MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
Fujian Key Laboratory of Polymer Science, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China.
Macromol Rapid Commun. 2021 Nov;42(22):e2100453. doi: 10.1002/marc.202100453. Epub 2021 Oct 13.
Poly(α-amino acid)s (PAAs) attract growing attention due to their essential role in the application as biomaterials. To synthesize PAAs with desired structures and properties, scientists have developed various synthetic techniques with respective advantages. Here, different approaches to preparing PAAs are inspected. Basic features and recent progresses of these methods are summarized, including polymerizations of amino acid N-carboxyanhydrides (NCAs), amino acid N-thiocarboxyanhydrides (NTAs), and N-phenoxycarbonyl amino acids (NPCs), as well as other synthetic routes. NCA is the most classical monomer to prepare PAAs with high molecular weights (MWs). NTA polymerizations are promising alternative pathways to produce PAAs, which can tolerate nucleophiles including alcohols, mercaptans, carboxyl acids, and water. By various techniques including choosing appropriate solvents or using organic acids as promoters, NTAs polymerize to produce polypeptoids and polypeptides with narrow dispersities and designed MWs up to 55.0 and 57.0 kg mol , respectively. NPC polymerizations are phosgene-free ways to synthesize polypeptides and polypeptoids. For the future prospects, detail investigations into polymerization mechanisms of NTA and NPC are expected. The synthesis of PAAs with designed topologies and assembly structures is another intriguing topic. The advantages and unsettled problems in various synthetic ways are discussed for readers to choose appropriate approaches for PAAs.
聚（α-氨基酸）（PAAs）由于在作为生物材料的应用中的重要作用而引起了越来越多的关注。为了合成具有所需结构和性能的 PAAs，科学家们已经开发了具有各自优势的各种合成技术。在这里，检查了制备 PAAs 的不同方法。总结了这些方法的基本特征和最新进展，包括氨基酸 N-羧酸酐（NCAs）、氨基酸 N-硫代羧酸酐（NTAs）和 N-苯甲酰基氨基酸（NPCs）以及其他合成途径的聚合。NCA 是制备高分子量（MW）PAAs 的最经典单体。NTA 聚合是制备 PAAs 的很有前途的替代途径，可以容忍包括醇、硫醇、羧酸和水在内的亲核试剂。通过包括选择合适的溶剂或使用有机酸作为促进剂在内的各种技术，NTA 聚合可以产生分子量分布窄且设计分子量高达 55.0 和 57.0 kg/mol 的多肽和多肽。NPC 聚合是合成多肽和多肽的无光气方法。未来展望方面，预计将对 NTA 和 NPC 的聚合机理进行详细研究。具有设计拓扑结构和组装结构的 PAAs 的合成是另一个有趣的课题。为了让读者选择合适的 PAAs 合成方法，讨论了各种合成方法的优缺点和未解决的问题。
