J
Abstract: Luminescent solar concentrators based on molecular dyes are a promising approach to light collection.
Graft polymerization: Grafting poly(styrene) from cellulose via Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization
Publisher: American Chemical Society (ACS)
Date: 16-11-2005
DOI: 10.1021/MA0515026
Effect of the amino acid composition of cyclic peptides on their self-assembly in lipid bilayers
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4OB02041C
Abstract: The effect of amino acid composition on the formation of transmembrane channels in lipid bilayers upon self-assembly of alt-( l , d )-α-cyclic octapeptides has been investigated.
Bioapplications of RAFT polymerization
Publisher: American Chemical Society (ACS)
Date: 18-09-2009
DOI: 10.1021/CR9001403
Stochasticity of poly(2-oxazoline) oligomer hydrolysis determined by tandem mass spectrometry
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2PY00437B
Abstract: Tandem mass spectrometry can be used to better understand modification sites of synthetic polymer structures providing more complete chemical knowledge which is necessary for their accurate synthesis and potential applications.
Single addition of an allylamine monomer enables access to end-functionalized RAFT polymers for native chemical ligation
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CC06010B
Abstract: A novel method for the introduction of a single protected amine-functional monomer at the chain end of RAFT polymers has been developed to enable native chemical ligation with peptide thioesters.
100th Anniversary of Macromolecular Science Viewpoint: User’s Guide to Supramolecular Peptide–Polymer Conjugates
Publisher: American Chemical Society (ACS)
Date: 25-01-2021
DOI: 10.1021/ACSMACROLETT.0C00734
Abstract: This Viewpoint highlights the design principles and development of peptide-based supramolecular polymers. Here we delve deep into the practicalities of synthesizing and characterizing these macromolecular structures and provide a thorough overview of the benefits and challenges that come with these systems. This Viewpoint emphasizes to beginners and experts alike the importance of understanding the fundamental behavior and self-assembly processes when designing these complex and dynamic functional materials.
Bis(trithiocarbonate) Disulfides: From Chain Transfer Agent Precursors to Iniferter Control Agents in RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 16-07-2021
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
Ordered microphase separation in thin films of pmma-pba synthesized by RAFT: Effect of block polydispersity
Publisher: American Chemical Society (ACS)
Date: 26-03-2009
DOI: 10.1021/MA9004428
Synthesis of poly(methyl acrylate) grafted onto silica particles by z-supported RAFT Polymerization
Publisher: Wiley
Date: 13-04-2007
Polymerisation-related changes in THz transmission in SU8 and polystyrene
Publisher: IEEE
Date: 09-2006
Dendritic and hyperbranched polymers from macromolecular units: Elegant approaches to the synthesis of functional polymers
Publisher: American Chemical Society (ACS)
Date: 26-08-2011
DOI: 10.1021/MA200656H
Preparation of fluorinated methacrylic copolymers by copper mediated living radical polymerization
Publisher: Elsevier BV
Date: 05-2002
Lateral phase separation in grafted diblock copolymer films
Publisher: American Chemical Society (ACS)
Date: 13-09-2010
DOI: 10.1021/MA101093F
Synthesis of silica particles grafted with weil-defined living polymeric chains by combination of RAFT polymerization and coupling reaction
Publisher: American Chemical Society (ACS)
Date: 11-08-2009
DOI: 10.1021/MA900604V
Stepwise Light-Induced Dual Compaction of Single-Chain Nanoparticles
Publisher: Wiley
Date: 04-07-2017
Abstract: A photochemical strategy for the sequential dual compaction of single polymer chains is introduced. Two photoreactive methacrylates, with side chains bearing either a phenacyl sulfide (PS) or an α-methylbenzaldehyde (photoenol, PE) moiety, are selectively incorporated by one-pot iterative reversible-addition fragmentation chain transfer copolymerization into the outer blocks of a well-defined poly(methyl methacrylate) based ABC triblock copolymer possessing a nonfunctional spacer block (M
Hierarchical assembly of branched supramolecular polymers from (cyclic peptide)-polymer conjugates
Publisher: American Chemical Society (ACS)
Date: 14-10-2014
DOI: 10.1021/BM501062D
Abstract: We report the synthesis and assembly of (N-methylated cyclic peptide)-polymer conjugates for which the cyclic peptide is attached to either the α- or both α- and ω- end groups of a polymer. A combination of chromatographic, spectroscopic, and scattering techniques reveals that the assembly of the conjugates follows a two-level hierarchy, initially driven by H-bond formation between two N-methylated cyclic peptides, followed by unspecific, noncovalent aggregation of this peptide into small domains that behave as branching points and lead to the formation of branched supramolecular polymers.
Polymerization induced self-Assembly: Tuning of morphology using ionic strength and pH
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY00552K
Abstract: It is demonstrated how the morphology of polymeric nanoparticles produced via polymerization-induced self-assembly (PISA) in dispersion can be conveniently tuned via the pH and ionic strength.
Selective one-pot synthesis of trithiocarbonates, xanthates, and dithiocarbamates for use in RAFT/MADIX living radical polymerizations
Publisher: American Chemical Society (ACS)
Date: 26-01-2006
DOI: 10.1021/OL0525617
Abstract: [reaction: see text] We report a facile route for the production of chain transfer agents for reversible addition fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations, via a one-pot reaction. 1,1'-Thiocarbonyl diimidazole (TCDI) undergoes controlled monosubstitution when reacted with secondary thiols or alcohols. The intermediate S/O-esters of imidazole-N-thionocarboxylic acid react efficiently with a range of primary thiols, alcohols, and amines to form asymmetrical dithiocarbonates, trithiocarbonates, and dithiocarbamates, respectively. The synthesis provides a facile approach to the controlled radical polymerization of vinyl monomers through the reversible addition-fragmentation chain transfer (RAFT) mechanism.
Poly(ethylene glycol)‐based amphiphilic model conetworks: Synthesis by RAFT polymerization and characterization
Publisher: Wiley
Date: 13-10-2008
DOI: 10.1002/POLA.23061
Manganese-Catalyzed Batch and Continuous Flow Cationic RAFT Polymerization Induced by Visible Light
Publisher: American Chemical Society (ACS)
Date: 21-04-2021
DOI: 10.1021/ACSMACROLETT.1C00180
Abstract: We present a robust manganese-catalyzed cationic reversible addition-fragmentation chain transfer (RAFT) polymerization induced by visible light. Well-defined poly(vinyl ether)s with controlled molecular weight and molecular weight distributions (MWDs) can be conveniently prepared at room temperature without monomer purification. The commercially available manganese carbonyl bromide is used as the photocatalyst for cationic RAFT polymerization. Moreover, this method has been further applied in both batch and continuous flow systems, providing a visible light induced flow cationic polymerization under mild conditions.
“Clickable” polymers via a combination of RAFT polymerization and isocyanate chemistry
Publisher: Wiley
Date: 02-05-2011
DOI: 10.1002/POLA.24710
Polydimethylsiloxane-Based Giant Glycosylated Polymersomes with Tunable Bacterial Affinity
Publisher: American Chemical Society (ACS)
Date: 29-01-2019
DOI: 10.1021/ACS.BIOMAC.8B01709
Abstract: A synthetic cell mimic in the form of giant glycosylated polymersomes (GGPs) comprised of a novel hiphilic diblock copolymer is reported. A synthetic approach involving a poly(dimethylsiloxane) (PDMS) macro-chain transfer agent (macroCTA) and postpolymerization modification was used to marry the hydrophobic and highly flexible properties of PDMS with the biological activity of glycopolymers. 2-Bromoethyl acrylate (BEA) was first polymerized using a PDMS macroCTA ( M
Click chemistry and radical polymerization: Potential loss of orthogonality
Publisher: American Chemical Society (ACS)
Date: 15-08-2008
DOI: 10.1021/MA8010262
Preparation of Fluorinated Copolymers by Copper-Mediated Living Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 04-11-2003
DOI: 10.1021/MA0259822
Imaging Proton Transport in Giant Vesicles through Cyclic Peptide–Polymer Conjugate Nanotube Transmembrane Ion Channels
Publisher: Wiley
Date: 16-02-2018
Abstract: Since their discovery in 1993, interest in various aspects of cyclic peptides (CPs) has expanded rapidly. Of particular note is their potential to form artificial ion channels in lipid membranes, an attractive characteristic in supramolecular chemistry and biological research. The design and synthesis of cyclic peptide-polymer conjugates (CPPCs) that can self-assemble within lipid bilayers into nanotubes, mimicking naturally occurring membrane channels and pores, has been reported. However, methods that allow direct detection of the transport process with high levels of certainty are still lacking. This work focuses on the development of a simple but reliable approach to verify and quantify proton transport across a bilayer membrane. Giant unilamellar vesicles (GUVs) are created via the electroformation method and CPPCs are incorporated in GUV membranes at varying concentrations (0-10%). Confocal fluorescence microscopy is used to demonstrate full inclusion of fluorescein-labeled CPPCs in the GUV membranes. The pH-sensitive dye carboxyfluorescein is encapsulated within the water pool of the GUVs and used as an indicator of proton transport. This assay is versatile and can be exploited on other existing proton transporter systems, providing a consistent tool to compare their performances. It should also aid the development of novel antineoplastics and drug delivery systems.
Ultra-fast microwave enhanced reversible addition-fragmentation chain transfer (RAFT) polymerization: Monomers to polymers in minutes
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B703386A
Abstract: Microwave mediated RAFT polymerization leads to ultra-fast polymerizations, whilst keeping excellent control over molecular weights and molecular weight distributions this is the first ex le of such a dramatic effect of microwaves on living radical polymerization kinetics, and it shows the potential for chemists to produce very well controlled polymers in a matter of minutes.
Influence of Grafting Density and Distribution on Material Properties Using Well-Defined Alkyl Functional Poly(Styrene- co-Maleic Anhydride) Architectures Synthesized by RAFT
Publisher: American Chemical Society (ACS)
Date: 20-01-2019
Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers
Publisher: American Chemical Society (ACS)
Date: 14-09-2017
Obtaining kinetic information from the chain-length distribution of polymers produced by RAFT
Publisher: American Chemical Society (ACS)
Date: 29-04-2009
DOI: 10.1021/JP900684T
Abstract: We describe a simple model for the kinetics and chain-length distribution of polymers made by living radical techniques. Living radical methods give good control over the molecular weight of a linear polymer by capping the growing end and forming a dormant chain. The polymer is predominantly capped, and occasionally decaps to form a radical that propagates for a short period before recapping. Our model uses this mechanism to describe the chain-length distribution of polymers made by living radical methods. We focus on oligomers made by reversible addition-fragmentation chain transfer (RAFT) polymerization as model systems. Our model can determine optimal reaction conditions for desired polymer properties and test hypotheses about reaction schemes by using only two parameters, with each parameter related to the kinetics. The first parameter is the mean number of monomers added when a chain decaps. A broad distribution results if many monomers are added upon decapping. The second parameter is the mean number of times a polymer decaps. Many decapping events indicate high monomer conversion. Our model gives kinetic information by directly fitting to an experimental chain-length distribution, which is the reverse of other kinetic models that generate the distribution from rate coefficients. Our approach has also the advantage of being simpler than previously published kinetic schemes, which use many rate coefficients as inputs. Our model was tested against three monomers (acrylic acid, butyl acrylate, and styrene) and two RAFT agents. In each case, we successfully describe the chain-length distribution, and give information about the kinetics, especially the probability of propagation versus deactivation by the RAFT mechanism. This excellent agreement with a priori expectations and quantum calculations makes our model a powerful tool for predicting the structure of polymers obtained by living radical polymerization.
