sulfenic acids

Summary

Summary: Oxy acids of sulfur with the general formula RSOH, where R is an alkyl or aryl group such as CH3. They are often encountered as esters and halides. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed)

Top Publications

  1. Reddie K, Seo Y, Muse Iii W, Leonard S, Carroll K. A chemical approach for detecting sulfenic acid-modified proteins in living cells. Mol Biosyst. 2008;4:521-31 pubmed publisher
    ..For this approach, we have synthesized the probe DAz-1, which is chemically selective for sulfenic acids and cell permeable...
  2. Klomsiri C, NELSON K, Bechtold E, Soito L, Johnson L, Lowther W, et al. Use of dimedone-based chemical probes for sulfenic acid detection evaluation of conditions affecting probe incorporation into redox-sensitive proteins. Methods Enzymol. 2010;473:77-94 pubmed publisher
    b>Sulfenic acids, formed as transient intermediates during the reaction of cysteine residues with peroxides, play significant roles in enzyme catalysis and regulation, and are also involved in the redox regulation of transcription factors ..
  3. Kettenhofen N, Wood M. Formation, reactivity, and detection of protein sulfenic acids. Chem Res Toxicol. 2010;23:1633-46 pubmed publisher
    ..Pioneering studies that have provided a framework for our current understanding of protein-SOH as well as state-of-the-art proteomic strategies designed for global assessments of this post-translational modification are highlighted. ..
  4. Reynaert N, van Der Vliet A, Guala A, McGovern T, Hristova M, Pantano C, et al. Dynamic redox control of NF-kappaB through glutaredoxin-regulated S-glutathionylation of inhibitory kappaB kinase beta. Proc Natl Acad Sci U S A. 2006;103:13086-91 pubmed
    ..Collectively, these findings demonstrate the physiological relevance of the S-glutathionylation-GRX redox module in controlling the magnitude of activation of the NF-kappaB pathway. ..
  5. Noguchi T, Nojiri M, Takei K, Odaka M, Kamiya N. Protonation structures of Cys-sulfinic and Cys-sulfenic acids in the photosensitive nitrile hydratase revealed by Fourier transform infrared spectroscopy. Biochemistry. 2003;42:11642-50 pubmed
    ..There is further speculation that either of these groups is hydrogen bonded to a reactant water molecule, increasing its basicity to facilitate the nucleophilic attack on the nitrile substrate bound to the iron center. ..
  6. Carballal S, Radi R, Kirk M, Barnes S, Freeman B, Alvarez B. Sulfenic acid formation in human serum albumin by hydrogen peroxide and peroxynitrite. Biochemistry. 2003;42:9906-14 pubmed
  7. Poole L, Karplus P, Claiborne A. Protein sulfenic acids in redox signaling. Annu Rev Pharmacol Toxicol. 2004;44:325-47 pubmed
    ..Depending on environment, sometimes the sulfenic acid provides a metastable oxidized form, and other times it is a fleeting intermediate giving rise to more stable disulfide, sulfinic acid, or sulfenyl-amide forms. ..
  8. Vaidya V, Ingold K, Pratt D. Garlic: source of the ultimate antioxidants--sulfenic acids. Angew Chem Int Ed Engl. 2009;48:157-60 pubmed publisher
  9. Charles R, Schröder E, May G, Free P, Gaffney P, Wait R, et al. Protein sulfenation as a redox sensor: proteomics studies using a novel biotinylated dimedone analogue. Mol Cell Proteomics. 2007;6:1473-84 pubmed
    Protein sulfenic acids are reactive intermediates in the catalytic cycles of many enzymes as well as the in formation of other redox states...

More Information

Publications62

  1. Leonard S, Reddie K, Carroll K. Mining the thiol proteome for sulfenic acid modifications reveals new targets for oxidation in cells. ACS Chem Biol. 2009;4:783-99 pubmed publisher
    ..The combination of selective chemical enrichment and live-cell compatibility makes DAz-2 a powerful new tool with the potential to reveal new regulatory mechanisms in signaling pathways and identify new therapeutic targets. ..
