Electroreflectance spectroscopic study of the electron transfer rate of cytochrome c electrostatically immobilized on the ω-carboxyl alkanethiol monolayer modified gold electrode

Zhi Qiang Feng, Shinichiro Imabayashi, Takashi Kakiuchi, Katsumi Niki

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Abstract

Horse heart cytochrome c was immobilized electrostatically on self-assembled monolayers (SAMs) of carboxylic-acid-terminated alkanethiols, HS(CH2)nCOOH (n = 2, 10) on gold electrodes, The rate constants of the electrode reaction of cytochrome c at the SAM-modified gold electrodes were determined by the frequency dependence of a.c. modulated UV-visible electroreflectance signals. The apparent standard electrode reaction rate constants of cytochrome c were 880 s-1 and 72 s-1 at the HS(CH2)2COOH and HS(CH2)10COOH SAM modified gold electrodes respectively. The rate constant at HS(CH2)2COOH was much smaller than expected from Marcus theory. However, the rate constant at HS(CH2)10COOH could be explained in terms of the through-bond tunnelling mechanism with tunnelling parameter β = 8.2 nm-1.

Original languageEnglish
Pages (from-to)149-154
Number of pages6
JournalJournal of Electroanalytical Chemistry
Volume394
Issue number1-2
Publication statusPublished - 1995 Sep 19
Externally publishedYes

Fingerprint

Cytochromes c
Gold
Monolayers
Rate constants
Proteins
Self assembled monolayers
Electrodes
Electrons
Carboxylic Acids
Carboxylic acids
Reaction rates

Keywords

  • Cytochrome c
  • Electron transfer rate
  • Gold electrode
  • Self-assembled monolayers

ASJC Scopus subject areas

  • Electrochemistry
  • Analytical Chemistry
  • Chemical Engineering(all)

Cite this

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title = "Electroreflectance spectroscopic study of the electron transfer rate of cytochrome c electrostatically immobilized on the ω-carboxyl alkanethiol monolayer modified gold electrode",
abstract = "Horse heart cytochrome c was immobilized electrostatically on self-assembled monolayers (SAMs) of carboxylic-acid-terminated alkanethiols, HS(CH2)nCOOH (n = 2, 10) on gold electrodes, The rate constants of the electrode reaction of cytochrome c at the SAM-modified gold electrodes were determined by the frequency dependence of a.c. modulated UV-visible electroreflectance signals. The apparent standard electrode reaction rate constants of cytochrome c were 880 s-1 and 72 s-1 at the HS(CH2)2COOH and HS(CH2)10COOH SAM modified gold electrodes respectively. The rate constant at HS(CH2)2COOH was much smaller than expected from Marcus theory. However, the rate constant at HS(CH2)10COOH could be explained in terms of the through-bond tunnelling mechanism with tunnelling parameter β = 8.2 nm-1.",
keywords = "Cytochrome c, Electron transfer rate, Gold electrode, Self-assembled monolayers",
author = "Feng, {Zhi Qiang} and Shinichiro Imabayashi and Takashi Kakiuchi and Katsumi Niki",
year = "1995",
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TY - JOUR

T1 - Electroreflectance spectroscopic study of the electron transfer rate of cytochrome c electrostatically immobilized on the ω-carboxyl alkanethiol monolayer modified gold electrode

AU - Feng, Zhi Qiang

AU - Imabayashi, Shinichiro

AU - Kakiuchi, Takashi

AU - Niki, Katsumi

PY - 1995/9/19

Y1 - 1995/9/19

N2 - Horse heart cytochrome c was immobilized electrostatically on self-assembled monolayers (SAMs) of carboxylic-acid-terminated alkanethiols, HS(CH2)nCOOH (n = 2, 10) on gold electrodes, The rate constants of the electrode reaction of cytochrome c at the SAM-modified gold electrodes were determined by the frequency dependence of a.c. modulated UV-visible electroreflectance signals. The apparent standard electrode reaction rate constants of cytochrome c were 880 s-1 and 72 s-1 at the HS(CH2)2COOH and HS(CH2)10COOH SAM modified gold electrodes respectively. The rate constant at HS(CH2)2COOH was much smaller than expected from Marcus theory. However, the rate constant at HS(CH2)10COOH could be explained in terms of the through-bond tunnelling mechanism with tunnelling parameter β = 8.2 nm-1.

AB - Horse heart cytochrome c was immobilized electrostatically on self-assembled monolayers (SAMs) of carboxylic-acid-terminated alkanethiols, HS(CH2)nCOOH (n = 2, 10) on gold electrodes, The rate constants of the electrode reaction of cytochrome c at the SAM-modified gold electrodes were determined by the frequency dependence of a.c. modulated UV-visible electroreflectance signals. The apparent standard electrode reaction rate constants of cytochrome c were 880 s-1 and 72 s-1 at the HS(CH2)2COOH and HS(CH2)10COOH SAM modified gold electrodes respectively. The rate constant at HS(CH2)2COOH was much smaller than expected from Marcus theory. However, the rate constant at HS(CH2)10COOH could be explained in terms of the through-bond tunnelling mechanism with tunnelling parameter β = 8.2 nm-1.

KW - Cytochrome c

KW - Electron transfer rate

KW - Gold electrode

KW - Self-assembled monolayers

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