Gold nanoparticle–polypyrrole composite modified TiO2 nanotube array electrode for the amperometric sensing of ascorbic acid

Titanium dioxide (TiO2) nanotubes were fabricated by anodisation of titanium foil in 0.15 M ammonium fluoride in an aqueous solution of glycerol (90 % v/v). Electropolymerisation of pyrrole and deposition of gold nanoparticles on to the TiO2 nanotube array electrode were carried out by cyclic voltammetry (CV). Electrochemical characterization of the sensor was performed by CV and electrochemical impedance spectroscopy. The morphology of the electrode was studied after every step of modification using field emission scanning electron microscope and atomic force microscope. The sensor was tested for AA and other biomolecules in phosphate buffered saline solution of pH 7 using CV, differential pulse voltammetry and amperometry. The sensor exhibited very high sensitivity of 63.912 μA mM−1 cm−2 and excellent selectivity to ascorbic acid (AA) in the presence of other biomolecules such as uric acid, dopamine, glucose and para-acetaminophen. It also showed very good linearity (R = 0.9995) over a wide range (1 μM–5 mM) of detection. The sensor was tested for AA in lemon and found its concentration to be 339 mg ml−1.

[1]  Haitao Huang,et al.  Bioelectrocatalytic application of titania nanotube array for molecule detection. , 2007, Biosensors & bioelectronics.

[2]  P. Kannan,et al.  Determination of nanomolar uric and ascorbic acids using enlarged gold nanoparticles modified electrode. , 2009, Analytical biochemistry.

[3]  David J. Pena,et al.  Electrochemical properties of colloidal Au-based surfaces : Multilayer assemblies and seeded colloid films , 1999 .

[4]  T. Ohsaka,et al.  An extraordinary electrocatalytic reduction of oxygen on gold nanoparticles-electrodeposited gold electrodes ☆ , 2002 .

[5]  Craig A. Grimes,et al.  A Sentinel Sensor Network for Hydrogen Sensing , 2003 .

[6]  Aicheng Chen,et al.  Coadsorption of horseradish peroxidase with thionine on TiO2 nanotubes for biosensing. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[7]  Craig A. Grimes,et al.  Highly-ordered TiO2 nanotube arrays up to 220 µm in length: use in water photoelectrolysis and dye-sensitized solar cells , 2007 .

[8]  Ming‐Chang Wu,et al.  Quantification of L‐ascorbic acid and total ascorbic acid in fruits and spinach by capillary zone electrophoresis , 2001, Electrophoresis.

[9]  Somnath C. Roy,et al.  The effect of TiO2 nanotubes in the enhancement of blood clotting for the control of hemorrhage. , 2007, Biomaterials.

[10]  Suw Young Ly,et al.  Detection of dopamine in the pharmacy with a carbon nanotube paste electrode using voltammetry. , 2006, Bioelectrochemistry.

[11]  Craig A. Grimes,et al.  A Self-Cleaning, Room-Temperature Titania-Nanotube Hydrogen Gas Sensor , 2003 .

[12]  A. Malinauskas.  Electrocatalysis at conducting polymers , 1999 .

[13]  F. Marken,et al.  Characterisation of hydrophobic carbon nanofiber-silica composite film electrodes for redox liquid immobilisation , 2006 .

[14]  Craig A Grimes,et al.  Use of highly-ordered TiO(2) nanotube arrays in dye-sensitized solar cells. , 2006, Nano letters.

[15]  Jing‐Juan Xu,et al.  Interfacing myoglobin to graphite electrode with an electrodeposited nanoporous ZnO film. , 2006, Analytical biochemistry.

[16]  Qingyun Cai,et al.  An amperometric glucose biosensor fabricated with Pt nanoparticle-decorated carbon nanotubes/TiO2 nanotube arrays composite , 2009 .

[17]  Craig A. Grimes,et al.  A room-temperature TiO2-nanotube hydrogen sensor able to self-clean photoactively from environmental contamination , 2004 .

[18]  Craig A. Grimes,et al.  Synthesis and application of highly ordered arrays of TiO2 nanotubes , 2007 .

