Полициклические ароматические углеводороды: структура и свойства

Hydrocarbon composed of multiple aromatic rings

A polycyclic aromatic hydrocarbon (PAH) is a class of organic compounds that is composed of multiple aromatic rings. The simplest representative is naphthalene, having two aromatic rings, and the three ring compounds anthracene and phenanthrene. PAHs are uncharged, non polar and planar. Many are colorless. Many of them are found in coal and in oil deposits, and are also produced by the incomplete combustion of organic matter—for example, in engines and incinerators or when biomass burns in forest fires. Polycyclic aromatic hydrocarbons are discussed as possible starting materials for abiotic syntheses of materials required by the earliest forms of life. or polynuclear aromatic hydrocarbon (abbreviated as PNA) are also used for this concept. Other authors consider PAHs to start with the tricyclic species phenanthrene and anthracene. Most authors exclude compounds that include heteroatoms in the rings, or carry substituents. A polyaromatic hydrocarbon may have rings of various sizes, including some that are not aromatic. Those that have only six membered rings are said to be alternant. The following are examples of PAHs that vary in the number and arrangement of their rings:

Most PAHs, like naphthalene, anthracene, and coronene, are planar. This geometry is a consequence of the fact that the σ bonds that result from the merger of sp2 hybrid orbitals of adjacent carbons lie on the same plane as the carbon atom. Those compounds are achiral, since the plane of the molecule is a symmetry plane. In rare cases, PAHs are not planar. In some cases, the non planarity may be forced by the topology of the molecule and the stiffness (in length and angle) of the carbon carbon bonds. For example, unlike coronene, corannulene adopts a bowl shape in order to reduce the bond stress. The two possible configurations, concave and convex, are separated by a relatively low energy barrier (about 11 kcal/mol). In theory, there are 51 structural isomers of coronene that have six fused benzene rings in a cyclic sequence, with two edge carbons shared between successive rings. All of them must be non planar and have considerable higher bonding energy (computed to be at least 130 kcal/mol) than coronene; and, as of 2002, none of them had been synthesized. Other PAHs that might seem to be planar, considering only the carbon skeleton, may be distorted by repulsion or steric hindrance between the hydrogen atoms in their periphery. Benzo[c]phenantrene, with four rings fused in a "C" shape, has a slight helical distortion due to repulsion between the closest pair of hydrogen atoms in the two extremal rings. This effect also causes distortion of picene. Adding another benzene ring to form dibenzo[c,g]phenantrene creates steric hindrance between the two extreme hydrogen atoms. Adding two more rings on the same sense yields heptahelicene in which the two extreme rings overlap. These non planar forms are chiral, and their enantiomers can be isolated.

The benzenoid hydrocarbons have been defined as condensed polycyclic unsaturated fully conjugated hydrocarbons whose molecules are essentially planar with all rings six membered. Full conjugation means that all carbon atoms and carbon carbon bonds must have the sp2 structure of benzene. This class is largely a subset of the alternant PAHs, but is considered to include unstable or hypothetical compounds like triangulene or heptacene. the resonance structure of a PAH that has the largest number of disjoint aromatic pi sextets—i. e. benzene like moieties—is the most important for the characterization of the properties of that PAH. For example, phenanthrene has two Clar structures: one with just one aromatic sextet (the middle ring), and the other with two (the first and third rings). The latter case is therefore the more characteristic electronic nature of the two. Therefore, in this molecule the outer rings have greater aromatic character whereas the central ring is less aromatic and therefore more reactive. In contrast, in anthracene the resonance structures have one sextet each, which can be at any of the three rings, and the aromaticity spreads out more evenly across the whole molecule. This difference in number of sextets is reflected in the differing ultraviolet–visible spectra of these two isomers, as higher Clar pi sextets are associated with larger HOMO LUMO gaps; the highest wavelength absorbance of phenanthrene is at 293 nm, while anthracene is at 374 nm. Three Clar structures with two sextets each are present in the four ring chrysene structure: one having sextets in the first and third rings, one in the second and fourth rings, and one in the first and fourth rings. Superposition of these structures reveals that the aromaticity in the outer rings is greater (each has a sextet in two of the three Clar structures) compared to the inner rings (each has a sextet in only one of the three).

The dominant sources of PAHs in the environment are from human activity: wood burning and combustion of other biofuels such as dung or crop residues contribute more than half of annual global PAH emissions, particularly due to biofuel use in India and China. As of 2004, industrial processes and the extraction and use of fossil fuels made up slightly more than one quarter of global PAH emissions, dominating outputs in industrial countries such as the United States. Lower temperature combustion, such as tobacco smoking or wood burning, tends to generate low molecular weight PAHs, whereas high temperature industrial processes typically generate PAHs with higher molecular weights. PAHs are typically found as complex mixtures.

