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• W1964540139 abstract "Association constants in weak molecular complexes can be determined by analysis of chemical shifts variations resulting from changes of guest to host concentration ratio. In the regime of very fast exchange, i.e., when exchange rate is several orders of magnitude larger than the Larmor angular frequency difference of the observed resonance in free and complexed molecule, the apparent position of averaged resonance is a population-weighted mean of resonances of particular forms involved in the equilibrium. The assumption of very fast exchange is often, however, tacitly admitted in literature even in cases where the process of interest is much slower than required. We show that such an unjustified simplification may, under certain circumstances, lead to significant underestimation of association constant and, in consequence, to non-negligible errors in Gibbs free energy under determination. We present a general method, based on iterative numerical NMR line shape analysis, which allows one for the compensation of chemical exchange effects, and delivers both the correct association constants and the exchange rates. The latter are not delivered by the other mentioned method. Practical application of our algorithm is illustrated by the case of camphor-alpha-cyclodextrin complexes." @default.
• W1964540139 created "2016-06-24" @default.
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• W1964540139 date "2006-08-01" @default.
• W1964540139 modified "2023-10-01" @default.
• W1964540139 title "Determination of association constants at moderately fast chemical exchange: Complexation of camphor enantiomers by α-cyclodextrin" @default.
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• W1964540139 doi "https://doi.org/10.1016/j.jmr.2006.06.001" @default.
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