title: A cis-prenyltransferase from Methanosarcina acetivorans catalyzes both head-to-tail and nonhead-to-tail prenyl condensation.
abstract: Cis-prenyltransferase usually consecutively catalyzes the head-to-tail condensation reactions of isopentenyl diphosphate to allylic prenyl diphosphate in the production of (E,Z-mixed) polyprenyl diphosphate, which is the precursor of glycosyl carrier lipids. Some recently discovered homologs of the enzyme, however, catalyze the nonhead-to-tail condensation reactions between allylic prenyl diphosphates. In this study, we characterize a cis-prenyltransferase homolog from a methanogenic archaeon, Methanosarcina acetivorans, to obtain information on the biosynthesis of the glycosyl carrier lipids within it. This enzyme catalyzes both head-to-tail and nonhead-to-tail condensation reactions. The kinetic analysis shows that the main reaction of the enzyme is consecutive head-to-tail prenyl condensation reactions yielding polyprenyl diphosphates, while the chain lengths of the major products seem shorter than expected for the precursor of glycosyl carrier lipids. On the other hand, a subsidiary reaction of the enzyme, i.e., nonhead-to-tail condensation between dimethylallyl diphosphate and farnesyl diphosphate, gives a novel diterpenoid compound, geranyllavandulyl diphosphate.
authors.affiliation: Department of Applied Molecular Bioscience, Graduate School of Bioagricultural Sciences, Nagoya University, Aichi, Japan.
authors.forename: Takuya
authors.initials: T
authors.lastname: Ogawa
authors.affiliation: Department of Applied Molecular Bioscience, Graduate School of Bioagricultural Sciences, Nagoya University, Aichi, Japan.
authors.forename: Koh-Ichi
authors.initials: K
authors.lastname: Emi
authors.affiliation: Department of Applied Molecular Bioscience, Graduate School of Bioagricultural Sciences, Nagoya University, Aichi, Japan.
authors.forename: Kazushi
authors.initials: K
authors.lastname: Koga
authors.affiliation: Department of Applied Molecular Bioscience, Graduate School of Bioagricultural Sciences, Nagoya University, Aichi, Japan.
authors.forename: Tohru
authors.initials: T
authors.lastname: Yoshimura
authors.affiliation: Department of Applied Molecular Bioscience, Graduate School of Bioagricultural Sciences, Nagoya University, Aichi, Japan.
authors.forename: Hisashi
authors.initials: H
authors.lastname: Hemmi
mesh_terms: D002384:Catalysis; D003001:Cloning, Molecular; D007700:Kinetics; D008055:Lipids / Q000096:biosynthesis / Q000737:chemistry*; D017020:Methanosarcina / Q000201:enzymology*; D009387:Neoprene / Q000737:chemistry / Q000378:metabolism*; D013379:Substrate Specificity; D014166:Transferases / Q000737:chemistry* / Q000235:genetics / Q000378:metabolism
chemical_list: D008055:Lipids; C016077:prenyl; D009387:Neoprene; D014166:Transferases; C106821:cis-prenyl transferase
keywords: archaea; cis-prenyltransferase; diterpenoid; glycosyl carrier lipid; isoprenoid