Reversible addition–fragmentation chain transfer (RAFT) radical polymerization and the synthesis of water-soluble (co)polymers under homogeneous conditions in organic and aqueous media

Abstract Reversible addition–fragmentation chain transfer (RAFT) radical polymerization has, since its discovery by CSIRO, evolved into an extremely powerful synthetic tool for polymer chemists. The versatility of RAFT, with respect to reaction conditions and monomer class, now facilitates the preparation of materials which, only 10 years ago, could not be prepared with well-defined molecular characteristics. One particularly advantageous feature of RAFT is its applicability to the synthesis of water-soluble (co)polymers both directly in aqueous media under homogeneous conditions as well as in organic media. The ease of access to an almost infinite number of RAFT mediating agents now affords the synthetic chemist the ability to polymerize virtually any activated, and some non-activated, water-soluble/hydrophilic monomers. We highlight herein the application of RAFT to the synthesis of water-soluble/dispersible (co)polymers under homogeneous reaction conditions in both aqueous and organic media. Additionally, we review the aqueous solution properties of advanced stimuli–responsive systems with a particular emphasis on the stimulus-induced, and often reversible, supramolecular self-assembly characteristics of the materials. Limitations of homogeneous aqueous RAFT are also highlighted.

[1]  B. Mandal,et al.  Living radical polymerization. II. Improved atom transfer radical polymerization of acrylamide in aqueous glycerol media with a novel pentamethyldiethylenetriamine‐based soluble copper(I) complex catalyst system , 2004 .

[2]  B. Sumerlin,et al.  Controlled/“Living” Polymerization of Sulfobetaine Monomers Directly in Aqueous Media via RAFT† , 2002 .

[3]  J. Jagur-grodzinski.  Living and controlled polymerization : synthesis, characterization and properties of the respective polymers and copolymers , 2005 .

[4]  Sydney S. Weinstein,et al.  Flip/flop , 1993 .

[5]  G. Moad,et al.  Living Radical Polymerization , 2005 .

[6]  J. DeSimone,et al.  Well‐defined glycopolymer amphiphiles for liquid and supercritical carbon dioxide applications , 2001 .

[7]  Shiping Zhu,et al.  Atom transfer radical polymerization of 2‐(dimethylamino)ethyl methacrylate in aqueous media , 2000 .

[8]  T. A. Hatton,et al.  Diblock, ABC triblock, and random methacrylic polyampholytes: synthesis by group transfer polymerization and solution behavior , 1994 .

[9]  K. Wooley,et al.  Determination of the bioavailability of biotin conjugated onto shell cross-linked (SCK) nanoparticles. , 2004, Journal of the American Chemical Society.

[10]  J. Lai,et al.  Functional Polymers from Novel Carboxyl-Terminated Trithiocarbonates as Highly Efficient RAFT Agents , 2002 .

[11]  Y. Morishima,et al.  pH-Responsive Micellization of Amine-Containing Cationic Diblock Copolymers Prepared by Reversible Addition-Fragmentation Chain Transfer (RAFT) Radical Polymerization , 2005 .

[12]  Shiping Zhu,et al.  Modeling the reversible addition–fragmentation transfer polymerization process , 2003 .

[13]  A. Müller,et al.  Benzyl and Cumyl Dithiocarbamates as Chain Transfer Agents in the RAFT Polymerization of N-Isopropylacrylamide. In Situ FT-NIR and MALDI−TOF MS Investigation , 2002 .

[14]  Junlian Huang,et al.  Radical Copolymerization of Maleimide with Ethyl - Ethylacrylate and -Ethylacrylic Acid via RAFT , 2004 .

[15]  D. Haddleton,et al.  Amphiphilic diblock, triblock, and star block copolymers by living radical polymerization: Synthesis and aggregation behavior , 2002 .

[16]  R. Hester,et al.  Hydrolytic Susceptibility of Dithioester Chain Transfer Agents and Implications in Aqueous RAFT Polymerizations , 2004 .

[17]  A. Rassat,et al.  Synthesis of water‐soluble nitroxides and their use as mediators in aqueous‐phase controlled radical polymerization , 2002 .

[18]  R. Jerome,et al.  Dynamics of Poly((dimethylamino)alkyl methacrylate-block-sodium methacrylate) Micelles. Influence of Hydrophobicity and Molecular Architecture on the Exchange Rate of Copolymer Molecules , 1998 .

[19]  S. Armes,et al.  Synthesis and aqueous solution properties of near-monodisperse tertiary amine methacrylate homopolymers and diblock copolymers , 2001 .

[20]  Tadashi Kawai,et al.  Amphiphilic Polymer Brushes Grown from the Silicon Surface by Atom Transfer Radical Polymerization , 2001 .

[21]  C. Barner‐Kowollik,et al.  Effect of an added base on (4-cyanopentanoic acid)-4-dithiobenzoate mediated RAFT polymerization in water , 2006 .

[22]  William J. Brittain,et al.  Synthesis of Polymer Brushes on Silicate Substrates via Reversible Addition Fragmentation Chain Transfer Technique , 2002 .

[23]  C. Barner‐Kowollik,et al.  Synthesis of poly(vinyl alcohol) combs via MADIX/RAFT polymerization , 2006 .

[24]  R. Jerome,et al.  Living Anionic Homopolymerization and Block Copolymerization of (Dimethylamino)ethyl Methacrylate , 1997 .

[25]  K. Edwards,et al.  A New Double-Responsive Block Copolymer Synthesized via RAFT Polymerization: Poly(N-isopropylacrylamide)-block-poly(acrylic acid) , 2004 .

[26]  K. Baek,et al.  Possibility of Living Radical Polymerization of Vinyl Acetate Catalyzed by Iron(I) Complex1 , 2002 .

[27]  D. Charmot,et al.  Dithiocarbamates as universal reversible addition-fragmentation chain transfer agents , 2000 .

[28]  S. Armes,et al.  Synthesis and aqueous solution properties of novel zwitterionic block copolymers , 1997 .

