writer：Jiawei Lu, Changkui Fu, Shiqi Wang, Lei Tao,* Litang Yan,* David M. Haddleton, Gaojian Chen,* Yen Wei
keywords：http://pubs.acs.org/doi/abs/10.1021/ma500664u
source：期刊
specific source：Macromolecules, Article ASAP DOI: 10.1021/ma500664u
Issue time：2014年

A novel, highly efficient methodology to synthesize gradient glycopolymers has been successfully developed involving concurrent enzymatic monomer transformation and reversible addition–fragmentation chain transfer (RAFT) polymerization. By synchronizing enzymatic monomer transformation with polymerization, a continuous supply of the second monomer (glycomonomer) is achieved during the polymerization, resulting in a gradient sugar distribution in the final polymer. Detailed studies of the process using GPC and NMR indicate that the gradient glycopolymers synthesized by RAFT were well controlled. Subsequently, 1,2:3,4-di-O-isopropylidene-6-O-methacryloyl-α-d-galactopyranose (DIMAG) moieties were deprotected to regenerate the sugar and achieve amphiphilic bioactive glycopolymers. We demonstrate the synthesis of a set of glycopolymers with different sequential structures, such as statistical, gradient and block glycopolymers. The glycopolymers with block structure show higher affinities toward the RCA₁₂₀ lectin receptor compared with other structural counterparts. Furthermore, simulation of the self-assembly of three types of copolymers and their binding to lectins provides fundamental insight into this result, revealing the mechanisms underlying the dependence of self-assembling structures and protein adsorption kinetics on the molecular architectures of copolymers.