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In
chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, structure, proper ...
, a radical, also known as a free radical, is an
atom Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, a ...
,
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and b ...
, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes. A notable example of a radical is the hydroxyl radical (HO·), a molecule that has one unpaired electron on the oxygen atom. Two other examples are triplet oxygen and triplet carbene (꞉) which have two unpaired electrons. Radicals may be generated in a number of ways, but typical methods involve redox reactions. Ionizing radiation, heat, electrical discharges, and
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from n ...
are known to produce radicals. Radicals are intermediates in many chemical reactions, more so than is apparent from the balanced equations. Radicals are important in
combustion Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
, atmospheric chemistry,
polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many f ...
, plasma chemistry,
biochemistry Biochemistry or biological chemistry is the study of chemical processes within and relating to living organisms. A sub-discipline of both chemistry and biology, biochemistry may be divided into three fields: structural biology, enzymology and ...
, and many other chemical processes. A majority of natural products are generated by radical-generating enzymes. In living organisms, the radicals superoxide and nitric oxide and their reaction products regulate many processes, such as control of vascular tone and thus blood pressure. They also play a key role in the intermediary metabolism of various biological compounds. Such radicals can even be messengers in a process dubbed redox signaling. A radical may be trapped within a solvent cage or be otherwise bound.


Formation

Radicals are either (1) formed from spin-paired molecules or (2) from other radicals. Radicals are formed from spin-paired molecules through homolysis of weak bonds or electron transfer, also known as reduction. Radicals are formed from other radicals through substitution, addition, and elimination reactions.


Radical formation from spin-paired molecules


Homolysis

Homolysis makes two new radicals from a spin-paired molecule by breaking a covalent bond, leaving each of the fragments with one of the electrons in the bond. Because breaking a chemical bond requires energy, homolysis occurs under the addition of heat or light. The bond dissociation energy associated with homolysis depends on the stability of a given compound, and some weak bonds are able to homolyze at relatively lower temperatures. Some homolysis reactions are particularly important because they serve as an initiator for other radical reactions. One such example is the homolysis of halogens, which occurs under light and serves as the driving force for radical halogenation reactions. Another notable reaction is the homolysis of dibenzoyl peroxide, which results in the formation of two benzoyloxy radicals and acts as an initiator for many radical reactions.


Reduction

Radicals can also form when a single electron is added to a spin-paired molecule, resulting in an electron transfer. This reaction, also called reduction, usually takes place with an alkali metal donating an electron to another spin-paired molecule.


Radical formation from other radicals


Abstraction

Hydrogen abstraction describes when a hydrogen atom is removed from a hydrogen donor molecule (e.g. tin or silicon hydride) with its one electron. Abstraction produces a new radical and a new spin-paired molecule. This is different from homolysis, which results in two radicals from a single spin-paired molecule and doesn’t include a radical as its reactant. Hydrogen abstraction is a fundamental process in radical chemistry because it serves as the final propagation step in many chemical reactions, converting carbon radicals into stable molecules. The figure to the right shows a radical abstraction between a benzoyloxy radical and a hydrogen bromide molecule, resulting in the production of a benzoic acid molecule and a bromine radical.


Addition

Radical addition describes when a radical is added to a spin-paired molecule to form a new radical. The figure on the right shows the addition of a bromine radical to an alkene. Radical addition follows the Anti -Markovnikov rule, where the substituent is added to the less substituted carbon atom.


Elimination

Radical elimination can be viewed as the reverse of radical addition. In radical elimination, an unstable radical compound breaks down into a spin-paired molecule and a new radical compound. Shown below is an example of a radical elimination reaction, where a benzoyloxy radical breaks down into a phenyl radical and a carbon dioxide molecule.


Stability


Stability of organic radicals

Although organic radicals are generally stable intrinsically (in isolation), practically speaking their existence is only transient because they tend to dimerize. Some are quite long-lived. Generally organic radicals are stabilized by any or all of these factors: presence of electronegativity, delocalization, and steric hindrance. The compound 2,2,6,6-tetramethylpiperidinyloxyl illustrates the combination of all three factors. It is a commercially available solid that, aside from being magnetic, behaves like a normal organic compound.


