壳聚糖/有机锂皂石纳米复合材料的制备及抗菌性能研究

doi:10.15541/jim20150509

摘要/Abstract

摘要：

采用离子交换法将季铵盐及壳聚糖插层到锂皂石层间, 制备锂皂石基二次插层复合物。所制备的两种二次插层复合物的层间距相比于纯的锂皂石分别增加了0.276 nm和0.262 nm。用大肠杆菌(E. coli)和金黄色葡萄球菌(S. cereus)为模拟体系对二次插层复合物的抗菌性进行了检验, 利用抑菌环和平板计数法测定两种二次插层复合物的抗菌能力。抗菌结果显示, 细菌与两种复合物接触24 h后, 锂皂石/十四烷基三甲基溴化铵/壳聚糖对大肠杆菌的抗菌率可达100%, 对S.cereus的抗菌率可达85%以上, 锂皂石/十六烷基三甲基溴化铵/壳聚糖对大肠杆菌和金黄色葡萄球菌的抗菌率均可达99%以上。采用扫描电镜法及β-半乳糖苷酶活性考察了两种复合物对大肠杆菌和金黄色葡萄球菌抑菌过程及机理, 结果表明: 复合物首先通过表面带的正电荷将表面带负电的细菌吸附到材料表面, 随后借助有机物阳离子的疏水作用, 穿透细菌细胞膜, 从而达到杀菌效果。

关键词: 有机锂皂石, 壳聚糖, 抗菌机理, 二次插层, 纳米复合物

Abstract:

Laponite-based secondary intercalation compound was prepared by ion exchange method through intercalating quaternary ammonium salts and chitosan into the layers of hectorite. The layer spacing of the two kinds of secondary intercalation compounds were increased 0.276 nm and 0.262 nm, respectively, compared to the pure laponite. The antibacterial of secondary intercalation compound was tested by Escherichia coli (E. coli) and Staphylococcus aureus (S. cereus). Antibacterial ability of the two kinds of secondary intercalation compounds were determined by using bacteriostatic ring and plate count methods. The results showed that, after being contacted with the two compounds for 24 h, the bacteriostatic rate of the laponite/myristyl trimethyl ammonium bromide/chitosan on E. coli reached up to 100% and 85% on S.cereus. Meanwhile, the laponite/cetyl trimethyl ammonium bromide/chitosan was up to 99% on E. coli and S. cereus. The antibacterial process and mechanism on E. coli and S. cereus of the two kinds of compounds were investigated by scanning electron microscope and β-galactosidase activity. The results showed that the compound adsorbed bacterial through the role of mutual attraction between positive and negative charges at first, then the compound penetrated the bacterial cell membrane with the help of hydrophobic interaction of organic cation, and finally exerted the sterilization effect.

Key words: organic laponite, chitosan, antibacterial mechanism, secondary intercalation, nanocomposites

中图分类号:

TB33

付海丽, 张雯, 张华, 宋少波, 李伟. 壳聚糖/有机锂皂石纳米复合材料的制备及抗菌性能研究[J]. 无机材料学报, 2016, 31(5): 479-484.

FU Hai-Li, ZHANG Wen, ZHANG Hua, SONG Shao-Bo, LI Wei. Preparation and Antibacterial Activity of Chitosan/Organic Laponite Nanocomposites[J]. Journal of Inorganic Materials, 2016, 31(5): 479-484.

图/表 9

图1 有机锂皂石的制备机理示意图

Fig. 1 Preparation mechanism of organic laponite nanocomposites

图2 锂皂石与壳聚糖/有机锂皂石的XRD图谱

Fig. 2 XRD pattems of laponite and chitosan/modified laponite (a) LAP; (b) LTTC; (c) LCTC

图3 锂皂石(a, c)和壳聚糖/改性锂皂石(b, d)的SEM(a, b)和TEM(c, d)照片

Fig. 3 SEM (a,b) and TEM (c,d) images of laponite and chitosan/modified laponite

图4 改性锂皂石对大肠杆菌(A-E)和金黄色葡萄球菌(A’-E’)的抑菌圈

Fig. 4 Antimicrobial activity of LTT (A, A’), LCT (B, B’), LC (C, C’), LTTC (D, D’) and LCTC (E, E’) against E. coli and S. aureus

表1 LTTC和LCTC的抑菌率

Table 1 Bactericidal ratio of LTTC and LCTC

Samples	E. coli		S.cereus
Samples	Recovered bacteria count /(cfu•mL^-1)	Antimicrobial ratio /%	Recovered bacteria count /(cfu•mL^-1)	Antimicrobial ratio /%
Blank	2.59×10⁸	0	3.40×10⁹	0
LTTC	0	100.0	5.00×10⁸	85.3
LCTC	1.10×10⁴	99.9	1.00×10⁴	99.9
Positive control	2.30×10⁴	99.9	1.00×10³	99.9
Negative control	3.30×10⁸	0	2.86×10⁹	15.9

图5 大肠杆菌(a~d)和金黄色葡萄球菌(a’~d’)处理后的壳聚糖/有机锂皂石的SEM照片

Fig. 5 SEM images of chitosan/modified laponite after treatment with E.coli (a-d) and S.cereus (a’-d’)

表2 LAP、LTTC和LCTC的Zeta电位值

Table 2 Zeta potential of LAP, LTTC and LCTC (n=3)

Sample	Static dissipative	Zeta potential/mV
LAP	-	-27.6±4.8
LTTC	+	43.0±1.6
LCTC	+	82.3±2.1

图6 不同样品对大肠杆菌和金黄色葡萄球菌的抗菌效果比较

Fig. 6 Comparison of S.cereus (a-c) and E. coli (a’-c’) activity under different samples (a) Blank; (b) LTTC; (c) LCTC

图7 经过壳聚糖/改性锂皂石处理后内膜渗透性变化

Fig. 7 Change of permeability of bacterial inner membrane under the condition of chitosan/modified laponite (a) LTTC; (b)LCTC; (c) Blank

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