skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Self-induced redox cycling coupled luminescence on nanopore recessed disk-multiscale bipolar electrodes

Abstract

Self-induced redox cycling at nanopore ring-disk electrodes is coupled, through a bipolar electrode, to a remote fluorigenic reporter reaction. We present a new configuration for coupling fluorescence microscopy and voltammetry using self-induced redox cycling for ultrasensitive electrochemical measurements. An array of nanopores, each supporting a recessed disk electrode separated by 100 nm in depth from a planar multiscale bipolar top electrode, was fabricated using multilayer deposition, nanosphere lithography, and reactive-ion etching. Self-induced redox cycling was induced on the disk electrode producing ~30× current amplification, which was independently confirmed by measuring induced electrogenerated chemiluminescence from Ru(bpy)32/3+/tri-n-propylamine on the floating bipolar electrode. In this design, redox cycling occurs between the recessed disk and the top planar portion of a macroscopic thin film bipolar electrode in each nanopore. Electron transfer also occurs on a remote (mm-distance) portion of the planar bipolar electrode to maintain electroneutrality. This couples the electrochemical reactions of the target redox pair in the nanopore array with a reporter, such as a potential-switchable fluorescent indicator, in the cell at the distal end of the bipolar electrode. Oxidation or reduction of reversible analytes on the disk electrodes were accompanied by reduction or oxidation, respectively, on the nanopore portion of the bipolarmore » electrode and then monitored by the accompanying oxidation of dihydroresorufin or reduction of resorufin at the remote end of the bipolar electrode, respectively. In both cases, changes in fluorescence intensity were triggered by the reaction of the target couple on the disk electrode, while recovery was largely governed by diffusion of the fluorescent indicator. Reduction of 1 nM of Ru(NH3)63+ on the nanoelectrode array was detected by monitoring the fluorescence intensity of resorufin, demonstrating high sensitivity fluorescence-mediated electrochemical sensing coupled to self-induced redox cycling.« less

Authors:
 [1];  [1];  [2]
  1. Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry; Univ. of Notre Dame, IN (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)
OSTI Identifier:
1371875
Grant/Contract Number:  
SC0006642; NSF1404744
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 5; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ma, Chaoxiong, Zaino III, Lawrence P., and Bohn, Paul W. Self-induced redox cycling coupled luminescence on nanopore recessed disk-multiscale bipolar electrodes. United States: N. p., 2015. Web. doi:10.1039/c5sc00433k.
Ma, Chaoxiong, Zaino III, Lawrence P., & Bohn, Paul W. Self-induced redox cycling coupled luminescence on nanopore recessed disk-multiscale bipolar electrodes. United States. doi:10.1039/c5sc00433k.
Ma, Chaoxiong, Zaino III, Lawrence P., and Bohn, Paul W. Wed . "Self-induced redox cycling coupled luminescence on nanopore recessed disk-multiscale bipolar electrodes". United States. doi:10.1039/c5sc00433k. https://www.osti.gov/servlets/purl/1371875.
@article{osti_1371875,
title = {Self-induced redox cycling coupled luminescence on nanopore recessed disk-multiscale bipolar electrodes},
author = {Ma, Chaoxiong and Zaino III, Lawrence P. and Bohn, Paul W.},
abstractNote = {Self-induced redox cycling at nanopore ring-disk electrodes is coupled, through a bipolar electrode, to a remote fluorigenic reporter reaction. We present a new configuration for coupling fluorescence microscopy and voltammetry using self-induced redox cycling for ultrasensitive electrochemical measurements. An array of nanopores, each supporting a recessed disk electrode separated by 100 nm in depth from a planar multiscale bipolar top electrode, was fabricated using multilayer deposition, nanosphere lithography, and reactive-ion etching. Self-induced redox cycling was induced on the disk electrode producing ~30× current amplification, which was independently confirmed by measuring induced electrogenerated chemiluminescence from Ru(bpy)32/3+/tri-n-propylamine on the floating bipolar electrode. In this design, redox cycling occurs between the recessed disk and the top planar portion of a macroscopic thin film bipolar electrode in each nanopore. Electron transfer also occurs on a remote (mm-distance) portion of the planar bipolar electrode to maintain electroneutrality. This couples the electrochemical reactions of the target redox pair in the nanopore array with a reporter, such as a potential-switchable fluorescent indicator, in the cell at the distal end of the bipolar electrode. Oxidation or reduction of reversible analytes on the disk electrodes were accompanied by reduction or oxidation, respectively, on the nanopore portion of the bipolar electrode and then monitored by the accompanying oxidation of dihydroresorufin or reduction of resorufin at the remote end of the bipolar electrode, respectively. In both cases, changes in fluorescence intensity were triggered by the reaction of the target couple on the disk electrode, while recovery was largely governed by diffusion of the fluorescent indicator. Reduction of 1 nM of Ru(NH3)63+ on the nanoelectrode array was detected by monitoring the fluorescence intensity of resorufin, demonstrating high sensitivity fluorescence-mediated electrochemical sensing coupled to self-induced redox cycling.},
doi = {10.1039/c5sc00433k},
journal = {Chemical Science},
number = 5,
volume = 6,
place = {United States},
year = {2015},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Real-Time pH Microscopy down to the Molecular Level by Combined Scanning Electrochemical Microscopy/Single-Molecule Fluorescence Spectroscopy
journal, July 2004

