Porphyrin: Difference between revisions
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{{Short description|Heterocyclic organic compound with four modified pyrrole subunits}} |
{{Short description|Heterocyclic organic compound with four modified pyrrole subunits}} |
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{{Distinguish|Perforin|Porphyran}} |
{{Distinguish|Perforin|Porphyran}} |
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[[File:Porphyrin.svg|thumb|right|[[Porphine]], the parent porphyrin.]] |
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[[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.)]] |
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{{Use dmy dates|date=May 2022}} |
{{Use dmy dates|date=May 2022}} |
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'''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| |
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'''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| |
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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 |
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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]]. |
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==Structure== |
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[[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> |
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==Complexes of porphyrins== |
==Complexes of porphyrins== |
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{{main|Transition metal porphyrin complexes}} |
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<gallery caption="Representative porphyrins and derivatives" widths="140px" heights="100px"> |
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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: |
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File:Porphyrin.svg|[[Porphin]] is the simplest porphyrin, a rare compound of theoretical interest. |
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: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 |
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<gallery caption="Representative porphyrins and derivatives" widths="140px" heights="140px"> |
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File:PPIXtransH.png|Derivatives of [[protoporphyrin IX]] are common in nature, the precursor to [[heme]]s. |
File:PPIXtransH.png|Derivatives of [[protoporphyrin IX]] are common in nature, the precursor to [[heme]]s. |
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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: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. |
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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: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. |
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File:Heme |
File:Heme B.svg|Simplified view of [[heme]], a complex of a protoporphyrin IX. |
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CP40model.png|A macrocycle of 40 porphyrin molecules, model |
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CP40-STM.png|A macrocycle of 40 porphyrin molecules, [[scanning tunneling microscope|STM image]] |
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</gallery> |
</gallery> |
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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: |
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: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 |
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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. |
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==Ancient porphyrins== |
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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> |
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===In nature=== |
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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}} |
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Several heterocycles related to porphyrins are found in nature, almost always bound to metal ions. These include |
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{| class="wikitable" |
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|+ Caption text |
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! N4-macrocycle !! Cofactor name!! metal!! comment |
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| [[corrin]] || vitamin B12 || cobalt||several variants of B12 exist |
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| corphin || [[Cofactor F430]] || nickel||highly reduced macrocycle |
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| [[Sirohydrochlorin]]||none||nickel||biosynthetic intermediate en route to cofactor F430 |
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|- |
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| [[Chlorin]] || chlorophyll || magnesium||several versions of chlorophyll exist |
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| [[bacteriochlorin]]|| [[bacteriochlorophyll]] || magnesium|||several versions of bacteriochlorophyll exist |
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| [[isobacteriochlorin]]||[[isobacteriochlorin]]|| magnesium|| |
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===Synthetic=== |
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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> |
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====Non-natural porphyrin isomers==== |
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[[File:First Porphycene synthesis.tif|thumb|Porphycene, first porphyrin isomer, synthesised from bipyrrole dialdehyde through [[McMurry reaction|McMurry coupling reaction]]]] |
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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. |
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[[File:Isomers of porphyrins soman.jpg|500 px|thumb|center|Various reported Isomers of porphyrin]] |
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==Natural formation== |
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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> |
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==Synthesis== |
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==Biosynthesis== |
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In non-photosynthetic [[eukaryotes]] such as animals, insects, fungi, and [[protozoa]], as well as the |
In non-photosynthetic [[eukaryotes]] such as animals, insects, fungi, and [[protozoa]], as well as the |
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==Laboratory synthesis== |
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{{main|Rothemund reaction}} |
{{main|Rothemund reaction}} |
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[[Image:Tetratolylporphyrin.jpg|thumb|right|Brilliant crystals of ''meso''-tetratolylporphyrin, prepared from [[4-methylbenzaldehyde]] and pyrrole in refluxing [[propionic acid]]]] |
[[Image:Tetratolylporphyrin.jpg|thumb|right|Brilliant crystals of ''meso''-tetratolylporphyrin, prepared from [[4-methylbenzaldehyde]] and pyrrole in refluxing [[propionic acid]]]] |
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A common synthesis 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]]. |
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:[[Image:H2TPPsyn.png|400px]] |
:[[Image:H2TPPsyn.png|400px]] |
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==Potential applications== |
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==Metal complexes== |
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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. |
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==Applications== |
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===Photodynamic therapy=== |
===Photodynamic therapy=== |
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Porphyrins have been evaluated in the context of [[photodynamic therapy]] (PDT) since they strongly absorb light, which is then converted to |
Porphyrins have been evaluated in the context of [[photodynamic therapy]] (PDT) since they strongly absorb light, which is then converted to 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> |
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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> |
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> |
