End-Functionalized Poly(N-isopropylacrylamide) with d-Glucosamine through Different Initiator from C-1 and C-2 Positions via Atom Transfer Radical Polymerization

Guihua Cui; Zhengguo Gao; Nannan Qiu; Toshifumi Satoh; Toyoji Kakuchi; Qian Duan

doi:10.3390/ma9110913

End-Functionalized Poly(N-isopropylacrylamide) with d-Glucosamine through Different Initiator from C-1 and C-2 Positions via Atom Transfer Radical Polymerization

Materials (Basel). 2016 Nov 10;9(11):913. doi: 10.3390/ma9110913.

Authors

Guihua Cui^{1

2}, Zhengguo Gao³, Nannan Qiu⁴, Toshifumi Satoh⁵, Toyoji Kakuchi⁶, Qian Duan⁷

Affiliations

¹ Department of Chemistry, Jilin Medical College, Jilin 132013, China. cuiyuhan1981_0@sohu.com.
² Department of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, China. cuiyuhan1981_0@sohu.com.
³ Chemical and Engineering College, Yantai University, Yantai 264005, China. zggao_80@163.com.
⁴ Department of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, China. jlmukjc@126.com.
⁵ Division of Biotechnology and Macromolecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan. Satoh@polymer.ac.jp.
⁶ Division of Biotechnology and Macromolecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan. Kakuchi@polymer.ac.jp.
⁷ Department of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, China. duanqian88@hotmail.com.

Abstract

Regioselective modification of d-glucosamine (2-amino-2-deoxy-d-glucopyranose, GA) through C-1 and C-2 positions to synthesized thermo-responsive D-Glucosamine-poly(N-iso-propylacrylamide) (PNIPAM) via atom transfer radical polymerization (ATRP) was investigated for the first time. Two different schemes of the synthesis for GA derivatives (GA-PNIPAM (i) and (ii)) with well-defined structures using 3,4,6-tri-o-acetyl-2-deoxy-2-phthalimido-β-d-glucopyranose and 1,3,4,6-tetra-o-acetyl-2-amino-2-deoxy-β-d-glucopyranose intermediates were examined. The GA-PNIPAM (ii) had an amino at C-2 position, while there was a hydroxyl in GA-PNIPAM (i) at this position. Both the resulting oligomers (i) and (ii) had a narrow dispersity, and no significant cytotoxic response of copolymers (i) and (ii) was observed in the cell line over the concentration range from 0.1 μg/mL to 1000 μg/mL at any of the exposure times. In addition, it was discovered that GA-PNIPAM (i) and (ii) inhibited the proliferation of Human Hepatocellular Carcinoma Cells HepG2 as the concentration and the time changed, and the inhibitory activity of polymer (ii) was higher than that of he (i). The results suggest that the GA-PNIPAM polymers show excellent biocompatibility in vitro.

Keywords: ">d-glucosamine (GA); atom transfer radical polymerization (ATRP); lower critical solution temperature (LCST); poly(N-isopropylacrylamide) (PNIPAM).