Pyrophosphate

Pyrophosphate
Other names Diphosphate
Identifiers
PubChem	644102
ChemSpider	559142 Y
DrugBank	DB04160
ChEBI	CHEBI:18361 Y
Jmol-3D images	Image 1
SMILES [O-]P(=O)([O-])OP(=O)([O-])[O-]
InChI InChI=1S/H4O7P2/c1-8(2,3)7-9(4,5)6/h(H2,1,2,3)(H2,4,5,6)/p-4 Y Key: XPPKVPWEQAFLFU-UHFFFAOYSA-J Y 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
Properties
Molecular formula	P2O74−
Y (verify) (what is: Y/N?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

In chemistry, the anion, the salts, and the esters of pyrophosphoric acid are called pyrophosphates. Any salt or ester containing two phosphate groups is called a diphosphate. As a food additive, diphosphates are known as E450.

Chemistry

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 polyphosphates.

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.

The synthesis of tetraethyl pyrophosphate was first described in 1854 by Philip de Clermount at a meeting of the French Academy of Sciences.

In biochemistry

Main article: Biochemistry

Pyrophosphates are very important in biochemistry. The anion P₂O₇⁴⁻ is abbreviated PP_i and is formed by the hydrolysis of ATP into AMP in cells.

ATP → AMP + PP_i

For example, when a nucleotide is incorporated into a growing DNA or RNA strand by a polymerase, pyrophosphate (PP_i) is released. Pyrophosphorolysis is the reverse of the polymerization reaction in which pyrophosphate reacts with the 3'-nucleotidemonophosphate (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 P₂O₇⁴⁻, and is an acid anhydride of phosphate. It is unstable in aqueous solution and hydrolyzes into inorganic phosphate:

P₂O₇⁴⁻ + H₂O → 2 HPO₄²⁻

or in biologists' shorthand notation:

PP_i + H₂O → 2 P_i

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.^[1]

(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 PP_i irreversible, and biochemical reactions coupled to this hydrolysis are irreversible as well.

PP_i 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).^[2] Cells may channel intracellular PP_i into ECF.^[3] ANK is a nonenzymatic plasma-membrane PP_i channel that supports extracellular PP_i levels.^[3] Defective function of the membrane PP_i channel ANK is associated with low extracellular PP_i and elevated intracellular PP_i.^[2] Ectonucleotide pyrophosphatase/phosphodiesterase (ENPP) may function to raise extracellular PP_i.^[3]

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

AMP + ATP → 2 ADP

2 ADP + 2 P_i → 2 ATP

See also

• Adenosine monophosphate
• Adenosine diphosphate
• Adenosine triphosphate
• ATPase
• ATP hydrolysis
• ATP synthase
• Biochemistry
• Bone
• Calcium pyrophosphate
• Calcium pyrophosphate dihydrate deposition disease
• Catalysis
• DNA
• High energy phosphate
• Inorganic pyrophosphatase
• List of biochemical phosphate reactions
• List of human ATPase genes
• Nucleoside triphosphate
• Nucleotide
• Organophosphate
• Oxidative phosphorylation
• Phosphate
• Phosphate homeostasis
• Phosphate reaction
• Phosphoric acid
• Phosphoric acids and phosphates
• Ribonucleoside monophosphate
• RNA
• Sodium pyrophosphate
• Structural phosphate
• Superphosphate
• Thiamine pyrophosphate
• Tooth
• Zinc pyrophosphate

References

1. ^ Huebner PWA, Milburn RM (May 1980). "Hydrolysis of pyrophosphate to orthophosphate promoted by cobalt(III). Evidence for the role of polynuclear species". Inorg Chem. 19 (5): 1267–72. doi:10.1021/ic50207a032. 
2. ^ ^{a b} 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. doi:10.1126/science.289.5477.265. PMID 10894769. 
3. ^ ^{a b c} 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. http://www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pmcentrez&artid=1850320. 

Further reading

• Schröder HC, Kurz L, Muller WEG, Lorenz B (Mar 2000). "Polyphosphate in bone". Biochemistry (Moscow). 65 (3): 296–303. http://protein.bio.msu.su/biokhimiya/contents/v65/pdf/bcm_0296.pdf. 

External links

• MeSH Pyrophosphates