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基于改性 SiO2 粒子的 WPU 基超双疏涂层的制备及其抗生物膜机制。

Preparation of WPU-based super-amphiphobic coatings functionalized by modified SiO particles and their anti-biofilm mechanism.

机构信息

National & Local Joint Engineering Research Center of Storage, Processing and Safety Control Technology for Fresh Agricultural and Aquatic Products, College of Food Science and Engineering, Bohai University, Jinzhou 121013, China.

Beijing Laboratory of Food Quality and Safety, Beijing Technology and Business University, Beijing 100048, China.

出版信息

Biomater Sci. 2021 Nov 9;9(22):7504-7521. doi: 10.1039/d1bm01285a.

Abstract

Fabrication of anti-wetting coatings with anti-biofouling and anti-biofilm properties has become a hot spot of attention in recent years. However, the anti-biofilm mechanism of anti-bacterial adhesion coatings with different wet resistance properties has not been explored in detail. In this work, SiO micro-nano particles were prepared by the Stöber method and were modified. The SiO/waterborne polyurethane (WPU) coatings were prepared by the drop coating method, and the coatings with different hydrophobic and oleophobic properties were constructed by modifying the process conditions using SiO micro-nano particles as the roughness construction factor. Taking the dominant spoilage bacteria of aquatic products, as the object, the anti-bacterial adhesion properties and anti-biofilm mechanism of the SiO/WPU coatings were investigated. The results show that, with the unmodified SiO particles increasing from 1.2% (w/V) to 4.0% (w/V), the hydrophobicity and thermal stability of the SiO/WPU coatings are significantly enhanced, but the oil repellency becomes worse due to the mesoporous structure. After SiO micro-nano particles are modified with 1,1,2,2-perfluorooctyl trichlorosilane (PFOTS), the surface energy of the SiO/WPU coatings is decreased, the liquid repellency is improved, and the surfaces are rough with the appearance of fluorocarbon compounds, but the thermal stabilities are slightly reduced. Among them, after the secondary modification of SiO micro-nano particles, the SiO/WPU coatings showed excellent oil repellency, lower surface energies and higher fluorocarbon content on the surface. Particularly, SiO/WPU coatings exhibited super-amphiphobicity after adjusting the amount of concentrated ammonia added during the secondary modification process. Meanwhile, we found that for the hydrophobic SiO/WPU coatings, the stronger the oleophobic property, the greater the anti-bacterial adhesion ability is, while the anti-bacterial adhesion ability of hydrophobic and selectively oleophobic or superhydrophobic and oleophobic SiO/WPU coatings is poor than that of amphiphilic SiO/WPU coatings. However, because the super-amphiphobic SiO/WPU coatings can be in the Cassie state with the bacterial solution for a long time, it can "capture" enough air to inhibit the irreversible adhesion of the bacteria. More importantly, the coatings can also inhibit the metabolic activity, secretion of extracellular polysaccharides, and activities of ATPase and AKP of the adherent bacteria, so it has a better anti-biofilm property. The anti-biofilm coatings can be used as food packaging materials or coated on the inner surface of packaging boxes to prevent the microbial infection.

摘要

近年来,具有抗生物污损和抗生物膜性能的防湿涂层的制备已成为研究热点。然而,具有不同耐湿性的抗菌附着涂层的抗生物膜机制尚未得到详细探讨。在这项工作中,采用 Stöber 法制备了 SiO 微纳米颗粒,并对其进行了改性。采用滴涂法制备了 SiO/水性聚氨酯(WPU)涂层,并通过改变工艺条件,以 SiO 微纳米颗粒作为粗糙度构建因子,构建了具有不同疏水性和疏油性的涂层。以水产制品的主要腐败菌为对象,研究了 SiO/WPU 涂层的抗菌附着性能和抗生物膜机制。结果表明,随着未改性 SiO 颗粒含量从 1.2%(w/V)增加到 4.0%(w/V),SiO/WPU 涂层的疏水性和热稳定性显著提高,但由于介孔结构,疏油性变差。经 1,1,2,2-全氟辛基三氯硅烷(PFOTS)改性后的 SiO 微纳米颗粒,SiO/WPU 涂层的表面能降低,液体排斥性提高,表面粗糙,出现氟碳化合物,但热稳定性略有降低。其中,SiO 微纳米颗粒经二次改性后,SiO/WPU 涂层表现出优异的疏油性、较低的表面能和更高的表面氟碳含量。特别是通过调整二次改性过程中添加的浓氨水的量,SiO/WPU 涂层表现出超疏油性。同时,我们发现对于疏水性的 SiO/WPU 涂层,疏油性越强,抗菌附着能力越强,而疏水性和选择性疏油性或超疏水性和疏油性的 SiO/WPU 涂层的抗菌附着能力则不如亲水性的 SiO/WPU 涂层。然而,由于超疏水性的 SiO/WPU 涂层可以长时间处于 Cassie 状态,它可以“捕获”足够的空气来抑制细菌的不可逆附着。更重要的是,涂层还可以抑制附着细菌的代谢活性、胞外多糖的分泌以及 ATPase 和 AKP 的活性,因此具有更好的抗生物膜性能。这种抗生物膜涂层可用作食品包装材料或涂覆在包装盒的内表面上,以防止微生物感染。

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