Pyrophosphate

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Ball-and-stick model of the pyrophosphate anion, P2O74−
Ball-and-stick model of the pyrophosphate anion, P2O74−

In chemistry, the anion, the salts, and the esters of pyrophosphoric acid are called pyrophosphates. The anion P2O74− is abbreviated PPi and 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 where 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 rapidly hydrolyzes into inorganic phosphate:

  • P2O74− + H2O → 2 HPO42−

or in shorthand notation:

  • PPi + H2O → 2 Pi

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.

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

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

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

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.

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