  • Boldt, Frank-Mario; Heinze, Jürgen; Diez, Manuel
  • Analytical Chemistry, Vol. 76, Issue 13
  • DOI: 10.1021/ac049635x

A Large-Scale, Wireless Electrochemical Bipolar Electrode Microarray
journal, June 2009

  • Chow, Kwok-Fan; Mavré, François; Crooks, John A.
  • Journal of the American Chemical Society, Vol. 131, Issue 24
  • DOI: 10.1021/ja902683f

Redox Cycling on Recessed Ring-Disk Nanoelectrode Arrays in the Absence of Supporting Electrolyte
journal, May 2014

  • Ma, Chaoxiong; Contento, Nicholas M.; Bohn, Paul W.
  • Journal of the American Chemical Society, Vol. 136, Issue 20
  • DOI: 10.1021/ja502052s

Highly sensitive detection of reversible species by self-induced redox cycling
journal, May 1992

  • Tabei, Hisao; Horiuchi, Tsutomu; Niwa, Osamu
  • Journal of Electroanalytical Chemistry, Vol. 326, Issue 1-2
  • DOI: 10.1016/0022-0728(92)80521-5

Redox cycling with facing interdigitated array electrodes as a method for selective detection of redox species
journal, January 2007

  • Dam, V. A. T.; Olthuis, W.; van den Berg, A.
  • The Analyst, Vol. 132, Issue 4
  • DOI: 10.1039/b616667a

On the Nature of DNA Self-Assembled Monolayers on Au: Measuring Surface Heterogeneity with Electrochemical in Situ Fluorescence Microscopy
journal, March 2009

  • Murphy, Jeffrey N.; Cheng, Alan K. H.; Yu, Hua-Zhong
  • Journal of the American Chemical Society, Vol. 131, Issue 11
  • DOI: 10.1021/ja808696p

Coupling of Electrochemistry and Fluorescence Microscopy at Indium Tin Oxide Microelectrodes for the Analysis of Single Exocytotic Events
journal, June 2006

  • Amatore, Christian; Arbault, Stéphane; Chen, Yong
  • Angewandte Chemie International Edition, Vol. 45, Issue 24
  • DOI: 10.1002/anie.200600510

Single-molecule fluorescence imaging of nanocatalytic processes
journal, January 2010

  • Chen, Peng; Zhou, Xiaochun; Shen, Hao
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/b909052p

Fluorescence microscopy coupled to electrochemistry: a powerful tool for the controlled electrochemical switch of fluorescent molecules
journal, January 2008

  • Miomandre, Fabien; Meallet-Renault, Rachel; Vachon, Jean-Jacques
  • Chemical Communications, Issue 16
  • DOI: 10.1039/b718899d

Bipolar Electrodes: A Useful Tool for Concentration, Separation, and Detection of Analytes in Microelectrochemical Systems
journal, November 2010

