ORCID Profile
0000-0003-2629-3895
Current Organisation
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 | Functional Materials | Membrane and Separation Technologies | Physical Chemistry Of Macromolecules | Chemical Engineering | Macromolecular materials | Colloid and surface chemistry | Optical Properties of Materials | Synthesis of Materials | Organic Chemical Synthesis | Polymerisation Mechanisms | Characterisation Of Macromolecules | Nanochemistry and Supramolecular Chemistry | Polymers | Macromolecular and materials chemistry | Nanofabrication growth and self assembly | Nanomaterials | Mineral Processing/Beneficiation | Nanotechnology | Resources Engineering and Extractive Metallurgy | Materials Engineering | Composite and Hybrid Materials | Nanofabrication, Growth and Self Assembly
ANZSRC Socio-Economic Objective (SEO)
Expanding Knowledge in Engineering | Plastics in primary forms | Polymeric materials (e.g. paints) | Expanding Knowledge in the Chemical Sciences | Synthetic resins and rubber | Plastic products (incl. Construction materials) | First Stage Treatment of Ores and Minerals not elsewhere classified | Expanding Knowledge in Technology | Industrial Energy Conservation and Efficiency | Physical and Chemical Conditions of Water for Urban and Industrial Use | Diagnostic Methods | Industrial Chemicals and Related Products not elsewhere classified | Concentrating Processes of Base Metal Ores (excl. Aluminium and Iron Ores) |
Related Links
Publications
Some recent developments in RAFT polymerization
Publisher: American Chemical Society
Date: 2012
Synthesis of Symmetrical, Substituted (alkane-α,ω-diyl)(bis[3,3′-allyl dithioethers]) Monomers for Photoplastic Polymer Networks
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH12278
Abstract: Novel symmetrical (alkane-α,ω-diyl)(bis[3,3′-allyl dithioethers]) compounds and their ether analogues, have been synthesised from (alkane-α,ω-diyl)bis([2-{chloromethyl}allyl]sulfane) precursors, for use in crosslinked polymers which exhibit photoplastic behaviour. Facile synthesis and purification of these monomers was achieved if the alkane-α,ω-diyl moiety had at least one oxygen atom in this linker. The number of sulfur atoms in these monomers was varied from four to two to zero to produce monomers which can be used to evaluate their importance on the photoplasticity behaviour.
Controlled RAFT polymerization in a continuous flow microreactor
Publisher: American Chemical Society (ACS)
Date: 10-03-2011
DOI: 10.1021/OP1003314
REACTION OF TERT-BUTOXY RADICALS WITH CYCLIC ALKENES STUDIED BY THE NITROXIDE RADICAL-TRAPPING TECHNIQUE
Publisher: CSIRO Publishing
Date: 1991
DOI: 10.1071/CH9911407
Abstract: The pattern of reactions occurring between t- butoxy radicals and a number of cyclic alkenes has been investigated by the nitroxide radical-trapping technique. The major reaction pathway is allylic abstraction unless this position is at a bridgehead as in norbornene where the major pathway is radical addition. The technique is sufficiently sensitive to identify minor reaction pathways of non-allylic substitution and radical addition when in the presence of extensive allylic substitution. Some stereoselective effects are also detected.
Universal (Switchable) RAFT Agents
Publisher: American Chemical Society (ACS)
Date: 29-04-2009
DOI: 10.1021/JA901955N
Abstract: The polymerization of most monomers that are polymerizable by radical polymerization can be controlled by the reversible addition-fragmentation chain transfer (RAFT) process. However, it is usually required that the RAFT agent be selected according to the types of monomer being polymerized. Thus, RAFT agents (dithioesters, trithiocarbonates) suitable for controlling polymerization of "more activated" monomers (MAMs e.g., styrene, acrylates, methacrylates, etc.) tend to inhibit polymerization of "less activated" monomers (LAMs e.g., vinyl acetate, N-vinylpyrrolidone, etc.). Similarly RAFT agents suitable for polymerizations of LAMs (xanthates, certain dithiocarbamates) tend to give little or poor control over polymerizations of MAMs. We now report a new class of "switchable" RAFT agents, N-(4-pyridinyl)-N-methyldithiocarbamates, that provide excellent control over polymerization of LAMs and, after addition of 1 equiv of a protic or Lewis acid, become effective in controlling polymerization of MAMs, allowing the synthesis of poly(MAM)-block-poly(LAM) with narrow molecular weight distributions.
Attempted Synthesis and Unexpected -Fragmentation of a Hindered -Keto Nitroxide
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH17203
Abstract: The attempted synthesis of a β-keto imidazolidinone nitroxide by oxidation of the β-hydroxy imidazolidinone precursor with hydrogen peroxide and sodium tungstate led to an unexpected ring-opening reaction to produce 1,4-diazaspiro[4.5]dec-1-en-3-oxo-2-pentanoic acid 1-oxide (13) in high yield. The structure of 13 was confirmed by X-ray crystallographic analysis. A β-fragmentation mechanism is suggested for the oxidative ring-opening reaction.
One pot synthesis of higher order quasi-block copolymer libraries via sequential RAFT polymerization in an automated synthesizer
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4PY00496E
Abstract: The utility of automated high-throughput methods for the one pot synthesis of functional polymers of increased complexity is reported.
CHAIN TRANSFER ACTIVITY OF SOME ACTIVATED ALLYLIC COMPOUNDS
Publisher: Springer Science and Business Media LLC
Date: 11-1990
DOI: 10.1007/BF00395571
RAFT polymerization: Adding to the picture
Publisher: Wiley
Date: 02-2007
Polymer Nanodiscs and Their Bioanalytical Potential
Publisher: Wiley
Date: 30-07-2021
Abstract: Membrane proteins (MPs) play a pivotal role in cellular function and are therefore predominant pharmaceutical targets. Although detailed understanding of MP structure and mechanistic activity is invaluable for rational drug design, challenges are associated with the purification and study of MPs. This review delves into the historical developments that became the prelude to currently available membrane mimetic technologies before shining a spotlight on polymer nanodiscs. These are soluble nanosized particles capable of encompassing MPs embedded in a phospholipid ring. The expanding range of reported hipathic polymer nanodisc materials is presented and discussed in terms of their tolerance to different solution conditions and their nanodisc properties. Finally, the analytical scope of polymer nanodiscs is considered in both the demonstration of basic nanodisc parameters as well as in the elucidation of structures, lipid–protein interactions, and the functional mechanisms of reconstituted membrane proteins. The final emphasis is given to the unique benefits and applications demonstrated for native nanodiscs accessed through a detergent free process.
Free radical initiation mechanisms in the polymerization of methyl methacrylate and styrene with 1,1,3,3-tetramethylbutyl peroxypivalate: Addition of neopentyl radicals
Publisher: American Chemical Society (ACS)
Date: 11-1997
DOI: 10.1021/JA972240T
Advances in switchable RAFT polymerization
Publisher: Wiley
Date: 04-2015
Alkoxyamine‐mediated “living” radical polymerization: MS investigation of the early stages of styrene polymerization initiated by cumyl‐TEISO
Publisher: Wiley
Date: 28-02-2001
DOI: 10.1002/POLA.1100
Sonochemical preparation of polymer–metal nanocomposites with catalytic and plasmonic properties
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1NA00120E
Abstract: Ultrasound is employed for in situ preparation of polymer–Au and polymer–Pd nanocomposites, which possess superior plasmonic properties and improved catalytic activities.
Effect of Cross-Link Density on Photoplasticity of Epoxide Networks Containing Allylic Dithioether Moieties
Publisher: American Chemical Society (ACS)
Date: 30-11-2012
DOI: 10.1021/MA301557Z
RAFT-mediated polymerization-induced self-assembly (RAFT-PISA): current status and future directions
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2SC00762B
Abstract: A review that summarizes recent advances in the emerging field of polymerization-induced self-assembly. Topics ranging from initiation processes, morphologies and complex functional materials to applications and future directions are covered.
Poly(: N -isopropylacrylamide) capped plasmonic nanoparticles as resonance intensity-based temperature sensors with linear correlation
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7TC04051B
Abstract: Under aggregation-free conditions, linear relationships between longitudinal plasmonic peak intensity and temperature have been revealed for poly( N -isopropylacrylamide)-capped gold nanorods and nanobipyramids.
