Voltammetric behavior of rutin at a boron-doped diamond electrode. Its electroanalytical determination in a pharmaceutical formulation

This paper examined for the first time, the possibilities of the usage of a boron-doped diamond electrode for the redox behavior of rutin using cyclic and adsorptive stripping voltammetry. The cyclic voltammograms showed a pair of redox peaks at lower potentials followed by an irreversible oxidation peak at higher positive potential. Using square-wave adsorptive stripping voltammetry, the compound yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 4.0 at +0.48 V (vs. Ag/AgCl) (after 60 s accumulations at a fixed potential of 0.2 V). The calibration curve was linear in the concentration range from 0.01 µg mL^?1 to 0.1 µg mL^?1 (1.64×10^?8 M ? 1.64×10^?7 M). A detection limit of 0.0017 µg mL^?1 (2.78×10^?9 M) was observed without any chemical modifications and electrochemical surface pretreatments. As an example, the practical applicability of boron-doped diamond electrode was tested with the measurement of rutin in dietary supplement products.      

Differential pulse adsorptive stripping voltammetric determination of methotrexate using a functionalized carbon nanotubes-modified glassy carbon electrode

A glassy carbon electrode (GC) containing multiwalled functionalized carbon nanotubes (MWCNTs) immobilized within a dihexadecylhydrogenphosphate film (DHP) is proposed as a nanostructured platform for determination of methotrexate (MTX) concentration (a drug used in cancer treatment) using differential pulse adsorptive stripping voltammetry (DPAdSV). The voltammograms for a MTX solution using MWCNTs-DHP/GC electrode presented an oxidation peak potential at 0.98 V vs. Ag/AgCl (3.0 mol L^?1 KCl) in a 0.1 mol L^?1 sulphuric acid. The apparent heterogeneous electron transfer rate constant of 0.46 s^?1 was calculated. The recovery area of 2.62×10^?9 mol cm² was also obtained. Under the optimal experimental conditions, the analytical curve was linear in the MTX concentration range from 5.0×10^?8 to 5.0×10^?6 mol L^?1, with a detection limit of 3.3×10^?8 mol L^?1. The MWCNTs-DHP/GC electrode can be easily prepared and was applied for the determination of MTX in pharmaceutical formulations, with results similar to those obtained using a high-performance liquid chromatography comparative method.      

Voltammetric behavior and quantitative determination of ambazone concentrations in urine and in a pharmaceutical formulation

The use of square wave adsorptive stripping voltammetry (SWAdSV) in conjunction with a cyclic renewable silver amalgam film electrode (Hg(Ag)FE) for the analytical determination of ambazone in urine samples and pharmaceutical formulations is described. A single reduction peak in Britton-Robinson buffer at pH 4.0 was detected at about ?1.4 V versus Ag/AgCl. Mechanistic studies have shown that the compound can act as an electrocatalyst. The method was validated. The analytical curve was linear in the concentration range from 1.0×10^?9 to 1.0×10^?7 mol L^?1. The detection and quantification limits were found to be 3.0×10^?10 mol L^?1 and 1.0×10^?9 mol L^?1, respectively. The proposed method was successfully applied to ambazone determination in real samples.      

Voltammetric quantitation at the mercury electrode of the anticholinergic drug flavoxate hydrochloride in bulk and in a pharmaceutical formulation

Flavoxate hydrochloride, 2-piperidinoethyl 3-methyl-4-oxo-2-phenyl-4-H-chromene-8-carboxylate, is a smooth muscle antispasmodic. Its electrochemical behavior was studied at the mercury electrode in buffered solutions containing 30% (v/v) methanol using dc-polarography, differential-pulse polarography, cyclic voltammetry, and linear sweep-and square-wave adsorptive stripping voltammetry. Sensitive and precise procedures were developed for determination of bulk flavoxate hydrochloride and in the pharmaceutical formulation Genurin® S.F, without sample pretreatment or extraction. Limits of quantitation (LOQ) of 1 × 10^?5, 5 × 10^?6, 1 × 10^?8 and 1 × 10^?9 M flavoxate hydrochloride were achieved by dc-polarography, differential-pulse polarography, linear sweep and square-wave adsorptive stripping voltammetric, respectively.      

A low-cost automated flow analyzer based on low temperature co-fired ceramic and LED photometer for ascorbic acid determination

An automated flow analyzer based on low temperature co-fired ceramic (LTCC), a solid-phase reactor (SPR) and a low-cost photometer was designed for ascorbic acid (AA) determination in pharmaceutical formulations. It consists of a peristaltic pump, three-way solenoid valves, SPR to chemically convert Cu(II) into Cu(I), and a LTCC device for mixing the liberated copper with bathocuproine and detection. The flow cell in the LTCC employed an ultrabright LED — photodiode photometer. The analyzer successfully determined AA in pharmaceutical formulations. The analytical curve from 8.5×10^?6 to 7.0×10^?4 M gave a detection limit of 7.0×10^?7 M and a RSD of 2.1% for a 2.0×10^?4 M AA solution (n = 10). A high sampling frequency of 102 h^?1 and low reagent and sample consumption (150 µL) resulted.      

