polyphosphate

Image:Triphosphorsäure.svg|Structure of triphosphoric acid

Image:Polyphosphoric acid.svg|Polyphosphoric acid

Image:Trimetaphosphat.svg|Cyclic trimetaphosphate

Image:Adenosindiphosphat protoniert.svg|Adenosine diphosphate (ADP)

The structure of tripolyphosphoric acid illustrates the principles which define the structures of polyphosphates. It consists of three tetrahedral PO₄ units linked together by sharing oxygen centres. For the linear chains, the end phosphorus groups share one oxide and the others phosphorus centres share two oxide centres. The corresponding phosphates are related to the acids by loss of the acidic protons. In the case of the cyclic trimer each tetrahedron shares two vertices with adjacent tetrahedra.

Sharing of three corners is possible. This motif represents crosslinking of the linear polymer. Crosslinked polyphosphates adopt the sheet-structure Phyllosilicates, but such structures occur only under extreme conditions.

Polyphosphates arise by polymerization of phosphoric acid derivatives. The process begins with two phosphate units coming together in a condensation reaction.

:2 H(PO₄)²⁻ {{eqm}} (P₂O₇)⁴⁻ + H₂O

The condensation is shown as an equilibrium because the reverse reaction, hydrolysis, is also possible. The process may continue in steps; at each step another (PO₃)⁻ unit is added to the chain, as indicated by the part in brackets in the illustration of polyphosphoric acid. P₄O₁₀ can be seen as the end product of condensation reactions, where each tetrahedron shares three corners with the others. Conversely, a complex mix of polymers is produced when a small amount of water is added to phosphorus pentoxide.

Polyphosphates are weak bases. A lone pair of electrons on an oxygen atom can be donated to a hydrogen ion (proton) or a metal ion in a typical Lewis acid-Lewis base interaction. This has profound significance in biology. For instance, adenosine triphosphate is about 25% protonated in aqueous solution at pH 7.{{cite journal|author-link2=Athel Cornish-Bowden|vauthors=Storer A, Cornish-Bowden A | title = Concentration of MgATP2- and other ions in solution. Calculation of the true concentrations of species present in mixtures of associating ions | pmc=1164030 | journal = Biochem J | volume = 159 | issue = 1 | pages = 1–5 | year = 1976 | pmid = 11772 | doi=10.1042/bj1590001}}

:ATP⁴⁻ + H⁺ {{eqm}} ATPH³⁻, pK_a $\backslash approx$ 6.6

Further protonation occurs at lower pH values.

ATP forms chelate complexes with metal ions. The stability constant for the equilibrium

:ATP⁴⁻ + Mg²⁺ {{eqm}} MgATP²⁻, log β $\backslash approx$ 4

is particularly large.{{cite journal |vauthors=Wilson J, Chin A | title = Chelation of divalent cations by ATP, studied by titration calorimetry | journal = Anal Biochem | volume = 193 | issue = 1 | pages = 16–9 | year = 1991 | pmid = 1645933| doi=10.1016/0003-2697(91)90036-S}} The formation of the magnesium complex is a critical element in the process of ATP hydrolysis, as it weakens the link between the terminal phosphate group and the rest of the molecule.{{cite journal |vauthors=Garfinkel L, Altschuld R, Garfinkel D | title = Magnesium in cardiac energy metabolism | journal = J Mol Cell Cardiol | volume = 18 | issue = 10 | pages = 1003–13 | year = 1986 | pmid = 3537318 | doi = 10.1016/S0022-2828(86)80289-9 }}

The energy released in ATP hydrolysis,

:ATP⁴⁻ + H₂O → ADP³⁻ + P_i⁻

at ΔG $\backslash approx$ -36.8 kJ mol⁻¹ is large by biological standards. P_i stands for inorganic phosphate, which is protonated at biological pH. However, it is not large by inorganic standards. The term "high energy" refers to the fact that it is high relative to the amount of energy released in the organic chemical reactions that can occur in living systems.

High molecular weight polyphosphates are well known.{{Greenwood&Earnshaw2nd}} One derivative is the glassy (i.e., amorphous) Graham's salt. Crystalline high molecular weight polyphosphates include Kurrol’s salt and Maddrell’s salt (white powder practically insoluble in water). These species have the formula [NaPO₃]_n[NaPO₃(OH)]₂ where n can be as great as 2000. In terms of their structures, these polymers consist of PO₃⁻ "monomers", with the chains are terminated by protonated phosphates.Klaus Schrödter, Gerhard Bettermann, Thomas Staffel, Friedrich Wahl, Thomas Klein, Thomas Hofmann "Phosphoric Acid and Phosphates" in Ullmann’s Encyclopedia of Industrial Chemistry 2008, Wiley-VCH, Weinheim. {{doi|10.1002/14356007.a19_465.pub3}}

High-polymeric inorganic polyphosphates were found in living organisms by L. Liberman in 1890. These compounds are linear polymers containing a few to several hundred residues of orthophosphate linked by energy-rich phosphoanhydride bonds.

