Stephenson Institute for Renewable Energy, Department of Chemistry, University of Liverpool , Crown Street, Liverpool L69 7ZD, U.K.
Open Innovation Hub for Antimicrobial Surfaces at the Surface Science Research Centre, University of Liverpool , Oxford Street, L69 3BX Liverpool, U.K.
ACS Appl Mater Interfaces. 2017 Nov 8;9(44):38364-38372. doi: 10.1021/acsami.7b14642. Epub 2017 Oct 27.
Application of mesoporous silica nanoparticles (MSNs) as antifouling/antibacterial carriers is limited and specifically with a dual synergetic effect. In the present work, MSNs modified with quaternary ammonium salts (QASs) and loaded with the biocide Parmetol S15 were synthesized as functional fillers for antifouling/antibacterial coatings. From the family of the MSNs, MCM-48 was selected as a carrier because of its cubic pore structure, high surface area, and high specific pore volume. The QASs used for the surface modification of MCM-48 were dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and dimethyltetradecyl[3-(triethoxysilyl)propyl]ammonium chloride. The QAS-modified MCM-48 reveals strong covalent bonds between the QAS and the surface of the nanoparticles. The surface functionalization was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and ζ-potential measurements. Additional loading of the QAS-modified MCM-48 with a commercially available biocide (Parmetol S15) resulted in a synergetic dual antibacterial/antifouling effect. Either loaded or unloaded QAS-modified MSNs exhibited high antibacterial performance confirming their dual activity. The QAS-modified MCM-48 loaded with the biocide Parmetol S15 killed all exposed bacteria after 3 h of incubation and presented 100% reduction at the antibacterial tests against Gram-negative and Gram-positive bacteria. Furthermore, the QAS-modified MCM-48 without Parmetol S15 presented 77-89% reduction against the exposed Gram-negative bacteria and 78-94% reduction against the exposed Gram-positive bacteria. In addition, the modified MCM-48 was mixed with coating formulations, and its antifouling performance was assessed in a field test trial in northern Red Sea. All synthesized paints presented significant antifouling properties after 5 months of exposure in real seawater conditions, and the dual antifouling effect of the nanoparticles was confirmed.
介孔硅纳米粒子（MSNs）作为防污/抗菌载体的应用受到限制，特别是具有协同增效的双重作用。在本工作中，合成了季铵盐（QAS）改性并负载杀生物剂 Parmetol S15 的 MSNs 作为防污/抗菌涂层的功能填料。从 MSNs 家族中选择 MCM-48 作为载体，因为它具有立方孔结构、高表面积和高比孔体积。用于 MCM-48 表面改性的 QAS 是二甲基十八烷基[3-（三甲氧基硅基）丙基]氯化铵和二甲基十四烷基[3-（三乙氧基硅基）丙基]氯化铵。QAS 改性的 MCM-48 显示出 QAS 与纳米颗粒表面之间的强共价键。通过傅里叶变换红外光谱、热重分析、元素分析和 ζ-电位测量证实了表面功能化。用市售杀生物剂（Parmetol S15）进一步负载 QAS 改性的 MCM-48 导致协同的双重抗菌/防污作用。负载或未负载 QAS 的改性 MSNs 均表现出高抗菌性能，证实了它们的双重活性。负载杀生物剂 Parmetol S15 的 QAS 改性 MCM-48 在孵育 3 小时后杀死了所有暴露的细菌，并在针对革兰氏阴性菌和革兰氏阳性菌的抗菌测试中达到 100%的减少。此外，未负载 Parmetol S15 的 QAS 改性 MCM-48 对暴露的革兰氏阴性菌的减少率为 77-89%，对暴露的革兰氏阳性菌的减少率为 78-94%。此外，改性 MCM-48 与涂料配方混合，并在红海北部的现场试验中评估其防污性能。所有合成涂料在实际海水条件下暴露 5 个月后均表现出显著的防污性能，证实了纳米粒子的双重防污效果。
