Pyrene

Last updated
Pyrene
Pyrene.svg
Pyrene molecule from xtal ball.png
Names
Preferred IUPAC name
Pyrene
Other names
Benzo[def]phenanthrene
Identifiers
3D model (JSmol)
1307225
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.004.481
84203
KEGG
PubChem CID
RTECS number
  • UR2450000
Properties
C 16 H 10
Molar mass 202.256 g·mol−1
Appearancecolorless solid

(yellow impurities are often found at trace levels in many samples).

Contents

Density 1.271 g/mL
Melting point 145 to 148 °C (293 to 298 °F; 418 to 421 K)
Boiling point 404 °C (759 °F; 677 K)
0.135 mg/L
-147.9·10−6 cm3/mol
Hazards
Main hazards irritant
R-phrases (outdated) 36/37/38-45-53
S-phrases (outdated) 24/25-26-36
NFPA 704 (fire diamond)
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no codePyrene
1
2
0
Flash point non-flammable
Related compounds
Related PAHs
benzopyrene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)
Infobox references

Pyrene is a polycyclic aromatic hydrocarbon (PAH) consisting of four fused benzene rings, resulting in a flat aromatic system. The chemical formula is C
16
H
10
. This yellow solid is the smallest peri-fused PAH (one where the rings are fused through more than one face). Pyrene forms during incomplete combustion of organic compounds.

Occurrence and properties

Pyrene was first isolated from coal tar, where it occurs up to 2% by weight. As a peri-fused PAH, pyrene is much more resonance-stabilized than its five-member-ring containing isomer fluoranthene. Therefore, it is produced in a wide range of combustion conditions. For example, automobiles produce about 1 μg/km. [1]

Reactions

Oxidation with chromate affords perinaphthenone and then naphthalene-1,4,5,8-tetracarboxylic acid. It undergoes a series of hydrogenation reactions, and it is susceptible to halogenation, Diels-Alder additions, and nitration, all with varying degrees of selectivity. [1] Bromination occurs at one of the 3-positions. [2]

Photophysics

Pyrene and its derivatives are used commercially to make dyes and dye precursors, for example pyranine and naphthalene-1,4,5,8-tetracarboxylic acid. It has strong absorbance in UV-Vis in three sharp bands at 330 nm in DCM. The emission is close to the absorption, but moving at 375 nm. [3] The morphology of the signals change with the solvent. Its derivatives are also valuable molecular probes via fluorescence spectroscopy, having a high quantum yield and lifetime (0.65 and 410 nanoseconds, respectively, in ethanol at 293 K). Pyrene was the first molecule for which excimer behavior was discovered. [4] Such excimer appears around 450 nm. Theodor Förster reported this in 1954. [5]

Applications

Br4Py self-assembly on Au.jpg
Br4Py self-assembly on Au 2.jpg
STM image of self-assembled Br4Py molecules on Au(111) surface (top) and its model (bottom; pink spheres are Br atoms). [6]

Pyrene's fluorescence emission spectrum is very sensitive to solvent polarity, so pyrene has been used as a probe to determine solvent environments. This is due to its excited state having a different, non-planar structure than the ground state. Certain emission bands are unaffected, but others vary in intensity due to the strength of interaction with a solvent.

Diagram showing the numbering and ring fusion locations of pyrene according to IUPAC nomenclature of organic chemistry. Pyrene numbered.png
Diagram showing the numbering and ring fusion locations of pyrene according to IUPAC nomenclature of organic chemistry.

Although it is not as problematic as benzopyrene, animal studies have shown pyrene is toxic to the kidneys and liver. It is now known that pyrene affects several living functions in fish and algae. [7] [8] [9] [10]

Experiments in pigs show that urinary 1-hydroxypyrene is a metabolite of pyrene, when given orally. [11]

Pyrenes are strong electron donor materials and can be combined with several materials in order to make electron donor-acceptor systems which can be used in energy conversion and light harvesting applications. [3]

See also

Related Research Articles

An aromatic hydrocarbon or arene is a hydrocarbon with sigma bonds and delocalized pi electrons between carbon atoms forming a circle. In contrast, aliphatic hydrocarbons lack this delocalization. The term "aromatic" was assigned before the physical mechanism determining aromaticity was discovered, and referred simply to the fact that many such compounds have a sweet or pleasant odour; however, not all aromatic compounds have a sweet odour, and not all compounds with a sweet odour are aromatic. The configuration of six carbon atoms in aromatic compounds is called a "benzene ring", after the simplest possible such hydrocarbon, benzene. Aromatic hydrocarbons can be monocyclic (MAH) or polycyclic (PAH).