[29]  A. Hashidzume,et al.  Characterization of pH-dependent micellization of polystyrene-based cationic block copolymers prepared by reversible addition-fragmentation chain transfer (RAFT) radical polymerization , 2006 .

[30]  T. Chung,et al.  A Novel “Stable” Radical Initiator Based on the Oxidation Adducts of Alkyl-9-BBN , 1996 .

[31]  T. Kowalewski,et al.  Environmentally-Responsive, Entirely Hydrophilic, Shell Cross-linked (SCK) Nanoparticles , 2001 .

[32]  S. Zard.  ON THE TRAIL OF XANTHATES: SOME NEW CHEMISTRY FROM AN OLD FUNCTIONAL GROUP , 1997 .

[33]  D. Oupický,et al.  Temperature-controlled properties of DNA complexes with poly(ethylenimine)-graft-poly(N-isopropylacrylamide). , 2006, Biomacromolecules.

[34]  Brian S. Hawkett,et al.  Effective ab Initio Emulsion Polymerization under RAFT Control , 2002 .

[35]  B. Sumerlin,et al.  The direct polymerization of 2-methacryloxyethyl glucoside via aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization , 2003 .

[36]  S. Armes,et al.  A Schizophrenic Water-Soluble Diblock Copolymer. , 2001, Angewandte Chemie.

[37]  S. Armes,et al.  Synthesis and aqueous solution properties of novelhydrophilic–hydrophilic block copolymers based on tertiary aminemethacrylates , 1997 .

[38]  Wei Liu,et al.  Synthesis of zwitterionic block copolymers via RAFT polymerization , 2005 .

[39]  Christopher Barner-Kowollik,et al.  Poly(vinyl alcohol) star polymers prepared via MADIX/RAFT polymerisation. , 2004, Chemical communications.

[40]  M. Sawamoto,et al.  RAFT Polymerization of N-Isopropylacrylamide in the Absence and Presence of Y(OTf)3: Simultaneous Control of Molecular Weight and Tacticity , 2004 .

[41]  S. Armes,et al.  Direct Verification of the Core-Shell Structure of Shell Cross-Linked Micelles in the Solid State Using X-ray Photoelectron Spectroscopy , 2002 .

[42]  Y. Itoh,et al.  Syntheses of amphiphilic block copolymers. Block copolymers of methacrylic acid and p-N,N-dimethylaminostyrene , 1982 .

[43]  Michael K. C. Tam,et al.  Novel pH Responsive Amphiphilic Diblock Copolymers with Reversible Micellization Properties , 2003 .

[44]  Sébastien Perrier,et al.  Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization , 2005 .

[45]  Hu,et al.  “Gradient” Polymer Prepared by Complex-Radical Terpolymerization of Styrene, Maleic Anhydride, and N-Vinyl Pyrrolidone via γ-Ray Irradiation by Use of a RAFT Process: Synthesis, Mechanism, and Characterization , 2006 .

[46]  S. Thayumanavan,et al.  Controlled polymerization of N‐isopropylacrylamide with an activated methacrylic ester , 2004 .

[47]  T. P. Davis,et al.  Chemoenzymatic synthesis of narrow-polydispersity glycopolymers: poly(6-O-vinyladipoyl-D-glucopyranose). , 2004, Biomacromolecules.

[48]  C. Pichot,et al.  Latex particles bearing hydrophilic grafted hairs with controlled chain length and functionality synthesized by reversible addition–fragmentation chain transfer , 2003 .

[49]  C. Barner‐Kowollik,et al.  Long‐lived intermediates in reversible addition–fragmentation chain‐transfer (RAFT) polymerization generated by γ radiation , 2002 .

[50]  Leonie Barner,et al.  Reversible addition–fragmentation chain transfer polymerization initiated with γ-radiation at ambient temperature: An overview , 2003 .

[51]  B. Sumerlin,et al.  Water-soluble Polymers. 84. Controlled Polymerization in Aqueous Media of Anionic Acrylamido Monomers via RAFT , 2001 .

[52]  C. Barner‐Kowollik,et al.  Synthesis of various glycopolymer architectures via RAFT polymerization: from block copolymers to stars. , 2006, Biomacromolecules.

[53]  Leonie Barner,et al.  Living free radical polymerisation under a constant source of gamma radiation: An example of reversible addition-fragmentation chain transfer or reversible termination? , 2002 .

[54]  S. Armes,et al.  Synthesis and aqueous solution properties of novel sugar methacrylate-based homopolymers and block copolymers. , 2003, Biomacromolecules.

[55]  S. Perrier,et al.  First report of reversible addition-fragmentation chain transfer (RAFT) polymerisation in room temperature ionic liquids. , 2002, Chemical communications.

[56]  Renzo M. Paulus,et al.  Systematic Parallel Investigation of RAFT Polymerizations for Eight Different (Meth)Acrylates: A Basis for the Designed Synthesis of Block and Random Copolymers , 2005 .

[57]  K. Matyjaszewski,et al.  Stereoblock copolymers and tacticity control in controlled/living radical polymerization. , 2003, Journal of the American Chemical Society.

[58]  C. McCormick,et al.  Aqueous RAFT Polymerization of Acrylamide and N,N‐Dimethylacrylamide at Room Temperature , 2005 .

[59]  K. Matyjaszewski.  Advances in Controlled/living radical polymerization , 2003 .

[60]  S. Armes,et al.  Polymeric Surfactants for the New Millennium: A pH‐Responsive, Zwitterionic, Schizophrenic Diblock Copolymer , 2002 .

[61]  C. S. Patrickios,et al.  Synthesis and aqueous solution characterization of catalytically active homopolymers, block copolymers and networks containing imidazole , 2000 .

[62]  Thomas P. Davis,et al.  RAFTing down under: Tales of missing radicals, fancy architectures, and mysterious holes , 2003 .