[19]  T. Ramachandran,et al.  Gold Nanoparticles Modified Titania Nanotube Arrays for Amperometric Determination of Ascorbic Acid , 2010 .

[20]  Craig A. Grimes,et al.  Anodic Growth of Highly Ordered TiO2 Nanotube Arrays to 134 μm in Length , 2006 .

[21]  T. Ohsaka,et al.  Electroanalytical applications of cationic self-assembled monolayers: square-wave voltammetric determination of dopamine and ascorbate. , 2001, Bioelectrochemistry.

[22]  Jinhan Cho,et al.  Nanostructured Electrochemical Sensor Based on Dense Gold Nanoparticle Films , 2003 .

[23]  John H T Luong,et al.  Electrochemical determination of arsenite using a gold nanoparticle modified glassy carbon electrode and flow analysis. , 2006, Analytical chemistry.

[24]  C. Grimes,et al.  Application of highly-ordered TiO2 nanotube-arrays in heterojunction dye-sensitized solar cells , 2006 .

[25]  S. A. John,et al.  Size dependent electrocatalytic activity of gold nanoparticles immobilized onto three dimensional sol-gel network , 2008 .

[26]  Lixia Yang,et al.  An electro-catalytic biosensor fabricated with Pt-Au nanoparticle-decorated titania nanotube array. , 2008, Bioelectrochemistry.

[27]  K. Rajeshwar,et al.  Nanoporous TiO2 and WO3 films by anodization of titanium and tungsten substrates: influence of process variables on morphology and photoelectrochemical response. , 2006, The journal of physical chemistry. B.

[28]  E. Lust,et al.  Characterisation of activated nanoporous carbon for supercapacitor electrode materials , 2007 .

[29]  D. Astruc,et al.  Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. , 2004, Chemical reviews.

[30]  R. Murray,et al.  Monolayer-protected cluster molecules. , 2000, Accounts of chemical research.

[31]  K. G. Ong,et al.  A Transcutaneous Hydrogen Sensor: From Design to Application , 2006 .

[32]  B. Jena,et al.  Efficient electrocatalytic oxidation of NADH at gold nanoparticles self-assembled on three-dimensional sol-gel network. , 2005, Chemical communications.

[33]  Christopher J. Kiely,et al.  From monolayers to nanostructured materials: an organic chemist's view of self-assembly , 1996 .

[34]  Luyuan Zhang,et al.  Ti/TiO2 Nanotube Array/Ni Composite Electrodes for Nonenzymatic Amperometric Glucose Sensing , 2010 .

[35]  Xiangqin Lin,et al.  Simultaneous determination of dopamine and serotonin on gold nanocluster/overoxidized-polypyrrole composite modified glassy carbon electrode , 2007 .

[36]  Craig A. Grimes,et al.  Hydrogen sensing using titania nanotubes , 2003 .

[37]  Craig A. Grimes,et al.  Backside illuminated dye-sensitized solar cells based on titania nanotube array electrodes , 2006 .

[38]  C. Grimes,et al.  Initial Studies on the Hydrogen Gas Sensing Properties of Highly-Ordered High Aspect Ratio TiO 2 Nanotube-Arrays 20 μ m to 222 μ m in Length , 2006 .

[39]  Chunzhong Li,et al.  Electrocatalytic activity of Pt doped TiO2 nanotubes catalysts for glucose determination , 2010 .

[40]  R. G. Freeman,et al.  Preparation and Characterization of Au Colloid Monolayers , 1995 .

[41]  Jingming Gong,et al.  Electrochemical biosensing of methyl parathion pesticide based on acetylcholinesterase immobilized onto Au-polypyrrole interlaced network-like nanocomposite. , 2009, Biosensors & bioelectronics.

[42]  T. Chou,et al.  Criteria for Designing a Polypyrrole Glucose Biosensor by Galvanostatic Electropolymerization , 2002 .

[43]  Shengfu Wang,et al.  Electrochemical parameters of ethamsylate at multi-walled carbon nanotube modified glassy carbon electrodes. , 2007, Bioelectrochemistry.