INITIATION MECHANISMS IN RADICAL POLYMERIZATION - REACTION OF TERT-BUTOXY RADICALS WITH ALLYL METHACRYLATE
Publisher: CSIRO Publishing
Date: 1985
DOI: 10.1071/CH9850689
Abstract: The radical-trapping technique employing 1,1,3,3-tetramethylisoindolin- 2-yloxyl (1) as scavenger has been used to study the reactions of t-butoxy radicals with allyl methacrylate (2). Extensive hydrogen abstraction as well as addition to both allyl and acryloyl double bonds was observed. One unusual feature of the reaction, the formation of considerably more (Z)- alkene than (E)- alkene from trapping of radicals derived from the allyloxy moiety, is also discussed.
Facile synthesis of well-controlled poly(1-vinyl imidazole) by the RAFT process
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY00985G
Abstract: Synthesis of well-controlled poly(1-vinyl imidazole).
Temperature-responsive methacrylamide polyampholytes
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7RA04723A
Abstract: The effective modulation of polymer cloud points in water is demonstrated through a series of charged, temperature-responsive methacrylamide-based poly holytes.
Reaction of t-butoxy radicals with norbornadiene
Publisher: Elsevier BV
Date: 1985
Synthesis of Defined Polymers by Reversible Addition—Fragmentation Chain Transfer: The RAFT Process
Publisher: American Chemical Society
Date: 15-08-2000
Preparation of Macromonomers via Chain Transfer with and without Added Chain Transfer Agent
Publisher: American Chemical Society
Date: 15-08-2000
Reversible Addition Fragmentation Chain Transfer Polymerization of Methyl Methacrylate in the Presence of Lewis Acids: An Approach to Stereocontrolled Living Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 28-11-2007
DOI: 10.1021/MA071100T
Effect of solvents on the RAFT polymerization of N-(2-hydroxypropyl) methacrylamide
Publisher: Elsevier BV
Date: 06-2019
A facile synthesis of pH stimuli biocompatible block copolymer poly(methacrylic acid)-block-poly(N-vinylpyrrolidone) utilizing switchable RAFT agents
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9PY00110G
Abstract: Synthesis of block copolymer PMAA- b -PNVP utilizing switchable RAFT agents and its self-assembly.
Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFT Process
Publisher: American Chemical Society (ACS)
Date: 22-07-1998
DOI: 10.1021/MA9804951
Synthesis and fluorescence of a series of multichromophoric acenaphthenyl compounds
Publisher: American Chemical Society (ACS)
Date: 04-02-2005
DOI: 10.1021/JO047899D
Abstract: A novel free radical trapping reaction based on a stepwise radical reversible addition-fragmentation mechanism has been utilized to synthesize a series of acenaphthenyl dimers and trimers. The synthetic procedure involves the reaction of acenaphthylene with dithiobenzoate compounds (S=C(Ph)-SR) in the presence of a free radical initiator followed by reduction of the dithiobenzoyl end group with tributyltin hydride. Stereoisomers of the compounds have been isolated and their structures determined by proton NMR and X-ray crystallography. The solution fluorescence of the compounds has been characterized to reveal the requirements for intramolecular excimer (excited-state dimer) formation. Only in compounds containing identical stereochemical arrangements of adjacent acenaphthenyl groups is excimer fluorescence observed following photoexcitation.
Living Radical Polymerization by the RAFT Process - A Second Update
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH09311
Abstract: This paper provides a second update to the review of reversible deactivation radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition–fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379–410). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669–692). This review cites over 500 papers that appeared during the period mid-2006 to mid-2009 covering various aspects of RAFT polymerization ranging from reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses and a erse range of applications. Significant developments have occurred, particularly in the areas of novel RAFT agents, techniques for end-group removal and transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.
Living free radical polymerisation under a constant source of gamma radiation - An example of reversible addition-fragmentation chain transfer or reversible termination?
Publisher: Wiley
Date: 08-2002
DOI: 10.1002/1521-3927(20020801)23:12<717::AID-MARC717>3.0.CO;2-I
“All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 21-05-2021
Radical Addition-Fragmentation Chemistry and RAFT Polymerization
Publisher: Elsevier
Date: 2012
Nanoparticle Surface Cross-Linking: A Universal Strategy to Enhance the Mechanical Properties of Latex Films
Publisher: American Chemical Society (ACS)
Date: 29-06-2022
CHAIN TRANSFER BY RADICAL ADDITION-FRAGMENTATION MECHANISMS - SYNTHESIS OF MACROMONOMERS AND END-FUNCTIONAL OLIGOMERS
Publisher: Wiley
Date: 07-1995
Polymerization-Induced Self-Assembly (PISA) and host-Guest Complexation-Directed Polymer/Gold Nanocomposites
Publisher: American Chemical Society (ACS)
Date: 06-04-2020
Living Radical Polymerization by the RAFT Process
Publisher: CSIRO Publishing
Date: 2005
DOI: 10.1071/CH05072
Abstract: This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.
Aggregation-Induced Emission Polymers via Reversible-Deactivation Radical Polymerization
Publisher: Authorea, Inc.
Date: 20-04-2023
DOI: 10.22541/AU.168202998.89799739/V1
Abstract: Aggregation-Induced Emission (AIE) is a unique phenomenon whereby aggregation of molecules induces fluorescence emission as opposed to the more commonly known Aggregation-Caused Quenching (ACQ). AIE has the potential to be utilized in the large-scale production of AIE-active polymeric materials because of their wide range of practical applications such as stimuli-responsive sensors, biological imaging agents, and drug delivery systems. This is evident from the increasing number of publications over the years since AIE was first discovered. In addition, the ever-growing interest in this field has led many researchers around the world to develop new and creative methods in the design of monomers, initiators and crosslinkers, with the goal of broadening the scope and utility of AIE polymers. One of the most promising approaches to the design and synthesis of AIE polymers is the use of the Reversible-Deactivation Radical Polymerization (RDRP) techniques, which enabled the production of well-controlled AIE materials that are often difficult to achieve by other methods. In this review, a summary of some recent works that utilize RDRP for AIE polymer design and synthesis is presented, including (1) the design of AIE-related monomers, initiators/crosslinkers the achievements in preparation of AIE polymers using (2) Reversible Addition-Fragmentation Chain Transfer (RAFT) technique (3) Atom Transfer Radical Polymerization (ATRP) technique (4) other techniques such as Cu(0)-RDRP technique and Nitroxide-Mediated Polymerization (NMP) technique (5) the possible applications of these AIE polymers and finally (6) a summary erspective and the future direction of AIE polymers.
Synthesis of novel architectures by radical polymerization with reversible addition fragmentation chain transfer (RAFT polymerization)
Publisher: Wiley
Date: 03-2003
RAFT Polymerization: Materials of The Future, Science of Today: Radical Polymerization - The Next Stage
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH09549
RAFT‐Derived Polymer–Drug Conjugates: Poly(hydroxypropyl methacrylamide) (HPMA)–7‐Ethyl‐10‐hydroxycamptothecin (SN‐38) Conjugates
Publisher: Wiley
Date: 05-12-2011
Abstract: A series of well-defined polymer-drug conjugates were prepared in order to modify the physical properties of a known cytotoxic drug, 7-ethyl-10-hydroxyc tothecin (SN-38), the active metabolite of irinotecan (CPT-11). Reversible addition-fragmentation chain transfer (RAFT) polymerisation was used to covalently and site-specifically append a defined N-(2-hydroxypropyl)methacrylamide (HPMA) polymer to SN-38 using a graft-from process. These poly-HPMA-SN-38 conjugates displayed excellent aqueous solubility and stability, whilst retaining the cytotoxic activity of the parent SN-38. In vitro co-culture assays containing both cancer and noncancer cell lines demonstrated the specificity of RAFT-derived poly-HPMA-SN-38 conjugates for cancerous cells. The concept of post-optimisation modification of small-molecule drugs through a graft-from polymer conjugation method is introduced.
