Theoretical studies of mononuclear non-heme iron active sites
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
The quantum chemical investigations presented in this thesis use hybrid density functional theory to shed light on the catalytic mechanisms of mononuclear non-heme iron oxygenases, accommodating a ferrous ion in their active sites. More specifically, the dioxygen activation process and the subsequent oxidative reactions in the following enzymes were studied: tetrahydrobiopterin-dependent hydroxylases, naphthalene 1,2-dioxygenase and α-ketoglutarate-dependent enzymes. In light of many experimental efforts devoted to the functional mimics of non-heme iron oxygenases, the reactivity of functional analogues was also examined.
The computed energetics and the available experimental data served to assess the feasibility of the reaction mechanisms investigated. Dioxygen activation in tetrahydrobiopterin- and α-ketoglutarate-dependent enzymes were found to involve a high-valent iron-oxo species, which was then capable of substrate hydroxylation. In the case of naphthalene 1,2-dioxygenase, the reactivity of an iron(III)-hydroxperoxo species toward the substrate was investigated and compared to the biomimetic counterpart.
Place, publisher, year, edition, pages
Stockholm: Fysikum , 2004. , 86 p.
quantum chemistry, enzyme catalysis, iron enzymes
IdentifiersURN: urn:nbn:se:su:diva-103ISBN: 91-7265-857-6OAI: oai:DiVA.org:su-103DiVA: diva2:189257
2004-05-07, sal FA32, AlbaNova universitetscentrum, Roslagstullsbacken 21, Stockholm, 10:00
Shaik, Sason, Prof
Siegbahn, Per E. M., Prof
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