PAHs may result from the incomplete combustion of organic matter in natural wildfires. PAHs can also be produced geologically when organic sediments are chemically transformed into fossil fuels such as oil and coal. The rare minerals idrialite, curtisite, and carpathite consist almost entirely of PAHs that originated from such sediments, that were extracted, processed, separated, and deposited by very hot fluids. High levels of such PAHs have been detected in the Cretaceous Tertiary (K T) boundary, more than 100 times the level in adjacent layers. The spike was attributed to massive fires that consumed about 20% of the terrestrial above ground biomass in a very short time.

PAHs are prevalent in the interstellar medium (ISM) of galaxies in both the nearby and distant Universe and make up a dominant emission mechanism in the mid infrared wavelength range, containing as much as 10% of the total integrated infrared luminosity of galaxies. PAHs generally trace regions of cold molecular gas, which are optimum environments for the formation of stars. In June 2013, PAHs were detected in the upper atmosphere of Titan, the largest moon of the planet Saturn.

Volcanic eruptions may emit PAHs.

Most PAHs are insoluble in water, which limits their mobility in the environment, although PAHs sorb to fine grained organic rich sediments. Aqueous solubility of PAHs decreases approximately logarithmically as molecular mass increases. Two ringed PAHs, and to a lesser extent three ringed PAHs, dissolve in water, making them more available for biological uptake and degradation. Further, two to four ringed PAHs volatilize sufficiently to appear in the atmosphere predominantly in gaseous form, although the physical state of four ring PAHs can depend on temperature. In contrast, compounds with five or more rings have low solubility in water and low volatility; they are therefore predominantly in solid state, bound to particulate air pollution, soils, or sediments.

Human exposure varies across the globe and depends on factors such as smoking rates, fuel types in cooking, and pollution controls on power plants, industrial processes, and vehicles. Developed countries with stricter air and water pollution controls, cleaner sources of cooking (i. e., gas and electricity vs. coal or biofuels), and prohibitions of public smoking tend to have lower levels of PAH exposure, while developing and undeveloped countries tend to have higher levels. Burning solid fuels such as coal and biofuels in the home for cooking and heating is a dominant global source of PAH emissions that in developing countries leads to high levels of exposure to indoor particulate air pollution containing PAHs, particularly for women and children who spend more time in the home or cooking. In industrial countries, people who smoke tobacco products, or who are exposed to second hand smoke, are among the most highly exposed groups; tobacco smoke contributes to 90% of indoor PAH levels in the homes of smokers. Exposure also occurs through drinking alcohol aged in charred barrels, flavored with peat smoke, or made with roasted grains. PAHs are typically at low concentrations in drinking water. Catalytic converters are estimated to reduce PAH emissions from gasoline fired vehicles by 25 fold. Industrial activity that can produce and distribute PAHs includes aluminum, iron, and steel manufacturing; coal gasification, tar distillation, shale oil extraction; production of coke, creosote, carbon black, and calcium carbide; road paving and asphalt manufacturing; rubber tire production; manufacturing or use of metal working fluids; and activity of coal or natural gas power stations. Soil and river sediment near industrial sites such as creosote manufacturing facilities can be highly contaminated with PAHs. Two and three ringed PAHs can disperse widely while dissolved in water or as gases in the atmosphere, while PAHs with higher molecular weights can disperse locally or regionally adhered to particulate matter that is suspended in air or water until the particles land or settle out of the water column. Most vertebrates metabolize and excrete PAHs relatively rapidly. Soil consuming invertebrates such as earthworms speed PAH degradation, either through direct metabolism or by improving the conditions for microbial transformations.

The British Geological Survey reported the amount and distribution of PAH compounds including parent and alkylated forms in urban soils at 76 locations in Greater London. The study showed that parent (16 PAH) content ranged from 4 to 67 mg/kg (dry soil weight) and an average PAH concentration of 18 mg/kg (dry soil weight) whereas the total PAH content (33 PAH) ranged from 6 to 88 mg/kg and fluoranthene and pyrene were generally the most abundant PAHs. the normal background concentration of BaP in the London urban sites was 6.9 mg/kg (dry soil weight). Burning of moorland vegetation such as heather initially generates high amounts of two and three ringed PAHs relative to four to six ringed PAHs in surface sediments, however, this pattern is reversed as the lower molecular weight PAHs are attenuated by biotic decay and photodegradation. Consequently, the concentrations of pollutants in estuaries tends to decrease at the river mouth. Understanding of sediment hosted PAHs in estuaries is important for the protection of commercial fisheries (such as mussels) and general environmental habitat conservation because PAHs can impact the health of suspension and sediment feeding organism. River estuary surface sediments in the UK tend to have a lower PAH content than sediments buried 10–60 cm from the surface reflecting lower present day industrial activity combined with improvement in environmental legislation of PAH. In general estuarine sediments with a higher natural total organic carbon content (TOC) tend to accumulate PAHs due to high sorption capacity of organic matter.