Novel Amphiphilic Block Copolymers for the Formation of Stimuli-Responsive Non-Lamellar Lipid Nanoparticles
Publisher: MDPI AG
Date: 15-06-2021
DOI: 10.3390/MOLECULES26123648
Abstract: Non-lamellar lyotropic liquid crystalline (LLC) lipid nanoparticles contain internal multidimensional nanostructures such as the inverse bicontinuous cubic and the inverse hexagonal mesophases, which can respond to external stimuli and have the potential of controlling drug release. To date, the internal LLC mesophase responsiveness of these lipid nanoparticles is largely achieved by adding ionizable small molecules to the parent lipid such as monoolein (MO), the mixture of which is then dispersed into nanoparticle suspensions by commercially available poly(ethylene oxide)–poly(propylene oxide) block copolymers. In this study, the Reversible Addition-Fragmentation chain Transfer (RAFT) technique was used to synthesize a series of novel hiphilic block copolymers (ABCs) containing a hydrophilic poly(ethylene glycol) (PEG) block, a hydrophobic block and one or two responsive blocks, i.e., poly(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl acrylate) (PTBA) and/or poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA). High throughput small angle X-ray scattering studies demonstrated that the synthesized ABCs could simultaneously stabilize a range of LLC MO nanoparticles (vesicles, cubosomes, hexosomes, inverse micelles) and provide internal particle nanostructure responsiveness to changes of hydrogen peroxide (H2O2) concentrations, pH and temperature. It was found that the novel functional ABCs can substitute for the commercial polymer stabilizer and the ionizable additive in the formation of next generation non-lamellar lipid nanoparticles. These novel formulations have the potential to control drug release in the tumor microenvironment with endogenous H2O2 and acidic pH conditions.
Room temperature synthesis of block copolymer nano-objects with different morphologies: via ultrasound initiated RAFT polymerization-induced self-assembly (sono-RAFT-PISA)
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY00461H
Abstract: The first room temperature synthesis of diblock copolymer nano-objects with different morphologies using ultrasound (990 kHz) initiated reversible addition-fragmentation chain transfer PISA (sono-RAFT-PISA) in aqueous system.
Enhanced energy transfer efficiency in star-shaped light-harvesting block copolymers prepared by RAFT polymerization
Publisher: Wiley
Date: 02-2006
INITIATION MECHANISMS IN RADICAL POLYMERIZATION - REACTION OF ISOPROPOXYL RADICALS WITH METHYL-METHACRYLATE
Publisher: Royal Society of Chemistry (RSC)
Date: 1991
DOI: 10.1039/P19910001351
Functionalization of liquid metal nanoparticles: Via the RAFT process
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1PY00257K
Abstract: The proper design and selection of RAFT agents allow the preparation of eutectic gallium–indium (EGaIn) based liquid metal nanoparticles with grafted polymers.
The application of a novel profluorescent nitroxide to monitor thermo-oxidative degradation of polypropylene
Publisher: Elsevier BV
Date: 09-2005
An arm-first approach to cleavable mikto-arm star polymers by RAFT polymerization
Publisher: Wiley
Date: 06-02-2014
Abstract: Redox-cleavable mikto-arm star polymers are prepared by an "arm-first" approach involving copolymerization of a dimethacrylate mediated by a mixture of macroRAFT agents. Thus, RAFT copolymerization of the monomers BMA, DMAEMA, and OEGMA, with the disulfide dimethacrylate cross-linker (DSDMA), bis(2-methacryloyl)oxyethyl disulfide, mediated by a 1:1:1 mixture of three macroRAFT agents with markedly different properties [hydrophilic, poly[oligo(ethylene glycol) methacrylate]-P(OEGMA)8-9 cationizable, poly[2-(dimethylamino)ethyl methacrylate]-P(DMAEMA) hydrophobic, poly(n-butyl methacrylate)-P(BMA)] provides low dispersity mikto-arm star polymers. Good control (Đ < 1.3) is observed for the target P(DMAEMA)/P(OEGMA)/P(BMA) (3:3:1) mikto-arm star, a double hydrophilic P(DMAEMA)/P(OEGMA) (3:3) mikto-arm star and a hydrophobic P(BMA) homo-arm star. However, Đ for the target mikto-arm stars increases with an increase in either the ratio [DSDMA]:[total macroRAFT] or the fraction of hydrophobic P(BMA) macroRAFT agent. The quaternized mikto-arm star in dilute aqueous solution shows a monomodal particle size distribution and an average size of ≈145 nm.
The reactivity of nitroxides towards alkenes
Publisher: Elsevier BV
Date: 05-2000
Living Polymers by the Use of Trithiocarbonates as Reversible Addition−Fragmentation Chain Transfer (RAFT) Agents: ABA Triblock Copolymers by Radical Polymerization in Two Steps
Publisher: American Chemical Society (ACS)
Date: 2000
DOI: 10.1021/MA991451A
Binary copolymerization with catalytic chain transfer. A method for synthesizing macromonomers based on monosubstituted monomers
Publisher: American Chemical Society (ACS)
Date: 04-10-2005
DOI: 10.1021/MA0501949
Advances in RAFT polymerization: the synthesis of polymers with defined end-groups
Publisher: Elsevier BV
Date: 09-2005
Derivatives of sucrose 3′,4′-epoxide
Publisher: Elsevier BV
Date: 09-1983
Living radical polymerization by the RAFT process a third update
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH12295
Abstract: This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a erse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.
Machine learning based temperature prediction of poly(: N -isopropylacrylamide)-capped plasmonic nanoparticle solutions
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CP04544A
Abstract: Machine learning techniques can predict the solution temperature of thermosensitive polymer-capped nanoparticle solutions to within 1 °C of accuracy.
Mechanism and Kinetics of RAFT-Based Living Radical Polymerizations of Styrene and Methyl Methacrylate
Publisher: American Chemical Society (ACS)
Date: 2001
DOI: 10.1021/MA0009451
RAFT agent design and synthesis
Publisher: American Chemical Society (ACS)
Date: 21-05-2012
DOI: 10.1021/MA300410V
Continuous Flow Aminolysis of RAFT Polymers Using Multistep Processing and Inline Analysis
Publisher: American Chemical Society (ACS)
Date: 24-11-2014
DOI: 10.1021/MA501628F
Polystyrene-block-poly(vinyl acetate) through the Use of a Switchable RAFT Agent
Publisher: American Chemical Society (ACS)
Date: 16-11-2009
DOI: 10.1021/MA9021086
Combinatorial Discovery of Novel Amphiphilic Polymers for the Phase Transfer of Magnetic Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 31-08-2009
DOI: 10.1021/JP904846E
Synthesis, self-assembly, and base-pairing of nucleobase end-functionalized block copolymers in aqueous solution
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8PY01201F
Abstract: As a novel strategy, nucleobase-containing copolymers are created for molecular recognition and nucleobase releasing.
Functional polymers for optoelectronic applications by RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0PY00179A
Chain Transfer to Polymer: A Convenient Route to Macromonomers
Publisher: American Chemical Society (ACS)
Date: 06-10-1999
DOI: 10.1021/MA990488S
A fluorescence strategy for direct quantification of arm components in mikto-arm star copolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1PY01656C
Abstract: The arm components of mikto-arm star polymers were quantitatively analyzed with a novel fluorescence strategy.
Amphiphilic acenaphthylene-maleic acid light-harvesting alternating copolymers: Reversible addition - Fragmentation chain transfer synthesis and fluorescence
Publisher: American Chemical Society (ACS)
Date: 16-03-2005
DOI: 10.1021/MA047361+
Formation of 3′,6′-anhydrosucrose by Mitsunobu dehydration of sucrose
Publisher: Elsevier BV
Date: 05-1988
Reversible Addition–Fragmentation Chain Transfer Polymerization
Publisher: Wiley
Date: 2009
DOI: 10.1002/0471440264.PST564
Abstract: This article reviews the mechanistic and practical aspects of free radical polymerization with reversible addition–fragmentation chain transfer—the reversible addition–fragmentation chain transfer (RAFT) process. RAFT is conducted by the addition of a thiocarbonylthio compound (ZC(S)SR) to a conventional radical polymerization. Suitable RAFT agents include dithioesters, trithiocarbonates, dithiocarbamates, and xanthates. These thiocarbonylthio compounds confer living characteristics to the radical polymerization by a mechanism of reversible addition–fragmentation chain transfer and provide exceptional control over molecular weight, molecular weight distribution, composition, and architecture of the resulting polymers. The process can be applied to most monomers polymerizable by radical polymerization and offers a convenient route to well‐defined homo‐, gradient, diblock, triblock, and star polymers as well as more complex architectures including microgels and polymer brushes.