Electronegativity

Organic radicals are inherently electron deficient thus the greater the electronegativity of the atom on which the unpaired electron resides the less stable the radical. Between carbon, nitrogen, and oxygen, for example, carbon is the most stable and oxygen the least stable. Electronegativity also factors into the stability of carbon atoms of different hybridizations. Greater s-character correlates to higher electronegativity of the carbon atom (due to the close proximity of s orbitals to the nucleus), and the greater the electronegativity the less stable a radical. sp-hybridized carbons (50% s-character) form the least stable radicals compared to sp3-hybridized carbons (25% s-character) which form the most stable radicals.


Delocalization

The delocalization of electrons across the structure of a radical, also known as its ability to form one or more resonance structures, allows for the electron-deficiency to be spread over several atoms, minimizing instability. Delocalization usually occurs in the presence of electron-donating groups, such as hydroxyl groups (−OH), ethers (−OR), adjacent alkenes, and amines (−NH2 or −NR), or electron-withdrawing groups, such as C=O or C≡N. Delocalization effects can also be understood using
molecular orbital theory In chemistry, molecular orbital theory (MO theory or MOT) is a method for describing the electronic structure of molecules using quantum mechanics. It was proposed early in the 20th century. In molecular orbital theory, electrons in a molec ...
as a lens, more specifically, by examining the intramolecular interaction of the unpaired electron with a donating group’s pair of electrons or the empty π* orbital of an electron-withdrawing group in the form of a molecular orbital diagram. The HOMO of a radical is singly-occupied hence the orbital is aptly referred to as the SOMO, or the Singly-Occupied Molecular Orbital. For an electron-donating group, the SOMO interacts with the lower energy lone pair to form a new lower-energy filled bonding-orbital and a singly-filled new SOMO, higher in energy than the original. While the energy of the unpaired electron has increased, the decrease in energy of the lone pair forming the new bonding orbital outweighs the increase in energy of the new SOMO, resulting in a net decrease of the energy of the molecule. Therefore, electron-donating groups help stabilize radicals. With a group that is instead electron-withdrawing, the SOMO then interacts with the empty π* orbital. There are no electrons occupying the higher energy orbital formed, while a new SOMO forms that is lower in energy. This results in a lower energy and higher stability of the radical species. Both donating groups and withdrawing groups stabilize radicals. Another well-known albeit weaker form of delocalization is hyperconjugation. In radical chemistry, radicals are stabilized by hyperconjugation with adjacent alkyl groups. The donation of sigma (σ) C−H bonds into the partially empty radical orbitals helps to differentiate the stabilities of radicals on tertiary, secondary, and primary carbons. Tertiary carbon radicals have three σ C-H bonds that donate, secondary radicals only two, and primary radicals only one. Therefore, tertiary radicals are the most stable and primary radicals the least stable.


Steric hindrance

Most simply, the greater the steric hindrance the more difficult it is for reactions to take place, and the radical form is favored by default. For example, compare the hydrogen-abstracted form of ''N''-hydroxypiperidine to the molecule
TEMPO In musical terminology, tempo ( Italian, 'time'; plural ''tempos'', or ''tempi'' from the Italian plural) is the speed or pace of a given piece. In classical music, tempo is typically indicated with an instruction at the start of a piece (ofte ...
. TEMPO, or (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl, is too sterically hindered by the additional methyl groups to react making it stable enough to be sold commercially in its radical form. ''N''-Hydroxypiperidine, however, does not have the four methyl groups to impede the way of a reacting molecule so the structure is unstable.


Facile H-atom donors

The stability of many (or most) organic radicals is not indicated by their isolability but is manifested in their ability to function as donors of H. This property reflects a weakened bond to hydrogen, usually O−H but sometimes N−H or C−H. This behavior is important because these H donors serve as antioxidants in biology and in commerce. Illustrative is
α-tocopherol α-Tocopherol is a type of vitamin E. It has E number "E307". Vitamin E exists in eight different forms, four tocopherols and four tocotrienols. All feature a chromane ring, with a hydroxyl group that can donate a hydrogen atom to reduce free r ...
( vitamin E). The tocopherol radical itself is insufficiently stable for isolation, but the parent molecule is a highly effective hydrogen-atom donor. The C−H bond is weakened in triphenylmethyl (trityl) derivatives. upright=1.1, 2,2,6,6-Tetramethylpiperidinyloxyl is an example of a robust organic radical.


