Synthesis and Characterization of α,ω-end Orthogonally Functionalizable Glycopolymers from Native Glycans

ORCID ID

Xue-Long Sun https://orcid.org/0000-0001-6483-1709

Document Type

Article

Publication Date

4-2024

Publication Title

Polymer Chemistry

Abstract

Glycopolymers have been employed as biomimetic glycoconjugates in both biological and biomedical research and applications. Among them, chain-end functionalized glycopolymers are often explored for protein modification, microarray, biosensor, bioprobe and other applications. Herein, we report a straightforward synthesis of α,ω-end orthogonally functionalizable glycopolymers. Specifically, glycopolymers with an alkyne or azide group at one end and an O-cyanate on the other end were synthesized via cyanoxyl-mediated free-radical polymerization from native glycans without protection and deprotection. The alkyne chain-end can react with azide-containing molecules via click chemistry. The azide chain-end can react with alkyne-containing molecules via click chemistry or copper free click chemistry. On the other hand, O-cyanate can react with an amine group via isourea bond, affording a site-specific bioconjugation as well. Furthermore, chain-end heterofunctionalizations of the glycopolymers were demonstrated via sequential or one-pot click chemistry and isourea bond formation, respectively. Finally, end-to-end dimerization of the glycopolymers was demonstrated via chain-end click chemistry. These α,ω-end orthogonally functionalizable glycopolymers will be useful in many biological and biomedical research applications

Comments

This work was supported by grants from the NIH (1R15HL138544-01, X.-L. Sun), National Science Foundation MRI Grant (CHE-1126384, X.-L. Sun) and Research Fund from the Center for Gene Regulation in Health and Disease (GRHD) (X.-L. Sun) and Graduate Student Research Award (J. M. Keil and K. K. Chan) at Cleveland State University.

DOI

10.1039/d4py00191e

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