Mechanism of copper-catalyzed autoxidation of cysteine
The kinetics of copper-catalyzed autoxidation of cysteine and its derivatives were investigated using oxygen consumption, spectroscopy and hydroxyl radical detection by fluorescence of a coumarin probe. The process has complex two-phase kinetics. During the first phase a stoichiometric amount of oxy...
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| Veröffentlicht in: | Free radical research 1999-01, Vol.31 (1), p.23-34 |
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| creator | Kachur, Alexander V. Koch, Cameron J. Biaglow, John E. |
| description | The kinetics of copper-catalyzed autoxidation of cysteine and its derivatives were investigated using oxygen consumption, spectroscopy and hydroxyl radical detection by fluorescence of a coumarin probe. The process has complex two-phase kinetics. During the first phase a stoichiometric amount of oxygen (0.25 moles per mole of thiol) is consumed without production of hydroxyl radicals. In the second reaction phase excess oxygen is consumed in a hydrogen peroxide-mediated process with significant ·OH production. The reaction rate in the second phase is decreased for cysteine derivatives with a free aminogroup and increased for compounds with a modified aminogroup. The kinetic data suggest the catalytic action of copper in the form of a cysteine complex. The reaction mechanism consists of two simultaneous reactions (superoxide-dependent and peroxide-dependent) in the first phase, and peroxide-dependent in the second phase. The second reaction phase begins after oxidation of free thiol. This consists of a Fenton-type reaction between cuprous-cysteinyl complex and following oxidation of cysteinyl radical to sulfonate with the consumption of excessive oxygen and significant production of hydroxyl radicals. |
| doi_str_mv | 10.1080/10715769900300571 |
| format | Article |
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The process has complex two-phase kinetics. During the first phase a stoichiometric amount of oxygen (0.25 moles per mole of thiol) is consumed without production of hydroxyl radicals. In the second reaction phase excess oxygen is consumed in a hydrogen peroxide-mediated process with significant ·OH production. The reaction rate in the second phase is decreased for cysteine derivatives with a free aminogroup and increased for compounds with a modified aminogroup. The kinetic data suggest the catalytic action of copper in the form of a cysteine complex. The reaction mechanism consists of two simultaneous reactions (superoxide-dependent and peroxide-dependent) in the first phase, and peroxide-dependent in the second phase. The second reaction phase begins after oxidation of free thiol. This consists of a Fenton-type reaction between cuprous-cysteinyl complex and following oxidation of cysteinyl radical to sulfonate with the consumption of excessive oxygen and significant production of hydroxyl radicals.</description><identifier>ISSN: 1071-5762</identifier><identifier>EISSN: 1029-2470</identifier><identifier>DOI: 10.1080/10715769900300571</identifier><identifier>PMID: 10489117</identifier><language>eng</language><publisher>England: Informa UK Ltd</publisher><subject>Catalase - pharmacology ; copper ; Copper - chemistry ; Cysteine ; Cysteine - chemistry ; Glutathione - chemistry ; hydrogen peroxide ; hydroxyl radical ; Hydroxyl Radical - chemistry ; Kinetics ; Oxidation-Reduction ; Oxygen - chemistry ; Superoxide Dismutase - pharmacology</subject><ispartof>Free radical research, 1999-01, Vol.31 (1), p.23-34</ispartof><rights>1999 Informa UK Ltd All rights reserved: reproduction in whole or part not permitted 1999</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c468t-d905a4f3e687cf03e1431fd939ba38e14ddcfd7b5574966632481ecab51e88553</citedby><cites>FETCH-LOGICAL-c468t-d905a4f3e687cf03e1431fd939ba38e14ddcfd7b5574966632481ecab51e88553</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.tandfonline.com/doi/pdf/10.1080/10715769900300571$$EPDF$$P50$$Ginformaworld$$H</linktopdf><linktohtml>$$Uhttps://www.tandfonline.com/doi/full/10.1080/10715769900300571$$EHTML$$P50$$Ginformaworld$$H</linktohtml><link.rule.ids>314,780,784,27924,27925,59647,60436,61221,61402</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/10489117$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kachur, Alexander V.</creatorcontrib><creatorcontrib>Koch, Cameron J.</creatorcontrib><creatorcontrib>Biaglow, John E.</creatorcontrib><title>Mechanism of copper-catalyzed autoxidation of cysteine</title><title>Free radical research</title><addtitle>Free Radic Res</addtitle><description>The kinetics of copper-catalyzed autoxidation of cysteine and its derivatives were investigated using oxygen consumption, spectroscopy and hydroxyl radical detection by fluorescence of a coumarin probe. The process has complex two-phase kinetics. During the first phase a stoichiometric amount of oxygen (0.25 moles per mole of thiol) is consumed without production of hydroxyl radicals. In the second reaction phase excess oxygen is consumed in a hydrogen peroxide-mediated process with significant ·OH production. The reaction rate in the second phase is decreased for cysteine derivatives with a free aminogroup and increased for compounds with a modified aminogroup. The kinetic data suggest the catalytic action of copper in the form of a cysteine complex. The reaction mechanism consists of two simultaneous reactions (superoxide-dependent and peroxide-dependent) in the first phase, and peroxide-dependent in the second phase. The second reaction phase begins after oxidation of free thiol. This consists of a Fenton-type reaction between cuprous-cysteinyl complex and following oxidation of cysteinyl radical to sulfonate with the consumption of excessive oxygen and significant production of hydroxyl radicals.