Alotaibi Hadil Faris, Kumar Anjan, Jadeja Yashwantsinh, Ballal Suhas, Al-Hasnaawei Shaker, Singh Abhayveer, Krithiga T, Ray Subhashree, Joshi Kamal Kant
Department of Pharmaceutical Sciences, College of Pharmacy, Princess Nourah Bint AbdulRahman University, Riyadh, 11671, Saudi Arabia.
Department of electronics and communication engineering, GLA University, Mathura, 281406, India.
Sci Rep. 2025 Jul 15;15(1):25547. doi: 10.1038/s41598-025-11275-5.
This study explores the enhancement of adsorption properties of penicillamine (PCA) in both neutral and zwitterionic forms through the use of magnesium oxide (MgO) fullerene-like cages, supported by density functional theory (DFT) and molecular dynamics (MD) simulations. Results indicate that PCA adsorption is spontaneous and exothermic, with the cage preferentially abstracting a hydrogen atom from surface hydroxyl groups, leading to strong interactions evidenced by adsorption energies of -2.250 eV in water and - 2.204 eV in chloroform. Charge transfer from the MgO cage to PCA was approximately 0.299 |e| in water and 0.278 |e| in chloroform, resulting in decreased global hardness and increased chemical potential of the complex, suggesting enhanced reactivity. During the adsorption process, PCA in zwitterionic form exhibited the highest increase in dipole moment, with a value of 12.540 Debye (complex F), compared to the neutral form with the value of 11.382 (complex C) Debye, suggesting enhanced solubility of the system. Dynamic simulations showed that binding energies fluctuate and reach equilibrium after 120 ps. Time-dependent DFT analyses revealed solvent-dependent effects on exciton stability and absorption spectra: water stabilizes charges and enhances absorption, while chloroform induces peak broadening and redshift due to Coulomb interactions. Infrared spectroscopy demonstrated significant spectral shifts upon PCA adsorption, particularly via its carboxyl group, which exhibited the lowest energy gap (E) and favorable electronic interactions. Our findings suggest that MgO cages hold significant potential as biosensors and delivery vehicles for penicillamine, with solvent environment playing a crucial role in adsorption characteristics.
本研究通过使用氧化镁（MgO）类富勒烯笼，在密度泛函理论（DFT）和分子动力学（MD）模拟的支持下，探索了中性和两性离子形式的青霉胺（PCA）吸附性能的增强。结果表明，PCA的吸附是自发的且放热的，笼子优先从表面羟基提取一个氢原子，导致在水中吸附能为-2.250 eV，在氯仿中吸附能为-2.204 eV，从而证明了强相互作用。在水中，从MgO笼到PCA的电荷转移约为0.299 |e|，在氯仿中为0.278 |e|，导致配合物的整体硬度降低，化学势增加，表明反应活性增强。在吸附过程中，两性离子形式的PCA偶极矩增加最高，值为12.540德拜（配合物F），而中性形式的值为11.382德拜（配合物C），表明系统的溶解度增强。动态模拟表明，结合能波动，并在120 ps后达到平衡。含时DFT分析揭示了溶剂对激子稳定性和吸收光谱的影响：水使电荷稳定并增强吸收，而氯仿由于库仑相互作用导致峰展宽和红移。红外光谱表明，PCA吸附后光谱发生了显著变化，特别是通过其羧基，羧基表现出最低的能隙（E）和良好的电子相互作用。我们的研究结果表明MgO笼作为青霉胺的生物传感器和递送载体具有巨大潜力，溶剂环境在吸附特性中起着关键作用。