Polymer Synthesis with More Than One Form of Living Polymerization Method
Publisher: Wiley
Date: 20-09-2018
Abstract: Controlled radical polymerization (CRP) or controlled/living radical polymerization has revolutionized the polymer industry as a tool for the preparation of a wide variety of polymers. This process enables the preparation of polymers with good control of molecular weight, narrow polydispersity, and a range of architectures including block and graft copolymers, star polymers, and other functional polymers. The mechanistic transformation reaction provides a great opportunity to tune chemical and physical properties of copolymers. It can be applied to combine different homopolymers using post-modification techniques or by the use of a dual initiator, allowing the combination of mechanistically distinct polymerization reactions. This review will cover CRP transformations including the synthesis of block copolymers with both linear structures (AB, ABA, (AB)
Multi-responsive (diethylene glycol)methyl ether methacrylate (DEGMA)-based copolymer systems
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6RA14425J
Abstract: RAFT polymerisation was used to synthesise stimuli-responsive DEGMA-based copolymer systems, and their solution properties and aggregation behaviour were then studied.
Initiation mechanisms for radical polymerization of styrene and methyl methacrylate with highly substituted peroxypivalate initiators
Publisher: Elsevier BV
Date: 03-1999
Core Degradable Star RAFT Polymers: Synthesis, Polymerization, and Degradation Studies
Publisher: American Chemical Society (ACS)
Date: 21-11-2013
DOI: 10.1021/MA402122Z
Photoluminescent polymer cubosomes prepared by RAFT-mediated polymerization-induced self-assembly
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2PY00701K
Abstract: The preparation of photoluminescent polymer assemblies with a wide range of morphologies, including spongosomes and cubosomes, via an efficient RAFT-mediated polymerization-induced self-assembly (RAFT-PISA) process, was demonstrated.
Radical addition–fragmentation chemistry in polymer synthesis
Publisher: Elsevier BV
Date: 03-2008
INITIATION MECHANISMS IN RADICAL POLYMERIZATION - REACTION OF TERT-BUTOXY RADICALS WITH ALLYL ACRYLATE AND WITH DIALLYL ETHER
Publisher: Royal Society of Chemistry (RSC)
Date: 1988
DOI: 10.1039/P19880000485
Glycosylated Reversible Addition-Fragmentation Chain Transfer Polymers with Varying Polyethylene Glycol Linkers Produce Different Short Interfering RNA Uptake, Gene Silencing, and Toxicity Profiles.
Publisher: American Chemical Society (ACS)
Date: 09-11-2017
DOI: 10.1021/ACS.BIOMAC.7B01168
Abstract: Achieving efficient and targeted delivery of short interfering (siRNA) is an important research challenge to overcome to render highly promising siRNA therapies clinically successful. Challenges exist in designing synthetic carriers for these RNAi constructs that provide protection against serum degradation, extended blood retention times, effective cellular uptake through a variety of uptake mechanisms, endosomal escape, and efficient cargo release. These challenges have resulted in a significant body of research and led to many important findings about the chemical composition and structural layout of the delivery vector for optimal gene silencing. The challenge of targeted delivery vectors remains, and strategies to take advantage of nature's self-selective cellular uptake mechanisms for specific organ cells, such as the liver, have enabled researchers to step closer to achieving this goal. In this work, we report the design, synthesis, and biological evaluation of a novel polymeric delivery vector incorporating galactose moieties to target hepatic cells through clathrin-mediated endocytosis at asialoglycoprotein receptors. An investigation into the density of carbohydrate functionality and its distance from the polymer backbone is conducted using reversible addition-fragmentation chain transfer polymerization and postpolymerization modification.
Synthesis of Acyclic, Symmetrical 3,3'-Allyl Dithioethers, from the Alkylation of 3-Mercapto-2-mercaptomethylprop-1-ene in the Presence of Sodium Hydride
Publisher: CSIRO Publishing
Date: 2011
DOI: 10.1071/CH11117
Abstract: A novel method where 3,3′-allyl dithioethers have been prepared from 3-mercapto-2-mercaptomethylprop-1-ene and two mol equivalent of alkyl halide in the presence of two mol equivalent of sodium hydride has been developed. Using this method, bisepoxide, 2,2′-(2-methylenepropane-1,3-diyl)bis(sulfanediyl)bis(methylene)dioxirane (8) has been synthesized from epichlorohydrin, whereas potassium carbonate was unable to deliver this product. These 3,3′-allyl dithioethers can be utilized either as monomers, or with further chemical reactions transformed into more complex monomers, for photoplastic polymer networks.
Living Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT Polymerization) Using Dithiocarbamates as Chain Transfer Agents
Publisher: American Chemical Society (ACS)
Date: 24-09-1999
DOI: 10.1021/MA9906837
A New Double-Responsive Block Copolymer Synthesized via RAFT Polymerization: Poly(N-isopropylacrylamide)-block-poly(acrylic acid)
Publisher: American Chemical Society (ACS)
Date: 21-09-2004
DOI: 10.1021/MA035838W
New Free-Radical Ring-Opening Acrylate Monomers
Publisher: American Chemical Society (ACS)
Date: 12-1994
DOI: 10.1021/MA00104A062
THE STRUCTURES OF THE FREE-RADICAL SCAVENGER 1,1,3,3-TETRAMETHYLISOINDOLIN-2-YLOXYL, AND OF THE ALKOXY AMINE DERIVATIVE 5-(1,1,3,3-TETRAMETHYLISOINDOLIN-2-YLOXY)-1-VINYLPYRROLIDIN-2-ONE
Publisher: CSIRO Publishing
Date: 1986
DOI: 10.1071/CH9860357
Abstract: The structures of the title nitroxide , C12H16NO (1), and the alkoxy amine derivative, C18H24N2O2 (2), have been determined by single-crystal X-ray structural analyses. Crystals of (1) are monoclinic, space group Cc with a 11.585(6), b 11.697(10), c 16.753(8)Ǻ, β 94.33(6)°, Z 8 R was 0.064 for 1226 independent reflections. The -C(NO)C- group is essentially planar (sum trigonal angles 359.9, 359.9°, as is the five- membered ring. The N-O distances are 1.249(6), 1.252(8)Ǻ. Crystals of (2) are monoclinic, space group P21/c, a 8.295(2), b 13.567(5), c 15.294(3)Ǻ, β 98.82(2)°, Z 4 R was 0.051 for 1445 independent reflections. By contrast to (1) the geometry about the nitrogen atom is pyramidal (sum trigonal angles 328°), and the corresponding five-membered ring has an envelope conformation with a nitrogen displacement of 0.45Ǻ. The N-O distance is 1.439(4)Ǻ. The high-resolution solid state 13C n.m.r . spectrum of (2) is discussed in relation to the X-ray structure.