  2. Wetzelberger K, Baba S, Thirunavukkarasu M, Ho Y, Maulik N, Barski O, et al. Postischemic deactivation of cardiac aldose reductase: role of glutathione S-transferase P and glutaredoxin in regeneration of reduced thiols from sulfenic acids. J Biol Chem. 2010;285:26135-48 pubmed publisher
    ..During myocardial ischemia, the activity of AR is increased due to the oxidation of its cysteine residues to sulfenic acids. It is not known, however, whether the activated, sulfenic form of the protein (AR-SOH) is converted back to ..
  3. Lo Conte M, Carroll K. The redox biochemistry of protein sulfenylation and sulfinylation. J Biol Chem. 2013;288:26480-8 pubmed publisher
    ..This minireview discusses selected recent examples of protein sulfenylation and sulfinylation from the literature, highlighting the role of these post-translational modifications in cell signaling. ..
  4. Salmeen A, Andersen J, Myers M, Meng T, Hinks J, Tonks N, et al. Redox regulation of protein tyrosine phosphatase 1B involves a sulphenyl-amide intermediate. Nature. 2003;423:769-73 pubmed
  5. Seo Y, Carroll K. Profiling protein thiol oxidation in tumor cells using sulfenic acid-specific antibodies. Proc Natl Acad Sci U S A. 2009;106:16163-8 pubmed publisher
  6. Turell L, Carballal S, Botti H, Radi R, Alvarez B. Oxidation of the albumin thiol to sulfenic acid and its implications in the intravascular compartment. Braz J Med Biol Res. 2009;42:305-11 pubmed
    ..Oxidized forms of albumin are increased in different pathophysiological conditions and sulfenic acid lies in a mechanistic junction, relating oxidizing species to final thiol oxidation products. ..
  7. Wu J, Cheng Z, Reddie K, Carroll K, Hammad L, Karty J, et al. RegB kinase activity is repressed by oxidative formation of cysteine sulfenic acid. J Biol Chem. 2013;288:4755-62 pubmed publisher
    ..Cys-265 thus functions as a complex redox switch that can form multiple thiol modifications in response to different redox signals to control the kinase activity of RegB. ..
  8. Yeh J, Claiborne A, Hol W. Structure of the native cysteine-sulfenic acid redox center of enterococcal NADH peroxidase refined at 2.8 A resolution. Biochemistry. 1996;35:9951-7 pubmed publisher
    ..J., III, Parsonage, D., Poole, L. B., & Claiborne, A. (1995) Biochemistry 34, 14114-14124] has also been generated to assist in analyzing the chemical mechanism of sulfenic acid reduction...
  9. Saurin A, Neubert H, Brennan J, Eaton P. Widespread sulfenic acid formation in tissues in response to hydrogen peroxide. Proc Natl Acad Sci U S A. 2004;101:17982-7 pubmed
    ..signal generation was fully blocked by pretreatment with dimedone, consistent with its reactivity with sulfenic acids to form a covalent adduct that is nonreducible by thiols...
  10. Fuangthong M, Helmann J. The OhrR repressor senses organic hydroperoxides by reversible formation of a cysteine-sulfenic acid derivative. Proc Natl Acad Sci U S A. 2002;99:6690-5 pubmed
    ..In the presence of organic hydroperoxides, OhrR is inactivated by the reversible oxidation of a single conserved cysteine residue to the corresponding cysteine-sulfenic acid, and perhaps to higher oxidation states. ..
  11. Turell L, Botti H, Carballal S, Radi R, Alvarez B. Sulfenic acid--a key intermediate in albumin thiol oxidation. J Chromatogr B Analyt Technol Biomed Life Sci. 2009;877:3384-92 pubmed publisher
  12. Claiborne A, Miller H, Parsonage D, Ross R. Protein-sulfenic acid stabilization and function in enzyme catalysis and gene regulation. FASEB J. 1993;7:1483-90 pubmed
    b>Sulfenic acids (R-SOH) result from the stoichiometric oxidations of thiols with mild oxidants such as H2O2; in solution, however, these derivatives accumulate only transiently due to rapid self-condensation reactions, further oxidations ..
