Macromolecular design of poly(vinyl alcohol) by RAFT polymerization

Smith, Anders; Hussmann, Thomas; Elich, Joseph; Postma, Almar; Alves, Marie-Hélène; Zelikin, Alexander N.

doi:10.1039/c1py00429h

Cited by 37 publications

(47 citation statements)

References 24 publications

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“…An elegant example of functional PVAc has been published by Smith et al [62] with an ω-amino-PVA obtained by RAFT polymerization of VAc. In order to overcome the incompatibility of the amine and xanthate functions, the authors developed a phthalimido xanthate [131] (Scheme 8) and controlled the polymerization of VAc up to 60,000 g·mol…”

Section: Methodsmentioning

confidence: 99%

“…Some unusual leaving groups which have been used to control VAc polymerization include N-phthalimidomethyl [62,131], which can be transformed via hydrazinolysis to an amine group, and methylene bis(phosphonate) esters [53]. Some guidelines for selection of an R-group are given in Scheme 6.…”

Section: Methodsmentioning

confidence: 99%

“…Stereoblock copolymers of PVAc, containing atactic and syndiotactic segments, could be produced by partially polymerizing VAc in bulk at 60 °C, then adding hexafluoroisopropanol and cooling to 0 °C to complete the reaction. Finally, Zelikin et al recently reported the preparation of highly syndiotactic PVAc oligomers (racemic diad content of 69% ± 8%) using S-(N-phthalimido)methyl O-ethyl xanthate as chain transfer agent [62]. High syndiotacticities were only observed at 50 °C while using a high concentration of RAFT agent ([VAc]/[RAFT] = 33); the same RAFT concentration at 60 °C or a lower RAFT concentration at 37 °C resulted in atactic polymer (racemic diad content of 53%).…”

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confidence: 99%

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RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

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This article is the first comprehensive review on the study and use of vinyl ester monomers in reversible addition fragmentation chain transfer (RAFT) polymerization. It covers all the synthetic aspects associated with the definition of precision polymers comprising poly(vinyl ester) building blocks, such as the choice of RAFT agent and reaction conditions in order to progress from simple to complex macromolecular architectures. Although vinyl acetate was by far the most studied monomer of the range, many vinyl esters have been considered in order to tune various polymer properties, in particular, solubility in supercritical carbon dioxide (scCO 2 ). A special emphasis is given to novel poly(vinyl alkylate)s with enhanced solubilities in scCO 2 , with applications as reactive stabilizers for dispersion polymerization and macromolecular surfactants for CO 2 media. Other miscellaneous uses of poly(vinyl ester)s synthesized by RAFT, for instance as a means to produce poly(vinyl alcohol) with controlled characteristics for use in the biomedical area, are also covered.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

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“…A [285] VAc [285] 235 [520,521] 236 O S S A* (NES) [290] (BES) [290] (Continued ) [293] VAc [293] 238…”

Section: Pcl Macro-raft Agentmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 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 diverse 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.

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“…For FM, samples of HNP were prepared using commercial PVA mixed with custom made, fluorescently labelled PVA. For the latter, RAFT--derived, amine--terminated PVA was reacted with fluorescein isothiocyanate and purified via precipitation into methanol, 39 as described in detail in the Experimental Section. Resulting preparation of HNP revealed excellent colloidal stability and presented FM image confirms the expected size of HNP.…”

Section: +Particlementioning

confidence: 99%

Poly(vinyl alcohol) Physical Hydrogel Nanoparticles, Not Polymer Solutions, Exert Inhibition of Nitric Oxide Synthesis in Cultured Macrophages

et al. 2013

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Hydrogel nanoparticles (HNP) are an emerging tool of biomedicine with unique materials characteristics, scope, and utility. These hydrated, soft colloidal carriers can penetrate through voids with dimensions narrower than the size of the particle, provide stabilization for fragile biological cargo and allow diffusion and exchange of solutes with external phase. However, techniques to assemble HNP are few; solitary examples exist of biocompatible polymers being formulated into HNP; and knowledge on the biomedical properties of HNP remains rather cursory. In this work, we investigate assembly of HNP based on a polymer with decades of prominence in the biomedical field, poly(vinyl alcohol), PVA. We develop a novel method for production of PVA HNP through nanoprecipitation-based assembly of polymer nanoparticles and subsequent physical hydrogelation of the polymer. Polymer nanoparticles and HNP were visualized using scanning electron microscopy and fluorescence imaging, and characterized using dynamic light scattering and zeta potential measurements. Interaction of PVA HNP with mammalian cells was investigated using flow cytometry, viability screening, and measurements of nitric oxide production by cultured macrophages. The latter analyses revealed that PVA administered as a polymer solution or in the form of HNP resulted in no measurable increase in production of the inflammation marker. Unexpectedly, PVA HNP exerted a pronounced inhibition of NO synthesis by stimulated macrophages, that is, had an anti-inflammatory activity. This effect was accomplished with a negligible change in the cell viability and was not observed when PVA was administered as a polymer solution. To the best of our knowledge, this is the first observation of inhibition of NO synthesis in macrophages by administered nanoparticles and specifically hydrogel nanoparticles. Taken together, our results present PVA HNP as promising colloidal hydrogel nanocarriers for biomedical applications, specifically drug delivery and assembly of intracellular biosensors. Corresponding author : E-mail: zelikin@chem.au.dk ABSTRACT Hydrogel nanoparticles (HNP) are an emerging tool of biomedicine with unique materials characteristics, scope, and utility. These hydrated, soft colloidal carriers can penetrate through voids with dimensions narrower than the size of the particle, provide stabilization for fragile biological cargo, and allow diffusion and exchange of solutes with external phase. However, techniques to assemble HNP are few; solitary examples exist of biocompatible polymers being formulated into HNP; and knowledge on the biomedical properties of HNP remains rather cursory. In this work, we investigate assembly of HNP based on a polymer with decades of prominence in the biomedical filed, poly(vinyl alcohol), PVA. We develop a novel method for production of PVA HNP through nanoprecipitation -based assembly of polymer nanoparticles and subsequent physical hydrogelation of the polymer. Polymer nanoparticles and HNP were visualized using scanning ele...

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Macromolecular design of poly(vinyl alcohol) by RAFT polymerization

Abstract: Modern tools of polymer design yield superior PVA with drastically enhanced utility in biomedicine.

Cited by 37 publications

References 24 publications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

Living Radical Polymerization by the RAFT Process – A Third Update

Poly(vinyl alcohol) Physical Hydrogel Nanoparticles, Not Polymer Solutions, Exert Inhibition of Nitric Oxide Synthesis in Cultured Macrophages

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