RESUMO
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.
RESUMO
Organic acids are prevalent in the environment and their acidity and the corresponding dissociation constants can change under varying environmental conditions. The impact of nanoconfinement (when acids are confined within nanometer-scale domains) on physicochemical properties of chemical species is poorly understood and is an emerging field of study. By combining infrared and Raman spectroscopies with molecular dynamics (MD) simulations, we quantified the effect of nanoconfinement in silica nanopores on one of the fundamental chemical reactions-the dissociation of organic acids. The pKa of formic and acetic acids confined within cylindrical silica nanopores with 4 nm diameters were measured. MD models were constructed to calculate the shifts in the pKa values of acetic acid nanoconfined within 1, 2, 3, and 4 nm silica slit pores. Both experiments and MD models indicate a decrease in the apparent acid dissociation constants (i.e., increase in the pKa values) when organic acids are nanoconfined. Therefore, nanoconfinement stabilizes the protonated species. We attribute this observation to (1) a decrease in the average dielectric response of nanoconfined aqueous solutions where charge screening may be decreased; or (2) an increase in proton concentration inside nanopores, which would shift the equilibrium towards the protonated form. Overall, the results of this study provide the first quantification of the pKa values for nanoconfined formic and acetic acids and pave the way for a unifying theory predicting the impact of nanoconfinement on acid-base chemistry.
