Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.
Identifieur interne : 000097 ( Main/Exploration ); précédent : 000096; suivant : 000098Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.
Auteurs : RBID : pubmed:24417718Abstract
An optical impedance spectroscopy (OIS) technique based on a single-mode electro-active-integrated optical waveguide (EA-IOW) was developed to investigate electron-transfer processes of redox adsorbates. A highly sensitive single-mode EA-IOW device was used to optically follow the time-dependent faradaic current originated from a submonolayer of cytochrome c undergoing redox exchanges driven by a harmonic modulation of the electric potential at several dc bias potentials and at several frequencies. To properly retrieve the faradaic current density from the ac-modulated optical signal, we introduce here a mathematical formalism that (i) accounts for intrinsic changes that invariably occur in the optical baseline of the EA-IOW device during potential modulation and (ii) provides accurate results for the electro-chemical parameters. We are able to optically reconstruct the faradaic current density profile against the dc bias potential in the working electrode, identify the formal potential, and determine the energy-width of the electron-transfer process. In addition, by combining the optically reconstructed faradaic signal with simple electrical measurements of impedance across the whole electrochemical cell and the capacitance of the electric double-layer, we are able to determine the time-constant connected to the redox reaction of the adsorbed protein assembly. For cytochrome c directly immobilized onto the indium tin oxide (ITO) surface, we measured a reaction rate constant of 26.5 s(-1). Finally, we calculate the charge-transfer resistance and pseudocapacitance associated with the electron-transfer process and show that the frequency dependence of the redox reaction of the protein submonolayer follows as expected the electrical equivalent of an RC-series admittance diagram. Above all, we show here that OIS with single-mode EA-IOW's provide strong analytical signals that can be readily monitored even for small surface-densities of species involved in the redox process (e.g., fmol/cm(2), 0.1% of a full protein monolayer). This experimental approach, when combined with the analytical formalism described here, brings additional sensitivity, accuracy, and simplicity to electro-chemical analysis and is expected to become a useful tool in investigations of redox processes.
DOI: 10.1021/ac4030736
PubMed: 24417718
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.</title><author><name sortKey="Han, Xue" uniqKey="Han X">Xue Han</name><affiliation wicri:level="1"><nlm:affiliation>Department of Physics and Astronomy, University of Louisville , Louisville, Kentucky 40292, United States.</nlm:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Physics and Astronomy, University of Louisville , Louisville, Kentucky 40292</wicri:regionArea></affiliation></author><author><name sortKey="Mendes, Sergio B" uniqKey="Mendes S">Sergio B Mendes</name></author></titleStmt><publicationStmt><date when="2014">2014</date><idno type="doi">10.1021/ac4030736</idno><idno type="RBID">pubmed:24417718</idno><idno type="pmid">24417718</idno><idno type="wicri:Area/Main/Corpus">000213</idno><idno type="wicri:Area/Main/Curation">000213</idno><idno type="wicri:Area/Main/Exploration">000097</idno></publicationStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">An optical impedance spectroscopy (OIS) technique based on a single-mode electro-active-integrated optical waveguide (EA-IOW) was developed to investigate electron-transfer processes of redox adsorbates. A highly sensitive single-mode EA-IOW device was used to optically follow the time-dependent faradaic current originated from a submonolayer of cytochrome c undergoing redox exchanges driven by a harmonic modulation of the electric potential at several dc bias potentials and at several frequencies. To properly retrieve the faradaic current density from the ac-modulated optical signal, we introduce here a mathematical formalism that (i) accounts for intrinsic changes that invariably occur in the optical baseline of the EA-IOW device during potential modulation and (ii) provides accurate results for the electro-chemical parameters. We are able to optically reconstruct the faradaic current density profile against the dc bias potential in the working electrode, identify the formal potential, and determine the energy-width of the electron-transfer process. In addition, by combining the optically reconstructed faradaic signal with simple electrical measurements of impedance across the whole electrochemical cell and the capacitance of the electric double-layer, we are able to determine the time-constant connected to the redox reaction of the adsorbed protein assembly. For cytochrome c directly immobilized onto the indium tin oxide (ITO) surface, we measured a reaction rate constant of 26.5 s(-1). Finally, we calculate the charge-transfer resistance and pseudocapacitance associated with the electron-transfer process and show that the frequency dependence of the redox reaction of the protein submonolayer follows as expected the electrical equivalent of an RC-series admittance diagram. Above all, we show here that OIS with single-mode EA-IOW's provide strong analytical signals that can be readily monitored even for small surface-densities of species involved in the redox process (e.g., fmol/cm(2), 0.1% of a full protein monolayer). This experimental approach, when combined with the analytical formalism described here, brings additional sensitivity, accuracy, and simplicity to electro-chemical analysis and is expected to become a useful tool in investigations of redox processes.