An electrochemical Ni(II)-selective sensor-based on a newly synthesized dioxime derivative as a neutral ionophore

doi:10.1016/j.snb.2005.12.008

Sensors and Actuators B: Chemical

Volume 119, Issue 1, 24 November 2006, Pages 167-173

https://doi.org/10.1016/j.snb.2005.12.008 Get rights and content

Abstract

The suitability of a dioxime derivative, (2E, 3E)-2H-1,4-benzothiazine-2,3(4H)-dione dioxime as a neutral ionophore for the preparation of a PVC membrane electrode for Ni(II) ions was investigated. It can be used for at least 4 months without any considerable divergence in potentials and it has a relatively fast response of <10 s. The prepared membrane exhibits a near Nernstian response for Ni²⁺ ions over a wide concentration range (1.0 × 10⁻⁶ to 1.0 M) with a detection limit of 1.6 × 10⁻⁶ M. At a working pH range of 2.0–6.5 the proposed membrane electrode revealed very good selectivity for Ni²⁺ ions over a wide variety of other cations. It was applied successfully as an indicator electrode in potentiometric titration of nickel ions with EDTA, and in the determination of Ni²⁺ in some water samples.

Introduction

The dioxime ligands are known to coordinate metal ions as neutral dioximes [1], [2]. The chemistry of the bis-dioximate complexes of transition metal ions has been attracting continuous attention because of their importance with reference to dioxygen carriers [3], catalysis in chemical transformations [4], [5], [6], intramolecular hydrogen bonding and metal–metal interaction [7], [8], [9]. In 1905, Tschugaeff discovered the vicinal dioxime metal complex bis-dimethylgloximatonickel(II) [10], initiating an area of coordination chemistry which has been widely explored during the past century. On the other hand, carrier-based ion-selective electrodes are well-established analytical tools that are used routinely to measure a wide variety of different ions selectively and directly in complex samples. In the past years, a large variety of mainly cation-selective carriers have been synthesized by various research groups and published articles on ionophore-based ion-selective electrodes (ISEs) are increasingly developed [11], [12], [13], [14]. The increasing use of ion sensors in the fields of environmental, agricultural and medical analysis is stimulating analytical chemists to develop new sensors for fast, accurate, reproducible and selective determination of various species.

Nickel is well known as a toxic element that can cause cancer of nasal lungs, dermatitis, asthma and disorders of central nervous system [15]. Thus, due to the urgent need for selective monitoring of Ni²⁺ in many industrial, environmental and food samples, there have been a number of recent reports in the literature [16], [17], [18], [19], [20]. However, most of them possess either one, two or, in some cases, all of the following problems: (1) high limit of detection; (2) narrow working concentration range; (3) weak reversibility; (4) serious interferences from other cations. We have recently found that a dioxime having a lipophilic moiety can be used as a suitable neutral ionophore in preparation of a PVC-based Ni²⁺ ion-selective electrode. The results presented in this article show that the sensor, developed for Ni(II) ions-based on a newly synthesized (2E, 3E)-2H-1,4-benzothiazine-2,3(4H)-dione dioxime (HL, Fig. 1), due to its highly selective complexation with Ni²⁺ ions and negligible water solubility, has a wide working concentration range, fast response time and gives reproducible results.

Section snippets

Reagents

Reagent grade bis(2-ethylhexyl)sebacate (DOS), tris(2-ethylhexyl)butylphthalate (TBP), dioctylphthalate (DOP), dibutylphthalate (DBP), sodium tetrakis(para-chlorophenyl)borate (NaTPB), tetrahydrofuran (THF), tetraethylammoniumperclorate (TEAP) and poly(vinyl chloride) (PVC) of high relative molecular weight (all from Merck) were used as received. Nitrate and chloride salts of all cations used were of the highest purity available (all from Merck) and used without any further purification. Doubly

Results and discussion

In order to find a clue about the stability and selectivity of its complexes in a non-aqueous solvent, in preliminary experiments the complexation of HL with nickel metal ions and some other cations such as Cd²⁺, Zn²⁺, Cu²⁺, Co²⁺ and Pb²⁺ was investigated spectrophotometrically in acetonitrile. The results showed a good selectivity of HL for Ni(II) over other preliminary tested ions. Thus, based on the selectivity of HL for Ni(II) as well as its high lipophilic character the ligand was expected

Conclusions

On the basis of the above mentioned results, the Ni(II) ion-selective electrode which was designed in this work has many advantages including: easy preparation, low cost, wide dynamic range, low detection limit, suitable pH range and good reproducibility. The sensor was used successfully to the titration of Ni(II) with EDTA and water samples.

Abdollah Yari has been a Professor of analytical chemistry at Lorestan University of Khorramabad, Iran, since 1996. He received his BS degree in pure chemistry in 1991 from Razi University of Kermanshah, Iran, MS degree in analytical chemistry in 1993 from Tehran University, and PhD in analytical chemistry from Razi University. His research interests are in chemical sensors (optical and electrochemical) in analytical chemistry.

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Sedigheh Azizi has been a graduate student of analytical chemistry at Lorestan University since 2003. Her research interests are development of electrochemical sensors for heavy metal ions.

Ali Kakanejadifard has been a Professor of organic chemistry at Lorestan University of Khorramabad, Iran, since 1994. He received his BS degree in organic chemistry in 1988 from Chamran University of Ahwaz, Iran, and PhD in organic chemistry in 1994 from Tehran University. His research interests are the study of the chemistry of dioximes and their pharmaceutical applications.

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An electrochemical Ni(II)-selective sensor-based on a newly synthesized dioxime derivative as a neutral ionophore

Abstract

Introduction

Section snippets

Reagents

Results and discussion

Conclusions

Coord. Chem. Rev.

Ion Sel. Electrode Rev.

Anal. Chim. Acta

Sens. Actuators B

Anal. Chim. Acta

Sens. Actuators B

Anal. Chim. Acta

Anal. Chim. Acta

Anal. Chim. Acta

Nonclassical packing of metal dioximates superexchange through a diamagnetic metal cation

Inorg. Chem.

Effective new cobalt(II) dioxygen carriers derived from dimethylglyoxime by the replacement of the linking protons with difluoroboron

Inorg. Chem.

Bull. Chem. Soc. Jpn.

Mononuclear bis(dimethylglyoximato)ruthenium(III) complexes with different appended axial groups: highly efficient catalysts for water oxidation

J. Mol. Catal.

Gtrans-dioxo-bis(dimethylglyoximato)ruthenium(VII) perchlorate: an active oxidation catalyst for the electrochemical epoxidation of olefins

J. Mol. Catal.

Acta Crystallogr., Sect. B

Metal–metal interactions in transition-metal complexes containing infinite chains of metal atoms

Chem. Soc. Rev.

Crystal and molecular structure of bis(triphenylphosphine)tetrakis(dimethylglyoximato)dirhodium. Length of a rhodium(II)-to-rhodium(II) single bond

J. Am. Chem. Soc.

Development of α-dioximes as reagents for group VIIIB metals

Chem. Ber.