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{{Short description|Heterocyclic organic compound with four modified pyrrole subunits}}
{{Distinguish|Perforin|Porphyran}}
[[File:Porphyrin.svg|thumb|right|[[Porphine]], the parent porphyrin.]]
[[File:Porphin-18e.png|thumb|The 18-electron cycle of porphin, the parent structure of porphyrin, highlighted. (Several other choices of atoms, through the pyrrole nitrogens, for example, also give 18-electron cycles.)]]
{{Use dmy dates|date=May 2022}}
'''Porphyrins''' ({{IPAc-en|ˈ|p|ɔːr|f|ər|ɪ|n}} {{respell|POR|fər|in}}) are a group of [[heterocyclic compound|heterocyclic]] [[macrocycle]] [[organic compound]]s, composed of four modified [[pyrrole]] subunits interconnected at their [[Alpha and beta carbon|αあるふぁ carbon]] atoms via [[methine]] bridges (=CH−). In [[vertebrate]]s, an essential member of the porphyrin group is [[heme]], which is a component of [[hemoprotein]]s, whose functions include carrying [[oxygen]] in the [[Circulatory system|bloodstream]]. In [[plants]], an essential porphyrin derivative is [[chlorophyll]], which is involved in [[light-harvesting complex|light harvesting]] and [[electron transfer]] in [[photosynthesis]].
'''Porphyrins''' ({{IPAc-en|ˈ|p|ɔːr|f|ər|ɪ|n}} {{respell|POR|fər|in}}) are a group of [[heterocyclic compound|heterocyclic]] [[macrocycle]] [[organic compound]]s, composed of four modified [[pyrrole]] subunits interconnected at their [[Alpha and beta carbon|αあるふぁ carbon]] atoms via [[methine]] bridges (=CH−). The parent of porphyrin is [[porphine]], a rare chemical compound of exclusively theoretical interest. Substituted porphines are called porphyrins.<ref>{{cite journal | vauthors = Rayati S, Malekmohammadi S |title=Catalytic activity of multi-wall carbon nanotube supported manganese (III) porphyrin: an efficient, selective and reusable catalyst for oxidation of alkenes and alkanes with urea–hydrogen peroxide |journal=Journal of Experimental Nanoscience |date=2016 |volume=11 |issue=11 |page=872 |doi=10.1080/17458080.2016.1179802|bibcode=2016JENan..11..872R |doi-access=free }}</ref> With a total of 26 πぱい-electrons, of which 18 πぱい-electrons form a planar, continuous cycle, the porphyrin ring structure is often described as [[aromaticity|aromatic]].<ref>{{cite journal | vauthors = Ivanov AS, Boldyrev AI | title = Deciphering aromaticity in porphyrinoids via adaptive natural density partitioning | journal = Organic & Biomolecular Chemistry | volume = 12 | issue = 32 | pages = 6145–6150 | date = August 2014 | pmid = 25002069 | doi = 10.1039/C4OB01018C }}</ref><ref>{{cite journal|author-link1=Timothy D. Lash | vauthors = Lash TD |journal= Journal of Porphyrins and Phthalocyanines |volume= 15 |issue= 11n12 |pages= 1093–1115 |year= 2011 |doi= 10.1142/S1088424611004063 |title= Origin of aromatic character in porphyrinoid systems }}</ref> One result of the large [[conjugated system]] is that porphyrins typically absorb strongly in the visible region of the electromagnetic spectrum, i.e. they are deeply colored. The name "porphyrin" derives from the [[Greek language|Greek]] word πορφύρα (''porphyra''), meaning ''purple''.<ref>{{cite web| vauthors = Harper D, Buglione DC |title=porphyria (n.)|url=http://www.etymonline.com/index.php?allowed_in_frame=0&search=porphyrin&searchmode=none|website=The Online Etymology Dictionary|access-date=14 September 2014}}</ref>
 
The parent of porphyrins is [[porphine]], a rare chemical compound of exclusively theoretical interest. Substituted porphines are called porphyrins.<ref>{{cite journal | vauthors = Rayati S, Malekmohammadi S |title=Catalytic activity of multi-wall carbon nanotube supported manganese (III) porphyrin: an efficient, selective and reusable catalyst for oxidation of alkenes and alkanes with urea–hydrogen peroxide |journal=Journal of Experimental Nanoscience |date=2016 |volume=11 |issue=11 |page=872 |doi=10.1080/17458080.2016.1179802|bibcode=2016JENan..11..872R |doi-access=free }}</ref> With a total of 26 πぱい-electrons, of which 18 πぱい-electrons form a planar, continuous cycle, the porphyrin ring structure is often described as [[aromaticity|aromatic]].<ref>{{cite journal | vauthors = Ivanov AS, Boldyrev AI | title = Deciphering aromaticity in porphyrinoids via adaptive natural density partitioning | journal = Organic & Biomolecular Chemistry | volume = 12 | issue = 32 | pages = 6145–6150 | date = August 2014 | pmid = 25002069 | doi = 10.1039/C4OB01018C }}</ref><ref>{{cite journal|author-link1=Timothy D. Lash | vauthors = Lash TD |journal= Journal of Porphyrins and Phthalocyanines |volume= 15 |issue= 11n12 |pages= 1093–1115 |year= 2011 |doi= 10.1142/S1088424611004063 |title= Origin of aromatic character in porphyrinoid systems }}</ref> One result of the large [[conjugated system]] is that porphyrins typically absorb strongly in the visible region of the electromagnetic spectrum, i.e. they are deeply colored. The name "porphyrin" derives from the [[Greek language|Greek]] word πορφύρα (''porphyra''), meaning ''purple''.<ref>{{cite web| vauthors = Harper D, Buglione DC |title=porphyria (n.)|url=http://www.etymonline.com/index.php?allowed_in_frame=0&search=porphyrin&searchmode=none|website=The Online Etymology Dictionary|access-date=14 September 2014}}</ref>
Metal complexes derived from porphyrins occur naturally. One of the best-known families of porphyrin complexes is [[heme]], the pigment in red [[blood cell]]s, a [[Cofactor (biochemistry)|cofactor]] of the protein [[hemoglobin]].
 