[63]  K. Neoh,et al.  Functional and surface-active membranes from poly(vinylidene fluoride)-graft-poly(acrylic acid) prepared via RAFT-mediated graft copolymerization. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[64]  S. Perrier,et al.  Thermoresponsive micelles from well-defined block copolymers synthesized via reversible addition–fragmentation chain transfer polymerization , 2005 .

[65]  B. Sumerlin,et al.  Raft Polymerization of N,N-Dimethylacrylamide Utilizing Novel Chain Transfer Agents Tailored for High Reinitiation Efficiency and Structural Control† , 2002 .

[66]  M. Arotçaréna,et al.  Switching the inside and the outside of aggregates of water-soluble block copolymers with double thermoresponsivity. , 2002, Journal of the American Chemical Society.

[67]  A. Gast,et al.  Characterizing the Structure of pH Dependent Polyelectrolyte Block Copolymer Micelles , 1999 .

[68]  Leonie Barner,et al.  RAFT Polymerization of N‐Isopropylacrylamide and Acrylic Acid under γ‐Irradiation in Aqueous Media , 2006 .

[69]  C. Pan,et al.  Direct Synthesis of Biotinylated Stimuli-Responsive Polymer and Diblock Copolymer by RAFT Polymerization Using Biotinylated Trithiocarbonate as RAFT Agent , 2006 .

[70]  K. Matyjaszewski,et al.  Controlled/Living Radical Polymerization of Methacrylic Monomers in the Presence of Lewis Acids: Influence on Tacticity , 2004 .

[71]  L. Radom,et al.  Ab initio evidence for slow fragmentation in RAFT polymerization. , 2003, Journal of the American Chemical Society.

[72]  B. Sumerlin,et al.  Synthesis of Block Copolymers of 2- and 4-Vinylpyridine by RAFT Polymerization† , 2003 .

[73]  S. Armes,et al.  Synthesis of Biocompatible Polymers. 1. Homopolymerization of 2-Methacryloyloxyethyl Phosphorylcholine via ATRP in Protic Solvents: An Optimization Study , 2002 .

[74]  P. Lochon,et al.  Controlled Polymerization of Functional Monomers and Synthesis of Block Copolymers Using a β-Phosphonylated Nitroxide , 2003 .

[75]  A. Lowe,et al.  Surface Modification of Gold Nanorods with Polymers Synthesized by Reversible Addition-Fragmentation Chain Transfer Polymerization , 2007 .

[76]  J. Storsberg,et al.  New chain transfer agents for reversible addition-fragmentation chain transfer (RAFT) polymerisation in aqueous solution , 2004 .

[77]  C. Pichot,et al.  MALDI-TOF MS Investigation of the RAFT Polymerization of a Water-Soluble Acrylamide Derivative , 2004 .

[78]  C. Barner‐Kowollik,et al.  Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation , 2006 .

[79]  M. Coote.  Ab Initio Study of the Addition−Fragmentation Equilibrium in RAFT Polymerization: When Is Polymerization Retarded? , 2004 .

[80]  N. Dörr,et al.  Controlled Radical Polymerization of Acrylic Acid in Protic Media , 2001 .

[81]  Y. Morishima,et al.  Heat-Induced Association and Dissociation Behavior of Amphiphilic Diblock Copolymers Synthesized via Reversible Addition−Fragmentation Chain Transfer Radical Polymerization , 2004 .

[82]  W. Jaeger,et al.  Polymeric Betaines: Synthesis, Characterization, and Application , 2006 .

[83]  Leonie Barner,et al.  Living free‐radical polymerization of styrene under a constant source of γ radiation , 2002 .

[84]  K. Matyjaszewski,et al.  Controlled/living radical polymerization in aqueous media: homogeneous and heterogeneous systems , 2001 .

[85]  C. McCormick,et al.  Synthesis and solution properties of zwitterionic polymers. , 2002, Chemical reviews.

[86]  Futian Liu,et al.  Synthesis of poly(tert-butyl acrylate)-block-polystyrene-block-poly(4-vinylpyridine) by living anionic polymerization. , 2003, Angewandte Chemie.

[87]  C. McCormick,et al.  Aqueous RAFT polymerization: recent developments in synthesis of functional water-soluble (co)polymers with controlled structures. , 2004, Accounts of chemical research.

[88]  C. Barner‐Kowollik,et al.  Well-defined diblock glycopolymers from RAFT polymerization in homogeneous aqueous medium , 2005 .

[89]  Y. Miura,et al.  Chemoenzymatically synthesized glycoconjugate polymers. , 2003, Biomacromolecules.

[90]  C. Barner‐Kowollik,et al.  Origin of Inhibition Effects in the Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate , 2002 .

[91]  Graeme Moad,et al.  Living Polymers by the Use of Trithiocarbonates as Reversible Addition−Fragmentation Chain Transfer (RAFT) Agents: ABA Triblock Copolymers by Radical Polymerization in Two Steps , 2000 .

[92]  Yuting Li,et al.  RAFT Synthesis of a Thermally Responsive ABC Triblock Copolymer Incorporating N-Acryloxysuccinimide for Facile in Situ Formation of Shell Cross-Linked Micelles in Aqueous Media† , 2006 .

[93]  A. Lowe,et al.  Polyelectrolytes and Polyzwitterions: Synthesis, Properties, and Applications , 2006 .

[94]  G. Levesque,et al.  Kinetics and mechanism of polythioamidation in solution. 1. Reaction of mono- and bis(dithioester)s with excess amine , 1990 .

[95]  C. McCORMICK.  Stimuli-Responsive Water Soluble and Amphiphilic Polymers , 2000 .

[96]  N. Ayres,et al.  Facile, controlled, room-temperature RAFT polymerization of N-isopropylacrylamide. , 2004, Biomacromolecules.

[97]  N. Gaillard,et al.  Block copolymers of acrylic acid and butyl acrylate prepared by reversible addition–fragmentation chain transfer polymerization: Synthesis, characterization, and use in emulsion polymerization , 2003 .