Cancer is a primary human health risk of exposure to PAHs. Exposure to PAHs has also been linked with cardiovascular disease and poor fetal development.

PAHs have been linked to skin, lung, bladder, liver, and stomach cancers in well established animal model studies. In 1775, Percivall Pott, a surgeon at St. Bartholomew's Hospital in London, observed that scrotal cancer was unusually common in chimney sweepers and proposed the cause as occupational exposure to soot. A century later, Richard von Volkmann reported increased skin cancers in workers of the coal tar industry of Germany, and by the early 1900s increased rates of cancer from exposure to soot and coal tar was widely accepted. In 1915, Yamigawa and Ichicawa were the first to experimentally produce cancers, specifically of the skin, by topically applying coal tar to rabbit ears.

The structure of a PAH influences whether and how the individual compound is carcinogenic. Some carcinogenic PAHs are genotoxic and induce mutations that initiate cancer; others are not genotoxic and instead affect cancer promotion or progression. PAHs that affect cancer initiation are typically first chemically modified by enzymes into metabolites that react with DNA, leading to mutations. When the DNA sequence is altered in genes that regulate cell replication, cancer can result. Mutagenic PAHs, such as benzo[a]pyrene, usually have four or more aromatic rings as well as a "bay region", a structural pocket that increases reactivity of the molecule to the metabolizing enzymes. Mutagenic metabolites of PAHs include diol epoxides, quinones, and radical PAH cations. These metabolites can bind to DNA at specific sites, forming bulky complexes called DNA adducts that can be stable or unstable. Stable adducts may lead to DNA replication errors, while unstable adducts react with the DNA strand, removing a purine base (either adenine or guanine). PAH exposure can increase production of the cytochrome enzymes, allowing the enzymes to convert PAHs into mutagenic diol epoxides at greater rates. Low molecular weight PAHs that have bay or bay like regions can dysregulate gap junction channels, interfering with intercellular communication, and also affect mitogen activated protein kinases that activate transcription factors involved in cell proliferation. PAHs are among the complex suite of contaminants in tobacco smoke and particulate air pollution and may contribute to cardiovascular disease resulting from such exposures. In laboratory experiments, animals exposed to certain PAHs have shown increased development of plaques (atherogenesis) within arteries. Potential mechanisms for the pathogenesis and development of atherosclerotic plaques may be similar to the mechanisms involved in the carcinogenic and mutagenic properties of PAHs. Biomarkers of exposure to PAHs in humans have been associated with inflammatory biomarkers that are recognized as important predictors of cardiovascular disease, suggesting that oxidative stress resulting from exposure to PAHs may be a mechanism of cardiovascular disease in humans.

Multiple epidemiological studies of people living in Europe, the United States, and China have linked in utero exposure to PAHs, through air pollution or parental occupational exposure, with poor fetal growth, reduced immune function, and poorer neurological development, including lower IQ.

A spectral database exists Detection of PAHs in materials is often done using gas chromatography mass spectrometry or liquid chromatography with ultraviolet visible or fluorescence spectroscopic methods or by using rapid test PAH indicator strips. Structures of PAHs have been analyzed using infrared spectroscopy. PAHs possess very characteristic UV absorbance spectra. These often possess many absorbance bands and are unique for each ring structure. Thus, for a set of isomers, each isomer has a different UV absorbance spectrum than the others. This is particularly useful in the identification of PAHs. Most PAHs are also fluorescent, emitting characteristic wavelengths of light when they are excited (when the molecules absorb light). The extended pi electron electronic structures of PAHs lead to these spectra, as well as to certain large PAHs also exhibiting semi conducting and other behaviors.

PAHs may be abundant in the universe. They seem to have been formed as early as a couple of billion years after the Big Bang, and are associated with new stars and exoplanets. More than 20% of the carbon in the universe may be associated with PAHs. This report was considered a controversial hypothesis that as nebulae of the same type as the Red Rectangle approach the ends of their lives, convection currents cause carbon and hydrogen in the nebulae's cores to get caught in stellar winds, and radiate outward. As they cool, the atoms supposedly bond to each other in various ways and eventually form particles of a million or more atoms. Adolf Witt and his team inferred]]

PAHs, subjected to interstellar medium (ISM) conditions, are transformed, through hydrogenation, oxygenation, and hydroxylation, to more complex organic compounds—"a step along the path toward amino acids and nucleotides, the raw materials of proteins and DNA, respectively". Further, as a result of these transformations, the PAHs lose their spectroscopic signature which could be one of the reasons "for the lack of PAH detection in interstellar ice grains, particularly the outer regions of cold, dense clouds or the upper molecular layers of protoplanetary disks."