Silica core-polystyrene shell nanoparticle synthesis and assembly in three dimensions
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5NR06400G
Abstract: Monodisperse silica nanoparticles (SiNPs) grafted with well-defined and highly dense polystyrene brushes are used as building blocks for the formation of three-dimensional (3D) colloidal crystals.
The synthesis of well-defined poly(vinylbenzyl chloride)-grafted nanoparticles via RAFT polymerization
Publisher: Beilstein Institut
Date: 25-06-2013
DOI: 10.3762/BJOC.9.139
Abstract: We describe the use of one of the most advanced radical polymerization techniques, the reversible addition fragmentation chain transfer (RAFT) process, to produce highly functional core–shell particles based on a silica core and a shell made of functional polymeric chains with very well controlled structure. The versatility of RAFT polymerization is illustrated by the control of the polymerization of vinylbenzyl chloride (VBC), a highly functional monomer, with the aim of designing silica core–poly(VBC) shell nanoparticles. Optimal conditions for the control of VBC polymerization by RAFT are first established, followed by the use of the “grafting from” method to yield polymeric brushes that form a well-defined shell surrounding the silica core. We obtain particles that are monodisperse in size, and we demonstrate that the exceptional control over their dimensions is achieved by careful tailoring the conditions of the radical polymerization.
Microwave‐Accelerated RAFT Polymerization of Polar Monomers
Publisher: Wiley
Date: 19-02-2007
Controlled/Living Radical Polymerization in Dispersed Systems: An Update
Publisher: American Chemical Society (ACS)
Date: 27-08-2015
DOI: 10.1021/CR500625K
Fluorescent bowl-shaped nanoparticles from 'clicked' porphyrin-polymer conjugates
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4PY00250D
Abstract: We report the synthesis and post-synthetic modification of a library of hydrophilic and hydrophobic ‘clicked’ triazole-linked porphyrin–polymer conjugates (PPCs), and their subsequent assembly into fluorescent bowl-shaped nanoparticles.
Synthesis of well-defined conjugated copolymers by RAFT polymerization using cysteine and glutathione-based chain transfer agents
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B708293B
Abstract: Novel cysteine and glutathione-based chain transfer agents were synthesized and successfully applied to the straightforward synthesis of well-defined conjugates via a RAFT process.
Cyclic Peptide-Polymer Nanotubes as Efficient and Highly Potent Drug Delivery Systems for Organometallic Anticancer Complexes
Publisher: American Chemical Society (ACS)
Date: 14-12-2018
DOI: 10.1021/ACS.BIOMAC.7B01491
Abstract: Functional drug carrier systems have potential for increasing solubility and potency of drugs while reducing side effects. Complex polymeric materials, particularly anisotropic structures, are especially attractive due to their long circulation times. Here, we have conjugated cyclic peptides to the biocompatible polymer poly(2-hydroxypropyl methacrylamide) (pHPMA). The resulting conjugates were functionalized with organoiridium anticancer complexes. Small angle neutron scattering and static light scattering confirmed their self-assembly and elongated cylindrical shape. Drug-loaded nanotubes exhibited more potent antiproliferative activity toward human cancer cells than either free drug or the drug-loaded polymers, while the nanotubes themselves were nontoxic. Cellular accumulation studies revealed that the increased potency of the conjugate appears to be related to a more efficient mode of action rather than a higher cellular accumulation of iridium.
Investigating the Impact of Hydrophobic Polymer Segments on the Self-Assembly Behavior of Supramolecular Cyclic Peptide Systems via Asymmetric-Flow Field Flow Fractionation
Publisher: American Chemical Society (ACS)
Date: 26-08-2023
Cyclic peptide-poly(HPMA) nanotubes as drug delivery vectors: In vitro assessment, pharmacokinetics and biodistribution
Publisher: Elsevier BV
Date: 09-2018
DOI: 10.1016/J.BIOMATERIALS.2018.03.047
Abstract: Size and shape have progressively appeared as some of the key factors influencing the properties of nanosized drug delivery systems. In particular, elongated materials are thought to interact differently with cells and therefore may allow alterations of in vivo fate without changes in chemical composition. A challenge, however, remains the creation of stable self-assembled materials with anisotropic shape for delivery applications that still feature the ability to disassemble, avoiding organ accumulation and facilitating clearance from the system. In this context, we report on cyclic peptide-polymer conjugates that self-assemble into supramolecular nanotubes, as confirmed by SANS and SLS. Their behaviour ex and in vivo was studied: the nanostructures are non-toxic up to a concentration of 0.5 g L
Pushing the limit of the RAFT process: Multiblock copolymers by one-pot rapid multiple chain extensions at full monomer conversion
Publisher: American Chemical Society (ACS)
Date: 14-05-2014
DOI: 10.1021/MA402435N
Bottlebrush copolymers for gene delivery: influence of architecture, charge density, and backbone length on transfection efficiency
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2TB00490A
Abstract: The influence of polymer architecture of cationic polymers on gene transfection is investigated. Bottle brush copolymers are shown to outperform linear counterparts.
Copper(I)‐mediated radical polymerization of methacrylates in aqueous solution
Publisher: Wiley
Date: 04-04-2001
DOI: 10.1002/POLA.1147
Pyridyl Disulfide Reaction Chemistry: An Efficient Strategy toward Redox-Responsive Cyclic Peptide-Polymer Conjugates
Publisher: American Chemical Society (ACS)
Date: 27-09-2019
Exploitation of the nanoreactor concept for efficient synthesis of multiblock copolymers via macroraft-mediated emulsion polymerization
Publisher: American Chemical Society (ACS)
Date: 23-07-2019
DOI: 10.1021/ACSMACROLETT.9B00534
Abstract: Multiblock copolymers are a class of polymeric materials with a range of potential applications. We report here a strategy for the synthesis of multiblock copolymers based on methacrylates. Reversible addition-fragmentation chain transfer (RAFT) polymerization is implemented as an emulsion polymerization to generate seed particles as nanoreactors, which can subsequently be employed in sequential RAFT emulsion polymerizations. The segregation effect allowed the synthesis of a high molar mass (>100,000 g·mol
Reversible Addition-Fragmentation Chain Transfer Polymerization from Surfaces
Publisher: Springer International Publishing
Date: 2015
DOI: 10.1007/12_2015_316
Study of (Cyclic Peptide)–Polymer Conjugate Assemblies by Small-Angle Neutron Scattering
Publisher: Wiley
Date: 10-11-2016
Abstract: We present a fundamental study into the self-assembly of (cyclic peptide)-polymer conjugates as a versatile supramolecular motif to engineer nanotubes with defined structure and dimensions, as characterised in solution using small-angle neutron scattering (SANS). This work demonstrates the ability of the grafted polymer to stabilise and/or promote the formation of unaggregated nanotubes by the direct comparison to the unconjugated cyclic peptide precursor. This ideal case permitted a further study into the growth mechanism of self-assembling cyclic peptides, allowing an estimation of the cooperativity. Furthermore, we show the dependency of the nanostructure on the polymer and peptide chemical functionality in solvent mixtures that vary in the ability to compete with the intermolecular associations between cyclic peptides and ability to solvate the polymer shell.
Synthesis of polystyrene-based hyperbranched polymers by thiol-yne chemistry: A detailed investigation
Publisher: American Chemical Society (ACS)
Date: 30-09-2014
DOI: 10.1021/MA500702C
Sulfonated Copolymers as Heparin-Mimicking Stabilizer of Fibroblast Growth Factor: Size, Architecture, and Monomer Distribution Effects
Publisher: American Chemical Society (ACS)
Date: 13-12-2019
DOI: 10.1021/ACS.BIOMAC.8B01451
Abstract: Fibroblast growth factors (FGF) are involved in a wide range of biological processes such as cell proliferation and differentiation. In living organisms, the binding of FGF to its receptors are mediated through electrostatic interactions between FGF and naturally occurring heparin. Despite its prevalent use in medicine, heparin carries notable limitations namely, its extraction from natural sources (expensive, low yield and extensive purification), viral contamination, and batch-to-batch heterogeneity. In this work a range of synthetic homopolymers and copolymers of sodium 2-acrylamido-2-methylpropanesulfonate were evaluated as potential FGF stabilizers. This was studied by measuring the proliferation of BaF3-FR1c cells, as a model assay, and the results will be compared with the natural stabilization and activation of FGF by heparin. This study explores the structure-activity relationship of these polysulfonated polymers with a focus on the effect of molecular weight, comonomer type, charge dispersion, and polymer architecture on protein stabilization.
Assessment of the influence of microwave irradiation on conventional and RAFT radical polymerization of styrene
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2PY20434G
Hyperbranched alternating block copolymers using thiol–yne chemistry: Materials with tuneable properties
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CC02429E
Abstract: Alternating-block hyperbranched polymers were synthesized using the highly versatile thiol-yne reaction. Dimethyl acrylamide-styrene and tert-butyl acrylate-styrene polymers were prepared, with subsequent hydrolysis of the tert-butyl ester to acrylic acid. The dimethyl acrylamide-styrene hyperbranched polymers self-assembled into large aggregates, as did the acrylic acid-styrene system at low pH. However, high pH triggers the formation of very well defined small particles in the latter system.
Polymerization-induced self-assembly: Via RAFT in emulsion: Effect of Z-group on the nucleation step
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0PY01311K
Abstract: It is demonstrated that the nature of the Z-group of trithiocarbonate RAFT agents can have a major effect on the nucleation step of aqueous RAFT PISA performed as emulsion polymerization.
Surface structure of thin asymmetric PS-b-PMMA diblock copolymers investigated by atomic force microscopy
Publisher: Elsevier BV
Date: 03-2007
Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media
Publisher: American Chemical Society (ACS)
Date: 03-09-2020
Thermal gating in lipid membranes using thermoresponsive cyclic peptide-polymer conjugates
Publisher: American Chemical Society (ACS)
Date: 21-05-2014
DOI: 10.1021/JA5024699
Abstract: The partition and self-assembly of a new generation of cyclic peptide-polymer conjugates into well-defined phospholipid trans-bilayer channels is presented. By varying the structural parameters of the cyclic peptide-polymer conjugates through the ligation of hydrophobic and hydrophilic polymers, both the structure of the artificial channels using large unilamellar vesicle assays and the structural parameters required for phospholipid bilayer partitioning are elucidated. In addition, temperature was used as an external stimulus for the modulation of transbilayer channel formation without requiring the redesign and synthesis of the cyclic peptide core. The thermoresponsive character of the cyclic peptide-polymer conjugates lays the foundation for on-demand control over phospholipid transmembrane transport, which could lead to viable alternatives to current transport systems that traditionally rely on endocytic pathways.
On the Use of Redox Initiation in Aqueous RAFT Polymerisation
Publisher: American Chemical Society
Date: 2018
'Pseudo-star' copolymers formed by a combination of RAFT polymerization and isocyanate-coupling
Publisher: CSIRO Publishing
Date: 2011
DOI: 10.1071/CH11133
Abstract: We describe the formation of pseudo-star copolymers via incorporation of an isocyanate-bearing monomer, dimethyl meta-isopropenyl benzyl isocyanate (TMI) into a homopolymer of butyl acrylate (BA) using a one-pot, two-step synthesis. The resultant product maintains the functionality of the isocyanate moiety, which is used to attach poly(ethylene glycol) methyl ether onto the copolymeric chain under benign reaction conditions. The resultant pseudo-star copolymers were isolated and their self-assembly in the presence of water studied.
Thermoresponsive cyclic peptide – poly(2-ethyl-2-oxazoline) conjugate nanotubes
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/C3CC42327A
Abstract: We describe the synthesis of self-assembling cyclic octapeptides of alternating D- and L-chirality conjugated to two poly(2-ethyl-2-oxazoline) chains. The resulting conjugates form nanotubes in water, which are reversibly transformed into microparticles as the temperature reaches the cloud point temperature of the conjugate.
