Synthesis and Characterization of MWNTs/Au NPs/HS(CH2)6Fc Nanocomposite: Application to Electrochemical Determination of Ascorbic Acid

In this article, a detailed electrochemical study of a novel 6-ferrocenylhexanethiol (HS(CH2)6Fc) self-assembled multiwalled carbon nanotubes-Au nanoparticles (MWNTs/Au NPs) composite film was demonstrated. MWNTs/Au NPs were prepared by one-step in situ synthesis using linear polyethyleneimine (PEI) as bifunctionalizing agent. HS(CH2)6Fc, which acted as the redox mediator, was self-assembled to MWNTs/Au NPs via Au-S bond. Transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), Fourier transformed infrared absorption spectroscopy (FT-IR), UV-visible absorption spectroscopy, and cyclic voltammetry were used to characterize the properties of the MWNTs/Au NPs/HS(CH2)6Fc nanocomposite. The preparation of the nanocomposite was very simple and effectively prevented the leakage of the HS(CH2)6Fc mediator during measurements. The electrooxidation of AA could be catalyzed by Fc/Fc+ couple as a mediator and had a higher electrochemical response due to the unique performance of MWNTs/Au NPs. The nanocomposite modified electrode exhibited excellent catalytic efficiency, high sensitivity, good stability, fast response (within 3 s) and low detection limit toward the oxidation of AA at a lower potential.

[1]  J. Raoof,et al.  Carbon paste electrode spiked with ferrocene carboxylic acid and its application to the electrocatalytic determination of ascorbic acid , 2001 .

[2]  Shaojun Dong,et al.  Preparation of hybrid thin film modified carbon nanotubes on glassy carbon electrode and its electrocatalysis for oxygen reduction. , 2004, Chemical communications.

[3]  R. Leubolt,et al.  Determination of sulphite and ascorbic acid by high-performance liquid chromatography with electrochemical detection , 1993 .

[4]  Paul Calvert,et al.  Nanotube composites: A recipe for strength , 1999, Nature.

[5]  Fwu-Shan Sheu,et al.  Selective Voltammetric Detection of Uric Acid in the Presence of Ascorbic Acid at Well‐Aligned Carbon Nanotube Electrode , 2003 .

[6]  S. Dong,et al.  Electrocatalytic Oxidation of Catechol at Multi‐Walled Carbon Nanotubes Modified Electrode , 2004 .

[7]  Guodong Liu,et al.  Electrochemical detection of DNA hybridization based on carbon-nanotubes loaded with CdS tags , 2003 .

[8]  L. Miller,et al.  FAST OXIDANTS FOR NADH AND ELECTROCHEMICAL DISCRIMINATION BETWEEN ASCORBIC ACID AND NADH , 1981 .

[9]  X. Qiu,et al.  Amperometric glucose sensor based on enzyme-modified boron-doped diamond electrode by cross-linking method , 2004 .

[10]  Huaping Peng,et al.  Ferrocene-modified Fe3O4@SiO2 magnetic nanoparticles as building blocks for construction of reagentless enzyme-based biosensors , 2007 .

[11]  M. N. Myers,et al.  Theoretical and experimental characterization of flow field-flow fractionation , 1976 .

[12]  Dan Du,et al.  Differential pulse voltammetry determination of ascorbic acid with ferrocene-l-cysteine self-assembled supramolecular film modified electrode , 2004 .

[13]  S. Lim,et al.  Electrochemical genosensing properties of gold nanoparticle?carbon nanotube hybrid , 2004 .

[14]  Lenys Fernández,et al.  Electrochemical evaluation of ferrocene carboxylic acids confined on surfactant–clay modified glassy carbon electrodes: oxidation of ascorbic acid and uric acid , 2005 .

[15]  G. Rivas,et al.  Carbon nanotubes paste electrode , 2003 .

[16]  Yongsheng Chen,et al.  Noncovalent nanohybrid of ferrocene with single-walled carbon nanotubes and its enhanced electrochemical property , 2006 .

[17]  G. Rivas,et al.  Enzymatic Biosensors Based on Carbon Nanotubes Paste Electrodes , 2005 .

[18]  Richard G Compton,et al.  Iron oxide particles are the active sites for hydrogen peroxide sensing at multiwalled carbon nanotube modified electrodes. , 2006, Nano letters.

[19]  R. Adams,et al.  Probing brain chemistry with electroanalytical techniques. , 1976, Analytical chemistry.

[20]  Qiang Gao,et al.  Layer-by-layer assembled multilayer films of redox polymers for electrocatalytic oxidation of ascorbic acid , 2005 .