Inorganic radicals

A large variety of inorganic radicals are stable and in fact isolable. Examples include most first-row transition metal complexes. With regard to main group radicals, the most abundant radical in the universe is also the most abundant chemical in the universe, H. Most main group radicals are not however ''isolable'', despite their intrinsic stability. Hydrogen radicals for example combine eagerly to form H2. Nitric oxide (NO) is well known example of an isolable inorganic radical. Fremy's salt (Potassium nitrosodisulfonate, (KSO3)2NO) is a related example. Many thiazyl radicals are known, despite limited extent of π resonance stabilization. Many radicals can be envisioned as the products of breaking of covalent bonds by homolysis. The homolytic bond dissociation energies, usually abbreviated as "Δ''H''°" are a measure of bond strength. Splitting H2 into 2 H, for example, requires a Δ''H''° of +435
kJ/mol The joule per mole (symbol: J·mol−1 or J/mol) is the unit of energy per amount of substance in the International System of Units (SI), such that energy is measured in joules, and the amount of substance is measured in moles. It is also an S ...
, while splitting Cl2 into two Cl requires a Δ''H''° of +243 kJ/mol. For weak bonds, homolysis can be induced thermally. Strong bonds require high energy photons or even flames to induce homolysis.


Diradicals

Diradicals are molecules containing two radical centers. Dioxygen (O2) is an important example of a stable diradical. Singlet oxygen, the lowest-energy non-radical state of dioxygen, is less stable than the diradical due to
Hund's rule of maximum multiplicity Hund's rule of maximum multiplicity is a rule based on observation of atomic spectra, which is used to predict the ground state of an atom or molecule with one or more open electronic shells. The rule states that for a given electron configuratio ...
. The relative stability of the oxygen diradical is primarily due to the spin-forbidden nature of the triplet-singlet transition required for it to grab electrons, i.e., "oxidize". The diradical state of oxygen also results in its paramagnetic character, which is demonstrated by its attraction to an external magnet. Diradicals can also occur in metal-oxo complexes, lending themselves for studies of spin forbidden reactions in
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
chemistry.
Carbene In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is or where the R represents substituents or hydrogen atoms. The term "carbene" m ...
s in their triplet state can be viewed as diradicals centred on the same atom, while these are usually highly reactive persistent carbenes are known, with N-heterocyclic carbenes being the most common example. Triplet
carbene In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is or where the R represents substituents or hydrogen atoms. The term "carbene" m ...
s and nitrenes are diradicals. Their chemical properties are distinct from the properties of their singlet analogues.


Occurrence of radicals


Combustion

A familiar radical reaction is
combustion Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
. The
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
molecule is a stable diradical, best represented by O–O. Because
spins The spins (as in having "the spins")Diane Marie Leiva. ''The Florida State University College of Education''Women's Voices on College Drinking: The First-Year College Experience"/ref> is an adverse reaction of intoxication that causes a state of v ...
of the electrons are parallel, this molecule is stable. While the ground state of oxygen is this unreactive spin-unpaired ( triplet) diradical, an extremely reactive spin-paired ( singlet) state is available. For combustion to occur, the
energy barrier In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules pe ...
between these must be overcome. This barrier can be overcome by heat, requiring high temperatures. The triplet-singlet transition is also " forbidden". This presents an additional barrier to the reaction. It also means molecular oxygen is relatively unreactive at room temperature except in the presence of a catalytic heavy atom such as iron or copper. Combustion consists of various radical chain reactions that the singlet radical can initiate. The flammability of a given material strongly depends on the concentration of radicals that must be obtained before initiation and propagation reactions dominate leading to
combustion Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
of the material. Once the combustible material has been consumed, termination reactions again dominate and the flame dies out. As indicated, promotion of propagation or termination reactions alters flammability. For example, because lead itself deactivates radicals in the gasoline-air mixture, tetraethyl lead was once commonly added to gasoline. This prevents the combustion from initiating in an uncontrolled manner or in unburnt residues (
engine knocking In spark ignition internal combustion engines, knocking (also knock, detonation, spark knock, pinging or pinking) occurs when combustion of some of the air/fuel mixture in the cylinder does not result from propagation of the flame front ignit ...
) or premature ignition ( preignition). When a hydrocarbon is burned, a large number of different oxygen radicals are involved. Initially, hydroperoxyl radical (HOO) are formed. These then react further to give
organic hydroperoxide In organic chemistry, organic peroxides are organic compounds containing the peroxide functional group (). If the R′ is hydrogen, the compounds are called hydroperoxides, which are discussed in that article. The O−O bond of peroxides easily b ...
s that break up into hydroxyl radicals (HO).