33rd Australasian polymer symposium
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH12346
Hyperbranched poly(ethylenimine-: Co -oxazoline) by thiol-yne chemistry for non-viral gene delivery: Investigating the role of polymer architecture
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8PY01648H
Abstract: Synthesis of long-chain hyperbranched poly(ethylenimine-co-oxazoline)s by AB 2 thiol–yne chemistry is reported, and their application as pDNA transfection agents studied.
Orthogonal Cationic and Radical RAFT Polymerizations to Prepare Bottlebrush Polymers
Publisher: Wiley
Date: 10-03-2020
Abstract: An orthogonal combination of cationic and radical RAFT polymerizations is used to synthesize bottlebrush polymers using two distinct RAFT agents. Selective consumption of the first RAFT agent is used to control the cationic RAFT polymerization of a vinyl ether monomer bearing a secondary dormant RAFT agent, which subsequently allows side‐chain polymers to be grafted from the pendant RAFT agent by a radical‐mediated RAFT polymerization of a different monomer, thus completing the synthesis of bottlebrush polymers. The high efficiency and selectivity of the cationic and radical RAFT polymerizations allow both polymerizations to be conducted in one‐pot tandem without intermediate purification.
Cellulose modification by polymer grafting: A review
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B808639G
Abstract: This critical review is concerned with the recent advances in graft polymerisation techniques involving cellulose and its derivatives. It summarises some of the features of cellulose structure and cellulose reactivity. Also described are the various techniques for grafting synthetic polymers from the cellulosic substrate. In addition to the traditional grafting techniques, we highlight the recent developments in polymer synthesis that allow increased control over the grafting process and permit the production of functional celluloses that possess improved physical properties and chemical properties (189 references).
PCR-RAFT: Rapid high throughput oxygen tolerant RAFT polymer synthesis in a biology laboratory
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9PY01521C
Abstract: We performed high-throughput oxygen tolerant ultra-fast RAFT polymerisation producing complex polymer libraries utilising PCR thermocyclers. This now enables the preparation of these libraries in under 5 min without chemistry equipment.
One-pot ATRP synthesis of a triple hydrophilic block copolymer with dual LCSTs and its thermo-induced association behavior
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2SM26360B
Novel difunctional Reversible Addition Fragmentation Chain Transfer (RAFT) agent for the synthesis of telechelic and ABA triblock methacrylate and acrylate copolymers
Publisher: American Chemical Society (ACS)
Date: 13-03-2007
DOI: 10.1021/MA061372G
Anchor Group Bottlebrush Polymers as Oil Additive Friction Modifiers
Publisher: American Chemical Society (ACS)
Date: 09-10-2023
Merrifield resin-supported chain transfer agents, precursors for RAFT polymerization
Publisher: American Chemical Society (ACS)
Date: 12-07-2005
DOI: 10.1021/OL051078T
Abstract: The modification of Merrifield resins to form chain transfer agent (CTA) precursors for reversible addition fragmentation chain transfer (RAFT) polymerization is investigated. A series of CTA precursor resins were prepared and characterized by FTIR and elemental analysis (EA). [reaction: see text]
Complex multiblock bottle-brush architectures by RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC07241D
Abstract: The combination of the reversible addition fragmentation chain transfer (RAFT) polymerization R-group grafting from approach and RAFT one-pot acrylamide multiblock methodology is used to synthesise complex bottle-brush architectures.
Polymer Functionalization by RAFT Interchange
Publisher: American Chemical Society (ACS)
Date: 14-09-2023
Introduction to polymerisation-induced self assembly
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0PY90190C
Abstract: Steve Armes, Sébastien Perrier and Per Zetterlund introduce the Polymer Chemistry themed collection on polymerisation-induced self assembly.
Comparative Study of the Cellular Uptake and Intracellular Behavior of a Library of Cyclic Peptide–Polymer Nanotubes with Different Self-Assembling Properties
Publisher: American Chemical Society (ACS)
Date: 22-12-2020
Original approach to multiblock copolymers via reversible addition–fragmentation chain transfer polymerization
Publisher: Wiley
Date: 19-04-2007
DOI: 10.1002/POLA.21985
Drug conjugation to cyclic peptide-polymer self-assembling nanotubes
Publisher: Wiley
Date: 21-08-2014
Abstract: We show for the first time how polymeric nanotubes (NTs) based on self-assembled conjugates of polymers and cyclic peptides can be used as an efficient drug carrier. RAPTA-C, a ruthenium-based anticancer drug, was conjugated to a statistical co-polymer based on poly(2-hydroxyethyl acrylate) (pHEA) and poly(2-chloroethyl methacrylate) (pCEMA), which formed the shell of the NTs. Self-assembly into nanotubes (length 200-500 nm) led to structures exhibiting high activity against cancer cells.
Exploitation of the degenerative transfer mechanism in RAFT polymerization for synthesis of polymer of high livingness at full monomer conversion
Publisher: American Chemical Society (ACS)
Date: 09-01-2014
DOI: 10.1021/MA402286E
Efficient Artificial Light-Harvesting System Based on Supramolecular Peptide Nanotubes in Water
Publisher: American Chemical Society (ACS)
Date: 22-12-2020
DOI: 10.1021/JACS.0C11060
50th Anniversary Perspective: RAFT Polymerization - A User Guide
Publisher: American Chemical Society (ACS)
Date: 27-09-2017
Origin of initial uncontrolled polymerization and its suppression in the copper(0)-mediated living radical polymerization of methyl acrylate in a nonpolar solvent
Publisher: American Chemical Society (ACS)
Date: 28-09-2011
DOI: 10.1021/MA201568H
Cationic Bottlebrush Copolymers from Partially Hydrolyzed Poly(oxazoline)s
Publisher: American Chemical Society (ACS)
Date: 11-10-2021
Parallel and antiparallel cyclic d/l peptide nanotubes
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC00846E
Abstract: Novel X-ray crystal structures of cyclic d / l peptide nanotubes in antiparallel and parallel configurations.
Well-defined hyperstar copolymers based on a thiol-yne hyperbranched core and a poly(2-oxazoline) shell for biomedical applications
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY00303J
Abstract: Well defined ‘hyperstar’ copolymers were synthesized by combining hyperbranched polymers produced by thiol–yne chemistry with poly(oxazoline)s.
RAFT Emulsion Polymerization as a Platform to Generate Well‐Defined Biocompatible Latex Nanoparticles
Publisher: Wiley
Date: 07-08-2018
Abstract: Current approaches to generate core-shell nanoparticles for biomedical applications are limited by factors such as synthetic scalability and circulatory desorption of cytotoxic surfactants. Developments in controlled radical polymerization, particularly in dispersed states, represent a promising method of overcoming these challenges. In this work, well-defined PEGylated nanoparticles are synthesized using reversible addition fragmentation chain transfer emulsion polymerization to control particle size and surface composition and were further characterized with light scattering, electron microscopy, and size exclusion chromatography. Importantly, the nanoparticles are found to be tolerated both in vitro and in vivo, without the need for any purification after particle synthesis. Pharmacokinetic and biodistribution studies in mice, following intraperitoneal injection of the nanoparticles, reveal a long (>76 h) circulation time and accumulation in the liver.
Highly branched and hyperbranched glycopolymers via reversible addition-fragmentation chain transfer polymerization and click chemistry
Publisher: American Chemical Society (ACS)
Date: 04-01-2010
DOI: 10.1021/MA902587R
Initiating efficiency of poly(ethylene glycol)-based initiators for transition metal mediated living radical polymerisation
Publisher: Elsevier BV
Date: 10-2004
Well-Defined Alkyl Functional Poly(Styrene- co-Maleic Anhydride) Architectures as Pour Point and Viscosity Modifiers for Lubricating Oil
Publisher: American Chemical Society (ACS)
Date: 16-07-2019
Self-assembly and disassembly of stimuli responsive tadpole-like single chain nanoparticles using a switchable hydrophilic/hydrophobic boronic acid cross-linker
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY00828G
Abstract: pH/sugar responsive behaviour of tadpole-like single chain nanoparticles based on a switchable hydrophilic/hydrophobic boronic acid cross-linker is described.
RAFT graft polymerization of 2-(dimethylaminoethyl) methacrylate onto cellulose fibre
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06247
Abstract: Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) was grafted from cellulose by reversible addition–fragmentation chain transfer (RAFT) polymerization. The use of a free chain transfer agent in solution allowed for a better control over graft ratio, chain length of grafted polymer, monomer conversion, and homopolymer formation in solution. An increase in polymerization time or degree of polymerization led to an increase in graft ratio, as expected from a living system.
RAFT polymerization kinetics: Combination of apparently conflicting models
Publisher: American Chemical Society (ACS)
Date: 16-08-2008
DOI: 10.1021/MA800388C
Systematic study of the structural parameters affecting the self-assembly of cyclic peptide-poly(ethylene glycol) conjugates
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8SM01133H
Abstract: Self-assembling cyclic peptides (CP) consisting of amino acids with alternating d - and l -chirality form nanotubes by hydrogen bonding, hydrophobic interactions, and π–π stacking in solution.
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
Functional multisite copolymer by one-pot sequential RAFT copolymerization of styrene and maleic anhydride
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY00787F
Abstract: Functional multisite copolymers with a controlled number and position of side chains were synthesized by a one-pot RAFT polymerization process and post-functionalization.
Looped flow RAFT polymerization for multiblock copolymer synthesis
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY00630F
Abstract: A flexible, robust and time-efficient scale-up of multiblock copolymers with low dispersity and high livingness.
Polymerization induced self-assembly: Tuning of nano-object morphology by use of CO2
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4PY01632G
Abstract: A novel method for synthesis of polymeric nano-objects via polymerization-induced self-assembly in a CO 2 -expanded medium has been developed.
Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface
Publisher: American Chemical Society (ACS)
Date: 24-06-2015
DOI: 10.1021/JACS.5B04051
Facile synthesis of hyperbranched and star-shaped polymers by RAFT polymerization based on a polymerizable trithiocarbonate
Publisher: American Chemical Society (ACS)
Date: 11-03-2011
DOI: 10.1021/MA1024736
Thermoresponsive micelles from well‐defined block copolymers synthesized via reversible addition–fragmentation chain transfer polymerization
Publisher: Wiley
Date: 06-07-2005
DOI: 10.1002/POLA.20785
Investigating Cell Uptake of Guanidinium-Rich RAFT Polymers: Impact of Comonomer and Monomer Distribution
Publisher: American Chemical Society (ACS)
Date: 11-06-2018
DOI: 10.1021/ACS.BIOMAC.8B00146
Abstract: A range of well-defined guanidinium-rich linear polymers with demonstrable efficiency for cellular internalization were developed. A protected guanidinium-functional acrylamide monomer (di-Boc-guanidinium ethyl acrylamide, GEA
Pushing the limits of copper mediated azide-alkyne cycloaddition (CuAAC) to conjugate polymeric chains to cyclic peptides
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2PY00510G
RAFT Emulsion Polymerization for (Multi)block Copolymer Synthesis: Overcoming the Constraints of Monomer Order
Publisher: American Chemical Society (ACS)
Date: 05-01-2021
RAFT polymerization: A powerful tool for the synthesis and study of oligomers
Publisher: American Chemical Society
Date: 2012
Mechanism of Action of Oxazoline‐Based Antimicrobial Polymers Against Staphylococcus aureus: In Vivo Antimicrobial Activity Evaluation
Publisher: Wiley
Date: 06-09-2023
Abstract: Antimicrobial resistant pathogens have reached alarming levels, becoming one of the most pressing global health issues. Hence, new treatments are necessary for the fight against antimicrobial resistance. Synthetic nanoengineered antimicrobial polymers (SNAPs) have emerged as a promising alternative to antimicrobial peptides, overcoming some of their limitations while keeping their key features. Herein, a library of hiphilic oxazoline‐based SNAPs using cationic ring‐opening polymerization has been designed and hipathic compounds with 70% cationic content exhibited the highest activity against clinically relevant S. aureus isolates, maintaining good biocompatibility in vitro and in vivo. The mechanism of action of the lead compounds against S. aureus was assessed using various microscopy techniques, indicating cell membrane disruption, while the cell wall remained unaffected. Furthermore, a potential interaction of the compounds with bacterial DNA was shown, with possible implications on bacterial ision. Finally, one of the compounds exhibited high efficacy in vivo in an insect infection model. This article is protected by copyright. All rights reserved
Ultrafast RAFT polymerization: Multiblock copolymers within minutes
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4PY01251H
Abstract: A remarkably efficient and versatile procedure for the preparation of multiblock copolymers is presented.