[21]  M. Porter,et al.  Infrared spectroelectrochemical characterization of ferrocene-terminated alkanethiolate monolayers at gold , 1992 .

[22]  M. Sastry,et al.  Optical Absorption Study of the Biotin−Avidin Interaction on Colloidal Silver and Gold Particles , 1998 .

[23]  Jianding Qiu,et al.  A Nanocomposite Chitosan Based on Ferrocene-Modified Silica Nanoparticles and Carbon Nanotubes for Biosensor Application , 2007 .

[24]  Shaojun Dong,et al.  In situ synthesis and characterization of multiwalled carbon nanotube/Au nanoparticle composite materials. , 2006, The journal of physical chemistry. B.

[25]  A. Dhirani,et al.  Electrochemical properties of ferrocenylalkane dithiol-gold nanoparticle films prepared by layer-by-layer self-assembly , 2007 .

[26]  R. Compton,et al.  Apparent 'electrocatalytic' activity of multiwalled carbon nanotubes in the detection of the anaesthetic halothane: occluded copper nanoparticles. , 2006, The Analyst.

[27]  S. Creager,et al.  Competitive self-assembly and electrochemistry of some ferrocenyl-n-alkanethiol derivatives on gold , 1994 .

[28]  H. Askal,et al.  Selective spectrophotometric method for the determination of ascorbic acid in pharmaceutical preparations and fresh fruit juices. , 1991, The Analyst.

[29]  Shen-ming Chen,et al.  Electrochemical preparation and electrocatalytic properties of PEDOT/ferricyanide film-modified electrodes , 2005 .

[30]  Malcolm L. H. Green,et al.  Bioelectrochemical single-walled carbon nanotubes. , 2002, Journal of the American Chemical Society.

[31]  Y. Osajima,et al.  Ascorbate electrode for determination of L-ascorbic acid in food. , 1981, Analytical chemistry.

[32]  S. Ivanov,et al.  Conductometric transducing in electrocatalytical sensors: Detection of ascorbic acid , 2006 .

[33]  Joseph Wang,et al.  Ultrasensitive electrical biosensing of proteins and DNA: carbon-nanotube derived amplification of the recognition and transduction events. , 2004, Journal of the American Chemical Society.

[34]  Yuehe Lin,et al.  Low-potential stable NADH detection at carbon-nanotube-modified glassy carbon electrodes , 2002 .

[35]  A. Salimi,et al.  Amperometric Detection of Morphine at Preheated Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes , 2005 .

[36]  H. Seo,et al.  Electrochemical and Vibrational Spectroscopic Characterization of Self-Assembled Monolayers of 1,1‘-Disubstituted Ferrocene Derivatives on Gold , 2000 .

[37]  Juozas Kulys,et al.  Printed electrochemical sensor for ascorbic acid determination , 1991 .

[38]  E. Wang,et al.  Electrocatalytic oxidation of ascorbic acid by norepinephrine embedded in lipid cast film at glassy carbon electrode , 2001 .

[39]  W. D. de Heer,et al.  Carbon Nanotubes--the Route Toward Applications , 2002, Science.

[40]  M. Sastry,et al.  On the stability of carboxylic acid derivatized gold colloidal particles: the role of colloidal solution pH studied by optical absorption spectroscopy , 1997 .

[41]  Pulickel M. Ajayan,et al.  Carbon nanotube electrode for oxidation of dopamine , 1996 .

[42]  Yuehe Lin,et al.  Solubilization of carbon nanotubes by Nafion toward the preparation of amperometric biosensors. , 2003, Journal of the American Chemical Society.

[43]  K. Yokoyama,et al.  Electrochemical characterization of an enzyme electrode based on a ferrocene-containing redox polymer , 1999 .

[44]  H. Dai,et al.  Noncovalent sidewall functionalization of single-walled carbon nanotubes for protein immobilization. , 2001, Journal of the American Chemical Society.

[45]  L T Kubota,et al.  Exploiting micellar environment for simultaneous electrochemical determination of ascorbic acid and dopamine. , 2005, Talanta.

[46]  M. Petersson.  Electrocatalytic oxidation of ascorbic acid and voltammetric determination with a ferrocene-modified platinum electrode , 1986 .

[47]  Wei‐De Zhang,et al.  Anodic oxidation of hydrazine at carbon nanotube powder microelectrode and its detection. , 2002, Talanta.

[48]  Zhennan Gu,et al.  Direct electrochemistry of cytochrome c at a glassy carbon electrode modified with single-wall carbon nanotubes. , 2002, Analytical chemistry.