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Chemical exchange in tissue extracts revisited: Bicarbonate and deuterium isotope effects on 31 P resonances of phosphoethanolamine and phosphocreatine
Author(s) -
Bezabeh Tedros,
Ackerman Joseph J. H.
Publication year - 1992
Publication title -
nmr in biomedicine
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.278
H-Index - 114
eISSN - 1099-1492
pISSN - 0952-3480
DOI - 10.1002/nbm.1940050608
Subject(s) - chemistry , deuterium , phosphocreatine , bicarbonate , kinetic isotope effect , isotope , chemical shift , aqueous solution , resonance (particle physics) , nuclear magnetic resonance spectroscopy , nuclear magnetic resonance , inorganic chemistry , stereochemistry , organic chemistry , medicine , physics , quantum mechanics , particle physics , energy metabolism
It is not sufficiently appreciated that chemical exchange can markedly affect the appearance of 31 P tissue extract NMR spectra. In addition to the commonly recognized 31 P chemical shift effects of divalent metal cation (e.g. Mg 2+ ) binding upon ATP resonances, multiple resonances for phosphoethanolamine (PE) and phosphocreatine (PCr) are observed under certain conditions of pH, temperature, and D 2 O and bicarbonate concentrations. In the presence of bicarbonate ion (commonly used to neutralize acidic extractions) carbamate formation causes a second 31 P resonance for PE to appear. This effect has been described previously for 13 C and 1 H amino acid resonances in tissue extracts [Sherry et al. J. Magn. Reson. 89 , 391––398 (1990)]. The observation of a splitting of the PCr 31 P resonance in aqueous solutions containing D 2 O has been recently ascribed to proton scalar coupling but was described earlier in an underappreciated report [Kupriyanov et al. Biochem. Biophys. Res. Comm. 114 , 1117–1125 (1983)] as due to a deuterium isotope effect. These effects, carbamate formation and deuterium isotope shift, are verified herein to cause marked shifts in PE and PCr 31 P resonances. The dependence upon experimental parameters is explored.