文献类型：期刊文献

英文题名：Organocatalytic Ring-Opening Polymerization Toward Poly(γ-amide-ε-caprolactone)s with Tunable Lower Critical Solution Temperatures

作者：Wen, Lianlei[1];Zhang, Shaoze[2];Xiao, Yan[1];He, Jin[1];Zhu, Shuang[1];Zhang, Jun[1];Wu, Zihan[1];Lang, Meidong[1]

机构：[1]East China Univ Sci & Technol, Sch Mat Sci & Engn, Minist Educ, Shanghai Key Lab Adv Polymer Mat,Key Lab Ultrafin, Shanghai 200237, Peoples R China;[2]Kunming Univ Sci & Technol, Natl Engn Lab Vacuum Met, Engn Lab Adv Battery & Mat Yunnan Prov, Kunming 650093, Yunnan, Peoples R China

年份：2020

卷号：53

期号：13

起止页码：5096

外文期刊名：MACROMOLECULES

收录：;EI(收录号：20202808929615);WOS:【SCI-EXPANDED(收录号:WOS:000551424200009)】；

基金：We are grateful for the financial support by the National Natural Science Foundation of the People's Republic of China (21674037), National Key Research and Development Program (2016YFC1100703), Natural Science Foundation of Shanghai (18ZR1410200), and Science and Technology Commission of Shanghai Municipality (18JC1410802).

语种：英文

外文关键词：Density functional theory - Biocompatibility - Computation theory - Biodegradability - Nickel compounds - Enzyme activity - Amides - Hydrophilicity

摘要：gamma-Amide-e-caprolactones including 7-oxo-N-propyloxepane-4-carboxamide (NNCL), N-isopropyl-7-oxooxepane-4-carboxamide (NICL), N,N-diethyl-7-oxooxepane-4-carboxamide (DECL), and 5-(pyrrolidine-1-carbonyl)oxepan-2-one (VPyCL) were initially designed and synthesized to achieve biodegradable and thermosensitive materials. Ring-opening polymerization (ROP) of these newly developed caprolactones was thoroughly investigated by both theoretical calculation and experimental verification. Density functional theory revealed that the ring-opening enthalpy of gamma-amide-epsilon-caprolactones was more negative than that of gamma-estere-caprolactone (EMCL). Experimental results showed that ROP of NICL, DECL, and VPyCL catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene with benzyl alcohol (BnOH) as an initiator underwent in a living and controlled manner, while that of NNCL and EMCL did not. Computational calculation consistently proved that a variety of substitutions greatly affected the ROP process. PNICL, PDECL, and PVPyCL exhibited reversible lower critical solution temperature-type phase transitions tuned by manipulating the feed ratio and hydrophilicity of comonomers. Furthermore, poly(gamma-amide-epsilon-caprolactone)s with excellent biodegradability and biocompatibility were demonstrated as an enzyme activity regulator, holding great promise for smart biomaterial application.