[98]  R. Jerome,et al.  Controlled radical polymerization of styrene by quinone transfer radical polymerization (QTRP) , 2005 .

[99]  Ruke Bai,et al.  Controlled polymerization of acrylic acid under 60Co irradiation in the presence of dibenzyl trithiocarbonate , 2001 .

[100]  K. Ishihara,et al.  Synthesis of well-defined amphiphilic block copolymers having phospholipid polymer sequences as a novel biocompatible polymer micelle reagent. , 2005, Biomacromolecules.

[101]  S. Armes,et al.  Unusual Aggregation Behavior of a Novel Tertiary Amine Methacrylate-Based Diblock Copolymer: Formation of Micelles and Reverse Micelles in Aqueous Solution , 1998 .

[102]  Alexander D. Q. Li,et al.  Thermosensitive gold nanoparticles. , 2004, Journal of the American Chemical Society.

[103]  K. Matyjaszewski.  Controlled/living radical polymerization : progress in ATRP, NMP, and RAFT , 2000 .

[104]  J. Storsberg,et al.  Stimuli responsive amphiphilic block copolymers for aqueous media synthesised via reversible addition fragmentation chain transfer polymerisation (RAFT) , 2005 .

[105]  C. Ladavière,et al.  Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization , 2004 .

[106]  L. Radom,et al.  The reversible addition-fragmentation chain transfer process and the strength and limitations of modeling: Comment on “the magnitude of the fragmentation rate coefficient” , 2003 .

[107]  C. Pichot,et al.  Polymer of Controlled Chain Length Carrying Hydrophilic Galactose Moieties for Immobilization of DNA Probes , 2002 .

[108]  T. Kowalewski,et al.  Water-Soluble Knedel-like Structures: The Preparation of Shell-Cross-Linked Small Particles , 1996 .

[109]  Zhang,et al.  Controlled/"Living" Radical Polymerization of 2-(Dimethylamino)ethyl Methacrylate. , 1998, Macromolecules.

[110]  C. Wieland,et al.  New Water Soluble Agents for Reversible Addition−Fragmentation Chain Transfer Polymerization and Their Application in Aqueous Solutions , 2005 .

[111]  Y. Morishima,et al.  pH-Responsive Micellization of Amphiphilic Diblock Copolymers Synthesized via Reversible Addition−Fragmentation Chain Transfer Polymerization , 2003 .

[112]  R. A. Jackson,et al.  Direct synthesis of novel acidic and zwitterionic block copolymers via TEMPO-mediated living free-radical polymerization , 1999 .

[113]  E. Beckman,et al.  Poly(ethylene glycol)-block-poly(N-vinylformamide) Copolymers Synthesized by the RAFT Methodology , 2003 .

[114]  Biomimetic Honeycomb-Structured Surfaces Formed from Block Copolymers Incorporating Acryloyl Phosphorylcholine , 2003 .

[115]  T. Akaike,et al.  Synthesis of a Well-Defined Glycopolymer by Nitroxide-Controlled Free Radical Polymerization , 1998 .

[116]  S. Armes,et al.  Well-defined sulfobetaine-based statistical copolymers as potential antibioadherent coatings. , 2000, Journal of biomedical materials research.

[117]  Almar Postma,et al.  Living free radical polymerization with reversible addition : fragmentation chain transfer (the life of RAFT) , 2000 .

[118]  R. Pelton,et al.  Novel Cationic Macromonomers by Living Anionic Polymerization of (Dimethylamino)ethyl Methacrylate , 2001 .

[119]  A. Hoffman,et al.  Reversible meso-scale smart polymer--protein particles of controlled sizes. , 2004, Bioconjugate chemistry.

[120]  C. Pan,et al.  Dihydroxyl-terminated telechelic polymers prepared by RAFT polymerization using functional trithiocarbonate as chain transfer agent , 2004 .

[121]  E. Rizzardo,et al.  Ambient temperature reversible addition–fragmentation chain transfer polymerisation , 2001 .

[122]  B. Sumerlin,et al.  RAFT Polymerization of N,N-Dimethylacrylamide in Water† , 2002 .

[123]  M. Kijima,et al.  Photochemical isomerization of azobenzene incorporated in poly(N,N-dimethyl-4-vinylphenethylamine-block-styrene) diblock copolymer by cross linkage , 1997 .

[124]  N. Ayres,et al.  Water-Soluble Polymers , 2004 .

[125]  K. Wooley,et al.  Solution and Surface Charge Properties of Shell Cross-Linked Knedel Nanoparticles , 1999 .

[126]  C. Barner‐Kowollik,et al.  Using the reversible addition–fragmentation chain transfer process to synthesize core‐crosslinked micelles , 2006 .

[127]  J. Watanabe,et al.  Synthesis of sequence‐controlled copolymers from extremely polar and apolar monomers by living radical polymerization and their phase‐separated structures , 2005 .

[128]  S. Zard,et al.  Vinylogous thionothio compounds for RAFT polymerization , 2006 .

[129]  N. Kuramoto,et al.  Preparation of thermally responsive and electroactive poly(N-acryloylpyrrolidine-co-vinylferrocene) , 1994 .

[130]  J. Yoshida,et al.  Mechanism-based invention of high-speed living radical polymerization using organotellurium compounds and azo-initiators. , 2003, Journal of the American Chemical Society.

[131]  S. Armes,et al.  Synthesis and Properties of Low-Polydispersity Poly(sulfopropylbetaine)s and Their Block Copolymers , 1999 .

[132]  S. Armes,et al.  Synthesis and characterization of shell cross-linked micelles with hydroxy-functional coronas: a pragmatic alternative to dendrimers? , 2005, Langmuir : the ACS journal of surfaces and colloids.

[133]  C. Barner‐Kowollik,et al.  Addition Fragmentation Chain Transfer (RAFT) Agents: F-RAFT , 2005 .

[134]  R. Grubbs,et al.  Water-Soluble Ruthenium Alkylidenes: Synthesis, Characterization, and Application to Olefin Metathesis in Protic Solvents , 2000 .

