Simultaneous Electrochemical Speciation of Oxidized and Reduced Glutathione. Redox Profiling of Oxidative Stress in Biological Fluids with a Modified Carbon Electrode
The simultaneous electrochemical quantification of oxidized (GSSG) and reduced glutathione (GSH), biomarkers of oxidative stress, is demonstrated in biological fluids. The detection was accomplished by the development of a modified carbon electrode and was applied to the analysis of biological fluid...
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| Veröffentlicht in: | Analytical chemistry (Washington) 2017-10, Vol.89 (20), p.10726-10733 |
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| creator | Olmos Moya, Patricia M Martínez Alfaro, Minerva Kazemi, Rezvan Alpuche-Avilés, Mario A Griveau, Sophie Bedioui, Fethi Gutiérrez Granados, Silvia |
| description | The simultaneous electrochemical quantification of oxidized (GSSG) and reduced glutathione (GSH), biomarkers of oxidative stress, is demonstrated in biological fluids. The detection was accomplished by the development of a modified carbon electrode and was applied to the analysis of biological fluids of model organisms under oxidative stress caused by lead intoxication. Nanocomposite molecular material based on cobalt phthalocyanine (CoPc) and multiwalled carbon nanotubes functionalized with carboxyl groups (MWCNTf) was developed to modify glassy carbon electrodes (GCE) for the detection of reduced and oxidized glutathione. The morphology of the nanocomposite film was characterized by scanning electron microscopy (SEM) and profilometry. The electrochemical behavior of the modified electrode was assessed by cyclic voltammetry (CV) to determine the surface coverage (Γ) by CoPc. The electrocatalytic behavior of the modified electrode toward reduced (GSH) and oxidized (GSSG) forms of glutathione was assessed by CV studies at physiological pH. The obtained results show that the combined use of CoPc and MWCNTf results in an electrocatalytic activity for GSH oxidation and GSSG reduction, enabling the simultaneous detection of both species. Differential pulse voltammetry reveals detection limits of 100 μM for GSH and 8.3 μM for GSSG, respectively. The potential interference from ascorbic acid, cysteine, glutamic acid, and glucose was also studied, and the obtained results show limited effects from these species. Finally, the hybrid electrode was used for the determination of GSH and GSSG in rat urine and plasma samples, intoxicated or not by lead. Both glutathione forms were detected in these complex biological matrixes without any pretreatment. Our results portray the role of GSH and GSSG as markers of oxidative stress in live organisms under lead intoxication. |
| doi_str_mv | 10.1021/acs.analchem.7b01690 |
| format | Article |
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Redox Profiling of Oxidative Stress in Biological Fluids with a Modified Carbon Electrode</title><source>ACS Publications</source><source>MEDLINE</source><creator>Olmos Moya, Patricia M ; Martínez Alfaro, Minerva ; Kazemi, Rezvan ; Alpuche-Avilés, Mario A ; Griveau, Sophie ; Bedioui, Fethi ; Gutiérrez Granados, Silvia</creator><creatorcontrib>Olmos Moya, Patricia M ; Martínez Alfaro, Minerva ; Kazemi, Rezvan ; Alpuche-Avilés, Mario A ; Griveau, Sophie ; Bedioui, Fethi ; Gutiérrez Granados, Silvia</creatorcontrib><description>The simultaneous electrochemical quantification of oxidized (GSSG) and reduced glutathione (GSH), biomarkers of oxidative stress, is demonstrated in biological fluids. The detection was accomplished by the development of a modified carbon electrode and was applied to the analysis of biological fluids of model organisms under oxidative stress caused by lead intoxication. Nanocomposite molecular material based on cobalt phthalocyanine (CoPc) and multiwalled carbon nanotubes functionalized with carboxyl groups (MWCNTf) was developed to modify glassy carbon electrodes (GCE) for the detection of reduced and oxidized glutathione. The morphology of the nanocomposite film was characterized by scanning electron microscopy (SEM) and profilometry. The electrochemical