  • Mavré, François; Anand, Robbyn K.; Laws, Derek R.
  • Analytical Chemistry, Vol. 82, Issue 21
  • DOI: 10.1021/ac101262v

Electrochemical Detection of Single Molecules
journal, February 1995


Electrochemistry coupled to fluorescence spectroscopy: a new versatile approach
journal, March 2004


Single-molecule fluorescence spectroelectrochemistry of cresyl violet
journal, January 2008

  • Lei, Chenghong; Hu, Dehong; Ackerman, Eric J.
  • Chemical Communications, Issue 43
  • DOI: 10.1039/b812161c

Fluorescence Coupling for Direct Imaging of Electrocatalytic Heterogeneity
journal, December 2012

  • Guerrette, Joshua P.; Percival, Stephen J.; Zhang, Bo
  • Journal of the American Chemical Society, Vol. 135, Issue 2
  • DOI: 10.1021/ja310401b

Limiting Current Enhancement by Self-Induced Redox Cycling on a Micro-Macro Twin Electrode
journal, January 1991

  • Horiuchi, Tsutomu
  • Journal of The Electrochemical Society, Vol. 138, Issue 12
  • DOI: 10.1149/1.2085457

Fabrication and electrochemical characterization of interdigitated nanoelectrode arrays
journal, February 2005


Dual Fluorescence and Electrochemical Detection on an Electrophoresis Microchip
journal, July 2002

  • Lapos, Julie A.; Manica, Drew P.; Ewing, Andrew G.
  • Analytical Chemistry, Vol. 74, Issue 14
  • DOI: 10.1021/ac025504p

Electrogenerated chemiluminescent determination of tris(2,2'-bipyridine)ruthenium ion (Ru(bpy)32+) at low levels
journal, November 1984

  • Ege, Deniz.; Becker, William G.; Bard, Allen J.
  • Analytical Chemistry, Vol. 56, Issue 13
  • DOI: 10.1021/ac00277a036

Electrochemical Sensing in Microfluidic Systems Using Electrogenerated Chemiluminescence as a Photonic Reporter of Redox Reactions
journal, November 2002

  • Zhan, Wei; Alvarez, Julio; Crooks, Richard M.
  • Journal of the American Chemical Society, Vol. 124, Issue 44
  • DOI: 10.1021/ja020907s

Redox cycling in nanofluidic channels using interdigitated electrodes
journal, January 2009

  • Goluch, Edgar D.; Wolfrum, Bernhard; Singh, Pradyumna S.
  • Analytical and Bioanalytical Chemistry, Vol. 394, Issue 2
  • DOI: 10.1007/s00216-008-2575-x

Detection of Reversible Redox Species by Substitutional Stripping Voltammetry
journal, April 1994

  • Horiuchi, Tsutomu.; Niwa, Osamu.; Tabei, Hisao.
  • Analytical Chemistry, Vol. 66, Issue 8
  • DOI: 10.1021/ac00080a005

Electrogenerated Chemiluminescence: An Oxidative-Reduction Type ECL Reaction Sequence Using Tripropyl Amine
journal, January 1990

  • Leland, Jonathan K.; Powell, Michael J.
  • Journal of The Electrochemical Society, Vol. 137, Issue 10, p. 3127-3131
  • DOI: 10.1149/1.2086171

Electrolysis in nanochannels for in situ reagent generation in confined geometries
journal, January 2011

  • Contento, Nicholas M.; Branagan, Sean P.; Bohn, Paul W.
  • Lab on a Chip, Vol. 11, Issue 21
  • DOI: 10.1039/c1lc20570f

Coupled Electrochemical Reactions at Bipolar Microelectrodes and Nanoelectrodes
journal, January 2012

  • Guerrette, Joshua P.; Oja, Stephen M.; Zhang, Bo
  • Analytical Chemistry, Vol. 84, Issue 3
  • DOI: 10.1021/ac2028672

Nanofluidic Redox Cycling Amplification for the Selective Detection of Catechol
journal, February 2008