  13. Poole L, Klomsiri C, Knaggs S, Furdui C, NELSON K, Thomas M, et al. Fluorescent and affinity-based tools to detect cysteine sulfenic acid formation in proteins. Bioconjug Chem. 2007;18:2004-17 pubmed
  14. Dalle Donne I, Carini M, Orioli M, Vistoli G, Regazzoni L, Colombo G, et al. Protein carbonylation: 2,4-dinitrophenylhydrazine reacts with both aldehydes/ketones and sulfenic acids. Free Radic Biol Med. 2009;46:1411-9 pubmed publisher
    ..we demonstrate that DNPH is not exclusively selective for carbonyl groups, because it also reacts with sulfenic acids, forming a DNPH adduct, through the acid-catalyzed formation of a thioaldehyde intermediate that is further ..
  15. Mansuy D, Dansette P. Sulfenic acids as reactive intermediates in xenobiotic metabolism. Arch Biochem Biophys. 2011;507:174-85 pubmed publisher
    ..However few data are presently available on the formation and fate of sulfenic acids as reactive intermediates during the metabolism of xenobiotics...
  16. Turell L, Botti H, Carballal S, Ferrer Sueta G, Souza J, Duran R, et al. Reactivity of sulfenic acid in human serum albumin. Biochemistry. 2008;47:358-67 pubmed
    ..6 +/- 0.2, 2.9 +/- 0.5, 9.3 +/- 0.9, and 55 +/- 3 M-1 s-1 (25 degrees C, pH 7.4), respectively, supporting a role for HSA-SOH in the formation of mixed disulfides. ..
  17. Carballal S, Alvarez B, Turell L, Botti H, Freeman B, Radi R. Sulfenic acid in human serum albumin. Amino Acids. 2007;32:543-51 pubmed
    ..Sulfenic acid in HSA could be involved in mixed disufide formation, supporting a role of HSA-Cys34 as an important redox regulator in extracellular compartments. ..
  18. Van Montfort R, Congreve M, Tisi D, Carr R, Jhoti H. Oxidation state of the active-site cysteine in protein tyrosine phosphatase 1B. Nature. 2003;423:773-7 pubmed
    ..The sulphenyl-amide is a protective intermediate in the oxidative inhibition of PTP1B. In addition, it may facilitate reactivation of PTP1B by biological thiols and signal a unique state of the protein. ..
  19. Reddie K, Carroll K. Expanding the functional diversity of proteins through cysteine oxidation. Curr Opin Chem Biol. 2008;12:746-54 pubmed publisher
  20. Rehder D, Borges C. Cysteine sulfenic acid as an intermediate in disulfide bond formation and nonenzymatic protein folding. Biochemistry. 2010;49:7748-55 pubmed publisher
    ..In total, the data presented expose a chemically ubiquitous role for Cys-SOH in solutions of free cysteine-containing protein exposed to air. ..
  21. Tom C, Crellin J, Motiwala H, Stone M, Davda D, Walker W, et al. Chemoselective ratiometric imaging of protein S-sulfenylation. Chem Commun (Camb). 2017;53:7385-7388 pubmed publisher
    Here we report a ratiometric fluorescent probe for chemoselective conjugation to sulfenic acids in living cells...
  22. Dansette P, Libraire J, Bertho G, Mansuy D. Metabolic oxidative cleavage of thioesters: evidence for the formation of sulfenic acid intermediates in the bioactivation of the antithrombotic prodrugs ticlopidine and clopidogrel. Chem Res Toxicol. 2009;22:369-73 pubmed publisher
    ..They also provide a first detailed mechanism for the previously described formation of pharmacologically active thiols such as 3a upon oxidative metabolism of ticlopidine and clopidogrel. ..