behavior of the modified electrode was assessed by cyclic voltammetry (CV) to determine the surface coverage (Γ) by CoPc. The electrocatalytic behavior of the modified electrode toward reduced (GSH) and oxidized (GSSG) forms of glutathione was assessed by CV studies at physiological pH. The obtained results show that the combined use of CoPc and MWCNTf results in an electrocatalytic activity for GSH oxidation and GSSG reduction, enabling the simultaneous detection of both species. Differential pulse voltammetry reveals detection limits of 100 μM for GSH and 8.3 μM for GSSG, respectively. The potential interference from ascorbic acid, cysteine, glutamic acid, and glucose was also studied, and the obtained results show limited effects from these species. Finally, the hybrid electrode was used for the determination of GSH and GSSG in rat urine and plasma samples, intoxicated or not by lead. Both glutathione forms were detected in these complex biological matrixes without any pretreatment. Our results portray the role of GSH and GSSG as markers of oxidative stress in live organisms under lead intoxication.</description><identifier>ISSN: 0003-2700</identifier><identifier>EISSN: 1520-6882</identifier><identifier>DOI: 10.1021/acs.analchem.7b01690</identifier><identifier>PMID: 28853561</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Analytical chemistry ; Animals ; Ascorbic acid ; Biological effects ; Biomarkers ; Body Fluids - metabolism ; Carbon ; Chemical Sciences ; Chemistry ; Cobalt ; Computational fluid dynamics ; Detection limits ; Electrochemical analysis ; Electrochemical Techniques - methods ; Electrochemistry ; Electrodes ; Electron microscopy ; Fluids ; Glassy carbon ; Glutamic acid ; Glutathione ; Glutathione - analysis ; Glutathione - blood ; Glutathione - urine ; Glutathione Disulfide - analysis ; Glutathione Disulfide - blood ; Glutathione Disulfide - urine ; Indoles - chemistry ; Intoxication ; Lead ; Limit of Detection ; Male ; Multi wall carbon nanotubes ; Nanocomposites ; Nanocomposites - chemistry ; Nanotechnology ; Nanotubes ; Nanotubes, Carbon - chemistry ; Organometallic Compounds - chemistry ; Oxidation ; Oxidation-Reduction ; Oxidative Stress ; pH effects ; Pretreatment ; Rats ; Rats, Wistar ; Scanning electron microscopy ; Speciation ; Urine ; Voltammetry</subject><ispartof>Analytical chemistry (Washington), 2017-10, Vol.89 (20), p.10726-10733</ispartof><rights>Copyright © 2017 American Chemical Society</rights><rights>Copyright American Chemical Society Oct 17, 2017</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a410t-da32c70e3822d3ab1a4b87135b78e36286e6f5f987af805bd3938d30ef86b1c3</citedby><cites>FETCH-LOGICAL-a410t-da32c70e3822d3ab1a4b87135b78e36286e6f5f987af805bd3938d30ef86b1c3</cites><orcidid>0000-0003-2615-4115 ; 0000-0002-7983-7721</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.analchem.7b01690$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.analchem.7b01690$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28853561$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-03919368$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Olmos Moya, Patricia M</creatorcontrib><creatorcontrib>Martínez Alfaro, Minerva</creatorcontrib><creatorcontrib>Kazemi, Rezvan</creatorcontrib><creatorcontrib>Alpuche-Avilés, Mario A</creatorcontrib><creatorcontrib>Griveau, Sophie</creatorcontrib><creatorcontrib>Bedioui, Fethi</creatorcontrib><creatorcontrib>Gutiérrez Granados, Silvia</creatorcontrib><title>Simultaneous Electrochemical Speciation of Oxidized and Reduced Glutathione. Redox Profiling of Oxidative Stress in Biological Fluids with a Modified Carbon Electrode</title><title>Analytical chemistry (Washington)</title><addtitle>Anal. Chem</addtitle><description>The simultaneous electrochemical quantification of oxidized (GSSG) and reduced glutathione (GSH), biomarkers of oxidative stress, is demonstrated in biological fluids. The detection was accomplished by the development of a modified carbon electrode and was applied to the analysis of biological fluids of model organisms under oxidative stress caused by lead intoxication. Nanocomposite