新型羧甲基壳聚糖水凝胶的合成与表征

doi:10.7503/cjcu20131019

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (4): 863.doi: 10.7503/cjcu20131019

新型羧甲基壳聚糖水凝胶的合成与表征

朱寿进¹, 刘法谦¹, 王璟朝¹, 宿烽¹(), 李速明²()

1. 青岛科技大学高性能聚合物研究院, 青岛 266042
2. 蒙彼利埃二大学欧洲膜研究所, 法国蒙彼利埃 34095

收稿日期:2013-10-18 出版日期:2014-04-10 发布日期:2014-03-11
作者简介:联系人简介: 李速明, 男, 博士, 教授, 主要从事高分子生物材料研究. E-mail: lisuming@hotmail.com; 宿烽, 女, 博士, 副教授, 主要从事生物医药领域的研究. E-mail: sue827@163.com
基金资助:
国家自然科学基金(批准号: 50873030, 51073041)资助

Systhesis and Characterization of Novel Carboxymethyl Chitosan Hydrogel^†

ZHU Shoujin¹, LIU Faqian¹, WANG Jingzhao¹, SU Feng^1,^*(), LI Suming^2,^*()

1. Institute of High Performance Polymer, Qingdao University of Science and Technology, Qingdao 266042, China
2. Institut Europeen des Membranes, UMR CNRS 5635, Universite Montpellier II, Montpellier 34095, France

Received:2013-10-18 Online:2014-04-10 Published:2014-03-11
Contact: SU Feng,LI Suming E-mail:sue827@163.com;lisuming@hotmail.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.50873030, 51073041)

摘要/Abstract

摘要：

通过1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)/N-羟基琥珀酰亚胺(NHS)催化体系使羧甲基壳聚糖(CMCS)交联, 制备了新型羧甲基壳聚糖水凝胶. 探讨了EDC用量和EDC/NHS质量比对水凝胶特性的影响. CMCS水凝胶具有pH响应特性, 在等电位点溶胀率最小. 降解实验结果表明, 水凝胶浸泡在磷酸盐缓冲溶液中, 10 d失重率在15%~45%之间, 主要是未交联部分溶解所致. 而浸泡在含有0.2 mg/mL溶菌酶的磷酸盐缓冲溶液中, 低交联度水凝胶80 h基本降解, 高交联度水凝胶不易降解. 初步研究了CMCS水凝胶包埋牛血清白蛋白(BSA)的释放行为.

关键词: 羧甲基壳聚糖, 水凝胶, pH响应, 降解, 药物释放

Abstract:

Novel hydrogels were prepared by crosslinking carboxymethyl chitosan(CMCS) with 1-ethyl-3-(3-dimethyl-aminopropyl)-1-carbodiimide/N-hydroxysuccinimide(EDC/NHS) as catalyst at room temperature. The amount of EDC and EDC/NHS mass ratio revealed to be influencing factors on the reaction. The hydrogels exhibited typical pH-responsive character. Solid-state ¹³C nuclear magnetic resonance(NMR) and differential scanning calorimetry(DSC) measurements confirmed the effective crosslinking of carboxymethyl chitosan. A minimum swelling ratio is obtained at the isoelectric point in the pH range of 3—5. Degradation of hydrogels was carried out at 37 ℃ in phosphate buffered saline(PBS) or in PBS containing 0.2 mg/mL lysozyme. The hydrogels appeared rather stable in PBS for 10 d. The initial mass loss of 15%—45% was assigned to the dissolution of uncrosslinked CMCS. The hydrogel with low crosslink density was degraded after 80 h in the pre-sence of lysozyme, while the hydrogel with high crosslink density was hardly degraded. A model drug, bovine serum albumin(BSA) was loaded in CMCS hydrogels. Preliminary drug release studies show that the hydrogels are promising carrier of hydrophilic drugs.

Key words: Carboxymethyl chitosan, Hydrogel, pH Sensitivity, Degradation, Drug release

中图分类号:

O631

TrendMD:

朱寿进, 刘法谦, 王璟朝, 宿烽, 李速明. 新型羧甲基壳聚糖水凝胶的合成与表征. 高等学校化学学报, 2014, 35(4): 863.

ZHU Shoujin, LIU Faqian, WANG Jingzhao, SU Feng, LI Suming. Systhesis and Characterization of Novel Carboxymethyl Chitosan Hydrogel^†. Chem. J. Chinese Universities, 2014, 35(4): 863.

图/表 11

Fig.1 Vial inverting of CMCS samples after crosslinking reaction(A) Control; (B) sample Ⅰ; (C) sample Ⅱ; (D) sample Ⅲ.

Table 1 Synthesis of CMCS hydrogels by crosslinking reaction using EDC/NHS catalytic system

Sample	m_CMCS/g	m_EDC/mg	m_NHS/mg	Product
Ⅰ	1	96	0	Solution
Ⅱ	1	96	59	Gel
Ⅲ	1	192	118	Gel
Control	1	0	0	Solution

Scheme 1 Crossinking reaction of carboxymethyl chitosan using EDC/NHS catalytic systemThe numbers 1—8 correspond to the carbons in Fig.2.

Fig.2 Solid-state 13C NMR spectra of CMCS(a) and CMCS hydrogel(sample Ⅱ)(b)

Fig.3 DSC curves of CMCS and freeze dried hydrogels for carboxymethyl chitosan(a), sample Ⅱ(b), sample Ⅲ(c)

Fig.4 Swelling ratio changes of CMCS hydrogels(sample Ⅱ and sample Ⅲ) with different pH values

Fig.5 IR spectra of sample Ⅱ after swelling at different pH values pH: a. 1.2; b. 4.0; c. 9.0.

Fig.6 Mass remaining changes of CMCS hydrogels in PBS solution for sample Ⅱ(a) and sample Ⅲ(b)

Fig.7 Mass remaining changes of CMCS hydrogels in PBS solution containing lysozyme for sample Ⅱ(a) and sample Ⅲ(b)

Fig.8 BSA release from CMCS hydrogel (sample Ⅱ) in PBS at 37 ℃

Scheme 2 Schematic presentation of drug loading and BSA release from CMCS hydrogels

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新型羧甲基壳聚糖水凝胶的合成与表征

Systhesis and Characterization of Novel Carboxymethyl Chitosan Hydrogel^†

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新型羧甲基壳聚糖水凝胶的合成与表征

Systhesis and Characterization of Novel Carboxymethyl Chitosan Hydrogel†

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Systhesis and Characterization of Novel Carboxymethyl Chitosan Hydrogel^†