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{{Short description|Class of chemical compounds}} |
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{{Hatnote|"Diphosphate" redirects here. It can also refer to any salt containing two ] groups.}} |
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{{Chembox |
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{{Chembox |
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| verifiedrevid = 444075863 |
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| verifiedrevid = 444077628 |
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| ImageFile = Pyrophosphate_anion.png |
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| ImageFile = Pyrophosphate_anion.png |
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| ImageSize = 150px |
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| ImageFile1 = Pyrophosphate-3D-balls.png |
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| ImageFile1 = Pyrophosphate-3D-balls.png |
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| ImageSize1 = 150px |
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| ImageAlt1 = |
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| ImageCaption1 = {{legend|orange|], P}}{{legend|red|], O}} |
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| ImageAlt1 = |
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| ImageName1 = Pyrophosphate anion |
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| ImageName1 = Pyrophosphate anion |
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| IUPACName = |
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| IUPACName = Diphosphate |
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| SystematicName = Dipolyphosphate |
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| OtherNames = Diphosphate |
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| OtherNames = Pyrophosphate<br/>Phosphonatophosphate |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 14000-31-8 |
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| CASNo2_Ref = {{cascite|unknown|CAS}} |
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| CASNo2 = 13472-36-1 |
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| CASNo2_Comment = (tetrasodium decahydrate salt) |
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| CASNo3_Ref = {{cascite|unknown|CAS}} |
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| CASNo3 = 7758-16-9 |
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| CASNo3_Comment = (disodium salt) |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 18361 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 559142 |
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| ChemSpiderID = 559142 |
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| DrugBank_Ref = {{drugbankcite|correct|drugbank}} |
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| DrugBank = DB04160 |
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| KEGG = |
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| Gmelin = 26938 |
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| UNII = X3SSV2V6L3 |
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| InChI = 1/H4O7P2/c1-8(2,3)7-9(4,5)6/h(H2,1,2,3)(H2,4,5,6)/p-4 |
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| InChI = 1/H4O7P2/c1-8(2,3)7-9(4,5)6/h(H2,1,2,3)(H2,4,5,6)/p-4 |
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| InChIKey = XPPKVPWEQAFLFU-XBHQNQODAI |
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| InChIKey = XPPKVPWEQAFLFU-XBHQNQODAI |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = XPPKVPWEQAFLFU-UHFFFAOYSA-J |
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| StdInChIKey = XPPKVPWEQAFLFU-UHFFFAOYSA-J |
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| CASNo = |
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| PubChem = 644102 |
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| PubChem = 644102 |
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| DrugBank_Ref = {{drugbankcite|correct|drugbank}} |
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| DrugBank = DB04160 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 18361 |
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| SMILES = P(=O)()OP(=O)() |
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| SMILES = P(=O)()OP(=O)() |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = P<sub>2</sub>O<sub>7</sub><sup>4−</sup> |
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| Formula = {{chem2|P2O7(4-)}} |
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| P=2|O=7 |
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| MolarMass = |
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| ConjugateAcid = ] |
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| Appearance = |
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}} |
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| Density = |
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|Section3={{Chembox Hazards |
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| MeltingPt = |
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| BoilingPt = |
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| Solubility = }} |
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| Section3 = {{Chembox Hazards |
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| MainHazards = |
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| MainHazards = |
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| FlashPt = |