==Structure==
 
[[Porphyrin complexes]] consist of a square planar MN<sub>4</sub> core. The periphery of the porphyrins, consisting of sp<sup>2</sup>-hybridized carbons, generally display small deviations from planarity. "Ruffled" or saddle-shaped porphyrins is attributed to interactions of the system with its environment.<ref>{{cite journal | vauthors = Senge MO, MacGowan SA, O'Brien JM | title = Conformational control of cofactors in nature - the influence of protein-induced macrocycle distortion on the biological function of tetrapyrroles | journal = Chemical Communications | volume = 51 | issue = 96 | pages = 17031–17063 | date = December 2015 | pmid = 26482230 | doi = 10.1039/C5CC06254C | hdl-access = free | hdl = 2262/75305 }}</ref> Additionally, the metal is often not centered in the N<sub>4</sub> plane.<ref>{{cite book |doi=10.1002/9781119951438.eibc0104 |chapter=Iron Porphyrin Chemistry |title=Encyclopedia of Inorganic and Bioinorganic Chemistry |year=2011 | vauthors = Walker FA, Simonis U |isbn=9781119951438 }}</ref> For free porphyrins, the two pyrrole protons are mutually trans and project out of the N<sub>4</sub> plane.<ref> {{cite journal | vauthors = Jentzen W, Ma JG, Shelnutt JA | title = Conservation of the conformation of the porphyrin macrocycle in hemoproteins | journal = Biophysical Journal | volume = 74 | issue = 2 Pt 1 | pages = 753–763 | date = February 1998 | pmid = 9533688 | pmc = 1302556 | doi = 10.1016/S0006-3495(98)74000-7 | bibcode = 1998BpJ....74..753J }}</ref> These nonplanar distortions are associated with altered chemical and physical properties. [[Chlorophyll]]-rings are more distinctly nonplanar, but they are more saturated than porphyrins.<ref>{{Cite journal | vauthors = Senge MO, Ryan AA, Letchford KA, MacGowan SA, Mielke T | year = 2014 | title = Chlorophylls, Symmetry, Chirality, and Photosynthesis | journal = Symmetry | volume = 6 | issue = 3 | pages = 781–843 | doi = 10.3390/sym6030781 | bibcode = 2014Symm....6..781S | doi-access = free | hdl = 2262/73843 | hdl-access = free }}</ref>
 
==Complexes of porphyrins==
{{main|Transition metal porphyrin complexes}}
<gallery caption="Representative porphyrins and derivatives" widths="140px" heights="100px">
Concomitant with the displacement of two N-''H'' protons, porphyrins bind metal ions in the N4 "pocket". The metal [[ion]] usually has a charge of 2+ or 3+. A schematic equation for these syntheses is shown:
File:Porphyrin.svg|[[Porphin]] is the simplest porphyrin, a rare compound of theoretical interest.
:H<sub>2</sub>porphyrin + [ML<sub>n</sub>]<sup>2+</sup> → M(porphyrinate)L<sub>n−4</sub> + 4 L + 2 H<sup>+</sup>, where M = metal ion and L = a ligand
 
<gallery caption="Representative porphyrins and derivatives" widths="140px" heights="140px">
File:PPIXtransH.png|Derivatives of [[protoporphyrin IX]] are common in nature, the precursor to [[heme]]s.
File:H2octaethylporphyrin.png |[[Octaethylporphyrin]] (H<sub>2</sub>OEP) is a synthetic analogue of protoporphyrin IX. Unlike the natural porphyrin ligands, OEP<sup>2−</sup> is highly symmetrical.
File:H2TPP.png|[[Tetraphenylporphyrin]] (H<sub>2</sub>TPP)is another synthetic analogue of protoporphyrin IX. Unlike the natural porphyrin ligands, TPP<sup>2−</sup> is highly symmetrical. Another difference is that its methyne centers are occupied by phenyl groups.
File:Heme bB.svg|Simplified view of [[heme]], a complex of a protoporphyrin IX.
CP40model.png|A macrocycle of 40 porphyrin molecules, model
CP40-STM.png|A macrocycle of 40 porphyrin molecules, [[scanning tunneling microscope|STM image]]
</gallery>
Porphyrins are the conjugate acids of [[ligand]]s that bind [[metals]] to form [[complex (chemistry)|complexes]]. The metal [[ion]] usually has a charge of 2+ or 3+. A schematic equation for these syntheses is shown:
:H<sub>2</sub>porphyrin + [ML<sub>n</sub>]<sup>2+</sup> → M(porphyrinate)L<sub>n−4</sub> + 4 L + 2 H<sup>+</sup>, where M = metal ion and L = a ligand
A porphyrin without a metal-ion in its cavity is a ''free base''. Some iron-containing porphyrins are called hemes. Heme-containing [[protein]]s, or ''[[hemoprotein]]s'', are found extensively in nature. [[Hemoglobin]] and [[myoglobin]] are two [[Oxygen|O<sub>2</sub>]]-binding proteins that contain iron porphyrins. Various [[cytochrome]]s are also hemoproteins.
 
