Square Wave Voltammetric Determination of Various Pharmaceuticals

Cochin University of Science & Technology

New voltammetry-based technique for the determination of tebuthiuron in crystal and brown sugar samples

Sugar is widely consumed worldwide and Brazil is the largest producer, consumer, and exporter of this product. To guarantee proper development and productivity of sugar cane crops, it is necessary to apply large quantities of agrochemicals, especially herbicides and pesticides. The herbicide tebuthiuron (TBH) prevents pre- and post-emergence of infesting weed in sugarcane cultures. Considering that it is important to ensure food safety for the population, this paper proposes a reliable method to analyse TBH in sugar matrixes (brown and crystal) using square wave voltammetry (SWV) and differential pulse voltammetry (DPV) at bare glassy carbon electrode and investigate the electrochemical behavior of this herbicide by cyclic voltammetry (CV). Our results suggest that TBH or the product of its reaction with a supporting electrolyte is oxidized through irreversible transfer of one electron between the analyte and the working electrode, at a potential close to +1.16 V vs. Ag |AgClsat in 0.10 mol L-1 KOH as supporting electrolyte solution. Both DPV and SWV are satisfactory for the quantitative analysis of the analyte. DPV is more sensitive and selective, with detection limits of 0.902, 0.815 and 0.578 mg kg-1, and quantification limits of 0.009, 0.010 and 0.008 mg kg-1 in the absence of the matrix and in the presence of crystal and brown sugar matrix, respectively. Repeatability lay between 0.53 and 13.8%, precision ranged between 4.14 and 15.0%, and recovery remained between 84.2 and 113% in the case of DPV conducted in the absence of matrix and in the presence of the crystal sugar matrix, respectively.

New voltammetry-based analytical method for indirect determination of procymidone in brazilian apples

Procymidone, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to apple crops. In this work, we propose a reliable and sensitive method to determine procymidone in Brazilian apples. The method involves differential pulse (DPV) and square-wave voltammetry (SWV) techniques on a glassy carbon electrode. In a supporting electrolyte solution of 0.5 mol L−1 NaOH, procymidone undergoes an irreversible one-electron oxidation at +1.42 V by cyclic voltammetric vs. Ag|AgCl, KCl 3 M reference electrode. The proposed DPV and SWV methods have a good linear response in the 8.00–20.0 mg L−1 range, with limits of detection (LOD) of 0.678 and 0.228 mg L−1, respectively, in the absence of the matrix. We obtained improved LOD (0.097 mg L−1) in the presence of apple matrix and the supporting electrolyte solution. We used three commercial apple samples to evaluate recovery, and we achieved recovery percentages ranging from 94.6 to 110 % for procymidone determinations. We also tested the proposed voltammetric method for reproducibility, repeatability, and potential interferents, and the results were satisfactory for electroanalytical purposes.

Reactivities of Modified and Unmodified Exfoliated Graphite Electrodes in Selected Redox Systems

The electrochemical profiles of exfoliated graphite electrodes (EG) and glassy carbon electrodes (GCE) were recorded using cyclic voltammetry and square wave voltammetry in the presence of various supporting electrolytes and Fe(CN)(6)](3-/4-), Ru(NH3)(6)](2+/3+), ferrocene redox probes. In the supporting electrolytes (KCl, H2SO4, NaOH, tetrabutylammoniumtetraflouroborate, phosphate buffers), the potential windows of EG were found in some cases to be about 200 mV larger than that of GCE. The electroactive surface area of EG was estimated to be 19.5 % larger than the GCE which resulted in higher peak currents on the EG electrode. Furthermore, EG was modified with various nanomaterials such as poly (propylene imine) dendrimer, gold nanoparticles, and dendrimer-gold nanoparticles composite. The morphologies of the modified electrodes were studied using scanning electron microscopy and their electrochemical reactivities in the three redox probes were investigated. The current and the reversibility of redox probes were enhanced with the presence of modifiers in different degrees with dendrimer and gold nanoparticles having a favorable edge.

