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Title: Partially Reduced Graphene Oxide Modified Tetrahedral Amorphous Carbon Thin-Film Electrodes as a Platform for Nanomolar Detection of Dopamine

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [2];  [3];  [1];  [4];  [1]; ORCiD logo [2]
  1. Aalto Univ., Otaniemi (Finland). Dept. of Materials Science
  2. Aalto Univ., Otaniemi (Finland). Dept. of Electrical Engineering and Automation
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Sychrotron Radiation Lightsource
  4. Aalto Univ., Otaniemi (Finland). Dept. of Forest Products Technology

Here, we present for the first time tetrahedral amorphous carbon (ta-C)—a partially reduced graphene oxide (PRGO) hybrid electrode nanomaterial platform for electrochemical sensing of dopamine (DA). Graphene oxide was synthesized with the modified Hummer’s method. Before modification of ta-C by drop casting, partial reduction of the GO was carried out to improve electrochemical properties and adhesion to the ta-C thin film. A facile nitric acid treatment that slightly reoxidized the surface and modified the surface chemistry was subsequently performed to further improve the electrochemical properties of the electrodes. The largest relative increase was seen in carboxyl groups. The HNO3 treatment increased the sensitivity toward DA and AA and resulted in a cathodic shift in the oxidation of AA. The fabricated hybrid electrodes were characterized with scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and electrochemical impedance spectroscopy (EIS). Moreover, compared to the plain ta-C electrode the hybrid electrode was shown to exhibit superior sensitivity and selectivity toward DA in the presence of ascorbic acid (AA), enabling simultaneous sensing of AA and DA close to the physiological concentrations by cyclic voltammetry (CV) and by differential pulse voltammetry (DPV). Two linear ranges of 0–1 μM and 1–100 μM and a detection limit (S/N = 3.3) of 2.6 nM for DA were determined by means of cyclic voltammetry. Thus, the current work provides a fully CMOS-compatible carbon based hybrid nanomaterial that shows potential for in vivo measurements of DA.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-76SF00515; AC02-05CH11231; AC02-06CH11357; 259595; 285015; 285526; 211488
OSTI ID:
1361077
Journal Information:
Journal of Physical Chemistry. C, Vol. 121, Issue 14; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

References (76)