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| Autoignition = }} |
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}} |
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}} |
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}} |
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In ], '''pyrophosphates''' are ] ]s that contain two phosphorus atoms in a {{chem2|P\sO\sP}} linkage. A number of pyrophosphate salts exist, such as ] ({{chem2|Na2H2P2O7}}) and ] ({{chem2|Na4P2O7}}), among others. Often pyrophosphates are called '''diphosphates'''. The parent pyrophosphates are derived from partial or complete neutralization of ]. 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 {{chem2|P\sO\sP}} bond, and which mirrors the nomenclature for ]. Pyrophosphates are found in ] and other ] triphosphates, which are important in biochemistry. The term pyrophosphate is also the name of ]s formed by the condensation of a phosphorylated biological compound with ], as for ]. This bond is also referred to as a ] bond. |
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==Acidity== |
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In ], the ], the ]s, and the ]s of ] are called '''pyrophosphates'''. Any salt or ester containing two phosphate groups is called a '''diphosphate'''. As a ], diphosphates are known as '''E450'''. |
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Pyrophosphoric acid is a tetraprotic acid, with four distinct ]'s:<ref>{{cite journal |doi=10.1039/d1qi00209k|title=Induced fit activity-based sensing: A mechanistic study of pyrophosphate detection with a "flexible" Fe-salen complex |year=2021 |last1=Yadav |first1=Prerna |last2=Blacque |first2=Olivier |last3=Roodt |first3=Andreas |last4=Zelder |first4=Felix |journal=Inorganic Chemistry Frontiers |volume=8 |issue=19 |pages=4313–4323 |pmid=34603734 |pmc=8477187 }}</ref> |
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:{{chem2|H4P2O7 ⇌ − + H+}}, p''K''<sub>a1</sub> = 0.85 |
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:{{chem2|− ⇌ (2−) + H+}}, p''K''<sub>a2</sub> = 1.96 |
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:{{chem2|(2−) ⇌ (3−) + H+}}, p''K''<sub>a3</sub> = 6.60 |
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:{{chem2|(3−) ⇌ (4−) + H+}}, p''K''<sub>a4</sub> = 9.41 |
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The pKa's occur in two distinct ranges because deprotonations occur on separate phosphate groups. For comparison with the p''K''<sub>a</sub>'s for ] are 2.14, 7.20, and 12.37. |
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At physiological ]'s, pyrophosphate exists as a mixture of doubly and singly protonated forms. |
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== Chemistry == |
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Pyrophosphates were originally prepared by heating phosphates ('''pyro-''' from the Greek, meaning ''fire''). Pyrophosphates are good complexing agents and have many uses in industrial chemistry. Pyrophosphate is the first member of an entire series of ]s. |
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==Preparation== |
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The term pyrophosphate is also the name of esters formed by the ] of a phosphorylated biological compound with inorganic phosphate as for ]. This bond is also referred to as a ] bond. |
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Disodium pyrophosphate is prepared by thermal condensation of ] or by partial deprotonation of pyrophosphoric acid.<ref>{{cite book |doi=10.1002/9780470132340.ch24|chapter=Sodium Pyrophosphates (Sodium Diphosphates) |year=1950 |last1=Bell |first1=R. N.|title=Inorganic Syntheses |pages=98–101 |isbn=9780470132340|volume=3 }}</ref> |
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Pyrophosphates are generally white or colorless. The ] salts are water-soluble.<ref>C.Michael Hogan. 2011. </ref> 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 ]s.<ref>{{Greenwood&Earnshaw2nd}}</ref> |
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The synthesis of tetraethyl pyrophosphate was first described in 1854 by Philip de Clermount at a meeting of the French Academy of Sciences. |
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== In biochemistry == |
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== In biochemistry == |
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The anion {{chem2|P2O7(4−)}} is abbreviated '''PP<sub>i</sub>''', standing for '''''i'''norganic '''p'''yro'''p'''hosphate''. It is formed by the ] of ] into ] in ]. |
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{{main|Biochemistry}} |
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:ATP → AMP + PP<sub>i</sub> |
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Pyrophosphates are very important in biochemistry. The anion P<sub>2</sub>O<sub>7</sub><sup>4−</sup> is abbreviated '''PP<sub>i</sub>''' and is formed by the ] of ] into ] in ]. |
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:ATP → ] + PP<sub>i</sub> |
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For example, when a nucleotide is incorporated into a growing ] or ] strand by a ], pyrophosphate (PP<sub>i</sub>) is released. Pyrophosphorolysis is the reverse of the ] reaction in which pyrophosphate reacts with the 3'-nucleotidemonophosphate (] or ]), which is removed from the ] to release the corresponding triphosphate (dNTP from DNA, or NTP from RNA). |