  23. Krämer A, Thulstrup P, Lund M, Davies M. Key role of cysteine residues and sulfenic acids in thermal- and H2O2-mediated modification of ?-lactoglobulin. Free Radic Biol Med. 2016;97:544-555 pubmed publisher
    ..These mechanistic insights provide potential strategies for modulating the extent of modification of proteins exposed to thermal and oxidant treatment. ..
  24. Burns R, Moniri N. Agonist- and hydrogen peroxide-mediated oxidation of the ?2 adrenergic receptor: evidence of receptor s-sulfenation as detected by a modified biotin-switch assay. J Pharmacol Exp Ther. 2011;339:914-21 pubmed publisher
    ..ROS, specifically H(2)O(2), are able to post-translationally oxidize protein cysteine sulfhydryls to cysteine-sulfenic acids, the goal of the current study was to assess whether ROS are capable of S-sulfenating ?(2)AR...
  25. Truong T, Garcia F, Seo Y, Carroll K. Isotope-coded chemical reporter and acid-cleavable affinity reagents for monitoring protein sulfenic acids. Bioorg Med Chem Lett. 2011;21:5015-20 pubmed publisher
    We have developed an approach that allows relative quantification of protein sulfenic acids using a pair of light and heavy isotope labled probes, DAz-2 and d(6)-DAz-2...
  26. Bonnet D, Stevens J, de Sousa R, Sari M, Mansuy D, Artaud I. New inhibitors of iron-containing nitrile hydratases. J Biochem. 2001;130:227-33 pubmed
    ..in the literature emphasizing the significance of the post-translational modification of cysteine thiols to sulfenic acids (SOH), which have been found in a number of proteins...
  27. Peixoto A, Geyer R, Iqbal A, Truzzi D, Soares Moretti A, Laurindo F, et al. Peroxynitrite preferentially oxidizes the dithiol redox motifs of protein-disulfide isomerase. J Biol Chem. 2018;293:1450-1465 pubmed publisher
    ..confirmed that peroxynitrite preferentially oxidizes the redox-active Cys residues of PDI to the corresponding sulfenic acids, which reacted with the resolving thiols at the active sites to produce disulfides (i.e...
  28. Kim H, Kim J. Thioredoxin as a reducing agent for mammalian methionine sulfoxide reductases B lacking resolving cysteine. Biochem Biophys Res Commun. 2008;371:490-4 pubmed publisher
    ..The present study provides evidence that the sulfenic acid intermediate of oxidized MsrBs lacking resolving Cys could interact with Trx and be directly reduced by this protein. ..
  29. Heppner D, Janssen Heininger Y, van Der Vliet A. The role of sulfenic acids in cellular redox signaling: Reconciling chemical kinetics and molecular detection strategies. Arch Biochem Biophys. 2017;616:40-46 pubmed publisher
    ..Cysteine oxidation is diverse in nature and involves various post-translational modifications (sulfenic acids, disulfides, etc...
  30. Reisz J, Bechtold E, King S, Poole L, Furdui C. Thiol-blocking electrophiles interfere with labeling and detection of protein sulfenic acids. FEBS J. 2013;280:6150-61 pubmed publisher
    ..The implications of this reactivity on detection methods for protein sulfenic acids and S-nitrosothiols are discussed.
  31. Bruschi M, Petretto A, Candiano G, Musante L, Movilli E, Santucci L, et al. Determination of the oxido-redox status of plasma albumin in hemodialysis patients. J Chromatogr B Analyt Technol Biomed Life Sci. 2008;864:29-37 pubmed publisher
    ..LC-ESI-MS/MS was crucial to characterize albumin in conditions of oxidation stress; surrogate techniques can mirror conformational changes induced by oxidation. ..
  32. Tutunji M, Qaisi A, El Eswed B, Tutunji L. Reactions of sulfenic acid with 2-mercaptoethanol: a mechanism for the inhibition of gastric (H+-K+)-adenosine triphosphate by omeprazole. J Pharm Sci. 2007;96:196-208 pubmed
    ..Due to this irreversibility, D+ and sulfenic acid were not rapidly interconvertable. The present work suggests that the active inhibitor is the sulfenic acid. ..