New trends in the electrochemical sensing of dopamine journal December 2012
What has been learnt from study of dopamine receptors in Parkinson's disease? journal September 2006
Evaluating Dopamine Reward Pathway in ADHD journal September 2009
Association between obsessive-compulsive disorder and polymorphisms of genes encoding components of the serotonergic and dopaminergic pathways journal May 2000
The size and burden of mental disorders and other disorders of the brain in Europe 2010 journal September 2011
Carbon Microelectrodes with a Renewable Surface journal March 2010
Comparison and Reappraisal of Carbon Electrodes for the Voltammetric Detection of Dopamine journal December 2013
Control of Catechol and Hydroquinone Electron-Transfer Kinetics on Native and Modified Glassy Carbon Electrodes journal October 1999
Improving the function of dopamine electrodes with novel carbon materials conference July 2013
New electrochemically improved tetrahedral amorphous carbon films for biological applications journal October 2014
Diamond-like carbon (DLC) thin film bioelectrodes: Effect of thermal post-treatments and the use of Ti adhesion layer journal January 2014
Osteogenesis of human mesenchymal stem cells on micro-patterned surfaces journal November 2011
Formation and retention of staphylococcal biofilms on DLC and its hybrids compared to metals used as biomaterials journal January 2013
Adhesion, spreading and osteogenic differentiation of mesenchymal stem cells cultured on micropatterned amorphous diamond, titanium, tantalum and chromium coatings on silicon journal August 2009
Bacterial adhesion to diamond‐like carbon as compared to stainless steel
  • Soininen, Antti; Tiainen, Veli‐Matti; Konttinen, Yrjö T.
  • Journal of Biomedical Materials Research Part B: Applied Biomaterials, Vol. 90B, Issue 2 https://doi.org/10.1002/jbm.b.31359
journal April 2009
Ultrathin undoped tetrahedral amorphous carbon films: The role of the underlying titanium layer on the electronic structure journal August 2015
Psychoanalytical Electrochemistry: Dopamine and Behavior journal October 2003
Detecting Subsecond Dopamine Release with Fast-Scan Cyclic Voltammetry in Vivo journal October 2003
Correlation between sp 3 -to-sp 2 Ratio and Surface Oxygen Functionalities in Tetrahedral Amorphous Carbon (ta-C) Thin Film Electrodes and Implications of Their Electrochemical Properties journal April 2016
Carbon nanotube (CNT) forest grown on diamond-like carbon (DLC) thin films significantly improves electrochemical sensitivity and selectivity towards dopamine journal May 2015
Graphene for electrochemical sensing and biosensing journal October 2010
Definitive Evidence for Fast Electron Transfer at Pristine Basal Plane Graphite from High-Resolution Electrochemical Imaging journal April 2012
Carbon Nanotubes Contain Residual Metal Catalyst Nanoparticles even after Washing with Nitric Acid at Elevated Temperature Because These Metal Nanoparticles Are Sheathed by Several Graphene Sheets journal May 2007
Electrochemistry of graphene, graphene oxide and other graphenoids: Review journal November 2013
Carbon nanotube growth by PECVD: a review journal April 2003
Catalyst-Free Efficient Growth, Orientation and Biosensing Properties of Multilayer Graphene Nanoflake Films with Sharp Edge Planes journal November 2008
Highly sensitive and selective detection of dopamine in the presence of ascorbic acid at graphene oxide modified electrode journal September 2013
Simultaneous determination of dopamine, ascorbic acid and uric acid at electrochemically reduced graphene oxide modified electrode journal March 2014
Graphene‐Modified Carbon Fiber Microelectrode for the Detection of Dopamine in Mice Hippocampus Tissue journal March 2011
Electrochemical sensor based on nitrogen doped graphene: Simultaneous determination of ascorbic acid, dopamine and uric acid journal April 2012
The role of oxygen functionalities and edge plane sites on screen-printed carbon electrodes for simultaneous determination of dopamine, uric acid and ascorbic acid journal April 2008
Effect of pH and Surface Functionalities on the Cyclic Voltammetric Responses of Carbon-Fiber Microelectrodes journal July 1999
Functional groups modulate the sensitivity and electron transfer kinetics of neurochemicals at carbon nanotube modified microelectrodes journal January 2011
The electrochemical effect of acid functionalisation of carbon nanotubes to be used in sensors development journal February 2011
Highly concentrated, stable nitrogen-doped graphene for supercapacitors: Simultaneous doping and reduction journal February 2012
Preparation of Graphitic Oxide journal March 1958
Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations journal March 1999
An XPS round robin investigation on analysis of wood pulp fibres and filter paper journal June 2005
Enhanced secondary electron yield from oxidized regions on amorphous carbon films studied by x-ray spectromicroscopy
  • Díaz, Javier; Anders, Simone; Cossy-Favre, Aline
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 17, Issue 5 https://doi.org/10.1116/1.581938
journal September 1999
NEXAFS studies of complex alcohols and carboxylic acids on the Si(111)(7×7) surface journal June 1987
NEXAFS Spectroscopy book January 1992
Near-edge x-ray absorption fine structure spectroscopy study of nitrogen incorporation in chemically reduced graphene oxide
  • Dennis, Robert V.; Schultz, Brian J.; Jaye, Cherno
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 31, Issue 4 https://doi.org/10.1116/1.4813058
journal July 2013
The Structure of Graphite Oxide: Investigation of Its Surface Chemical Groups journal May 2010
Dual Path Mechanism in the Thermal Reduction of Graphene Oxide journal November 2011
Analysis of polyurethanes using core excitation spectroscopy. Part II: Inner shell spectra of ether, urea and carbamate model compounds journal August 1995
The oscillator strengths for C1s and O1s excitation of some saturated and unsaturated organic alcohols, acids and esters journal January 1988
Photon stimulated desorption of hydrogen from diamond surfaces via core-level excitations: fundamental processes and applications to surface studies journal July 2006
Quantum Confinement and Fullerenelike Surface Reconstructions in Nanodiamonds journal January 2003
A near edge X-ray absorption fine structure study of oxidized single crystal and polycrystalline diamond surfaces journal May 2014
Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide journal June 2007
Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects journal July 2007
Raman spectroscopy for the study of reduction mechanisms and optimization of conductivity in graphene oxide thin films journal January 2013
Raman Spectra of Graphite Oxide and Functionalized Graphene Sheets journal January 2008
Graphene Oxide Papers Modified by Divalent Ions—Enhancing Mechanical Properties via Chemical Cross-Linking journal March 2008
Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets journal December 2006
Structural evolution during the reduction of chemically derived graphene oxide journal June 2010
The Role of Oxygen during Thermal Reduction of Graphene Oxide Studied by Infrared Absorption Spectroscopy journal September 2011
Infrared Spectroscopy of Carbon Materials:  A Quantum Chemical Study of Model Compounds journal July 2003
Changes in surface chemistry of activated carbons by wet oxidation journal January 2000
Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. journal October 1965
Measurement of the diffusion coefficients of [Ru(NH3)6]3+ and [Ru(NH3)6]2+ in aqueous solution using microelectrode double potential step chronoamperometry journal March 2011
Diffusion coefficients determined with microelectrodes journal April 1991
Electrocatalysis at graphite and carbon nanotube modified electrodes: edge-plane sites and tube ends are the reactive sites journal January 2005
Oxygenated Edge Plane Sites Slow the Electron Transfer of the Ferro-/Ferricyanide Redox Couple at Graphite Electrodes journal June 2006
Differentiation between graphene oxide and reduced graphene by electrochemical impedance spectroscopy (EIS) journal July 2012
Electrochemical reactions of catechol, methylcatechol and dopamine at tetrahedral amorphous carbon (ta-C) thin film electrodes journal October 2015
Simultaneous voltammetric detection of ascorbic acid, dopamine and uric acid using a pyrolytic graphite electrode modified into dopamine solution journal March 2008
A simple electroanalytical methodology for the simultaneous determination of dopamine, serotonin and ascorbic acid using an unmodified edge plane pyrolytic graphite electrode journal February 2007
A carbon nanofiber based biosensor for simultaneous detection of dopamine and serotonin in the presence of ascorbicacid journal April 2013
Simultaneous Determination of Ascorbic Acid, Dopamine and Uric Acid at Pt Nanoparticles Decorated Multiwall Carbon Nanotubes Modified GCE journal March 2010
Simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid based on nitrogen doped porous carbon nanopolyhedra journal January 2013
Advanced Carbon Electrode Materials for Molecular Electrochemistry journal July 2008
Improved voltammetric peak separation and sensitivity of uric acid and ascorbic acid at nanoplatelets of graphitic oxide journal April 2010
Atomic and electronic structure of tetrahedral amorphous carbon surfaces from density functional theory: Properties and simulation strategies journal October 2014
Growth Mechanism and Cross-Sectional Structure of Tetrahedral Amorphous Carbon Thin Films journal April 1998
Application of graphene-modified electrode for selective detection of dopamine journal April 2009

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