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="In-Process"><PMID Version="1">24417718</PMID><DateCreated><Year>2014</Year><Month>02</Month><Day>04</Day></DateCreated><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1520-6882</ISSN><JournalIssue CitedMedium="Internet"><Volume>86</Volume><Issue>3</Issue><PubDate><Year>2014</Year><Month>Feb</Month><Day>4</Day></PubDate></JournalIssue><Title>Analytical chemistry</Title><ISOAbbreviation>Anal. Chem.</ISOAbbreviation></Journal><ArticleTitle>Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.</ArticleTitle><Pagination><MedlinePgn>1468-77</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1021/ac4030736</ELocationID><Abstract><AbstractText>An optical impedance spectroscopy (OIS) technique based on a single-mode electro-active-integrated optical waveguide (EA-IOW) was developed to investigate electron-transfer processes of redox adsorbates. A highly sensitive single-mode EA-IOW device was used to optically follow the time-dependent faradaic current originated from a submonolayer of cytochrome c undergoing redox exchanges driven by a harmonic modulation of the electric potential at several dc bias potentials and at several frequencies. To properly retrieve the faradaic current density from the ac-modulated optical signal, we introduce here a mathematical formalism that (i) accounts for intrinsic changes that invariably occur in the optical baseline of the EA-IOW device during potential modulation and (ii) provides accurate results for the electro-chemical parameters. We are able to optically reconstruct the faradaic current density profile against the dc bias potential in the working electrode, identify the formal potential, and determine the energy-width of the electron-transfer process. In addition, by combining the optically reconstructed faradaic signal with simple electrical measurements of impedance across the whole electrochemical cell and the capacitance of the electric double-layer, we are able to determine the time-constant connected to the redox reaction of the adsorbed protein assembly. For cytochrome c directly immobilized onto the indium tin oxide (ITO) surface, we measured a reaction rate constant of 26.5 s(-1). Finally, we calculate the charge-transfer resistance and pseudocapacitance associated with the electron-transfer process and show that the frequency dependence of the redox reaction of the protein submonolayer follows as expected the electrical equivalent of an RC-series admittance diagram. Above all, we show here that OIS with single-mode EA-IOW's provide strong analytical signals that can be readily monitored even for small surface-densities of species involved in the redox process (e.g., fmol/cm(2), 0.1% of a full protein monolayer). This experimental approach, when combined with the analytical formalism described here, brings additional sensitivity, accuracy, and simplicity to electro-chemical analysis and is expected to become a useful tool in investigations of redox processes.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Han</LastName><ForeName>Xue</ForeName><Initials>X</Initials><Affiliation>Department of Physics and Astronomy, University of Louisville , Louisville, Kentucky 40292, United States.</Affiliation></Author><Author ValidYN="Y"><LastName>Mendes</LastName><ForeName>Sergio B</ForeName><Initials>SB</Initials></Author></AuthorList><Language>eng</Language><GrantList CompleteYN="Y"><Grant><GrantID>R21 RR022864</GrantID><Acronym>RR</Acronym><Agency>NCRR NIH HHS</Agency><Country>United States</Country></Grant><Grant><GrantID>RR022864</GrantID><Acronym>RR</Acronym><Agency>NCRR NIH HHS</Agency><Country>United States</Country></Grant></GrantList><PublicationTypeList><PublicationType>Journal Article</PublicationType><PublicationType>Research Support, N.I.H., Extramural</PublicationType><PublicationType>Research Support, Non-U.S. Gov't</PublicationType><PublicationType>Research Support, U.S. Gov't, Non-P.H.S.</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2014</Year><Month>01</Month><Day>21</Day></ArticleDate></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>Anal Chem</MedlineTA><NlmUniqueID>0370536</NlmUniqueID><ISSNLinking>0003-2700</ISSNLinking></MedlineJournalInfo><CitationSubset>IM</CitationSubset><CommentsCorrectionsList><CommentsCorrections RefType="Cites"><RefSource>Anal Chem. 2003 Mar 1;75(5):1080-8</RefSource><PMID Version="1">12641226</PMID></CommentsCorrections><CommentsCorrections RefType="Cites"><RefSource>Biochem J. 1959 Mar;71(3):570-2</RefSource><PMID Version="1">13638266</PMID></CommentsCorrections><CommentsCorrections RefType="Cites"><RefSource>J Am Chem Soc. 2008 Feb 6;130(5):1572-3</RefSource><PMID Version="1">18193877</PMID></CommentsCorrections></CommentsCorrectionsList><OtherID Source="NLM">NIHMS562878</OtherID><OtherID Source="NLM">PMC3983008</OtherID></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="aheadofprint"><Year>2014</Year><Month>1</Month><Day>21</Day></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2014</Year><Month>1</Month><Day>15</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2014</Year><Month>1</Month><Day>15</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2014</Year><Month>1</Month><Day>15</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1021/ac4030736</ArticleId><ArticleId IdType="pubmed">24417718</ArticleId><ArticleId IdType="pmc">PMC3983008</ArticleId><ArticleId IdType="mid">NIHMS562878</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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