Voltammetric detection of cadmium ions at glutathione-modified gold electrodes.

An electrochemical sensor for the detection of cadmium ions is described using immobilized glutathione as a selective ligand. First, a self-assembled monolayer of 3-mercaptopropionic acid (MPA) was formed on a gold electrode. The carboxyl terminus then allowed attachment of glutathione (GSH)via carbodiimide coupling to give the MPA-GSH modified electrode. A cadmium ion forms a complex with glutathione via the free sulfhydryl group and also to the carboxyl groups. The complexed ion is reduced by linear and Osteryoung square wave voltammetry with a detection limit of 5 nM. The effect of the kinetics of accumulation of cadmium on the measured current was investigated and modeled. Increasing the temperature of accumulation and electrochemical analysis caused an increase in the voltammetric peak of approximately 4% per degrees C around room temperature. The modified electrode could be regenerated, being stable for more than 16 repeated uses and more than two weeks if used once a day. Some interference from Pb(2+) and Cu(2+) was observed but the effects of Zn(2+), Ni(2+), Cr(3+) and Ba(2+) were insignificant.

[1]  M. Nishizawa,et al.  Underpotential Deposition of Silver onto Gold Substrates Covered with Self-Assembled Monolayers of Alkanethiols To Induce Intervention of the Silver between the Monolayer and the Gold Substrate , 1998 .

[2]  D. Cui,et al.  Voltammetric determination of cadmium(II) using a chemically modified electrode , 2001, Fresenius' journal of analytical chemistry.

[3]  L. Bülow,et al.  Metal-binding proteins and peptides in bioremediation and phytoremediation of heavy metals. , 2001, Trends in biotechnology.

[4]  Xingyao Zhou,et al.  Voltammetry and EQCM Investigation of Glutathione Monolayer and Its Complexation with Cu2 , 2003 .

[5]  L. Kane-Maguire,et al.  HIGH FIELD NMR STUDY OF THE BINDING OF LEAD(II) TO CYSTEINE AND GLUTATHIONE , 1993 .

[6]  D. Rabenstein,et al.  Nuclear magnetic resonance studies of the solution chemistry of metal complexes. IX. The binding of cadmium, zinc, lead, and mercury by glutathione. , 1973, Journal of the American Chemical Society.

[7]  M. Aihara,et al.  An ion‐gate response of a glutathione monolayer assembly highly sensitive to lanthanide ions , 1994 .

[8]  D. B. Hibbert,et al.  Sub-ppt detection limits for copper ions with Gly-Gly-His modified electrodes. , 2001, Chemical communications.

[9]  A. Krężel,et al.  Coordination chemistry of glutathione. , 1999, Acta biochimica Polonica.

[10]  J. Justin Gooding,et al.  Redox voltammetry of sub-parts per billion levels of Cu2+ at polyaspartate-modified gold electrodes , 2001 .

[11]  Dafu Cui,et al.  Amperometric sensor for simultaneous determination of Cd2+ and Pb2+ , 2001, Other Conferences.

[12]  J. C. Hoogvliet,et al.  Electrochemical pretreatment of polycrystalline gold electrodes to produce a reproducible surface roughness for self-assembly: a study in phosphate buffer pH 7.4 , 2000, Analytical chemistry.

[13]  M. Nishizawa,et al.  Underpotential Deposition of Copper on Gold Electrodes through Self-Assembled Monolayers of Propanethiol , 1997 .

[14]  D. B. Hibbert,et al.  Electrochemical Metal Ion Sensors. Exploiting Amino Acids and Peptides as Recognition Elements , 2001 .

[15]  F. Zhao,et al.  Voltammetric Response of Glutathione and 3‐Mercaptopropionic Acid Self‐Assembled Monolayer Modified Gold Electrodes to Cu(II) , 2002 .

[16]  W. Kadima,et al.  Nuclear magnetic resonance studies of the solution chemistry of metal complexes. 26. Mixed ligand complexes of cadmium, nitrilotriacetic acid, glutathione, and related ligands. , 1990, Journal of inorganic biochemistry.

[17]  D. B. Hibbert,et al.  Exploring the use of the tripeptide Gly-Gly-his as a selective recognition element for the fabrication of electrochemical copper sensors. , 2003, The Analyst.

[18]  D. Arrigan,et al.  A study of L-cysteine adsorption on gold via electrochemical desorption and copper(II) ion complexation , 1999 .

[19]  R. Tauler,et al.  Application of multivariate curve resolution to voltammetric data. II. Study of metal-binding properties of the peptides. , 1996, Analytical biochemistry.

[20]  M. Porter,et al.  Selective Determination of Cadmium in Water Using a Chromogenic Crown Ether in a Mixed Micellar Solution , 1997 .

[21]  J. Justin Gooding,et al.  Characterisation of gold electrodes modified with self-assembled monolayers of l-cysteine for the adsorptive stripping analysis of copper , 2001 .

[22]  S. Kuwabata,et al.  Underpotential deposition behavior of metals onto gold electrodes coated with self-assembled monolayers of alkanethiols , 1999 .

[23]  R. Tauler,et al.  CADMIUM-BINDING PROPERTIES OF GLUTATHIONE: A CHEMOMETRICAL ANALYSIS OF VOLTAMMETRIC DATA , 1997 .

[24]  Miquel Esteban,et al.  Multivariate Curve Resolution of Cyclic Voltammetric Data: Application to the Study of the Cadmium-Binding Properties of Glutathione , 1999 .

[25]  J. Justin Gooding,et al.  Self-Assembled Monolayers into the 21st Century: Recent Advances and Applications , 2003 .

[26]  Chun‐hsien Chen,et al.  Application of cysteine monolayers for electrochemical determination of sub-ppb copper(II) , 1999 .

[27]  M. Aihara,et al.  An ion-gate response of the glutathione monolayer assembly formed on a gold electrode: Part 1. The effect of pH, K+ and Ca2+ , 1992 .

[28]  R. Plackett,et al.  THE DESIGN OF OPTIMUM MULTIFACTORIAL EXPERIMENTS , 1946 .

[29]  David N. Reinhoudt,et al.  Sensor functionalities in self-assembled monolayers , 2000 .

[30]  Daniel Mandler,et al.  Self-assembled monolayers in electroanalytical chemistry: Application of .omega.-mercaptocarboxylic acid monolayers for electrochemical determination of ultralow levels of cadmium(II) , 1994 .