Solid-state NMR and computational chemistry study of mononucleotides adsorbed to alumina

Solid-state NMR spectroscopy and ab initio computational chemistry are used to determine the structure of the complex formed upon adsorption of the mononucleotide 2'-deoxyadenosine 5'-monophosphate (dAMP) to the surface of a mesoporous alumina. In this multi-technique approach, rotational-echo double-resonance NMR results reveal that the phosphate group of dAMP interacts predominantly with octahedrally coordinated aluminum species at the surface, and therefore, adsorption is modeled with both mono-and bidentate sorption of the nucleotide phosphate group with octahedral aluminum. P-31 chemical shielding tensors are calculated from the structure of the lowest energy conformations, and these results are compared to tensor values extracted from analysis of spinning-sideband patterns in the experimental P-31 cross-polarization magic-angle-spinning NMR spectrum. The chemical shift anisotropy and asymmetry parameter indicate that the binding is via a monodentate, inner-sphere complex.