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For example, when a nucleotide is incorporated into a growing ] or ] strand by a ], pyrophosphate (PP<sub>i</sub>) is released. Pyrophosphorolysis is the reverse of the ] reaction in which pyrophosphate reacts with the 3′-nucleosidemonophosphate (] or dNMP), which is removed from the ] to release the corresponding triphosphate (] from DNA, or ] from RNA). |
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The pyrophosphate anion has the structure P<sub>2</sub>O<sub>7</sub><sup>4−</sup>, and is an ] of ]. It is unstable in ] and ]s into inorganic phosphate: |
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The pyrophosphate anion has the structure {{chem2|P2O7(4−)}}, and is an ] of ]. It is unstable in ] and ]s into inorganic phosphate: |
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:{{chem2|P2O7(4−) + H2O → 2 HPO4(2−)}} |
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:P<sub>2</sub>O<sub>7</sub><sup>4−</sup> + H<sub>2</sub>O → 2 HPO<sub>4</sub><sup>2−</sup> |
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or in biologists' shorthand notation: |
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or in biologists' shorthand notation: |
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:PP<sub>i</sub> + H<sub>2</sub>O → 2 P<sub>i</sub> |
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:{{chem2|PP_{i} + H2O → 2 P_{i} + 2 H+}} |
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In the absence of enzymic catalysis, hydrolysis reactions of simple polyphosphates such as pyrophosphate, linear triphosphate, ], and ATP normally proceed extremely slowly in all but highly acidic media.<ref name=Huebner>{{ cite journal |author=Huebner PWA, Milburn RM |title=Hydrolysis of pyrophosphate to orthophosphate promoted by cobalt(III). Evidence for the role of polynuclear species |journal=Inorg Chem. |year=1980 |volume=19 |issue=5 |pages=1267–72 |month=May |pmid= |doi=10.1021/ic50207a032 }}</ref> |
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In the absence of enzymic catalysis, hydrolysis reactions of simple polyphosphates such as pyrophosphate, linear triphosphate, ], and ATP normally proceed extremely slowly in all but highly acidic media.<ref name="Wazer">{{ cite journal |vauthors=Van Wazer JR, Griffith EJ, McCullough JF |title=Structure and Properties of the Condensed Phosphates. VII. Hydrolytic Degradation of Pyro- and Tripolyphosphate |journal=J. Am. Chem. Soc. |date=Jan 1955 |volume=77 |issue=2 |pages=287–291 |doi=10.1021/ja01607a011}}</ref> |
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(The reverse of this reaction is a method of preparing pyrophosphates by heating phosphates.) |
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(The reverse of this reaction is a method of preparing pyrophosphates by heating phosphates.) |
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This hydrolysis to inorganic phosphate effectively renders the cleavage of ATP to AMP and PP<sub>i</sub> ], and biochemical reactions coupled to this hydrolysis are irreversible as well. |
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This hydrolysis to inorganic phosphate effectively renders the cleavage of ATP to AMP and PP<sub>i</sub> ], and biochemical reactions coupled to this hydrolysis are irreversible as well. |
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PP<sub>i</sub> occurs in ], ], and ] at levels sufficient to block ] and may be a natural inhibitor of ] formation in ] (ECF).<ref name=Ho>{{ cite journal |author=Ho AM, Johnson MD, Kingsley DM |title=Role of the mouse ank gene in control of tissue calcification and arthritis |journal=Science. |year=2000 |month=Jul |volume=289 |issue=5477 |pages=265–70 |pmid=10894769 |doi=10.1126/science.289.5477.265 }}</ref> Cells may channel intracellular PP<sub>i</sub> into ECF.<ref name=Rutsch>{{ cite journal |author=Rutsch F, Vaingankar S, Johnson K, Goldfine I, Maddux B, Schauerte P, Kalhoff H, Sano K, Boisvert WA, Superti-Furga A, Terkeltaub R |title=PC-1 nucleoside triphosphate pyrophosphohydrolase deficiency in idiopathic infantile arterial calcification |journal=Am J Pathol. |year=2001 |month=Feb |volume=158 |issue=2 |pages=543–54 |pmid=11159191 |pmc=1850320 |doi=10.1016/S0002-9440(10)63996-X}}</ref> ] is a nonenzymatic plasma-membrane PP<sub>i</sub> channel that supports extracellular PP<sub>i</sub> levels.<ref name=Rutsch/> Defective function of the membrane PP<sub>i</sub> channel ANK is associated with low extracellular PP<sub>i</sub> and elevated intracellular PP<sub>i</sub>.<ref name=Ho/> ] (ENPP) may function to raise extracellular PP<sub>i</sub>.<ref name=Rutsch/> |
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PP<sub>i</sub> occurs in ], ], and ] at levels sufficient to block ] and may be a natural inhibitor of ] formation in ] (ECF).<ref name=Ho>{{ cite journal |vauthors=Ho AM, Johnson MD, Kingsley DM |title=Role of the mouse ank gene in control of tissue calcification and arthritis |journal=Science |date=Jul 2000 |volume=289 |issue=5477 |pages=265–70 |pmid=10894769 |doi=10.1126/science.289.5477.265 |bibcode=2000Sci...289..265H}}</ref> Cells may channel intracellular PP<sub>i</sub> into ECF.<ref name=Rutsch>{{ cite journal |vauthors=Rutsch F, Vaingankar S, Johnson K, Goldfine I, Maddux B, Schauerte P, Kalhoff H, Sano K, Boisvert WA, Superti-Furga A, Terkeltaub R |title=PC-1 nucleoside triphosphate pyrophosphohydrolase deficiency in idiopathic infantile arterial calcification |journal=Am J Pathol |date=Feb 2001 |volume=158 |issue=2 |pages=543–54 |pmid=11159191 |pmc=1850320 |doi=10.1016/S0002-9440(10)63996-X}}</ref> ] is a nonenzymatic plasma-membrane PP<sub>i</sub> channel that supports extracellular PP<sub>i</sub> levels.<ref name=Rutsch/> Defective function of the membrane PP<sub>i</sub> channel ANK is associated with low extracellular PP<sub>i</sub> and elevated intracellular PP<sub>i</sub>.<ref name=Ho/> ] (ENPP) may function to raise extracellular PP<sub>i</sub>.<ref name=Rutsch/> |
