She ridoc disco11/11/2022 ![]() ![]() ![]() This mechanism deviates from the standard ‘in‐line attack’ paradigm for enzymatic phosphoryl transfer that typically involves a phosphoryl‐enzyme intermediate, but definitive evidence is sparse. Mechanistic scrutiny of this unusual intramolecular O‐to‐C phosphoryl transfer began with the discovery of Ppm in 1988 and concluded in 2008 with computational evidence supporting a concerted phosphoryl transfer via a dissociative metaphosphatelike transition state. Biosynthesis almost universally originates from the enzyme phosphoenolpyruvate mutase (Ppm), EC 5.4.2.9, which catalyzes O‐P bond cleavage in phosphoenolpyruvate (PEP) and forms a high energy C‐P bond in phosphonopyruvate (PnPy). Phosphonates are produced across all domains of life and used widely in medicine and agriculture. Add to this the favorable 1H and 31P T1/T2 relaxation times and biocompatibility, pTMPC represents a conceptually new diagnostic, whose discovery opens up new possibilities in the field of 31P‐MR spectroscopy and imaging. In addition, pTMPC can serve as a sensitive 31P‐MR sensor of pathological conditions in vivo because it undergoes oxidation‐induced structural changes in the presence of reactive oxygen species. The developed probe (pTMPC) is a well‐defined water‐soluble macromolecule characterized by a high content of naturally rare phosphorothioate groups providing a high‐intensity 31P‐MR signal clearly distinguishable from biological background both in vitro and in vitro. Herein, we describe the synthesis and MR characterization of a pioneering metal‐free 31P‐MR probe based on phosphorus‐containing polymeric zwitterion. However, due to the low physiological level of phosphorus‐containing biomolecules, precise imaging requires the administration of an exogenous probe. 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.ģ1P‐magnetic resonance (MR) is an important diagnostic technique currently used for tissue metabolites assessing, but it also has great potential for visualizing the internal body structures. 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. This review also summarizes the role of phosphorylation on unusual amino acids in proteins (N- and S-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. Information on biological source, biological activity, and biosynthesis is included, if known. In this review we thoroughly categorize P–N, P–S, and P–C natural organophosphorus compounds. While rare, these moieties play critical roles in many processes and in all forms of life. 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. ![]() Phosphorous-containing molecules are essential constituents of all living cells. ![]()
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