Poly(oligo(ethylene glycol) vinyl acetate)s: A Versatile Class of Thermoresponsive and Biocompatible Polymers

Hedir, Guillaume; Arno, Maria C.; Langlais, Marvin; Husband, Jonathan; O’Reilly, Rachel K.; Dove, Andrew P.

doi:10.1002/anie.201703763

Cited by 58 publications

(51 citation statements)

References 52 publications

(19 reference statements)

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“…33,34 Recent years have seen a resurgence of interest in CKAs, which may be explained, at least in part, by their ability to copolymerize with traditional vinyl monomers (e.g., vinyl acetate, methacrylic esters) by both conventional free-radical polymerization and RDRP techniques. [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] However, to the best of our knowledge, there is no example of PISA systems or emulsion/dispersion (co)polymerizations based on CKAs. Only two related studies have been published so far.…”

Section: Introductionmentioning

confidence: 99%

Radical Ring-Opening Copolymerization-Induced Self-Assembly (rROPISA)

et al. 2019

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Radical ring-opening copolymerization-induced self-assembly (rROPISA) was performed by copolymerizing benzyl methacrylate (BzMA) and cyclic ketene acetals (CKA), such as 2methylene-4-phenyl-1,3-dioxolane (MPDL) or 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), in heptane at 90 °C by reversible addition-fragmentation chain transfer (RAFT) polymerization from a poly(lauryl methacrylate) (PLMA) macro RAFT agent. The chain lengths of both the solvophilic macro-RAFT agent and the solvophobic block, together with the initial amount of CKA were independently varied to achieve various compositions. The amount of CKA in the copolymers was ranged from 4 to ~40 mol.% by adjusting the monomer stoichiometry, leading to nearly complete degradation for CKA contents above ~15 mol.%. rROPISA led to stable nanoparticles in all cases, ranging from 40 to 500 nm in diameter, depending on the experimental conditions, as assessed by DLS and TEM. Low average diameters and very narrow particle size distributions were obtained for CKA contents below 20 mol.%, except for a targeted solvophobic chain length of 300 that gave narrow particle size distributions up to 50 mol.% in CKA. Morphological investigation revealed the formation of spheres for all copolymer compositions, which was assigned to both the nature of the RAFT agent used and insertion of CKA in the solvophobic block, that prevent formation of other morphologies.

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Section: Introductionmentioning

confidence: 99%

Radical Ring-Opening Copolymerization-Induced Self-Assembly (rROPISA)

et al. 2019

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“…[9,10] Indeed, the copolymerization of vinyl-based monomers and CKAs has been used to prepare (bio)degradable polyethylene, [21] fluoropolymers, [22] polymethyl methacrylate materials, [18] marine anti-biofouling coatings, [23,24] etc.,o ffering ap romising route to reduce plastic pollution. This approach has also been used to confer (bio)degradability to many vinyl-based biomaterials such as polymer prodrugs, [25] nanoparticles, [26,27] thermo-responsive materials, [20,28,29] icerecrystallization inhibitors, [30] etc. To confer efficient (bio)degradability,the incorporation of ester bonds into the polymer backbone has to be performed randomly,a sd emonstrated theoretically by Lefay et al [31] using kinetic modelling.…”

Section: Introductionmentioning

confidence: 99%

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

et al. 2020

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Radical ring‐opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring‐opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl‐based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring‐opening and ring‐retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring‐open under all experimental conditions. In this article we investigate the radical ring‐opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring‐opening ability of CKA monomers.

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“…A key advantage for amphiphilic polymers and block polymers is their ability to undergo assembly in water. The self‐assembly of amphiphilic block copolymers into micelles or other nanostructures in aqueous solution allows for investigation of their use as nanoscopic objects with potential implementation in a range of vital applications from biomedical to engineering applications . Degradable polymers are of great interest as they can enable straightforward end‐of‐use options for polymeric systems, and a tunable cargo release based on the degradation rate of the polymeric scaffold .…”

Section: Introductionmentioning

confidence: 99%

Construction of nanostructures in aqueous solution from amphiphilic glucose‐derived polycarbonates

Osumi

Felder

Wang

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.ABSTRACT: Carbohydrates are the fundamental building blocks of many natural polymers, their wide bioavailability, high chemical functionality, and stereochemical diversity make them attractive starting materials for the development of new synthetic polymers. In this work, one such carbohydrate, D-glucopyranoside, was utilized to produce a hydrophobic five-membered cyclic carbonate monomer to afford sugar-based amphiphilic copolymers and block copolymers via organocatalyzed ring-opening polymerizations with 4-methylbenzyl alcohol and methoxy poly(ethylene glycol) as initiator and macroinitiator, respectively. To modulate the amphiphilicities of these polymers acidic benzylidene cleavage reactions were performed to deprotect the sugar repeat units and present hydrophilic hydroxyl side chain groups. Assembly of the polymers under aqueous conditions revealed interesting morphological differences, based on the polymer molar mass and repeat unit composition. The initial polymers, prior to the removal of the benzylidenes, underwent a morphological change from micelles to vesicles as the sugar block length was increased, causing a decrease in the hydrophilichydrophobic ratio. Deprotection of the sugar block increased the hydrophilicity and gave micellar morphologies. This tunable polymeric platform holds promise for the production of advanced materials for implementation in a diverse range of applications.Morphological control over the supramolecular assembly of amphiphilic polymers has been studied widely in the bulk and solution states. [21][22][23][24][25][26] A key advantage for amphiphilic polymers and block polymers is their ability to undergo assembly in water. The self-assembly of amphiphilic block copolymers into micelles or other nanostructures in aqueous solution allows Additional supporting information may be found in the online version of this article. † Shota Osumi and Simcha E. Felder contributed equally to this study.

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Poly(oligo(ethylene glycol) vinyl acetate)s: A Versatile Class of Thermoresponsive and Biocompatible Polymers

Cited by 58 publications

References 52 publications

Radical Ring-Opening Copolymerization-Induced Self-Assembly (rROPISA)

Radical Ring-Opening Copolymerization-Induced Self-Assembly (rROPISA)

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

Construction of nanostructures in aqueous solution from amphiphilic glucose‐derived polycarbonates

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