Electrocatalytic oxidation and determination of deferasirox and deferiprone on a nickel oxyhydroxide-modified electrode

doi:10.1016/j.ab.2007.10.030

Analytical Biochemistry

Volume 373, Issue 2, 15 February 2008, Pages 337-348

https://doi.org/10.1016/j.ab.2007.10.030 Get rights and content

Abstract

The electrocatalytic oxidation of two orally administered iron chelator drugs (deferiprone, CP20, and deferasirox, ICL670) was investigated on a nickel oxyhydroxide-modified nickel electrode in alkaline solution. The oxidation process involved and its kinetics were investigated using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy techniques, as well as steady-state polarization measurements. Voltammetric studies indicated that in the presence of the drugs under study, the anodic peak current of low-valence nickel species increased, followed by a decrease in the corresponding cathodic current. This result indicates that the drugs were oxidized via oxyhydroxide species immobilized on the electrode surface via an EC′ mechanism. A mechanism based on the electrochemical generation of Ni(III) active sites and their subsequent consumption by the drugs in question was also investigated. The corresponding rate law under the control of charge transfer was developed, and kinetic parameters were derived. In this context, the charge-transfer resistance accessible both theoretically and through impedancemetry was used as a criterion. The rate constants of the catalytic oxidation of the drugs and the electron-transfer coefficients are reported. A sensitive, simple, and time-saving amperometric procedure was developed for the analysis of deferasirox and deferiprone, with detection limits of 28 and 19 μM, respectively. The electrode was used for the direct assay of deferasirox and deferiprone tablets.

Section snippets

Materials and methods

All chemicals used were analytical grade from Merck (Darmstadt, Germany) and were used without further purification. All solutions were prepared with doubly distilled water. Deferiprone was received as a gift from Arasto Pharmaceutical Chemicals Inc., Tehran, Iran. Deferasirox was synthesized according to Ref. [39]. The deferiprone and deferasirox tablets were obtained as gifts from Avicenna Laboratories, Saveh, Iran, and Osveh Laboratories, Tehran, Iran, respectively. Standard solutions of the

Results and discussion

To investigate the surface morphology of the anodic hydroxide film formed on nickel in sodium hydroxide solution, the surface was examined by SEM. The micrographs taken after the nickel electrode was repeatedly cycled between the potentials of 100 and 900 mV in 100 mM sodium hydroxide are shown in Fig. 1, at two different magnifications. At the electrode surface, the scratch marks from the polishing can be easily seen. A closer look at the surface images indicates that the surface has a highly

Conclusion

A nickel oxyhydroxide-modified nickel electrode was checked for electrooxidation of deferasirox and deferiprone in alkaline medium. The electrode showed electrocatalytic oxidation of these drugs. Chronoamperometric studies demonstrated a large anodic current at the oxidation potential of low-valence nickel hydroxide, in further support of the mediated electrooxidation. A kinetic model was developed and the kinetic parameters were calculated using the drug concentration dependencies of

Acknowledgments

The financial support of the Research Councils of K.N. Toosi University of Technology and University of Tehran is gratefully acknowledged. The authors are also grateful to Dr A. Parsaye for his useful comments.

References (48)

J.G. Redepenning
Chemically modified electrodes: A general overview
Trends Anal. Chem.
(1987)
S. Majdi et al.
Electrocatalytic oxidation of some amino acids on a nickel–curcumin complex modified glassy carbon electrode
Electrochim. Acta
(2007)
M. Jafarian et al.
Electrocatalytic oxidation of methane at nickel hydroxide modiﬁed nickel electrode in alkaline solution
Electrochem. Commun.
(2003)
S.M.A. Shibli et al.
Nano nickel oxide/nickel incorporated nickel composite coating for sensing and estimation of acetylcholine
Biosens. Bioelectron.
(2006)
D.E. Reisner et al.
Nickel hydroxide and other nanophase cathode materials for rechargeable batteries
J. Power Sources
(1997)
D.D. Zhao et al.
Preparation of hexagonal nanoporous nickel hydroxide film and its application for electrochemical capacitor
Electrochem. Commun.
(2007)
P. Xu et al.
Characterization of an ultrafine β-nickel hydroxide from supersonic co-precipitation method
J. Alloys Compd.
(2007)
S. Berchmans et al.
Electrooxidation of alcohols and sugars catalysed on a nickel oxide modified glassy carbon electrode
J. Electroanal. Chem.
(1995)
K.V. Gobi et al.
Monomolecular films of a nickel(II) pentaazamacrocyclic complex for the electrocatalytic oxidation of hydrogen peroxide at gold electrodes
J. Electroanal. Chem.
(1998)
S.Y. Yi et al.
Resolution of dopamine and ascorbic acid using nickel(II) complex polymer-modiﬁed electrodes
J. Electroanal. Chem.
(2007)

