HNTs-NaClO2复合材料的制备及抑菌效果

doi:10.16085/j.issn.1000-6613.2022-0082

摘要/Abstract

摘要：

由于抗生素耐药性的流行，新型抗菌材料日益受到关注。本文利用埃洛石（HNTs）独特的结构和性质，以经过碱法预处理的HNTs为载体，通过真空抽吸法制备了HNTs-NaClO₂复合材料。采用XRD、FTIR、TEM、EDS等手段对复合材料结构和化学组成进行表征，TEM显示负载NaClO₂的HNTs管体表面有明显的晶体出现。探索了不同负载工艺对NaClO₂负载量的影响，研究了HNTs-NaClO₂的释放性能和抑菌性能，通过急性经口毒性实验考察了HNTs-NaClO₂的生物安全性。结果表明，改变HNTs在饱和亚氯酸钠溶液中的搅拌时间和负载比例可以提高NaClO₂的负载量，在搅拌时间为2h时负载量为4.91%，在负载比例为1∶4时负载量为7.61%；释放在第4天时趋于稳定，释放的亚氯酸钠质量分数为1.43%；抑菌活性评价表明，该复合材料对大肠杆菌和金黄色葡萄球菌均有抑制作用；HNTs-NaClO₂对雌雄小鼠的LD₅₀均大于5.00g/kg_BW。HNTs-NaClO₂复合材料可稳定持续释放，且具有一定的抑菌性，属于低毒级别。

关键词: 埃洛石纳米管, 亚氯酸钠, 复合材料, 抑菌

Abstract:

Due to the prevalence of antibiotic resistance, novel antimicrobial materials have received increasing attention. Taking advantage of the unique structure and properties of halloysites (HNTs), HNTs-NaClO₂ composites were prepared by vacuum suction method using HNTs pretreated by alkali method as carriers. The structure and chemical composition of the composites were characterized by means of XRD, FTIR, TEM and EDS. TEM showed that the surface of the HNTs loaded with NaClO₂ had obvious crystals. The effects of different loading processes on the loading of NaClO₂ were explored, the release properties and bacteriostatic properties of HNTs-NaClO₂ were studied, and the biosafety of HNTs-NaClO₂ was investigated by acute oral toxicity experiments. The results showed that changing the stirring time and loading ratio of HNTs in saturated sodium chlorite solution could increase the loading of NaClO₂. When the stirring time was 2h, the loading was 4.91%, and when the loading ratio was 1∶4, the loading was 7.61%. On the 4th day, the release tended to be stable, and the content of sodium chlorite release was 1.43%. The antibacterial activity evaluation indicated that the composite material had inhibitory effects on Escherichia coli and Staphylococcus aureus. HNTs-NaClO₂ had inhibitory effects on male and female mice with LD₅₀ of greater than 5.00g/kg_BW. The HNTs-NaClO₂ composite material could be released stably and continuously, and had a certain antibacterial property, which belonged to the low toxicity level.

Key words: halloysite nanotubes, sodium chlorite, composites, bacteriostatic

中图分类号:

O613.72

谷娜, 赵东亚, 高金龙, 林翠, 任伟杰, 王田田, 刘欣伟. HNTs-NaClO₂复合材料的制备及抑菌效果[J]. 化工进展, 2022, 41(11): 6011-6017.

GU Na, ZHAO Dongya, GAO Jinlong, LIN Cui, REN Weijie, WANG Tiantian, LIU Xinwei. Preparation and antibacterial effect of HNTs-NaClO₂ composites[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6011-6017.

图/表 12

图1 制备HNTs-NaClO2复合材料的实验流程

表1 急性毒性分级标准

剂量浓度/g· $k g B W - 1$	毒性级别
>5000	无毒
500~5000	低毒
50~500	中等毒
1~50	高毒
<1	剧毒

表1 急性毒性分级标准

剂量浓度/g· $k g B W - 1$	毒性级别
>5000	无毒
500~5000	低毒
50~500	中等毒
1~50	高毒
<1	剧毒

图2 原始HNTs、HNTs-NaClO2复合材料和NaClO2的XRD图

图3 原始HNTs、HNTs-NaClO2复合材料和NaClO2的FTIR图谱

图4 原始HNTs和HNTs-NaClO2复合材料的TEM图

表2 原始HNTs和HNTs-NaClO2元素质量分数

项目	元素/%
项目	C	O	Al	Si	Na	Cl
原始HNTs	19.68	57.01	11.55	11.76	—	—
HNTs-NaClO₂(1∶3)	44.95	46.07	3.57	3.66	1.00	0.75
HNTs-NaClO₂(1∶4)	40.38	41.57	2.76	2.87	6.64	5.78
HNTs-NaClO₂(1∶5)	43.76	41.75	2.67	2.84	4.85	4.13
HNTs-NaClO₂(1∶6)	42.41	43.33	3.40	3.28	4.34	3.24

图5 原始HNTs和HNTs-NaClO2的EDS图

表3 不同负载工艺对NaClO2的负载量的影响

搅拌时间/min	负载量/%	浸泡时间/min	负载量/%	负载比例	负载量/%
60	4.05	0	3.01	1∶3	6.89
90	4.42	10	2.97	1∶4	7.61
120	4.91	20	2.99	1∶5	5.27
150	4.87	30	3.00	1∶6	5.01
180	4.63	40	2.98	—	—

图6 负载比例对HNTs-NaClO2复合材料的释放结果的影响

图7 浓度对HNTs-NaClO2复合材料抑菌结果的影响

表4 浓度对HNTs-NaClO2复合材料的抑菌圈直径的影响（±SD） (mm)

菌种	浓度/g·L^-1
菌种	1.25	2.50	3.75	5.00	6.25	7.50
大肠杆菌	8.85±0.56	9.66±0.46	10.44±0.55	10.97±0.48	11.31±0.13	11.72±0.43
金黄色葡萄球菌	8.01±0.14	9.08±0.29	9.65±0.53	10.54±0.51	11.07±0.46	11.36±0.39

表5 各组小鼠实验结果

分组	性别	给药浓度 /g·kg^-1_BW	动物只数	给药前质量/g	给药后质量/g	死亡只数
实验组	雌	2.15	5	18.36±0.21	24.52±0.64	0
	雄	2.15	5	19.42±0.32	27.14±0.74	0
	雌	4.64	5	18.45±0.35	25.13±0.53	1
	雄	4.64	5	19.37±0.17	27.05±0.89	2
	雌	10.00	5	—	—	5
	雄	10.00	5	—	—	5
	雌	21.50	5	—	—	5
	雄	21.50	5	—	—	5
对照组	雌	生理盐水	5	18.22±0.20	24.92±0.72	0
对照组	雄	生理盐水	5	19.24±0.25	27.01±0.81	0

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HNTs-NaClO₂复合材料的制备及抑菌效果

Preparation and antibacterial effect of HNTs-NaClO₂ composites

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