Department of Bioengineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8565, Japan.
Langmuir. 2023 Nov 21;39(46):16522-16531. doi: 10.1021/acs.langmuir.3c02472. Epub 2023 Nov 6.
In this study, cationic poly(2-(methacryloyloxy)ethyl) trimethylammonium chloride) (PMTAC) brush surfaces were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP), and their properties were systematically investigated to discuss the factors affecting their bactericidal properties and interactions with proteins. Model equations for the analysis of electrophoretic behaviors were considered for accurate parameter estimation to indicate the charge density at the interface. The zeta potential dependency of the PMTAC brushes was successfully analyzed using Smolchowski's equation and the Gouy-Chapman model, which describes the diffusive electric double layer. The analysis of the quartz crystal microbalance with dissipation (QCM-D) indicated that the electrostatic interaction promoted protein adsorption, with a large quantity of a negatively charged protein, bovine serum albumin (BSA), being adsorbed. The bactericidal efficiency of the high-graft-density polymer brush (0.45 chains nm) was higher than that of the low-graft-density polymer brush (0.06 chains nm). To investigate the mechanism of this phenomenon, we applied the dissipation change (Δ) of QCM-D analysis. The BSA was likewise adsorbed when the brush structure was changed; however, the negative Δ indicated that the BSA-adsorbed, high-graft-density PMTAC brush became a rigid state. In the bacteria culture media, the behaviors were the same as BSA adsorption, and the high-graft-density polymer brush was also estimated to be more rigid than the low-graft-density polymer brush. Moreover, for adhesion after incubating in TSB, a small slope of Δ/Δ plots considered initial adsorption of bacteria on the high-graft-density polymer brush strongly interacted compared to that of the low-graft-density polymer brush. The scattered value of the slope of Δ/Δ on the high-graft-density polymer brush was considered to be due to the dead bacteria between the bacteria and the polymer brush interface. These investigations for a well-defined cationic polymer brush will contribute to the design of antibacterial surfaces.
在这项研究中,通过表面引发原子转移自由基聚合(SI-ATRP)制备了阳离子聚(2-(甲基丙烯酰氧基)乙基)三甲基氯化铵)(PMTAC)刷表面,并系统地研究了它们的性质,以讨论影响其杀菌性能和与蛋白质相互作用的因素。考虑了用于分析电泳行为的模型方程,以进行准确的参数估计,从而指示界面处的电荷密度。使用 Smolchowski 方程和描述扩散双电层的 Gouy-Chapman 模型成功分析了 PMTAC 刷的 ζ 电位依赖性。石英晶体微天平耗散(QCM-D)分析表明,静电相互作用促进了蛋白质的吸附,大量带负电荷的蛋白质,牛血清白蛋白(BSA)被吸附。高接枝密度聚合物刷(0.45 链 nm)的杀菌效率高于低接枝密度聚合物刷(0.06 链 nm)。为了研究这种现象的机制,我们应用了 QCM-D 分析的耗散变化(Δ)。当刷结构发生变化时,同样吸附了 BSA;然而,负 Δ 表明 BSA 吸附的高接枝密度 PMTAC 刷变成了刚性状态。在细菌培养介质中,行为与 BSA 吸附相同,并且高接枝密度聚合物刷也被估计比低接枝密度聚合物刷更刚性。此外,对于在 TSB 中孵育后的粘附,考虑到初始细菌吸附在高接枝密度聚合物刷上的Δ/Δ 图的小斜率与低接枝密度聚合物刷上的相比强烈相互作用。高接枝密度聚合物刷上Δ/Δ 斜率的分散值被认为是由于死细菌在细菌和聚合物刷界面之间。这些针对明确定义的阳离子聚合物刷的研究将有助于设计抗菌表面。