Rapid photochromic nanopatterns from block copolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B920133E
Hyperbranched polymers by thiol-yne chemistry: From small molecules to functional polymers
Publisher: American Chemical Society (ACS)
Date: 30-11-2009
DOI: 10.1021/JA908206A
Abstract: A new synthesis of hyperbranched polymers is outlined. This paper presents the synthesis of hyperbranched polymers by the recently highlighted thiol-yne reaction. In the thiol-yne reaction, a catalytic amount of photoinitiator and UV radiation are used to add two thiols across one alkyne bond at room temperature. This work demonstrates how the thiol-yne reaction can be used to form hyperbranched polymers from both small organic molecules and polymeric chains bearing an alkyne and a thiol. The UV-catalyzed reaction is fast, forming high-molecular-weight polymers after 20 min of UV irradiation. Hyperbranched polymers made by the thiol-yne reaction have the potential to serve as new materials for a variety of applications from catalytic support and drug delivery to viscosity modification.
Manganese carbonyl induced cationic reversible addition–fragmentation chain transfer (C-RAFT) polymerization under visible light
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9PY01785B
Abstract: Vinyl ethers were polymerized by C-RAFT polymerization on the basis of halide abstraction reaction of manganese carbonyl and organic halide.
Synthesis of polymers and nanoparticles bearing polystyrene sulfonate brushes for chemokine binding
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6OB00270F
Abstract: This paper describes the synthesis of polymers and silica nanoparticles, both bearing polystyrene sulfonate brushes, and the measurement of their binding affinity for the chemokine monocyte chemoattractant protein-1 (MCP-1) in monomeric and dimeric form.
The type VII secretion system protects Staphylococcus aureus against antimicrobial host fatty acids
Publisher: Springer Science and Business Media LLC
Date: 09-09-2020
DOI: 10.1038/S41598-020-71653-Z
Abstract: The Staphylococcus aureus type VII secretion system (T7SS) exports several proteins that are pivotal for bacterial virulence. The mechanisms underlying T7SS-mediated staphylococcal survival during infection nevertheless remain unclear. Here we report that S. aureus lacking T7SS components are more susceptible to host-derived antimicrobial fatty acids. Unsaturated fatty acids such as linoleic acid (LA) elicited an increased inhibition of S. aureus mutants lacking T7SS effectors EsxC, EsxA and EsxB, or the membrane-bound ATPase EssC, compared to the wild-type (WT). T7SS mutants generated in different S. aureus s train backgrounds also displayed an increased sensitivity to LA. Analysis of bacterial membrane lipid profiles revealed that the esxC mutant was less able to incorporate LA into its membrane phospholipids. Although the ability to bind labelled LA did not differ between the WT and mutant strains, LA induced more cell membrane damage in the T7SS mutants compared to the WT. Furthermore, proteomic analyses of WT and mutant cell fractions revealed that, in addition to compromising membranes, T7SS defects induce oxidative stress and h er their response to LA challenge. Thus, our findings indicate that T7SS contribute to maintaining S. aureus membrane integrity and homeostasis when bacteria encounter antimicrobial fatty acids.
Janus cyclic peptide-polymer nanotubes
Publisher: Springer Science and Business Media LLC
Date: 13-11-2013
DOI: 10.1038/NCOMMS3780
Abstract: Self-assembled nanotubular structures have numerous potential applications but these are limited by a lack of control over size and functionality. Controlling these features at the molecular level may allow realization of the potential of such structures. Here we report a new generation of self-assembled cyclic peptide-polymer nanotubes with dual functionality in the form of either a Janus or mixed polymeric corona. A 'relay' synthetic strategy is used to prepare nanotubes with a demixing or mixing polymeric corona. Nanotube structure is assessed in solution using (1)H-(1)H nuclear Overhauser effect spectroscopy NMR, and in bulk using differential scanning calorimetry. The Janus nanotubes form artificial pores in model phospholipid bilayers. These molecules provide a viable pathway for the development of intriguing nanotubular structures with dual functionality via a demixing or a mixing polymeric corona and may provide new avenues for the creation of synthetic transmembrane protein channel mimics.
New methods of polymer synthesis
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2PY90007F
Reversible addition-fragmentation chain transfer polymerization of methacrylate, acrylate and styrene monomers in 1-alkyl-3-methylimidazolium hexfluorophosphate
Publisher: Elsevier BV
Date: 03-2003
Living radical polymerization of styrene mediated by copper(I)/N-n-alkyl-2-pyridylmethanimine catalysts
Publisher: American Chemical Society (ACS)
Date: 09-03-2002
DOI: 10.1021/MA011667O
Efficient click-addition sequence for polymer-polymer couplings
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6PY00954A
Abstract: Controlled radical polymerization methods and click chemistry form a versatile toolbox for creating complex polymer architectures.
Tunable Length of Cyclic Peptide-Polymer Conjugate Self-Assemblies in Water
Publisher: American Chemical Society (ACS)
Date: 19-09-2016
DOI: 10.1021/ACSMACROLETT.6B00586
Abstract: Polymers conjugated to cyclic peptides capable of forming strong hydrogen bonds can self-assemble into supramolecular bottlebrushes even in aqueous solutions. However, controlling the aggregation of these supramolecular assemblies remains an obstacle that is yet to be overcome. By introducing pH-responsive poly(dimethylamino ethyl methacrylate) (pDMAEMA) arms, the repulsive forces were tuned by adjusting the degree of protonation on the polymer arms. Neutron scattering experiments demonstrated that conjugates in an uncharged state will self-assemble into supramolecular bottlebrushes. Reducing the pH in the system led to a decrease in the number of aggregation, which was reversible by addition of base. Potentiometric titration showed a correlation between the number of aggregation and the degree of ionization of the pDMAEMA arms. Hence, a balance between the strength of the hydrogen bonds and the repulsive electrostatic interactions determines the number of aggregation and extent of self-assembly. The presented work demonstrates that conjugate self-association can be controlled by tuning the charge density on the conjugated polymer arms, paving the way for the use of responsive cyclic peptide conjugates in pharmaceutical applications.
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.
Modular design for the controlled production of polymeric nanotubes from polymer/peptide conjugates
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1PY00202C
Unexpected behavior of polydimethylsiloxane/poly(2-(dimethylamino)ethyl acrylate) (charged) amphiphilic block copolymers in aqueous solution
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3PY21038C
Dose- and time-dependent tolerability and efficacy of organo-osmium complex FY26 and its tissue pharmacokinetics in hepatocarcinoma-bearing mice
Publisher: Oxford University Press (OUP)
Date: 11-12-2020
Abstract: The organo-osmium complex [OsII(ɳ6-p-cym)(PhAzPy-NMe2)I]+ (FY26) exhibits promising in vitro antitumour activity against mouse hepatocarcinoma Hepa1–6 and other mouse or human cancer cell lines. Here, we drastically enhance water solubility of FY26 through the replacement of the PF6− counter-anion with chloride using a novel synthesis method. FY26⋅PF6 and FY26⋅Cl displayed similar in vitro cytotoxicity in two cancer cell models. We then show the moderate and late anticancer efficacy of FY26⋅PF6 and FY26⋅Cl in a subcutaneous murine hepatocarcinoma mouse model. Both efficacy and tolerability varied according to FY26 circadian dosing time in hepatocarcinoma tumour-bearing mice. Tumour and liver uptake of the drug were determined over 48 h following FY26⋅Cl administration at Zeitgeber time 6 (ZT6), when the drug is least toxic (in the middle of the light span when mice are resting). Our studies suggest the need to administer protracted low doses of FY26 at ZT6 in order to optimize its delivery schedule, for ex le through the use of chrono-releasing nanoparticles.
Polymeric Nanotubes as Drug Delivery Vectors─Comparison of Covalently and Supramolecularly Assembled Constructs
Publisher: American Chemical Society (ACS)
Date: 12-06-2036
Influence of reaction parameters on the synthesis of hyperbranched polymers via reversible addition fragmentation chain transfer (RAFT) polymerization
Publisher: Elsevier BV
Date: 08-2005
Monodisperse, charge-stabilized, core-shell particles via silica-supported reversible addition-fragmentation chain transfer polymerization for cell imaging
Publisher: American Chemical Society (ACS)
Date: 20-08-2013
DOI: 10.1021/CM401957M
Synthesis of a cellulose supported chain transfer agent and its application to RAFT polymerization
Publisher: Wiley
Date: 24-08-2010
DOI: 10.1002/POLA.24232
Water-soluble and pH-responsive polymeric nanotubes from cyclic peptide templates
Publisher: Wiley
Date: 07-01-2013
Poly(ethylene glycol) as a 'green solvent' for the RAFT polymerization of methyl methacrylate
Publisher: Elsevier BV
Date: 08-2010
Design of complex polymeric architectures and nanostructured materials/hybrids by living radical polymerization of hydroxylated monomers
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0PY00160K
Characterization Across a Dispersity: Polymer Mass Spectrometry in the Second Dimension
Publisher: American Chemical Society (ACS)
Date: 15-07-2021
Thermal stability of reversible addition–fragmentation chain transfer/macromolecular architecture design by interchange of xanthates chain‐transfer agents
Publisher: Wiley
Date: 14-11-2006
DOI: 10.1002/POLA.21803
Synthesis of Poly(methyl acrylate) Grafted onto Silica Particles by Z‐supported RAFT Polymerization
Publisher: Wiley
Date: 02-2007
Supramolecular switching of the self-assembly of cyclic peptide-polymer conjugates: Via host-guest chemistry
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CC01914F
Abstract: A supramolecular strategy of switching the self-assembly of cyclic peptide–polymer conjugates using host–guest chemistry is proposed.
Microscale synthesis of multiblock copolymers using ultrafast RAFT polymerisation
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8PY01437J
Abstract: We demonstrate that ultrafast RAFT in the presence of air can be scaled down to 2 μL with good control using microvolume insert vials as the polymerisation vessel.
Aggregation‐Induced Emission Featured Supramolecular Tubisomes for Imaging‐Guided Drug Delivery
Publisher: Wiley
Date: 14-01-2022
Abstract: Polymeric cylinders, a fascinating type of nanostructures with high surface area, internal volume and rigidity, have been exploited as novel drug delivery vehicles over the past decade. However, it's still an open challenge to afford cylindrical nanostructures using polymeric building blocks via traditional self‐assembly processes. Herein, we report a hierarchical self‐assembly strategy of preparing cylindrical aggregates (tubisomes) from an hiphilic supramolecular bottlebrush polymer in which a cyclic peptide nanotube is employed as the noncovalent backbone. Additionally, an aggregation‐induced emission (AIE) effect was introduced into the tubisomes to endow them with excellent fluorescent properties. Intriguingly, by encapsulating with the anticancer drug doxorubicin (DOX), both the fluorescence of tubisome and DOX can be quenched due to the energy transfer relay (ETR) effect. The release of DOX can induce the interruption of the ETR effect and recover the silenced fluorescence, thereby permitting the in‐situ imaging of drug release. The AIE‐featured supramolecular tubisomes reported here provide an alternative approach for fabricating cylindrical polymeric nanostructures and holds great potential for imaging‐guided drug delivery.
