Solvation, Reorganization Energy, and Biological Catalysis*

The question of how enzymes greatly enhance the rate of reactions has been discussed for years but remains a vigorously debated issue. Rapid progress has been made on the mechanism of individual enzymes by a combination of kinetic, chemical, and structural approaches. The push and pull of electrons and the resulting bond changes are well understood for many enzymes. However, the larger question of general features that enzymes use to produce rate accelerations of 10–10 has remained a contentious issue. We believe that such rate accelerations can be readily explained by reasonable physical principles (1). Though much of this understanding stems from research done in the 1970s and 1980s, these insights are often underappreciated or even completely neglected when examining enzymic rate accelerations. Perhaps this is because of our intense focus on enzymes themselves and relative neglect of the reference solution reactions to which they are compared, consequentially, resulting in a mechanistic tunnel vision.

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