No abstract

The complexation by -cyclodextrin ( -CD) of three organophosphorus pesticides, fenitrothion, parathion and methylparathion, and of their carboxylic ester analogues was analyzed using PM3 and molecular mechanics methods. The objective was to elucidate structural features and energy changes that accompany the complexation and could possibly affect the hydrolysis process, which is catalyzed by -CD in the case of carboxylic esters but inhibited for the pesticides, in alkaline medium. The complexation of fenitrothion was further explored, since experiments proved its hydrolysis is relatively less inhibited and progresses mainly through a different pathway than that usually accepted. The results of this study show that complex structures involving esters enable effective interactions between the guest carbonyl and the rim of the host; methylparathion and parathion, however, appear to be deeply included in the cavity of -CD. Therefore the conditions for a nucleophilic attack by the -CD are favorable for the carboxylic esters but not for the two pesticides. Different complex geometries resulted for fenitrothion depending on its mode of inclusion in the cavity, none apparently being prone to an attack by the -CD, but favoring instead the approach of an external OHgroup, in agreement with the experiment.

An analytical isotherm equation that describes the multilayer adsorption on fractal surfaces with adsorbate-adsorbate interactions (measured in terms of free energy) different from that of bulk liquid was developed. Assuming mathematical functionalities for the variation of the free energy, it is possible to evaluate the influence of the adsorbate-adsorbate interactions on the adsorption capacity of solids of high degree of surface irregularity. For those surfaces with relatively low degree of irregularity, it results that the free energy variation with the layer number in the multilayer region affects considerably the sorption capacity of the adsorbent, even for water activities lower than those corresponding to the monolayer moisture content. The energy interactions between adjacent adsorbate layers become less important as the fractal dimension of the adsorbent increases. For a fractal surface, the growing of the multilayer seems to mainly controlled by the degree of surface roughness characteristic of microporous adsorbents, where the volume and pore dimension are the true limitants to the sorption capacity. The isotherm equations obtained were tested fitting published experimental equilibrium data of various water vapor-biopolymer systems.