Electron Capture Dissociation of Trithiocarbonate-Terminated Acrylamide Homo- and Copolymers: A Terminus-Directed Mechanism?
Publisher: American Chemical Society (ACS)
Date: 09-09-2020
SuFEx-a selectively triggered chemistry for fast, efficient and equimolar polymer-polymer coupling reactions
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY01636K
Abstract: The synergy between controlled radical polymerization methods and click chemistry enables the design of complex and well-defined materials.
Investigation of polymer blends of polyamide-6 and poly(methyl methacrylate) synthesized by RAFT polymerization
Publisher: Springer Science and Business Media LLC
Date: 24-10-2010
Dual self-assembly of supramolecular peptide nanotubes to provide stabilisation in water
Publisher: Springer Science and Business Media LLC
Date: 17-10-2019
DOI: 10.1038/S41467-019-12586-8
Abstract: Self-assembling peptides have the ability to spontaneously aggregate into large ordered structures. The reversibility of the peptide hydrogen bonded supramolecular assembly make them tunable to a host of different applications, although it leaves them highly dynamic and prone to disassembly at the low concentration needed for biological applications. Here we demonstrate that a secondary hydrophobic interaction, near the peptide core, can stabilise the highly dynamic peptide bonds, without losing the vital solubility of the systems in aqueous conditions. This hierarchical self-assembly process can be used to stabilise a range of different β-sheet hydrogen bonded architectures.
Thermo‐responsive Poly(methyl methacrylate)‐block‐poly(N‐isopropylacrylamide) Block Copolymers Synthesized by RAFT Polymerization: Micellization and Gelation
Publisher: Wiley
Date: 29-09-2006
Unexpected viability of pyridyl methanimine-based ligands for transition-metal-mediated living radical polymerization in aqueous media at ambient temperature
Publisher: American Chemical Society (ACS)
Date: 16-12-2001
DOI: 10.1021/MA001397U
Short chain amphiphilic diblock co-oligomers via RAFT polymerization
Publisher: Wiley
Date: 09-11-2012
DOI: 10.1002/POLA.25061
Supramolecular hybrids of cellulose and synthetic polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2PY20385E
The structure of randomly branched polymers synthesized by living radical methods
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0PY00064G
Reversible addition-fragmentation chain transfer graft polymerization mediated by fumed silica supported chain transfer agents
Publisher: American Chemical Society (ACS)
Date: 08-11-2007
DOI: 10.1021/MA0716783
Synthetic Star Nanoengineered Antimicrobial Polymers as Antibiofilm Agents: Bacterial Membrane Disruption and Cell Aggregation
Publisher: American Chemical Society (ACS)
Date: 10-06-2023
Tuning the color switching of naphthopyrans via the control of polymeric architectures
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B617865K
Living radical polymerization of isoprene via the RAFT process
Publisher: American Chemical Society (ACS)
Date: 06-02-2007
DOI: 10.1021/MA061889S
Synthesis of monocyclic and linear polystyrene using the reversible coupling/cleavage of thiol/disulfide groups
Publisher: American Chemical Society (ACS)
Date: 12-2006
DOI: 10.1021/MA061070E
Modulating catalytic activity of polymer-based cuAAC click reactions
Publisher: Wiley
Date: 09-08-2011
DOI: 10.1002/POLA.24896
Versatile Chain Transfer Agents for Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization to Synthesize Functional Polymeric Architectures
Publisher: American Chemical Society (ACS)
Date: 06-03-2004
DOI: 10.1021/MA035468B
Design, synthesis and thermal behaviour of a series of well-defined clickable and triggerable sulfonate polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5RA13867A
Abstract: In the printing industry, the exploitation of triggerable materials that can have their surface properties altered on application of a post-deposition external stimulus has been crucial for the production of robust layers and patterns.
One-pot hyperbranched polymer synthesis mediated by reversible addition fragmentation chain transfer (RAFT) polymerization
Publisher: American Chemical Society (ACS)
Date: 12-02-2005
DOI: 10.1021/MA048035X
A simple route to functional highly branched structures: RAFT homopolymerization of divinylbenzene
Publisher: American Chemical Society (ACS)
Date: 04-2011
DOI: 10.1021/MA102537H
Hydroxyapatite mineralization in the presence of anionic polymers
Publisher: American Chemical Society (ACS)
Date: 28-08-2013
DOI: 10.1021/CG400447E
Polymer folding: ABC of molecular origami
Publisher: Springer Science and Business Media LLC
Date: 21-02-2011
DOI: 10.1038/NCHEM.995
Antibacterial cellulose fiber via RAFT surface graft polymerization
Publisher: American Chemical Society (ACS)
Date: 08-12-2008
DOI: 10.1021/BM700849J
Abstract: 2-(dimethylamino)ethyl methacrylate (DMAEMA) was polymerized from cellulosic filter paper via reversible addition-fragmentation chain transfer (RAFT) polymerization. The tertiary amino groups of the grafted PDMAEMA chains were subsequently quaternized with alkyl bromides of different chain lengths (C8-C16) to provide a large concentration of quaternary ammonium groups on the cellulose surface. The antibacterial activity of the quaternized and nonquaternized PDMAEMA-grafted cellulosic fibers was tested against Escherichia coli. The antibacterial activity was found to depend on the alkyl chain length and on the degree of quaternization, i.e., the amount of quaternary amino groups present in the cellulose graft copolymers. The PDMAEMA-grafted cellulose fiber with the highest degree of quaternization and quaternized with the shortest alkyl chains was found to exhibit particularly high activity against E. coli.
Polymers with Well-Defined End Groups via RAFT - Synthesis, Applications and Postmodifications
Publisher: Wiley
Date: 23-01-2008
Facile synthesis of star‐shaped copolymers via combination of RAFT and ring opening polymerization
Publisher: Wiley
Date: 22-10-2009
DOI: 10.1002/POLA.23680
Abstract: Reversible addition fragmentation chain transfer (RAFT) polymerization and bifunctional sparteine/thiourea organocatalyst‐mediated ring opening polymerization (ROP) were combined to produce poly( L ‐lactide) star polymers and poly( L ‐lactide‐ co ‐styrene) miktoarm star copolymers architecture following a facile experimental procedure, and without the need for specialist equipment. RAFT was used to copolymerize ethyl acrylate (EA) and hydroxyethyl acrylate (HEA) into poly(EA‐ co ‐HEA) co‐oligomers of degree of polymerization 10 with 2, 3, and 4 units of HEA, which were in turn used as multifunctional initiators for the ROP of L ‐lactide, using a bifunctional thiourea organocatalytic system. Furthermore, taking advantage of the living nature of RAFT polymerization, the multifunctional initiators were chain extended with styrene (poly((EA‐ co ‐HEA)‐ b ‐styrene) copolymers), and used as initiators for the ROP of L ‐lactide, to yield miktoarm star copolymers. The ROP reactions were allowed to proceed to high conversions ( %) with good control over molecular weights (ca. 28,000‐230,000 g/mol) and polymer structures being observed, although the molecular weight distributions are generally broader (1.3–1.9) than those normally observed for ROP reactions. The orthogonality of both polymerization techniques, coupled with the ubiquity of HEA, which is used as a monomer for RAFT polymerization and as an initiator for ROP, offer a versatile approach to star‐shaped copolymers. Furthermore, this approach offers a practical approach to the synthesis of polylactide star polymers without a glove box or stringent reaction conditions. The phase separation properties of the miktoarm star copolymers were demonstrated via thermal analyses. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6396–6408, 2009
Hierarchical Self‐Assembled Photo‐Responsive Tubisomes from a Cyclic Peptide‐Bridged Amphiphilic Block Copolymer
Publisher: Wiley
Date: 25-03-2020
Abstract: Typically, the morphologies of the self‐assembled nanostructures from block copolymers are limited to spherical micelles, wormlike micelles and vesicles. Now, a new generation of materials with unique shape and structures, cylindrical soft matter particles (tubisomes), are obtained from the hierarchical self‐assembly of cyclic peptide‐bridged hiphilic diblock copolymers. The capacity of obtained photo‐responsive tubisomes as potential drug carriers is evaluated. The supramolecular tubisomes pave an alternative way for fabricating polymeric tubular structures, and will expand the toolbox for the rational design of functional hierarchical nanostructures.
In situ monitoring of PISA morphologies
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1PY00239B
Abstract: Fluorescent spectroscopy is a convenient method for monitoring the progression of polymerization-induced self-assembly (PISA).
Energy transfer in pendant perylene diimide copolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6TC02555B
Abstract: We report the synthesis and characterisation of novel copolymers comprising asymmetric perylene diimide acrylate monomers.
Multi-shell soft nanotubes from cyclic peptide templates
Publisher: Wiley
Date: 03-01-2013
The limits of precision monomer placement in chain growth polymerization
Publisher: Springer Science and Business Media LLC
Date: 02-2016
DOI: 10.1038/NCOMMS10514
Abstract: Precise control over the location of monomers in a polymer chain has been described as the ‘Holy Grail’ of polymer synthesis. Controlled chain growth polymerization techniques have brought this goal closer, allowing the preparation of multiblock copolymers with ordered sequences of functional monomers. Such structures have promising applications ranging from medicine to materials engineering. Here we show, however, that the statistical nature of chain growth polymerization places strong limits on the control that can be obtained. We demonstrate that monomer locations are distributed according to surprisingly simple laws related to the Poisson or beta distributions. The degree of control is quantified in terms of the yield of the desired structure and the standard deviation of the appropriate distribution, allowing comparison between different synthetic techniques. This analysis establishes experimental requirements for the design of polymeric chains with controlled sequence of functionalities, which balance precise control of structure with simplicity of synthesis.
Successful dispersion polymerization in supercritical CO2 using polyvinylalkylate hydrocarbon surfactants synthesized and anchored via RAFT
Publisher: American Chemical Society (ACS)
Date: 21-08-2008
DOI: 10.1021/JA8046156
Abstract: New CO2-philic hydrocarbon molecules were synthesized by reversible addition fragmentation chain-transfer polymerization. These poly(vinyl alkylates) show the highest solubility in supercritical CO2 of any hydrocarbon reported to date. By utilizing the anchoring ability of the thiocarbonylthio end group, the dispersion polymerization of N-vinyl pyrrolidone was successfully achieved in scCO2 leading to high yields of well-defined spherical polymer particles.
Antimicrobial polymers: Mimicking amino acid functionality, sequence control and three-dimensional structure of host-defense peptides
Publisher: Bentham Science Publishers Ltd.
Date: 23-08-2017
Hyperbranched Polymers with High Degrees of Branching and Low Dispersity Values: Pushing the Limits of Thiol-Yne Chemistry
Publisher: American Chemical Society (ACS)
Date: 02-02-2016
Synthesis of mannosylated and PEGylated nanoparticles via RAFT emulsion polymerisation, and investigation of particle-lectin aggregation using turbidimetric and DLS techniques
Publisher: Elsevier BV
Date: 12-2016
Fluorescent Labeling and Biodistribution of Latex Nanoparticles Formed by Surfactant-Free RAFT Emulsion Polymerization
Publisher: Wiley
Date: 14-12-2017
Abstract: The authors report the preparation of a novel range of functional polyacrylamide stabilized polystyrene nanoparticles, obtained by surfactant-free reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization, their fluorescent tagging, cellular uptake, and biodistribution. The authors show the versatility of the RAFT emulsion process for the design of functional nanoparticles of well-defined size that can be used as drug delivery vectors. Functionalization with a fluorescent tag offers a useful visualization tool for tracing, localization, and clearance studies of these carriers in biological models. The studies are carried out by labeling the sterically stabilized latex particles chemically with rhodamine B. The fluorescent particles are incubated in a healthy human renal proximal tubular cell line model, and intravenously injected into a mouse model. Cellular localization and biodistribution of these particles on the biological models are explored.