==RelatedAncient speciesporphyrins==
A geoporphyrin, also known as a petroporphyrin, is a porphyrin of geologic origin.<ref name=handbook>{{cite book|title=The Porphyrin Handbook|publisher=[[Elsevier]]|isbn=9780123932006|url=https://books.google.com/books?id=Ci7rIe0Ohn8C&pg=PA381| veditors = Kadish KM |page=381|date=1999}}</ref> They can occur in [[crude oil]], [[oil shale]], coal, or sedimentary rocks.<ref name=handbook/><ref>{{cite journal| vauthors = Zhang B, Lash TD |title=Total synthesis of the porphyrin mineral abelsonite and related petroporphyrins with five-membered exocyclic rings|journal=Tetrahedron Letters|date=September 2003|volume=44|issue=39|page=7253|doi=10.1016/j.tetlet.2003.08.007}}</ref> [[Abelsonite]] is possibly the only geoporphyrin mineral, as it is rare for porphyrins to occur in isolation and form crystals.<ref>{{cite journal| vauthors = Mason GM, Trudell LG, Branthaver JF |title=Review of the stratigraphic distribution and diagenetic history of abelsonite|journal=Organic Geochemistry|year=1989|volume=14|issue=6|page=585|doi=10.1016/0146-6380(89)90038-7|bibcode=1989OrGeo..14..585M }}</ref>
===In nature===
 
The field of [[organic geochemistry]] had its origins in the isolation of porphyrins from petroleum.{{Citation needed|date=July 2020}} This finding helped establish the biological origins of petroleum. Petroleum is sometimes "fingerprinted" by analysis of trace amounts of nickel and [[vanadyl]] porphyrins.{{Citation needed|date=July 2020}}
Several heterocycles related to porphyrins are found in nature, almost always bound to metal ions. These include
{| class="wikitable"
|+ Caption text
|-
! N4-macrocycle !! Cofactor name!! metal!! comment
|-
| [[corrin]] || vitamin B12 || cobalt||several variants of B12 exist
|-
| corphin || [[Cofactor F430]] || nickel||highly reduced macrocycle
|-
| [[Sirohydrochlorin]]||none||nickel||biosynthetic intermediate en route to cofactor F430
|-
| [[Chlorin]] || chlorophyll || magnesium||several versions of chlorophyll exist
|-
| [[bacteriochlorin]]|| [[bacteriochlorophyll]] || magnesium|||several versions of bacteriochlorophyll exist
|-
| [[isobacteriochlorin]]||[[isobacteriochlorin]]|| magnesium||
|}
 
===Synthetic===
A '''benzoporphyrin''' is a porphyrin with a benzene ring fused to one of the pyrrole units. e.g. [[verteporfin]] is a benzoporphyrin derivative.<ref name=Scott2000>{{cite journal | vauthors = Scott LJ, Goa KL | title = Verteporfin | journal = Drugs & Aging | volume = 16 | issue = 2 | pages = 139–146; discussion 146–8 | date = February 2000 | pmid = 10755329 | doi = 10.2165/00002512-200016020-00005 }}</ref>
 
====Non-natural porphyrin isomers====
[[File:First Porphycene synthesis.tif|thumb|Porphycene, first porphyrin isomer, synthesised from bipyrrole dialdehyde through [[McMurry reaction|McMurry coupling reaction]]]]
 
The first synthetic porphyrin [[isomer]] was reported by Emanual Vogel and coworkers in 1986. This isomer [18]porphyrin-(2.0.2.0) is named as '''porphycene''', and the central N<sub>4</sub> Cavity forms a [[rectangle]] shape as shown in figure.<ref>{{cite journal | vauthors = Vogel E, Köcher M |title=Porphycene—a Novel Porphin Isomer |journal=Angewandte Chemie |date=March 1986 |volume=25 |issue=3 |page=257 |doi=10.1002/anie.198602571 }}</ref> Porphycenes showed interesting [[Photochemistry|photophysical]] behavior and found versatile compound towards the [[photodynamic therapy]].<ref>{{cite journal | vauthors = Dougherty TJ |title=Basic principles of photodynamic therapy |journal=Journal of Porphyrins and Phthalocyanines |date=2001 |volume=5 |issue=2 |page=105 |doi=10.1002/jpp.328 }}</ref> This inspired Vogel and [[Jonathan Sessler|Sessler]] to took up the challenge of preparing [18]porphyrin-(2.1.0.1) and named it as '''Corrphycene''' or '''Porphycerin'''.<ref>{{cite journal | vauthors = Vogel E, Guilard R |title=New Porphycene Ligands: Octaethyl‐ and Etioporphycene (OEPc and EtioPc)—Tetra‐ and Pentacoordinated Zinc Complexes of OEPc |journal=Angewandte Chemie International Edition |date=November 1993 |volume=32 |issue=11 |page=1600 |doi=10.1002/anie.199316001 }}</ref> The third porphyrin that is [18]porphyrin-(2.1.1.0), was reported by Callot and Vogel-Sessler. Vogel and coworkers reported successful isolation of [18]Porphyrin-(3.0.1.0) or '''Isoporphycene'''.<ref>{{cite journal | vauthors = Vogel E, Scholz P, Demuth R, Erben C, Bröring M, Schmickler H, Lex J, Hohlneicher G, Bremm D, Wu YD | display-authors = 6 | title = Isoporphycene: The Fourth Constitutional Isomer of Porphyrin with an N(4) Core-Occurrence of E/Z Isomerism | journal = Angewandte Chemie | volume = 38 | issue = 19 | pages = 2919–2923 | date = October 1999 | pmid = 10540393 | doi = 10.1002/(SICI)1521-3773(19991004)38:19<2919::AID-ANIE2919>3.0.CO;2-W }}</ref> The Japanese scientist Furuta<ref>{{cite journal | vauthors = Hiroyuki F |title="N-Confused Porphyrin": A New Isomer of Tetraphenylporphyrin |journal=J. Am. Chem. Soc. |year=1994 |volume=116 |issue=2 |page=767 |doi=10.1021/ja00081a047 }}</ref> and Polish scientist Latos-Grażyński<ref>{{cite journal | vauthors = Chmielewski PJ, Latos-Grażyński L, Rachlewicz K, Glowiak T |title=Tetra‐p‐tolylporphyrin with an Inverted Pyrrole Ring: A Novel Isomer of Porphyrin |journal=Angewandte Chemie International Edition |date=18 April 1994 |volume=33 |issue=7 |page=779 |doi=10.1002/anie.199407791 }}</ref> almost simultaneously reported the '''N-Confused porphyrins'''. The inversion of one of the pyrrolic subunits in the macrocyclic ring resulted to face one of the nitrogen atom outside of the core of the macrocycle.
[[File:Isomers of porphyrins soman.jpg|500 px|thumb|center|Various reported Isomers of porphyrin]]
 