Bismuth and Bismuth-Chitosan modified electrodes for determination of two synthetic food colorants by net analyte signal standard addition method

In this paper, an electrochemical application of bismuth film modified glassy carbon electrode for azo-colorants determination was investigated. Bismuth-film electrode (BiFE) was prepared by ex-situ depositing of bismuth onto glassy carbon electrode. The plating potential was ?0.78 V (vs. SCE) in a solution of 0.15 mg mL^?1 Bi(III) and 0.05 mg mL^?1 KBr for 180 s. In the next step, a thin film of chitosan was deposited on the surface of bismuth modified glassy carbon electrode, thus the bismuth-chitosan thin film modified glassy carbon electrode (Bi-CHIT/GCE) was fabricated and compared with bare GCE and bismuth modified GCE. Azo-colorants such as Sunset Yellow and Carmoisine were determined on these electrodes by differential pulse voltammetry. Due to overlapping peaks of Sunset Yellow and Carmoisine, simultaneous determination of them is not possible, so net analyte signal standard addition method (NASSAM) was used for this determination. The results showed that coated chitosan can enhance the bismuth film sensitivity, improve the mechanical stability without caused contamination of surface electrode. The Bi-CHIT/GC electrode behaved linearly to Sunset Yellow and Carmoisine in the concentration range of 5×10^?6 to 2.38×10^?4 M and 1×10^?6 to 0.41×10^?4 M with a detection limit of 10 µM (4.52 µg mL^?1) and 10 µM (5.47 µg mL^?1), respectively      

Solid contact Zn2+ -selective electrode with low detection limit and stable and reversible potential

A new solid contact Zn²⁺ polyvinylchloride membrane sensor with 2-(2-Hydroxy-1-naphthylazo)-1,3,4 -thiadiazole as an ionophore has been prepared. For the electrode construction, ionic liquids, alkylmethylimidazolium chlorides are used as transducer media and as a lipophilic ionic membrane component. The addition of ionic liquid to the membrane phase was found to reduce membrane resistance and determine the potential of an internal reference Ag/AgCl electrode. The electrode with the membrane composition: ionophore: PVC: o-NPOE: ionic liquid in the percentage ratio of (wt.) 1:30:66:3, respectively, exhibited the best performance, having a slope of 29.8 mV decade^?1 in the concentration range 3×10^?7–1×10^?1 M. The detection limit is 6.9×10^?8 M. It has a fast response time of 5–7 s and exhibits stable and reproducible potential. It has a fast response time of 5–7 s and exhibits stable and reproducible potential, which does not depend on pH in the range 3.8–8.0. The proposed sensor shows a good and satisfactory selectivity towards Zn²⁺ ion in comparison with other cations including alkali, alkaline earth, transition and heavy metal ions. It was successfully applied for direct determination of zinc ions in tap water and as an indicator electrode in potentiometric titration of Zn²⁺ ions with EDTA.      

Adsorptive stripping voltammetric determination of the anti-inflammatory drug tolmetin in bulk form, pharmaceutical formulation and human serum

The electro-reduction of tolmetin at the hanging mercury drop electrode was studied in different supporting electrolytes using cyclic voltammetry and square-wave stripping voltammetry techniques. Voltammograms of tolmetin exhibited a single well-defined 2-electron irreversible cathodic peak in media of pH < 4, which may be attributed to reduction of the >C=O double bond of the analyte molecule. Adsorption of tolmetin onto the surface of the hanging mercury electrode was identified and each adsorbed tolmetin molecule was found to occupy an area of 0.23 nm². A square-wave adsorptive cathodic stripping voltammetric procedure was described for the direct determination of tolmetin in bulk form and pharmaceutical formulation (Rumatol® capsules) with a limit of quantitation of 2 × 10^?9 M and a mean percentage recovery of 98.35 ± 1.21% to 99.57 ± 1.23. Moreover, the described procedure was successfully applied for the direct assay of tolmetin in spiked human serum without pretreatment or extraction prior to the analysis while a quantitation limit of 5 × 10^?9 M tolmetin was achieved.      