Cyclic peptide–polymer conjugates: Grafting‐to vs grafting‐from
Publisher: Wiley
Date: 20-10-2015
DOI: 10.1002/POLA.27937
Macromolecular design via reversible addition–fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization
Publisher: Wiley
Date: 05-10-2005
DOI: 10.1002/POLA.20986
Synthesis of natural-synthetic hybrid materials from cellulose via the RAFT process
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B711248N
Secondary Self‐Assembly of Supramolecular Nanotubes into Tubisomes and Their Activity on Cells
Publisher: Wiley
Date: 21-11-2018
Patterned chemisorption of proteins by thin polymer film dewetting
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3SM27241A
Altering peptide fibrillization by polymer conjugation
Publisher: American Chemical Society (ACS)
Date: 07-08-2012
DOI: 10.1021/BM3007117
Abstract: A strategy is presented that exploits the ability of synthetic polymers of different nature to disturb the strong self-assembly capabilities of amyloid based β-sheet forming peptides. Following a convergent approach, the peptides of interest were synthesized via solid-phase peptide synthesis (SPPS) and the polymers via reversible addition-fragmentation chain transfer (RAFT) polymerization, followed by a copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) to generate the desired peptide-polymer conjugates. This study focuses on a modified version of the core sequence of the β-amyloid peptide (Aβ), Aβ(16-20) (KLVFF). The influence of attaching short poly(N-isopropylacrylamide) and poly(hydroxyethylacrylate) to the peptide sequences on the self-assembly properties of the hybrid materials were studied via infrared spectroscopy, TEM, circular dichroism and SAXS. The findings indicate that attaching these polymers disturbs the strong self-assembly properties of the biomolecules to a certain degree and permits to influence the aggregation of the peptides based on their β-sheets forming abilities. This study presents an innovative route toward targeted and controlled assembly of amyloid-like fibers to drive the formation of polymeric nanomaterials.
Hydrogel and Organogel Formation by Hierarchical Self-Assembly of Cyclic Peptides Nanotubes
Publisher: Wiley
Date: 21-11-2018
Abstract: Breaking away from the linear structure of previously reported peptide‐based gelators, this study reports the first ex le of gel formation based on the use of cyclic peptides made of alternating d ‐ and l ‐amino acids, known to self‐assemble in solution to form long nanotubes. Herein, a library of cyclic peptides was systemically studied for their gelation properties in various solvents, uncovering key parameters driving both organogel and hydrogel formation. The hierarchical nature of the self‐assembly process in water was characterised by a combination of electron microscopy imaging and small‐angle X‐ray scattering, revealing a porous network of entangled nanofibres composed by the aggregation of several cyclic peptide nanotubes. Rheology measurements then confirmed the formation of soft hydrogels.
Self-assembling macromolecular chimeras: Controlling fibrillization of a β-sheet forming peptide by polymer conjugation
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0SM01237H
Hierarchical Self‐Assembled Photo‐Responsive Tubisomes from a Cyclic Peptide‐Bridged Amphiphilic Block Copolymer
Publisher: Wiley
Date: 25-03-2020
Abstract: Typically, the morphologies of the self‐assembled nanostructures from block copolymers are limited to spherical micelles, wormlike micelles and vesicles. Now, a new generation of materials with unique shape and structures, cylindrical soft matter particles (tubisomes), are obtained from the hierarchical self‐assembly of cyclic peptide‐bridged hiphilic diblock copolymers. The capacity of obtained photo‐responsive tubisomes as potential drug carriers is evaluated. The supramolecular tubisomes pave an alternative way for fabricating polymeric tubular structures, and will expand the toolbox for the rational design of functional hierarchical nanostructures.
Rapid and quantitative one-pot synthesis of sequence-controlled polymers by radical polymerization
Publisher: Springer Science and Business Media LLC
Date: 30-09-2013
DOI: 10.1038/NCOMMS3505
Abstract: A long-standing challenge in polymer chemistry has been to prepare synthetic polymers with not only well-defined molecular weight, but also precisely controlled microstructure in terms of the distribution of monomeric units along the chain. Here we describe a simple and scalable method that enables the synthesis of sequence-controlled multiblock copolymers with precisely defined high-order structures, covering a wide range of functional groups. We develop a one-pot, multistep sequential polymerization process with yields >99%, giving access to a wide range of such multifunctional multiblock copolymers. To illustrate the enormous potential of this approach, we describe the synthesis of a dodecablock copolymer, a functional hexablock copolymer and an icosablock (20 blocks) copolymer, which represents the largest number of blocks seen to date, all of very narrow molecular weight distribution for such complex structures. We believe this approach paves the way to the design and synthesis of a new generation of synthetic polymers.
Synthetic strategies for the design of peptide/polymer conjugates
Publisher: Informa UK Limited
Date: 22-04-2011
Supramolecular peptide nanotubes as artificial enzymes for catalysing ester hydrolysis
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3PY00993A
Fluorescent Supramolecular Polymersomes Based on Pillararene/Paraquat Molecular Recognition for pH-controlled Drug Release
Publisher: Springer Science and Business Media LLC
Date: 27-09-2019
Photonic porous silicon as a pH sensor
Publisher: Springer Science and Business Media LLC
Date: 21-08-2014
Well-defined colloidal crystal films from the 2D self-assembly of core-shell semi-soft nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5PY00912J
Abstract: Silica core–polymer shell particles are obtained from surface mediated RAFT polymerisation and assembled into ordered 2D colloidal crystals.
Synthesis of Sub‐100 nm Glycosylated Nanoparticles via a One Step, Free Radical, and Surfactant Free Emulsion Polymerization
Publisher: Wiley
Date: 02-05-2018
Abstract: The facile synthesis of sub-100 nm glyco nanoparticles is presented via a one-step, free radical, and surfactant free emulsion polymerization. It is shown that by using sterically large, hydrophilic glycomonomers such as a lactose acrylamide with the charged azo initiator 4,4'-azobis(4-cyanovaleric acid), growing particles are stabilized enough to reproducibly produce well defined (PDi ≤ 0.1) glycoparticles with diameters below 100 nm.
Putting the RAFT in GRAFT: intermolecular graft exchange between bottlebrush polymers using reversible addition–fragmentation chain transfer
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1PY01510A
Abstract: A versatile synthetic methodology is presented for the preparation of graft copolymers with mixed graft distributions using reversible addition–fragmentation chain transfer (RAFT) polymerisation.
Exploitation of Compartmentalization in RAFT Miniemulsion Polymerization to Increase the Degree of Livingness
Publisher: Wiley
Date: 05-02-2019
DOI: 10.1002/POLA.29329
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
'Green' reversible addition-fragmentation chain-transfer (RAFT) polymerization
Publisher: Springer Science and Business Media LLC
Date: 23-09-2010
DOI: 10.1038/NCHEM.853
Abstract: Reversible addition-fragmentation chain-transfer (RAFT) polymerization has revolutionized the field of polymer synthesis as a versatile tool for the production of complex polymeric architectures. As for all chemical processes, research and development in RAFT have to focus on the design and application of chemical products and processes that have a minimum environmental impact, and follow the principles of 'green' chemistry. In this Review, we summarize some of the green features of the RAFT process, and review the recent advances in the production of degradable polymers obtained from RAFT polymerization. Its use to modify biodegradable and renewable inorganic and organic materials to yield more functional products with enhanced applications is also covered. RAFT is a promising candidate for answering both the increasing need of modern society to employ highly functional polymeric materials and the global requirements for developing sustainable chemicals and processes.
Polymer-peptide chimeras for the multivalent display of immunogenic peptides
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B924112D
Abstract: Chimeras of poly(n-isopropyl acrylamide) and immunogenic peptides from the cancer-associated glycoprotein MUC1 were synthesised using a combination of solid-phase peptide synthesis, RAFT polymerisation and copper-catalysed alkyne-azide cycloaddition reactions.
Dual pH-Responsive Macrophage-Targeted Isoniazid Glycoparticles for Intracellular Tuberculosis Therapy
Publisher: American Chemical Society (ACS)
Date: 02-08-2021
Reverse-phase high performance liquid chromatography (RP-HPLC) as a powerful tool to characterise complex water-soluble copolymer architectures
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8PY00966J
Abstract: A novel analytical method, based on RP-HPLC, for the characterisation of monomer distribution in charged water-soluble copolymers.
Structure elucidation and control of cyclic peptide-derived nanotube assemblies in solution
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3SC00064H
Secondary Self-Assembly of Supramolecular Nanotubes into Tubisomes and Their Activity on Cells
Publisher: Wiley
Date: 21-11-2018
Abstract: The properties and structures of viruses are directly related to the three-dimensional structure of their capsid proteins, which arises from a combination of hydrophobic and supramolecular interactions, such as hydrogen bonds. The design of synthetic materials demonstrating similar synergistic interactions still remains a challenge. Herein, we report the synthesis of a polymer/cyclic peptide conjugate that combines the capability to form supramolecular nanotubes via hydrogen bonds with the properties of an hiphilic block copolymer. The analysis of aqueous solutions by scattering and imaging techniques revealed a barrel-shaped alignment of single peptide nanotubes into a large tubisome (length: 260 nm (from SANS)) with a hydrophobic core (diameter: 16 nm) and a hydrophilic shell. These systems, which have a structure that is similar to those of viruses, were tested in vitro to elucidate their activity on cells. Remarkably, the rigid tubisomes are able to perforate the lysosomal membrane in cells and release a small molecule into the cytosol.
Branched and Dendritic Polymer Architectures: Functional Nanomaterials for Therapeutic Delivery
Publisher: Wiley
Date: 10-04-2019
Synthesis of silica-polymer core-shell nanoparticles by reversible addition-fragmentation chain transfer polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CC45319G
Abstract: Hybrid nanoparticles hold great promise for a range of applications such as drug-delivery vectors or colloidal crystal self-assemblies. The challenge of preparing highly monodisperse particles for these applications has recently been overcome by using living radical polymerization techniques. In particular, the use of reversible addition-fragmentation chain transfer (RAFT), initiated from silica surfaces, yields well-defined particles from a range of precursor monomers resulting in nanoparticles of tailored sizes that are accessible via the rational selection of polymerization conditions. Furthermore, using RAFT allows post-polymerization modification to afford multifunctional, monodisperse, nanostructures under mild and non-stringent reaction conditions.
Preparation of complex multiblock copolymers via aqueous RAFT polymerization at room temperature
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5PY00478K
Abstract: Room temperature RAFT polymerisation for the design of multiblock acrylate/acrylamide copolymers.
A guide to supramolecular polymerizations
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9PY01342C
Abstract: Supramolecular polymers are non-covalent assemblies of unimeric building blocks connected by secondary interactions and hold great promises due to their dynamic nature.
Surface-initiated SET living radical polymerisation for the synthesis of silica-polymer core-shell nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6PY01290F
Abstract: We report the use of surface-initiated single-electron transfer living radical polymerisation (SI SET-LRP) to prepare inorganic–organic core–shell nanoparticles with functional grafted chains of high molecular weight.
