Pistonesi Denise B, Fernández-Leyes Marcos D, Ritacco Hernán, Rivero Paula S, Sica María G, Benedini Luciano A, Centurión María E, Messina Paula V
INQUISUR - CONICET, Department of Chemistry, Universidad Nacional del Sur, Bahía Blanca B8000CPB, Argentina.
Department of Physics, Universidad Nacional del Sur, IFISUR- CONICET, Bahía Blanca B8000CPB, Argentina.
Langmuir. 2025 Aug 19;41(32):21509-21524. doi: 10.1021/acs.langmuir.5c02214. Epub 2025 Aug 6.
The increasing use of silver nanoparticles (AgNPs) in medical applications highlights the need for thorough studies of their health effects, particularly at the cellular level. Due to the complexity of replicating real cell membranes, Langmuir monolayers (LMs) are employed as simplified models of the initial biological barrier. These systems allow for controlled conditions to investigate molecular behavior at the membrane interface, offering insights into the fundamental mechanisms involved. In this research, we explore the effects of the shape and electronic anisotropy of AgNPs on bacterial and erythrocyte membrane models using dipalmitoylphosphatidylcholine (DPPC) and DPPC/cholesterol (CHOL) combinations. The interaction between the lipids and silver nanoparticles was investigated using film balance measurements by analyzing surface pressure (π-) and membrane potential (Δ-) isotherms. These measurements were complemented by X-ray reflectometry to obtain detailed structural information at the interface. Additionally, experiments were conducted to provide a behavioral profile of the nanoparticles' effects, linking physicochemical interactions with cellular responses. Our findings demonstrate that the shape anisotropy of prism-like silver nanoparticles (p-AgNPs) significantly impacts membrane structural integrity and mechanical properties, with the extent of these effects depending on membrane composition and cholesterol content. Prism-like silver nanoparticles interact more strongly with DPPC monolayers than spherical nanoparticles (s-AgNPs), inducing higher surface pressure and a decrease in membrane rigidity due to lipid extraction. In DPPC/CHOL monolayers, p-AgNPs promote CHOL microdomain formation and disrupt DPPC organization, with these effects becoming more pronounced at higher CHOL concentrations. Prism-like nanosilver also enhances lipid extraction and membrane permeability in bacterial-like membranes, while in erythrocyte-mimetic membranes, it disrupts membrane organization and reduces rigidity, with cholesterol modulating this impact. These results suggest that p-AgNPs exhibit potent antibacterial properties but also pose risks of destabilizing eukaryotic cell membranes. Overall, the study explores the concentration-dependent antibacterial and cytotoxic effects of p-AgNPs, highlighting how their morphological anisotropy plays a decisive role in modulating nanoparticle/membrane interactions. By uncovering specific mechanisms at the bionano interface, this work sets an important precedent for the rational design of nanosilver-based devices and treatments, contributing valuable knowledge to the safe and effective application of anisotropic nanomaterials in biomedicine.
银纳米颗粒（AgNPs）在医学应用中的使用日益增加，这凸显了对其健康影响进行全面研究的必要性，尤其是在细胞水平上。由于复制真实细胞膜的复杂性，朗缪尔单分子层（LMs）被用作初始生物屏障的简化模型。这些系统允许在可控条件下研究膜界面处的分子行为，从而深入了解其中涉及的基本机制。在本研究中，我们使用二棕榈酰磷脂酰胆碱（DPPC）和DPPC/胆固醇（CHOL）组合，探索了AgNPs的形状和电子各向异性对细菌和红细胞膜模型的影响。通过分析表面压力（π-）和膜电位（Δ-）等温线，利用膜天平测量研究了脂质与银纳米颗粒之间的相互作用。这些测量通过X射线反射测量得到补充，以获取界面处的详细结构信息。此外，还进行了实验以提供纳米颗粒效应的行为概况，将物理化学相互作用与细胞反应联系起来。我们的研究结果表明，棱柱状银纳米颗粒（p-AgNPs）的形状各向异性对膜结构完整性和力学性能有显著影响，这些影响的程度取决于膜组成和胆固醇含量。棱柱状银纳米颗粒与DPPC单分子层的相互作用比球形纳米颗粒（s-AgNPs）更强，由于脂质提取导致表面压力升高和膜刚性降低。在DPPC/CHOL单分子层中，p-AgNPs促进CHOL微区形成并破坏DPPC组织，在较高CHOL浓度下这些影响更为明显。棱柱状纳米银还增强了类细菌膜中的脂质提取和膜通透性，而在模拟红细胞膜中，它破坏膜组织并降低刚性，胆固醇可调节这种影响。这些结果表明，p-AgNPs具有强大的抗菌性能，但也存在破坏真核细胞膜稳定性的风险。总体而言,该研究探索了p-AgNPs浓度依赖性的抗菌和细胞毒性作用，强调了其形态各向异性在调节纳米颗粒/膜相互作用中起决定性作用。通过揭示生物纳米界面的特定机制，这项工作为基于纳米银的装置和治疗的合理设计树立了重要先例，为各向异性纳米材料在生物医学中的安全有效应用贡献了宝贵知识。