M.G. Zurlo et al.

Survival and causes of death in thalassemia major

Lancet

(1989)

E. Nisbet-Brown et al.

Effectiveness and safety of ICL670 in iron-loaded patients with thalassaemia: a randomised, double-blind, placebo-controlled, dose-escalation trial

Lancet

(2003)

C. Hershko et al.

ICL670A: A new synthetic oral chelator: evaluation in hypertransfused rats with selective radioiron probes of hepatocellular and reticuloendothelial iron stores and in iron-loaded rat heart cells in culture

Blood

(2001)

M. Jafarian et al.

A study of the electro-catalytic oxidation of methanol on a cobalt hydroxide modified glassy carbon electrode

Electrochim. Acta

(2003)

H. Heli et al.

Electro-oxidation of methanol on copper in alkaline solution

Electrochim. Acta

(2004)

J. Losada et al.

Redox and electrocatalytic properties of electrodes modified by films of polypyrrole nickel(II) Schiff-base complexes

J. Electroanal. Chem.

(1998)

E. Laviron

General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems

J. Electroanal. Chem.

(1979)

G. Roslonek et al.

Application of glassy-carbon electrode modified with Ni–tetraazamacrocyclic complexes in carbonate solutions to electrocatalytic oxidation of alcohols

Electrochim. Acta

(1994)

J.A. Harrison et al.

The oxidation of hydrazine on platinum in acid solution

J. Electroanal. Chem.

(1970)

A. Maritan et al.

On skewed arc plots of impedance of electrodes with an irreversible electrode process

Electrochim. Acta

(1990)

J.M. Zen et al.

Recent updates of chemically modified electrodes in analytical chemistry

Electroanalysis

(2003)

R.J. Mortimer

Electrochromic materials

Chem. Soc. Rev.

(1997)

S. Majdi et al.

A study of the electrocatalytic oxidation of aspirin on a nickel hydroxide-modified nickel electrode

J. Solid State Electrochem.

(2007)

Y.L. Lo et al.

In situ Raman studies on cathodically deposited nickel hydroxide films and electroless Ni–P electrodes in 1 M KOH solution

Langmuir

(1998)

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Electrocatalytic oxidation and determination of deferasirox and deferiprone on a nickel oxyhydroxide-modified electrode

Abstract

Section snippets

Materials and methods

Results and discussion

Conclusion

Acknowledgments

Trends Anal. Chem.

Electrochim. Acta

Electrochem. Commun.

Biosens. Bioelectron.

J. Power Sources

Electrochem. Commun.

J. Alloys Compd.

J. Electroanal. Chem.

J. Electroanal. Chem.

J. Electroanal. Chem.

Lancet

Lancet

Blood

Electrochim. Acta

Electrochim. Acta

J. Electroanal. Chem.

J. Electroanal. Chem.

Electrochim. Acta

J. Electroanal. Chem.

Electrochim. Acta

Recent updates of chemically modified electrodes in analytical chemistry

Electroanalysis

Electrochromic materials

Chem. Soc. Rev.

A study of the electrocatalytic oxidation of aspirin on a nickel hydroxide-modified nickel electrode

J. Solid State Electrochem.

In situ Raman studies on cathodically deposited nickel hydroxide films and electroless Ni–P electrodes in 1 M KOH solution

Langmuir