Reaction of tert-alkoxyl and alkyl radicals with styrene studied by the nitroxide radical-trapping technique
Publisher: American Chemical Society (ACS)
Date: 08-1997
DOI: 10.1021/JO9707489
Thiocarbonylthio Compounds [SC(Ph)S−R] in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Role of the Free-Radical Leaving Group (R)
Publisher: American Chemical Society (ACS)
Date: 15-03-2003
DOI: 10.1021/MA020882H
Living Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT): Direct ESR Observation of Intermediate Radicals
Publisher: American Chemical Society (ACS)
Date: 22-07-1999
DOI: 10.1021/MA990316V
Inhibition of influenza virus in vivo by siRNA delivered using ABA triblock copolymer synthesized by reversible addition-fragmentation chain-transfer polymerization
Publisher: Future Medicine Ltd
Date: 06-2014
DOI: 10.2217/NNM.13.119
Abstract: Aim: Influenza virus remains a major threat, with outbreaks continuing to occur. Few treatment options are available and drug resistance can emerge rapidly. New drugs that can quickly be adapted to virus mutations are needed. Several highly effective siRNAs targeting influenza that inhibit virus replication are known however, effective delivery of these siRNAs remains a challenge. The aim of this study was to demonstrate the safety and efficacy of ABA triblock copolymer-delivered siRNA to inhibit influenza virus replication in vivo. Materials & methods: We report on the delivery of a siRNA targeting the influenza virus in chicken embryos using an ABA triblock copolymer prepared by reversible addition-fragmentation chain-transfer polymerization, containing a central cationic block and two outer hydrophilic polyethylene glycol blocks. Results: A significant reduction of virus titer was observed with the polymer/anti-influenza siRNA complexes, whereas the control with polymer/control siRNA complexes showed no effect. Conclusion: These data suggest that a reversible addition-fragmentation chain transfer-based siRNA delivery platform may be suitable for combating infectious diseases in vivo. Original submitted 21 December 2012 Revised submitted 10 May 2013
Thiocarbonylthio Compounds (SC(Z)S−R) in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Effect of the Activating Group Z
Publisher: American Chemical Society (ACS)
Date: 15-03-2003
DOI: 10.1021/MA020883+
The mechanism of initiation in the free radical polymerization of N-vinylcarbazole and N-vinylpyrrolidone
Publisher: Elsevier BV
Date: 1989
Controlled synthesis of luminescent polymers using a bis-dithiobenzoate RAFT agent
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B716471H
Abstract: A higher efficiency of excitation energy transfer occurs to a luminescent diphenylanthracenyl acceptor incorporated at the centre, rather than the end, of an acenaphthylene polymer chain.
Controlled growth free radical polymerization of methacrylate esters-reversible chain transfer vs. reversible termination
Publisher: American Chemical Society
Date: 08-01-1998
Asymmetric Aldol Reaction on Water Using an Organocatalyst Tethered on a Thermoresponsive Block Copolymer
Publisher: The Chemical Society of Japan
Date: 05-12-2013
DOI: 10.1246/CL.130711
Substituent effects on RAFT polymerization with benzyl aryl trithiocarbonates
Publisher: Wiley
Date: 26-02-2010
Gas‐Responsive Self‐Assemblies for Mimicking the Alveoli
Publisher: Wiley
Date: 14-03-2021
Abstract: In human body, alveoli are the primary sites for gas exchange which are formed by the dilation and protrusion of bronchioles at the end of the lung, and the rapid gas‐exchanging process in the alveoli ensures normal life activities. Based on the unique structures and functions of alveoli, it is necessary to study the regulation mechanism of its formation, respiration, and apoptosis. Herein, a class of reversible addition−fragmentation chain transfer (RAFT)‐derived hiphilic triblock copolymers, PEO‐ b ‐P(DEAEMA‐ co ‐FMA)‐ b ‐PS is designed and synthesized. Due to the hiphilic and gas‐responsive segments, these triblock copolymers can self‐assemble in aqueous solution and undergo the morphological transition from nanotubes to vesicles under gas stimulation meanwhile, in the cycles of CO 2 /O 2 stimulation, these vesicles can further realize the volume expansion and contraction, eventually rupture. The gas‐driven morphological transformations of these aggregates successfully imitate the formation, respiration, and apoptosis of alveoli, and provide an essential basis for revealing the life phenomena.
Tailored amphiphilic star-shaped light-harvesting copolymers
Publisher: Wiley
Date: 05-12-2006
DOI: 10.1002/PI.1911
Bifunctional RAFT Agent Directed Preparation of Polymer/Graphene Oxide Composites
Publisher: Wiley
Date: 20-09-2021
Abstract: Polymer/graphene oxide (GO) composites, which combine the physical properties of GO and the processability of polymers, are of increasing interest in a variety of applications ranging from conductive foams, sensors, to bioelectronics. However, the preparation of these composites through physical blending demands the polymers with functional groups that interact strongly with the GO. Here the design and synthesis of a new bifunctional reversible addition–fragmentation chain transfer (RAFT) agent are demonstrated, which allows the synthesis of polymers with predetermined molecular weights and low dispersibilities ( Ð ), while having functionalities at both polymer termini that allow strong binding to GO. To access polymers with erse thermal and mechanical properties, acrylonitrile–styrene–acrylate (ASA) copolymers with different types of acrylates, both short and long side chains, are synthesized under the control of the bifunctional RAFT agent. Furthermore, the strong binding between GO and the synthesized polymers is verified and explored to prepare polymer/GO composites with erse tensile strengths and conductivity in the range of semiconductors. Overall, this novel RAFT agent is expected to expand the utility of polymer/GO composites by providing well‐defined polymers with tunable properties and strong binding with GO.
Effect of end-groups on sulfobetaine homopolymers with the tunable upper critical solution temperature (UCST)
Publisher: Elsevier BV
Date: 06-2020
Polymerization-Induced Hierarchical Self-Assembly: From Monomer to Complex Colloidal Molecules and Beyond
Publisher: American Chemical Society (ACS)
Date: 10-08-2021
Abstract: The nanoscale hierarchical design that draws inspiration from nature's biomaterials allows the enhancement of material performance and enables multifarious applications. Self-assembly of block copolymers represents one of these artificial techniques that provide an elegant bottom-up strategy for the synthesis of soft colloidal hierarchies. Fast-growing polymerization-induced self-assembly (PISA) renders a one-step process for the polymer synthesis and
A novel synthesis of functional dithioesters, dithiocarbamates, xanthates and trithiocarbonates
Publisher: Elsevier BV
Date: 03-1999
Chain Transfer Activity of ω-Unsaturated Methyl Methacrylate Oligomers
Publisher: American Chemical Society (ACS)
Date: 1996
DOI: 10.1021/MA960852C
Aggregation‐induced emission polymers via reversible‐deactivation radical polymerization
Publisher: Wiley
Date: 06-09-2023
DOI: 10.1002/AGT2.414
Imidazolidinone Nitroxide-Mediated Polymerization
Publisher: American Chemical Society (ACS)
Date: 10-1999
DOI: 10.1021/MA9904868
RAFT polymerization of a RGD peptide-based methacrylamide monomer for cell adhesion
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7PY01887H
Abstract: The present study provides a robust method for the preparation of RGD peptide-based polymers that has important implications in the synthesized biomaterials that support cell adhesion.
Synthesis of some thiosucrose derivatives
Publisher: CSIRO Publishing
Date: 1984
DOI: 10.1071/CH9841925
Abstract: Treatment of 3,3',4',6'-tetra-O-acetylsucrose in dimethylformamide with thioacetic acid, triphenyl- phosphine and diethyl azodicarboxylate, followed by acetylation, gave 6-thiosucrose octaacetate in good yield. Similar treatment of 4,6:2,1'-di-O-isopropylidenesucrose followed by removal of the isopropylidene groups and acetylation gave 6'-thiosucrose octaacetate. Treatment of sucrose itself under these conditions gave 6,6'-dithiosucrose octaacetate. 6,6'-Dithiosucrose octaacetate was readily converted into 6,6'-dideoxysucrose by treatment with Raney nickel followed by deacetylation.
Synthesis of functional miktoarm star polymers in an automated parallel synthesizer
Publisher: Elsevier BV
Date: 11-2021
Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06229
Abstract: Thermolysis provides a simple and efficient way of eliminating thiocarbonylthio groups from RAFT-synthesized polymers. The course of thermolysis of poly(methyl methacrylate) (PMMA) prepared with dithiobenzoate and trithiocarbonate RAFT agents was followed by thermogravimetric analysis (TGA), 1H NMR spectroscopy, and gel permeation chromatography (GPC). The weight loss profile observed depends strongly on the RAFT agent used during polymer synthesis. PMMA with a methyl trithiocarbonate end group undergoes loss of that end group at ~180°C, at least in part, by a mechanism believed to involve homolysis of the C–CS2SCH3 bond and subsequent depropagation. In contrast, PMMA with a dithiobenzoate end appears more stable. Only the end group is lost at ~180°C and the dominant mechanism is proposed to be a concerted elimination process analogous to that involved in the Chugaev reaction.