  33. Arakawa T, Kawano Y, Kataoka S, Katayama Y, Kamiya N, Yohda M, et al. Structure of thiocyanate hydrolase: a new nitrile hydratase family protein with a novel five-coordinate cobalt(III) center. J Mol Biol. 2007;366:1497-509 pubmed
  34. Denu J, Tanner K. Specific and reversible inactivation of protein tyrosine phosphatases by hydrogen peroxide: evidence for a sulfenic acid intermediate and implications for redox regulation. Biochemistry. 1998;37:5633-42 pubmed
    ..A chemical mechanism for reversible inactivation involving a cysteine sulfenic acid intermediate is proposed. ..
  35. Grigoryan H, Li H, Iavarone A, Williams E, Rappaport S. Cys34 adducts of reactive oxygen species in human serum albumin. Chem Res Toxicol. 2012;25:1633-42 pubmed publisher
    ..Parallel measurements of a negative control detected only small amounts of the Cys34 sulfonic acid and the (proposed) sulfinamide and did not detect the sulfinic acid...
  36. Kulathu Y, Garcia F, Mevissen T, Busch M, Arnaudo N, Carroll K, et al. Regulation of A20 and other OTU deubiquitinases by reversible oxidation. Nat Commun. 2013;4:1569 pubmed publisher
    ..Using chemical tools to detect sulphenic acid intermediates, we show that many ovarian tumour deubiquitinases undergo reversible oxidation upon treatment with H2O2, revealing a new mechanism to regulate deubiquitinase activity. ..
  37. Race P, Bentley M, Melvin J, Crow A, Hughes R, Smith W, et al. Crystal structure of Streptococcus pyogenes sortase A: implications for sortase mechanism. J Biol Chem. 2009;284:6924-33 pubmed publisher
    ..These new insights into sortase structure and function could have important consequences for inhibitor design. ..
  38. Ali S, Karamat S, Kóňa J, Fabian W. Theoretical prediction of pKa values of seleninic, selenenic, sulfinic, and carboxylic acids by quantum-chemical methods. J Phys Chem A. 2010;114:12470-8 pubmed publisher
    ..54, R(2) = 0.94, a = 0.83). Sulfenic (selenenic) acid tautomers are significantly more stable than the corresponding sulfoxide (selenoxide) forms. ..
  39. Poor C, Chen P, Duguid E, Rice P, He C. Crystal structures of the reduced, sulfenic acid, and mixed disulfide forms of SarZ, a redox active global regulator in Staphylococcus aureus. J Biol Chem. 2009;284:23517-24 pubmed publisher
    ..These structures help to understand redox-mediated virulence regulation in S. aureus and activation of the MarR family proteins in general. ..
  40. Burgoyne J, Eaton P. A rapid approach for the detection, quantification, and discovery of novel sulfenic acid or S-nitrosothiol modified proteins using a biotin-switch method. Methods Enzymol. 2010;473:281-303 pubmed publisher
    ..This chapter provides an overview of these biotin-switch methods, and explores its impact on the field of redox biology, including recent advances as well as limitations associated with this technique. ..
  41. Picklo M, Idso J, Jackson M. S-Glutathionylation of hepatic and visceral adipose proteins decreases in obese rats. Obesity (Silver Spring). 2013;21:297-305 pubmed publisher
    ..The tissue levels of protein sulfenic acids (PSOH) and PSSG in liver, visceral adipose tissue, and skeletal muscle derived from glucose intolerant, obese-..
  42. Truong T, Carroll K. Redox regulation of epidermal growth factor receptor signaling through cysteine oxidation. Biochemistry. 2012;51:9954-65 pubmed publisher
  43. Aversa M, Barattucci A, Bonaccorsi P, Marino Merlo F, Mastino A, Sciortino M. Synthesis and biological testing of thioalkane- and thioarene-spaced bis-beta-D-glucopyranosides. Bioorg Med Chem. 2009;17:1456-63 pubmed publisher
    ..A more detailed investigation of one of the two compounds ascertains that this effect is attributable to induction of cell death by apoptosis. ..
