Pyrophosphate

In chemistry, pyrophosphates are phosphorus oxyanions that contain two phosphorus atoms in a P–O–P linkage. A number of pyrophosphate salts exist, such as disodium pyrophosphate (Na2H2P2O7) and tetrasodium pyrophosphate (Na4P2O7), among others. Often pyrophosphates are called diphosphates. The parent pyrophosphates are derived from partial or complete neutralization of pyrophosphoric acid. The pyrophosphate bond is also sometimes referred to as a phosphoanhydride bond, a naming convention which emphasizes the loss of water that occurs when two phosphates form a new P–O–P bond, and which mirrors the nomenclature for anhydrides of carboxylic acids. Pyrophosphates are found in ATP and other nucleotide triphosphates, which are important in biochemistry. The term pyrophosphate is also the name of esters formed by the condensation of a phosphorylated biological compound with inorganic phosphate, as for dimethylallyl pyrophosphate. This bond is also referred to as a high-energy phosphate bond.

"Diphosphate" redirects here. It can also refer to any salt containing two phosphate groups.
Pyrophosphate
Pyrophosphate anion
Names
IUPAC name
Diphosphate
Systematic IUPAC name
Dipolyphosphate
Other names
Pyrophosphate
Phosphonatophosphate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
DrugBank
E number E450 (thickeners, ...)
26938
UNII
  • InChI=1S/H4O7P2/c1-8(2,3)7-9(4,5)6/h(H2,1,2,3)(H2,4,5,6)/p-4 checkY
    Key: XPPKVPWEQAFLFU-UHFFFAOYSA-J checkY
  • InChI=1/H4O7P2/c1-8(2,3)7-9(4,5)6/h(H2,1,2,3)(H2,4,5,6)/p-4
    Key: XPPKVPWEQAFLFU-XBHQNQODAI
  • [O-]P(=O)([O-])OP(=O)([O-])[O-]
Properties
P2O4−7
Molar mass 173.943 g·mol−1
Conjugate acid Pyrophosphoric acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Infobox references

Acidity

Pyrophosphoric acid is a tetraprotic acid, with four distinct pKa's:[1]

H4P2O7 ⇌ [H3P2O7]− + H+, pKa = 0.85
[H3P2O7]− ⇌ [H2P2O7]2− + H+, pKa = 1.96
[H2P2O7]2− ⇌ [HP2O7]3− + H+, pKa = 6.60
[HP2O7]3− ⇌ [P2O7]4− + H+, pKa = 9.41

The pKa's occur in two distinct ranges because deprotonations occur on separate phosphate groups. For comparison with the pKa's for phosphoric acid are 2.14, 7.20, and 12.37.

At physiological pH's, pyrophosphate exists as a mixture of doubly and singly protonated forms.

Preparation

Disodium pyrophosphate is prepared by thermal condensation of sodium dihydrogen phosphate or by partial deprotonation of pyrophosphoric acid.[2]

Pyrophosphates are generally white or colorless. The alkali metal salts are water-soluble.[3] They are good complexing agents for metal ions (such as calcium and many transition metals) and have many uses in industrial chemistry. Pyrophosphate is the first member of an entire series of polyphosphates.[4]

In biochemistry

The anion P
2O4−
7 is abbreviated PPi, standing for inorganic pyrophosphate. It is formed by the hydrolysis of ATP into AMP in cells.

ATP → AMP + PPi

For example, when a nucleotide is incorporated into a growing DNA or RNA strand by a polymerase, pyrophosphate (PPi) is released. Pyrophosphorolysis is the reverse of the polymerization reaction in which pyrophosphate reacts with the 3′-nucleosidemonophosphate (NMP or dNMP), which is removed from the oligonucleotide to release the corresponding triphosphate (dNTP from DNA, or NTP from RNA).

The pyrophosphate anion has the structure P
2O4−
7, and is an acid anhydride of phosphate. It is unstable in aqueous solution and hydrolyzes into inorganic phosphate:

P
2O4−
7 + H2O → 2 HPO2−
4

or in biologists' shorthand notation:

PPi + H2O → 2 Pi + 2 H+

In the absence of enzymic catalysis, hydrolysis reactions of simple polyphosphates such as pyrophosphate, linear triphosphate, ADP, and ATP normally proceed extremely slowly in all but highly acidic media.[5]

(The reverse of this reaction is a method of preparing pyrophosphates by heating phosphates.)

This hydrolysis to inorganic phosphate effectively renders the cleavage of ATP to AMP and PPi irreversible, and biochemical reactions coupled to this hydrolysis are irreversible as well.

