Arsenite Oxidase, Small Subunit
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In chemistry, an arsenite is a chemical compound containing an
arsenic Arsenic is a chemical element; it has Symbol (chemistry), symbol As and atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is not ...
oxyanion An oxyanion, or oxoanion, is an ion with the generic formula (where A represents a chemical element and O represents an oxygen atom). Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determine ...
where arsenic has oxidation state +3. Note that in fields that commonly deal with groundwater chemistry, arsenite is used generically to identify soluble AsIII anions. IUPAC have recommended that arsenite compounds are to be named as arsenate(III), for example ortho-arsenite is called trioxidoarsenate(III). Ortho-arsenite contrasts to the corresponding anions of the lighter members of group 15,
phosphite The general structure of a phosphite ester showing the lone pairs on the P In organic chemistry, a phosphite ester or organophosphite usually refers to an organophosphorous compound with the formula P(OR)3. They can be considered as esters of ...
which has the structure and
nitrite The nitrite polyatomic ion, ion has the chemical formula . Nitrite (mostly sodium nitrite) is widely used throughout chemical and pharmaceutical industries. The nitrite anion is a pervasive intermediate in the nitrogen cycle in nature. The name ...
, which is bent. A number of different arsenite anions are known: * ortho-arsenite, an ion of
arsenous acid Arsenous acid (or arsorous acid) is the inorganic compound with the formula H3AsO3. It is known to occur in aqueous solutions, but it has not been isolated as a pure material, although this fact does not detract from the significance of As(OH)3. ...
, with a pyramidal shape * meta-arsenite, a polymeric chain anion. * pyro-arsenite, * ''catena''-triarsenite, * ''catena''-tetraarsenite, * ''cyclo''-tetraarsenite *, a polymeric anion In all of these the geometry around the AsIII centers are approximately trigonal, the lone pair on the arsenic atom is stereochemically active. Well known examples of arsenites include sodium meta-arsenite which contains a polymeric linear anion, , and silver ortho-arsenite, , which contains the trigonal anion.


Preparation of arsenites

Some arsenite salts can be prepared from an aqueous solution of . Examples of these are the meta-arsenite salts and at low temperature, hydrogen arsenite salts can be prepared, such as , , and .


Arsenite minerals

A number of minerals contain arsenite anions:
reinerite Reinerite is a rare arsenite (arsenate(III)) mineral with chemical formula Zn3(AsO3)2. It crystallizes in the orthorhombic crystal system. Physical properties Reinerite is most commonly found as a sky blue colored mineral, however, it may also b ...
, ; finnemanite, ; paulmooreite, ; stenhuggarite, (contains a complex polymeric anion); schneiderhöhnite, FeFe; magnussonite, ; trippkeite, ; trigonite, ; tooeleite, .


Arsenites in the environment

Arsenic can enter
groundwater Groundwater is the water present beneath Earth's surface in rock and Pore space in soil, soil pore spaces and in the fractures of stratum, rock formations. About 30 percent of all readily available fresh water in the world is groundwater. A unit ...
due to naturally occurring arsenic at deeper levels or from mine workings. Arsenic(III) can be removed from water by a number of methods, oxidation of AsIII to AsV for example with chlorine followed by coagulation with for example iron(III) sulfate. Other methods include ion-exchange and filtration. Filtration is only effective if arsenic is present as particulates, if the arsenite is in solution it passes through the filtration membrane.


Uses

Sodium arsenite is used in the
water gas shift reaction Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known living organisms ( ...
to remove carbon dioxide. Fowler's solution first introduced in the 18th century was made up from as a solution of potassium meta-arsenite, . Arsenic in its trioxide, As2O3, (brand name Trisenox, ATO) is used as a chemotherapy drug against acute promyelocytic leukaemia (APL), a type of myeloid leukemia. The detailed mechanism of action is unknown, but it is suspected to speed up apoptosis of cancer cells. Arsenic trioxide triggers morphological changes and DNA fragmentations in NB4 ''in vitro'' model for APL. It also degrades retinoic acid receptor alpha (RARA). RARA gene is important regulator of premyelocytic immune cell development, differentiation, and apoptosis.