Block copolymer synthesis through the use of switchable RAFT agents
Publisher: American Chemical Society
Date: 2011
Initiation mechanisms for radical polymerization of methyl methacrylate with tert-butyl peroxypivalate
Publisher: American Chemical Society (ACS)
Date: 1996
DOI: 10.1021/JA962341B
Towards next generation high throughput ion exchange membranes for downstream bioprocessing: A review
Publisher: Elsevier BV
Date: 04-2022
Thiocarbonylthio End Group Removal from RAFT-Synthesized Polymers by Radical-Induced Reduction
Publisher: American Chemical Society (ACS)
Date: 22-05-2007
DOI: 10.1021/MA062919U
RAFT polymerization and some of its applications
Publisher: Wiley
Date: 18-04-2013
Abstract: Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents.
Tailored polymers by free radical processes
Publisher: Wiley
Date: 08-1999
The effect of RAFT-derived cationic block copolymer structure on gene silencing efficiency
Publisher: Elsevier BV
Date: 10-2012
DOI: 10.1016/J.BIOMATERIALS.2012.06.090
Abstract: In this work a series of ABA tri-block copolymers was prepared from oligo(ethylene glycol) methyl ether methacrylate (OEGMA(475)) and N,N-dimethylaminoethyl methacrylate (DMAEMA) to investigate the effect of polymer composition on cell viability, siRNA uptake, serum stability and gene silencing. Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization was used as the method of polymer synthesis as this technique allows the preparation of well-defined block copolymers with low polydispersity. Eight block copolymers were prepared by systematically varying the central cationic block (DMAEMA) length from 38 to 192 monomer units and the outer hydrophilic block (OEGMA(475)) from 7 to 69 units. The polymers were characterized using size exclusion chromatography and (1)H NMR. Chinese Hamster Ovary-GFP and Human Embryonic Kidney 293 cells were used to assay cell viability while the efficiency of block copolymers to complex with siRNA was evaluated by agarose gel electrophoresis. The ability of the polymer-siRNA complexes to enter into cells and to silence the targeted reporter gene enhanced green fluorescent protein (EGFP) was measured by using a CHO-GFP silencing assay. The length of the central cationic block appears to be the key structural parameter that has a significant effect on cell viability and gene silencing efficiency with block lengths of 110-120 monomer units being the optimum. The ABA block copolymer architecture is also critical with the outer hydrophilic blocks contributing to serum stability and overall efficiency of the polymer as a delivery system.
RAFT Polymer-Based Surfactants for Minerals Recovery
Publisher: American Chemical Society (ACS)
Date: 18-10-2023
Chain Transfer Kinetics of Acid/Base Switchable N-Aryl-N-Pyridyl Dithiocarbamate RAFT Agents in Methyl Acrylate, N-Vinylcarbazole and Vinyl Acetate Polymerization
Publisher: American Chemical Society (ACS)
Date: 14-05-2012
DOI: 10.1021/MA300616G
Syntheses and effectiveness of functional peptide-based RAFT agents
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC05316A
Abstract: These functional peptide-based RAFT agents provide researchers a straightforward access to complex bioconjugates for biomedical applications.
Toward Living Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 14-08-2008
DOI: 10.1021/AR800075N
Abstract: Radical polymerization is one of the most widely used processes for the commercial production of high-molecular-weight polymers. The main factors responsible for the preeminent position of radical polymerization are the ability to polymerize a wide array of monomers, tolerance of unprotected functionality in monomer and solvent, and compatibility with a variety of reaction conditions. Radical polymerization is simple to implement and inexpensive in relation to competitive technologies. However, conventional radical polymerization severely limits the degree of control that researchers can assert over molecular-weight distribution, copolymer composition, and macromolecular architecture. This Account focuses on nitroxide-mediated polymerization (NMP) and polymerization with reversible addition-fragmentation chain transfer (RAFT), two of the more successful approaches for controlling radical polymerization. These processes illustrate two distinct mechanisms for conferring living characteristics on radical polymerization: reversible deactivation (in NMP) and reversible or degenerate chain transfer (in RAFT). We devised NMP in the early 1980s and have exploited this method extensively for the synthesis of styrenic and acrylic polymers. The technique has undergone significant evolution since that time. New nitroxides have led to faster polymerization rates at lower temperatures. However, NMP is only applicable to a restricted range of monomers. RAFT was also developed at CSIRO and has proven both more robust and more versatile. It is applicable to the majority of monomers subject to radical polymerization, but the success of the polymerization depends upon the selection of the RAFT agent for the monomers and reaction conditions. We and other groups have proposed guidelines for selection, and the polymerization of most monomers can be well-controlled to provide minimal retardation and a high fraction of living chains by using one of just two RAFT agents. For ex le, a tertiary cyanoalkyl trithiocarbonate is suited to (meth)acrylate, (meth)acrylamide, and styrenic monomers, while a cyanomethyl xanthate or dithiocarbamate works with vinyl monomers, such as vinyl acetate or N-vinylpyrrolidone. With the appropriate choice of reagents and polymerization conditions, these reactions possess most of the attributes of living polymerization. We have used these methods in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, including microgels and polymer brushes. Applications of these polymers include novel surfactants, dispersants, coatings and adhesives, biomaterials, membranes, drug-delivery media, electroactive materials, and other nanomaterials.
RAFT Copolymerization and Its Application to the Synthesis of Novel Dispersants—Intercalants—Exfoliants for Polymer—Clay Nanocomposites
Publisher: American Chemical Society
Date: 07-09-2006
Membrane interaction and selectivity of novel alternating cationic lipid-nanodisc assembling polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3BM00477E
Abstract: The polymer–lipid nanodisc forming ability of a novel class of hipathic copolymer comprised of an alternating sequence was established. Selective membrane disruption was shown to be tuneable in relation to polymer hydrophobicity.
Synthesis of light harvesting polymers by RAFT methods
Publisher: Royal Society of Chemistry (RSC)
Date: 11-09-2002
DOI: 10.1039/B206166J
Abstract: Polymers prepared by RAFT polymerisation containing acenaphthyl energy donors and a terminal anthryl energy acceptor have a narrow molecular weight distribution and exhibit excitation energy transfer efficiencies up to 70%.
End functionalised copolymers prepared by the addition–fragmentation chain transfer method: styrene/methacrylonitrile system
Publisher: Elsevier BV
Date: 06-2000
Molecular Weight Characterization of Poly(N-isopropylacrylamide) Prepared by Living Free-Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 09-08-2000
DOI: 10.1021/MA0003102
Comparing Gene Silencing and Physiochemical Properties in siRNA Bound Cationic Star-Polymer Complexes
Publisher: American Chemical Society (ACS)
Date: 03-11-2016
DOI: 10.1021/ACS.BIOMAC.6B01029
Abstract: The translation of siRNA into clinical therapies has been significantly delayed by issues surrounding the delivery of naked siRNA to target cells. Here we investigate siRNA delivery by cationic acrylic polymers developed by Reversible Addition-Fragmentation chain Transfer (RAFT) mediated free radical polymerization. We investigated cell uptake and gene silencing of a series of siRNA-star polymer complexes both in the presence and absence of a protein "corona". Using a multidisciplinary approach including quantitative nanoscale mechanical-atomic force microscopy, dynamic light scattering and nanoparticle tracking analysis we have characterized the nanoscale morphology, stiffness, and surface charge of the complexes with and without the protein corona. This is one of the first ex les of a comprehensive physiochemical analysis of siRNA-polymer complexes being performed alongside in vitro biological assays, allowing us to describe a set of desirable physical features of cationic polymer complexes that promote gene silencing. Multifaceted studies such as this will improve our understanding of structure-function relationships in nanotherapeutics, facilitating the rational design of polymer-mediated siRNA delivery systems for novel treatment strategies.
