Citation: Yu Zhu, Wen-ling Ye, Zhi-feng Liu, Wei Deng, Mei-na Liu. Synthesis and Properties of Well-defined Glycopolymers via Combining Ring-opening Metathesis Polymerization and CuAAC Reaction[J]. Acta Polymerica Sinica, ;2019, 50(1): 44-54. doi: 10.11777/j.issn1000-3304.2018.18167 shu

Synthesis and Properties of Well-defined Glycopolymers via Combining Ring-opening Metathesis Polymerization and CuAAC Reaction

Yu Zhu ¹ ,
Wen-ling Ye ¹ ,
Zhi-feng Liu ¹ ,
Wei Deng ^1,, ,
Mei-na Liu ^1,2,3,,

1.
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418
2.
State Key Laboratory of Polymer Molecular Engineering, Department of Polymer Science, Fudan University, Shanghai 200433
3.
Key Laboratory of Organic Functional Molecular Synthesis and Assembly Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Wei Deng, dengw@sit.edu.cn Mei-na Liu, meina.liu@sit.edu.cn
Received Date: 20 July 2018
Revised Date: 24 August 2018
Available Online: 12 October 2018

A series of glycopolymers were prepared through combining ring-opening metathesis polymerization (ROMP) and CuAAC reaction. Firstly, a wide range of exo-7-oxanorbornene derivative glycomonomers without protecting groups were synthesized via a copper(I)-catalyzed azide-alkyne Huisgen cycloaddition (CuAAC) reaction, including α-D-mannose, β-D-glucose, and β-D-galactose. A series of well-defined glycopolymers were then obtained from various types and proportions of the above glycomonomers using ring-opening metathesis polymerization (ROMP) with the 3^rd Grubbs catalyst in homogeneous organic solvent. Molecular weight and polydispersity index (PDI) of the glycopolymers were characterized by NMR spectroscopy and GPC, from which the well-controlled molecular weight (M_n = 1.3 × 10⁴ − 2.7 × 10 ⁴) in narrow distribution (PDI = 1.22 ~ 1.45) was confirmed. Turbidity measurement, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC) were carried out to investigate the specific recognition of glycopolymers with concanavalin A (Con A). Turbidimetric study suggested a stronger binding ability of glycopolymers with Con A at higher ratio of α-D-mannose in glycopolymers. In comparison, those composed solely of β-D-galactose (P9) or β-D-glucose (P5) could not bind to Con A. Dynamic light scattering experiments demonstrated that the particle sizes of glycopolymers containing α-D-mannose approached 1000 nm with the addition of Con A (originally 100 nm), while the glycopolymers without α-D-mannose showed little size variation. Binding constants (K_a) of the three glycopolymers P3 (50 mol% α-D-mannose, 50 mol% β-D-glucose), P7 (50 mol% α-D-mannose, 50 mol% β-D-galactose), and P11 (50 mol% α-D-mannose, 50 mol% non-sugar motif) with Con A were 1.58 × 10⁶, 2.23 × 10⁶, and 2.05 × 10⁵ L/mol, respectively, as measured by isothermal titration calorimetry. P11 exhibited much weaker ability to bind with Con A than P3 andP7 did, which implied a synergistic effect of β-D-glucose and β-D-galactose on the recognition of α-D-mannose with Con A.
- Ring-opening metathesis polymerization,
- Glycopolymers,
- CuAAC reaction,
- Lectin recognition,
- Concanavalin A
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis and Properties of Well-defined Glycopolymers via Combining Ring-opening Metathesis Polymerization and CuAAC Reaction

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com