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 S_N1-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.

在本次重点回顾中，讨论了基于非天然糖和蛋白质的聚合物的最新发展及其未来的生物应用。已经提出了一种新的非天然寡氨基糖，它带有在天然生物系统中无法制备的N -1,2-糖苷键。为了制备低聚物，具有 2-甲基-2-恶唑啉 (MeOx) 环的糖单体通过阳离子开环聚合进行聚合。这种聚合不是通过经典的 MeOx 机制进行的，而是通过涉及顺序 S _N 1 型反应的新机制进行的。这种非天然的寡糖由于非天然的N而不会被天然酶分解-1,2-糖苷键，表明在应用中作为一类新的糖材料的前景。此外，最近开发了使用蛋白质-聚合物缀合物和聚合物链折叠纳米粒子稳定蛋白质的技术。带有聚乙二醇 (PEG) 和氟侧链的两亲性/甲基丙烯酸氟系无规共聚物分别在水和 2 H ,3 H -全氟戊烷 (2HPFP) 中形成可逆的 PEG 和氟区室。这些共聚物是无细胞毒性的并且成功地与溶菌酶结合。他们还稳定了 2HPFP 中的溶菌酶和α-胰凝乳蛋白酶，从 2HPFP 中提取后这些酶没有变性。