水解可控功能切换型聚合刷的构筑及表面性能

doi:10.7503/cjcu20131092

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (5): 1093.doi: 10.7503/cjcu20131092

水解可控功能切换型聚合刷的构筑及表面性能

史素青(), 赵洋, 张琴, 高娜, 杨扬, 宫永宽

西北大学合成与天然功能分子化学教育部重点实验室, 化学与材料科学学院, 西安710069

收稿日期:2013-11-11 出版日期:2014-05-10 发布日期:2014-03-26
作者简介:联系人简介: 史素青, 女, 博士, 副教授, 主要从事防生物污染表/界面方面的研究. E-mail:shisq@nwu.edu.cn
基金资助:
国家自然科学基金(批准号: 21004047)、陕西省自然科学基础研究计划项目(批准号: 2010JQ2004)和教育部博士点新教师基金(批准号: 20106101120005)资助

Fabrication and Surface Properties of Hydrolyticly Function-switchable Polymer Brush^†

SHI Suqing^*(), ZHAO Yang, ZHANG Qin, GAO Na, YANG Yang, GONG Yongkuan

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Ministry of Education,College of Chemistry & Materials Science, Northwest University, Xi’an 710069, China

Received:2013-11-11 Online:2014-05-10 Published:2014-03-26
Contact: SHI Suqing E-mail:shisq@nwu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21004047), the Natural Science Basic Research Plan in Shaanxi Province of China(No.2010JQ2004) and Doctoral Fund of Youth Scholars of Ministry of Education of China(No.20106101120005)

摘要/Abstract

摘要：

采用表面受限光接枝技术在玻璃表面构筑末端酯键可水解的羧酸甜菜碱酯阳离子聚合物刷(PCBMA-1C2), 通过调节氨水浓度控制羧酸甜菜碱酯末端酯键的水解程度, 实现表面聚合物刷中季铵阳离子和羧酸甜菜碱两性离子基团分配比例的改变. 通过X射线光电子能谱(XPS)和接触角测试表征了改性表面的化学结构和亲/疏水性能, 通过蛋白质吸附和血小板黏附实验研究了玻璃表面改性前后及水解前后电荷性质对生物分子相互作用的影响. 结果发现, 当氨水浓度为0.1, 0.2, 0.3和0.4 mol/L时, 聚合物刷PCBMA-1C2改性表面羧酸甜菜碱酯末端酯键的水解率分别为6%, 43%, 56%和~100%, 随着水解程度的增大, 改性表面牛血清白蛋白(BSA)的吸附量依次降低了3%, 76%, 93%, 96%, 纤维蛋白原(Fg)吸附量则依次降低了11%, 45%, 90%和96%; 当水解率>50%时, 改性表面表现出优异的抗蛋白质吸附和血小板黏附性能.

关键词: 羧酸甜菜碱酯, 水解, 功能切换, 聚合物刷, 表面性能

Abstract:

A hydrolysable cationic polycarboxybetaine ester polymer brush(PCBMA-1C2) was fabricated by photografting method with surface-coupled tertiary amine as hetergenous hydrogen donor and benzophenone(BP) as photosensitizer. The hydrolysis of PCBMA-1C2 modified surface was evaluated by studying the hydrolysis behavior of CBMA-1C2 monomer under different ammonium hydroxide concentrations. X-ray photoelectron spectroscopy(XPS) and water contact angle were used to monitor the chemical changes and hydrophilicity, respectively. The protein adsorption and platelet adhesion experiments were used to evaluate the interaction between the material surface and the biomolecules. The results show that when the concentrations of ammonium hydroxide are 0.1, 0.2, 0.3 and 0.4 mol/L, the degrees of hydrolysis(DH) of terminal ester of CBMA-1C2 monomer are 6%, 43%, 56% and almost 100%, respectively. Compared with Glass-PCBMA-1C2 surface, with the increase of DH, the protein adsorption of BSA are reduced by 3%, 76%, 93% and 96%, and that of Fg are reduced by 11%, 45%, 90% and 96%, respectively. When DH>50%, the hydrolyzed Glass-PCBMA-1C2 surface exhibits good resistance of protein adsorption and platelet adhesion.

Key words: Carboxybetaine ester, Hydrolysis, Function switch, Polymer brush, Surface property

中图分类号:

O631

TrendMD:

史素青, 赵洋, 张琴, 高娜, 杨扬, 宫永宽. 水解可控功能切换型聚合刷的构筑及表面性能. 高等学校化学学报, 2014, 35(5): 1093.

SHI Suqing, ZHAO Yang, ZHANG Qin, GAO Na, YANG Yang, GONG Yongkuan. Fabrication and Surface Properties of Hydrolyticly Function-switchable Polymer Brush^†. Chem. J. Chinese Universities, 2014, 35(5): 1093.

图/表 9

Fig.1 1H NMR spectrum of CBMA-1C2(D2O)

Fig.2 Fabrication and hydrolysis of PCBMA-1C2 polymer brush on glass surface

Fig.3 1H NMR spectra of the hydrolyzed products of CBMA-1C2 in ammonium water of 0.1(a), 0.2(b), 0.3(c) and 0.4 mol/L(d), respectively

Fig.4 XPS spectra of glass surface before and after photografting^a. Blank glass; b. Glass-OH; c. Glass-N(CH3)2; d. Glass-PCBMA-1C2; e. Glass-PCBMA.

Table 1 Relative atomic contents(%) of glass surface

Glass	C	O	N	Si
Blank glass	12.58	58.11		29.31
Glass-OH	5.51	60.99		33.49
Glass-N(CH₃)₂	34.90	38.22	5.37	21.51
Glass-PCBMA-1C2	66.52	26.38	6.04	1.06
Glass-PCBMA	59.39	23.03	5.74	1.84

Table 2 Thickness, grafting density and degree of polymerization(DP) ofPCBMA-1C2 grafted glass surface

Sample	d/nm^a	DP^b	$M ˉ n$	σ/(Chain·nm^-2)^c
Glass-N(CH₃)₂	1.51
Glass-PCBMA-1C2	10.25	40.2	9830	0.63

Table 2 Thickness, grafting density and degree of polymerization(DP) ofPCBMA-1C2 grafted glass surface

Sample	d/nm^a	DP^b	$M ˉ n$	σ/(Chain·nm^-2)^c
Glass-N(CH₃)₂	1.51
Glass-PCBMA-1C2	10.25	40.2	9830	0.63

Fig.5 Static water contact angle for the glass surface^(A) Blank glass; (B) Glass-OH; (C) Glass-N(CH3)2; (D) Glass-PCBMA-1C2; (E) Glass-A-PCBMA-1C2;(F) Glass-B-PCBMA-1C2; (G) Glass-C-PCBMA-1C2; (H) Glass-PCBMA.

Fig.6 Protein adsorption for the glass surface^ Blank glass; Glass-PCBMA-1C2; Glass-A-PCBMA-1C2;

Fig.7 Platelet adhesion for the glass surface^(A) Blank glass; (B) Glass-PCBMA-1C2; (C) Glass-A-PCBMA-1C2; (D) Glass-B-PCBMA-1C2;(E) Glass-C-PCBMA-1C2; (F) Glass-PCBMA.

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水解可控功能切换型聚合刷的构筑及表面性能

Fabrication and Surface Properties of Hydrolyticly Function-switchable Polymer Brush^†

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水解可控功能切换型聚合刷的构筑及表面性能

Fabrication and Surface Properties of Hydrolyticly Function-switchable Polymer Brush†

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Fabrication and Surface Properties of Hydrolyticly Function-switchable Polymer Brush^†