Electrochemical correlation spectroscopy in nanofluidic cavities

Marcel A.G. Zevenbergen; Pradyumna S. Singh; Edgar D. Goluch; Bernhard L. Wolfrum; Serge G. Lemay

doi:10.1021/ac9014885

Electrochemical correlation spectroscopy in nanofluidic cavities

Marcel A.G. Zevenbergen, Pradyumna S. Singh, Edgar D. Goluch, Bernhard L. Wolfrum, Serge G. Lemay

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66 Scopus citations

Abstract

We introduce both theoretically and experimentally a new electrochemical technique based on measuring the fluctuations of the faradaic current during redox cycling. By analogy with fluorescence correlation spectroscopy (FCS), we refer to this technique as electrochemical correlation spectroscopy (ECS). We first derive an analytical expression of the power spectral density for the fluctuations in a thin-layer-cell geometry. We then show agreement with measurements using ferrocenedimethanol, Fc(MeOH)₂, in water and in acetonitrile in microfabricated thin-layer cells with a ∼70 nm electrode spacing. The fluctuation spectra provide detailed information about the adsorption dynamics of Fc(MeOH)₂, which cause an apparent slowing of Brownian motion. We furthermore observe high-frequency fluctuations from which we estimate the rates of adsorption and desorption.

Original language	English
Pages (from-to)	8203-8212
Number of pages	10
Journal	Analytical Chemistry
Volume	81
Issue number	19
DOIs	https://doi.org/10.1021/ac9014885
State	Published - 1 Oct 2009
Externally published	Yes

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title = "Electrochemical correlation spectroscopy in nanofluidic cavities",

abstract = "We introduce both theoretically and experimentally a new electrochemical technique based on measuring the fluctuations of the faradaic current during redox cycling. By analogy with fluorescence correlation spectroscopy (FCS), we refer to this technique as electrochemical correlation spectroscopy (ECS). We first derive an analytical expression of the power spectral density for the fluctuations in a thin-layer-cell geometry. We then show agreement with measurements using ferrocenedimethanol, Fc(MeOH)2, in water and in acetonitrile in microfabricated thin-layer cells with a ∼70 nm electrode spacing. The fluctuation spectra provide detailed information about the adsorption dynamics of Fc(MeOH)2, which cause an apparent slowing of Brownian motion. We furthermore observe high-frequency fluctuations from which we estimate the rates of adsorption and desorption.",

author = "Zevenbergen, {Marcel A.G.} and Singh, {Pradyumna S.} and Goluch, {Edgar D.} and Wolfrum, {Bernhard L.} and Lemay, {Serge G.}",

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T1 - Electrochemical correlation spectroscopy in nanofluidic cavities

AU - Zevenbergen, Marcel A.G.

AU - Singh, Pradyumna S.

AU - Goluch, Edgar D.

AU - Wolfrum, Bernhard L.

AU - Lemay, Serge G.

PY - 2009/10/1

Y1 - 2009/10/1

N2 - We introduce both theoretically and experimentally a new electrochemical technique based on measuring the fluctuations of the faradaic current during redox cycling. By analogy with fluorescence correlation spectroscopy (FCS), we refer to this technique as electrochemical correlation spectroscopy (ECS). We first derive an analytical expression of the power spectral density for the fluctuations in a thin-layer-cell geometry. We then show agreement with measurements using ferrocenedimethanol, Fc(MeOH)2, in water and in acetonitrile in microfabricated thin-layer cells with a ∼70 nm electrode spacing. The fluctuation spectra provide detailed information about the adsorption dynamics of Fc(MeOH)2, which cause an apparent slowing of Brownian motion. We furthermore observe high-frequency fluctuations from which we estimate the rates of adsorption and desorption.

AB - We introduce both theoretically and experimentally a new electrochemical technique based on measuring the fluctuations of the faradaic current during redox cycling. By analogy with fluorescence correlation spectroscopy (FCS), we refer to this technique as electrochemical correlation spectroscopy (ECS). We first derive an analytical expression of the power spectral density for the fluctuations in a thin-layer-cell geometry. We then show agreement with measurements using ferrocenedimethanol, Fc(MeOH)2, in water and in acetonitrile in microfabricated thin-layer cells with a ∼70 nm electrode spacing. The fluctuation spectra provide detailed information about the adsorption dynamics of Fc(MeOH)2, which cause an apparent slowing of Brownian motion. We furthermore observe high-frequency fluctuations from which we estimate the rates of adsorption and desorption.

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U2 - 10.1021/ac9014885

DO - 10.1021/ac9014885

M3 - Article

AN - SCOPUS:70349616559

SN - 0003-2700

VL - 81

SP - 8203

EP - 8212

JO - Analytical Chemistry

JF - Analytical Chemistry

IS - 19

ER -

Electrochemical correlation spectroscopy in nanofluidic cavities

Abstract

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