Synthesis of 1,4-hydroquinone-terminated alkanethiol and self-assembly on gold as characterized by interfacial electrochemistry, electrocatalysis application and ab initio calculation based on comparison with catechol-presenting analogue

Koji Nakano, Kimihiko Ohkubo, Hiroaki Taira, Makoto Takagi, Nobuaki Soh, Toshihiko Imato

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10 Citations (Scopus)

Abstract

Synthesis and self-assembly of a mercaptoundecaneamide derivative having a terminus of 1,4-hydroquinone (QT) are described. Electrochemical measurements on the QT-modified Au electrode revealed that the alkanethiol compound undergoes self-assembly to exhibit specific electrochemical activity originates from the reversible quinone/hydroquinone redox reaction at the terminus. We have achieved to obtain the electrochemical active surface coverage (0.11 nmol cm-2), formal potential (+246 mV, pH 3, Ag/AgCl) that changes pH-dependently (58 mV per pH) and also a set of the electron transfer reaction parameters, all of which were consistent with those of the previously reported structural isomer, catechol-terminated mercaptoundecaneamide (CT). Contrastingly, we found that these alkanethiol monolayers give marked contrast in an elecrocatalysis application: the CT-monolayer electrodes showed electrocatalytic capability in oxidation of NADH solution species while the QT-monolayer electrodes did not at all. By comparing some results of theoretical approach, we have attributed the surface selectivity to the spatiality of particular molecular orbital in the catalysis molecule. This observation should be important as an example of spatiality-reactivity relationships in a molecular design of chemically modified electrode.

Original languageEnglish
Pages (from-to)49-53
Number of pages5
JournalJournal of Electroanalytical Chemistry
Volume623
Issue number1
DOIs
Publication statusPublished - Nov 1 2008

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Electrocatalysis
Electrochemistry
Gold
Self assembly
Monolayers
Electrodes
Redox reactions
Molecular orbitals
Isomers
NAD
Catalysis
Derivatives
Oxidation
Molecules
catechol
hydroquinone
Electrons

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

Cite this

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title = "Synthesis of 1,4-hydroquinone-terminated alkanethiol and self-assembly on gold as characterized by interfacial electrochemistry, electrocatalysis application and ab initio calculation based on comparison with catechol-presenting analogue",
abstract = "Synthesis and self-assembly of a mercaptoundecaneamide derivative having a terminus of 1,4-hydroquinone (QT) are described. Electrochemical measurements on the QT-modified Au electrode revealed that the alkanethiol compound undergoes self-assembly to exhibit specific electrochemical activity originates from the reversible quinone/hydroquinone redox reaction at the terminus. We have achieved to obtain the electrochemical active surface coverage (0.11 nmol cm-2), formal potential (+246 mV, pH 3, Ag/AgCl) that changes pH-dependently (58 mV per pH) and also a set of the electron transfer reaction parameters, all of which were consistent with those of the previously reported structural isomer, catechol-terminated mercaptoundecaneamide (CT). Contrastingly, we found that these alkanethiol monolayers give marked contrast in an elecrocatalysis application: the CT-monolayer electrodes showed electrocatalytic capability in oxidation of NADH solution species while the QT-monolayer electrodes did not at all. By comparing some results of theoretical approach, we have attributed the surface selectivity to the spatiality of particular molecular orbital in the catalysis molecule. This observation should be important as an example of spatiality-reactivity relationships in a molecular design of chemically modified electrode.",
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T1 - Synthesis of 1,4-hydroquinone-terminated alkanethiol and self-assembly on gold as characterized by interfacial electrochemistry, electrocatalysis application and ab initio calculation based on comparison with catechol-presenting analogue

AU - Nakano, Koji

AU - Ohkubo, Kimihiko

AU - Taira, Hiroaki

AU - Takagi, Makoto

AU - Soh, Nobuaki

AU - Imato, Toshihiko

PY - 2008/11/1

Y1 - 2008/11/1

N2 - Synthesis and self-assembly of a mercaptoundecaneamide derivative having a terminus of 1,4-hydroquinone (QT) are described. Electrochemical measurements on the QT-modified Au electrode revealed that the alkanethiol compound undergoes self-assembly to exhibit specific electrochemical activity originates from the reversible quinone/hydroquinone redox reaction at the terminus. We have achieved to obtain the electrochemical active surface coverage (0.11 nmol cm-2), formal potential (+246 mV, pH 3, Ag/AgCl) that changes pH-dependently (58 mV per pH) and also a set of the electron transfer reaction parameters, all of which were consistent with those of the previously reported structural isomer, catechol-terminated mercaptoundecaneamide (CT). Contrastingly, we found that these alkanethiol monolayers give marked contrast in an elecrocatalysis application: the CT-monolayer electrodes showed electrocatalytic capability in oxidation of NADH solution species while the QT-monolayer electrodes did not at all. By comparing some results of theoretical approach, we have attributed the surface selectivity to the spatiality of particular molecular orbital in the catalysis molecule. This observation should be important as an example of spatiality-reactivity relationships in a molecular design of chemically modified electrode.

AB - Synthesis and self-assembly of a mercaptoundecaneamide derivative having a terminus of 1,4-hydroquinone (QT) are described. Electrochemical measurements on the QT-modified Au electrode revealed that the alkanethiol compound undergoes self-assembly to exhibit specific electrochemical activity originates from the reversible quinone/hydroquinone redox reaction at the terminus. We have achieved to obtain the electrochemical active surface coverage (0.11 nmol cm-2), formal potential (+246 mV, pH 3, Ag/AgCl) that changes pH-dependently (58 mV per pH) and also a set of the electron transfer reaction parameters, all of which were consistent with those of the previously reported structural isomer, catechol-terminated mercaptoundecaneamide (CT). Contrastingly, we found that these alkanethiol monolayers give marked contrast in an elecrocatalysis application: the CT-monolayer electrodes showed electrocatalytic capability in oxidation of NADH solution species while the QT-monolayer electrodes did not at all. By comparing some results of theoretical approach, we have attributed the surface selectivity to the spatiality of particular molecular orbital in the catalysis molecule. This observation should be important as an example of spatiality-reactivity relationships in a molecular design of chemically modified electrode.

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