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From the standpoint of ] accounting, the hydrolysis of ATP to AMP and PP<sub>i</sub> requires two high-energy phosphates, as to reconstitute AMP into ATP requires two ] reactions. |
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From the standpoint of ] accounting, the hydrolysis of ATP to AMP and PP<sub>i</sub> requires two high-energy phosphates, as to reconstitute AMP into ATP requires two ] reactions. |
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:AMP + ATP → 2 ] |
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:AMP + ATP → 2 ] |
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:2 ADP + 2 P<sub>i</sub> → 2 ATP |
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:2 ADP + 2 P<sub>i</sub> → 2 ATP |
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The plasma concentration of inorganic pyrophosphate has a reference range of 0.58–3.78 ] (95% prediction interval).<ref>{{cite journal |vauthors=Ryan LM, Kozin F, McCarty DJ |title=Quantification of human plasma inorganic pyrophosphate. I. Normal values in osteoarthritis and calcium pyrophosphate dihydrate crystal deposition disease |journal=Arthritis Rheum. |volume=22 |issue=8 |pages=886–91 |year=1979 |pmid=223577 |doi= 10.1002/art.1780220812 |doi-access=}}</ref> |
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===Terpenes=== |
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] converts to ], the precursor to tens of thousands of ]s and ].<ref>{{cite book|title=Terpenes: Flavors, Fragrances, Pharmaca, Pheromones|url=https://archive.org/details/terpenes00brei|url-access=limited|pages=–23|chapter=Hemi- and Monoterpenes|author=Eberhard Breitmaier|year= 2006|doi=10.1002/9783527609949.ch2|isbn=9783527609949}}</ref><ref name=KO>{{cite book |doi=10.1002/0471238961.2005181602120504.a01.pub2|chapter=Terpenoids |title=Kirk-Othmer Encyclopedia of Chemical Technology |year=2006 |last1=Sell |first1=Charles S. |isbn=0471238961 }}</ref> |
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] (IPP) and ] (DMAPP) condense to produce ], precursor to all terpenes and terpenoids.]] |
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==As a food additive==<!-- linked from redirect ] --> |
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Various diphosphates are used as ]s, ]s, ]s, ]s, ]s, and ]s in food processing.<ref>'']'' '''1A''', 2nd ed, 1995, pp. 71, 82, 91</ref> They are classified in the ] scheme under E450:<ref>D. J. Jukes, ''Food Legislation of the UK: A Concise Guide'', Elsevier, 2013, p. 60–61</ref> |
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*E450(a): ]; ''tri''sodium diphosphate; ] (TSPP); tetrapotassium diphosphate |
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*E450(b): ''penta''sodium and ''penta''potassium triphosphate |
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*E450(c): sodium and potassium polyphosphates |
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In particular, various formulations of diphosphates are used to stabilize ].<ref>Ricardo A. Molins, ''Phosphates in Food'', p. 115</ref> |
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== See also == |
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== See also == |
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==References== |
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==References== |
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{{reflist|2}} |
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{{Reflist}} |
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==Further reading== |
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==Further reading== |
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* {{ cite journal |author=Schröder HC, Kurz L, Muller WEG, Lorenz B |title=Polyphosphate in bone |journal=Biochemistry (Moscow). |month=Mar |year=2000 |volume=65 |issue=3 |pages=296–303 |url=http://protein.bio.msu.su/biokhimiya/contents/v65/pdf/bcm_0296.pdf }} |
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* {{cite journal |vauthors=Schröder HC, Kurz L, Muller WE, Lorenz B |title=Polyphosphate in bone |journal=Biochemistry (Moscow) |date=Mar 2000 |volume=65 |issue=3 |pages=296–303 |pmid=10739471 |url=http://protein.bio.msu.su/biokhimiya/contents/v65/pdf/bcm_0296.pdf |url-status=dead |archive-url=https://web.archive.org/web/20110825053648/http://protein.bio.msu.su/biokhimiya/contents/v65/pdf/bcm_0296.pdf |archive-date=2011-08-25}} |
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==External links== |
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==External links== |
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{{Wiktionary|diphosphate|pyrophosphate}} |
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{{Wiktionary|diphosphate|pyrophosphate}} |
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* {{MeshName|Pyrophosphates}} |
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*{{Commons category-inline|Pyrophosphates}} |
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*{{MeshName|Pyrophosphates}} |
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