Deuterium/protium fractionation factors for polyfunctional organic molecules: direct determination by carbon-13 NMR spectroscopy

The isotope exchange processes between water and readily exchangeable groups (e.g., OH, NH, and SH) are of interest in studying reaction mechanisms and elucidating the structural dynamics of biological macromolecules. A knowledge of the equilibrium partitioning of deuterium and protium between the different types of exchangeable hydrogens is needed for a detailed interpretation of kinetic and equilibrium data and for the understanding of these processes. This paper describes a method for the direct determination of fractionation factors from the integrated intensities of the carbon-13 resonances of deuterio and protio species under conditions of slow chemical exchange