氨基酸改性壳聚糖基金属离子吸附材料的制备和性能*

doi:10.11901/1005.3093.2015.769

材料研究学报

2016, Vol. 30

Issue (11): 825-833 DOI: 10.11901/1005.3093.2015.769

论文

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氨基酸改性壳聚糖基金属离子吸附材料的制备和性能*

张毅,张转玲,张昊(

),黎淑婷

天津工业大学天津 300387

Preparation and Properties of Amino Acid-modified Chitosan-based Material for Metal Ion Adsorption

Yi ZHANG,Zhuanlin ZHANG,Hao ZHANG(

),Shuting LI

School of Textiles, Tianjin Polytechnic University, Tianjin 300387, China

引用本文:

张毅, 张转玲, 张昊, 黎淑婷. 氨基酸改性壳聚糖基金属离子吸附材料的制备和性能*[J]. 材料研究学报, 2016, 30(11): 825-833.
Yi ZHANG, Zhuanlin ZHANG, Hao ZHANG, Shuting LI. Preparation and Properties of Amino Acid-modified Chitosan-based Material for Metal Ion Adsorption[J]. Chinese Journal of Materials Research, 2016, 30(11): 825-833.

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摘要:

以壳聚糖(CS)为基体、以1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC.HCl)为缩合剂、N-羟基-丁二酰亚胺(NHS)为偶联剂, 将L-精氨酸固载到CS大分子上, L-精氨酸接枝壳聚糖CS-L-Arginine(CA), 通过单因素实验优化接枝工艺, 制备出一种天然高分子基重金属螯合材料。应用元素分析、红外光谱(FT-IR)、拉曼光谱(RAM)和X-射线衍射(XRD)等手段表征了产物的结构组成, 研究了接枝机理。用坂口反应并结合凯氏定氮法测定了产物的接枝率GR。结果表明, 当反应物物质的量比为nCS:nArg:nEDC=1:1:1、 nEDC:nNHS=3:1、反应时间12 h、体系的pH值=5时, 接枝率(GR)可达16.85%。调整反应物的投入比, 可制备出接枝率不同的接枝产物。吸附实验结果表明, 与CS相比, CA(GR=16.85%)使高浓度溶液中的Cu²⁺、Ni²⁺离子的去除率显著提高, CA的抗菌性比CS也显著增强, GR为16.85%的CA几乎完全抑制了大肠杆菌和金黄色葡萄球菌的生长。

关键词 ：有机高分子材料, 氨基酸改性壳聚糖, 接枝, 金属离子吸附, 抗菌性

Abstract：

For improving the heavy metal ion chelating ability of chelatingheavy metal ions and the microbiological stability of chitosan (CS), L-arginine (L-Arg) was immobilized on CS molecules, in presence of condensing agent 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl) and coupling reagent N-Hydroxysuccinimide (NHS), using chitosan as a matrix, a new kind of natural-macromolecular-based heavy metal ion chelating material, L-arginine GRafted Chitosan (CA)of chelating heavy metal ions, was prepared by grafting L-arginine (L-Arg) onto CS molecules, with chitosan as raw mate-rial, 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl) ascondensing agent and N-Hydroxysuccinimide (NHS) coupling reagent. The GRafting mechanism was deeply discussed and the GRafted conditions were optimized by signal factor experiments. The structure and composition of the product were characterized by elemental analysis, infrared spectrum (FT-IR), Raman spectra (RAM) and x-ray diffraction (XRD). Then, the processing parameters were optimized via experiments with single factor. The results show that a grafting ratio (GR) of 16.85% may be acquired when the for the following parameters: molar ratios of reagents CS:Arg:EDC =1:1:1 and EDC:NHS =3:1, reaction time 12 h and pH=5, the GRating ratio (GR) was up to 16.85%. By adjusting the ratio of reactants, products with different GR levels could be obtained. The results of adsorption experiments showed CA (GR=16.85%) had higher removalefficiency of high-concentrated Cu²⁺ and Ni²⁺ ions than CS.CA also possessedhigher antibacterial property compared with CS, whilst the CA with 16.85% GRof was up to 16.85%, it can almost completely inhibited the growth of colibacillus and staphylococcus aureus.

Key words： organic polymer materials amino acid-modified Chitosan GRaft metal ion absorption antibacterial property

收稿日期: 2015-12-30

基金资助:* 国家自然科学基金5150030497和国家级现代农业产业技术体系专项CARS-44-D资助项目

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https://www.cjmr.org/CN/10.11901/1005.3093.2015.769 或 https://www.cjmr.org/CN/Y2016/V30/I11/825

图1 EDC/NHS存在下壳聚糖与精氨酸的接枝反应机理

图2 溶液的pH值对CA接枝率的影响, 其它反应条件: nCS:nArg:nEDC=1:1:1, nEDC:nNHS=3:1, 反应时间12 h

图3 NHS与EDC的摩尔比对CA接枝率的影响, 其它反应条件: nCS:nArg:nEDC=1:1:1, pH=5, 反应时间12 h

表1 不同反应物的投入量对CA接枝率的影响, 其它反应条件:nEDC:nNHS=3:1, pH=5, 反应时间12 h

表2 L-Arg、CS与CA的氮含量以及接枝率

图4 CS和CA的红外/拉曼谱图

图5 CS和CA的X-射线衍射图

表3 几种吸附材料对Cu+2、Ni+2离子的吸附能力

表4 CS和CA对两种革兰氏菌的抑菌性

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