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Discovery of Multiple Modified F430 Coenzymes in Methanogens and Anaerobic Methanotrophic Archaea Suggests Possible New Roles for F430 in Nature

机译:在产甲烷菌和厌氧甲烷营养古细菌中发现多种修饰的F430辅酶表明F430在自然界中可能具有新的作用

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Methane is a potent greenhouse gas that is generated and consumed in anaerobic environments through the energy metabolism of methanogens and anaerobic methanotrophic archaea (ANME), respectively. Coenzyme F_(430) is essential for methanogenesis, and a structural variant of F_(430), 17~(2)-methylthio-F_(430) (F_(430)-2), is found in ANME and is presumably essential for the anaerobic oxidation of methane. Here we use liquid chromatography–high-resolution mass spectrometry to identify several new structural variants of F_(430) in the cell extracts of selected methanogens and ANME. Methanocaldococcus jannaschii and Methanococcus maripaludis contain an F_(430) variant (denoted F_(430)-3) that has an M~(+) of 1,009.2781. This mass increase of 103.9913 over that of F_(430) corresponds to C_(3)H_(4)O_(2)S and is consistent with the addition of a 3-mercaptopropionate moiety bound as a thioether followed by a cyclization. The UV absorbance spectrum of F_(430)-3 was different from that of F_(430) and instead matched that of an F_(430) derivative where the 17~(3) keto moiety had been reduced. This is the first report of a modified F_(430) in methanogens. In a search for F_(430)-2 and F_(430)-3 in other methanogens and ANME, we have identified a total of nine modified F_(430) structures. One of these compounds may be an abiotic oxidative product of F_(430), but the others represent naturally modified versions of F_(430). This work indicates that F_(430)-related molecules have additional functions in nature and will inspire further research to determine the biochemical role(s) of these variants and the pathways involved in their biosynthesis.
机译:甲烷是一种有力的温室气体,它在厌氧环境中分别通过产甲烷菌和厌氧甲烷营养古生菌(ANME)的能量代谢而产生和消耗。辅酶F_(430)对于甲烷生成至关重要,F_(430)的结构变体17〜(2)-甲硫基-F_(430)(F_(430)-2)在ANME中发现,可能对甲烷的厌氧氧化。在这里,我们使用液相色谱-高分辨率质谱法在选定的产甲烷菌和ANME的细胞提取物中鉴定出F_(430)的几个新结构变体。詹氏甲烷球菌和马氏甲烷球菌含有一个F_(430)变体(表示为F_(430)-3),其M〜(+)为1,009.2781。与F_(430)相比,该质量增加103.9913对应于C_(3)H_(4)O_(2)S,并且与添加作为硫醚键合的3-巯基丙酸酯部分加成环后一致。 F_(430)-3的紫外吸收光谱不同于F_(430)的吸收光谱,而是与F_(430)衍生物的17〜(3)酮部分被还原的紫外吸收光谱匹配。这是产甲烷菌中修饰的F_(430)的首次报道。在寻找其他产甲烷菌和ANME中的F_(430)-2和F_(430)-3时,我们确定了总共9个修饰的F_(430)结构。这些化合物之一可能是F_(430)的非生物氧化产物,但其他化合物则代表F_(430)的天然修饰形式。这项工作表明,与F_(430)相关的分子在自然界中具有其他功能,并将激发进一步的研究以确定这些变异体的生化作用及其参与生物合成的途径。

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