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

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.