Bacteria using and generating arsenite

Some species of
bacteria Bacteria (; : bacterium) are ubiquitous, mostly free-living organisms often consisting of one Cell (biology), biological cell. They constitute a large domain (biology), domain of Prokaryote, prokaryotic microorganisms. Typically a few micr ...
obtain their energy by
oxidizing Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
various fuels while reducing
arsenate The arsenate is an ion with the chemical formula . Bonding in arsenate consists of a central arsenic atom, with oxidation state +5, double bonded to one oxygen atom and single bonded to a further three oxygen atoms. The four oxygen atoms orien ...
s to form arsenites. The
enzyme An enzyme () is a protein that acts as a biological catalyst by accelerating chemical reactions. The molecules upon which enzymes may act are called substrate (chemistry), substrates, and the enzyme converts the substrates into different mol ...
s involved are known as
arsenate reductase The arsenate is an ion with the chemical formula . Bonding in arsenate consists of a central arsenic atom, with oxidation state +5, double bonded to one oxygen atom and single bonded to a further three oxygen atoms. The four oxygen atoms orien ...
s. In 2008, bacteria were discovered that employ a version of
photosynthesis Photosynthesis ( ) is a system of biological processes by which photosynthetic organisms, such as most plants, algae, and cyanobacteria, convert light energy, typically from sunlight, into the chemical energy necessary to fuel their metabo ...
with arsenites as
electron donor In chemistry, an electron donor is a chemical entity that transfers electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process. An obsolete definition equated an electron dono ...
s, producing arsenates (just like ordinary photosynthesis uses water as electron donor, producing molecular oxygen). The researchers conjectured that historically these photosynthesizing organisms produced the arsenates that allowed the arsenate-reducing bacteria to thrive."Arsenic-loving bacteria rewrite photosynthesis rules"
''Chemistry World'', 15 August 2008
In humans, arsenite inhibits
pyruvate dehydrogenase Pyruvate dehydrogenase is an enzyme that catalyzes the reaction of pyruvate and a lipoamide to give the acetylated dihydrolipoamide and carbon dioxide. The conversion requires the coenzyme thiamine pyrophosphate. Pyruvate dehydrogenase is ...
(PDH complex) in the
pyruvate Pyruvic acid (CH3COCOOH) is the simplest of the alpha-keto acids, with a carboxylic acid and a ketone functional group. Pyruvate, the conjugate base, CH3COCOO−, is an intermediate in several metabolic pathways throughout the cell. Pyruvic ...
-
acetyl CoA Acetyl-CoA (acetyl coenzyme A) is a molecule that participates in many biochemical reactions in protein, carbohydrate and lipid metabolism. Its main function is to deliver the acetyl group to the citric acid cycle (Krebs cycle) to be oxidized fo ...
reaction, by binding to the –SH group of
lipoamide Lipoamide is a trivial name for 6,8-dithiooctanoic amide. It is the functional form of lipoic acid, i.e the carboxyl group is attached to protein via an amine with an amide linkage. Illustrative of the biochemical role of lipoamide is in the conve ...
, a participant coenzyme. It also inhibits the
oxoglutarate dehydrogenase complex The oxoglutarate dehydrogenase complex (OGDC) or α-ketoglutarate dehydrogenase complex is an enzyme complex, most commonly known for its role in the citric acid cycle. Units Much like pyruvate dehydrogenase complex (PDC), this enzyme forms a co ...
by the same mechanism. The inhibition of these enzymes disrupts energy production.


References

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External links


Case Studies in Environmental Medicine - Arsenic Toxicity
Pnictogen oxyanions Arsenic(III) compounds