Metalloenzymes, computational methods

This chapter mainly focuses on the reactivity of 02 and its partially reduced forms. Over the past 5 years, oxygen isotope fractionation has been applied to a number of mechanistic problems. The experimental and computational methods developed to examine the relevant oxidation/reduction reactions are initially discussed. The use of oxygen equilibrium isotope effects as structural probes of transition metal 02 adducts will then be presented followed by a discussion of density function theory (DFT) calculations, which have been vital to their interpretation. Following this, studies of kinetic isotope effects upon defined outer-sphere and inner-sphere reactions will be described in the context of an electron transfer theory framework. The final sections will concentrate on implications for the reaction mechanisms of metalloenzymes that react with 02, 02 -, and H202 in order to illustrate the generality of the competitive isotope fractionation method. 

When the prediction or interpretation of spectroscopic properties and reactivities of metalloenzymes is the aim, QM-based methods - and DFT in particular - have proven to be the methods of choice [498]. Some of the recent results in the area of blue-copper proteins have been discussed above, and the methods used to interpret and predict spectroscopic parameters are provided in Chapter 10. Here, we concentrate on computational studies related to the understanding of the reactivity of... 

Woodcock HL, Miller BT, Hodoscek M, Okur A, Larkin JD, Pond JW, Brooks BR (2011) MSCALE a general utility for multiscale modeling. J Chem Theory Comput 7 1208-1219 Chung LW, Hirao H, Li X, Morokuma K (2012) The ONIOM method its foundation and applications to metalloenzymes and phombiology. Wiley Interdiscip Rev Comput Mol Sci 2 327-350... 

Chung LW, Hirao H, Li X, Morokuma K (2011) The ONIOM method its foundation and applications to metalloenzymes and photobiology. Wiley Interdisc Rev Comput Mol Sci 2 327-350... 

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