Density functional methods applied to metalloenzymes
2003 (English)In: Coordination chemistry reviews, ISSN 0010-8545, E-ISSN 1873-3840, Vol. 238, 211-232 p.Article, review/survey (Refereed) Published
Density functional calculations for structures, spin states, redox energetics and reaction pathways are presented for some selected metalloenzymes. The specific enzymes examined are: (1) Fe and Mn superoxide dismutase for redox energetics and the role of second shell residues; (2) galactose oxidase (Cu enzyme) and (3) glyoxalase I (Zn enzyme) for reaction pathways, mechanisms, intermediates, and transition states (reaction barriers); (4) iron-oxo dimer enzymes methane monooxygenase and ribonucleotide reductase for characterizing the oxidized and reduced forms in terms of structures and protonation states, and for a proposed structure for the high-valent intermediate Q in MMO. The interaction of the active site with the surrounding protein environment is also explored in a number of cases either by using expanded quantum mechanically treated clusters, or by using electrostatic/ dielectric representations of the protein-solvent environment.
Place, publisher, year, edition, pages
2003. Vol. 238, 211-232 p.
density functional, broken symmetry, iron-oxo enzymes, methane monooxygenase, ribonucleotide reductase, catalytic cycle, redox, Poisson-Boltzmann, electrostatics, electron transfer, proton transfer, H atom transfer, pi-cation interaction, coli ribonucleotide reductase, manganese superoxide-dismutase, tyrosyl radical-diiron(iii) cofactor, soluble methane monooxygenase, methylococcus-capsulatus bath, iron-sulfur clusters, reversible dioxygen binding, enzyme galactose-oxidase, radical x-intermediate, active-site clusters
IdentifiersURN: urn:nbn:se:kth:diva-22515ISI: 000182957600012OAI: oai:DiVA.org:kth-22515DiVA: diva2:341213
QC 201005252010-08-102010-08-10Bibliographically approved