Polymerization

Many
polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many f ...
reactions are initiated by radicals. Polymerization involves an initial radical adding to non-radical (usually an alkene) to give new radicals. This process is the basis of the radical chain reaction. The art of polymerization entails the method by which the initiating radical is introduced. For example, methyl methacrylate (MMA) can be polymerized to produce Poly(methyl methacrylate) (PMMA - Plexiglas or Perspex) via a repeating series of radical addition steps: upright=3.35, center, Radical intermediates in the formation of polymethacrylate (plexiglas or perspex) Newer radical polymerization methods are known as living radical polymerization. Variants include reversible addition-fragmentation chain transfer ( RAFT) and atom transfer radical polymerization ( ATRP). Being a prevalent radical, O2 reacts with many organic compounds to generate radicals together with the
hydroperoxide Hydroperoxides or peroxols are compounds containing the hydroperoxide functional group (ROOH). If the R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. ...
radical. Drying oils and alkyd paints harden due to radical crosslinking initiated by oxygen from the atmosphere.


Atmospheric radicals

The most common radical in the lower atmosphere is molecular dioxygen. Photodissociation of source molecules produces other radicals. In the lower atmosphere, important radical are produced by the photodissociation of nitrogen dioxide to an oxygen atom and nitric oxide (see below), which plays a key role in smog formation—and the photodissociation of ozone to give the excited oxygen atom O(1D) (see below). The net and return reactions are also shown ( and , respectively). In the upper atmosphere, the photodissociation of normally unreactive
chlorofluorocarbon Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) are fully or partly halogenated hydrocarbons that contain carbon (C), hydrogen (H), chlorine (Cl), and fluorine (F), produced as volatile derivatives of methane, ethane, and p ...
s (CFCs) by solar ultraviolet radiation is an important source of radicals (see eq. 1 below). These reactions give the
chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
radical, Cl, which catalyzes the conversion of
ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the l ...
to O2, thus facilitating ozone depletion (– below). Such reactions cause the depletion of the ozone layer, especially since the chlorine radical is free to engage in another reaction chain; consequently, the use of chlorofluorocarbons as
refrigerant A refrigerant is a working fluid used in the refrigeration cycle of air conditioning systems and heat pumps where in most cases they undergo a repeated phase transition from a liquid to a gas and back again. Refrigerants are heavily regulated ...
s has been restricted.


