THE NONEXISTENCE OF SPECIALLY STABILIZED HYDROGEN-BONDS IN ENZYMES

Ab initio calculations are used to test a recent suggestion that enzym ic catalysis can be aided by strengthening of a hydrogen bond in a key intermediate, occurring when this bond is shortened and the pK(a)'s o f 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 w here one subunit is charged, on the other hand, can be very high. Thes e 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 equalizat ion of the pK(a)'s.