Insights on adsorption of pyocyanin in montmorillonite using molecular dynamics simulation

Pyocyanin is an important virulence factor in the resistance of Pseudomonas aeruginosa to antibiotics. Pyocyanin is a planar three ring aromatic molecule that occurs as zwitterionic (PYO) or protonated species (PYOH+). Our earlier studies have shown that montmorillonite, through adsorption and transformation, can inactivate both PYO and PYOH+ in the interlayer space. The objective of this study was to elucidate the interaction mechanisms between montmorillonite and the adsorbed pyocyanin and to characterize the structure of the pyocyanin-montmorillonite complex via molecular dynamics (MD) simulations. The MD simulations were performed for the complexes of hydrated Na-montmorillonite (HM) with (i) neutral pyocyanin (HMP) and (ii) protonated pyocyanin (HMPH); and dehydrated Na-montmorillonite (DM) with (iii) neutral pyocyanin (DMP) and (iv) protonated pyocyanin (DMPH). The simulations indicated that in dry conditions, both PYO and PYOH+ were well-ordered in the midplane of the interlayer of montmorillonite, with the three aromatic rings almost parallel to the basal surface and sandwiched in-between basal surface-adsorbed Na+ planes. In humid conditions, the pyocyanin and Na+ were solvated in the interlayer space and the pyocyanin was less ordered compared to dehydrated models. Ion-dipole interaction (Na-O) was the dominant interaction for the dehydrated complexes DMPH and DMP but the interaction was stronger in the latter. The Na-O ion-dipole interaction remained the dominant interaction in hydrated HMP while in HMPH, water outcompeted PYOH+ for Na+ resulting in water-Na interaction being the dominant interaction. These results revealed the arrangement of the two species of pyocyanin in the interlayer spaces of montmorillonite and the mechanism of interaction between the pyocyanin and montmorillonite. This experiment-guided molecular simulation study provided insight on the interaction mechanisms between montmorillonite and different species (neutral and protonated) of pyocyanin at different moisture conditions.