Diamidophosphate Explained
Diamidophosphate (DAP) is the simplest phosphorodiamidate ion, with formula PO2(NH2)2−. It is a phosphorylating ion and was first used for the phosphorylation of sugars in aqueous medium.[1] DAP has attracted interest in the area of primordial chemistry.[2]
Salts
Several salts of the formula MPO2(NH2)2(H2O)x are known.
- The sodium salt can be made by base hydrolysis of phenyl phosphorodiamidate. It crystallises as a hexahydrate. It can be dehydrated.
- The silver salt AgPO2(NH2)2 can react using double decomposition with bromides forming other salts.
- The potassium dithiophosphate salt KPO2(NH2)2 is also known.
- Phosphorodiamidic acid crystallizes as a trihydrate.[3]
Reactions
Heating anhydrous sodium diamidophosphate causes polymerization:[4]
- At 160 °C, Na2P2O4(NH)(NH2)2, Na3P3O6(NH)2(NH2)2, Na4P4O8(NH)3(NH2)2, Na5P5O10(NH)4(NH2)2 and Na6P6O12(NH)5(NH2)2 are produced. These substances contain P-N-P backbones. These can be separated by paper chromatography.
- At 200 °C the hexa-phosphate is produced.
- At 250 °C the typical chain length is 18.
Heating hydrated salts induces the loss of ammonia to form oligophosphates and polyphosphates.[4]
Diamidophosphate inhibits urease enzymes by blocking up the active site, binding to two nickel centers. Diamidophosphate mimics the urea hydrolysis intermediate.[5]
Diamidophosphate is tribasic, and the amine groups may also lose hydrogen to form more metallic salts. With silver, further reactions can yield explosive salts: tetrasilver orthodiamidophosphate (AgO)3P(NH2)NHAg, and pentasilver orthodiamidophosphate (AgO)3P(NHAg)2.[6]
Organic esters and amides
thumb|left|Phenyl phosphorodiamidate, an inhibitor of urease, is a controlled release fertilizer.[7] Numerous organic derivatives are known. One example is phenyl phosphorodiamidate.[8]
Reactions with nucleosides
DAP phosphorylates deoxynucleosides (the building blocks of DNA, and at the same time initiates polymerization to make DNA.[9] DAP facilitates the synthesis of larger RNA sequences (ribozymes) from smaller RNA strands.[10] Other nitrogenous derivatives of phosphorus derivatives have also been proposed in this context in a review article.[11]
See also
Other reading
- H. N. Stokes. On Diamidoorthophosphoric and Diamidotrihydroxyphosphoric Acids. American Chemical Journal. 1894. 16. 2. 123.
Notes and References
- Krishnamurthy . Ramanarayanan . Guntha . Sreenivasulu . Eschenmoser . Albert . 4 July 2000 . Regioselective α-Phosphorylation of Aldoses in Aqueous Solution . Angewandte Chemie International Edition . en . 39 . 13 . 2281–2285 . 10.1002/1521-3773(20000703)39:13<2281::AID-ANIE2281>3.0.CO;2-2 . 10941064 . 1521-3773.
- 10.1038/nchem.2878. Phosphorylation, oligomerization and self-assembly in water under potential prebiotic conditions. 2018. Gibard. Clémentine. Bhowmik. Subhendu. Karki. Megha. Kim. Eun-Kyong. Krishnamurthy. Ramanarayanan. Nature Chemistry. 10. 2. 212–217. 29359747. 6295206.
- Coggins. Adam J.. Powner. Matthew W.. Prebiotic synthesis of phosphoenol pyruvate by α-phosphorylation-controlled triose glycolysis Supplementary Information Compound 8. Nature Chemistry. 10 October 2016. 9. 4. 310–317. 10.1038/nchem.2624. 28338685. en. 1755-4349. 2017NatCh...9..310C. 205296677.
- Klement. R.. Biberacher. G.. Das thermische Verhalten von Natriumdiamidophosphat, Darstellung von kondensierten Imidophosphaten. Zeitschrift für Anorganische und Allgemeine Chemie. May 1956. 285. 1–2. 74–85. 10.1002/zaac.19562850109.
- Book: Deborah Zamble. Rowińska-Żyrek. Magdalena. Kozlowski. Henryk. The Biological Chemistry of Nickel. 2017. Royal Society of Chemistry. 9781788010580. 73–74, 83. en.
- Book: Bretherick. L.. Bretherick's Handbook of Reactive Chemical Hazards. 2016. Elsevier. 9781483162508. 19. en.
- 10.1016/j.agee.2016.08.019. Ammonia Volatilization from Synthetic Fertilizers and its Mitigation Strategies: A Global Synthesis. 2016. Pan. Baobao. Lam. Shu Kee. Mosier. Arvin. Luo. Yiqi. Chen. Deli. Agriculture, Ecosystems & Environment. 232. 283–289. 2016AgEE..232..283P .
- Book: Kiss. S.. Simihaian. M.. Improving Efficiency of Urea Fertilizers by Inhibition of Soil Urease Activity. 2013. Springer Science & Business Media. 9789401718431. 105–108. en.
- Krishnamurthy. Ramanarayanan. Jiménez. Eddy I.. Gibard. Clémentine. Prebiotic Phosphorylation and Concomitant Oligomerization of Deoxynucleosides to form DNA. Angewandte Chemie International Edition. 2020. 60. 19. 10775–10783. en. 10.1002/anie.202015910. 33325148. 229281953. 1521-3773.
- Song. Emilie Yeonwha. Jiménez. Eddy Ivanhoe. Lin. Huacan. Vay. Kristian Le. Krishnamurthy. Ramanarayanan. Mutschler. Hannes. Prebiotically Plausible RNA Activation Compatible with Ribozyme-Catalyzed Ligation. Angewandte Chemie International Edition. 2020. 60. 6. en. 2952–2957. 10.1002/anie.202010918. 33128282. 7898671. 1521-3773. free.
- Karki. Megha. Gibard. Clémentine. Bhowmik. Subhendu. Krishnamurthy. Ramanarayanan. 2017-07-29. Nitrogenous Derivatives of Phosphorus and the Origins of Life: Plausible Prebiotic Phosphorylating Agents in Water. Life. en. 7. 3. 32. 10.3390/life7030032. 28758921. 5617957. 2017Life....7...32K. free.