Exploring the biointerfaces: ab initio investigation of nano-montmorillonite clay, and its interaction with unnatural amino acids.

We investigated the interaction between biomimetic Fe and Mg co-doped montmorillonite nanoclay and eleven unnatural amino acids. Employing three different functionals (PBE-GGA, PBE-GGA + U, and HSE06), we examined the clay's structural, electronic, and magnetic properties. Our results revealed the necessity of using PBE-GGA + U with U ≥ 4 eV to accurately describe key clay properties. We identified amino acids that strongly interacted with the clay surface, with steric orientation playing a crucial role in facilitating binding. Our DFT calculations highlighted significant electrostatic interactions between the amino acids and the clay slab, with the amino group's predominant role in this interaction. These findings hold promise for designing amino acids for clay-amino acid systems, leading to innovative bio-material composites for various applications. Additionally, our ab-initio molecular dynamics simulations confirmed the stability of clay-amino acid systems under ambient conditions, and the introduction of an implicit water solvent enhanced the binding energy of amino acids on the clay surface.