基于银-硫配位的协同抗菌水凝胶的制备与性能

doi:10.16085/j.issn.1000-6613.2023-0828

摘要/Abstract

摘要：

1-烯丙氧基-2,3-环硫丙烷开环聚合得到侧基带乙烯基的线型聚硫醚（P1），通过巯-烯click反应引入足够量的羧基，赋予其水溶性。修饰后的线型聚硫醚（P2）将硝酸银原位还原成银纳米颗粒（Ag NPs），将其用作抗菌剂。TEM测试表明成功制备出粒径尺寸为5~20nm的Ag NPs；且XPS分析证明了Ag NPs与P2聚合物链上的硫元素形成银-硫配位键。P2与Ag NPs通过银-硫配位作用形成复合交联剂（Ag NPs@P2），在过硫酸钾（KPS）的引发下，再与丙烯酰胺（Am）进行自由基聚合制备抗菌水凝胶。对大肠杆菌进行抗菌实验，结果表明Ag NPs@P2/PAm具有协同抗菌的能力，且负载质量分数为2%的Ag NPs@P2抑菌效果最好。该水凝胶克服了传统抗生素水凝胶的耐药性问题以及无机/有机组分相容性差的缺陷，为设计新型协同抗菌水凝胶提供了一种全新的策略。

关键词: 银-硫配位, 协同抗菌, 银纳米颗粒, 水凝胶

Abstract:

Linear polysulfide (P1) with a vinyl side group was obtained by ring-opening polymerization of 1-allyl oxygen-2,3-cyclothiopropane, which was then water-soluble by the introduction of sufficient carboxyl group by thiol-olefin click. Modified linear polysulfide (P2) reduced silver nitrate in situ to silver nanoparticles (Ag NPs), which was used as antibacterial agents. TEM test showed that Ag NPs were successfully prepared with the particle size of 5—20nm. Moreover, XPS analysis proved that Ag NPs formed a silver-sulfur coordination bond with sulfur element in P2 polymer chain. The composite crosslinking agent (Ag NPs@P2) was formed by the Ag-S coordination of P2 and Ag NPs, and with the initiation of potassium persulfate (KPS), the antibacterial hydrogel was prepared by free radical polymerization with acrylamide (Am) and Ag NPs@P2. The antibacterial experiments on Escherichia coli indicated that Ag NPs@P2/PAm had the synergistic antibacterial capability, and Ag NPs@P2 loaded with mass fraction of 2% had the best bacteriostatic effect. The hydrogels overcome the resistance problem of traditional antibiotic hydrogels and the poor compatibility of inorganic and organic components, and provided a new strategy for the design of novel synergistic antibacterial hydrogels.

Key words: silver-sulfur coordination, synergistic antibacterial, silver nanoparticles, hydrogels

中图分类号:

TQ317

剧芳. 基于银-硫配位的协同抗菌水凝胶的制备与性能[J]. 化工进展, 2024, 43(2): 1039-1046.

JU Fang. Fabrication and properties of synergistic antibacterial hydrogels based on the silver-sulfur coordination[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 1039-1046.

图/表 14

图1 1-烯丙氧基-2,3-环氧丙烷（1）的核磁氢谱

图2 引发剂S-苯基对甲苯基硫代氨基甲酸酯（2）的核磁氢谱

图3 线型聚硫醚P1的核磁氢谱

图4 线型聚硫醚P1的凝胶渗透色谱

图5 线型聚硫醚P2的合成路线

图6 Ag NPs@P2的制备过程

图7 Ag NPs@P2/PAm复合水凝胶的合成工艺及内部结构

图8 P1与P2的红外光谱

图9 Ag NPs的TEM图像

图10 Ag NPs@P2中Ag 3d与S 2p的XPS图

图11 Ag NPs@P2/PAm水凝胶的SEM图及Ag和S复合、Ag和S的元素分布图

图12 5组样品培养24h后抑菌圈照片

表1 5组样品的抑菌圈直径

Ag NPs@P2质量分数/%	抑菌圈直径/mm			平均直径/mm
0	9，	9，	9	9
2	19，	20，	18	19
4	9，	10，	10	9.667
8	7，	8，	8	7.667
12	5，	5，	4	4.667

图13 Ag NPs@P2/PAm水凝胶在不同质量分数的Ag NPs@P2含量（0~12%）条件下的应力-应变曲线

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