Advantage of using tert-hexyl peroxypivalate as an initiator for the polymerization of methyl methacrylate
Publisher: American Chemical Society (ACS)
Date: 1996
DOI: 10.1021/MA9611127
In Focus Emerging Polymer Technologies Summit (EPTS'16)
Publisher: Wiley
Date: 04-10-2017
DOI: 10.1002/PI.5456
Cell-Penetrating, Peptide-Based RAFT Agent for Constructing Penetration Enhancers
Publisher: American Chemical Society (ACS)
Date: 04-02-2020
DOI: 10.1021/ACSMACROLETT.9B00647
Abstract: Peptide-polymer conjugates represent a promising class of compounds that can be used to overcome some of the limitations associated with peptides intended for therapeutic and diagnostic applications. The efficient generation of well-defined peptide rotein-polymer conjugates can promote the development of the design and synthesis of functional drugs and gene delivery platforms. In this research, a sequence defined cell penetrating peptide (i.e., Transportan 10 (TP 10))-based chain transfer agent (TP-CTA) was designed and synthesized in an automated peptide synthesizer. Thereafter, hiphilic block copolymers poly[oligo(ethylene glycol) methyl ether acrylate]-
Degradable pH and redox dual responsive nanoparticles for efficient covalent drug delivery
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8PY01583J
Abstract: Hydrophobic drug paclitaxel was modified into a polymerizable monomer and subsequently copolymerized with pH-sensitive monomers and redox-sensitive disulfide-based cyclic monomers.
Covalent-Cross-Linked Plasmene Nanosheets
Publisher: American Chemical Society (ACS)
Date: 30-05-2019
Abstract: Thiol-polystyrene (SH-PS)-capped plasmonic nanoparticles can be fabricated into free-standing, one-nanoparticle-thick superlattice sheets (termed plasmene) based on physical entanglement between ligands, which, however, suffer from irreversible dissociation in organic solvents. To address this issue, we introduce coumarin-based photo-cross-linkable moieties to the SH-PS ligands to stabilize gold nanoparticles. Once cross-linked, the obtained plasmene nanosheets consisting of chemically locked nanoparticles can well maintain structural integrity in organic solvents. Particularly, arising from ligand-swelling-induced enlargement of the interparticle spacing, these plasmene nanosheets show significant optical responses to various solvents in a specific as well as reversible manner, which may offer an excellent material for solvent sensing and dynamic plasmonic display.
End-functional polymers, thiocarbonylthio group removal/transformation and reversible addition-fragmentation-chain transfer (RAFT) polymerization
Publisher: Wiley
Date: 23-12-2011
DOI: 10.1002/PI.2988
End‐functionalized copolymers prepared by the addition–fragmentation chain‐transfer method: Vinyl acetate/methacrylonitrile system
Publisher: Wiley
Date: 10-07-2001
DOI: 10.1002/POLA.1271
Selective Sulfonylating Agents
Publisher: CSIRO Publishing
Date: 1987
DOI: 10.1071/CH9872133
Abstract: A variety of bulky sulfonyl chlorides have been investigated as sulfonylating reagents for polyol systems in an endeavour to find a selective reagent that would also give rise to a reactive sulfonate ester group.
Synthesis of star-shaped polyzwitterions with adjustable UCST and fast responsiveness by a facile RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY00318B
Abstract: We describe crosslinking of polyzwitterions for the formation of novel star-shaped polymers with low polydispersities and dual-responsiveness using RAFT polymerization.
Thermal decomposition mechanisms of tert-alkyl peroxypivalates studied by the nitroxide radical trapping technique
Publisher: American Chemical Society (ACS)
Date: 16-12-2000
DOI: 10.1021/JO990680S
Abstract: The thermolysis of a series of tert-alkyl peroxypivalates 1 in cumene has been investigated by using the nitroxide radical-trapping technique. tert-Alkoxyl radicals generated from the thermolysis underwent the unimolecular reactions, beta-scission, and 1,5-H shift, competing with hydrogen abstraction from cumene. The absolute rate constants for beta-scission of tert-alkoxyl radicals, which vary over 4 orders of magnitude, indicate the vastly different behavior of alkoxyl radicals. However, the radical generation efficiencies of 1 varied only slightly, from 53 (R = Me) to 63% (R = Bu(t)()), supporting a mechanism involving concerted two-bond scission within the solvent cage to generate the tert-butyl radical, CO(2), and an alkoxyl radical. The thermolysis rate constants of tert-alkyl peroxypivalates 1 were influenced by both inductive and steric effects [Taft-Ingold equation, log(rel k(d)) = (0.97 +/- 0. 14)Sigmasigma - (0.31 +/- 0.04)SigmaE(s)(c), was obtained].
A CONVENIENT SYNTHESIS OF 1-ALKYL-4,4-DIMETHYL-1,4,5,6-TETRAHYDROPYRIDINES
Publisher: Informa UK Limited
Date: 09-1993
Initiation mechanisms in radical polymerization: Reaction of tert-alkyl peroxypivalates with methyl methacrylate
Publisher: American Chemical Society (ACS)
Date: 05-1997
DOI: 10.1021/MA9615765
Tailored polymer architectures by reversible addition-frasmentation chain transfer
Publisher: Wiley
Date: 09-2001
DOI: 10.1002/1521-3900(200109)174:1<209::AID-MASY209>3.0.CO;2-O
A CONVENIENT SYNTHESIS OF 4,6-DICHLORO-5-BENZYLTHIOPYRIMIDINE
Publisher: Informa UK Limited
Date: 09-1993
Paclitaxel-loaded cubosome lipid nanocarriers stabilised with pH and hydrogen peroxide-responsive steric stabilisers as drug delivery vehicles
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2TB01530G
Abstract: Responsive nanoparticle delivery systems hold great potential for next-generation chemotherapeutic treatment with reduced off-target side effects.
Enzyme Degassing for Oxygen-Sensitive Reactions in Open Vessels of an Automated Parallel Synthesizer: RAFT Polymerizations
Publisher: American Chemical Society (ACS)
Date: 09-09-2019
DOI: 10.1021/ACSCOMBSCI.9B00082
Abstract: An enzyme degassing method for oxygen-intolerant polymerizations was implemented in a commercially available automated parallel synthesizer and tested for reversible addition-fragmentation chain transfer (RAFT) polymerizations performed in open vessels. For this purpose, a recently reported methodology that employs the enzyme glucose oxidase (GOx) to deplete oxygen in reaction media was utilized. The effectiveness of this approach to perform unattended parallel polymerization reactions in open vessels was demonstrated by comparing experimental results to those obtained under similar experimental conditions but utilizing the common degassing method of sparging N
Fundamentals of RAFT polymerization
Publisher: The Royal Society of Chemistry
Date: 04-04-2013
DOI: 10.1039/9781849737425-00205
Abstract: This chapter sets out to describe the fundamental aspects of radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization). Following a description of the mechanism we describe aspects of the kinetics of RAFT polymerization, how to select a RAFT agent to achieve optimal control over polymer molecular weight, composition and architecture, and how to avoid side reactions which might lead to retardation or inhibition.
Thermoresponsive chiral plasmonic nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1NR08343K
Abstract: Poly( N -isopropylacrylamide) (PNIPAM) has been used to modify chiral plasmonic nanoparticles. The thermoresponsive studies reveal the impact of achiral dielectric nanoenvironment on chiral plasmonic responses.
Living Radical Polymerization by the RAFT Process—A First Update
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06250
Abstract: This paper provides a first update to the review of living radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of Reversible Addition–Fragmentation chain Transfer (RAFT) published in June 2005. The time since that publication has witnessed an increased rate of publication on the topic with the appearance of well over 200 papers covering various aspects of RAFT polymerization ranging over reagent synthesis and properties, kinetics, and mechanism of polymerization, novel polymer syntheses, and erse applications.
Living free radical polymerization with reversible addition - fragmentation chain transfer (the life of RAFT)
Publisher: Wiley
Date: 2000
DOI: 10.1002/1097-0126(200009)49:9<993::AID-PI506>3.0.CO;2-6
Thermo-Induced Self-Assembly of Responsive Poly(DMAEMA-b-DEGMA) Block Copolymers into Multi- and Unilamellar Vesicles
Publisher: American Chemical Society (ACS)
Date: 19-11-2012
DOI: 10.1021/MA301867H
USE OF SUBSTITUTED ALLYLIC SULFIDES TO PREPARE END-FUNCTIONAL POLYMERS OF CONTROLLED MOLECULAR-WEIGHT BY FREE-RADICAL POLYMERIZATION
Publisher: American Chemical Society (ACS)
Date: 06-1991
DOI: 10.1021/MA00012A033
Synthesis of CO2-responsive gradient copolymers by switchable RAFT polymerization and their controlled self-assembly
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY01109F
Abstract: Switchable RAFT agents, so-called because they can be reversibly switched by an acid/base stimulus to offer very good control over polymerization of both MAMs and LAMs, provide a route to prepare well-defined polyMAM- block -polyLAM copolymers.