molecular material based on cobalt phthalocyanine (CoPc) and multiwalled carbon nanotubes functionalized with carboxyl groups (MWCNTf) was developed to modify glassy carbon electrodes (GCE) for the detection of reduced and oxidized glutathione. The morphology of the nanocomposite film was characterized by scanning electron microscopy (SEM) and profilometry. The electrochemical behavior of the modified electrode was assessed by cyclic voltammetry (CV) to determine the surface coverage (Γ) by CoPc. The electrocatalytic behavior of the modified electrode toward reduced (GSH) and oxidized (GSSG) forms of glutathione was assessed by CV studies at physiological pH. The obtained results show that the combined use of CoPc and MWCNTf results in an electrocatalytic activity for GSH oxidation and GSSG reduction, enabling the simultaneous detection of both species. Differential pulse voltammetry reveals detection limits of 100 μM for GSH and 8.3 μM for GSSG, respectively. The potential interference from ascorbic acid, cysteine, glutamic acid, and glucose was also studied, and the obtained results show limited effects from these species. Finally, the hybrid electrode was used for the determination of GSH and GSSG in rat urine and plasma samples, intoxicated or not by lead. Both glutathione forms were detected in these complex biological matrixes without any pretreatment. Our results portray the role of GSH and GSSG as markers of oxidative stress in live organisms under lead intoxication.</description><subject>Analytical chemistry</subject><subject>Animals</subject><subject>Ascorbic acid</subject><subject>Biological effects</subject><subject>Biomarkers</subject><subject>Body Fluids - metabolism</subject><subject>Carbon</subject><subject>Chemical Sciences</subject><subject>Chemistry</subject><subject>Cobalt</subject><subject>Computational fluid dynamics</subject><subject>Detection limits</subject><subject>Electrochemical analysis</subject><subject>Electrochemical Techniques - methods</subject><subject>Electrochemistry</subject><subject>Electrodes</subject><subject>Electron microscopy</subject><subject>Fluids</subject><subject>Glassy carbon</subject><subject>Glutamic acid</subject><subject>Glutathione</subject><subject>Glutathione - analysis</subject><subject>Glutathione - blood</subject><subject>Glutathione - urine</subject><subject>Glutathione Disulfide - analysis</subject><subject>Glutathione Disulfide - blood</subject><subject>Glutathione Disulfide - urine</subject><subject>Indoles - chemistry</subject><subject>Intoxication</subject><subject>Lead</subject><subject>Limit of Detection</subject><subject>Male</subject><subject>Multi wall carbon nanotubes</subject><subject>Nanocomposites</subject><subject>Nanocomposites - chemistry</subject><subject>Nanotechnology</subject><subject>Nanotubes</subject><subject>Nanotubes, Carbon - chemistry</subject><subject>Organometallic Compounds - chemistry</subject><subject>Oxidation</subject><subject>Oxidation-Reduction</subject><subject>Oxidative Stress</subject><subject>pH effects</subject><subject>Pretreatment</subject><subject>Rats</subject><subject>Rats, Wistar</subject><subject>Scanning electron microscopy</subject><subject>Speciation</subject><subject>Urine</subject><subject>Voltammetry</subject><issn>0003-2700</issn><issn>1520-6882</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp9kc1u1DAUhS0EokPhDRCyxAYWGa7j_DjLMuoP0qAipnvLsW86rjzxYCel8EA8Jw6ZKRILVrauvnPO1T2EvGawZJCzD0rHpeqV01vcLesWWNXAE7JgZQ5ZJUT-lCwAgGd5DXBCXsR4B8BYwp6Tk1yIkpcVW5BfG7sb3aB69GOk5w71EPxkabVydLNHbdVgfU99R68frLE_0VDVG_oVzajT_9KNgxq2CcHlNPQP9EvwnXW2vz2KksM90s0QMEZqe_rReudv_yRcuNGaSL_bYUsV_eyN7WxyXanQptDDPgZfkmedchFfHd5TcnNxfrO6ytbXl59WZ-tMFQyGzCie6xqQizw3XLVMFa2oGS_bWiCvclFh1ZVdI2rVCShbwxsuDAfsRNUyzU_J-9l2q5zcB7tT4Yf0ysqrs7WcZsAb1vBK3LPEvpvZffDfRoyD3Nmo0bn5ljJxvCmA8Sqhb_9B7_wYUncTJQDqooQ6UcVM6eBjDNg9bsBATpXLVLk8Vi4PlSfZm4P52O7QPIqOHScAZmCS_w3-n-dvfpG8QQ</recordid><startdate>20171017</startdate><enddate>20171017</enddate><creator>Olmos Moya, Patricia M</creator><creator>Martínez Alfaro, Minerva</creator><creator>Kazemi, Rezvan</creator><creator>Alpuche-Avilés, Mario