Rahimi Sakineh, Najafi Chermahini Alireza, Farrokhpour Hossein, Hajipour Abdol Reza
Department of Chemistry, Isfahan University of Technology, 84154-83111, Isfahan, Iran.
Department of Chemistry, Isfahan University of Technology, 84154-83111, Isfahan, Iran.
J Mol Graph Model. 2025 Jul;138:109038. doi: 10.1016/j.jmgm.2025.109038. Epub 2025 Mar 26.
This research pioneers a computational approach to design superior copper corrosion inhibitors by systematically exploring the impact of targeted methylation on oxalohydrazide (OXH). Leveraging density functional theory (DFT) and molecular dynamics (MD) simulations, we demonstrate that strategic methylation, particularly at the N' positions, significantly amplifies the adsorption energy of OXH derivatives on the Cu (111) surface, favoring a highly stable parallel adsorption mode. Beyond mere adsorption strength, we unveil the precise electronic mechanisms driving enhanced inhibition: calculated HOMO-LUMO energy gaps, hardness, and softness values reveal that methylated derivatives possess markedly improved electronic properties compared to OXH, directly correlating with enhanced corrosion protection. Furthermore, our MD simulations, conducted in an aqueous environment, uncover the nuanced interplay between water molecules and protonated inhibitors, providing critical insights into their real-world performance. This study establishes a novel, predictive framework for tailoring molecular structures to achieve optimal corrosion inhibition, offering a powerful tool for developing next-generation protective coatings for copper-based materials.
本研究开创了一种计算方法，通过系统地探索靶向甲基化对草酰肼（OXH）的影响来设计性能卓越的铜缓蚀剂。利用密度泛函理论（DFT）和分子动力学（MD）模拟，我们证明了策略性甲基化，特别是在N'位置，显著增强了OXH衍生物在Cu（111）表面的吸附能，有利于形成高度稳定的平行吸附模式。除了单纯的吸附强度外，我们还揭示了增强抑制作用的精确电子机制：计算得到的HOMO-LUMO能隙、硬度和软度值表明，甲基化衍生物与OXH相比具有明显改善的电子性质，这与增强的腐蚀防护直接相关。此外，我们在水性环境中进行的MD模拟揭示了水分子与质子化抑制剂之间细微的相互作用，为它们在实际应用中的性能提供了关键见解。本研究建立了一个新颖的预测框架，用于定制分子结构以实现最佳的腐蚀抑制效果，为开发用于铜基材料的下一代防护涂层提供了有力工具。
