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53549094768
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All kinetic measurements were performed at pH 2.9, at which decomposition in the absence CB7 is sufficiently slow to be accurately followed; at higher pH values, the active form is inefficiently formed, while at lower, more acidic, pH values, decomposition is too fast (seconds) to be accurately measured by conventional methods; see Ref. [13].
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All kinetic measurements were performed at pH 2.9, at which decomposition in the absence CB7 is sufficiently slow to be accurately followed; at higher pH values, the active form is inefficiently formed, while at lower, more acidic, pH values, decomposition is too fast (seconds) to be accurately measured by conventional methods; see Ref. [13].
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53549130787
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The activation rate (determined by UV spectroscopy) was independent, within error, of the CB7 concentration (50 μM 1a, 0.1-4 mM CB7), which suggests that the complexation by the macrocycle is not the rate-determining step in the formation of the active form, but is instead the reaction of 1 to 2 inside the complex.
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The activation rate (determined by UV spectroscopy) was independent, within error, of the CB7 concentration (50 μM 1a, 0.1-4 mM CB7), which suggests that the complexation by the macrocycle is not the rate-determining step in the formation of the active form, but is instead the reaction of 1 to 2 inside the complex.
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27
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53549084955
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The actual catalytic effect on the initial nucleophilic substitution step (Scheme 1) may be larger, because the observed rate for the formation of the active species 2 in the presence of CB7 includes a dehydration step as a follow-up reaction.
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The actual catalytic effect on the initial nucleophilic substitution step (Scheme 1) may be larger, because the observed rate for the formation of the active species 2 in the presence of CB7 includes a dehydration step as a follow-up reaction.
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28
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53549131339
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At any given pH value, the ratio of the monoprotonated prototropic forms II/I is given as 10pKa,2-pKa,1
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