Massé Guillaume, Belt Simon T, Rowland Steven J, Rohmer Michel
Petroleum and Environmental Geochemistry Group, School of Environmental Sciences, University of Plymouth, Drake Circus, Plymouth, Devon PL4 8AA, United Kingdom.
Proc Natl Acad Sci U S A. 2004 Mar 30;101(13):4413-8. doi: 10.1073/pnas.0400902101. Epub 2004 Mar 22.
Isoprenoid biosynthesis in the widespread diatomaceous algae, Rhizosolenia setigera (Brightwell) and Haslea ostrearia (Simonsen), results not only in the production of diterpenoids, triterpenoids, and sterols but, unusually for diatoms, also in the production of sesterterpenoids. By using 13C and 2H isotopic labeling techniques followed by NMR and mass spectrometry, specific inhibition of mevalonate (MVA) and methylerythritol (MEP) pathways, and comparison with the natural 13C/12C isotope ratios of the lipids, the different biosynthetic pathways of the sesterterpenes and other isoprenoids have now been determined. Surprisingly, whereas the sesterterpenes (Delta(7(20))-haslenes) in R. setigera were made by the MVA pathway, as were the related triterpenoid rhizenes and desmosterol, in H. ostrearia the structurally similar Delta(6(17))-haslenes and the major sterol, 24-ethylcholest-5-en-3beta-ol, were instead biosynthesized by the MEP route. Phytol was biosynthesized in both diatoms by the MEP route. Subfractionation of R. setigera cells revealed that although phytol was located in the chloroplasts, the haslenes, rhizenes, and sterols were present in the cytoplasm. The observations described here for R. setigera and H. ostrearia show that terpenoid biosynthesis in diatoms is species-dependent and cannot simply be grouped according to structural type. Triterpenes appear to be made by the MVA route as in higher plants, whereas sesterterpenes and sterols can be made by either the MVA or MEP routes. In neither organism were the isoprenoids biosynthesized by leucine metabolism. Sesterterpene and triterpene biosynthesis in diatoms has not been investigated previously.
在广泛分布的硅藻藻类,即布氏根管藻(Brightwell)和奥氏海链藻(Simonsen)中,类异戊二烯生物合成不仅产生二萜类、三萜类和甾醇,而且与硅藻的通常情况不同,还产生了倍半萜类。通过使用¹³C和²H同位素标记技术,随后进行核磁共振和质谱分析,对甲羟戊酸(MVA)和甲基赤藓糖醇(MEP)途径进行特异性抑制,并与脂质的天然¹³C/¹²C同位素比率进行比较,现已确定了倍半萜和其他类异戊二烯的不同生物合成途径。令人惊讶的是,虽然布氏根管藻中的倍半萜(Δ⁷(²⁰)-海链藻烯)是由MVA途径合成的,相关的三萜类根管藻烯和豆甾醇也是如此,但在奥氏海链藻中,结构相似的Δ⁶(¹⁷)-海链藻烯和主要甾醇24-乙基胆甾-5-烯-3β-醇却是通过MEP途径生物合成的。叶绿醇在这两种硅藻中均通过MEP途径生物合成。对布氏根管藻细胞进行亚分级分离发现,虽然叶绿醇位于叶绿体中,但海链藻烯、根管藻烯和甾醇存在于细胞质中。这里描述的布氏根管藻和奥氏海链藻的观察结果表明,硅藻中的萜类生物合成具有物种依赖性,不能简单地根据结构类型进行归类。三萜类似乎像在高等植物中一样通过MVA途径合成,而倍半萜和甾醇可以通过MVA或MEP途径合成。在这两种生物中,类异戊二烯都不是通过亮氨酸代谢生物合成的。硅藻中倍半萜和三萜生物合成以前尚未被研究过。