title: Independent evolution of four heme peroxidase superfamilies.
abstract: Four heme peroxidase superfamilies (peroxidase-catalase, peroxidase-cyclooxygenase, peroxidase-chlorite dismutase and peroxidase-peroxygenase superfamily) arose independently during evolution, which differ in overall fold, active site architecture and enzymatic activities. The redox cofactor is heme b or posttranslationally modified heme that is ligated by either histidine or cysteine. Heme peroxidases are found in all kingdoms of life and typically catalyze the one- and two-electron oxidation of a myriad of organic and inorganic substrates. In addition to this peroxidatic activity distinct (sub)families show pronounced catalase, cyclooxygenase, chlorite dismutase or peroxygenase activities. Here we describe the phylogeny of these four superfamilies and present the most important sequence signatures and active site architectures. The classification of families is described as well as important turning points in evolution. We show that at least three heme peroxidase superfamilies have ancient prokaryotic roots with several alternative ways of divergent evolution. In later evolutionary steps, they almost always produced highly evolved and specialized clades of peroxidases in eukaryotic kingdoms with a significant portion of such genes involved in coding various fusion proteins with novel physiological functions.
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria; Institute of Molecular Biology, Slovak Academy of Sciences, Dúbravská cesta 21, SK-84551 Bratislava, Slovakia. Electronic address: marcel.zamocky@boku.ac.at.
authors.forename: Marcel
authors.initials: M
authors.lastname: Zámocký
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria; Department for Structural and Computational Biology, Max F. Perutz Laboratories, University of Vienna, A-1030 Vienna, Austria.
authors.forename: Stefan
authors.initials: S
authors.lastname: Hofbauer
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
authors.forename: Irene
authors.initials: I
authors.lastname: Schaffner
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
authors.forename: Bernhard
authors.initials: B
authors.lastname: Gasselhuber
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
authors.forename: Andrea
authors.initials: A
authors.lastname: Nicolussi
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
authors.forename: Monika
authors.initials: M
authors.lastname: Soudi
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
authors.forename: Katharina F
authors.initials: KF
authors.lastname: Pirker
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
authors.forename: Paul G
authors.initials: PG
authors.lastname: Furtmüller
authors.affiliation: Department of Chemistry, Division of Biochemistry, VIBT - Vienna Institute of BioTechnology, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
authors.forename: Christian
authors.initials: C
authors.lastname: Obinger
mesh_terms: D005075:Biological Evolution; D002374:Catalase / Q000378:metabolism; D006418:Heme; D008958:Models, Molecular; D010544:Peroxidases / Q000737:chemistry / Q000378:metabolism*; D011451:Prostaglandin-Endoperoxide Synthases / Q000378:metabolism; D011487:Protein Conformation
chemical_list: D006418:Heme; D010544:Peroxidases; D002374:Catalase; D011451:Prostaglandin-Endoperoxide Synthases
keywords: Heme peroxidase; Peroxidase–catalase superfamily; Peroxidase–chlorite dismutase superfamily; Peroxidase–cyclooxygenase superfamily; Peroxidase–peroxygenase superfamily