Orbital steering mechanism

Orbitals, atomic, see Atomic orbitals Orbitals, molecular, see Molecular orbitals Orbital steering mechanism, 220-221 Oxyanion intermediates, 172,181,185,210 Oxyanion hole, 181... 

This analysis in many ways parallels the theoretical treatment presented by Dafforn and Koshland [see Ref. (37)] as an extension and refinement of the initial proposal of orbital steering. They clearly established that the total effect could be large even after allowing for residual internal freedom in the transition state and that a loose complex as exemplified by bromine combination could occur with little loss of entropy. The point which is developed more fully here is that the microscopic model used for the statistical mechanical calculations is not the same macroscopic model used in the original definition of orbital steering. 

So far in this chapter, the chemical biology reader has been introduced to examples of biocatalysts, kinetics assays, steady state kinetic analysis as a means to probe basic mechanisms and pre-steady-state kinetic analysis as a means to measure rates of on-catalyst events. In order to complete this survey of biocatalysis, we now need to consider those factors that make biocatalysis possible. In other words, how do biocatalysts achieve the catalytic rate enhancements that they do This is a simple question but in reality needs to be answered in many different ways according to the biocatalyst concerned. For certain, there are general principles that underpin the operation of all biocatalysts, but there again other principles are employed more selectively. Several classical theories of catalysis have been developed over time, which include the concepts of intramolecular catalysis, orbital steering , general acid-base catalysis, electrophilic catalysis and nucleophilic catalysis. Such classical theories are useful starting points in our quest to understand how biocatalysts are able to effect biocatalysis with such efficiency. 

Having compared these data with the geometry of the molecules calculated by the molecular mechanics method, the same authors concluded that in XXXVIIIc optimal orientation is achieved of the nucleo philic group OH with respect to carbonyl, namely, the angle of approach of 98°, while even insignificant deviations ( 10°) from it appreciably inhibit the reaction. The requirement for such refined adjustment of the reaction site became known as the orbital steering concept provoking lively discussion [118,119]. 

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