A</creator><creator>Griveau, Sophie</creator><creator>Bedioui, Fethi</creator><creator>Gutiérrez Granados, Silvia</creator><general>American Chemical Society</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>7QF</scope><scope>7QO</scope><scope>7QQ</scope><scope>7SC</scope><scope>7SE</scope><scope>7SP</scope><scope>7SR</scope><scope>7TA</scope><scope>7TB</scope><scope>7TM</scope><scope>7U5</scope><scope>7U7</scope><scope>7U9</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>H94</scope><scope>JG9</scope><scope>JQ2</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>P64</scope><scope>7X8</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0003-2615-4115</orcidid><orcidid>https://orcid.org/0000-0002-7983-7721</orcidid></search><sort><creationdate>20171017</creationdate><title>Simultaneous Electrochemical Speciation of Oxidized and Reduced Glutathione. Redox Profiling of Oxidative Stress in Biological Fluids with a Modified Carbon Electrode</title><author>Olmos Moya, Patricia M ; Martínez Alfaro, Minerva ; Kazemi, Rezvan ; Alpuche-Avilés, Mario A ; Griveau, Sophie ; Bedioui, Fethi ; Gutiérrez Granados, Silvia</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a410t-da32c70e3822d3ab1a4b87135b78e36286e6f5f987af805bd3938d30ef86b1c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Analytical chemistry</topic><topic>Animals</topic><topic>Ascorbic acid</topic><topic>Biological effects</topic><topic>Biomarkers</topic><topic>Body Fluids - metabolism</topic><topic>Carbon</topic><topic>Chemical Sciences</topic><topic>Chemistry</topic><topic>Cobalt</topic><topic>Computational fluid dynamics</topic><topic>Detection limits</topic><topic>Electrochemical analysis</topic><topic>Electrochemical Techniques - methods</topic><topic>Electrochemistry</topic><topic>Electrodes</topic><topic>Electron microscopy</topic><topic>Fluids</topic><topic>Glassy carbon</topic><topic>Glutamic acid</topic><topic>Glutathione</topic><topic>Glutathione - analysis</topic><topic>Glutathione - blood</topic><topic>Glutathione - urine</topic><topic>Glutathione Disulfide - analysis</topic><topic>Glutathione Disulfide - blood</topic><topic>Glutathione Disulfide - urine</topic><topic>Indoles - chemistry</topic><topic>Intoxication</topic><topic>Lead</topic><topic>Limit of Detection</topic><topic>Male</topic><topic>Multi wall carbon nanotubes</topic><topic>Nanocomposites</topic><topic>Nanocomposites - chemistry</topic><topic>Nanotechnology</topic><topic>Nanotubes</topic><topic>Nanotubes, Carbon - chemistry</topic><topic>Organometallic Compounds - chemistry</topic><topic>Oxidation</topic><topic>Oxidation-Reduction</topic><topic>Oxidative Stress</topic><topic>pH effects</topic><topic>Pretreatment</topic><topic>Rats</topic><topic>Rats, Wistar</topic><topic>Scanning electron microscopy</topic><topic>Speciation</topic><topic>Urine</topic><topic>Voltammetry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Olmos Moya, Patricia M</creatorcontrib><creatorcontrib>Martínez Alfaro, Minerva</creatorcontrib><creatorcontrib>Kazemi, Rezvan</creatorcontrib><creatorcontrib>Alpuche-Avilés, Mario A</creatorcontrib><creatorcontrib>Griveau, Sophie</creatorcontrib><creatorcontrib>Bedioui, Fethi</creatorcontrib><creatorcontrib>Gutiérrez Granados, Silvia</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Biotechnology Research Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion Abstracts</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Materials Business File</collection><collection>Mechanical & Transportation Engineering Abstracts</collection><collection>Nucleic Acids Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Toxicology Abstracts</collection><collection>Virology and AIDS Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Copper Technical Reference Library</collection><collection>AIDS and Cancer Research Abstracts</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>Civil Engineering Abstracts</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Computer and Information Systems Abstracts Academic</collection><collection>Computer and Information Systems Abstracts Professional</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Analytical