聚谷氨酸基超分子水凝胶的制备和表征

doi:10.7503/cjcu20150551

摘要/Abstract

摘要：

以接枝胆固醇的聚谷氨酸-聚乙二醇-聚谷氨酸三嵌段聚合物和接枝β-环糊精的聚谷氨酸为前躯体, 通过主客体作用制备聚谷氨酸基超分子水凝胶. 通过调控前躯体的浓度、胆固醇和环糊精的摩尔比, 得到不同力学性能的水凝胶; 改变三嵌段聚合物中聚谷氨酸的分子量, 调控聚谷氨酸基超分子水凝胶的力学强度、微观形貌、溶胀行为和降解性能. 研究结果表明, 当聚合物浓度为150 g/L、环糊精和胆固醇的摩尔比为1:1时, 水凝胶的储存模量最大; 聚谷氨酸的分子量越大, 水凝胶的储存模量越大; 水凝胶平均孔径10~30 μm, 溶胀度16%~30%, 降解时间为40~72 d. 水凝胶细胞毒性实验结果表明超分子水凝胶具有良好的生物相容性.

关键词: 聚谷氨酸, β-环糊精, 胆固醇, 超分子水凝胶, 储存模量, 生物相容性

Abstract:

Supermolecular hydrogels composed of cholesterol-modified triblock polymers poly(L-glutamic acid)-poly(ethylene glycol)-poly(L-glutamic acid)[(PLGA-b-PEG-b-PLGA)-g-Chol] and β-cyclodextrins(β-CD)-modified poly(L-glutamic acid)(PLGA-g-β-CD) were fabricated by host-guest interaction between cholesterol(Chol) and β-CD. This study presented the influence of concentrations and molar ratio on mechanical strength, PLGA molecular weight on mechanical strength, pore size, swelling ratios and biodegradability. The results showed that storage modulus was highest at concentrations of 150 g/L and Chol/β-CD molar ratio of 1:1. The average pore size of PLGA-based supermolecular hydrogels fabricated from concentrations of 150 g/L was between 10—30 μm. Swelling ratio was between 16%—32.5%. Degradation time could be controlled PLGA molecular weight from 40 d to 72 d. The excellent self-healing ability of hydrogels was performed. The cytotoxicity evaluation was observed that the adipose-derived stem cells treated with the polymers remained almost 100% viable, indicating good cytocompatibility of the hydrogels.

Key words: Poly(L-glutamic acid), β-Cyclodextrin, Cholesterol, Supermolecular hydrogel, Storage modulus, Cytocompatibility

中图分类号:

O636

TrendMD:

李贵飞, 吴杰, 王波, 张伟骏, 颜世峰, 尹静波. 聚谷氨酸基超分子水凝胶的制备和表征. 高等学校化学学报, 2015, 36(12): 2582.

LI Guifei, WU Jie, WANG Bo, ZHANG Weijun, YAN Shifeng, YIN Jingbo. Fabrication and Characterization of PLGA-based Supermolecular Hydrogel^†. Chem. J. Chinese Universities, 2015, 36(12): 2582.

图/表 12

Scheme 1 Synthesis of PLGA-b-PEG-b-PLGA

Fig.1 1H NMR spectra of PLGA-b-PEG-b-PLGA a. PLGA1433-b-PEG2000-b-PLGA1433; b. PLGA13494-b-PEG2000-b-PLGA13494; c. PLGA30250-b-PEG2000-b-PLGA30250.

Scheme 2 Synthetic routes of (PLGA-b-PEG-b-PLGA)-g-Chol and PLGA-g-β-CD

Fig.2 1H NMR spectra of (PLGA-b-PEG-b-PLGA)-g-Chol(A) and PLGA-g-β-CD(B) (A) a. (PLGA1433-b-PEG2000-b-PLGA1433)-g-Chol19.67%; b. cholesterol; c. PLGA1433-b-PEG2000-b-PLGA1433;(B) a. PLGA-g-β-CD; b. β-CD-NH2·HCl; c. PLGA.

Scheme 3 Preparation process of supermolecular hydrogels

Fig.3 Photographs of PLGA1433, PLGA13494 and PLGA30250 hydrogels

Fig.4 Storage modulus(G', a—c) and loss modulus(G″, a'—c') of hydrogels PLGA1433 with concentrations of 50 g/L(a, a'), 100 g/L(b, b') and 150 g/L(c, c')(nChol/nβ-CD= 1:1)

Fig.5 Storage modulus(G', a—c) and loss modulus(G″, a'—c') of PLGA1433(a, a'), PLGA13494(b, b'), and PLGA30250(c, c') at concentration of 150 g/L

Fig.6 Storage modulus(G', a—c) and loss modulus(G″, a'—c') of hydrogels PLGA1433 (150 g/mL) with different ratios of β-CD and Chol nChol/nβ-CD: a, a'. 1:1; b, b'. 1:2; c, c'. 2:1.

Fig.7 SEM images of hydrogels PLGA1433(A), PLGA13494(B) and PLGA30250(C) at concentration of 150 g/L for nChol/nβ-CD=1:1

Fig.8 Swelling ratio(A) and degradation of hydrogels(B) for molar ratio of Chol/β-CD being 1:1 at concentration of 150 g/L

Fig.9 Cytotoxicity evaluation of the mixture solutions of(PLGA-b-PEG-b-PLGA)-g-Chol with PLGA-g-β-CD Data are presented as the average±standard deviation(n = 3).

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