Embedding monomers and dimers of sulfonamideantibiotics into high silicazeolite Y: an experimental and computational study of the tautomeric forms involved

Abstract

This work is a second step towards the systematic study of the embedding of sulfonamide antibiotics into a synthetic high silica zeolite Y (HSZ-Y) with hydrophobic properties. In the previous paper [Braschi et al., Langmuir 2010, 31, 9524], the irreversible adsorption from water into HSZ-Y of three sulfonamides was studied by enlightening the host–guest interactions and, in the case of the smallest sized sulfadiazine, the guest–guest interactions of dimeric species inside the zeolite cage. Here the HSZ-Y was loaded with six sulfonamides, namely: sulfanilamide, sulfapyridine, sulfathiazole, sulfadimethoxine, sulfadoxine and sulfamerazine. With the exception of sulfanilamide, which showed scarce affinity for HSZ-Y (maximum loading 3% zeolite dry weight), the other sulfa drugs adsorbed at ca. 28% zeolite dry weight on average, and this is relevant for both water depollution and drug delivery issues. The low affinity of sulfanilamide for HSZ-Y was ascribed to its high hydrophilicity (water solubility 15–40 times higher than other drugs). The most stable tautomeric (amide or imide) form of each antibiotic adsorbed in zeolite Y was proposed by means of IR and solid state NMR spectroscopy augmented by computational modelling. The small dimensions and favourable stabilization energy allow the embedding of imidic and amidic dimers of sulfathiazole and sulfapyridine, respectively, inside the zeolite cage whereas the remaining sulfa drugs adsorbed in monomeric amidic forms.