This view shows enzymes only for those organisms listed below, in the list of taxa known to possess the pathway. If an enzyme name is shown in bold, there is experimental evidence for this enzymatic activity.
Synonyms: sulfate respiration
|Superclasses:||Degradation/Utilization/Assimilation → Inorganic Nutrients Metabolism → Sulfur Compounds Metabolism → Sulfate Reduction|
|Generation of Precursor Metabolites and Energy → Respiration → Anaerobic Respiration|
Some taxa known to possess this pathway include : Archaeoglobus fulgidus , Archaeoglobus profundus , Bilophila wadsworthia RZATAU , Desulfotomaculum australicum , Desulfotomaculum geothermicum , Desulfotomaculum kuznetsovii , Desulfotomaculum nigrificans , Desulfovibrio desulfuricans , Desulfovibrio gigas , Desulfovibrio multispirans , Desulfovibrio sulfodismutans , Desulfovibrio vulgaris , Desulfovibrio vulgaris Hildenborough , Thermodesulfobacterium commune , Thermodesulforhabdus norvegica , Thermodesulfovibrio yellowstonii
Sulfate is one of the most common electron acceptors for anaerobic respiration. Sulfate-reducing organisms are ubiquitous in anaerobic environments such as soil, sediments, marine and freshwaters, and the mouth and gut of many animals [Pires06]. Sulfate-reducers contribute greatly to the global cycling of carbon and sulfur, mostly in marine habitats, where the sulfate concentration is high. It is estimated that dissimilatory sulfate reduction is responsible for up to 50% of carbon remineralization in marine environments [Klenk97].
Dissimilatory sulfate-reducing prokaryotes are a heterogenous group of bacteria and archaea consisting of diverse phyla such as Archaeoglobi [Dahl01], Proteobacteria [Beeder95], Firmicutes [Daumas88], Nitrospirae [Henry94] and others that can use sulfate as a terminal electron acceptor. During the process, sulfate is ultimately reduced to hydrogen sulfide through the intermediates adenosine 5'-phosphosulfate (APS) and sulfite. The reduction of sulfate to sulfite requires two electrons at a standard redox potential (E0') of -516 mV, which is too high for physiological electron carriers [Thauer77]. This problem is solved by the formation of a mixed anhydride between the sulfate and phosphate, as in adenosine 5'-phosphosulfate (APS). This linkage lowers the potential to E0' = -60 mV, which is easilly negotiateded by biological reductants [Berndt04].
About This Pathway
All steps of sulfate reduction occur in the cytoplasm, implying that sulfate must be transported across the cytoplasmic membrane into the cell. Sulfate is activated with ATP in a reaction catalyzed by sulfate adenylyltransferase, resulting in the formation of adenosine 5'-phosphosulfate (APS) and pyrophosphate. This enzyme has an unfavorable equilibrium (Keq ~ 10-7 M) in the direction of APS formation, and it has been postulated that the reaction is driven by the hydrolysis of PPi by a ubiquitous inorganic pyrophosphatase [Segel87] and the favorable adenylylsulfate reductase reaction which consumes the product.
The next step is the reduction of APS to sulfite and AMP, which is catalyzed by adenylylsulfate reductase, for which the natural electron donor is not known.
The last enzyme in the pathway, dissimilatory sulfite reductase catalyzes the six-electron reduction of sulfite to sulfide, the main energy-conserving step in sulfate respiration. Dissimilatory sulfite reductases (DSRs) are present in all studied organisms capable of reducing sulfite to sulfide during anaerobic respiration. All DSR enzymes contain siroheme and [4Fe-4S] prosthetic centers, and they are classified according to their spectroscopic properties in four major groups which are: desulfoviridins (found in all Desulfovibrio strains [Lee71]), desulfurubidins (discovered in a mutant Desulfovibrio desulfuricans strain unable to synthethize desulfoviridin [Lee73]), desulfofuscidin (discovered in Thermodesulfobacterium commune [Hatchikian83]), and P582 (found in members of the Desulfotomaculum genus [Akagi73]).
The subunit structure was initially described as α2β2. Following the discovery of a third subunit, an α2β2γ2 structure was proposed for some organisms including Desulfovibrio vulgaris, Desulfovibrio gigas, Desulfovibrio desulfuricans [Pierik92] and Bilophila wadsworthia RZATAU [Laue01]. However, it is now accepted that the DsrC dimer is not a subunit of the sufite reductase, but rather a protein with which it interacts [Oliveira08].
A a mechanism for the process of sulfite reduction has been proposed: DsrAB persulfurates the DsrC sulfur carrier protein at one of its two conserved cysteine residues. DsrC then dissociates from the sulfite reductase, followed by the reduction of the persulfide by the second conserved cysteine. This results in release of hydrogen sulfide and the formation of an intramolecular disulfide in DsrC. Regeneration of the DsrC disulfide may be catalyzed by the DsrK subunit of the DsrMKJOP transmembrane complex (a membrane complex with disulfide/thiol reductase activity) [Oliveira08, Grein10].
