Iron–sulfur clusters are molecular ensembles of iron and sulfide. They are most often discussed in the context of the biological role for iron–sulfur proteins, which are pervasive.[2] Many Fe–S clusters are known in the area of organometallic chemistry and as precursors to synthetic analogues of the biological clusters (see Figure). It is believed that the last universal common ancestor had many iron-sulfur clusters.[3]
Structure of [Fe4S4(SMe)4]2−, a synthetic analogue of 4Fe–4S cofactors.[1]
Organometallic Fe–S clusters include the sulfido carbonyls with the formula Fe2S2(CO)6, H2Fe3S(CO)9, and Fe3S2(CO)9. Compounds are also known that incorporate cyclopentadienyl ligands, such as (C5H5)4Fe4S4.[4]
Figure. Illustrative synthetic Fe–S clusters. From left to right: Fe3S2(CO)9, [Fe3S(CO)9]2−, (C5H5)4Fe4S4, and [Fe4S4Cl4]2−.
Inorganic materialsedit
This section needs expansion. You can help by adding to it. (November 2022)
Iron–sulfur clusters occur in many biological systems, often as components of electron transfer proteins. The ferredoxin proteins are the most common Fe–S clusters in nature. They feature either 2Fe–2S or 4Fe–4S centers. They occur in all branches of life.[5]
Fe–S clusters can be classified according to their Fe:S stoichiometry [2Fe–2S], [4Fe–3S], [3Fe–4S], and [4Fe–4S].[6] The [4Fe–4S] clusters occur in two forms: normal ferredoxins and high potential iron proteins (HiPIP). Both adopt cuboidal structures, but they utilize different oxidation states. They are found in all forms of life.[7]
The relevant redox couple in all Fe–S proteins is Fe(II)/Fe(III).[7]
Many clusters have been synthesized in the laboratory with the formula [Fe4S4(SR)4]2−, which are known for many R substituents, and with many cations. Variations have been prepared including the incomplete cubanes [Fe3S4(SR)3]3−.[8]
The Rieske proteins contain Fe–S clusters that coordinate as a 2Fe–2S structure and can be found in the membrane bound cytochrome bc1 complex III in the mitochondria of eukaryotes and bacteria. They are also a part of the proteins of the chloroplast such as the cytochrome b6f complex in photosynthetic organisms. These photosynthetic organisms include plants, green algae, and cyanobacteria, the bacterial precursor to chloroplasts. Both are part of the electron transport chain of their respective organisms which is a crucial step in the energy harvesting for many organisms.[9]
In some instances Fe–S clusters are redox-inactive, but are proposed to have structural roles. Examples include endonuclease III and MutY.[5][10]
^Axel Kern; Christian Näther; Felix Studt; Felix Tuczek (2004). "Application of a Universal Force Field to Mixed Fe/Mo−S/Se Cubane and Heterocubane Clusters. 1. Substitution of Sulfur by Selenium in the Series [Fe4X4(YCH3)4]2-; X = S/Se and Y = S/Se". Inorg. Chem. 43 (16): 5003–5010. doi:10.1021/ic030347d. PMID 15285677.
^S. J. Lippard, J. M. Berg "Principles of Bioinorganic Chemistry" University Science Books: Mill Valley, CA; 1994. ISBN0-935702-73-3.
^Weiss, Madeline C., et al. "The physiology and habitat of the last universal common ancestor." Nature microbiology 1.9 (2016): 1-8.
^ abJohnson, D. C.; Dean, D. R.; Smith, A. D.; Johnson, M. K. (2005). "Structure, function, and formation of biological iron-sulfur clusters". Annual Review of Biochemistry. 74: 247–281. doi:10.1146/annurev.biochem.74.082803.133518. PMID 15952888.
^Lill, Roland (2015). "Issue of iron-sulfur protein". Biochimica et Biophysica Acta. 1853 (6): 1251–1252. doi:10.1016/j.bbamcr.2015.03.001. PMC5501863. PMID 25746719.
^ abFisher, N (1998). "Intramolecular electron transfer in [4Fe–4S)]". The EMBO Journal: 849–858.
^Rao, P. V.; Holm, R. H. (2004). "Synthetic Analogues of the Active Sites of Iron-Sulfur Proteins". Chem. Rev. 104 (2): 527─559. doi:10.1021/Cr020615+. PMID 14871134.
^BIOLOGICAL INORGANIC CHEMISTRY: structure and reactivity. [S.l.]: UNIVERSITY SCIENCE BOOKS. 2018. ISBN978-1-938787-96-6. OCLC 1048090793.
^Guan, Y.; Manuel, R. C.; Arvai, A. S.; Parikh, S. S.; Mol, C. D.; Miller, J. H.; Lloyd, S.; Tainer, J. A. (December 1998). "MutY catalytic core, mutant and bound adenine structures define specificity for DNA repair enzyme superfamily". Nature Structural Biology. 5 (12): 1058–1064. doi:10.1038/4168. ISSN 1072-8368. PMID 9846876. S2CID 22085836.
