Chou Kevin Chi-Chung, Yang Shang-Han, Wu Hsiang-Lin, Lin Pei-Yin, Chang Tsu-Liang, Sheu Fuu, Chen Kai-Hsien, Chiang Been-Huang
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.
J Agric Food Chem. 2017 Jan 11;65(1):74-86. doi: 10.1021/acs.jafc.6b04346. Epub 2016 Dec 21.
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-C]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 [C] fragments on the ring backbone were detected in the mass spectrum for [C]AQ, [C]4-AAQB, and their [C] 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.
从樟芝菌丝体中分离得到的安曲quinonol（AQ）和4-乙酰安曲quinonol B（4-AAQB），其化学骨架与辅酶Q（CoQ）相似。基于樟芝中AQ和4-AAQB的生物合成均起始于聚酮途径的假设，我们在含有[U-C]油酸的培养基中培养这种真菌，然后使用超高效液相色谱-质谱联用仪分析菌丝体的粗提物。我们发现AQ和4-AAQB的生物合成序列与CoQ相似。在本研究中发现的[C]AQ、[C]4-AAQB及其[C]中间体的质谱图中，在环骨架上检测到明显的[C]片段。通过聚酮途径由乙酰辅酶A和丙二酰辅酶A形成的苔色酸，被发现是AQ和4-AAQB的一种新型苯醌环前体。内源性合成的法尼基化中间体的鉴定使我们能够推测樟芝中AQ和4-AAQB的生物合成途径。