In biology

Radicals play important roles in biology. Many of these are necessary for life, such as the intracellular killing of bacteria by phagocytic cells such as granulocytes and macrophages. Radicals are involved in cell signalling processes, known as redox signaling. For example, radical attack of linoleic acid produces a series of 13-hydroxyoctadecadienoic acids and 9-hydroxyoctadecadienoic acids, which may act to regulate localized tissue inflammatory and/or healing responses, pain perception, and the proliferation of malignant cells. Radical attacks on arachidonic acid and docosahexaenoic acid produce a similar but broader array of signaling products. Radicals may also be involved in
Parkinson's disease Parkinson's disease (PD), or simply Parkinson's, is a long-term degenerative disorder of the central nervous system that mainly affects the motor system. The symptoms usually emerge slowly, and as the disease worsens, non-motor symptoms beco ...
, senile and drug-induced
deafness Deafness has varying definitions in cultural and medical contexts. In medical contexts, the meaning of deafness is hearing loss that precludes a person from understanding spoken language, an audiological condition. In this context it is written ...
,
schizophrenia Schizophrenia is a mental disorder characterized by continuous or relapsing episodes of psychosis. Major symptoms include hallucinations (typically hearing voices), delusions, and disorganized thinking. Other symptoms include social w ...
, and
Alzheimer's Alzheimer's disease (AD) is a neurodegenerative disease that usually starts slowly and progressively worsens. It is the cause of 60–70% of cases of dementia. The most common early symptom is difficulty in remembering recent events. As t ...
. The classic free-radical syndrome, the iron-storage disease
hemochromatosis Iron overload or hemochromatosis (also spelled ''haemochromatosis'' in British English) indicates increased total accumulation of iron in the body from any cause and resulting organ damage. The most important causes are hereditary haemochromatosi ...
, is typically associated with a constellation of free-radical-related symptoms including movement disorder, psychosis, skin pigmentary
melanin Melanin (; from el, μέλας, melas, black, dark) is a broad term for a group of natural pigments found in most organisms. Eumelanin is produced through a multistage chemical process known as melanogenesis, where the oxidation of the amino ...
abnormalities, deafness, arthritis, and diabetes mellitus. The free-radical theory of aging proposes that radicals underlie the
aging process Ageing ( BE) or aging ( AE) is the process of becoming older. The term refers mainly to humans, many other animals, and fungi, whereas for example, bacteria, perennial plants and some simple animals are potentially biologically immortal. In ...
itself. Similarly, the process of mito hormesis suggests that repeated exposure to radicals may extend life span. Because radicals are necessary for life, the body has a number of mechanisms to minimize radical-induced damage and to repair damage that occurs, such as the
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
s
superoxide dismutase Superoxide dismutase (SOD, ) is an enzyme that alternately catalyzes the dismutation (or partitioning) of the superoxide () radical into ordinary molecular oxygen (O2) and hydrogen peroxide (). Superoxide is produced as a by-product of oxygen ...
, catalase, glutathione peroxidase and glutathione reductase. In addition,
antioxidant Antioxidants are compounds that inhibit oxidation, a chemical reaction that can produce free radicals. This can lead to polymerization and other chain reactions. They are frequently added to industrial products, such as fuels and lubrica ...
s play a key role in these defense mechanisms. These are often the three vitamins, vitamin A,
vitamin C Vitamin C (also known as ascorbic acid and ascorbate) is a water-soluble vitamin found in citrus and other fruits and vegetables, also sold as a dietary supplement and as a topical 'serum' ingredient to treat melasma (dark pigment spots) ...
and vitamin E and
polyphenol antioxidant A polyphenol antioxidant is a hypothetical type of antioxidant containing a polyphenolic substructure and studied in vitro. Numbering over 4,000 distinct species mostly from plants, polyphenols may have antioxidant activity in vitro, but are unlik ...
s. Furthermore, there is good evidence indicating that
bilirubin Bilirubin (BR) ( Latin for "red bile") is a red-orange compound that occurs in the normal catabolic pathway that breaks down heme in vertebrates. This catabolism is a necessary process in the body's clearance of waste products that arise from t ...
and uric acid can act as antioxidants to help neutralize certain radicals. Bilirubin comes from the breakdown of
red blood cell Red blood cells (RBCs), also referred to as red cells, red blood corpuscles (in humans or other animals not having nucleus in red blood cells), haematids, erythroid cells or erythrocytes (from Greek ''erythros'' for "red" and ''kytos'' for "hol ...
s' contents, while uric acid is a breakdown product of
purine Purine is a heterocyclic aromatic organic compound that consists of two rings ( pyrimidine and imidazole) fused together. It is water-soluble. Purine also gives its name to the wider class of molecules, purines, which include substituted purines ...
s. Too much bilirubin, though, can lead to jaundice, which could eventually damage the central nervous system, while too much uric acid causes
gout Gout ( ) is a form of inflammatory arthritis characterized by recurrent attacks of a red, tender, hot and swollen joint, caused by deposition of monosodium urate monohydrate crystals. Pain typically comes on rapidly, reaching maximal intens ...
.