==Natural formation==
A geoporphyrin, also known as a petroporphyrin, is a porphyrin of geologic origin.<ref name=handbook>{{cite book|title=The Porphyrin Handbook|publisher=[[Elsevier]]|isbn=9780123932006|url=https://books.google.com/books?id=Ci7rIe0Ohn8C&pg=PA381| veditors = Kadish KM |page=381|date=1999}}</ref> They can occur in [[crude oil]], [[oil shale]], coal, or sedimentary rocks.<ref name=handbook/><ref>{{cite journal| vauthors = Zhang B, Lash TD |title=Total synthesis of the porphyrin mineral abelsonite and related petroporphyrins with five-membered exocyclic rings|journal=Tetrahedron Letters|date=September 2003|volume=44|issue=39|page=7253|doi=10.1016/j.tetlet.2003.08.007}}</ref> [[Abelsonite]] is possibly the only geoporphyrin mineral, as it is rare for porphyrins to occur in isolation and form crystals.<ref>{{cite journal| vauthors = Mason GM, Trudell LG, Branthaver JF |title=Review of the stratigraphic distribution and diagenetic history of abelsonite|journal=Organic Geochemistry|year=1989|volume=14|issue=6|page=585|doi=10.1016/0146-6380(89)90038-7}}</ref>
 
==Synthesis==
 
===Biosynthesis===
In non-photosynthetic [[eukaryotes]] such as animals, insects, fungi, and [[protozoa]], as well as the αあるふぁ-proteobacteria group of bacteria, the [[committed step]] for porphyrin [[biosynthesis]] is the formation of [[Aminolevulinic acid|δでるた-aminolevulinic acid]] (δでるた-ALA, 5-ALA or dALA) by the reaction of the [[amino acid]] [[glycine]] with [[succinyl-CoA]] from the [[citric acid cycle]]. In [[plants]], [[algae]], [[bacteria]] (except for the αあるふぁ-proteobacteria group) and [[archaea]], it is produced from [[glutamic acid]] via glutamyl-tRNA and [[glutamate-1-semialdehyde]]. The enzymes involved in this pathway are [[Aminoacyl tRNA synthetases, class I|glutamyl-tRNA synthetase]], [[glutamyl-tRNA reductase]], and [[glutamate-1-semialdehyde 2,1-aminomutase]]. This pathway is known as the C5 or Beale pathway.
 
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|}
 
===Laboratory synthesis===
{{main|Rothemund reaction}}
[[Image:Tetratolylporphyrin.jpg|thumb|right|Brilliant crystals of ''meso''-tetratolylporphyrin, prepared from [[4-methylbenzaldehyde]] and pyrrole in refluxing [[propionic acid]]]]
One of the mostA common synthesessynthesis for porphyrins is the [[Rothemund reaction]], first reported in 1936,<ref>{{cite journal | vauthors = Rothemund P | title = A New Porphyrin Synthesis. The Synthesis of Porphin | year = 1936 | journal = [[J. Am. Chem. Soc.]] | volume = 58 | issue = 4 | pages = 625–627 | doi = 10.1021/ja01295a027}}</ref><ref>{{cite journal | vauthors = Rothemund P | title = Formation of Porphyrins from Pyrrole and Aldehydes | year = 1935 | journal = J. Am. Chem. Soc. | volume = 57 | issue = 10 | pages = 2010–2011 | doi=10.1021/ja01313a510}}</ref> which is also the basis for more recent methods described by Adler and Longo.<ref>{{cite journal | vauthors = Adler AD, Longo FR, Finarelli JD, Goldmacher J, Assour J, Korsakoff L | title = A simplified synthesis for ''meso''-tetraphenylporphine | year = 1967 | journal = [[J. Org. Chem.]] | volume = 32 | issue = 2 | pages = 476 | doi = 10.1021/jo01288a053}}</ref> The general scheme is a [[condensation reaction|condensation]] and [[organic oxidation reaction|oxidation]] process starting with pyrrole and an [[aldehyde]].
 
:[[Image:H2TPPsyn.png|400px]]
Line 156 ⟶ 131:
{{-}}
 
==Potential applications==
==Metal complexes==
Concomitant with the displacement of two N-''H'' protons, porphyrins bind metal ions in the N4 "pocket". The insertion of the metal center is slow in the absence of catalysts. In nature, these catalysts (enzymes) are called [[chelatase]]s. When there is no metal ion (or atom) bound to the nitrogens in the center, then the compounds are called ''free porphine'' or ''free porphyrin''. If they are bonded to a metal in the center, then they are ''bound''. A porphyrin with an iron atom of the type found in [[myoglobin]], [[hemoglobin]], or certain [[cytochrome]]s is called [[heme]]. See the Porphyrin article for further details.
 
