Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, 77 Mass. Ave., Cambridge, MA 02139, USA.
Rufus Scientific, 37 The Moor, Melbourn, Royston, Herts SG8 6ED, UK.
Molecules. 2019 Feb 28;24(5):866. doi: 10.3390/molecules24050866.
Phosphorous-containing molecules are essential constituents of all living cells. While the phosphate functional group is very common in small molecule natural products, nucleic acids, and as chemical modification in protein and peptides, phosphorous can form P⁻N (phosphoramidate), P⁻S (phosphorothioate), and P⁻C (e.g., phosphonate and phosphinate) linkages. While rare, these moieties play critical roles in many processes and in all forms of life. In this review we thoroughly categorize P⁻N, P⁻S, and P⁻C natural organophosphorus compounds. Information on biological source, biological activity, and biosynthesis is included, if known. This review also summarizes the role of phosphorylation on unusual amino acids in proteins (- and -phosphorylation) and reviews the natural phosphorothioate (P⁻S) and phosphoramidate (P⁻N) modifications of DNA and nucleotides with an emphasis on their role in the metabolism of the cell. We challenge the commonly held notion that nonphosphate organophosphorus functional groups are an oddity of biochemistry, with no central role in the metabolism of the cell. We postulate that the extent of utilization of some phosphorus groups by life, especially those containing P⁻N bonds, is likely severely underestimated and has been largely overlooked, mainly due to the technological limitations in their detection and analysis.
含磷分子是所有活细胞的基本组成部分。虽然磷酸官能团在小分子天然产物、核酸以及蛋白质和肽的化学修饰中非常常见，但磷可以形成 P⁻N（膦酰胺）、P⁻S（硫代磷酸酯）和 P⁻C（例如，膦酸酯和膦酸酯）键。虽然这些基团很少见，但它们在许多过程和所有生命形式中都起着关键作用。在这篇综述中，我们彻底分类了 P⁻N、P⁻S 和 P⁻C 天然有机磷化合物。如果已知，还包括生物来源、生物活性和生物合成信息。本综述还总结了蛋白质中异常氨基酸的磷酸化作用（-和 -磷酸化），并综述了 DNA 和核苷酸中的天然硫代磷酸酯（P⁻S）和膦酰胺（P⁻N）修饰，重点介绍它们在细胞代谢中的作用。我们质疑这样一种普遍观点，即非磷酸有机磷官能团是生物化学中的一个奇特现象，在细胞代谢中没有核心作用。我们假设，生命对某些磷基团的利用程度，特别是那些含有 P⁻N 键的磷基团，很可能被严重低估，而且在很大程度上被忽视了，主要是由于在检测和分析这些磷基团方面存在技术限制。
