文献类型：期刊文献

英文题名：Identifying the Hydrolysis of Carbonyl Sulfide as a Side Reaction Impeding the Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride

作者：Zheng, Botuo[1];Bai, Tianwen[1];Tao, Xinfeng[1,2,3];Schlaad, Helmut[4];Ling, Jun[1]

机构：[1]Zhejiang Univ, Dept Polymer Sci & Engn, MOE Key Lab Macromol Synth & Functionalizat, Hangzhou 310027, Zhejiang, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Key Lab Adv Polymer Mat, Sch Mat Sci & Engn, Key Lab Ultrafine Mat,Minist Educ, Shanghai 200237, Peoples R China;[3]PSL Univ Paris, Chim ParisTech, CNRS, Inst Rech Chim Paris,UMR8247, 11 Rue Pierre & Marie Curie, F-75005 Paris, France;[4]Univ Potsdam, Inst Chem, Karl Liebknecht Str 24-25, D-14476 Potsdam, Germany

年份：2018

卷号：19

期号：11

起止页码：4263

外文期刊名：BIOMACROMOLECULES

收录：;EI(收录号：20184305979144);WOS:【SCI-EXPANDED(收录号:WOS:000450374100010)】；

基金：This work is sponsored by the National Natural Science Foundation of China (21674091, 21528402).

语种：英文

外文关键词：Reaction intermediates - Drug delivery - Quantum theory - Sulfur compounds - Density functional theory - Hydrolysis - Substitution reactions - Computation theory - Ring opening polymerization

摘要：Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization. Herein, we discover that during polymerization hydrogen sulfide evolves from the hydrolysis of carbonyl sulfide, which is the byproduct of ring-opening reaction, and reacts with NNTA to produce cyclic oligopeptoids. The capture of N-ethylethanethioic acid as an intermediate product confirms the reaction mechanism together with density functional theory quantum computational results. By bubbling the polymerization solution with argon, the side reaction can be suppressed to allow the synthesis of polysarcosine with high molar mass (M-n = 11,200 g/mol, D = 1.25) even in the presence of similar to 10,000 ppm of water.