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===Molecular electronics and sensors=== |
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===Organic geochemistry=== |
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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 |
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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}} |
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=== Biological applications === |
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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> |
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=== Toxicology === |
=== Toxicology === |
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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> |
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> |
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==Gallery== |
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=== Biological applications === |
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<gallery> |
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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> |
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File:H2TPP.png|Lewis structure for ''meso''-tetraphenylporphyrin |
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File:Meso-tetraphenylporphyrin UV-vis.JPG|[[Ultraviolet–visible spectroscopy|UV–vis]] readout for ''meso''-tetraphenylporphyrin |
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File:Porfirina activada con la luz.svg|Light-activated porphyrin. Monatomic oxygen. Cellular aging |
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</gallery> |
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{{-}} |
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==Potential applications== |
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==Related species== |
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===Biomimetic catalysis=== |
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===In nature=== |
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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> |
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Several heterocycles related to porphyrins are found in nature, almost always bound to metal ions. These include |
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===Molecular electronics and sensors=== |
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{| class="wikitable" |
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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 |
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|+ Caption text |
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|- |
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! N4-macrocycle !! Cofactor name!! metal!! comment |
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|- |
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|[[chlorin]]|| chlorophyll || magnesium||several versions of chlorophyll exist (sidechain; exception being [[chlorophyll c]]) |
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|- |
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|bacteriochlorin|| [[bacteriochlorophyll]] (in part) || magnesium|||several versions of bacteriochlorophyll exist (sidechain; some use a usual chlorin ring) |
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|- |
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| rowspan="2" | [[sirohydrochlorin]] (an isobacteriochlorin)||[[siroheme]]||iron||Important cofactor in sulfur assimilation |
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|- |
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| |
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| |
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|biosynthetic intermediate en route to cofactor F430 and B12 |
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|- |
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| [[corrin]] || vitamin B12 || cobalt||several variants of B12 exist (sidechain) |
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|- |
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| corphin || [[Cofactor F430]] || nickel||highly reduced macrocycle |
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|} |
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===Synthetic=== |
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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> |
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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> |
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====Non-natural porphyrin isomers==== |
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[[Phthalocyanine]]s, which are structurally related to porphyrins, are used in commerce as dyes and catalysts, but porphyrins are not. |
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[[File:First Porphycene synthesis.tif|thumb|Porphycene, first porphyrin isomer, synthesised from bipyrrole dialdehyde through [[McMurry reaction|McMurry coupling reaction]]]] |
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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. |
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===Supramolecular chemistry=== |
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[[File:Isomers of porphyrins soman.jpg|500 px|thumb|center|Various reported Isomers of porphyrin]] |
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[[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>]] |
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[[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>]] |
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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. |
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===Theoretical interest in aromaticity=== |
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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> |
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== See also == |
== See also == |
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* Corphins, the highly reduced porphyrin coordinated to nickel that binds the [[Cofactor F430]] active site in [[methyl coenzyme M reductase]] (MCR) |
* Corphins, the highly reduced porphyrin coordinated to nickel that binds the [[Cofactor F430]] active site in [[methyl coenzyme M reductase]] (MCR) |
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* Nitrogen-substituted porphyrins: [[phthalocyanine]] |
* Nitrogen-substituted porphyrins: [[phthalocyanine]] |
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==Gallery== |
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<gallery> |
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File:H2TPP.png|Lewis structure for ''meso''-tetraphenylporphyrin |
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File:Meso-tetraphenylporphyrin UV-vis.JPG|[[Ultraviolet–visible spectroscopy|UV–vis]] readout for ''meso''-tetraphenylporphyrin |
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File:Porfirina activada con la luz.svg|Light-activated porphyrin. Monatomic oxygen. Cellular aging |
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</gallery> |
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{{-}} |
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== References == |
== References == |
Latest revision as of 17:29, 21 February 2024
Porphyrins (/ˈpɔːrfərɪn/ POR-fər-in) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their
The parent of porphyrins is porphine, a rare chemical compound of exclusively theoretical interest. Substituted porphines are called porphyrins.[1] With a total of 26
Structure[edit]
Porphyrin complexes consist of a square planar MN4 core. The periphery of the porphyrins, consisting of sp2-hybridized carbons, generally display small deviations from planarity. "Ruffled" or saddle-shaped porphyrins is attributed to interactions of the system with its environment.[5] Additionally, the metal is often not centered in the N4 plane.[6] For free porphyrins, the two pyrrole protons are mutually trans and project out of the N4 plane.[7] These nonplanar distortions are associated with altered chemical and physical properties. Chlorophyll-rings are more distinctly nonplanar, but they are more saturated than porphyrins.[8]
Complexes of porphyrins[edit]
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:
- H2porphyrin + [MLn]2+ → M(porphyrinate)Ln−4 + 4 L + 2 H+, where M = metal ion and L = a ligand
-
Derivatives of protoporphyrin IX are common in nature, the precursor to hemes.