Excimer

An excimer is a short-lived dimeric or heterodimeric molecule formed from two species, at least one of which has completely filled valence shell by electrons. In this case, formation of molecules is possible only if such atom is in an electronic excited state. Heteronuclear molecules and molecules that have more than two species are also called exciplex molecules. Excimers are often diatomic and are composed of two atoms or molecules that would not bond if both were in the ground state. The lifetime of an excimer is very short, on the order of nanoseconds. Binding of a larger number of excited atoms forms Rydberg matter clusters, the lifetime of which can exceed many seconds.

Anthracene chemical compound

Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the production of the red dye alizarin and other dyes. Anthracene is colorless but exhibits a blue (400–500 nm peak) fluorescence under ultraviolet radiation.

Coronene polycyclic aromatic hydrocarbon (PAH) comprising six peri-fused benzene rings

Coronene is a polycyclic aromatic hydrocarbon (PAH) comprising six peri-fused benzene rings. Its chemical formula is C
24
H
12
. It is a yellow material that dissolves in common solvents including benzene, toluene, and dichloromethane. Its solutions emit blue light fluorescence under UV light. It has been used as a solvent probe, similar to pyrene.

Polycyclic aromatic hydrocarbon Hydrocarbons composed of multiple aromatic rings

Polycyclic aromatic hydrocarbons are hydrocarbons—organic compounds containing only carbon and hydrogen—that are composed of multiple aromatic rings. The simplest such chemicals are naphthalene, having two aromatic rings, and the three-ring compounds anthracene and phenanthrene.

Benzo(<i>a</i>)pyrene Chemical compound

Benzo[a]pyrene is a polycyclic aromatic hydrocarbon and the result of incomplete combustion of organic matter at temperatures between 300 °C (572 °F) and 600 °C (1,112 °F). The ubiquitous compound can be found in coal tar, tobacco smoke and many foods, especially grilled meats. The substance with the formula C20H12 is one of the benzopyrenes, formed by a benzene ring fused to pyrene. Its diol epoxide metabolites (more commonly known as BPDE) react and bind to DNA, resulting in mutations and eventually cancer. It is listed as a Group 1 carcinogen by the IARC. In the 18th century a scrotal cancer of chimney sweepers, the chimney sweeps' carcinoma, was already known to be connected to soot.

Fluoranthene chemical compound

Fluoranthene is a polycyclic aromatic hydrocarbon (PAH). The molecule can be viewed as the fusion of naphthalene and benzene unit connected by a five-membered ring. Although samples are often pale yellow, the compound is colorless. It is soluble in nonpolar organic solvents. It is a member of the class of PAHs known as non-alternant PAHs because it has rings other than those with six carbon atoms. It is a structural isomer of the alternant PAH pyrene. It is not as thermodynamically stable as pyrene. Its name is derived from its fluorescence under UV light.

Ovalene polycyclic aromatic hydrocarbon with the formula C32H14, which consists of ten peri-fused six-membered rings

Ovalene is a polycyclic aromatic hydrocarbon with the formula C32H14, which consists of ten peri-fused six-membered rings. It is very similar to coronene.

Chrysene Chemical compound

Chrysene is a polycyclic aromatic hydrocarbon (PAH) with the molecular formula C
18
H
12
that consists of four fused benzene rings. It is a natural constituent of coal tar, from which it was first isolated and characterized. It is also found in creosote at levels of 0.5-6 mg/kg.

<i>Pomatoschistus</i> genus of fishes

Pomatoschistus is a genus of gobies native to fresh, brackish and marine waters of Europe, the eastern Atlantic Ocean and the Mediterranean Sea.

Dicoronylene very large polycyclic aromatic hydrocarbon

Dicoronylene is the trivial name for a very large polycyclic aromatic hydrocarbon. Its formal name is benzo[10,11]phenanthro[2',3',4',5',6':4,5,6,7]chryseno[1,2,3-bc]coronene or benzo[1,2,3-bc:4,5,6-b'c']dicoronene. It has 15 rings and is a brick-red solid. Its formula is C
48
H
20
. Dicoronylene sublimes under high vacuum, 0.001 torr, between 250 °C and 300 °C.