Reactive oxygen species

Reactive oxygen species or ROS are species such as superoxide,
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 ...
, and hydroxyl radical, commonly associated with cell damage. ROS form as a natural by-product of the normal metabolism of
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
and have important roles in cell signaling. Two important oxygen-centered radicals are superoxide and hydroxyl radical. They derive from molecular oxygen under reducing conditions. However, because of their reactivity, these same radicals can participate in unwanted side reactions resulting in cell damage. Excessive amounts of these radicals can lead to cell injury and
death Death is the irreversible cessation of all biological functions that sustain an organism. For organisms with a brain, death can also be defined as the irreversible cessation of functioning of the whole brain, including brainstem, and brain ...
, which may contribute to many diseases such as
cancer Cancer is a group of diseases involving abnormal cell growth with the potential to invade or spread to other parts of the body. These contrast with benign tumors, which do not spread. Possible signs and symptoms include a lump, abnormal b ...
,
stroke A stroke is a disease, medical condition in which poor cerebral circulation, blood flow to the brain causes cell death. There are two main types of stroke: brain ischemia, ischemic, due to lack of blood flow, and intracranial hemorrhage, hemorr ...
,
myocardial infarction A myocardial infarction (MI), commonly known as a heart attack, occurs when blood flow decreases or stops to the coronary artery of the heart, causing damage to the heart muscle. The most common symptom is chest pain or discomfort which ma ...
,
diabetes Diabetes, also known as diabetes mellitus, is a group of metabolic disorders characterized by a high blood sugar level ( hyperglycemia) over a prolonged period of time. Symptoms often include frequent urination, increased thirst and increased ...
and major disorders. Many forms of
cancer Cancer is a group of diseases involving abnormal cell growth with the potential to invade or spread to other parts of the body. These contrast with benign tumors, which do not spread. Possible signs and symptoms include a lump, abnormal b ...
are thought to be the result of reactions between radicals and DNA, potentially resulting in
mutation In biology, a mutation is an alteration in the nucleic acid sequence of the genome of an organism, virus, or extrachromosomal DNA. Viral genomes contain either DNA or RNA. Mutations result from errors during DNA or viral replication, m ...
s that can adversely affect the
cell cycle The cell cycle, or cell-division cycle, is the series of events that take place in a cell that cause it to divide into two daughter cells. These events include the duplication of its DNA (DNA replication) and some of its organelles, and sub ...
and potentially lead to malignancy. Some of the symptoms of
aging Ageing ( BE) or aging ( AE) is the process of becoming older. The term refers mainly to humans, many other animals, and fungi, whereas for example, bacteria, perennial plants and some simple animals are potentially biologically immortal. In ...
such as atherosclerosis are also attributed to radical induced oxidation of cholesterol to 7-ketocholesterol. In addition radicals contribute to alcohol-induced
liver The liver is a major organ only found in vertebrates which performs many essential biological functions such as detoxification of the organism, and the synthesis of proteins and biochemicals necessary for digestion and growth. In humans, it i ...
damage, perhaps more than alcohol itself. Radicals produced by
cigarette A cigarette is a narrow cylinder containing a combustible material, typically tobacco, that is rolled into thin paper for smoking. The cigarette is ignited at one end, causing it to smolder; the resulting smoke is orally inhaled via the opp ...
smoke are implicated in inactivation of
alpha 1-antitrypsin Alpha-1 antitrypsin or α1-antitrypsin (A1AT, α1AT, A1A, or AAT) is a protein belonging to the serpin superfamily. It is encoded in humans by the ''SERPINA1'' gene. A protease inhibitor, it is also known as alpha1–proteinase inhibitor (A1PI) ...
in the lung. This process promotes the development of emphysema.
Oxybenzone Oxybenzone or benzophenone-3 or BP-3 ( trade names Milestab 9, Eusolex 4360, Escalol 567, KAHSCREEN BZ-3) is an organic compound. It is a pale-yellow solid that is readily soluble in most organic solvents. Oxybenzone belongs to the class of aro ...
has been found to form radicals in sunlight, and therefore may be associated with cell damage as well. This only occurred when it was combined with other ingredients commonly found in sunscreens, like titanium oxide and octyl methoxycinnamate. ROS attack the polyunsaturated fatty acid,
linoleic acid Linoleic acid (LA) is an organic compound with the formula COOH(CH2)7CH=CHCH2CH=CH(CH2)4CH3. Both alkene groups are ''cis''. It is a fatty acid sometimes denoted 18:2 (n-6) or 18:2 ''cis''-9,12. A linoleate is a salt or ester of this acid. ...
, to form a series of 13-hydroxyoctadecadienoic acid and 9-hydroxyoctadecadienoic acid products that serve as signaling molecules that may trigger responses that counter the tissue injury which caused their formation. ROS attacks other polyunsaturated fatty acids, e.g. arachidonic acid and docosahexaenoic acid, to produce a similar series of signaling products.