[135]  Y. Sugiura,et al.  Characterization of low-mass model 3-arm stars produced in reversible addition-fragmentation chain transfer (RAFT) process , 2004 .

[136]  E. Harth,et al.  New polymer synthesis by nitroxide mediated living radical polymerizations. , 2001, Chemical reviews.

[137]  M. Akashi,et al.  Preparation of a novel functional hydrogel consisting of sulfated glucoside-bearing polymer: activation of basic fibroblast growth factor. , 1998, Journal of biomedical materials research.

[138]  Y. K. Chong,et al.  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) , 2003 .

[139]  Shi-zhong Luo,et al.  Syntheses and self‐assembly of poly(benzyl ether)‐b‐poly(N‐isopropylacrylamide) dendritic–linear diblock copolymers , 2006 .

[140]  D. Massiot,et al.  Relationship between Solid-State 31 P NMR Parameters and X-ray Structural Data in Some Zinc Phosphonates , 1997 .

[141]  S. Zard,et al.  A convenient source of alkyl and acyl radicals , 1988 .

[142]  J. Chiefari,et al.  Thiocarbonylthio Compounds (SC(Z)S−R) in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Effect of the Activating Group Z , 2003 .

[143]  Heikki Tenhu,et al.  Aggregation behaviour of well defined amphiphilic diblock copolymers with poly(N-isopropylacrylamide) and hydrophobic blocks , 2004 .

[144]  M. Charreyre,et al.  Versatile precursors of functional RAFT agents. Application to the synthesis of bio-related end-functionalized polymers. , 2006, Journal of the American Chemical Society.

[145]  J. Chiefari,et al.  Synthesis of defined polymers by reversible addition-fragmentation chain transfer: The RAFT process , 2000 .

[146]  J. Yoshida,et al.  Highly versatile organostibine mediators for living radical polymerization. , 2004, Journal of the American Chemical Society.

[147]  M. Georges,et al.  Mechanism of Living Free Radical Polymerizations with Narrow Polydispersity: Electron Spin Resonance and Kinetic Studies , 1995 .

[148]  S. Armes,et al.  Well-Defined Biocompatible Block Copolymers via Atom Transfer Radical Polymerization of 2-Methacryloyloxyethyl Phosphorylcholine in Protic Media , 2003 .

[149]  R. Kane,et al.  Synthesis of copolymers containing an active ester of methacrylic acid by RAFT: controlled molecular weight scaffolds for biofunctionalization. , 2006, Biomacromolecules.

[150]  S. Rimmer,et al.  Highly Branched Poly(N-isopropylacrylamide)s with Imidazole End Groups Prepared by Radical Polymerization in the Presence of a Styryl Monomer Containing a Dithioester Group , 2005 .

[151]  Thomas P. Davis,et al.  Star polymer synthesis using trithiocarbonate functional β‐cyclodextrin cores (reversible addition–fragmentation chain‐transfer polymerization) , 2002 .

[152]  Bumjae Lee,et al.  Experimental Criteria for Living Polymerizations , 1992 .

[153]  M. Charreyre,et al.  Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process , 2006 .

[154]  C. Pan,et al.  Preparation and characterization of dendrimer-star PNIPAAM using dithiobenzoate-terminated PPI dendrimer via RAFT polymerization , 2006 .

[155]  H. Jiang,et al.  Synthesis of Gold Nanoparticles Grafted with a Thermoresponsive Polymer by Surface-Induced Reversible-Addition-Fragmentation Chain-Transfer Polymerization , 2003 .

[156]  R. Grubbs,et al.  Living Ring-Opening Metathesis Polymerization in Water , 1998 .

[157]  K. Tam,et al.  Controlled/living polymerization of 2‐(diethylamino)ethyl methacrylate and its block copolymer with tert‐butyl methacrylate by atom transfer radical polymerization , 2003 .

[158]  M. Sawamoto,et al.  Metal-catalyzed living radical polymerization. , 2001, Chemical reviews.

[159]  K. Ishihara,et al.  Suppression of the inflammatory response from adherent cells on phospholipid polymers. , 2003, Journal of biomedical materials research. Part A.

[160]  M. Kamachi,et al.  Synthesis of ionic block polymers for desalination membranes , 1973 .

[161]  C. McCormick,et al.  Direct Synthesis of Thermally Responsive DMA/NIPAM Diblock and DMA/NIPAM/DMA Triblock Copolymers via Aqueous, Room Temperature RAFT Polymerization† , 2006 .

[162]  S. Armes,et al.  Direct Synthesis and Aqueous Solution Properties of Well-Defined Cyclic Sugar Methacrylate Polymers , 2003 .

[163]  S. Armes,et al.  The remarkable `flip-flop' self assembly of a diblock copolymer in aqueous solution. , 2001 .

[164]  K. Iida,et al.  Organotellurium compounds as novel initiators for controlled/living radical polymerizations. Synthesis of functionalized polystyrenes and end-group modifications. , 2002, Journal of the American Chemical Society.

[165]  S. Armes,et al.  Synthesis of low polydispersity, controlled-structure sugar methacrylate polymers under mild conditions without protecting group chemistry. , 2002, Chemical communications.

[166]  Yuting Li,et al.  Thermally responsive vesicles and their structural "locking" through polyelectrolyte complex formation. , 2006, Angewandte Chemie.

[167]  J. Yoshida,et al.  Tailored synthesis of structurally defined polymers by organotellurium-mediated living radical polymerization (TERP): synthesis of poly(meth)acrylate derivatives and their di- and triblock copolymers. , 2002, Journal of the American Chemical Society.

[168]  E. Rizzardo,et al.  Molecular weight characterization of poly(N-isopropylacrylamide) prepared by living free-radical polymerization , 2000 .

[169]  R. Jerome,et al.  Self-association of double-hydrophilic copolymers of acrylic acid and poly(ethylene oxide) macromonomer , 2004 .

