122 resultados para CNDO CALCULATIONS


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The aim of this study was to compare accumulated oxygen deficit data derived using two different exercise protocols with the aim of producing a less time-consuming test specifically for use with athletes. Six road and four track male endurance cyclists performed two series of cycle ergometer tests. The first series involved five 10 min sub-maximal cycle exercise bouts, a (V) over dotO(2peak) test and a 115% (V) over dotO(2peak) test. Data from these tests were used to estimate the accumulated oxygen deficit according to the calculations of Medbo et al. (1988). In the second series of tests, participants performed a 15 min incremental cycle ergometer test followed, 2 min later, by a 2 min variable resistance test in which they completed as much work as possible while pedalling at a constant rate. Analysis revealed that the accumulated oxygen deficit calculated from the first series of tests was higher (P< 0.02) than that calculated from the second series: 52.3 +/- 11.7 and 43.9 +/- 6.4 ml . kg(-1), respectively (mean +/- s). Other significant differences between the two protocols were observed for (V) over dot O-2peak, total work and maximal heart rate; all were higher during the modified protocol (P

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Flash vacuum thermolysis (FVT) of 1-(dimethylamino)pyrrole-2,3-diones 5 causes extrusion of CO with formation of transient hydrazonoketenes 7. The transient ketenes 7 are observable in the form of weak bands at 2130 (7a) or 2115 cm(-1) (7b) in the Ar matrix IR spectra resulting from either FVT or photolysis of either 5 or 1,1- dimethylpyrazolium-5- oxides 8, and these absorptions are in excellent agreement with B3LYP/6-31G* frequency calculations. Under FVT conditions the ketenes 7 cyclize to pyrazolium oxides 8, which undergo 1,4-migration of a methyl group to yield 1,4-dimethyl-3-phenylpyrazole-5(4H)-one 9a and 1,4,4-trimethyl-3-phenylpyrazole-5(4H)-one 9b. All three tautomers of 9a have been characterized, viz. the CH form 9a (most stable form in the gas phase, the solid state and solvents of low polarity), the OH form 9a' (metastable solid at room temperature) and the NH form 9a (stable in aprotic dipolar solvents). The isomeric 1,4-dimethyl-5-phenylpyrazole-3(2H)-one 12 tautomerizes to the 3-hydroxypyrazole 12'. The crystal structure of the hydrochloride 14 of 9a'/9a is reported, representing the first structurally characterised example of a protonated 5-hydroxypyrazole.