1] Department of Chemistry and Lewis Sigler Institute for Integrative Genomics, Princeton University, Princeton, New Jersey 08540, USA [2].
1] Memorial Sloan Kettering Cancer Center, New York, New York 10065, USA [2].
Nature. 2014 Jun 12;510(7504):298-302. doi: 10.1038/nature13236. Epub 2014 May 4.
ATP is the dominant energy source in animals for mechanical and electrical work (for example, muscle contraction or neuronal firing). For chemical work, there is an equally important role for NADPH, which powers redox defence and reductive biosynthesis. The most direct route to produce NADPH from glucose is the oxidative pentose phosphate pathway, with malic enzyme sometimes also important. Although the relative contribution of glycolysis and oxidative phosphorylation to ATP production has been extensively analysed, similar analysis of NADPH metabolism has been lacking. Here we demonstrate the ability to directly track, by liquid chromatography-mass spectrometry, the passage of deuterium from labelled substrates into NADPH, and combine this approach with carbon labelling and mathematical modelling to measure NADPH fluxes. In proliferating cells, the largest contributor to cytosolic NADPH is the oxidative pentose phosphate pathway. Surprisingly, a nearly comparable contribution comes from serine-driven one-carbon metabolism, in which oxidation of methylene tetrahydrofolate to 10-formyl-tetrahydrofolate is coupled to reduction of NADP(+) to NADPH. Moreover, tracing of mitochondrial one-carbon metabolism revealed complete oxidation of 10-formyl-tetrahydrofolate to make NADPH. As folate metabolism has not previously been considered an NADPH producer, confirmation of its functional significance was undertaken through knockdown of methylenetetrahydrofolate dehydrogenase (MTHFD) genes. Depletion of either the cytosolic or mitochondrial MTHFD isozyme resulted in decreased cellular NADPH/NADP(+) and reduced/oxidized glutathione ratios (GSH/GSSG) and increased cell sensitivity to oxidative stress. Thus, although the importance of folate metabolism for proliferating cells has been long recognized and attributed to its function of producing one-carbon units for nucleic acid synthesis, another crucial function of this pathway is generating reducing power.
在动物中,ATP 是用于机械和电气工作(例如肌肉收缩或神经元放电)的主要能量来源。对于化学工作,NADPH 也起着同样重要的作用,它为氧化还原防御和还原生物合成提供动力。从葡萄糖产生 NADPH 的最直接途径是氧化戊糖磷酸途径,而苹果酸酶有时也很重要。虽然糖酵解和氧化磷酸化产生 ATP 的相对贡献已经得到了广泛的分析,但 NADPH 代谢的类似分析却一直缺乏。在这里,我们通过液相色谱-质谱法直接证明了追踪标记底物中的氘进入 NADPH 的能力,并将这种方法与碳标记和数学建模相结合,以测量 NADPH 通量。在增殖细胞中,细胞质 NADPH 的最大贡献者是氧化戊糖磷酸途径。令人惊讶的是,来自丝氨酸驱动的一碳代谢的贡献几乎与之相当,其中亚甲基四氢叶酸到 10-甲酰四氢叶酸的氧化与 NADP(+)还原为 NADPH 偶联。此外,追踪线粒体一碳代谢揭示了 10-甲酰四氢叶酸的完全氧化以产生 NADPH。由于叶酸代谢以前没有被认为是 NADPH 的产生者,因此通过敲低亚甲基四氢叶酸脱氢酶(MTHFD)基因来确认其功能意义。胞质或线粒体 MTHFD 同工酶的耗竭导致细胞 NADPH/NADP(+)和还原/氧化型谷胱甘肽比(GSH/GSSG)降低以及细胞对氧化应激的敏感性增加。因此,尽管叶酸代谢对增殖细胞的重要性早已得到认可,并归因于其为核酸合成产生一碳单位的功能,但该途径的另一个关键功能是产生还原能力。
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