Abstract
In this focus review, recent developments in unnatural sugar- and protein-based polymers and their future bioapplications are discussed. A new unnatural oligoaminosaccharide carrying N-1,2-glycosidic bonds that cannot be prepared in natural biological systems has been proposed. To prepare the oligomers, a sugar monomer possessing a 2-methyl-2-oxazoline (MeOx) ring was polymerized via cationic ring-opening polymerization. This polymerization did not proceed by the classical MeOx mechanism but by a new mechanism involving sequential SN1-type reactions. This unnatural oligosaccharide was not decomposed by the natural enzymes owing to the unnatural N-1,2-glycosidic bonds, indicating promise in applications as a new class of glycomaterials. Furthermore, technology for stabilizing proteins using protein–polymer conjugations and polymer chain-folding nanoparticles has recently been developed. Amphiphilic/fluorous methacrylate-based random copolymers bearing polyethylene glycol (PEG) and fluorous side chains formed reversible PEG and fluorous compartments in water and 2H,3H-perfluoropentane (2HPFP), respectively. These copolymers were noncytotoxic and successfully conjugated with lysozymes. They also stabilized lysozyme and α-chymotrypsin in 2HPFP, and the enzymes were not denatured after extraction from 2HPFP.
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Acknowledgements
The author appreciates the support of the Japan Society for the Promotion of Science (JSPS) KAKENHI for this research through a Grant-in-Aid for Young Scientists (B, 17K14494; 20K15336) for the unnatural saccharide project. The author further thanks his supervisors in the protein projects, Prof. Mituso Sawamoto (Chubu Univ.), Prof. Takaya Terashima (Kyoto Univ.) and Prof. Heather D. Maynard (University of California, Los Angeles; UCLA), for their kind support and guidance. The author is also grateful to JSPS for a Grant-in-Aid for JSPS Research Fellows (DC1: 24-6140) for his fluorous projects. The author would like to thank AJE for English language editing.
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Koda, Y. Unnatural biopolymers of saccharides and proteins conjugated with poly(2-oxazoline) and methacrylate-based polymers: from polymer design to bioapplication. Polym J 54, 1431–1444 (2022). https://doi.org/10.1038/s41428-022-00695-z
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DOI: https://doi.org/10.1038/s41428-022-00695-z