[170]  H. Maynard,et al.  Streptavidin as a macroinitiator for polymerization: in situ protein-polymer conjugate formation. , 2005, Journal of the American Chemical Society.

[171]  B. Sumerlin,et al.  Facile preparation of transition metal nanoparticles stabilized by well-defined (co)polymers synthesized via aqueous reversible addition-fragmentation chain transfer polymerization. , 2002, Journal of the American Chemical Society.

[172]  R. Sanderson,et al.  Characterization and rheological properties of model alkali‐soluble rheology modifiers synthesized by reversible addition–fragmentation chain‐transfer polymerization , 2003 .

[173]  J. Chiefari,et al.  Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process , 1998 .

[174]  M. Sawamoto,et al.  Synthesis of isotactic poly(N-isopropylacrylamide) by RAFT polymerization in the presence of Lewis acid , 2003 .

[175]  B. Sumerlin,et al.  Aqueous Solution Properties of pH-Responsive AB Diblock Acrylamido Copolymers Synthesized via Aqueous RAFT , 2003 .

[176]  John G. Tsavalas,et al.  Living radical polymerization in miniemulsion using reversible addition-fragmentation chain transfer , 2000 .

[177]  D. Taton,et al.  Direct Synthesis of Double Hydrophilic Statistical Di- and Triblock Copolymers Comprised of Acrylamide and Acrylic Acid Units via the MADIX Process , 2001 .

[178]  H. Tenhu,et al.  Dissolution and aggregation of a poly(NIPA-block-sulfobetaine) copolymer in water and saline aqueous solutions , 2002 .

[179]  M. Sawamoto,et al.  Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization , 1995 .

[180]  Yuting Li,et al.  Chiroptical Properties of Homopolymers and Block Copolymers Synthesized From the Enantiomeric Monomers N-acryloyl-L-alanine and N-acryloyl-D-alanine Using Aqueous RAFT Polymerization , 2006 .

[181]  R. P. Redman,et al.  Synthesis and characterisation of phosphorylcholine-based polymers useful for coating blood filtration devices. , 2000, Biomaterials.

[182]  Graeme Moad,et al.  A more versatile route to block copolymers and other polymers of complex architecture by living radical polymerization : The RAFT process , 1999 .

[183]  E. Chaikof,et al.  Glycosaminoglycan Mimetic Biomaterials. 2. Alkene- and Acrylate-Derivatized Glycopolymers via Cyanoxyl-Mediated Free-Radical Polymerization , 2001 .

[184]  S. Armes,et al.  ABC triblock polymethacrylates: Group transfer polymerization synthesis of the ABC, ACB, and BAC topological isomers and solution characterization , 1998 .

[185]  K. Wooley,et al.  REDOR determination of the composition of shell cross-linked amphiphilic core-shell nanoparticles and the partitioning of sequestered fluorinated guests , 2001 .

[186]  M. Pitsikalis,et al.  Controlled nitroxide‐mediated and reversible addition–fragmentation chain transfer polymerization of N‐vinylpyrrolidone: Synthesis of block copolymers with styrene and 2‐vinylpyridine , 2006 .

[187]  Lei Jiang,et al.  Synthesis and characterization of polystyrene/poly(4‐vinylpyridine) triblock copolymers by reversible addition–fragmentation chain transfer polymerization and their self‐assembled aggregates in water , 2003 .

[188]  R. Jerome,et al.  pH-dependent micellization of poly(2-vinylpyridine)-block-poly((dimethylamino)ethyl methacrylate) diblock copolymers , 2001 .

[189]  J. Jagur-grodzinski.  Preparation of functionalized polymers using living and controlled polymerizations , 2001 .

[190]  C. Pichot,et al.  Study of the RAFT Polymerization of a Water-Soluble Bisubstituted Acrylamide Derivative. 1. Influence of the Dithioester Structure , 2002 .

[191]  G. Moad,et al.  Living Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT): Direct ESR Observation of Intermediate Radicals , 1999 .

[192]  C. McCormick,et al.  Water-Soluble Polymers. 81. Direct Synthesis of Hydrophilic Styrenic-Based Homopolymers and Block Copolymers in Aqueous Solution via RAFT , 2001 .

[193]  M. Urban,et al.  Modification of Gold Surfaces With Water-Soluble (Co)polymers Prepared Via Aqueous Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization , 2003 .

[194]  B. Sumerlin,et al.  Conditions for Facile, Controlled RAFT Polymerization of Acrylamide in Water† , 2003 .

[195]  C. Barner‐Kowollik,et al.  Addition-Fragmentation Kinetics of Fluorodithioformates (F-RAFT) in Styrene, Vinyl Acetate, and Ethylene Polymerization: An Ab Initio Investigation , 2006 .

[196]  Thomas P. Davis,et al.  Xanthate Mediated Living Polymerization of Vinyl Acetate: A Systematic Variation in MADIX/RAFT Agent Structure , 2003 .

[197]  C. Pan,et al.  Synthesis of Water-Soluble Multiwalled Carbon Nanotubes with Grafted Temperature-Responsive Shells by Surface RAFT Polymerization , 2005 .

[198]  B. Klumperman,et al.  RAFT mediated polymerisation in heterogeneous media. , 2006, Soft matter.

[199]  Jianbo Shi,et al.  Synthesis and characterization of core–shell‐type polymeric micelles from diblock copolymers via reversible addition–fragmentation chain transfer , 2006 .

[200]  B. Klumperman,et al.  Initialisation in RAFT-mediated polymerisation of methyl acrylate. , 2004, Chemical communications.

[201]  S. Armes,et al.  Selective betainisation of tertiary amine methacrylate blockcopolymers , 1997 .

[202]  J. Yoshida,et al.  Practical protocols for organotellurium-mediated living radical polymerization by in situ generated initiators from AIBN and ditellurides , 2003 .

[203]  C. Pichot,et al.  Molecular Weight and Functional End Group Control by RAFT Polymerization of a Bisubstituted Acrylamide Derivative , 2003 .