External linksedit
December 15, 2023
iron, sulfur, cluster, biological, clusters, iron, sulfur, protein, molecular, ensembles, iron, sulfide, they, most, often, discussed, context, biological, role, iron, sulfur, proteins, which, pervasive, many, clusters, known, area, organometallic, chemistry, . For biological Fe S clusters see iron sulfur protein Iron sulfur clusters are molecular ensembles of iron and sulfide They are most often discussed in the context of the biological role for iron sulfur proteins which are pervasive 2 Many Fe S clusters are known in the area of organometallic chemistry and as precursors to synthetic analogues of the biological clusters see Figure It is believed that the last universal common ancestor had many iron sulfur clusters 3 Structure of Fe4S4 SMe 4 2 a synthetic analogue of 4Fe 4S cofactors 1 Contents 1 Organometallic clusters 2 Inorganic materials 3 Biological Fe S clusters 4 See also 5 References 6 External linksOrganometallic clusters editOrganometallic Fe S clusters include the sulfido carbonyls with the formula Fe2S2 CO 6 H2Fe3S CO 9 and Fe3S2 CO 9 Compounds are also known that incorporate cyclopentadienyl ligands such as C5H5 4Fe4S4 4 nbsp Figure Illustrative synthetic Fe S clusters From left to right Fe3S2 CO 9 Fe3S CO 9 2 C5H5 4Fe4S4 and Fe4S4Cl4 2 Inorganic materials editThis section needs expansion You can help by adding to it November 2022 nbsp Structure of potassium dithioferrate which features infinite chains of Fe III centers Biological Fe S clusters editMain article iron sulfur protein Iron sulfur clusters occur in many biological systems often as components of electron transfer proteins The ferredoxin proteins are the most common Fe S clusters in nature They feature either 2Fe 2S or 4Fe 4S centers They occur in all branches of life 5 Fe S clusters can be classified according to their Fe S stoichiometry 2Fe 2S 4Fe 3S 3Fe 4S and 4Fe 4S 6 The 4Fe 4S clusters occur in two forms normal ferredoxins and high potential iron proteins HiPIP Both adopt cuboidal structures but they utilize different oxidation states They are found in all forms of life 7 The relevant redox couple in all Fe S proteins is Fe II Fe III 7 Many clusters have been synthesized in the laboratory with the formula Fe4S4 SR 4 2 which are known for many R substituents and with many cations Variations have been prepared including the incomplete cubanes Fe3S4 SR 3 3 8 The Rieske proteins contain Fe S clusters that coordinate as a 2Fe 2S structure and can be found in the membrane bound cytochrome bc1 complex III in the mitochondria of eukaryotes and bacteria They are also a part of the proteins of the chloroplast such as the cytochrome b6f complex in photosynthetic organisms These photosynthetic organisms include plants green algae and cyanobacteria the bacterial precursor to chloroplasts Both are part of the electron transport chain of their respective organisms which is a crucial step in the energy harvesting for many organisms 9 In some instances Fe S clusters are redox inactive but are proposed to have structural roles Examples include endonuclease III and MutY 5 10 See also editBioinorganic chemistryReferences edit Axel Kern Christian Nather Felix Studt Felix Tuczek 2004 Application of a Universal Force Field to Mixed Fe Mo S Se Cubane and Heterocubane Clusters 1 Substitution of Sulfur by Selenium in the Series Fe4X4 YCH3 4 2 X S Se and Y S Se Inorg Chem 43 16 5003 5010 doi 10 1021 ic030347d PMID 15285677 S J Lippard J M Berg Principles of Bioinorganic Chemistry University Science Books Mill Valley CA 1994 ISBN 0 935702 73 3 Weiss Madeline C et al The physiology and habitat of the last universal common ancestor Nature microbiology 1 9 2016 1 8 Ogino H Inomata S Tobita H 1998 Abiological Iron Sulfur Clusters Chem Rev 98 6 2093 2122 doi 10 1021 cr940081f PMID 11848961 a b Johnson D C Dean D R Smith A D Johnson M K 2005 Structure function and formation of biological iron sulfur clusters Annual Review of Biochemistry 74 247 281 doi 10 1146 annurev biochem 74 082803 133518 PMID 15952888 Lill Roland 2015 Issue of iron sulfur protein Biochimica et Biophysica Acta 1853 6 1251 1252 doi 10 1016 j bbamcr 2015 03 001 PMC 5501863 PMID 25746719 a b Fisher N 1998 Intramolecular electron transfer in 4Fe 4S The EMBO Journal 849 858 Rao P V Holm R H 2004 Synthetic Analogues of the Active Sites of Iron Sulfur Proteins Chem Rev 104 2 527 559 doi 10 1021 Cr020615 PMID 14871134 BIOLOGICAL INORGANIC CHEMISTRY structure and reactivity S l UNIVERSITY SCIENCE BOOKS 2018 ISBN 978 1 938787 96 6 OCLC 1048090793 Guan Y Manuel R C Arvai A S Parikh S S Mol C D Miller J H Lloyd S Tainer J A December 1998 MutY catalytic core mutant and bound adenine structures define specificity for DNA repair enzyme superfamily Nature Structural Biology 5 12 1058 1064 doi 10 1038 4168 ISSN 1072 8368 PMID 9846876 S2CID 22085836 External links edit Retrieved from https en wikipedia org w index php title Iron sulfur cluster amp oldid 1177204732, wikipedia, wiki, book, books, library,