-
Octaethylporphyrin (H2OEP) is a synthetic analogue of protoporphyrin IX. Unlike the natural porphyrin ligands, OEP2− is highly symmetrical.
-
Tetraphenylporphyrin (H2TPP)is another synthetic analogue of protoporphyrin IX. Unlike the natural porphyrin ligands, TPP2− is highly symmetrical. Another difference is that its methyne centers are occupied by phenyl groups.
-
Simplified view of heme, a complex of a protoporphyrin IX.
-
A macrocycle of 40 porphyrin molecules, model
-
A macrocycle of 40 porphyrin molecules, STM image
Ancient porphyrins[edit]
A geoporphyrin, also known as a petroporphyrin, is a porphyrin of geologic origin.[9] They can occur in crude oil, oil shale, coal, or sedimentary rocks.[9][10] Abelsonite is possibly the only geoporphyrin mineral, as it is rare for porphyrins to occur in isolation and form crystals.[11]
The field of organic geochemistry had its origins in the isolation of porphyrins from petroleum.[citation needed] 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]
Biosynthesis[edit]
In non-photosynthetic eukaryotes such as animals, insects, fungi, and protozoa, as well as the
Two molecules of dALA are then combined by porphobilinogen synthase to give porphobilinogen (PBG), which contains a pyrrole ring. Four PBGs are then combined through deamination into hydroxymethyl bilane (HMB), which is hydrolysed to form the circular tetrapyrrole uroporphyrinogen III. This molecule undergoes a number of further modifications. Intermediates are used in different species to form particular substances, but, in humans, the main end-product protoporphyrin IX is combined with iron to form heme. Bile pigments are the breakdown products of heme.
The following scheme summarizes the biosynthesis of porphyrins, with references by EC number and the OMIM database. The porphyria associated with the deficiency of each enzyme is also shown:
Laboratory synthesis[edit]
A common synthesis for porphyrins is the Rothemund reaction, first reported in 1936,[12][13] which is also the basis for more recent methods described by Adler and Longo.[14] The general scheme is a condensation and oxidation process starting with pyrrole and an aldehyde.
Potential applications[edit]
Photodynamic therapy[edit]
Porphyrins have been evaluated in the context of photodynamic therapy (PDT) since they strongly absorb light, which is then converted to heat in the illuminated areas.[15] This technique has been applied in macular degeneration using verteporfin.[16]
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.[17] 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.[18]
Molecular electronics and sensors[edit]
Porphyrin-based compounds are of interest as possible components of molecular electronics and photonics.[19] Synthetic porphyrin dyes have been incorporated in prototype dye-sensitized solar cells.[20][21]
Biological applications[edit]
Porphyrins have been investigated as possible anti-inflammatory agents[22] and evaluated on their anti-cancer and anti-oxidant activity.[23] Several porphyrin-peptide conjugates were found to have antiviral activity against HIV in vitro.[24]
Toxicology[edit]
Heme biosynthesis is used as biomarker in environmental toxicology studies. While excess production of porphyrins indicate organochlorine exposure, lead inhibits ALA dehydratase enzyme.[25]
Gallery[edit]
-
Lewis structure for meso-tetraphenylporphyrin
-
UV–vis readout for meso-tetraphenylporphyrin
-
Light-activated porphyrin. Monatomic oxygen. Cellular aging
Related species[edit]
In nature[edit]
Several heterocycles related to porphyrins are found in nature, almost always bound to metal ions. These include
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) |
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[edit]
A benzoporphyrin is a porphyrin with a benzene ring fused to one of the pyrrole units. e.g. verteporfin is a benzoporphyrin derivative.[26]
Non-natural porphyrin isomers[edit]
The first synthetic porphyrin isomer was reported by Emanual Vogel and coworkers in 1986.[27] This isomer [18]porphyrin-(2.0.2.0) is named as porphycene, and the central N4 Cavity forms a rectangle shape as shown in figure.[28] Porphycenes showed interesting photophysical behavior and found versatile compound towards the photodynamic therapy.[29] This inspired Vogel and Sessler to took up the challenge of preparing [18]porphyrin-(2.1.0.1) and named it as corrphycene or porphycerin.[30] 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.[31] The Japanese scientist Furuta[32] and Polish scientist Latos-Grażyński[33] 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.
