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- W2077403506 abstract "During the course of an NMR titration, broadening or disappearance of the line sometimes occurs because of insufficiently rapid exchange between the two species lying at the extremes of the titration. This “fast-exchange broadening” is more likely to occur with the use of high magnetic fields and the study of nuclei having large chemical shift ranges. A theoretical framework is presented here for extracting rate constants from line broadening observed during formation of any diamagnetic complex including acid-base reactions, metal complexes, and enzyme-substrate complexes. In acid-base titrations where significant broadening occurs, the chemical shift vs pH curves may be nonsigmoidal and maximal broadening may occur at pH values as far as 0.30 pH units from the pKα value. Recent literature involving NMR histidine titrations is discussed in terms of these ideas. Addition of buffer and use of lower field magnets may reduce or eliminate fast-exchange broadening. Imidazole groups on protein surfaces appear to undergo diffusion-controlled acid-base reactions with rates comparable to those of free imidazole." @default.
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- W2077403506 date "1980-08-01" @default.
- W2077403506 modified "2023-09-27" @default.
- W2077403506 title "Dependence of NMR lineshape analysis upon chemical rates and mechanisms: Implications for enzyme histidine titrations" @default.
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- W2077403506 doi "https://doi.org/10.1016/0022-2364(80)90261-9" @default.
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