[44]  Qin Xu,et al.  Porous Gold-Nanoparticle−CaCO3 Hybrid Material: Preparation, Characterization, and Application for Horseradish Peroxidase Assembly and Direct Electrochemistry , 2006 .

[45]  C. Grimes,et al.  A titania nanotube-array room-temperature sensor for selective detection of hydrogen at low concentrations. , 2004, Journal of nanoscience and nanotechnology.

[46]  Aicheng Chen,et al.  A novel hydrogen peroxide biosensor based on the immobilization of horseradish peroxidase onto Au-modified titanium dioxide nanotube arrays. , 2008, Biosensors & bioelectronics.

[47]  Jing Li,et al.  Electrodeposition of gold nanoclusters on overoxidized polypyrrole film modified glassy carbon electrode and its application for the simultaneous determination of epinephrine and uric acid under coexistence of ascorbic acid. , 2007, Analytica chimica acta.

[48]  Ahmed I. Abdelrahman,et al.  Fabrication and electrochemical application of three-dimensional gold nanoparticles: self-assembly. , 2006, The journal of physical chemistry. B.

[49]  G. Bidan,et al.  Electroconducting conjugated polymers: New sensitive matrices to build up chemical or electrochemical sensors. A review☆ , 1992 .

[50]  Craig A. Grimes,et al.  Unprecedented ultra-high hydrogen gas sensitivity in undoped titania nanotubes , 2006 .

[51]  Aicheng Chen,et al.  High performance glucose biosensor based on the immobilization of glucose oxidase onto modified titania nanotube arrays , 2009 .

[52]  R. Hamers,et al.  Fabrication and characterization of vertically aligned carbon nanofiber electrodes for biosensing applications , 2006 .

[53]  Adriano Ambrosi,et al.  The application of conducting polymer nanoparticle electrodes to the sensing of ascorbic acid. , 2008, Analytica chimica acta.

[54]  P. Kannan,et al.  Electrocatalytic oxidation of ascorbic acid using a single layer of gold nanoparticles immobilized on 1,6-hexanedithiol modified gold electrode , 2007 .

[55]  N. Nakashima,et al.  Electroreflectance study of gold nanoparticles immobilized on an aminoalkanethiol monolayer coated on a polycrystalline gold electrode surface , 2002 .

[56]  Craig A. Grimes,et al.  A review on highly ordered, vertically oriented TiO2 nanotube arrays: Fabrication, material properties, and solar energy applications , 2006 .

[57]  Kai Zhu,et al.  Enhanced charge-collection efficiencies and light scattering in dye-sensitized solar cells using oriented TiO2 nanotubes arrays. , 2007, Nano letters.

[58]  Shanhong Xia,et al.  A micro-potentiometric hemoglobin immunosensor based on electropolymerized polypyrrole-gold nanoparticles composite. , 2009, Biosensors & bioelectronics.

[59]  M. Oyama,et al.  Gold nanoparticle-attached ITO as a biocompatible matrix for myoglobin immobilization : direct electrochemistry and catalysis to hydrogen peroxide , 2005 .

[60]  Fang Chen,et al.  Electrochemistry and voltammetry of procaine using a carbon nanotube film coated electrode. , 2006, Bioelectrochemistry.

[61]  A. Gopalan,et al.  Electrocatalytic oxidation and determination of ascorbic acid in the presence of dopamine at multiwalled carbon nanotube–silica network–gold nanoparticles based nanohybrid modified electrode , 2010 .

[62]  John H T Luong,et al.  Metallic nanoparticle-carbon nanotube composites for electrochemical determination of explosive nitroaromatic compounds. , 2006, Analytical chemistry.

[63]  Tejal A Desai,et al.  Decreased Staphylococcus epidermis adhesion and increased osteoblast functionality on antibiotic-loaded titania nanotubes. , 2007, Biomaterials.

[64]  C. Grimes,et al.  Fabrication and Catalytic Properties of Co−Ag−Pt Nanoparticle-Decorated Titania Nanotube Arrays , 2007 .

[65]  T. McCormac,et al.  Voltammetric behaviour, homogeneous charge transport dynamics and electrocatalytic properties of an Os2+ functionalised pyrrole monomer , 2004 .