title: Biosynthesis of Antroquinonol and 4-Acetylantroquinonol B via a Polyketide Pathway Using Orsellinic Acid as a Ring Precursor in Antrodia cinnamomea.
abstract: Antroquinonol (AQ) and 4-acetylantroquinonol B (4-AAQB), isolated from the mycelium of Antrodia cinnamomea, have a similar chemical backbone to coenzyme Q (CoQ). Based on the postulation that biosynthesis of both AQ and 4-AAQB in A. cinnamomea starts from the polyketide pathway, we cultivated this fungus in a culture medium containing [U-13C]oleic acid, and then we analyzed the crude extracts of the mycelium using UHPLC-MS. We found that AQ and 4-AAQB follow similar biosynthetic sequences as CoQ. Obvious [13C2] fragments on the ring backbone were detected in the mass spectrum for [13C2]AQ, [13C2]4-AAQB, and their [13C2] intermediates found in this study. The orsellinic acid, formed from acetyl-CoA and malonyl-CoA via the polyketide pathway, was found to be a novel benzoquinone ring precursor for AQ and 4-AAQB. The identification of endogenously synthesized farnesylated intermediates allows us to postulate the routes of AQ and 4-AAQB biosynthesis in A. cinnamomea.
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Kevin Chi-Chung
authors.initials: KC
authors.lastname: Chou
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Shang-Han
authors.initials: SH
authors.lastname: Yang
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Hsiang-Lin
authors.initials: HL
authors.lastname: Wu
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Pei-Yin
authors.initials: PY
authors.lastname: Lin
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Tsu-Liang
authors.initials: TL
authors.lastname: Chang
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Fuu
authors.initials: F
authors.lastname: Sheu
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Kai-Hsien
authors.initials: KH
authors.lastname: Chen
authors.affiliation: Department of Horticulture and Landscape Architecture, ‡Joint Center for Instruments and Researches, College of Bioresources and Agriculture, and §Institute of Food Science and Technology, National Taiwan University , Taipei, Taiwan 10617, ROC.
authors.forename: Been-Huang
authors.initials: BH
authors.lastname: Chiang
mesh_terms: D015107:4-Butyrolactone / Q000031:analogs & derivatives* / Q000096:biosynthesis / Q000737:chemistry; D055491:Antrodia / Q000737:chemistry / Q000378:metabolism*; D053898:Biosynthetic Pathways; D003512:Cyclohexanones / Q000737:chemistry; D005656:Fungal Proteins / Q000378:metabolism; D015394:Molecular Structure; D025282:Mycelium / Q000737:chemistry / Q000378:metabolism; D061065:Polyketides / Q000378:metabolism*; D012118:Resorcinols / Q000378:metabolism*; D014451:Ubiquinone / Q000031:analogs & derivatives* / Q000096:biosynthesis / Q000737:chemistry
chemical_list: D003512:Cyclohexanones; D005656:Fungal Proteins; D061065:Polyketides; D012118:Resorcinols; C501612:orsellinic acid; D014451:Ubiquinone; C555021:4-acetylantroquinonol B; C545357:antroquinonol; D015107:4-Butyrolactone
keywords: 4-acetylantroquinonol B; Antrodia cinnamomea; antroquinonol; orsellinic acid; polyketide pathway