End-functionalised copolymers prepared by the addition-fragmentation chain transfer method Styrene/methyl methacrylate system
Publisher: Elsevier BV
Date: 1999
RAFT Polymers: Novel Precursors for Polymer—Protein Conjugates
Publisher: American Chemical Society
Date: 26-06-2003
Mass spectra of isoindoline nitroxides
Publisher: Wiley
Date: 10-1988
A More Versatile Route to Block Copolymers and Other Polymers of Complex Architecture by Living Radical Polymerization: The RAFT Process
Publisher: American Chemical Society (ACS)
Date: 24-02-1999
DOI: 10.1021/MA981472P
Slow nitrogen inversion–N–O rotation in 2-alkoxy-1,1,3,3-tetramethylisoindolines
Publisher: Royal Society of Chemistry (RSC)
Date: 1985
DOI: 10.1039/C39850001249
Nonmigratory Poly(vinyl chloride)-block-polycaprolactone Plasticizers and Compatibilizers Prepared by Sequential RAFT and Ring-Opening Polymerization (RAFT-T̵-ROP)
Publisher: American Chemical Society (ACS)
Date: 11-02-2019
Synthesis of cleavable multi-functional mikto-arm star polymer by RAFT polymerization: Example of an anti-cancer drug 7-ethyl-10-hydroxycamptothecin (SN-38) as functional moiety
Publisher: Springer Science and Business Media LLC
Date: 05-06-2014
RAFT Polymerization in Bulk Monomer or in (Organic) Solution
Publisher: Wiley
Date: 23-01-2008
Kinetics and Mechanism of RAFT Polymerization
Publisher: American Chemical Society
Date: 26-06-2003
Facile Synthesis of CO2‐Responsive Nano‐Objects: Batch versus Semi‐Batch RAFT Copolymerization
Publisher: Wiley
Date: 26-04-2021
A novel organic peroxyester as an exclusive source of tert-butyl radicals
Publisher: The Chemical Society of Japan
Date: 11-1997
DOI: 10.1246/CL.1997.1093
RAFT synthesis of linear and star-shaped light harvesting polymers using di- and hexafunctional ruthenium polypyridine reagents
Publisher: Royal Society of Chemistry (RSC)
Date: 2003
DOI: 10.1039/B303576J
Thermal decomposition of 1-cyclohexyl-1-methylethyl peroxypivalate
Publisher: The Chemical Society of Japan
Date: 10-1998
DOI: 10.1246/CL.1998.965
Mechanisms of excimer formation in poly(acenaphthylene)
Publisher: CSIRO Publishing
Date: 2004
DOI: 10.1071/CH04087
Abstract: Excimer (excited state dimer) formation mechanisms in solution have been investigated for a series of acenaphthyl-containing compounds comprising dimers, higher oligomers, and a poly(acenaphthylene) (PAcN) homopolymer. Excimer fluorescence is observed only for dimers with a threo-diisotactic arrangement of the acenaphthyl groups indicating that interactions between nearest-neighbour chromophores are able to play a role in excimer formation in PAcN. An increase in excimer emission is observed with increasing chain length and attributed to additional excimer formation and energy migration processes.
Synthesis of multifunctional miktoarm star polymers via an RGD peptide-based RAFT agent
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8PY01355A
Abstract: A “grafting from” approach for facile access of multifunctional miktoarm star polymers containing peptide arms.
Triggered Degradable Colloidal Particles with Ordered Inverse Bicontinuous Cubic and Hexagonal Mesophases
Publisher: American Chemical Society (ACS)
Date: 03-2021
Control of polymer structure by chain transfer processes
Publisher: Wiley
Date: 12-1996
PREPARATION OF CONTROLLED MOLECULAR-WEIGHT, OLEFIN-TERMINATED POLYMERS BY FREE-RADICAL METHODS - CHAIN TRANSFER USING ALLYLIC SULFIDES
Publisher: American Chemical Society (ACS)
Date: 10-1988
DOI: 10.1021/MA00188A039
d-fructose derivatives modified at C-4 by direct displacementand by oxirane opening
Publisher: Elsevier BV
Date: 05-1982
Synthesis of functionalized RAFT agents for light harvesting macromolecules
Publisher: American Chemical Society (ACS)
Date: 25-06-2004
DOI: 10.1021/MA049037K
Conformational transitions and dynamics of thermal responsive poly(N-isopropylacrylamide) polymers as revealed by molecular simulation
Publisher: Elsevier BV
Date: 06-2014
Spindle-like and telophase-like self-assemblies mediated by complementary nucleobase molecular recognition
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8CC09923E
Abstract: Supramolecular nanoparticles based on complementary nucleobase interactions have aroused wide interest.
Radical Addition–Fragmentation Chemistry and RAFT Polymerization
Publisher: Elsevier
Date: 2016
Preparation of 1 : 1 alternating, nucleobase-containing copolymers for use in sequence-controlled polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4PY01247J
Abstract: Despite recent advances in template polymerization, control of repeat unit sequence requires further development. We describe herein the synthesis of StyThy- alt -MAh sequence-regulated copolymers.
Versatile Approach for Preparing PVC-Based Mikto-Arm Star Additives Based on RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 19-05-2020
Chain Transfer Activity of ω-Unsaturated Methacrylic Oligomers in Polymerizations of Methacrylic Monomers
Publisher: American Chemical Society (ACS)
Date: 18-05-2004
DOI: 10.1021/MA049813O
Improved stability of unsealed quasi-solid-state dye-sensitized solar cell using poly(3,4-ethylenedioxythiophene) film as layer electrolyte
Publisher: Trans Tech Publications, Ltd.
Date: 11-2011
DOI: 10.4028/WWW.SCIENTIFIC.NET/MSF.663-665.852
Abstract: Quasi-solid/solid polymer electrolytes have been the subject of extensive research for an alternative of liquid electrolyte for dye-sensitized solar cells (DSSCs) because of their advantages such as alleviated leakage, lower environmental impact and ease of device fabrication. In this work, the performance of the unsealed quasi-solid-state DSSCs based on composite poly (ethylene oxide) (PEO) electrolyte and N719 dye-sensitizer was examined on aging under atmospheric condition. The energy conversion efficiency of DSSC using the composite PEO electrolyte was 5.62 % under sun simulated light, AM 1.5 (100 mW cm-2) but gradually decreased to 0.95 % on aging for 90 days. An additional layer of poly(3,4-ethylenedioxythiophene) (PEDOT) electrolyte was incorporated with the composite polymer electrolyte for DSSC fabrication. The PEDOT layer was prepared by electrochemical polymerization of bis-ethylenedioxythiophene (bis-EDOT) and characterized by Raman spectroscopy and cyclic voltammetry. It was found that the energy conversion efficiency of DSSC based on the composite polymer electrolyte incorporated with PEDOT layer was 5.57 % and gradually decreased to 1.76 % under the same aging condition. Thus an additional layer of PEDOT electrolyte provided an improved stability of DSSC.
Frontispiece: Polymer Nanodiscs and Their Bioanalytical Potential
Publisher: Wiley
Date: 2021
Initiating free radical polymerization
Publisher: Wiley
Date: 06-2002
DOI: 10.1002/1521-3900(200206)182:1<65::AID-MASY65>3.0.CO;2-E
New Features of the Mechanism of RAFT Polymerization
Publisher: American Chemical Society
Date: 13-08-2009
Switchable reversible addition-fragmentation chain transfer (raft) polymerization in aqueous solution, n, n -dimethylacrylamide
Publisher: American Chemical Society (ACS)
Date: 15-08-2011
DOI: 10.1021/MA200760Q
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