Haloperoxidase
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Haloperoxidases are
peroxidases Peroxidases or peroxide reductases ( EC numberbr>1.11.1.x are a large group of enzymes which play a role in various biological processes. They are named after the fact that they commonly break up peroxides. Functionality Peroxidases typically ca ...
that are able to mediate the
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...
of
halides In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fluor ...
by
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3% ...
. Both halides and hydrogen peroxide are widely available in the environment. The
Nernst equation In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction ( half-cell or full cell reaction) from the standard electrode potential, absolute tempe ...
shows that hydrogen peroxide can oxidize
chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride sa ...
(E°= 1.36 V),
bromide A bromide ion is the negatively charged form (Br−) of the element bromine, a member of the halogens group on the periodic table. Most bromides are colorless. Bromides have many practical roles, being found in anticonvulsants, flame-retardant ...
(E°= 1.09 V) and
iodide An iodide ion is the ion I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine de ...
(E°= 0.536 V) from a
thermodynamic Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of the ...
perspective under natural conditions, i.e., a temperature range of about 0–30 °C and a pH ranging from about 3 (
humic Humic substances (HS) are organic compounds that are important components of humus, the major organic fraction of soil, peat, and coal (and also a constituent of many upland streams, dystrophic lakes, and ocean water). For a long era in the 19th an ...
soil layer) to about 8 ( sea water). Fluoride (E°= 2.87 V) cannot be oxidized by hydrogen peroxide.


Classification

The table shows the classification of haloperoxidases according to the halides whose oxidation they are able to catalyze. The classification of these enzymes by substrate-usability does not necessarily indicate enzyme substrate ''preference.'' For example, although
eosinophil peroxidase Eosinophil peroxidase is an enzyme found within the eosinophil granulocytes, innate immune cells of humans and mammals. This oxidoreductase protein is encoded by the gene ''EPX'', expressed within these myeloid cells. EPO shares many similarities ...
is ''able'' to oxidize chloride, it preferentially oxidizes bromide. The mammalian haloperoxidases
myeloperoxidase Myeloperoxidase (MPO) is a peroxidase enzyme that in humans is encoded by the ''MPO'' gene on chromosome 17. MPO is most abundantly expressed in neutrophil granulocytes (a subtype of white blood cells), and produces hypohalous acids to carry ...
(MPO), lactoperoxidase (LPO) and
eosinophil peroxidase Eosinophil peroxidase is an enzyme found within the eosinophil granulocytes, innate immune cells of humans and mammals. This oxidoreductase protein is encoded by the gene ''EPX'', expressed within these myeloid cells. EPO shares many similarities ...
(EPO) are also capable of oxidizing the
pseudohalide Pseudohalogens are polyatomic analogues of halogens, whose chemistry, resembling that of the true halogens, allows them to substitute for halogens in several classes of chemical compounds. Pseudohalogens occur in pseudohalogen molecules, inorganic ...
thiocyanate Thiocyanate (also known as rhodanide) is the anion . It is the conjugate base of thiocyanic acid. Common derivatives include the colourless salts potassium thiocyanate and sodium thiocyanate. Mercury(II) thiocyanate was formerly used in pyr ...
(SCN). They each contain a
heme Heme, or haem (pronounced / hi:m/ ), is a precursor to hemoglobin, which is necessary to bind oxygen in the bloodstream. Heme is biosynthesized in both the bone marrow and the liver. In biochemical terms, heme is a coordination complex "consis ...
prosthetic group covalently bound by two ester linkages to aspartate and/or glutamate side-chains. MPO has a third covalent link through a methionine residue. Horseradish peroxidase is also capable of oxidizing these substrates, but its heme is not covalently bound and becomes damaged during turnover. A specific vanadium bromoperoxidase in marine organisms (fungi, bacteria, microalgae, perhaps other eukaryotes) uses
vanadate In chemistry, a vanadate is an anionic coordination complex of vanadium. Often vanadate refers to oxoanions of vanadium, most of which exist in its highest oxidation state of +5. The complexes and are referred to as hexacyanovanadate(III) and no ...
and hydrogen peroxide to brominate electrophilic organics.
Murex ''Murex'' is a genus of medium to large sized predatory tropical sea snails. These are carnivorous marine gastropod molluscs in the family Muricidae, commonly called "murexes" or "rock snails".Houart, R.; Gofas, S. (2010). Murex Linnaeus, 175 ...
snails have a
bromoperoxidase Bromide peroxidase (, ''bromoperoxidase'', ''haloperoxidase (ambiguous)'', ''eosinophil peroxidase'') is a family of enzymes with systematic name ''bromide:hydrogen-peroxide oxidoreductase''. These enzymes catalyses the following chemical reacti ...
used to produce
Tyrian purple Tyrian purple ( grc, πορφύρα ''porphúra''; la, purpura), also known as Phoenician red, Phoenician purple, royal purple, imperial purple, or imperial dye, is a reddish-purple natural dye. The name Tyrian refers to Tyre, Lebanon. It i ...
dye. The enzyme is very specific to bromide and physically stable, but has not been characterized as to its active site.


See also

* Vanadium bromoperoxidase


References

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