通过“点击”化学和“SET-NRC”反应一锅合成壳聚糖-g-(PEO-PLLA-PEO)。

One-pot synthesis of chitosan-g-(PEO-PLLA-PEO) via "click" chemistry and "SET-NRC" reaction.

机构信息

MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China.

出版信息

Carbohydr Polym. 2012 Nov 6;90(4):1515-21. doi: 10.1016/j.carbpol.2012.07.023. Epub 2012 Jul 16.

DOI:10.1016/j.carbpol.2012.07.023

PMID:22944410

Abstract

For the development of biocompatible and degradable biomaterials, a kind of well-defined graft copolymer consisting of chitosan back-bone and amphiphilic PEO-PLLA-PEO branch chains was synthesized by Cu(0) catalyzed one-pot strategy combining "click" chemistry and single electron transfer-nitroxide radical coupling (SET-NRC) reaction. First, the precursors of 6-azide-N-phthaloyl-chitosan, TEMPO-PEO-alkyne and mPEO-PLLA-Br were designed and produced. Then, the one-pot coupling reactions between these precursors were performed in the presence of nanosized Cu and PMDETA. The efficiencies of the coupling reactions were greater than 90% determined by the FTIR and ESR spectra. The structure of graft copolymer with 43% of the grafting ratio was confirmed by the spectral analysis. This work provided a route to prepare chitosan graft copolymer.

摘要

为了开发具有生物相容性和可降解性的生物材料，通过一锅法策略，结合“点击”化学和单电子转移-氮氧自由基偶联（SET-NRC）反应，使用纳米 Cu 和 PMDETA 作为催化剂，成功合成了一种由壳聚糖主链和两亲性 PEO-PLLA-PEO 支链组成的结构明确的接枝共聚物。首先，设计并制备了 6-叠氮-N-邻苯二甲酰壳聚糖、TEMPO-PEO-炔烃和 mPEO-PLLA-Br 的前体物。然后，在纳米 Cu 和 PMDETA 的存在下，进行这些前体之间的一锅偶联反应。通过傅里叶变换红外光谱（FTIR）和电子顺磁共振（ESR）谱确定，偶联反应的效率大于 90%。通过光谱分析证实了接枝率为 43%的接枝共聚物的结构。这项工作为制备壳聚糖接枝共聚物提供了一种途径。