Akagi73: Akagi JM, Adams V (1973). "Isolation of a bisulfite reductase activity from Desulfotomaculum nigrificans and its identification as the carbon monoxide-binding pigment P582." J Bacteriol 116(1);392-6. PMID: 4745421
Beeder95: Beeder J, Torsvik T, Lien T (1995). "Thermodesulforhabdus norvegicus gen. nov., sp. nov., a novel thermophilic sulfate-reducing bacterium from oil field water." Arch Microbiol 164(5);331-6. PMID: 8572886
Berndt04: Berndt C, Lillig CH, Wollenberg M, Bill E, Mansilla MC, de Mendoza D, Seidler A, Schwenn JD (2004). "Characterization and reconstitution of a 4Fe-4S adenylyl sulfate/phosphoadenylyl sulfate reductase from Bacillus subtilis." J Biol Chem 279(9);7850-5. PMID: 14627706
Daumas88: Daumas S, Cord-Ruwisch R, Garcia JL (1988). "Desulfotomaculum geothermicum sp. nov., a thermophilic, fatty acid-degrading, sulfate-reducing bacterium isolated with H2 from geothermal ground water." Antonie Van Leeuwenhoek 54(2);165-78. PMID: 3395110
Grein10: Grein F, Pereira IA, Dahl C (2010). "Biochemical Characterization of Individual Components of the Allochromatium vinosum DsrMKJOP Transmembrane Complex Aids Understanding of Complex Function In Vivo." J Bacteriol 192(24);6369-77. PMID: 20952577
Henry94: Henry EA, Devereux R, Maki JS, Gilmour CC, Woese CR, Mandelco L, Schauder R, Remsen CC, Mitchell R (1994). "Characterization of a new thermophilic sulfate-reducing bacterium Thermodesulfovibrio yellowstonii, gen. nov. and sp. nov.: its phylogenetic relationship to Thermodesulfobacterium commune and their origins deep within the bacterial domain." Arch Microbiol 161(1);62-9. PMID: 11541228
Klenk97: Klenk HP, Clayton RA, Tomb JF, White O, Nelson KE, Ketchum KA, Dodson RJ, Gwinn M, Hickey EK, Peterson JD, Richardson DL, Kerlavage AR, Graham DE, Kyrpides NC, Fleischmann RD, Quackenbush J, Lee NH, Sutton GG, Gill S, Kirkness EF, Dougherty BA, McKenney K, Adams MD, Loftus B, Peterson S, Reich CI, McNeil LK, Badger JH, Glodek A, Zhou L, Overbeek R, Gocayne JD, Weidman JF, McDonald L, Utterback T, Cotton MD, Spriggs T, Artiach P, Kaine BP, Sykes SM, Sadow PW, D'Andrea KP, Bowman C, Fujii C, Garland SA, Mason TM, Olsen GJ, Fraser CM, Smith HO, Woese CR, Venter JC (1997). "The complete genome sequence of the hyperthermophilic, sulphate-reducing archaeon Archaeoglobus fulgidus." Nature 390(6658);364-70. PMID: 9389475
Laue01: Laue H, Friedrich M, Ruff J, Cook AM (2001). "Dissimilatory sulfite reductase (desulfoviridin) of the taurine-degrading, non-sulfate-reducing bacterium Bilophila wadsworthia RZATAU contains a fused DsrB-DsrD subunit." J Bacteriol 183(5);1727-33. PMID: 11160104
Lee71: Lee JP, Peck HD (1971). "Purification of the enzyme reducing bisulfite to trithionate from Desulfovibrio gigas and its identification as desulfoviridin." Biochem Biophys Res Commun 45(3);583-9. PMID: 5128167
Lee73: Lee JP, Yi CS, LeGall J, Peck HD (1973). "Isolation of a new pigment, desulforubidin, from Desulfovibrio desulfuricans (Norway strain) and its role in sulfite reduction." J Bacteriol 115(1);453-5. PMID: 4717523
Oliveira08: Oliveira TF, Vonrhein C, Matias PM, Venceslau SS, Pereira IA, Archer M (2008). "The crystal structure of Desulfovibrio vulgaris dissimilatory sulfite reductase bound to DsrC provides novel insights into the mechanism of sulfate respiration." J Biol Chem 283(49);34141-9. PMID: 18829451
Pierik92: Pierik AJ, Duyvis MG, van Helvoort JM, Wolbert RB, Hagen WR (1992). "The third subunit of desulfoviridin-type dissimilatory sulfite reductases." Eur J Biochem 1992;205(1);111-5. PMID: 1555572
Pires06: Pires RH, Venceslau SS, Morais F, Teixeira M, Xavier AV, Pereira IA (2006). "Characterization of the Desulfovibrio desulfuricans ATCC 27774 DsrMKJOP complex--a membrane-bound redox complex involved in the sulfate respiratory pathway." Biochemistry 45(1);249-62. PMID: 16388601
Abola99: Abola AP, Willits MG, Wang RC, Long SR (1999). "Reduction of adenosine-5'-phosphosulfate instead of 3'-phosphoadenosine-5'-phosphosulfate in cysteine biosynthesis by Rhizobium meliloti and other members of the family Rhizobiaceae." J Bacteriol 181(17);5280-7. PMID: 10464198
Chen91c: Chen L, Liu MY, Le Gall J (1991). "Calcium is required for the reduction of sulfite from hydrogen in a reconstituted electron transfer chain from the sulfate reducing bacterium, Desulfovibrio gigas." Biochem Biophys Res Commun 1991;180(1);238-42. PMID: 1930220
Cort08: Cort JR, Selan U, Schulte A, Grimm F, Kennedy MA, Dahl C (2008). "Allochromatium vinosum DsrC: solution-state NMR structure, redox properties, and interaction with DsrEFH, a protein essential for purple sulfur bacterial sulfur oxidation." J Mol Biol 382(3);692-707. PMID: 18656485
Dahl90: Dahl, C., Koch, H., Keuken, O., Trueper, H.G. (1990). "Purification and characterization of ATP sulfurylase from the extremely thermophilic archaebacterial sulfate-reducer, Archaeoglobus fulgidus." FEMS Microbiol. Let. 67: 27-32.