==Applications==
===Photodynamic therapy===
Porphyrins have been evaluated in the context of [[photodynamic therapy]] (PDT) since they strongly absorb light, which is then converted to energy and heat in the illuminated areas.<ref>{{cite encyclopedia|title=Porphyrin conjugates for cancer therapy| vauthors = Giuntini F, Boyle R, Sibrian-Vazquez M, Vicente MG | veditors = Kadish KM, Smith KM, Guilard R |encyclopedia=Handbook of Porphyrin Science|year=2014|volume=27|pages=303–416}}</ref> This technique has been applied in [[macular degeneration]] using [[verteporfin]].<ref name="pmid17636693">{{cite journal | vauthors = Wormald R, Evans J, Smeeth L, Henshaw K | title = Photodynamic therapy for neovascular age-related macular degeneration | journal = The Cochrane Database of Systematic Reviews | issue = 3 | pages = CD002030 | date = July 2007 | pmid = 17636693 | doi = 10.1002/14651858.CD002030.pub3 | url = https://researchonline.lshtm.ac.uk/id/eprint/6367/1/Wormald_et_al-2007-The_Cochrane_library.pdf }}</ref>
 
PDT is considered a noninvasive cancer treatment, involving the interaction between light of a determined frequency, a photo-sensitizer, and oxygen. This interaction produces the formation of a highly reactive oxygen species (ROS), usually singlet oxygen, as well as superoxide anion, free hydroxyl radical, or hydrogen peroxide.<ref>{{cite journal | vauthors = Price M, Terlecky SR, Kessel D | title = A role for hydrogen peroxide in the pro-apoptotic effects of photodynamic therapy | journal = Photochemistry and Photobiology | volume = 85 | issue = 6 | pages = 1491–1496 | year = 2009 | pmid = 19659920 | pmc = 2783742 | doi = 10.1111/j.1751-1097.2009.00589.x }}</ref> These high reactive oxygen species react with susceptible cellular organic biomolecules such as; lipids, aromatic amino acids, and nucleic acid heterocyclic bases, to produce oxidative radicals that damage the cell, possibly inducing apoptosis or even necrosis.<ref>{{cite journal | vauthors = Singh S, Aggarwal A, Bhupathiraju NV, Arianna G, Tiwari K, Drain CM | title = Glycosylated Porphyrins, Phthalocyanines, and Other Porphyrinoids for Diagnostics and Therapeutics | journal = Chemical Reviews | volume = 115 | issue = 18 | pages = 10261–10306 | date = September 2015 | pmid = 26317756 | pmc = 6011754 | doi = 10.1021/acs.chemrev.5b00244 }}</ref>
 
===Molecular electronics and sensors===
===Organic geochemistry===
Porphyrin-based compounds are of interest as possible components of [[molecular electronics]] and photonics.<ref>{{cite journal | vauthors = Lewtak JP, Gryko DT | title = Synthesis of πぱい-extended porphyrins via intramolecular oxidative coupling | journal = Chemical Communications | volume = 48 | issue = 81 | pages = 10069–10086 | date = October 2012 | pmid = 22649792 | doi = 10.1039/c2cc31279d }}</ref> Synthetic porphyrin dyes have been incorporated in prototype [[dye-sensitized solar cells]].<ref>{{cite journal | journal = [[Journal of Porphyrins and Phthalocyanines]] | year = 2010 | volume = 14 | pages = 759–792 | doi= 10.1142/S1088424610002689 | title = Porphyrins and phthalocyanines in solar photovoltaic cells | vauthors = Walter MG, Rudine AB, Wamser CC | issue = 9}}</ref><ref>{{cite journal | vauthors = Yella A, Lee HW, Tsao HN, Yi C, Chandiran AK, Nazeeruddin MK, Diau EW, Yeh CY, Zakeeruddin SM, Grätzel M | display-authors = 6 | title = Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency | journal = Science | volume = 334 | issue = 6056 | pages = 629–634 | date = November 2011 | pmid = 22053043 | doi = 10.1126/science.1209688 | bibcode = 2011Sci...334..629Y | s2cid = 28058582 }}</ref>
The field of [[organic geochemistry]] had its origins in the isolation of porphyrins from petroleum.{{Citation needed|date=July 2020}} This finding helped establish the biological origins of petroleum. Petroleum is sometimes "fingerprinted" by analysis of trace amounts of nickel and [[vanadyl]] porphyrins.{{Citation needed|date=July 2020}}
 
=== Biological applications ===
Porphyrins have been investigated as possible anti-inflammatory agents<ref>{{cite journal | vauthors = Alonso-Castro AJ, Zapata-Morales JR, Hernández-Munive A, Campos-Xolalpa N, Pérez-Gutiérrez S, Pérez-González C | title = Synthesis, antinociceptive and anti-inflammatory effects of porphyrins | journal = Bioorganic & Medicinal Chemistry | volume = 23 | issue = 10 | pages = 2529–2537 | date = May 2015 | pmid = 25863493 | doi = 10.1016/j.bmc.2015.03.043 }}</ref> and evaluated on their anti-cancer and anti-oxidant activity.<ref>{{cite journal | vauthors = Bajju GD, Ahmed A, Devi G | title = Synthesis and bioactivity of oxovanadium(IV)tetra(4-methoxyphenyl)porphyrinsalicylates | journal = BMC Chemistry | volume = 13 | issue = 1 | pages = 15 | date = December 2019 | pmid = 31384764 | pmc = 6661832 | doi = 10.1186/s13065-019-0523-9 | doi-access = free }}</ref> Several porphyrin-peptide conjugates were found to have antiviral activity against HIV ''in vitro''.<ref>{{cite journal | vauthors = Mendonça DA, Bakker M, Cruz-Oliveira C, Neves V, Jiménez MA, Defaus S, Cavaco M, Veiga AS, Cadima-Couto I, Castanho MA, Andreu D, Todorovski T | display-authors = 6 | title = Penetrating the Blood-Brain Barrier with New Peptide-Porphyrin Conjugates Having anti-HIV Activity | journal = Bioconjugate Chemistry | volume = 32 | issue = 6 | pages = 1067–1077 | date = June 2021 | pmid = 34033716 | pmc = 8485325 | doi = 10.1021/acs.bioconjchem.1c00123 }}</ref>
 