Previously, it was considered either as “molecular fossil” or as only a phosphorus and energy source providing the survival of microorganisms under extreme conditions. These compounds are now known to also have regulatory roles, and to occur in representatives of all kingdoms of living organisms, participating in metabolic correction and control on both genetic and enzymatic levels. Polyphosphate is directly involved in the switching-over of the genetic program characteristic of the exponential growth stage of bacteria to the program of cell survival under stationary conditions, "a life in the slow lane". They participate in many regulatory mechanisms occurring in bacteria:

• They participate in the induction of rpoS, an RNA-polymerase subunit which is responsible for the expression of a large group of genes involved in adjustments to the stationary growth phase and many stressful agents.
• They are important for cell motility, biofilms formation and virulence.{{clarify|date=July 2017}}
• Polyphosphates and exopolyphosphatases participate in the regulation of the levels of the stringent response factor, guanosine 5'-diphosphate 3'-diphosphate (ppGpp), a second messenger in bacterial cells.
• Polyphosphates participate in the formation of channels across the living cell membranes. The above channels formed by polyphosphate and poly-b-hydroxybutyrate with Ca²⁺ are involved in the transport processes in a variety of organisms.
• An important function of polyphosphate in microorganisms—prokaryotes and the lower eukaryotes—is to handle changing environmental conditions by providing phosphate and energy reserves. Polyphosphates are present in animal cells, and there are many data on its participation in the regulatory processes during development and cellular proliferation and differentiation—especially in bone tissues and brain.

In humans polyphosphates are shown to play a key role in blood coagulation. Produced and released by platelets{{cite journal |vauthors=Ruiz FA, Lea CR, Oldfield E, Docampo R | title = Human platelet dense granules contain polyphosphate and are similar to acidocalcisomes of bacteria and unicellular eukaryotes | journal = J Biol Chem | volume = 279 | issue = 43 | pages = 44250–7 |date=Oct 2004 | pmid = 15308650 | doi = 10.1074/jbc.M406261200 | doi-access = free }} they activate blood coagulation factor XII which is essential for blood clot formation. Factor XII, also called Hageman factor, initiates fibrin formation and the generation of a proinflammatory mediator, bradykinin, that contributes to leakage from the blood vessels and thrombosis.{{cite journal | vauthors=Müller F, Mutch NJ, Schenk WA, Smith SA, Esterl L, Spronk HM, Schmidbauer S, Gahl WA, Morrissey JH, Renné T | title = Platelet polyphosphates are proinflammatory and procoagulant mediators in vivo | journal = Cell | volume = 139 | issue = 6 | pages = 1143–56 |date=Dec 2009 | pmid = 20005807 | pmc = 2796262 | doi = 10.1016/j.cell.2009.11.001}}{{cite web |url=http://www.physorg.com/news179673245.html |title=Newly discovered mechanism by which blood clots form |work=physorg.com |date=December 10, 2009|access-date=13 December 2009}}

Bacterial-derived polyphosphates impair the host immune response during infection and targeting polyphosphates with recombinant exopolyphosphatase improves sepsis survival in mice.{{cite journal | vauthors = Roewe J, Stavrides G, Strueve M, Sharma A, Marini F, Mann A, Smith SA, Kaya Z, Strobl B, Mueller M, Reinhardt C, Morrissey JH, Bosmann M | title = Bacterial polyphosphates interfere with the innate host defense to infection | journal = Nature Communications | volume = 11 | issue = 1 | pages = 4035 | date = August 2020 | pmid = 32788578 | doi = 10.1038/s41467-020-17639-x | pmc = 7423913 | bibcode = 2020NatCo..11.4035R | doi-access = free }}

Inorganic polyphosphates play a crucial role in tolerance of yeast cells to toxic heavy metal cations.{{cite journal |vauthors=Andreeva N, Ryazanova L, Dmitriev V, Kulakovskaya T, Kulaev I | title = Adaptation of Saccharomyces cerevisiae to toxic manganese concentration triggers changes in inorganic polyphosphates.| journal = FEMS Yeast Res | volume = 13 | issue = 5 | pages = 463–470 |date=Aug 2013| pmid = 23663411| doi = 10.1111/1567-1364.12049| doi-access = free}}