[204]  Graeme Moad,et al.  Living radical polymerization by the RAFT process , 2005 .

[205]  Allan S Hoffman,et al.  Poly(N-isopropylacrylamide-co-propylacrylic acid) copolymers that respond sharply to temperature and pH. , 2006, Biomacromolecules.

[206]  S. Armes,et al.  Unexpected Transesterification of Tertiary Amine Methacrylates during Methanolic ATRP at Ambient Temperature: A Cautionary Tale , 2002 .

[207]  S. Armes,et al.  Synthesis of polybetaines with narrow molecular mass distribution and controlled architecture , 1996 .

[208]  T. Endo,et al.  Synthesis of Well-Defined Glycopolymers by π-Allylnickel-Catalyzed Living Coordination Polymerization , 2001 .

[209]  C. S. Patrickios,et al.  Synthesis and aqueous solution characterization of catalytically active block copolymers containing imidazole , 1998 .

[210]  Masao Kato,et al.  Sugar-Installed Polymer Micelles: Synthesis and Micellization of Poly(ethylene glycol)−Poly(d,l-lactide) Block Copolymers Having Sugar Groups at the PEG Chain End , 1999 .

[211]  M. Vamvakaki,et al.  Synthesis and aqueous solution characterization of novel diblock polyampholytes containing imidazole , 2002 .

[212]  T. Fukuda,et al.  Synthesis of a well‐defined glycopolymer by atom transfer radical polymerization , 1998 .

[213]  S. Armes,et al.  Facile synthesis of well-defined, biocompatible phosphorylcholine-based methacrylate copolymers via atom transfer radical polymerization at 20 degrees C. , 2001, Journal of the American Chemical Society.

[214]  Shiping Zhu,et al.  A difference of six orders of magnitude: A reply to “the magnitude of the fragmentation rate coefficient” , 2003 .

[215]  S. Armes,et al.  Recent advances in the synthesis of polymeric surfactants , 2001 .

[216]  L. Véron,et al.  Synthetic and characterization aspects of dimethylaminoethyl methacrylate reversible addition fragmentation chain transfer (RAFT) polymerization , 2005 .

[217]  R. A. Jackson,et al.  Facile synthesis of well-defined water-soluble polymers via atom transfer radical polymerization in aqueous media at ambient temperature , 1999 .

[218]  Maud Save,et al.  Synthesis by RAFT of amphiphilic block and comblike cationic copolymers and their use in emulsion polymerization for the electrosteric stabilization of latexes , 2005 .

[219]  C. Barner‐Kowollik,et al.  Amphiphilic block copolymers based on poly(2-acryloyloxyethyl phosphorylcholine) prepared via RAFT polymerisation as biocompatible nanocontainers. , 2004, Macromolecular bioscience.

[220]  Yoshio Okamoto,et al.  Xanthate-Mediated Radical Polymerization of N-Vinylpyrrolidone in Fluoroalcohols for Simultaneous Control of Molecular Weight and Tacticity , 2005 .

[221]  S. Armes,et al.  First example of the atom transfer radical polymerisation of an acidic monomer: direct synthesis of methacrylic acid copolymers in aqueous media , 1999 .

[222]  R. Mayadunne,et al.  A novel synthesis of functional dithioesters, dithiocarbamates, xanthates and trithiocarbonates , 1999 .

[223]  C. Ladavière,et al.  Synthesis and Characterization of Poly(acrylic acid) Produced by RAFT Polymerization. Application as a Very Efficient Dispersant of CaCO3, Kaolin, and TiO2 , 2003 .

[224]  S. Armes,et al.  Synthesis and Characterization of Zwitterionic Block Copolymers , 1998 .

[225]  Xing Ding,et al.  Behavior of 3-vinylpyridine in nitroxide-mediated radical polymerization: The influence of nitroxide concentration, solvent, and temperature , 2000 .

[226]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[227]  LeeAnn O. Bailey,et al.  Peptide-derivatized shell-cross-linked nanoparticles. 2. Biocompatibility evaluation. , 2004, Bioconjugate chemistry.

[228]  B. Sumerlin,et al.  Aqueous solution properties of pH‐responsive AB diblock acrylamido–styrenic copolymers synthesized via aqueous reversible addition–fragmentation chain transfer , 2004 .

[229]  J. Lai,et al.  Controlled radical polymerization by carboxyl- and hydroxyl-terminated dithiocarbamates and xanthates , 2006 .

[230]  C. Pan,et al.  Preparation of star polymers based on polystyrene or poly(styrene-b-N-isopropyl acrylamide) and divinylbenzene via reversible addition-fragmentation chain transfer polymerization , 2005 .

[231]  Charles L. McCormick,et al.  Direct Controlled polymerization of a cationic methacrylamido monomer in aqueous media via the RAFT process , 2004 .

[232]  S. Armes,et al.  The biocompatibility of crosslinkable copolymer coatings containing sulfobetaines and phosphobetaines. , 2004, Biomaterials.

[233]  M. Szwarc,et al.  POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS1 , 1956 .

[234]  C. Barner‐Kowollik,et al.  Well-defined glycopolymers from RAFT polymerization: Poly(methyl 6-O-methacryloyl-α-D-glucoside) and Its Block Copolymer with 2-Hydroxyethyl Methacrylate , 2004 .

[235]  M. Monteiro,et al.  Characterization of 3- and 4-Arm Stars from Reactions of Poly(butyl acrylate) RAFT and ATRP Precursors , 2004 .

[236]  R. Sanderson,et al.  Beyond Inhibition:  A 1H NMR Investigation of the Early Kinetics of RAFT-Mediated Polymerization with the Same Initiating and Leaving Groups , 2004 .

[237]  C. McCormick,et al.  Sulfobetaine-Containing Diblock and Triblock Copolymers via Reversible Addition-Fragmentation Chain Transfer Polymerization in Aqueous Media , 2003 .

