Acetylacetone is isolated in hydrogen matrices and is investigated by means of infrared spectroscopy, combined with theoretical calculations. The two stable enol and keto tautomers are well characterized. The keto/enol ratio in solid parahydrogen is found to be higher than in classical matrices. While vibrational bands of the enol form are broad, with bandwidths depending on the vibrational mode, those of the keto form are narrow. A KrF laser excitation is used to induce the enol/keto tautomerization in solid parahydrogen. The kinetics of the interconversion is followed, highlighting a non-direct tautomerization process.
Geometrical structures and energetic properties for different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest singlet excited state potential energy surfaces are studied. Four t...
Selected derivatives of cyclophosphamide (CP) metabolites were synthesized and the solution chemistry of each was studied by "3"1P nuclear magnetic resonance (NMR) spectroscopy under a standard set of reaction conditions at physiological pH (7.4) and temperature (37"0C). Complementary "2H and "1"3C NMR spectral data was obtained using isotopically ("2G and "1"3C) enriched CP metabolites. The CP derivatives were synthesized by the ozonolysis of substituted 3-butenyl phosphorodiamidates, and were isolated as analogues of either cis and trans 4-hydroperoxy-CP or aldophosphamide (AP). The relative ratios of the tautomeric species, 4-hydroxy-CP and AP, and their half-lives (T/sub 1/2/) were measured by "3"1P NMR spectroscopy. The influence of CP metabolites on perfused U-937 cells, a CP-sensitive human lymphoma, was observed by high resolution "3"1P NMR spectroscopy. In this manner, it was possible to measure, for the first time, a rate constant for the intracellular ...