=== Toxicology ===
Heme biosynthesis is used as [[biomarker]] in environmental toxicology studies. While excess production of porphyrins indicate [[organochlorine]] exposure, [[lead]] inhibits [[ALA dehydratase]] enzyme.<ref>{{Cite book|title=Principles of Ecotoxicology| vauthors = Walker CH, Silby RM, Hopkin SP, Peakall DB |publisher=CRC Press|year=2012|isbn=978-1-4665-0260-4|location=Boca Raton, FL|pages=182}}</ref>
 
==Gallery==
=== Biological applications ===
<gallery>
Porphyrins have been investigated as possible anti-inflammatory agents<ref>{{cite journal | vauthors = Alonso-Castro AJ, Zapata-Morales JR, Hernández-Munive A, Campos-Xolalpa N, Pérez-Gutiérrez S, Pérez-González C | title = Synthesis, antinociceptive and anti-inflammatory effects of porphyrins | journal = Bioorganic & Medicinal Chemistry | volume = 23 | issue = 10 | pages = 2529–2537 | date = May 2015 | pmid = 25863493 | doi = 10.1016/j.bmc.2015.03.043 }}</ref> and evaluated on their anti-cancer and anti-oxidant activity.<ref>{{cite journal | vauthors = Bajju GD, Ahmed A, Devi G | title = Synthesis and bioactivity of oxovanadium(IV)tetra(4-methoxyphenyl)porphyrinsalicylates | journal = BMC Chemistry | volume = 13 | issue = 1 | pages = 15 | date = December 2019 | pmid = 31384764 | pmc = 6661832 | doi = 10.1186/s13065-019-0523-9 }}</ref> Several porphyrin-peptide conjugates were found to have antiviral activity against HIV ''in vitro''.<ref>{{cite journal | vauthors = Mendonça DA, Bakker M, Cruz-Oliveira C, Neves V, Jiménez MA, Defaus S, Cavaco M, Veiga AS, Cadima-Couto I, Castanho MA, Andreu D, Todorovski T | display-authors = 6 | title = Penetrating the Blood-Brain Barrier with New Peptide-Porphyrin Conjugates Having anti-HIV Activity | journal = Bioconjugate Chemistry | volume = 32 | issue = 6 | pages = 1067–1077 | date = June 2021 | pmid = 34033716 | pmc = 8485325 | doi = 10.1021/acs.bioconjchem.1c00123 }}</ref>
File:H2TPP.png|Lewis structure for ''meso''-tetraphenylporphyrin
File:Meso-tetraphenylporphyrin UV-vis.JPG|[[Ultraviolet–visible spectroscopy|UV–vis]] readout for ''meso''-tetraphenylporphyrin
File:Porfirina activada con la luz.svg|Light-activated porphyrin. Monatomic oxygen. Cellular aging
</gallery>
 
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==Potential applications==
==Related species==
===Biomimetic catalysis===
===In nature===
Although not commercialized, metalloporphyrin complexes are widely studied as catalysts for the oxidation of organic compounds. Particularly popular for such laboratory research are complexes of ''meso''-[[tetraphenylporphyrin]] and [[octaethylporphyrin]]. Complexes with Mn, Fe, and Co catalyze a variety of reactions of potential interest in [[organic synthesis]]. Some complexes emulate the action of various [[heme]] enzymes such as [[cytochrome P450]], [[lignin peroxidase]].<ref>{{cite journal | vauthors = Huang X, Groves JT | title = Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins | journal = Chemical Reviews | volume = 118 | issue = 5 | pages = 2491–2553 | date = March 2018 | pmid = 29286645 | pmc = 5855008 | doi = 10.1021/acs.chemrev.7b00373 }}</ref><ref>{{cite book | veditors = Kadish KM, Smith KM, Guilard R |title=Handbook of porphyrin science with applications to chemistry, physics, materials science, engineering, biology and medicine|date=2012|publisher=World Scientific|location=Singapore|isbn=9789814335492}}</ref> Metalloporphyrins are also studied as catalysts for water splitting, with the purpose of generating molecular hydrogen and oxygen for fuel cells.<ref>{{cite journal | vauthors = Zhang W, Lai W, Cao R | title = Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems | journal = Chemical Reviews | volume = 117 | issue = 4 | pages = 3717–3797 | date = February 2017 | pmid = 28222601 | doi = 10.1021/acs.chemrev.6b00299 }}</ref>
 