See also[edit]
- A porphyrin-related disease: porphyria
- Porphyrin coordinated to iron: heme
- A heme-containing group of enzymes: Cytochrome P450
- Porphyrin coordinated to magnesium: chlorophyll
- The one-carbon-shorter analogues: corroles, including vitamin B12, which is coordinated to a cobalt
- 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
References[edit]
- ^ Rayati S, Malekmohammadi S (2016). "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 of Experimental Nanoscience. 11 (11): 872. Bibcode:2016JENan..11..872R. doi:10.1080/17458080.2016.1179802.
- ^ Ivanov AS, Boldyrev AI (August 2014). "Deciphering aromaticity in porphyrinoids via adaptive natural density partitioning". Organic & Biomolecular Chemistry. 12 (32): 6145–6150. doi:10.1039/C4OB01018C. PMID 25002069.
- ^ Lash TD (2011). "Origin of aromatic character in porphyrinoid systems". Journal of Porphyrins and Phthalocyanines. 15 (11n12): 1093–1115. doi:10.1142/S1088424611004063.
- ^ Harper D, Buglione DC. "porphyria (n.)". The Online Etymology Dictionary. Retrieved 14 September 2014.
- ^ Senge MO, MacGowan SA, O'Brien JM (December 2015). "Conformational control of cofactors in nature - the influence of protein-induced macrocycle distortion on the biological function of tetrapyrroles". Chemical Communications. 51 (96): 17031–17063. doi:10.1039/C5CC06254C. hdl:2262/75305. PMID 26482230.
- ^ Walker FA, Simonis U (2011). "Iron Porphyrin Chemistry". Encyclopedia of Inorganic and Bioinorganic Chemistry. doi:10.1002/9781119951438.eibc0104. ISBN 9781119951438.
- ^ Jentzen W, Ma JG, Shelnutt JA (February 1998). "Conservation of the conformation of the porphyrin macrocycle in hemoproteins". Biophysical Journal. 74 (2 Pt 1): 753–763. Bibcode:1998BpJ....74..753J. doi:10.1016/S0006-3495(98)74000-7. PMC 1302556. PMID 9533688.
- ^ Senge MO, Ryan AA, Letchford KA, MacGowan SA, Mielke T (2014). "Chlorophylls, Symmetry, Chirality, and Photosynthesis". Symmetry. 6 (3): 781–843. Bibcode:2014Symm....6..781S. doi:10.3390/sym6030781. hdl:2262/73843.
- ^ a b Kadish KM, ed. (1999). The Porphyrin Handbook. Elsevier. p. 381. ISBN 9780123932006.
- ^ Zhang B, Lash TD (September 2003). "Total synthesis of the porphyrin mineral abelsonite and related petroporphyrins with five-membered exocyclic rings". Tetrahedron Letters. 44 (39): 7253. doi:10.1016/j.tetlet.2003.08.007.
- ^ Mason GM, Trudell LG, Branthaver JF (1989). "Review of the stratigraphic distribution and diagenetic history of abelsonite". Organic Geochemistry. 14 (6): 585. Bibcode:1989OrGeo..14..585M. doi:10.1016/0146-6380(89)90038-7.
- ^ Rothemund P (1936). "A New Porphyrin Synthesis. The Synthesis of Porphin". J. Am. Chem. Soc. 58 (4): 625–627. doi:10.1021/ja01295a027.