Sodium polyphosphate (E452(i)), potassium polyphosphate (E452(ii)), sodium calcium polyphosphate (E452(iii)) and calcium polyphosphate (E452(iv)) are used as food additives (emulsifiers, humectants, sequestrants, stabilisers, and thickeners).{{cite web |url=https://world.openfoodfacts.org/additive/e452-polyphosphates |title=E452 Polyphosphates |author= |website=openfoodfacts.org |access-date=2022-03-18 }} They are not known to pose any potential health risk other than those generally attributed to other phosphate sources (including those naturally occurring in food). While concerns have been raised regarding detrimental effects on the bones and cardiovascular diseases, as well as hyperphosphatemia, these seem to be relevant only for exaggerated consumption of phosphate sources. In all, reasonable consumption (up to 40 mg phosphate per kg of body weight per day) seems to pose no health risk.[https://efsa.onlinelibrary.wiley.com/doi/10.2903/j.efsa.2019.5674 EFSA Panel on Food Additives and Flavourings (FAF), Younes, M., Aquilina, G., Castle, L., Engel, K. H., Fowler, P., ... & Mennes, W. (2019). Re‐evaluation of phosphoric acid–phosphates–di‐, tri‐and polyphosphates (E 338–341, E 343, E 450–452) as food additives and the safety of proposed extension of use. EFSA Journal, 17(6), e05674.]Ritz, E., Hahn, K., Ketteler, M., Kuhlmann, M. K., & Mann, J. (2012). Phosphate additives in food—a health risk. Deutsches Ärzteblatt International, 109(4), 49.

Polyphosphates are widely recognized today as effective fire retardants due to their ability to promote char formation and inhibit flame propagation. When exposed to heat, polyphosphates decompose to form phosphoric acid, which facilitates the creation of a protective char layer on the material’s surface. This barrier reduces heat transfer, limits oxygen access, and suppresses the release of flammable gases, making polyphosphates a key component in modern fire-retardant formulations across various industries, including both polymer composites and wood based products.{{cite journal | last=Martinka | first=Jozef | last2=Mantanis | first2=George I. | last3=Lykidis | first3=Charalampos | last4=Antov | first4=Petar | last5=Rantuch | first5=Peter | title=The effect of partial substitution of polyphosphates by aluminium hydroxide and borates on the technological and fire properties of medium density fibreboard | journal=Wood Material Science & Engineering | volume=17 | issue=6 | date=2022-11-02 | issn=1748-0272 | doi=10.1080/17480272.2021.1933175 | pages=720–726}}{{cite journal | last=Mantanis | first=George I. | last2=Martinka | first2=Jozef | last3=Lykidis | first3=Charalampos | last4=Ševčík | first4=Libor |title=Technological properties and fire performance of medium density fibreboard (MDF) treated with selected polyphosphate-based fire retardants | journal=Wood Material Science & Engineering | volume=15 | issue=5 | date=2020-09-02 | issn=1748-0272 | doi=10.1080/17480272.2019.1596159 | pages=303–311 | url=https://www.tandfonline.com/doi/full/10.1080/17480272.2019.1596159 | access-date=2025-05-25}}

• Phosphoric acids
• Sodium trimetaphosphate
• Sodium hexametaphosphate

{{Reflist}}

• {{cite journal |vauthors=Pavlov E, Grimbly C, Diao CT, French RJ |title=A high-conductance mode of a poly-3-hydroxybutyrate/calcium/polyphosphate channel isolated from competent Escherichia coli cells |journal=FEBS Lett. |volume=579 |issue=23 |pages=5187–92 |date=September 2005 |pmid=16150446 |doi=10.1016/j.febslet.2005.08.032 |s2cid=35616647 |doi-access=free |bibcode=2005FEBSL.579.5187P }}
• {{cite journal |doi=10.1016/S1389-1723(99)80189-3 |vauthors=Kulaev I, Vagabov V, Kulakovskaya T |title=New aspects of inorganic polyphosphate metabolism and function |journal=J. Biosci. Bioeng. |volume=88 |issue=2 |pages=111–29 |year=1999 |pmid=16232585 }}
• {{cite journal |vauthors=Kulaev I, Kulakovskaya T |title=Polyphosphate and phosphate pump |journal=Annu. Rev. Microbiol. |volume=54 |pages=709–34 |year=2000 |pmid=11018142 |doi=10.1146/annurev.micro.54.1.709 }}

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Category:Phosphates

Category:Polymers

Category:Food stabilizers

Category:E-number additives

Category:Concrete admixtures