Several heterocycles related to porphyrins are found in nature, almost always bound to metal ions. These include
===Molecular electronics and sensors===
{| class="wikitable"
Porphyrin-based compounds are of interest as possible components of [[molecular electronics]] and photonics.<ref>{{cite journal | vauthors = Lewtak JP, Gryko DT | title = Synthesis of πぱい-extended porphyrins via intramolecular oxidative coupling | journal = Chemical Communications | volume = 48 | issue = 81 | pages = 10069–10086 | date = October 2012 | pmid = 22649792 | doi = 10.1039/c2cc31279d }}</ref> Synthetic porphyrin dyes have been incorporated in prototype [[dye-sensitized solar cells]].<ref>{{cite journal | journal = [[Journal of Porphyrins and Phthalocyanines]] | year = 2010 | volume = 14 | pages = 759–792 | doi= 10.1142/S1088424610002689 | title = Porphyrins and phthalocyanines in solar photovoltaic cells | vauthors = Walter MG, Rudine AB, Wamser CC | issue = 9}}</ref><ref>{{cite journal | vauthors = Yella A, Lee HW, Tsao HN, Yi C, Chandiran AK, Nazeeruddin MK, Diau EW, Yeh CY, Zakeeruddin SM, Grätzel M | display-authors = 6 | title = Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency | journal = Science | volume = 334 | issue = 6056 | pages = 629–634 | date = November 2011 | pmid = 22053043 | doi = 10.1126/science.1209688 | bibcode = 2011Sci...334..629Y | s2cid = 28058582 }}</ref>
|+ Caption text
|-
! N4-macrocycle !! Cofactor name!! metal!! comment
|-
|[[chlorin]]|| chlorophyll || magnesium||several versions of chlorophyll exist (sidechain; exception being [[chlorophyll c]])
|-
|bacteriochlorin|| [[bacteriochlorophyll]] (in part) || magnesium|||several versions of bacteriochlorophyll exist (sidechain; some use a usual chlorin ring)
|-
| rowspan="2" | [[sirohydrochlorin]] (an isobacteriochlorin)||[[siroheme]]||iron||Important cofactor in sulfur assimilation
|-
|
|
|biosynthetic intermediate en route to cofactor F430 and B12
|-
| [[corrin]] || vitamin B12 || cobalt||several variants of B12 exist (sidechain)
|-
| corphin || [[Cofactor F430]] || nickel||highly reduced macrocycle
|}
 
===Synthetic===
Metalloporphyrins have been investigated as sensors.<ref>{{cite journal | vauthors = Ding Y, Zhu WH, Xie Y | title = Development of Ion Chemosensors Based on Porphyrin Analogues | journal = Chemical Reviews | volume = 117 | issue = 4 | pages = 2203–2256 | date = February 2017 | pmid = 27078087 | doi = 10.1021/acs.chemrev.6b00021 }}</ref>
A '''benzoporphyrin''' is a porphyrin with a benzene ring fused to one of the pyrrole units. e.g. [[verteporfin]] is a benzoporphyrin derivative.<ref name=Scott2000>{{cite journal | vauthors = Scott LJ, Goa KL | title = Verteporfin | journal = Drugs & Aging | volume = 16 | issue = 2 | pages = 139–146; discussion 146–8 | date = February 2000 | pmid = 10755329 | doi = 10.2165/00002512-200016020-00005 | s2cid = 260491296 }}</ref>
 
====Non-natural porphyrin isomers====
[[Phthalocyanine]]s, which are structurally related to porphyrins, are used in commerce as dyes and catalysts, but porphyrins are not.
[[File:First Porphycene synthesis.tif|thumb|Porphycene, first porphyrin isomer, synthesised from bipyrrole dialdehyde through [[McMurry reaction|McMurry coupling reaction]]]]
 
