Molecular Modeling to Predict the Optimal Mineralogy of Smectites as Binders of Aflatoxin

Numerous experiments have verified that smectites can adsorb aflatoxin B 1 (AfB 1 ) effectively and the efficiency of this process depends heavily on the chemical, physical, and mineralogical characteristics of the smectite. Several relationships between these characteristics and AfB 1 sorption have been determined experimentally, but the molecular mechanisms underlying these were not investigated. In the current study the effects of charge density, type of exchange cation, and charge origin (octahedral vs. tetrahedral) on AfB 1 sorption on smectites were analyzed by a series of molecular simulations. The calculations confirmed the formation of water bridges between carbonyl groups of AfB 1 molecules and interlayer cations. Flat orientation of AfB 1 molecules on smectite surfaces was also confirmed. For larger amounts of AfB 1 molecules in the intercalates, self-association of two AfB 1 molecules bound by π–π interaction was shown. The thermodynamics of AfB 1 sorption depends heavily on the water content in the structure, being optimal for basal distances corresponding to two layers of water. A clear preference for sorption of AfB 1 on smectites with bivalent cations (Ba 2+ , Ca 2+ ) and an octahedral origin of its layer charge was confirmed and this was explained as steric hindrance between hydrated ions and AfB 1 molecules, which tend to lie flat on smectite surfaces devoid of ions. Ba-montmorillonite with a charge of 0.4 per half unit cell was shown to have the smallest and thus the best potential energy of adsorption compared to the other layer charges.