The Nonexistence of Specially Stabilized Hydrogen Bonds in Enzymes

Document Type


Journal/Book Title

Journal of the American Chemical Society

Publication Date



American Chemical Society




Ab initio calculations are used to test a recent suggestion that enzymic catalysis can be aided by strengthening of a hydrogen bond in a key intermediate, occurring when this bond is shortened and the pKa’s of the two groups are equalized. The requisite amount of energy is not available in electrically neutral H-bonds; no additional strengthening can be accomplished by shortening such a bond. Interaction energies where one subunit is charged, on the other hand, can be very high. These bonds are intrinsically very short, and the proton transfer profile contains a very low energy barrier. There is no special stabilization associated with the disappearance of the transfer barrier or equalization of the pKa’s.


Originally published in the Journal of the American Chemical Society by the American Chemical Society . Publisher’s PDF available through remote link. DOI: 10.1021/ja00131a020