The first synthetic porphyrin [[isomer]] was reported by Emanual Vogel and coworkers in 1986.<ref>{{cite journal | vauthors = Vogel E, Köcher M |title=Porphycene—a Novel Porphin Isomer |journal=Angewandte Chemie |date=March 1986 |volume=25 |issue=3 |page=257 |doi=10.1002/anie.198602571 }}</ref> This isomer [18]porphyrin-(2.0.2.0) is named as '''porphycene''', and the central N<sub>4</sub> Cavity forms a [[rectangle]] shape as shown in figure.<ref>{{cite journal | vauthors = Nagamaiah J, Dutta A, Pati NN, Sahoo S, Soman R, Panda PK |title=3,6,13,16-Tetrapropylporphycene: Rational Synthesis, Complexation, and Halogenation |journal=The Journal of Organic Chemistry |date=March 2022 |volume=87 |issue=5 |pages=2721–2729 |doi=10.1021/acs.joc.1c02652 |pmid=35061396 |s2cid=246165814 }}</ref> Porphycenes showed interesting [[Photochemistry|photophysical]] behavior and found versatile compound towards the [[photodynamic therapy]].<ref>{{cite journal | vauthors = Dougherty TJ |title=Basic principles of photodynamic therapy |journal=Journal of Porphyrins and Phthalocyanines |date=2001 |volume=5 |issue=2 |page=105 |doi=10.1002/jpp.328 }}</ref> This inspired Vogel and [[Jonathan Sessler|Sessler]] to took up the challenge of preparing [18]porphyrin-(2.1.0.1) and named it as '''corrphycene''' or '''porphycerin'''.<ref>{{cite journal | vauthors = Vogel E, Guilard R |title=New Porphycene Ligands: Octaethyl‐ and Etioporphycene (OEPc and EtioPc)—Tetra‐ and Pentacoordinated Zinc Complexes of OEPc |journal=Angewandte Chemie International Edition |date=November 1993 |volume=32 |issue=11 |page=1600 |doi=10.1002/anie.199316001 }}</ref> The third porphyrin that is [18]porphyrin-(2.1.1.0), was reported by Callot and Vogel-Sessler. Vogel and coworkers reported successful isolation of [18]porphyrin-(3.0.1.0) or '''isoporphycene'''.<ref>{{cite journal | vauthors = Vogel E, Scholz P, Demuth R, Erben C, Bröring M, Schmickler H, Lex J, Hohlneicher G, Bremm D, Wu YD | display-authors = 6 | title = Isoporphycene: The Fourth Constitutional Isomer of Porphyrin with an N(4) Core-Occurrence of E/Z Isomerism | journal = Angewandte Chemie | volume = 38 | issue = 19 | pages = 2919–2923 | date = October 1999 | pmid = 10540393 | doi = 10.1002/(SICI)1521-3773(19991004)38:19<2919::AID-ANIE2919>3.0.CO;2-W }}</ref> The Japanese scientist Furuta<ref>{{cite journal | vauthors = Hiroyuki F |title="N-Confused Porphyrin": A New Isomer of Tetraphenylporphyrin |journal=J. Am. Chem. Soc. |year=1994 |volume=116 |issue=2 |page=767 |doi=10.1021/ja00081a047 }}</ref> and Polish scientist Latos-Grażyński<ref>{{cite journal | vauthors = Chmielewski PJ, Latos-Grażyński L, Rachlewicz K, Glowiak T |title=Tetra‐p‐tolylporphyrin with an Inverted Pyrrole Ring: A Novel Isomer of Porphyrin |journal=Angewandte Chemie International Edition |date=18 April 1994 |volume=33 |issue=7 |page=779 |doi=10.1002/anie.199407791 }}</ref> almost simultaneously reported the '''N-confused porphyrins'''. The inversion of one of the pyrrolic subunits in the macrocyclic ring resulted in one of the nitrogen atoms facing outwards from the core of the macrocycle.
===Supramolecular chemistry===
[[File:Isomers of porphyrins soman.jpg|500 px|thumb|center|Various reported Isomers of porphyrin]]
[[File:Porphyrin on Au(111) STM.jpg|thumb|On a gold surface porphyrin derivative molecules (a) form chains and clusters (b). Each cluster in (c,d) contains 4 or 5 molecules in the core and 8 or 10 molecules in the outer shells ([[Scanning tunneling microscopy|STM]] images).<ref>{{cite journal | vauthors = Pham TA, Song F, Alberti MN, Nguyen MT, Trapp N, Thilgen C, Diederich F, Stöhr M | display-authors = 6 | title = Heat-induced formation of one-dimensional coordination polymers on Au(111): an STM study | journal = Chemical Communications | volume = 51 | issue = 77 | pages = 14473–14476 | date = October 2015 | pmid = 26278062 | doi = 10.1039/C5CC04940G | doi-access = free }}</ref>]]
[[Image:Host Guest Complex Porphyrin Sanders AngewChemIntEdEngl 1995 1096.jpg|thumb|An example of porphyrins involved in [[host–guest chemistry]]. Here, a four-porphyrin–zinc complex hosts a porphyrin guest.<ref name = sanders>{{cite journal | vauthors = Anderson S, Anderson HL, Bashall A, McPartlin M, Sanders JK | author5-link = Jeremy Sanders | title = Assembly and Crystal Structure of a Photoactive Array of Five Porphyrins | journal = [[Angew. Chem. Int. Ed. Engl.]] | year = 1995 | volume = 34 | pages = 1096–1099 | doi = 10.1002/anie.199510961 | issue = 10}}</ref>]]
Porphyrins are often used to construct structures in [[supramolecular chemistry]].<ref>{{Cite journal | vauthors = Kohn E, Shirly D, Fry CH, Caputo GA |date=2022-06-14 |title=Peptide‐assisted supramolecular polymerization of the anionic porphyrin meso‐tetra ( 4‐sulfonatophenyl )porphine |url=https://onlinelibrary.wiley.com/doi/10.1002/pep2.24288 |journal=Peptide Science |language=en |doi=10.1002/pep2.24288 |s2cid=249689192 |issn=2475-8817}}</ref> These systems take advantage of the Lewis acidity of the metal, typically zinc. An example of a host–guest complex that was constructed from a [[macrocycle]] composed of four porphyrins.<ref name = sanders/> A guest-free base porphyrin is bound to the center by coordination with its four-pyridine substituents.
 
===Theoretical interest in aromaticity===
Porphyrinoid macrocycles can show variable aromaticity.<ref>{{cite journal | vauthors = Wu JI, Fernández I, Schleyer PV | title = Description of aromaticity in porphyrinoids | journal = Journal of the American Chemical Society | volume = 135 | issue = 1 | pages = 315–321 | date = January 2013 | pmid = 23205604 | doi = 10.1021/ja309434t }}</ref> An Hückel aromatic porphyrin is porphycene.<ref>{{cite book | vauthors = Kadish KM, Smith KM, Guilard R |title=The Porphyrin Handbook |publisher=Academic Press |isbn=0123932009}}</ref> [[Antiaromaticity|antiaromatic]], [[Möbius aromaticity|Mobius aromatic]], and non aromatic porphyrinoid macrocycles are known.<ref>{{cite journal | vauthors = Yoon ZS, Osuka A, Kim D | title = Möbius aromaticity and antiaromaticity in expanded porphyrins | journal = Nature Chemistry | volume = 1 | issue = 2 | pages = 113–122 | date = May 2009 | pmid = 21378823 | doi = 10.1038/nchem.172 | author-link2 = Atsuhiro Osuka | bibcode = 2009NatCh...1..113Y }}</ref>
 
== See also ==
Line 201 ⟶ 195:
* Corphins, the highly reduced porphyrin coordinated to nickel that binds the [[Cofactor F430]] active site in [[methyl coenzyme M reductase]] (MCR)
* Nitrogen-substituted porphyrins: [[phthalocyanine]]
 
==Gallery==
<gallery>
File:H2TPP.png|Lewis structure for ''meso''-tetraphenylporphyrin
File:Meso-tetraphenylporphyrin UV-vis.JPG|[[Ultraviolet–visible spectroscopy|UV–vis]] readout for ''meso''-tetraphenylporphyrin
File:Porfirina activada con la luz.svg|Light-activated porphyrin. Monatomic oxygen. Cellular aging
</gallery>
 
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== References ==
Retrieved from "https://en.wikipedia.org/wiki/Porphyrin"