History and nomenclature

Until late in the 20th century the word "radical" was used in chemistry to indicate any connected group of atoms, such as a methyl group or a carboxyl, whether it was part of a larger molecule or a molecule on its own. The qualifier "free" was then needed to specify the unbound case. Following recent nomenclature revisions, a part of a larger molecule is now called a
functional group In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the r ...
or
substituent A substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (In organic chemistry and biochemistry, the terms ''substituent'' and ''functional group'', as well as '' side ...
, and "radical" now implies "free". However, the old nomenclature may still appear in some books. The term radical was already in use when the now obsolete radical theory was developed. Louis-Bernard Guyton de Morveau introduced the phrase "radical" in 1785 and the phrase was employed by Antoine Lavoisier in 1789 in his
Traité Élémentaire de Chimie ''Traité élémentaire de chimie'' (''Elementary Treatise on Chemistry'') is a textbook written by Antoine Lavoisier published in 1789 and translated into English by Robert Kerr in 1790 under the title ''Elements of Chemistry in a New Systemati ...
. A radical was then identified as the root base of certain acids (the Latin word "radix" meaning "root"). Historically, the term ''radical'' in radical theory was also used for bound parts of the molecule, especially when they remain unchanged in reactions. These are now called
functional group In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the r ...
s. For example, methyl alcohol was described as consisting of a methyl "radical" and a hydroxyl "radical". Neither are radicals in the modern chemical sense, as they are permanently bound to each other, and have no unpaired, reactive electrons; however, they can be observed as radicals in mass spectrometry when broken apart by irradiation with energetic electrons. In a modern context the first
organic Organic may refer to: * Organic, of or relating to an organism, a living entity * Organic, of or relating to an anatomical organ Chemistry * Organic matter, matter that has come from a once-living organism, is capable of decay or is the product ...
(carbon–containing) radical identified was the triphenylmethyl radical, (C6H5)3C. This species was discovered by Moses Gomberg in 1900. In 1933 Morris S. Kharasch and
Frank Mayo Frank Mayo may refer to: * Frank M. Mayo (1839–1896), American actor and comedian * Frank Mayo (actor) Frank Lorimer Mayo (June 28, 1889 – July 9, 1963) was an American actor. He appeared in 310 films between 1911 and 1949. Biograp ...
proposed that free radicals were responsible for anti-Markovnikov addition of
hydrogen bromide Hydrogen bromide is the inorganic compound with the formula . It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room tem ...
to allyl bromide. In most fields of chemistry, the historical definition of radicals contends that the molecules have nonzero electron spin. However, in fields including
spectroscopy Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter ...
and astrochemistry, the definition is slightly different. Gerhard Herzberg, who won the Nobel prize for his research into the electron structure and geometry of radicals, suggested a looser definition of free radicals: "any transient (chemically unstable) species (atom, molecule, or ion)". The main point of his suggestion is that there are many chemically unstable molecules that have zero spin, such as C2, C3, CH2 and so on. This definition is more convenient for discussions of transient chemical processes and astrochemistry; therefore researchers in these fields prefer to use this loose definition.28th International Symposium on Free Radicals
.


Depiction in chemical reactions

In chemical equations, radicals are frequently denoted by a dot placed immediately to the right of the atomic symbol or molecular formula as follows: :\mathrm_2 \; \xrightarrow \; 2 Radical reaction mechanisms use single-headed arrows to depict the movement of single electrons: The homolytic cleavage of the breaking bond is drawn with a 'fish-hook' arrow to distinguish from the usual movement of two electrons depicted by a standard curly arrow. The second electron of the breaking bond also moves to pair up with the attacking radical electron; this is not explicitly indicated in this case. Radicals also take part in radical addition and radical substitution as reactive intermediates. Chain reactions involving radicals can usually be divided into three distinct processes. These are ''initiation'', ''propagation'', and ''termination''. *''Initiation'' reactions are those that result in a net increase in the number of radicals. They may involve the formation of radicals from stable species as in Reaction 1 above or they may involve reactions of radicals with stable species to form more radicals. *''Propagation'' reactions are those reactions involving radicals in which the total number of radicals remains the same. *''Termination'' reactions are those reactions resulting in a net decrease in the number of radicals. Typically two radicals combine to form a more stable species, for example: *:2 Cl → Cl2


See also

*
Electron pair In chemistry, an electron pair or Lewis pair consists of two electrons that occupy the same molecular orbital but have opposite spins. Gilbert N. Lewis introduced the concepts of both the electron pair and the covalent bond in a landmark paper he ...
*
Globally Harmonized System of Classification and Labelling of Chemicals The Globally Harmonized System of Classification and Labelling of Chemicals (GHS) is an internationally agreed-upon standard managed by the United Nations that was set up to replace the assortment of hazardous material classification and labelli ...
* Hofmann–Löffler reaction ;Free radical research * ARC Centre of Excellence for Free Radical Chemistry and Biotechnology


References

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