title: Divergent mechanisms of iron-containing enzymes for hydrocarbon biosynthesis.
abstract: Increasing levels of energy consumption, dwindling resources, and environmental considerations have served as compelling motivations to explore renewable alternatives to petroleum-based fuels, including enzymatic routes for hydrocarbon synthesis. Phylogenetically diverse species have long been recognized to produce hydrocarbons, but many of the enzymes responsible have been identified within the past decade. The enzymatic conversion of Cnchain length fatty aldehydes (or acids) to Cn-1hydrocarbons, alkanes or alkenes, involves a C-C scission reaction. Surprisingly, the enzymes involved in hydrocarbon synthesis utilize non-heme mononuclear iron, dinuclear iron, and thiolate-ligated heme cofactors that are most often associated with monooxygenation reactions. In this review, we examine the mechanisms of several enzymes involved in hydrocarbon biosynthesis, with specific emphasis on the structural and electronic changes that enable this functional switch.
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA.
authors.forename: Courtney E
authors.initials: CE
authors.lastname: Wise
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA.
authors.forename: Job L
authors.initials: JL
authors.lastname: Grant
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA.
authors.forename: Jose A
authors.initials: JA
authors.lastname: Amaya
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA.
authors.forename: Steven C
authors.initials: SC
authors.lastname: Ratigan
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA.
authors.forename: Chun H
authors.initials: CH
authors.lastname: Hsieh
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA.
authors.forename: Olivia M
authors.initials: OM
authors.lastname: Manley
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, 29208, USA. makrist@mailbox.sc.edu.
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Makris
mesh_terms: D004798:Enzymes / Q000737:chemistry* / Q000378:metabolism*; D006838:Hydrocarbons / Q000737:chemistry / Q000378:metabolism*; D007501:Iron / Q000378:metabolism*
chemical_list: D004798:Enzymes; D006838:Hydrocarbons; D007501:Iron
keywords: Biosynthesis; Cofactor; Cytochrome; Electron paramagnetic resonance; Mossbauer spectroscopy