Naslov
Theoretical Studies of Radical Enzymes

Autori
Sandala, Greg ; Smith, David M. ; Radom, Leo

Vrsta, podvrsta i kategorija rada
Poglavlja u knjigama, znanstveni

Knjiga
Encyclopedia of Radicals in Chemistry, Biology and Materials

Urednik/ci
Chatgilialoglu, C. ; Studer, A.

Izdavač
John Wiley & Sons

Grad
Chichester

Godina
2012

Raspon stranica
1547-1576

ISBN
0-470-97125-8

Ključne riječi
radicals, reaction mechanism, enzyme catalysis, density functional theory, ab initio, computational chemistry

Sažetak
The understanding of the mechanisms of radical enzymes has benefited greatly from the contribution of theoretical computations. This review highlights that success for a series of selected examples within this broad field. For the coenzyme B12-dependent enzymes, theoretical investigations have provided explanations for the activation of the Co–C bond of coenzyme B12, the facilitation of the otherwise difficult rearrangement step, and how the inherent stability of the participating radical intermediates can profoundly affect the level of catalysis. Likewise, computational investigations have characterized intermediates and demonstrated the importance of certain active-site amino acid residues in the reactions catalyzed by pyruvate formate lyase, benzylsuccinate synthase, and class III ribonucleotide reductase. In the case of methyl-coenzyme M reductase, the use of theory has offered new mechanistic ideas as to how this enzyme operates, which can then be tested experimentally. Overall, it is clear that the combination of experimental and computational investigations provides an excellent and highly synergistic approach to elucidating the cause-and-effect actions that govern the workings of the fascinating world of radical enzymes.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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