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Selected examples of this approach to fitting can be found in (a) Zimmerle, C. T.; Frieden, C. Biochem. J. 1989, 258, 381-387 and in (b) Adam, L. C.; Fabian, I.; Susuki, K.; Gordon, G. Inorg. Chem. 1992, 31, 3534-3541.
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1842290238
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17 rate constants were obtained by fitting to the closed-form integrated expression of the rate equations with a time-shift parameter included to account for the fact that some reaction had occurred before the stopped-flow instrument recorded the first time. For all concentrations of hydroxide, least-squares fits gave a time shift of about 0.003 s.
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29
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1842291990
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note
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4) for enamine decomposition is needed to explain the kinetics for 2 but not for 1.
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1842376133
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note
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27 was used, and we used the average value of k′ IH over the range of values obtained at various concentrations of hydroxide.
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1842296190
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note
-
We cannot identify the peak at 2.4 ppm; it may arise from an impurity in the DCl solution used to acidify the sample, or it may be due to an unknown product formed once the acid is added. The latter possibility is considered unlikely since only a single unknown peak was observed. The remainder of the high-intensity peaks match the peaks seen in panel A.
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