Dahl93: Dahl C, Kredich NM, Deutzmann R, Truper HG (1993). "Dissimilatory sulphite reductase from Archaeoglobus fulgidus: physico-chemical properties of the enzyme and cloning, sequencing and analysis of the reductase genes." J Gen Microbiol 139(8);1817-28. PMID: 7691984
Frederiksen03: Frederiksen TM, Finster K (2003). "Sulfite-oxido-reductase is involved in the oxidation of sulfite in Desulfocapsa sulfoexigens during disproportionation of thiosulfate and elemental sulfur." Biodegradation 14(3);189-98. PMID: 12889609
Fritz00: Fritz G, Buchert T, Huber H, Stetter KO, Kroneck PM (2000). "Adenylylsulfate reductases from archaea and bacteria are 1:1 alphabeta-heterodimeric iron-sulfur flavoenzymes--high similarity of molecular properties emphasizes their central role in sulfur metabolism." FEBS Lett 473(1);63-6. PMID: 10802060
Fritz02: Fritz G, Roth A, Schiffer A, Buchert T, Bourenkov G, Bartunik HD, Huber H, Stetter KO, Kroneck PM, Ermler U (2002). "Structure of adenylylsulfate reductase from the hyperthermophilic Archaeoglobus fulgidus at 1.6-A resolution." Proc Natl Acad Sci U S A 99(4);1836-41. PMID: 11842205
Gavel98: Gavel OY, Bursakov SA, Calvete JJ, George GN, Moura JJ, Moura I (1998). "ATP sulfurylases from sulfate-reducing bacteria of the genus Desulfovibrio. A novel metalloprotein containing cobalt and zinc." Biochemistry 1998;37(46);16225-32. PMID: 9819214
Hatzfeld00: Hatzfeld Y, Lee S, Lee M, Leustek T, Saito K (2000). "Functional characterization of a gene encoding a fourth ATP sulfurylase isoform from Arabidopsis thaliana." Gene 2000;248(1-2);51-8. PMID: 10806350
Higuchi87: Higuchi, Y.,, Inaka, K., Yasuoka, N., Yagi, T. (1987). "Isolation and crystallization of high molecular weight cytochrome from Desulfovibrio vulgaris Hildenborough." Biochim. Biophys. Acta 911:341-348.
Huang91: Huang CJ, Barrett EL (1991). "Sequence analysis and expression of the Salmonella typhimurium asr operon encoding production of hydrogen sulfide from sulfite." J Bacteriol 173(4);1544-53. PMID: 1704886
KarkhoffSchweiz95: Karkhoff-Schweizer RR, Huber DP, Voordouw G (1995). "Conservation of the genes for dissimilatory sulfite reductase from Desulfovibrio vulgaris and Archaeoglobus fulgidus allows their detection by PCR." Appl Environ Microbiol 61(1);290-6. PMID: 7887608
Kobayashi72a: Kobayashi K, Takahashi E, Ishimoto M (1972). "Biochemical studies on sulfate-reducing bacteria. XI. Purification and some properties of sulfite reductase, desulfoviridin." J Biochem (Tokyo) 72(4);879-87. PMID: 4644321
Lampreia90: Lampreia J, Moura I, Teixeira M, Peck HD, Legall J, Huynh BH, Moura JJ (1990). "The active centers of adenylylsulfate reductase from Desulfovibrio gigas. Characterization and spectroscopic studies." Eur J Biochem 1990;188(3);653-64. PMID: 2158885
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