Electron transfer with self-assembled copper ions at Au-deposited biomimetic films : mechanistic "anomalies" disclosed by temperature- and pressure-assisted fast-scan voltammetry

2015
journal article
article
5
dc.abstract.enIt has been suggested that electron transfer (ET) processes occurring in complex environments capable of glass transitions, specifically in biomolecules, under certain conditions may experience the medium ’ s nonlinear response and nonergodic kinetic patterns. The interiors of self-assembled organic films (SAMs) deposited on solid conducting platforms (electrodes) are known to undergo glassy dynamics as well, hence they may also exhibit the abovementioned ‘ irregularities ’ . We took advantage of Cu 2+ ions as redox-active probes trapped in the Au-deposited − COOH-terminated SAMs, either L-cysteine, or 3-mercaptopropionic acid diluted by the inert 2-mercaptoethanol, to systematically study the impact of glassy dynamics on ET using the fast-scan voltammetry technique and its temperature and high-pressure extensions. We found that respective kinetic data can be rationalized within the extended Marcus theory, taking into account the frictionally controlled (adiabatic) mechanism for short-range ET, and complications due to the medium ’ s nonlinear response and broken ergodicity. This combination shows up in essential deviations from the conventional energy gap (overpotential) dependence and in essentially nonlinear temperature (Arrhenius) and high-pressure patterns, respectively. Biomimetic aspects for these systems are also discussed in the context of recently published results for interfacial ET involving self-assembled blue copper protein (azurin) placed in contact with a glassy environment.pl
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.contributor.authorKhoshtariya, Dimitri E.pl
dc.contributor.authorDolidze, Tinatin D.pl
dc.contributor.authorTretyakova, Tatyanapl
dc.contributor.authorvan Eldik, Rudi - 239234 pl
dc.date.accessioned2015-12-07T09:34:22Z
dc.date.available2015-12-07T09:34:22Z
dc.date.issued2015pl
dc.description.number25pl
dc.description.volume48pl
dc.identifier.articleid255402pl
dc.identifier.doi10.1088/0022-3727/48/25/255402pl
dc.identifier.eissn1361-6463pl
dc.identifier.issn0022-3727pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/17742
dc.languageengpl
dc.language.containerengpl
dc.rights.licencebez licencji
dc.subject.enAu-deposited biomimetic filmspl
dc.subject.enself-assembled copper ionspl
dc.subject.enelectron transferpl
dc.subject.enimpact of temperature and pressurepl
dc.subject.enmedium’s nonlinear responsepl
dc.subject.ennonergodic kinetic patternspl
dc.subtypeArticlepl
dc.titleElectron transfer with self-assembled copper ions at Au-deposited biomimetic films : mechanistic "anomalies" disclosed by temperature- and pressure-assisted fast-scan voltammetrypl
dc.title.journalJournal of Physics. D, Applied Physicspl
dc.typeJournalArticlepl
dspace.entity.typePublication
dc.abstract.enpl
It has been suggested that electron transfer (ET) processes occurring in complex environments capable of glass transitions, specifically in biomolecules, under certain conditions may experience the medium ’ s nonlinear response and nonergodic kinetic patterns. The interiors of self-assembled organic films (SAMs) deposited on solid conducting platforms (electrodes) are known to undergo glassy dynamics as well, hence they may also exhibit the abovementioned ‘ irregularities ’ . We took advantage of Cu 2+ ions as redox-active probes trapped in the Au-deposited − COOH-terminated SAMs, either L-cysteine, or 3-mercaptopropionic acid diluted by the inert 2-mercaptoethanol, to systematically study the impact of glassy dynamics on ET using the fast-scan voltammetry technique and its temperature and high-pressure extensions. We found that respective kinetic data can be rationalized within the extended Marcus theory, taking into account the frictionally controlled (adiabatic) mechanism for short-range ET, and complications due to the medium ’ s nonlinear response and broken ergodicity. This combination shows up in essential deviations from the conventional energy gap (overpotential) dependence and in essentially nonlinear temperature (Arrhenius) and high-pressure patterns, respectively. Biomimetic aspects for these systems are also discussed in the context of recently published results for interfacial ET involving self-assembled blue copper protein (azurin) placed in contact with a glassy environment.
dc.affiliationpl
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.contributor.authorpl
Khoshtariya, Dimitri E.
dc.contributor.authorpl
Dolidze, Tinatin D.
dc.contributor.authorpl
Tretyakova, Tatyana
dc.contributor.authorpl
van Eldik, Rudi - 239234
dc.date.accessioned
2015-12-07T09:34:22Z
dc.date.available
2015-12-07T09:34:22Z
dc.date.issuedpl
2015
dc.description.numberpl
25
dc.description.volumepl
48
dc.identifier.articleidpl
255402
dc.identifier.doipl
10.1088/0022-3727/48/25/255402
dc.identifier.eissnpl
1361-6463
dc.identifier.issnpl
0022-3727
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/17742
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights.licence
bez licencji
dc.subject.enpl
Au-deposited biomimetic films
dc.subject.enpl
self-assembled copper ions
dc.subject.enpl
electron transfer
dc.subject.enpl
impact of temperature and pressure
dc.subject.enpl
medium’s nonlinear response
dc.subject.enpl
nonergodic kinetic patterns
dc.subtypepl
Article
dc.titlepl
Electron transfer with self-assembled copper ions at Au-deposited biomimetic films : mechanistic "anomalies" disclosed by temperature- and pressure-assisted fast-scan voltammetry
dc.title.journalpl
Journal of Physics. D, Applied Physics
dc.typepl
JournalArticle
dspace.entity.type
Publication

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