PPi occurs in synovial fluid, blood plasma, and urine at levels sufficient to block calcification and may be a natural inhibitor of hydroxyapatite formation in extracellular fluid (ECF).[6] Cells may channel intracellular PPi into ECF.[7] ANK is a nonenzymatic plasma-membrane PPi channel that supports extracellular PPi levels.[7] Defective function of the membrane PPi channel ANK is associated with low extracellular PPi and elevated intracellular PPi.[6] Ectonucleotide pyrophosphatase/phosphodiesterase (ENPP) may function to raise extracellular PPi.[7]

From the standpoint of high energy phosphate accounting, the hydrolysis of ATP to AMP and PPi requires two high-energy phosphates, as to reconstitute AMP into ATP requires two phosphorylation reactions.

AMP + ATP → 2 ADP
2 ADP + 2 Pi → 2 ATP

The plasma concentration of inorganic pyrophosphate has a reference range of 0.58–3.78 µM (95% prediction interval).[8]

Terpenes

Isopentenyl pyrophosphate converts to geranyl pyrophosphate, the precursor to tens of thousands of terpeness and terpenoids.[9]

Isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP) condense to produce geranyl pyrophosphate, precursor to all terpenes and terpenoids.

As a food additive

Various diphosphates are used as emulsifiers, stabilisers, acidity regulators, raising agents, sequestrants, and water retention agents in food processing.[10] They are classified in the E number scheme under E450:[11]

E450(a): disodium dihydrogen diphosphate; trisodium diphosphate; tetrasodium diphosphate (TSPP); tetrapotassium diphosphate
E450(b): pentasodium and pentapotassium triphosphate
E450(c): sodium and potassium polyphosphates

In particular, various formulations of diphosphates are used to stabilize whipped cream.[12]

See also

References
  1. Yadav, Prerna; Blacque, Olivier; Roodt, Andreas; Zelder, Felix (2021). "Induced fit activity-based sensing: A mechanistic study of pyrophosphate detection with a "flexible" Fe-salen complex". Inorganic Chemistry Frontiers. 8 (19): 4313–4323. doi:10.1039/d1qi00209k. PMC 8477187. PMID 34603734.
  2. Bell, R. N. (1950). "Sodium Pyrophosphates (Sodium Diphosphates)". Inorganic Syntheses. Inorganic Syntheses. Vol. 3. pp. 98–101. doi:10.1002/9780470132340.ch24. ISBN 9780470132340.
  3. C.Michael Hogan. 2011. Phosphate. Encyclopedia of Earth. Topic ed. Andy Jorgensen. Ed.-in-Chief C.J.Cleveland. National Council for Science and the Environment. Washington DC
  4. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  5. Van Wazer JR, Griffith EJ, McCullough JF (Jan 1955). "Structure and Properties of the Condensed Phosphates. VII. Hydrolytic Degradation of Pyro- and Tripolyphosphate". J. Am. Chem. Soc. 77 (2): 287–291. doi:10.1021/ja01607a011.
  6. Ho AM, Johnson MD, Kingsley DM (Jul 2000). "Role of the mouse ank gene in control of tissue calcification and arthritis". Science. 289 (5477): 265–70. Bibcode:2000Sci...289..265H. doi:10.1126/science.289.5477.265. PMID 10894769.
  7. Rutsch F, Vaingankar S, Johnson K, Goldfine I, Maddux B, Schauerte P, Kalhoff H, Sano K, Boisvert WA, Superti-Furga A, Terkeltaub R (Feb 2001). "PC-1 nucleoside triphosphate pyrophosphohydrolase deficiency in idiopathic infantile arterial calcification". Am J Pathol. 158 (2): 543–54. doi:10.1016/S0002-9440(10)63996-X. PMC 1850320. PMID 11159191.
  8. Ryan LM, Kozin F, McCarty DJ (1979). "Quantification of human plasma inorganic pyrophosphate. I. Normal values in osteoarthritis and calcium pyrophosphate dihydrate crystal deposition disease". Arthritis Rheum. 22 (8): 886–91. doi:10.1002/art.1780220812. PMID 223577.
  9. Eberhard Breitmaier (2006). "Hemi‐ and Monoterpenes". Terpenes: Flavors, Fragrances, Pharmaca, Pheromones. pp. 10–23. doi:10.1002/9783527609949.ch2. ISBN 9783527609949.
  10. Codex Alimentarius 1A, 2nd ed, 1995, pp. 71, 82, 91
  11. D. J. Jukes, Food Legislation of the UK: A Concise Guide, Elsevier, 2013, p. 60–61
  12. Ricardo A. Molins, Phosphates in Food, p. 115

Further reading
Look up diphosphate or pyrophosphate in Wiktionary, the free dictionary.
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