Polymerisation‐Induced Self‐Assembly of Graft Copolymers
Publisher: Wiley
Date: 29-09-2022
Abstract: We report the polymerisation‐induced self‐assembly of poly(lauryl methacrylate)‐ graft ‐poly(benzyl methacrylate) copolymers during reversible addition‐fragmentation chain transfer (RAFT) grafting from polymerisation in a backbone‐selective solvent. Electron microscopy images suggest the phase separation of grafts to result in a network of spherical particles, due to the ability of the branched architecture to freeze chain entanglements and to bridge core domains. Small‐angle X‐ray scattering data suggest the architecture promotes the formation of multicore micelles, the core morphology of which transitions from spheres to worms, vesicles, and inverted micelles with increasing volume fraction of the grafts. A time‐resolved SAXS study is presented to illustrate the formation of the inverted phase during a polymerisation. The grafted architecture gives access to unusual morphologies and provides exciting new handles for controlling the polymer structure and material properties.
pH- and thermo-multi-responsive fluorescent micelles from block copolymers via reversible addition fragmentation chain transfer (RAFT) polymerization
Publisher: Elsevier BV
Date: 08-2009
Solubilization and functionalization of cellulose assisted by microwave irradiation
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH08491
Abstract: The dissolution and functionalization of cellulose in the DMAc/LiCl system assisted by microwave irradiation is investigated. Cellulose solutions were prepared using mono- and multimodal microwave radiation, as well as using a conventional heating method. The effect of microwave irradiation on the dissolution of cellulose was evaluated by comparison of physical properties such as the viscosity of the resulting solution and the size distribution of the cellulosic chains in solution. We demonstrate that monomodal microwave irradiation allows for a faster and easier dissolution of cellulose, when compared with the use of multimodal microwave irradiation, or conventional heating. Furthermore, we show that monomodal microwave irradiation can be used for a one-pot modification of cellulose undertaken in two steps, first dissolution of the cellulose followed by reaction of the functional groups. The concept is illustrated by the modification of cellulose with lauroyl chloride.
Anionic multiblock core cross-linked star copolymers via RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY01062A
Abstract: The synthesis of (multi)block copolymers sand star (multiblock) copolymers of poly(2-acrylamido-2-methylpropane sulfonic acid) by RAFT polymerisation is reported.
Influence of Block versus Random Monomer Distribution on the Cellular Uptake of Hydrophilic Copolymers
Publisher: American Chemical Society (ACS)
Date: 09-12-2016
RAFT polymerization under microwave irradiation: Toward mechanistic understanding
Publisher: American Chemical Society (ACS)
Date: 17-02-2011
DOI: 10.1021/MA102689D
Polymerization‐Induced Self‐Assembly under Compressed CO2: Control of Morphology Using a CO2‐Responsive MacroRAFT Agent
Publisher: Wiley
Date: 02-09-2018
Abstract: Polymerization-induced self-assembly of 2-hydroxypropyl methacrylate is conducted in water and water/MeOH using a CO
RAFT polymerization, a versatile tool for the production of functional soft nanoparticles
Publisher: American Chemical Society
Date: 13-08-2009
Cationic and hydrolysable branched polymers by RAFT for complexation and controlled release of dsRNA
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8PY00804C
Abstract: The complexation and sustained release of dsRNA from highly branched polymers prepared via RAFT polymerisation and copolymerisation of the monomers DMAEA, DMAPA, and DMAEMA, is reported.
Construction of temperature responsive hybrid crosslinked self-assemblies based on PEG-b-P(MMA-co-MPMA)-b-PNIPAAm triblock copolymer: ATRP synthesis and thermoinduced association behavior
Publisher: Wiley
Date: 03-2011
DOI: 10.1002/POLA.24606
Shaping block copolymer micelles by supramolecular polymerization: Making 'tubisomes'
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9PY00179D
Abstract: In contrast to the respective block copolymers, hiphilic cyclic peptide conjugates self-assemble into cylindrical micelles independent of the polymer compositions.
Australian European Self-Assembly through Macromolecular Interactions
Publisher: Wiley
Date: 10-2016
Describing the Structure of a Randomly Hyperbranched Polymer
Publisher: Wiley
Date: 12-07-2010
Optimization of the RAFT polymerization conditions for the in situ formation of nano-objects via dispersion polymerization in alcoholic medium
Publisher: Royal Society of Chemistry (RSC)
Date: 17-09-0006
DOI: 10.1039/C4PY00855C
Hierarchical bicontinuous porosity in metal-organic frameworks templated from functional block co-oligomer micelles
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3SC51336J
A study on the preparation of alkyne functional nanoparticles: Via RAFT emulsion polymerisation
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8PY01579A
Abstract: We evaluate the parameters surrounding the preparation of colloidally stable alkyne functional latex nanoparticles via RAFT emulsion polymerisation.
Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization
Publisher: American Chemical Society (ACS)
Date: 11-02-2016
DOI: 10.1021/ACS.BIOMAC.5B01633
Abstract: We present the preparation of 11 nm polyacrylamide-stabilized polystyrene latex particles for conjugation to a microRNA model by surfactant-free RAFT emulsion polymerization. Our synthetic strategy involved the preparation of hiphilic polyacrylamide-block-polystyrene copolymers, which were able to self-assemble into polymeric micelles and "grow" into polystyrene latex particles. The surface of these sterically stabilized particles was postmodified with a disulfide-bearing linker for the attachment of the microRNA model, which can be released from the latex particles under reducing conditions. These nanoparticles offer the advantage of ease of preparation via a scaleable process, and the versatility of their synthesis makes them adaptable to a range of applications.
Reversible addition-fragmentation chain transfer polymerization mediated by a solid supported chain transfer agent
Publisher: American Chemical Society (ACS)
Date: 14-07-2005
DOI: 10.1021/MA0506886
Investigation of the experimental factors affecting the trithiocarbonate-mediated RAFT polymerization of methyl acrylate
Publisher: CSIRO Publishing
Date: 2007
DOI: 10.1071/CH07171
Abstract: The reversible addition–fragmentation chain transfer polymerization of acrylates, using methyl acrylate (MA) as a monomer model, mediated by a trithiocarbonate was tested under several conditions where the experimental parameters were systematically altered. The most significant parameter in controlling the rate and control of the polymerization was found to be the ratio of chain transfer agent (CTA) to initiator. Decreasing this ratio increased the rate of polymerization and had little noticeable effect on the control over molecular weight distribution. A ratio of CTA to initiator of unity was shown to give the best compromise between rate and control of the polymerization. Targeted degrees of polymerization (equivalent to ratios of monomer to CTA) had negligible effect on the rate of polymerization and polydispersity index (PDI). Performing the polymerization in the presence of solvent (up to 41.2% (w/w) in toluene) had no negative effect on the rate of polymerization. Indeed, marginally higher conversions and lower PDIs than for bulk polymerization were achieved for similar reaction times. A higher amount of toluene (66.6% (w/w)) induced a lower rate of polymerization, but the evolution of molecular weight and PDI were unaffected. Polymerizations performed in the presence of toluene, N,N′-dimethylformamide, and methyl ethyl ketone showed that solvent polarity and aromaticity had no observable effect on the rate of polymerization and over the control of molecular weight distribution. The optimum conditions for the polymerization of MA, mediated by 2-ethylthiocarbonylsulfanyl-propionic acid ethyl ester at 50°C were found to be [CTA]/[AIBN] = 1/1 and ~40% solvent (w/w).
Controlled radical polymerization in dispersed systems for biological applications
Publisher: Elsevier BV
Date: 03-2020
Synthesis of silica-polymer hybrids by combination of RAFT polymerization and azide-alkyne cycloaddition 'click' reactions
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0PY00165A
Molecular Self-Assembly and Supramolecular Chemistry of Cyclic Peptides
Publisher: American Chemical Society (ACS)
Date: 03-05-2021
Orthogonal relay reactions for designing functionalized soft nanoparticles
Publisher: American Chemical Society (ACS)
Date: 20-01-2009
DOI: 10.1021/JA8075499
Abstract: The combination of reversible addition-fragmentation chain transfer (RAFT) chemistry followed by thiol-based "click" chemistry, known as an orthogonal "relay" reaction as one step complements the other, was used to produce surface-functionalized soft nanoparticles. Thiocarbonyl thio compounds were first used in the presence of vinyl monomers and a source of radicals to control the growth of the polymeric chains (via the RAFT process) and then reduced to thiols and utilized as a handle for functionalization of the resulting polymer chain ends (via a thiol-based click reaction). Both reactions occur under mild conditions and offer excellent control over the properties of the final product, and the thiol addition shows all the benefits of a click reaction, without requiring the use of a catalyst. This simple chemistry opens up the route to the production of a wide range of functional materials, and the concept is illustrated by the formation of nanoparticle-based gels, fluorescent-tagged particles, and protein-nanoparticle conjugates.
Synthesis of well-defined homopolymer and diblock copolymer grafted onto silica particles by Z-supported RAFT polymerization
Publisher: American Chemical Society (ACS)
Date: 08-11-2006
DOI: 10.1021/MA061586Y
Modeling highly branched structures: Description of the solution structures of dendrimers, polyglycerol, and glycogen
Publisher: Wiley
Date: 29-08-2011
DOI: 10.1002/POLB.22340
Design and properties of functional nanotubes from the self-assembly of cyclic peptide templates
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CS35172B
Abstract: β-Sheet forming self assembling cyclic peptides offer a versatile scaffold for the construction and control of hydrogen-bonded nanotube assemblies. These structures have major advantages over other nanoscale tubular structures, including sub-nanometer control over the internal diameter, and the ability to control internal and external chemical functionality. This Tutorial Review presents an overview of nanotubes derived from this class of cyclic peptides. The design rationale for functional nanotubes based on cyclic peptide ring size and chemical functionality is discussed. Additionally, we highlight the recent expansion of the nanotube toolbox through conjugation of (macro)molecules to the cyclic peptides. These provide additional functionality and control nanotube dimensions that could potentially prove beneficial in future applications.
Probing the Effect of Rigidity on the Cellular Uptake of Core‐Shell Nanoparticles: Stiffness Effects are Size Dependent
Publisher: Wiley
Date: 19-08-2022
Abstract: Nanoparticles are well established vectors for the delivery of a wide range of biomedically relevant cargoes. Numerous studies have investigated the impact of size, shape, charge, and surface functionality of nanoparticles on mammalian cellular uptake. Rigidity has been studied to a far lesser extent, and its effects are still unclear. Here, the importance of this property, and its interplay with particle size, is systematically explored using a library of core‐shell spherical PEGylated nanoparticles synthesized by RAFT emulsion polymerization. Rigidity of these particles is controlled by altering the intrinsic glass transition temperature of their constituting polymers. Three polymeric core rigidities are tested: hard, medium, and soft using two particle sizes, 50 and 100 nm diameters. Cellular uptake studies indicate that softer particles are taken up faster and threefold more than harder nanoparticles with the larger 100 nm particles. In addition, the study indicates major differences in the cellular uptake pathway, with harder particles being internalized through clathrin‐ and caveolae‐mediated endocytosis as well as macropinocytosis, while softer particles are taken up bycaveolae‐ and non‐receptormediated endocytosis. However, 50 nm derivatives do not show any appreciable differences in uptake efficiency, suggesting that rigidity as a parameter in the biological regime may be size dependent.
Cationic star copolymers obtained by the arm first approach for gene transfection
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3PY00352C
Abstract: Cationic polymers can be used as vectors to transport and efficiently protect nucleic acids.
