Predicting biomolecule adsorption on MoS2 nanosheets with high structural fidelity

A new force field, MoSu-CHARMM, for the description of bio-interfacial structures at the aqueous MoS2 interface is developed, based on quantum chemical data. The force field describes non-covalent interactions between the MoS2 surface and a wide range of chemistries including hydrocarbon, alcohol, aldehyde, ketone, carboxylic acid, amine, thiol, and amino acid groups. Density functional theory (DFT), using the vdW-DF2 functional, is employed to create training and validation datasets, comprising 330 DFT binding energies for 21 organic compounds. Development of MoSu-CHARMM is guided by two criteria: (i) minimisation of energetic differences compared to target DFT data and (ii) preservation of the DFT energetic rankings of the different binding configurations. Force-field performance is validated against existing high-quality structural experimental data regarding adsorption of four 26-residue peptides at the aqueous MoS2 interface. Adsorption free energies for all twenty amino acids in liquid water are calculated to provide guidance for future peptide design, and interpret the properties of existing experimentally-identified MoS2-binding peptides. This force field will enable large-scale simulations of biological interactions with MoS2 surfaces in aqueous media where an emphasis on structural fidelity is prioritised.