  • Wolfrum, Bernhard; Zevenbergen, Marcel; Lemay, Serge
  • Analytical Chemistry, Vol. 80, Issue 4
  • DOI: 10.1021/ac7016647

Strategy for Increasing the Electrode Density of Microelectrode Arrays by Utilizing Bipolar Behavior of a Metallic Film
journal, February 2014

  • Zhu, Feng; Yan, Jiawei; Pang, Shiwei
  • Analytical Chemistry, Vol. 86, Issue 6
  • DOI: 10.1021/ac404202p

Interdigitated array microelectrodes as electrochemical sensors
journal, January 1997


Redox Cycling in Nanoscale-Recessed Ring-Disk Electrode Arrays for Enhanced Electrochemical Sensitivity
journal, May 2013

  • Ma, Chaoxiong; Contento, Nicholas M.; Gibson, Larry R.
  • ACS Nano, Vol. 7, Issue 6
  • DOI: 10.1021/nn401542x

Recessed Ring–Disk Nanoelectrode Arrays Integrated in Nanofluidic Structures for Selective Electrochemical Detection
journal, September 2013

  • Ma, Chaoxiong; Contento, Nicholas M.; Gibson, Larry R.
  • Analytical Chemistry, Vol. 85, Issue 20
  • DOI: 10.1021/ac402417w

Coupling Amperometry and Total Internal Reflection Fluorescence Microscopy at ITO Surfaces for Monitoring Exocytosis of Single Vesicles
journal, April 2011

  • Meunier, Anne; Jouannot, Ouardane; Fulcrand, Rémy
  • Angewandte Chemie International Edition, Vol. 50, Issue 22
  • DOI: 10.1002/anie.201101148

Electrochemistry of Individual Molecules in Zeptoliter Volumes
journal, July 2008

  • Sun, Peng; Mirkin, Michael V.
  • Journal of the American Chemical Society, Vol. 130, Issue 26
  • DOI: 10.1021/ja711088j

Fast Electron-Transfer Kinetics Probed in Nanofluidic Channels
journal, August 2009

  • Zevenbergen, Marcel A. G.; Wolfrum, Bernhard L.; Goluch, Edgar D.
  • Journal of the American Chemical Society, Vol. 131, Issue 32
  • DOI: 10.1021/ja902331u

Fluorescent Cyclic Voltammetry of Immobilized Azurin: Direct Observation of Thermodynamic and Kinetic Heterogeneity
journal, July 2010

  • Salverda, Jante M.; Patil, Amol V.; Mizzon, Giulia
  • Angewandte Chemie International Edition, Vol. 49, Issue 33
  • DOI: 10.1002/anie.201001298

Single-Molecule Spectroelectrochemistry (SMS-EC)
journal, July 2006

  • Palacios, Rodrigo E.; Fan, Fu-Ren F.; Bard, Allen J.
  • Journal of the American Chemical Society, Vol. 128, Issue 28
  • DOI: 10.1021/ja062848e

Steady-State Voltammetry of a Microelectrode in a Closed Bipolar Cell
journal, October 2012

  • Cox, Jonathan T.; Guerrette, Joshua P.; Zhang, Bo
  • Analytical Chemistry, Vol. 84, Issue 20
  • DOI: 10.1021/ac302219p

Fluorescence-Enabled Electrochemical Microscopy with Dihydroresorufin as a Fluorogenic Indicator
journal, May 2014

  • Oja, Stephen M.; Guerrette, Joshua P.; David, Michelle R.
  • Analytical Chemistry, Vol. 86, Issue 12
  • DOI: 10.1021/ac501194j

    Works referencing / citing this record:

    Electrochemical Confinement Effects for Innovating New Nanopore Sensing Mechanisms
    journal, April 2018


    Wireless nanopore electrodes for analysis of single entities
    journal, June 2019


    Closed bipolar electrode-enabled dual-cell electrochromic detectors for chemical sensing
    journal, January 2016

    • Xu, Wei; Fu, Kaiyu; Ma, Chaoxiong
    • The Analyst, Vol. 141, Issue 21
    • DOI: 10.1039/c6an01415a