Reactions of peroxynitrite leading to either apoptotic or necrotic cell death

Peroxynitrite (sometimes called peroxonitrite) is an

ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...

with the formula ONOO⁻. It is a

structural isomer In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a compound is a compound that contains the same number and type of atoms, but with a different connectivity (i.e. arrangement of bonds) between them. The ...

nitrate Nitrate is a polyatomic ion with the chemical formula . salt (chemistry), Salts containing this ion are called nitrates. Nitrates are common components of fertilizers and explosives. Almost all inorganic nitrates are solubility, soluble in wa ...

Preparation

Peroxynitrite can be prepared by the reaction of

superoxide In chemistry, a superoxide is a compound that contains the superoxide ion, which has the chemical formula . The systematic name of the anion is dioxide(1−). The reactive oxygen ion superoxide is particularly important as the product of t ...

with

nitric oxide Nitric oxide (nitrogen oxide, nitrogen monooxide, or nitrogen monoxide) is a colorless gas with the formula . It is one of the principal oxides of nitrogen. Nitric oxide is a free radical: it has an unpaired electron, which is sometimes den ...

: : It is prepared by the reaction of

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 viscosity, viscous than Properties of water, water. It is used as an oxidizer, bleaching agent, and antiseptic, usua ...

with

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 ...

: : H₂O₂ + → ONOO⁻ + H₂O Its presence is indicated by the

absorbance Absorbance is defined as "the logarithm of the ratio of incident to transmitted radiant power through a sample (excluding the effects on cell walls)". Alternatively, for samples which scatter light, absorbance may be defined as "the negative log ...

at 302 nm (pH 12, ''ε''₃₀₂ = 1670 M⁻¹ cm⁻¹).

Reactions

Peroxynitrite is weakly basic with a p''K''_a of ~6.8. It is reactive toward

DNA Deoxyribonucleic acid (; DNA) is a polymer composed of two polynucleotide chains that coil around each other to form a double helix. The polymer carries genetic instructions for the development, functioning, growth and reproduction of al ...

and

protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residue (biochemistry), residues. Proteins perform a vast array of functions within organisms, including Enzyme catalysis, catalysing metab ...

s. ONOO⁻ reacts nucleophilically with

carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...

. ''In vivo'', the concentration of carbon dioxide is about 1 mM, and its reaction with ONOO⁻ occurs quickly. Thus, under physiological conditions, the reaction of ONOO⁻ with carbon dioxide to form nitrosoperoxycarbonate () is by far the predominant pathway for ONOO⁻. homolyzes to form carbonate radical and nitrogen dioxide, again as a pair of

caged Caged may refer to: Film and TV * ''Caged'' (1950 film), an American film noir directed by John Cromwell * ''Caged'' (2010 film), a French horror film directed by Yann Gozlan * ''Caged'' (2011 film), a Dutch feature film directed by Stephan Brennin ...

radicals. Approximately 66% of the time, these two radicals recombine to form carbon dioxide and nitrate. The other 33% of the time, these two radicals escape the solvent cage and become free radicals. It is these radicals ( carbonate radical and

nitrogen dioxide Nitrogen dioxide is a chemical compound with the formula . One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, is an intermediate in the s ...

) that are believed to cause peroxynitrite-related cellular damage.

Peroxynitrous acid

Its

conjugate acid A conjugate acid, within the Brønsted–Lowry acid–base theory, is a chemical compound formed when an acid gives a proton () to a base—in other words, it is a base with a hydrogen ion added to it, as it loses a hydrogen ion in the rever ...

peroxynitrous acid Peroxynitrous acid (HNO3) is a reactive nitrogen species (RNS). It is the conjugate acid of peroxynitrite (ONOO−). It has a p''K''a of approximately 6.8. It is formed ''in vivo'' from the diffusion-controlled reaction of nitrogen monoxide (O ...

is highly reactive, although peroxynitrite is stable in basic solutions.

References

{{Nitrogen compounds Nitrogen oxyanions Atmospheric chemistry Toxins

Preparation

Reactions

Peroxynitrous acid

See also

References