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Influence of local hydrophobic environment on acid dissociation constants of coordinated water molecules

Abstract

THE hydration of carbon dioxide by Zn(II) carbonic anhydrase is thought1,2 to occur through a mechanism in which a hydroxyl group coordinated to the zinc atom has an important function. As a consequence, the pK of the conjugate acid coordinated water molecule has been the subject of some discussion2,3. In Zn(II) (ref. 4) and Co(II) (ref. 5) carbonic anhydrase, the water molecule bound to the metal ion, apparently has a pK in the range 6.9–7.9, which is two units lower than the pK range quoted6 for the first protolysis of [Zn(H2O)6]2+ and [Co(H2O)6]2+.(The pK values quoted for [M(H2O)6]2+ exhibit a considerable variance and have been determined under a variety of experimental conditions. When M = Co, Ni, Cu and Zn mean pK values of 9.8, 10.3, 7.8 and 9.5, respectively, are derived from the range of values quoted at zero ionic strength and at 298 K (pK values for all four metal ions in 1 M NaClO4 are not available).)

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COATES, J., GENTLE, G. & LINCOLN, S. Influence of local hydrophobic environment on acid dissociation constants of coordinated water molecules. Nature 249, 773–775 (1974). https://doi.org/10.1038/249773a0

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