Cupric hexacyanoferrate nanoparticle modified carbon ceramic composite electrodes

Graphite powder-supported cupric hexacyanoferrate (CuHCF) nanoparticles were dispersed into methyltrimethoxysilane based gels to produce a conducting carbon ceramic Composite, which was used as electrode material to fabricate surface- renewable CuHCF-modified electrodes. Electrochemical behavior of the CuHCF-modifled carbon ceramic composite electrodes was characterized using cyclic and square-wave voltammetry. Cyclic voltammograms at various scan rates indicated that peak currents were surface-confined at low scan rates. In the presence of glutathione, a clear electrocatalytic response was observed at the CuHCF-modified composite electrodes. In addition, the electrodes exhibited a distinct advantage of reproducible surface-renewal by simple mechanical polishing on emery paper, as well as ease of preparation, and good chemical and mechanical stability in a flowing stream.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Sol-gel-derived alpha(2)-K7P2W17VO62/graphite/organoceramic composite as the electrode material for a renewable amperometric hydrogen peroxide sensor

The conductive alpha (2)-K7P2W17VO62/graphite/organoceramic composite was prepared by dispersing alpha (2)-K7P2W17VO62 and graphite powder in a propyltrimethoxysilane-based sol-gel solution; it was used as the electrode material for an amperometric hydrogen peroxide sensor. The modified electrode had a homogeneous mirror-like surface and showed well defined cyclic voltammograms. Square-wave voltammetry was employed to study the pH-dependent electrochemical behavior of c alpha (2)-K7P2W17VO62 doped in the graphite organoceramic matrix, and the experiment showed that both protons and sodium cations participated in the odor process. A hydrodynamic voltammetric experiment was performed to characterize the electrode as an amperometric sensor for the determination of hydrogen peroxide. The sensor can be renewed easily in a repeatable manner by a mechanical polishing step and has a long operational lifetime. (C) 2000 Elsevier Science B.V. All rights reserved.

PMo12-doped carbon ceramic composite electrode based on sol-gel chemistry and its electrocatalytic reduction of bromate

A conductive carbon ceramic composite electrode (CCE) comprised of cc-type 1:12 phosphomolybdic acid (PMo12) and carbon powder in an organically modified silicate matrix was fabricated using a sol-gel method and characterized by scanning electron microscopy, cyclic voltammetry, and Osteryoung square-wave voltammetry. Osteryoung square-wave voltammograms of the modified electrode immersed in different acidic aqueous solutions present the dependence of current and redox potential on pH. The PMo12-doped CCE shows more reversible reaction kinetics, good stability and reproducibility, especially the renewal repeatability by simple polishing in the event of surface fouling or dopant leaching. Moreover, the modified electrode shows good catalytic activity for the electrochemical reduction of bromate.

Fabrication and electrochemical behavior of a sol-gel-derived carbon ceramic composite electrode entrapping 2 : 18-molybdodiphosphate

A new type of inorganic-organic hybrid material incorporating carbon powder and alpha -type 2:18-molybdodiphosphate (P2Mo18) in a methyltrimethoxysilane (MTMOS) based gel has been produced by a sol-gel process and used to fabricate a chemically modified electrode. The P2Mo18-doped carbon ceramic composite electrode was characterized using SEM and cyclic voltammetry. Square-wave voltammetry with an excellent sensitivity was exploited to conveniently investigate the dependence of current and half-wave potential (E-1/2) on pH. The chemically modified electrode has some advantages over the modified film electrodes constructed by the conventional methods, such as long-term stability, reproducibility, and especially repeatability of surface-renewal by simple polishing in the event of surface fouling or dopant leaching. In addition, the modified electrode shows a good catalytic activity for the electrochemical reduction of bromate in an acidic aqueous solution. (C) 2000 Elsevier Science B.V. All rights reserved.

Sol-gel-derived carbon ceramic composite electrodes bulk-modified with 1 : 12-silicomolybdic acid

1:12-Silicomolybdic acid (SiMo12) doped carbon ceramic composite electrodes were fabricated by incorporating SiMo12 and graphite powder in a methyltrimethoxysilane-based gel and characterized by cyclic and square-wave voltammetry, It was demonstrated that the chemically modified electrodes were suitable for electrocatalytic reduction of bromate, The electrodes had the remarkable advantage of surface renewal owing to bulk modification, as web as simple preparation, good mechanical and chemical stability and reproducibility.