- ^ Rothemund P (1935). "Formation of Porphyrins from Pyrrole and Aldehydes". J. Am. Chem. Soc. 57 (10): 2010–2011. doi:10.1021/ja01313a510.
- ^ Adler AD, Longo FR, Finarelli JD, Goldmacher J, Assour J, Korsakoff L (1967). "A simplified synthesis for meso-tetraphenylporphine". J. Org. Chem. 32 (2): 476. doi:10.1021/jo01288a053.
- ^ Giuntini F, Boyle R, Sibrian-Vazquez M, Vicente MG (2014). "Porphyrin conjugates for cancer therapy". In Kadish KM, Smith KM, Guilard R (eds.). Handbook of Porphyrin Science. Vol. 27. pp. 303–416.
- ^ Wormald R, Evans J, Smeeth L, Henshaw K (July 2007). "Photodynamic therapy for neovascular age-related macular degeneration" (PDF). The Cochrane Database of Systematic Reviews (3): CD002030. doi:10.1002/14651858.CD002030.pub3. PMID 17636693.
- ^ Price M, Terlecky SR, Kessel D (2009). "A role for hydrogen peroxide in the pro-apoptotic effects of photodynamic therapy". Photochemistry and Photobiology. 85 (6): 1491–1496. doi:10.1111/j.1751-1097.2009.00589.x. PMC 2783742. PMID 19659920.
- ^ Singh S, Aggarwal A, Bhupathiraju NV, Arianna G, Tiwari K, Drain CM (September 2015). "Glycosylated Porphyrins, Phthalocyanines, and Other Porphyrinoids for Diagnostics and Therapeutics". Chemical Reviews. 115 (18): 10261–10306. doi:10.1021/acs.chemrev.5b00244. PMC 6011754. PMID 26317756.
- ^ Lewtak JP, Gryko DT (October 2012). "Synthesis of
π -extended porphyrins via intramolecular oxidative coupling". Chemical Communications. 48 (81): 10069–10086. doi:10.1039/c2cc31279d. PMID 22649792. - ^ Walter MG, Rudine AB, Wamser CC (2010). "Porphyrins and phthalocyanines in solar photovoltaic cells". Journal of Porphyrins and Phthalocyanines. 14 (9): 759–792. doi:10.1142/S1088424610002689.
- ^ Yella A, Lee HW, Tsao HN, Yi C, Chandiran AK, Nazeeruddin MK, et al. (November 2011). "Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency". Science. 334 (6056): 629–634. Bibcode:2011Sci...334..629Y. doi:10.1126/science.1209688. PMID 22053043. S2CID 28058582.
- ^ Alonso-Castro AJ, Zapata-Morales JR, Hernández-Munive A, Campos-Xolalpa N, Pérez-Gutiérrez S, Pérez-González C (May 2015). "Synthesis, antinociceptive and anti-inflammatory effects of porphyrins". Bioorganic & Medicinal Chemistry. 23 (10): 2529–2537. doi:10.1016/j.bmc.2015.03.043. PMID 25863493.
- ^ Bajju GD, Ahmed A, Devi G (December 2019). "Synthesis and bioactivity of oxovanadium(IV)tetra(4-methoxyphenyl)porphyrinsalicylates". BMC Chemistry. 13 (1): 15. doi:10.1186/s13065-019-0523-9. PMC 6661832. PMID 31384764.
- ^ Mendonça DA, Bakker M, Cruz-Oliveira C, Neves V, Jiménez MA, Defaus S, et al. (June 2021). "Penetrating the Blood-Brain Barrier with New Peptide-Porphyrin Conjugates Having anti-HIV Activity". Bioconjugate Chemistry. 32 (6): 1067–1077. doi:10.1021/acs.bioconjchem.1c00123. PMC 8485325. PMID 34033716.
- ^ Walker CH, Silby RM, Hopkin SP, Peakall DB (2012). Principles of Ecotoxicology. Boca Raton, FL: CRC Press. p. 182. ISBN 978-1-4665-0260-4.
- ^ Scott LJ, Goa KL (February 2000). "Verteporfin". Drugs & Aging. 16 (2): 139–146, discussion 146–8. doi:10.2165/00002512-200016020-00005. PMID 10755329. S2CID 260491296.
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