  44. Huang C, Zhu W, Xu Y, Qian X. [Chemical approaches for trapping protein thiols and their oxidative modification]. Yao Xue Xue Bao. 2012;47:280-90 pubmed
    ..We also look into the future of the development of fluorescent probes for protein thiols and their potential application in the research of reactive cysteine proteomes and early detection of redox-related diseases. ..
  45. Shen C, Hong Z, Parkin K. Fate and kinetic modeling of reactivity of alkanesulfenic acids and thiosulfinates in model systems and onion homogenates. J Agric Food Chem. 2002;50:2652-9 pubmed
  46. Raftery M, Yang Z, Valenzuela S, Geczy C. Novel intra- and inter-molecular sulfinamide bonds in S100A8 produced by hypochlorite oxidation. J Biol Chem. 2001;276:33393-401 pubmed
    ..Similar modifications in other proteins could potentially regulate normal and pathological processes during aging, atherogenesis, fibrosis, and neurogenerative diseases. ..
  47. Barrett T, Pattison D, Leonard S, Carroll K, Davies M, Hawkins C. Inactivation of thiol-dependent enzymes by hypothiocyanous acid: role of sulfenyl thiocyanate and sulfenic acid intermediates. Free Radic Biol Med. 2012;52:1075-85 pubmed publisher
    ..Experiments with DAz-2, a cell-permeable chemical trap for sulfenic acids, demonstrate that these intermediates are formed on many cellular proteins, including GAPDH and CK, in ..
  48. Ma L, Takanishi C, Wood M. Molecular mechanism of oxidative stress perception by the Orp1 protein. J Biol Chem. 2007;282:31429-36 pubmed
    ..The results of our study suggest that attempts to identify novel redox-regulated proteins and signal transduction pathways should focus on characterization of low pK(a) cysteines. ..
  49. Antico Arciuch V, Galli S, Franco M, Lam P, Cadenas E, Carreras M, et al. Akt1 intramitochondrial cycling is a crucial step in the redox modulation of cell cycle progression. PLoS ONE. 2009;4:e7523 pubmed publisher
    ..These results indicate that Akt1 intramitochondrial-cycling is central for redox modulation of cell fate. ..
  50. Heppner D, Hristova M, Ida T, Mijuskovic A, Dustin C, Bogdándi V, et al. Cysteine perthiosulfenic acid (Cys-SSOH): A novel intermediate in thiol-based redox signaling?. Redox Biol. 2018;14:379-385 pubmed publisher
    ..cysteine residues (Cys-SH) is a key reaction in cellular redox signaling involving initial formation of sulfenic acids (Cys-SOH), which are commonly detected using selective dimedone-based probes...
  51. Gupta V, Carroll K. Sulfenic acid chemistry, detection and cellular lifetime. Biochim Biophys Acta. 2014;1840:847-75 pubmed publisher
    ..Advanced methods allow for direct chemical trapping of protein sulfenic acids directly in cells and tissues...
  52. Yang J, Groen A, Lemeer S, Jans A, Slijper M, Roe S, et al. Reversible oxidation of the membrane distal domain of receptor PTPalpha is mediated by a cyclic sulfenamide. Biochemistry. 2007;46:709-19 pubmed
    ..Conformational changes associated with RPTPalpha D2 oxidation have implications for RPTPalpha quaternary structure and allosteric regulation of D1 phosphatase activity. ..
  53. Sohn J, Rudolph J. Catalytic and chemical competence of regulation of cdc25 phosphatase by oxidation/reduction. Biochemistry. 2003;42:10060-70 pubmed
    ..Thus, the chemistry and kinetics of the active-site cysteines of the Cdc25's support a physiological role for reversible redox-mediated regulation of the Cdc25's, important regulators of the eukaryotic cell cycle. ..