Aggregation‐Induced Emission Featured Supramolecular Tubisomes for Imaging‐Guided Drug Delivery
Publisher: Wiley
Date: 14-01-2022
Abstract: Polymeric cylinders, a fascinating type of nanostructures with high surface area, internal volume and rigidity, have been exploited as novel drug delivery vehicles over the past decade. However, it's still an open challenge to afford cylindrical nanostructures using polymeric building blocks via traditional self‐assembly processes. Herein, we report a hierarchical self‐assembly strategy of preparing cylindrical aggregates (tubisomes) from an hiphilic supramolecular bottlebrush polymer in which a cyclic peptide nanotube is employed as the noncovalent backbone. Additionally, an aggregation‐induced emission (AIE) effect was introduced into the tubisomes to endow them with excellent fluorescent properties. Intriguingly, by encapsulating with the anticancer drug doxorubicin (DOX), both the fluorescence of tubisome and DOX can be quenched due to the energy transfer relay (ETR) effect. The release of DOX can induce the interruption of the ETR effect and recover the silenced fluorescence, thereby permitting the in‐situ imaging of drug release. The AIE‐featured supramolecular tubisomes reported here provide an alternative approach for fabricating cylindrical polymeric nanostructures and holds great potential for imaging‐guided drug delivery.
Erratum: Monodisperse, charge-stabilized, core-shell particles via silica-supported reversible addition-fragmentation chain transfer polymerization for cell imaging (Chemistry of Materials (2013) 25:17 (3522-3527) (DOI 10.1021/cm401957m))
Publisher: American Chemical Society (ACS)
Date: 05-11-2013
DOI: 10.1021/CM403311Y
Searching for stars: Selective desulfurization and fluorescence spectroscopy as New tools in the search for cross termination side-products in RAFT polymerization
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH09242
Abstract: We present a novel approach to the examination of the ‘controversial’ three-armed stars that are argued to exist in rate-retarded reversible addition–fragmentation chain transfer (RAFT) polymerizations by using a fluorescent carbazole-containing RAFT agent that exhibits classical signs of retardation, and provides a route to polymer-RAFT agent cross termination. We also pioneer the use of an existing desulfurization technique for the purification of polymers by removal of the coloured RAFT derived moiety, with the added benefit of potentially isolating and identifying the presence of cross termination side-products. Our findings suggest that the rate retardation is either due to the RAFT intermediate being sufficiently stable that it does not cross terminate, or that most of cross termination events occur between the intermediate and short radicals. Our findings are consistent with a model proposed earlier by this group for rate retardation in RAFT systems, which assumed a slow rate for long-chain cross termination, and a fast short chain cross termination rate.
Coupling Electron Capture Dissociation and the Modified Kendrick Mass Defect for Sequencing of a Poly(2-ethyl-2-oxazoline) Polymer
Publisher: American Chemical Society (ACS)
Date: 10-09-2018
DOI: 10.1021/ACS.ANALCHEM.8B03591
Abstract: With increasing focus on the structural elucidation of polymers, advanced tandem mass spectrometry techniques will play a crucial role in the characterization of these compounds. In this contribution, synthesis and analysis of methyl-initiated and xanthate-terminated poly(2-ethyl-2-oxazoline) using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) was achieved. Electron capture dissociation (ECD) produced full end group characterization as well as backbone fragmentation including complete sequence coverage of the polymer. A method of fragment ion characterization is also presented with the use of the high-resolution-modified Kendrick mass defect plots as a means of grouping fragments from the same fragmentation pathways together. This type of data processing is applicable to all tandem mass spectrometry techniques for polymer analysis but is made more effective with high mass accuracy methods. ECD FT-ICR MS demonstrates its promising role as a structural characterization technique for polyoxazoline species.
Luminescent hyperbranched polymers: Combining thiol-yne chemistry with gold-mediated C-H bond activation
Publisher: American Chemical Society (ACS)
Date: 11-02-2011
DOI: 10.1021/OM200103F
Heparin‐Mimicking Sulfonated Polymer Nanoparticles via RAFT Polymerization‐Induced Self‐Assembly
Publisher: Wiley
Date: 12-07-2018
Abstract: Heparin plays a significant role in wound healing and tissue regeneration applications, through stabilization of fibroblast growth factors (FGF). Risks associated with batch-to-batch variability and contamination from its biological sources have led to the development of synthetic, highly sulfonated polymers as promising heparin mimics. In this work, a systematic study of an aqueous polymerization-induced self-assembly (PISA) of styrene from poly(2-acrylamido-2-methylpropane sodium sulfonate) (P(AMPS)) macro reversible addition-fragmentation chain transfer (macro-RAFT) agents produced a variety of spherical heparin-mimicking nanoparticles, which were further characterized with light scattering and electron microscopy techniques. None of the nanoparticles tested showed toxicity against mammalian cells however, significant hemolytic activity was observed. Nonetheless, the heparin-mimicking nanoparticles outperformed both heparin and linear P(AMPS) in cellular proliferation assays, suggesting increased bFGF stabilization efficiencies, possibly due to the high density of sulfonated moieties at the particle surface.
Australian European Self‐Assembly through Macromolecular Interactions II
Publisher: Wiley
Date: 10-2018
Nano-Engineered Multiblock Copolymer Nanoparticles via Reversible Addition-Fragmentation Chain Transfer Emulsion Polymerization
Publisher: American Chemical Society (ACS)
Date: 03-04-2019
Fluorinated nanotubes: synthesis and self-assembly of cyclic peptide–poly(vinylidene fluoride) conjugates
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1PY00355K
Abstract: Fluorinated hollow nanotubes were prepared from pre-assembled cyclic peptides bearing xanthate moieties by RAFT/MADIX of VDF.
Reversible addition-fragmentation chain transfer polymerization: End group modification for functionalized polymers and chain transfer agent recovery
Publisher: American Chemical Society (ACS)
Date: 15-02-2005
DOI: 10.1021/MA047611M
Solid-supported MADIX polymerization of vinyl acetate
Publisher: American Chemical Society (ACS)
Date: 06-09-2008
DOI: 10.1021/MA801328C
Copper(0)-mediated living radical polymerization of styrene
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B9PY00382G
Abstract: The use of zerovalent copper and commercially available ligands enables the control of the polymerisation of styrene at 90 °C in toluene.
Tailoring the luminescence of FRET systems built using supramolecular polymeric nanotubes
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2PY00557C
Abstract: Supramolecular polymeric nanotubes self-assembled from cyclic peptide–polymer conjugates are employed as general scaffolds to fabricate supramolecular FRET systems with tailorable and responsive luminescence.
Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials
Publisher: American Chemical Society (ACS)
Date: 09-2016
Development of a Gemcitabine-Polymer Conjugate with Prolonged Cytotoxicity against a Pancreatic Cancer Cell Line
Publisher: American Chemical Society (ACS)
Date: 26-04-2017
DOI: 10.1021/ACSMACROLETT.7B00160
Abstract: Gemcitabine (GEM) is a nucleoside analogue of deoxycytidine with limited therapeutic efficacy due to enzymatic hydrolysis by cytidine deaminase (CDA) resulting in compromised half-life in the bloodstream and poor pharmacokinetics. To overcome these limitations, we have developed a methacrylate-based GEM-monomer conjugate, which was polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization with high monomer conversion (∼90%) and low dispersity (<1.4). The resulting GEM-polymer conjugates were found to form well-defined sub-90 nm nanoparticles (NPs) in aqueous suspension. Subsequently, the GEM release was studied at different pH (∼7 and ∼5) with and without the presence of an enzyme, Cathepsin B. The GEM release profiles followed a pseudo zero-order rate and the GEM-polymer conjugate NPs were prone to acidic and enzymatic degradation, following a two-step hydrolysis mechanism. Furthermore, the NPs exhibited significant cytotoxicity in vitro against a model pancreatic cell line. Although, the half-maximal inhibitory concentration (IC
Probing the Dynamic Nature of Self-Assembling Cyclic Peptide–Polymer Nanotubes in Solution and in Mammalian Cells
Publisher: Wiley
Date: 07-11-2018
Evaluation of the Antimicrobial Activity in Host-Mimicking Media and In Vivo Toxicity of Antimicrobial Polymers as Functional Mimics of AMPs
Publisher: American Chemical Society (ACS)
Date: 12-07-2022
PH-Responsive, Amphiphilic Core-Shell Supramolecular Polymer Brushes from Cyclic Peptide-Polymer Conjugates
Publisher: American Chemical Society (ACS)
Date: 20-11-2017
Polymer Architectures via Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization
Publisher: Wiley
Date: 09-2004
Polymer chemistry: Sacrificial synthesis
Publisher: Springer Science and Business Media LLC
Date: 2007
DOI: 10.1038/445271A
Surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization from fine particles functionalized with trithiocarbonates
Publisher: American Chemical Society (ACS)
Date: 31-10-2011
DOI: 10.1021/MA202105Y
A facile route to functional hyperbranched polymers by combining reversible addition-fragmentation chain transfer polymerization, thiol-yne chemistry, and postpolymerization modification strategies
Publisher: American Chemical Society (ACS)
Date: 16-04-2013
DOI: 10.1021/MZ400118G
Abstract: This contribution reports on the preparation of functional hyperbranched polystyrene-based materials via a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization, thiol-yne chemistry, and postpolymerization modification reactions. The thiol-yne approach allows the rapid preparation of hyperbranched polymers under mild reaction conditions from polymeric chains bearing a thiol group at one chain end and an alkyne moiety at the other. Postpolymerization modifications of the focal thiol and peripheral alkyne functionalities present within the hyperbranched structures were conducted using two highly efficient strategies, i.e., phosphine-catalyzed thiol-ene reaction and copper-catalyzed azide-alkyne cycloaddition (CuAAC), respectively. In addition to introducing functionalities by postpolymerization modification onto the periphery of the hyperbranched polymers, the interior of the globular structure could also be functionalized by taking advantage of the isocyanate chemical handle of a poly(styrene-
Related Organisations
Université Montpellier Faculté Des Sciences De Montpellier
Location: France
University Of Warwick
Location: United Kingdom of Great Britain and Northern Ireland
University Of Leeds
Location: United Kingdom of Great Britain and Northern Ireland
Related Funding Activities
Follow On: Design Polymers
Start Date: 2007
End Date: 2008
Funder: Engineering and Physical Sciences Research Council
View Funded ActivityFunctional Soft Nanotubes From Molecular Engineering
Start Date: 2014
End Date: 2018
Funder: The Royal Society
View Funded ActivityDiscovery Projects - Grant ID: DP130100017
Start Date: 02-2013
End Date: 10-2013
Amount: $420,000.00
Funder: Australian Research Council
View Funded ActivityLinkage - International - Grant ID: LX0212039
Start Date: 2002
End Date: 12-2004
Amount: $68,022.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP110101608
Start Date: 04-2011
End Date: 12-2013
Amount: $360,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE110100203
Start Date: 2014
End Date: 12-2014
Amount: $250,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP160104196
Start Date: 03-2016
End Date: 12-2019
Amount: $441,295.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP140100241
Start Date: 2014
End Date: 12-2017
Amount: $480,000.00
Funder: Australian Research Council
View Funded ActivityARC Future Fellowships - Grant ID: FT120100536
Start Date: 12-2012
End Date: 09-2013
Amount: $931,168.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP170100081
Start Date: 2017
End Date: 08-2020
Amount: $326,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP1096651
Start Date: 04-2010
End Date: 11-2013
Amount: $320,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Projects - Grant ID: LP100200339
Start Date: 01-2011
End Date: 01-2015
Amount: $530,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP180103661
Start Date: 2018
End Date: 12-2020
Amount: $501,024.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE120100098
Start Date: 01-2012
End Date: 06-2014
Amount: $230,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE100100096
Start Date: 2010
End Date: 06-2011
Amount: $450,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP220103135
Start Date: 09-2022
End Date: 08-2025
Amount: $510,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP230101739
Start Date: 09-2023
End Date: 09-2026
Amount: $466,000.00
Funder: Australian Research Council
View Funded Activity