Renewable-surface amperometric nitrite sensor based on sol-gel-derived silicomolybdate-methylsilicate-graphite composite material

A new type of silicomolybdate-methylsilicate-graphite composite material was prepared by the sol-gel technique and used for the fabrication of an amperometric nitrite sensor. The silicomolybdic anion acts as a catalyst, the graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. Cyclic voltammetry, square-wave voltammetry and chronoamperometry were employed to characterize the sensor. The amperometric nitrite sensor exhibited a series of good properties: high sensitivity (1.771 mu A mmol(-1) dm(3)), a short response time (7 s), remarkable long-term stability and especially reproducibility of surface renewal in the event of electrode surface fouling.

Sol-gel-derived carbon ceramic electrode containing 9,10-phenanthrenequinone, and its electrocatalytic activity toward iodate

9,10-Phenanthrenequinone (PQ) supported on graphite powder by adsorption was dispersed in propyltrimethoxysilane-derived gels to yield a conductive composite which was used as electrode material to fabricate a PQ-modified carbon ceramic electrode. In this configuration, PQ acts as a catalyst, graphite powder guarantees conductivity by percolation, the silicate provides a rigid porous backbone, and the propyl groups endow hydrophobicity and thus limit the wetting region of the modified electrode. Square-wave voltammetry was exploited to investigate the pH-dependent electrochemical behavior of the composite electrode and an almost Nernstian response was obtained from pH 0.42 to 6.84. Because the chemically modified electrode can electrocatalyze the reduction of iodate in acidic aqueous solution (pH 2.45), it was used as an amperometric sensor for the determination of iodate in table salt. The advantages of the electrode are that it can be polished in the event of surface fouling, it is simple to prepare, has excellent chemical and mechanical stability, and the reproducibility of surface-renewal is good.

Sol-gel-derived graphite organosilicate composite electrodes bulk-modified with Keggin-type alpha-germanomolybdic acid

A novel inorganic-organic hybrid material incorporating graphite powder and Keggin-type alpha -germanomolybdic acid (GeMo12) in methyltrimethoxysilane-based gels has been produced by the sol-gel technique and used to fabricate a chemically bulk-modified electrode. GeMo12 acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The GeMo12-modified graphite organosilicate composite electrode was characterized by cyclic and square-wave voltammetry. The modified electrode shows a high electrocatalytic activity toward the reduction of bromate, nitrite and hydrogen peroxide in acidic aqueous solution. In addition, the chemically-modified electrode has some distinct advantages over the traditional polyoxometalate-modified electrodes, such as long-term stability and especially repeatability of surface-renewal by simple mechanical polishing.

Surface-renewable cobalt(II) hexacyanoferrate-modified graphite organosilicate electrode and its electrocatalytic oxidation of thiosulfate

Cobalt(II) hexacyanoferrate (CoHCF) was deposited on graphite powder by an in situ chemical deposition procedure and then dispersed into methyltrimethoxysilane-derived gels to prepare a surface-renewable CoHCF-modified electrode. The electrochemical behavior of the modified electrode in different supporting electrolyte solutions was characterized by cyclic voltammetry. In addition, square-wave voltammetry was employed to investigate the pNa-dependent electrochemical behavior of the electrode. The CoHCF-modified electrode showed a high electrocatalytic activity toward thiosulfate oxidation and could thus be used as an amperometric thiosulfate sensor.

Amperometric determination of thiosulfate at a surface-renewable nickel(II) hexacyanoferrate-modified carbon ceramic electrode

Graphite powder-supported nickel(II) hexacyanoferrate (NiHCF) was prepared by the in situ chemical deposition method and then dispersed into methyltrimethoxysilane-derived gels to form a conductive composite. The composite was used as electrode material to construct a surface-renewable three-dimensional NiHCF-modified carbon ceramic electrode. Electrochemical behavior of the chemically modified electrode was well characterized using cyclic and square-wave voltammetry. The electrode presented a good electrocatalytic activity toward the oxidization of thiosulfate and thus was used as an amperometric sensor for thiosulfate in the photographic waste effluent. In addition, the electrode exhibited a distinct advantage of surface-renewal by simple mechanical polishing, as well as simple preparation, good chemical and mechanical stability. (C) 2001 Elsevier Science B.V. All rights reserved.