In this review several applications of 31P high resolution solid state NMR spectroscopy in structural studies of bioorganic samples is reported. The problem of pseudopolymorphism of bis[6-O,6_-O-(1,2:3,4-diisopropylidene-_-D-galactopyranosyl) phosphorothioyl] disulfide 1 and application of 31P CP/MAS experiment to investigate of this phenomenon is discussed. The influence of weak C-H___S intermolecular contacts on molecular packing of 1,6-anhydro-2-O-tosyl-4-S-(5,5-dimethyl-2-thioxa-1,3,2-dioxaphosphorinan-2-yl)- _-D-glucopyranose 2 and SP, RP diastereomers of deoxyxylothymidyl-3_-O-acetylthymidyl (3_,5_)-O-(2-cyanoethyl) phosphorothioate 3 and their implication on 31P NMR spectra is shown. The final part of review describes the recent progress in structural studies of O-phosphorylated amino acids (serine, threonine, tyrosine), relationship between molecular structure and 31P chemical shift parameters _ii and influence of hydrogen bonding on values of principal elements of chemical shift tensor.
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