Gobiiformes order of fishes

The Gobiiformes are an order of fish that includes the gobies and their relatives. The order, which was previously considered a suborder of Perciformes, is made up of about 2,211 species that are divided between seven families. Phylogenetic relationships of the Gobiiformes have been elucidated using molecular data. Gobiiforms are primarily small species that live in marine water, but roughly 10% of these species inhabit fresh water. This order is composed chiefly of benthic or burrowing species; like many other benthic fishes, most gobiiforms do not have a gas bladder or any other means of controlling their buoyancy in water, so they must spend most of their time on or near the bottom.

Lipid bilayer fusion The membrane organization process that joins two lipid bilayers to form a single membrane.

In membrane biology, fusion is the process by which two initially distinct lipid bilayers merge their hydrophobic cores, resulting in one interconnected structure. If this fusion proceeds completely through both leaflets of both bilayers, an aqueous bridge is formed and the internal contents of the two structures can mix. Alternatively, if only one leaflet from each bilayer is involved in the fusion process, the bilayers are said to be hemifused. In hemifusion, the lipid constituents of the outer leaflet of the two bilayers can mix, but the inner leaflets remain distinct. The aqueous contents enclosed by each bilayer also remain separated.

Chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) are a group of compounds comprising polycyclic aromatic hydrocarbons with two or more aromatic rings and one or more chlorine atoms attached to the ring system. Cl-PAHs can be divided into two groups: chloro-substituted PAHs, which have one or more hydrogen atoms substituted by a chlorine atom, and chloro-added Cl-PAHs, which have two or more chlorine atoms added to the molecule. They are products of incomplete combustion of organic materials. They have many congeners, and the occurrences and toxicities of the congeners differ. Cl-PAHs are hydrophobic compounds and their persistence within ecosystems is due to their low water solubility. They are structurally similar to other halogenated hydrocarbons such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs). Cl-PAHs in the environment are strongly susceptible to the effects of gas/particle partitioning, seasonal sources, and climatic conditions.

Benzopyrene family of isomeric compounds

A benzopyrene is an organic compound with the formula C20H12. Structurally speaking, the colorless isomers of benzopyrene are pentacyclic hydrocarbons and are fusion products of pyrene and a phenylene group. Two isomeric species of benzopyrene are benzo[a]pyrene and the less common benzo[e]pyrene. They belong to the chemical class of polycyclic aromatic hydrocarbons.

Benzo(<i>j</i>)fluoranthene Chemical compound

Benzo[j]fluoranthene (BjF) is an organic compound with the chemical formula C20H12. Classified as a polycyclic aromatic hydrocarbon (PAH), it is a colourless solid that is poorly soluble in most solvents. Impure samples can appear off white. Closely related isomeric compounds include benzo[a]fluoranthene (BaF), bendo[b]fluoranthene (BbF), benzo[e]fluoranthene (BeF), and benzo[k]fluoranthene (BkF). BjF is present in fossil fuels and is released during incomplete combustion of organic matter. It has been traced in the smoke of cigarettes, exhaust from gasoline engines, emissions from the combustion of various types of coal and emissions from oil heating, as well as an impurity in some oils such as soybean oil.

Dibenzopyrenes group of chemical compounds

Dibenzopyrenes are a group of high molecular weight polycyclic aromatic hydrocarbons with the molecular formula C24H14. There are five isomers of dibenzopyrene which differ by the arrangement of aromatic rings: dibenzo[a,e]pyrene, dibenzo[a,h]pyrene, dibenzo[a,i]pyrene, dibenzo[a,l]pyrene, and dibenzo[e,l]pyrene.

Benzo(<i>c</i>)fluorene Chemical compound

Benzo[c]fluorene is a polycyclic aromatic hydrocarbon (PAH) with mutagenic activity. It is a component of coal tar, cigarette smoke and smog and thought to be a major contributor to its carcinogenic properties. The mutagenicity of benzo[c]fluorene is mainly attributed to formation of metabolites that are reactive and capable of forming DNA adducts. According to the KEGG it is a group 3 carcinogen. Other names for benzo[c]fluorene are 7H-benzo[c]fluorene, 3,4-benzofluorene, and NSC 89264.

(+)-Benzo(<i>a</i>)pyrene-7,8-dihydrodiol-9,10-epoxide Cancer-causing agent derived from tobacco smoke

(+)-Benzo[a]pyrene-7,8-dihydrodiol-9,10-epoxide is an organic compound with molecular formula C20H14O3. It is a metabolite and derivative of benzo[a]pyrene (found in tobacco smoke) as a result of oxidation to include hydroxyl and epoxide functionalities. (+)-Benzo[a]pyrene-7,8-dihydrodiol-9,10-epoxide binds to the N2 atom of a guanine nucleobase in DNA, distorting the double helix structure by intercalation of the pyrene moiety between base pairs through π-stacking. The carcinogenic properties of tobacco smoking are attributed in part to this compound binding and inactivating the tumor suppression ability of certain genes, leading to genetic mutations and potentially to cancer.