</description><subject>Catalase - pharmacology</subject><subject>copper</subject><subject>Copper - chemistry</subject><subject>Cysteine</subject><subject>Cysteine - chemistry</subject><subject>Glutathione - chemistry</subject><subject>hydrogen peroxide</subject><subject>hydroxyl radical</subject><subject>Hydroxyl Radical - chemistry</subject><subject>Kinetics</subject><subject>Oxidation-Reduction</subject><subject>Oxygen - chemistry</subject><subject>Superoxide Dismutase - pharmacology</subject><issn>1071-5762</issn><issn>1029-2470</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1999</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp9kD1PwzAQhi0EolD4ASyoE1vAF8exI1hQxZdUxAKz5dpnNVUSFzsRhF9PSjuAkDr5LD3vq7uHkDOgl0AlvQIqgIu8KChllHIBe-QIaFokaSbo_noWkAxAOiLHMS4pBZZxcUhGQDNZAIgjkj-jWeimjPXEu4nxqxWGxOhWV_0X2onuWv9ZWt2WvvkB-thi2eAJOXC6ini6fcfk7f7udfqYzF4enqa3s8RkuWwTW1CuM8cwl8I4yhAyBs4WrJhrJoeftcZZMedcZEWe5yzNJKDRcw4oJedsTC42vavg3zuMrarLaLCqdIO-i0oMl3Mu0wGEDWiCjzGgU6tQ1jr0Cqhay1L_ZA2Z8215N6_R_kps7AzAzQYoG-dDrT98qKxqdV_54IJuTBkV29V__Se-QF21C6MDqqXvQjOI27HdN-oMiPU</recordid><startdate>19990101</startdate><enddate>19990101</enddate><creator>Kachur, Alexander V.</creator><creator>Koch, Cameron J.</creator><creator>Biaglow, John E.</creator><general>Informa UK Ltd</general><general>Taylor & Francis</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>19990101</creationdate><title>Mechanism of copper-catalyzed autoxidation of cysteine</title><author>Kachur, Alexander V. ; Koch, Cameron J. ; Biaglow, John E.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c468t-d905a4f3e687cf03e1431fd939ba38e14ddcfd7b5574966632481ecab51e88553</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1999</creationdate><topic>Catalase - pharmacology</topic><topic>copper</topic><topic>Copper - chemistry</topic><topic>Cysteine</topic><topic>Cysteine - chemistry</topic><topic>Glutathione - chemistry</topic><topic>hydrogen peroxide</topic><topic>hydroxyl radical</topic><topic>Hydroxyl Radical - chemistry</topic><topic>Kinetics</topic><topic>Oxidation-Reduction</topic><topic>Oxygen - chemistry</topic><topic>Superoxide Dismutase - pharmacology</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kachur, Alexander V.</creatorcontrib><creatorcontrib>Koch, Cameron J.</creatorcontrib><creatorcontrib>Biaglow, John E.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Free radical research</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kachur, Alexander V.</au><au>Koch, Cameron J.</au><au>Biaglow, John E.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanism of copper-catalyzed autoxidation of cysteine</atitle><jtitle>Free radical research</jtitle><addtitle>Free Radic Res</addtitle><date>1999-01-01</date><risdate>1999</risdate><volume>31</volume><issue>1</issue><spage>23</spage><epage>34</epage><pages>23-34</pages><issn>1071-5762</issn><eissn>1029-2470</eissn><abstract>The kinetics of copper-catalyzed autoxidation of cysteine and its derivatives were investigated using oxygen consumption, spectroscopy and hydroxyl radical detection by fluorescence of a coumarin probe. The process has complex two-phase kinetics. During the first phase a stoichiometric amount of oxygen (0.25 moles per mole of thiol) is consumed without production of hydroxyl radicals. In the second reaction phase excess oxygen is consumed in a hydrogen peroxide-mediated process with significant ·OH production. The reaction rate in the second phase is decreased for cysteine derivatives with a free aminogroup and increased for compounds with a modified aminogroup. The kinetic data suggest the catalytic action of copper in the form of a cysteine complex. The reaction mechanism consists of two simultaneous reactions (superoxide-dependent and peroxide-dependent) in the first phase, and peroxide-dependent in the second phase. The second reaction phase begins after oxidation of free thiol. This consists of a Fenton-type reaction between cuprous-cysteinyl complex and following oxidation of cysteinyl radical to sulfonate with the consumption of excessive oxygen and significant production of hydroxyl radicals.</abstract><cop>England</cop><pub>Informa UK Ltd</pub><pmid>10489117</pmid><doi>10.1080/10715769900300571</doi><tpages>12</tpages></addata></record> |
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| language | eng |
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| source | MEDLINE; Taylor & Francis Journals Complete |
| subjects | Catalase - pharmacology copper Copper - chemistry Cysteine Cysteine - chemistry Glutathione - chemistry hydrogen peroxide hydroxyl radical Hydroxyl Radical - chemistry Kinetics Oxidation-Reduction Oxygen - chemistry Superoxide Dismutase - pharmacology |
| title | Mechanism of copper-catalyzed autoxidation of cysteine |
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