chemistry (Washington)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Olmos Moya, Patricia M</au><au>Martínez Alfaro, Minerva</au><au>Kazemi, Rezvan</au><au>Alpuche-Avilés, Mario A</au><au>Griveau, Sophie</au><au>Bedioui, Fethi</au><au>Gutiérrez Granados, Silvia</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Simultaneous Electrochemical Speciation of Oxidized and Reduced Glutathione. Redox Profiling of Oxidative Stress in Biological Fluids with a Modified Carbon Electrode</atitle><jtitle>Analytical chemistry (Washington)</jtitle><addtitle>Anal. Chem</addtitle><date>2017-10-17</date><risdate>2017</risdate><volume>89</volume><issue>20</issue><spage>10726</spage><epage>10733</epage><pages>10726-10733</pages><issn>0003-2700</issn><eissn>1520-6882</eissn><abstract>The simultaneous electrochemical quantification of oxidized (GSSG) and reduced glutathione (GSH), biomarkers of oxidative stress, is demonstrated in biological fluids. The detection was accomplished by the development of a modified carbon electrode and was applied to the analysis of biological fluids of model organisms under oxidative stress caused by lead intoxication. Nanocomposite molecular material based on cobalt phthalocyanine (CoPc) and multiwalled carbon nanotubes functionalized with carboxyl groups (MWCNTf) was developed to modify glassy carbon electrodes (GCE) for the detection of reduced and oxidized glutathione. The morphology of the nanocomposite film was characterized by scanning electron microscopy (SEM) and profilometry. The electrochemical behavior of the modified electrode was assessed by cyclic voltammetry (CV) to determine the surface coverage (Γ) by CoPc. The electrocatalytic behavior of the modified electrode toward reduced (GSH) and oxidized (GSSG) forms of glutathione was assessed by CV studies at physiological pH. The obtained results show that the combined use of CoPc and MWCNTf results in an electrocatalytic activity for GSH oxidation and GSSG reduction, enabling the simultaneous detection of both species. Differential pulse voltammetry reveals detection limits of 100 μM for GSH and 8.3 μM for GSSG, respectively. The potential interference from ascorbic acid, cysteine, glutamic acid, and glucose was also studied, and the obtained results show limited effects from these species. Finally, the hybrid electrode was used for the determination of GSH and GSSG in rat urine and plasma samples, intoxicated or not by lead. Both glutathione forms were detected in these complex biological matrixes without any pretreatment. Our results portray the role of GSH and GSSG as markers of oxidative stress in live organisms under lead intoxication.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>28853561</pmid><doi>10.1021/acs.analchem.7b01690</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0003-2615-4115</orcidid><orcidid>https://orcid.org/0000-0002-7983-7721</orcidid></addata></record> |
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| source | ACS Publications; MEDLINE |
| subjects | Analytical chemistry Animals Ascorbic acid Biological effects Biomarkers Body Fluids - metabolism Carbon Chemical Sciences Chemistry Cobalt Computational fluid dynamics Detection limits Electrochemical analysis Electrochemical Techniques - methods Electrochemistry Electrodes Electron microscopy Fluids Glassy carbon Glutamic acid Glutathione Glutathione - analysis Glutathione - blood Glutathione - urine Glutathione Disulfide - analysis Glutathione Disulfide - blood Glutathione Disulfide - urine Indoles - chemistry Intoxication Lead Limit of Detection Male Multi wall carbon nanotubes Nanocomposites Nanocomposites - chemistry Nanotechnology Nanotubes Nanotubes, Carbon - chemistry Organometallic Compounds - chemistry Oxidation Oxidation-Reduction Oxidative Stress pH effects Pretreatment Rats Rats, Wistar Scanning electron microscopy Speciation Urine Voltammetry |
| title | Simultaneous Electrochemical Speciation of Oxidized and Reduced Glutathione. Redox Profiling of Oxidative Stress in Biological Fluids with a Modified Carbon Electrode |
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