Stepan Kashtanov

Revisiting magnesium chelation by teichoic acid with phosphorus solid-state NMR and theoretical calculations.

Teichoic acids are essential components of the Gram-positive bacterial cell wall. One of their many functions is metal binding, a vital process for bacterial growth. With the combination of phosphorus-31 solid-state NMR spectroscopy and theoretical calculations using density functional theory (DFT), we have determined that the binding mode between teichoic acids and magnesium involves bidentate coordination by the phosphate groups of teichoic acid. Measurement of chemical shift anisotropy tensors gave a reduced anisotropy (delta) of 49.25 ppm and an asymmetry (eta) of 0.7. DFT calculations with diglycerol phosphate and triglycerol diphosphate model compounds were completed with Mg(2+) in anhydrous as well as partially hydrated bidentate and fully hydrated monodentate, bidentate, and bridging binding modes. (31)P CSA tensors were calculated from the energy-minimized model compounds using the combined DFT and GIAO methods, resulting in dramatically different tensor values for each binding mode. The anhydrous bidentate chelation mode was found to be a good approximation of the experimental data, an observation that alters the current monodentate paradigm for metal chelation by teichoic acids.

Characterization of aza-fullerene C58N2 isomers by X-ray spectroscopy

X-ray photoelectron and near-edge X-ray absorption fine-structure spectra (NEXAFS) of four isomers of C58N2 are predicted by means of density-functional theory calculations. A strong isomer depende ...