通过氰氧基介导的自由基聚合（CMFRP）合成链端功能化糖聚合物

Synthesis of Chain-End Functionalized Glycopolymers via Cyanoxyl-Mediated Free Radical Polymerization (CMFRP).

作者信息

Gruzdys Valentinas, Tang Jinshan, Chaikof Elliot, Sun Xue-Long

机构信息

Department of Chemistry, Chemical and Biomedical Engineering and Center for Gene Regulation in Health and Disease (GRHD), Cleveland State University, 2121 Euclid Ave., Cleveland, OH, 44115, USA.

Department of Surgery, Beth Israel Deaconess Medical Center, Harvard Medical School, Wyss Institute of Biologically Inspired Engineering at Harvard University, Boston, MA, 02115, USA.

出版信息

Methods Mol Biol. 2016;1367:3-12. doi: 10.1007/978-1-4939-3130-9_1.

DOI:10.1007/978-1-4939-3130-9_1

PMID:26537460

Abstract

Glycopolymers are often used as glyco-macroligands for biological research and biomedical applications in carbohydrate recognitions. Chain-end functionalized glycopolymers show more potential for practical applications, such as protein modification and solid-phase bioassays. In particular, the chain-end group allows for direct one-to-one attachment or facilitates site-specific and oriented immobilization onto solid surfaces. A series of derivatized arylamine initiators are used to generate chain-end functionalized glycopolymers by cyanoxyl-mediated free radical polymerization (CMFRP). Important features of this strategy include the capacity to produce polymers of low polydispersity (PDI <1.5) under aqueous conditions using unprotected monomers bearing a wide range of functional groups. In addition, it provides a one-pot method to synthesize α,ω-telechelic glycopolymers with derivatized arylamine at one site and O-cyanate at the other site. In the process, the capacity to orthogonally label glycopolymers or otherwise conjugate them to proteins and other molecules is greatly enhanced.

摘要

糖聚合物通常用作糖大分子配体，用于碳水化合物识别方面的生物学研究和生物医学应用。链端功能化的糖聚合物在实际应用中显示出更大的潜力，如蛋白质修饰和固相生物测定。特别是，链端基团允许直接一对一连接，或便于在固体表面进行位点特异性和定向固定。一系列衍生化的芳胺引发剂用于通过氰氧基介导的自由基聚合（CMFRP）生成链端功能化的糖聚合物。该策略的重要特点包括能够在水性条件下，使用带有各种官能团的未保护单体，制备低多分散性（PDI <1.5）的聚合物。此外，它提供了一种一锅法来合成在一个位点带有衍生化芳胺，在另一个位点带有O-氰酸酯的α,ω-遥爪糖聚合物。在此过程中，对糖聚合物进行正交标记或以其他方式将它们与蛋白质及其他分子偶联的能力大大增强。