[238]  C. Barner‐Kowollik,et al.  Poly(vinyl ester) star polymers via xanthate-mediated living radical polymerization: From poly(vinyl alcohol) to glycopolymer stars , 2005 .

[239]  K. Matyjaszewski,et al.  Atom Transfer Radical Polymerization of (Meth)acrylamides , 1999 .

[240]  Brian S. Hawkett,et al.  Miniemulsion Polymerization Stabilized by Amphipathic Macro RAFT Agents , 2003 .

[241]  W. Knoll,et al.  Synthesis of lipo-glycopolymer amphiphiles by nitroxide- mediated living free-radical polymerization , 2002 .

[242]  A. Fortes,et al.  Synthesis of carbohydrate based polymers , 2001 .

[243]  A. Laschewsky,et al.  New amphiphilic diblock copolymers: surfactant properties and solubilization in their micelles. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[244]  U. Schubert,et al.  RAFT Polymerization of 1-Ethoxyethyl Acrylate: A Novel Route toward Near-Monodisperse Poly(acrylic acid) and Derived Block Copolymer Structures. , 2005 .

[245]  T. Fukuda,et al.  Rate Retardation in Reversible Addition−Fragmentation Chain Transfer (RAFT) Polymerization: Further Evidence for Cross-Termination Producing 3-Arm Star Chain , 2004 .

[246]  S. Armes,et al.  Synthesis and Solution Properties of Water-Soluble Hydrophilic−Hydrophobic Block Copolymers , 1996 .

[247]  S. Yamago.  Development of organotellurium‐mediated and organostibine‐mediated living radical polymerization reactions , 2006 .

[248]  M. Benaglia,et al.  Controlled Radical Polymerization of Styrene with Phosphoryl- and (Thiophosphoryl)dithioformates as RAFT Agents , 2001 .

[249]  Ryan G. Ezell,et al.  Responsive nanoassemblies via interpolyelectrolyte complexation of amphiphilic block copolymer micelles , 2006 .

[250]  H. Jiang,et al.  Preparation of poly(N-isopropylacrylamide)-monolayer protected gold clusters: synthesis methods, core size and thickness of monolayer , 2003 .

[251]  S. Armes,et al.  Syntheses of shell cross-linked micelles using acidic ABC triblock copolymers and their application as pH-responsive particulate emulsifiers. , 2005, Journal of the American Chemical Society.

[252]  S. Armes,et al.  Facile Atom Transfer Radical Polymerization of Methoxy-Capped Oligo(ethylene glycol) Methacrylate in Aqueous Media at Ambient Temperature , 2000 .

[253]  B. Ray,et al.  Highly controlled synthesis of poly(N-vinylpyrrolidone) and its block copolymers by organostibine-mediated living radical polymerization , 2006 .

[254]  B. Mandal,et al.  Living Radical Polymerization. 1. The Case of Atom Transfer Radical Polymerization of Acrylamide in Aqueous-Based Medium , 2003 .

[255]  K. Okada,et al.  Biocompatible Block Copolymers Composed of Polydimethylsiloxane and Poly[(2-methacryloyloxy)ethyl phosphorylcholine] Segments , 1999 .

[256]  Y. Murata,et al.  A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition−Fragmentation Chain Transfer , 2002 .

[257]  Yutaka Kobayashi,et al.  A Systematic Study on Activation Processes in Organotellurium-Mediated Living Radical Polymerizations of Styrene, Methyl Methacrylate, Methyl Acrylate, and Vinyl Acetate , 2006 .

[258]  C. McCormick,et al.  Direct, controlled synthesis of the nonimmunogenic, hydrophilic polymer, poly(N-(2-hydroxypropyl)methacrylamide) via RAFT in aqueous media. , 2005, Biomacromolecules.

[259]  Ryan G. Ezell,et al.  Controlled/Living Polymerization of Methacrylamide In Aqueous Media via the RAFT Process , 2005 .

[260]  K. Matyjaszewski,et al.  Polymerization of acrylates by atom transfer radical polymerization. Homopolymerization of 2-hydroxyethyl acrylate , 1998 .

[261]  A. Lowe,et al.  Synthesis and Evaluation of New Dicarboxylic Acid Functional Trithiocarbonates: RAFT Synthesis of Telechelic Poly(n-butyl acrylate)s , 2005 .

[262]  Didier Benoit,et al.  Development of a Universal Alkoxyamine for “Living” Free Radical Polymerizations , 1999 .

[263]  F. Huang,et al.  Corona-Stabilized Interpolyelectrolyte Complexes of SiRNA with Nonimmunogenic, Hydrophilic/Cationic Block Copolymers Prepared by Aqueous RAFT Polymerization† , 2006 .

[264]  C. Barner‐Kowollik,et al.  Modeling the reversible addition–fragmentation chain transfer process in cumyl dithiobenzoate‐mediated styrene homopolymerizations: Assessing rate coefficients for the addition–fragmentation equilibrium , 2001 .

[265]  A. Laschewsky,et al.  Non-ionic amphiphilic block copolymers by RAFT-polymerization and their self-organization , 2006, Colloid and polymer science.

[266]  Krzysztof Matyjaszewski,et al.  Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes , 1995 .

[267]  T. Kitayama,et al.  Living Anionic Polymerization of N,N–Dimethylacrylamide and Copolymerization with Methyl Methacrylate in the presence of Bulky Aluminum Phenoxide , 2004 .

[268]  R. Sanderson,et al.  Solution and latex properties of model alkali‐soluble rheology modifiers, synthesized via the reversible addition–fragmentation chain transfer process, and the effects of the ethylene oxide chain length on the rheological properties , 2004 .

[269]  Sudalai,et al.  Phosphorus pentasulfide: A mild and versatile Catalyst/Reagent for the preparation of dithiocarboxylic esters , 2000, Organic letters.

[270]  Graeme Moad,et al.  Living Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT Polymerization) Using Dithiocarbamates as Chain Transfer Agents , 1999 .