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231225s2020 xx |||||o 00| ||eng c |
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|a 10.1021/acs.langmuir.0c00817
|2 doi
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|a pubmed24n1034.xml
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|a (NLM)32453577
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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| 100 |
1 |
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|a Zheng, Yilong
|e verfasserin
|4 aut
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| 245 |
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|a Potential-Modulated Total Internal Reflection Fluorescence for Measurement of the Electron Transfer Kinetics of Submonolayers on Optically Transparent Electrodes
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|c 2020
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
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|2 rdamedia
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|a ƒa Online-Ressource
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|2 rdacarrier
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|a Date Revised 23.06.2020
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|a published: Print-Electronic
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|a Citation Status PubMed-not-MEDLINE
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|a An electroreflectance method to determine the electron transfer rate constant of a film of redox-active chromophores immobilized on an optically transparent electrode when the surface coverage of the film is very low (<0.1 monolayer) is described herein. The method, potential-modulated total internal reflection fluorescence (PM-TIRF) spectroscopy, is a fluorescence version of potential-modulated attenuated total reflection (PM-ATR) spectroscopy that is applicable when the immobilized chromophores are luminescent. The method was tested using perylene diimide (PDI) molecules functionalized with p-phenylene phosphonic acid (PA) moieties that bind strongly to indium-tin oxide (ITO). Conditions to prepare PDI-phenyl-PA films that exhibit absorbance and fluorescence spectra characteristic of monomeric (i.e., nonaggregated) molecules were identified; the electrochemical surface coverage was approximately 0.03 monolayer. The tilt angle of the long axis of the PDI molecular plane is 58° relative to the ITO surface normal, 25° greater than the tilt angle of aggregated PDI-phenyl-PA films, which have a surface coverage of approximately one monolayer. The more in-plane orientation of monomeric films is likely due to the absence of cofacial π-π interactions present in aggregated films and possibly a difference in PA-ITO binding modes. The electron transfer rate constant (ks,opt) of monomeric PDI-phenyl-PA films was determined using PM-TIRF and compared with PM-ATR results obtained for aggregated films. For PDI monomers, ks,opt = 3.8 × 103 s-1, which is about 3.7-fold less than ks,opt for aggregated films. The slower kinetics are attributed to the absence of electron self-exchange between monomeric PDI molecules. Differences in the electroactivity of the binding sites on the ITO electrode surface also may play a role. This is the first demonstration of PM-TIRF for determining electron transfer rate constants at an electrode/organic film interface
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|a Journal Article
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|a Giordano, Anthony J
|e verfasserin
|4 aut
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|a Marder, Seth R
|e verfasserin
|4 aut
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|a Saavedra, S Scott
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Langmuir : the ACS journal of surfaces and colloids
|d 1992
|g 36(2020), 24 vom: 23. Juni, Seite 6728-6735
|w (DE-627)NLM098181009
|x 1520-5827
|7 nnns
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| 773 |
1 |
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|g volume:36
|g year:2020
|g number:24
|g day:23
|g month:06
|g pages:6728-6735
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|u http://dx.doi.org/10.1021/acs.langmuir.0c00817
|3 Volltext
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