Gordonia sp. nov. Q8 is a bacterium in the phylum of Actinobacteria. It was discovered in 2017 as one of eighteen new species isolated from the Jiangsu Wei5 oilfield in East China with the potential for bioremediation. Strain Q8 is rod-shaped and gram-positive with dimensions 1.0–4.0 μm × 0.5–1.2 μm and an optimal growth temperature of 40°C. Phylogenetically, it is most closely related to Gordonia paraffinivorans and Gordonia alkaliphila, both of which are known bioremediators. Q8 was assigned as a novel species based on a <70% ratio of DNA homology with other Gordonia bacteria.

References

  1. 1 2 Senkan, Selim and Castaldi, Marco (2003) "Combustion" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim.
  2. Gumprecht, W. H. (1968). "3-Bromopyrene". Org. Synth. 48: 30. doi:10.15227/orgsyn.048.0030.
  3. 1 2 Tagmatarchis, Nikos; Ewels, Christopher P.; Bittencourt, Carla; Arenal, Raul; Pelaez-Fernandez, Mario; Sayed-Ahmad-Baraza, Yuman; Canton-Vitoria, Ruben (2017-06-05). "Functionalization of MoS 2 with 1,2-dithiolanes: toward donor-acceptor nanohybrids for energy conversion". NPJ 2D Materials and Applications. 1 (1): 13. doi: 10.1038/s41699-017-0012-8 . ISSN   2397-7132.
  4. Van Dyke, David A.; Pryor, Brian A.; Smith, Philip G.; Topp, Michael R. (May 1998). "Nanosecond Time-Resolved Fluorescence Spectroscopy in the Physical Chemistry Laboratory: Formation of the Pyrene Excimer in Solution". Journal of Chemical Education. 75 (5): 615. doi:10.1021/ed075p615.
  5. Förster, Th.; Kasper, K. (June 1954). "Ein Konzentrationsumschlag der Fluoreszenz". Zeitschrift für Physikalische Chemie. 1 (5_6): 275–277. doi:10.1524/zpch.1954.1.5_6.275.
  6. Pham, Tuan Anh; Song, Fei; Nguyen, Manh-Thuong; Stöhr, Meike (2014). "Self-assembly of pyrene derivatives on Au(111): Substituent effects on intermolecular interactions". Chem. Commun. 50 (91): 14089. doi: 10.1039/C4CC02753A . PMID   24905327.
  7. Oliveira, M.; Ribeiro, A.; Hylland, K.; Guilhermino, L. (2013). "Single and combined effects of microplastics and pyrene on juveniles (0+ group) of the common goby Pomatoschistus microps (Teleostei, Gobiidae)". Ecological Indicators. 34: 641–647. doi:10.1016/j.ecolind.2013.06.019.
  8. Oliveira, M.; Gravato, C.; Guilhermino, L. (2012). "Acute toxic effects of pyrene on Pomatoschistus microps (Teleostei, Gobiidae): Mortality, biomarkers and swimming performance". Ecological Indicators. 19: 206–214. doi:10.1016/j.ecolind.2011.08.006.
  9. Oliveira, M.; Ribeiro, A.; Guilhermino, L. (2012). "Effects of exposure to microplastics and PAHs on microalgae Rhodomonas baltica and Tetraselmis chuii". Comparative Biochemistry and Physiology Part A: Molecular & Integrative Physiology. 163: S19–S20. doi:10.1016/j.cbpa.2012.05.062.
  10. Oliveira, M.; Ribeiro, A.; Guilhermino, L. (2012). "Effects of short-term exposure to microplastics and pyrene on Pomatoschistus microps (Teleostei, Gobiidae)". Comparative Biochemistry and Physiology Part A: Molecular & Integrative Physiology. 163: S20. doi:10.1016/j.cbpa.2012.05.063.
  11. Keimig, S. D.; Kirby, K. W.; Morgan, D. P.; Keiser, J. E.; Hubert, T. D. (1983). "Identification of 1-hydroxypyrene as a major metabolite of pyrene in pig urine". Xenobiotica. 13 (7): 415–20. doi:10.3109/00498258309052279. PMID   6659544.

Further reading