ABSTRACT
I. Introduction ...................................................................................................................... 475
II. Theoretical Approaches to the Study of Chemical Dynamics in Complex Systems ..... 476
III. Promoting Vibrations and the Dynamics of Hydrogen Transfer .................................... 479
A. Promoting Vibrations and the Symmetry of Coupling ........................................... 479
B. Promoting Vibrations — Corner Cutting and the Masking of KIEs ...................... 480
IV. Enzymatic Hydrogen Transfer and KIEs ........................................................................ 482
A. Alcohol Dehydrogenase ........................................................................................... 482
B. Lactate Dehydrogenase ............................................................................................ 487
V. Hydrogen Transfer Coupled to Electron Transfer — Kinetic Trends
in the Presence of a Promoting Vibration ....................................................................... 491
VI. Conclusions ...................................................................................................................... 495
Acknowledgments ........................................................................................................................ 495
References..................................................................................................................................... 495
Life of all forms depends on the acceleration of the rate of chemical reactions by enzymes. It is now
known that many enzymes function by lowering the free-energy barrier to a reaction. This
preferential binding of the enzyme to the transition state is a concept credited to Pauling.
