Origination of catalysis

Dickerson, T. J. Lovell, T Meijler, M. M. Noodleman, L. Janda, K. D. Nomicotine aqueous aldol reactions Synthetic and theoretical investigations into the origins of catalysis, 7. Org. Chem. 2004, 69, 6603-6609. 

Fig. 7 Schematic illustration of the origin of catalysis by the enrjrme ODCase. Arrows indicate the free energy decomposition of Eqs. 2 and 3 that separate the binding free energy into a protein distortion term and an intrinsic substrate-protein interaction component. The figure shows that the protein has a smaller distortion energy than that in the reactant state, so the change in protein conformational energy provides the predominant contribution to the lowering of the activation free energy of the catalyzed reaction...

Houk and coworkers provide a survey of the known biochemical, structural, and computational studies on ODCase. In particular, they examine what recent theoretical studies have discovered about the origins of catalysis in ODCase, including the possibility that dynamic effects and/or iminium ion formation might actually be important contributors to ODCase s proficiency. 

Overall, this volume shows how many different mechanistic tools—biochemical kinetics. X-ray crystallography, state-of-the-art computations—have been brought to bear in parallel and occasionally in concert on the problem of understanding the origins of catalysis by ODCase. Still, it is clear that a consensus has not yet been reached as to the catalytic mechanism. In fact, while very few mechanistic proposals have been disproven, many new mechanistic proposals have arisen. For example, as pointed out by several of our authors, dynamic effects may prove to be essential for catalysis in this peculiar enzyme. We hope that the diverse chemistry discussed in this volume will inspire not only additional calculations and experiments, but also new viewpoints from which the mystery of ODCase s catalytic mechanism may be unraveled. 

The understanding of the origin of catalysis in these reactions suffers severely from the lack of information about the structure of the host-guest complexes so that any explanatory attempt remains highly speculative at present. 

Electrochemical promotion of catalysis definition, 10 limits of, 180, 505 mechanism of, 189, 271 modeling of, 315, 503 origin, 189... 

Surface reconstruction, which had dominated much of surface science through LEED studies, was very much a central theme of STM in the early 1990s but with surprisingly little attention given to chemical reactivity and the origin of active sites in heterogeneous catalysis. This was in part due to the lack of in situ chemical information that could be directly related to the STM images and... 

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