Ishibe, Toru, Gonzalez-Martinez, Natalia, Georgiou, Panagiotis G., Murray, Kathryn A. and Gibson, Matthew I. (2022) Synthesis of poly(2-(methylsulfinyl)ethyl methacrylate) via oxidation of poly(2-(methylthio)ethyl methacrylate) : evaluation of the sulfoxide side chain on cryopreservation. ACS Polymers Au, 2 (6). pp. 449-457. doi:10.1021/acspolymersau.2c00028 ISSN 2694-2453.

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Abstract

Conventional cryopreservation solutions rely on the addition of organic solvents such as DMSO or glycerol, but these do not give full recovery for all cell types, and innovative cryoprotectants may address damage pathways which these solvents do not protect against. Macromolecular cryoprotectants are emerging, but there is a need to understand their structure–property relationships and mechanisms of action. Here we synthesized and investigated the cryoprotective behavior of sulfoxide (i.e., “DMSO-like”) side-chain polymers, which have been reported to be cryoprotective using poly(ethylene glycol)-based polymers. We also wanted to determine if the polarized sulfoxide bond (S+O– character) introduces cryoprotective effects, as this has been seen for mixed-charge cryoprotective polyampholytes, whose mechanism of action is not yet understood. Poly(2-(methylsulfinyl)ethyl methacrylate) was synthesized by RAFT polymerization of 2-(methylthio)ethyl methacrylate and subsequent oxidation to sulfoxide. A corresponding N-oxide polymer was also prepared and characterized: (poly(2-(dimethylamineoxide)ethyl methacrylate). Ice recrystallization inhibition assays and differential scanning calorimetry analysis show that the sulfoxide side chains do not modulate the frozen components during cryopreservation. In cytotoxicity assays, it was found that long-term (24 h) exposure of the polymers was not tolerated by cells, but shorter (30 min) incubation times, which are relevant for cryopreservation, were tolerated. It was also observed that overoxidation to the sulfone significantly increased the cytotoxicity, and hence, these materials require a precision oxidation step to be deployed. In suspension cell cryopreservation investigations, the polysulfoxides did not increase cell recovery 24 h post-thaw. These results show that unlike hydrophilic backboned polysulfides, which can aid cryopreservation, the installation of the sulfoxide group onto a polymer does not necessarily bring cryoprotective properties, highlighting the challenges of developing and discovering macromolecular cryoprotectants.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH):	Polymers, Cryobiology, Addition polymerization
Journal or Publication Title:	ACS Polymers Au
Publisher:	American Chemical Society (ACS)
ISSN:	2694-2453
Official Date:	14 December 2022
Dates:	Date Event 14 December 2022 Published 5 August 2022 Available 26 July 2022 Accepted
Volume:	2
Number:	6
Page Range:	pp. 449-457
DOI:	10.1021/acspolymersau.2c00028
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Open Access (Creative Commons)
Date of first compliant deposit:	9 August 2022
Date of first compliant Open Access:	18 August 2022
RIOXX Funder/Project Grant:	Project/Grant ID RIOXX Funder Name Funder ID 866056 [ERC] Horizon 2020 Framework Programme http://dx.doi.org/10.13039/100010661 814236 H2020 Marie Skłodowska-Curie Actions http://dx.doi.org/10.13039/100010665 191037 [RS] Royal Society http://dx.doi.org/10.13039/501100000288 WT-219429/Z/19/Z Wellcome Trust http://dx.doi.org/10.13039/100010269
Related URLs:	Related dataset

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