Polymer–protein conjugates from ω-aldehyde endfunctional poly(N-vinylpyrrolidone) synthesised via xanthate-mediated living radical polymerisation

Pound, Gwenaelle; McKenzie, Jean M.; Lange, Ronald F. M.; Klumperman, Bert

doi:10.1039/b803952f

Cited by 91 publications

(75 citation statements)

References 38 publications

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“…We attribute this to hydrolytic instability in water of the hemithioaminal group formed (arising from the dithiocarbamate end-group with a terminal NVP unit) in a reaction similar to that described by Pound et al 37 for the decomposition of a xanthate end group of PNVP. As this hydrolysis occurs at the terminal carbon of the NVP chain, 37 dithiocarbamates, xanthates, and other types of RAFT agents can be expected to behave similarly in this context. To the best of our knowledge there are no reports in the literature pertaining to the RAFT polymerization of LAMs (vinyl esters, vinyl amides, etc.)…”

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confidence: 87%

Switchable Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization in Aqueous Solution, N,N-Dimethylacrylamide

et al. 2011

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Reversible additionÀfragmentation chain transfer (RAFT) polymerization, 1À4 mediated by thiocarbonylthio chain transfer agents (or RAFT agents, 1) (Scheme 1), possesses several advantages over other forms of reversible deactivation radical polymerization (RDRP), 5 such as atom transfer radical polymerization (ATRP) 6 and nitroxide mediated polymerization (NMP). 7,8 These include the ability to control the polymerization of a broad range of functional monomers (including vinyl esters and amides) and the absence of potentially toxic transition metal catalysts. RAFT polymerizations are simple to implement, because experimental conditions can mirror those of conventional radical polymerization; differing only by the addition of a RAFT agent. 2À4 To achieve optimal control over a RAFT polymerization, addition of the monomer derived propagating radical (P n • ) to the thiocarbonyl of a RAFT agent 1 and subsequent fragmentation of the RAFT intermediate 2 must occur efficiently. To facilitate this, the selection of a RAFT agent suitable for the monomer system is critical. Because propagating radicals of "more-activated" monomers (MAMs) (e.g., methacrylic, acrylic and styrenic monomers) are somewhat stabilized by conjugation, they are less reactive than propagating radicals derived from the "less-activated" monomers (LAMs) (e.g., vinyl esters and vinylamides). As such, these two classes of monomer require RAFT agents that are tailored to their differing reactivity. For effective control over polymerization of MAMs, dithioesters (Z = alkyl or aryl) or trithiocarbonates (Z = SR) are generally used. When these RAFT agents are used in the polymerization of LAMs, inhibition/retardation is observed, as fragmentation of the more reactive LAMs derived propagating radical is slow with respect to propagation. 9 The presence of O or N as the "Z" group adjacent to the thiocarbonyl, as is the case with xanthates (Z = OR) or dithiocarbamates (Z = NR 2 ), both slows addition of radicals to the RAFT agent and promotes the subsequent fragmentation such that it is not the rate determining step in chain transfer. Hence, these RAFT agents are regularly used for control over LAMs polymerization. Generally, xanthates and dithiocarbamates are relatively unreactive toward MAM derived propagating radicals, 10 making them ineffective control agents for these monomers. However, they may be effective for MAMs when the substituent is part of an aromatic heterocycle 10 or when highly electron withdrawing groups are present on the heteroatom. 11 As the reactivity of commonly used RAFT agents are tailored to either MAMs or LAMs, preparation of low dispersity polyMAM-block-polyLAM is not possible using the conventional RAFT process. While some RAFT agents, such as the N,N-diaryldithiocarbamates, have been reported by Destarac et al. 12 and Malepu et al. 13 for the homopolymerization of both MAMs and LAMs, these RAFT agents give only moderate control with both monomer classes. 12,13 When they were used for the preparation of poly(methyl acrylate)-bloc...

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confidence: 87%

Switchable Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization in Aqueous Solution, N,N-Dimethylacrylamide

et al. 2011

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“…C Compounds not used as RAFT agents directly but served as precursors to other RAFT agents. (VAc) [55] NVP [55,379] 366 [380] NVPI [220] 367 [380] 368 [380] O S S 209 210* [283,381] O S S NVC [283,382,383] NVCL [384] NVP [381] NVPI [220] 366 [380] 367 [380] 368 [380] (VAc) [55] (NVP) [55] NVC-b-310 [382] NVC-b-311 [382] NVP-b-VAc [381] O S S O OH 211* [385] 212 [386] BA [387] (DEGMA) [386] EHA [387] St [72] VAc [388] (BA-b-AA) [386] VAc [55,385] NVP [55] (DEGMA-b-AA) [386] 213* [283] …”

Section: S S S O Hn Possmentioning

confidence: 99%

“…[224,418,484] Other End-Group Modification Processes PNVP chain ends formed with xanthate RAFT agents are susceptible to hydrolysis and can be converted into aldehyde chain ends (Scheme 12). [379] The aldehyde chain ends can be used for bioconjugation. End group stability may also be an issue during RAFT polymerization of NVP particularly at higher reaction temperatures (>60 • C).…”

Section: Click Reactionsmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process - A Second Update

Moad¹,

Rizzardo²,

Thang³

2009

Aust. J. Chem.

906

720

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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 diverse 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.

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“…Many efforts are being undertaken to implement the alternative use of PVP in functionalization and conjugation. PVP chain ends can be functionalized during the polymerization of vinylpyrrolidone (VP), using, for example, functional transfer agents or specifi c chain capping agents in controlled (living) polymerization, to obtain chain ended conjugates, [7][8][9][10][11][12] structurally similar to those obtained with PEG. However, there is a great interest in the preparation of multi and polyfunctional lateral chain conjugates similar for instance to the derivatives of poly-hydoxypropylmethylacrylamide (PHPMA).…”

Section: Introductionmentioning

confidence: 99%

Homologous Copolymerization Route to Functional and Biocompatible Polyvinylpyrrolidone

Tardajos

Nash

Rochev

et al. 2012

Macro Chemistry & Physics

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Linear multifunctional polyvinylpyrrolidone (PVP) chains bearing carboxylate (COO−) or/and sulfonate (SO3−) groups are prepared by standard radical copolymerization of homologous vinylpyrrolidone (VP) and the VP derivatives 3‐carboxyvinylpyrrolidone (VPC) and 3‐sulfoalkylvinylpyrrolidone (VPS). Functional PVP networks with homogeneous crosslinking density are also prepared using a new homologous water‐compatible VP‐R‐VP crosslinker. This homologous approach for the preparation of functionalized PVP systems is compared theoretically with the preparation of VP with commercial acrylic comonomers bearing similar functionalities. All the linear chains and networks are tested under basic in vitro cell cultures.

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Polymer–protein conjugates from ω-aldehyde endfunctional poly(N-vinylpyrrolidone) synthesised via xanthate-mediated living radical polymerisation

Abstract: Aldehyde omega-endfunctional poly(N-vinylpyrrolidone) was synthesised via quantitative conversion of a xanthate endfunctional precursor obtained via RAFT-mediated polymerisation.

Cited by 91 publications

References 38 publications

Switchable Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization in Aqueous Solution, N,N-Dimethylacrylamide

Switchable Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization in Aqueous Solution, N,N-Dimethylacrylamide

Living Radical Polymerization by the RAFT Process - A Second Update

Homologous Copolymerization Route to Functional and Biocompatible Polyvinylpyrrolidone

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