Development of a nanocomposite system and its application in biosensors construction

The present work describes the development of a nanocomposite system and its application in construction of a new amperometric biosensor applied in the determination of total polyphenolic content from propolis extracts. The nanocomposite system was based on covalent immobilization of laccase on functionalized indium tin oxide nanoparticles and it was morphologically and structural characterized. The casting of the developed nanocomposite system on the surface of a screen-printed electrode was used for biosensor fabrication. The analytical performance characteristics of the settled biosensor were determined for rosmarinic acid, caffeic acid and catechol (as laccase specific substrate). The linearity was obtained in the range of 1.06×10^?6 ? 1.50×10^?5 mol L^?1 for rosmarinic acid, 1.90×10^?7 ? 2.80×10^?6 mol L^?1 for caffeic acid and 1.66×10^?6 ? 7.00×10^?6 mol L^?1 for catechol. A good sensitivity of amperometric biosensor 141.15 nA µmol^?1 L^?1 and fair detection limit 7.08×10^?8 mol L^?1 were obtained for caffeic acid. The results obtained for polyphenolic content of propolis extracts were compared with the chromatographic data obtained by liquid-chromatography with diode array detection.      

Screen-printed electrodes modified with HRP-zirconium alcoxide film for the development of a biosensor for acetaminophen detection

The development of a biosensor based on the immobilization of horseradish peroxidase (HRP) within a zirconium alkoxide-polyetilenimine film onto screen-printed electrodes (SPE) for acetaminophen detection and acetaminophen quantification in pharmaceutical products is described. The biosensor operation mode is based on monitoring the amperometric signal produced by the electrochemical reduction of the enzymatically generated electroactive oxidized species of acetaminophen in the presence of hydrogen peroxide. The enzyme immobilization is performed by retention in a polyethylenimine-zirconium alcoxide porous gel film, a technique that offers good entrapping and a protective environment for the biocomponent due to the hydration properties of the immobilization layer. SPEs have the advantage of being easily mass-produced at low costs with superior characteristics in comparison with classical electrode materials. In this configuration, zirconium alkoxide demonstrates its electrocatalytic activity. The biosensor allows the quantification of acetaminophen with a limit of detection of 6.21×10^?8 M and a linear range between 4.35×10^?7 M and 4.98×10^?6 M. Finally, the biosensor is applied to the quantitative analysis of acetaminophen in Perdolan® tablets.

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Amperometric determination of sulfide ion by glassy carbon electrode modified with multiwall carbon nanotubes and copper (II) phenanthroline complex

Electrocatalytic oxidation of sulfide ion on a glassy carbon electrode (GCE) modified with multiwall carbon nanotubes (MWCNTs) and a copper (II) complex was investigated. The Cu(II) complex was used due to the reversibility of the Cu(II)/Cu(III) redox couple. The MWCNTs are evaluated as a transducer, stabilizer and immobilization matrix for the construction of amperometric sensor based on Cu(II) complex adsorbed on MWCNTs immobilized on the surface of GCE. The modified GCE was applied to the selective amperometric detection of sulfide at a potential of 0.47 V (vs. Ag/AgCl) at pH 8.0. The calibration graph was linear in the concentration range of 5 µM–400 µM; while the limit of detection was 1.2 µM, the sensitivity was 34 nA µM^?1. The interference effects of SO₃ ^2?, SO₄ ^2?, S₂O₃ ^2?, S₄O₆ ^2?, Cysteine, and Cystein were negligible at the concentration ratios more than 40 times. The modified electrode is more stable with time and more easily restorable than unmodified electrode surface. Also, modified electrode permits detection of sulfide ion by its oxidation at lower anodic potentials.      

Cobalt electrodeposition onto polycrystalline gold from ammoniacal solutions

In the present work, the cobalt electrodeposition onto polycrystalline gold electrodes from aqueous solutions containing 0.01M CoSO₄ + 1 M (NH₄)₂SO₄ at pH=7 was analyzed. Linear voltammetry results suggested a change in the kinetic of the cobalt electrodeposition. In all cases, the nucleation rate (A), the number of active nucleation sites (N ₀) and the saturation number of nuclei (N _s ) values were potential dependent. The calculated Gibbs free energy (ΔG) for this system was 1.88×10^?20 J nuclei^?1 and the transfer coefficient for the Hydrogen Electroreduction Reaction (HER) was 0.47.      

A highly sensitive sensor of paracetamol based on zinc-layered hydroxide-<Emphasis Type="Italic">L</Emphasis>-phenylalanate-modified multiwalled carbon nanotube paste electrode

A new zinc-layered hydroxide-L-phenylalanate (ZLH-LP)-modified multiwalled carbon nanotube (MWCNT) was prepared as a new material of paste electrode for the detection of paracetamol (PCM) in 1.0?×?10^?1 M phosphate buffer solution and at pH 7.5. The electrochemical characterization of the MWCNTs/ZLH-LP paste electrode was characterized by square wave voltammetry, electrochemical impedance spectroscopy, and cyclic voltammetry while the morphology properties of the MWCNTs, ZLH-LP, and MWCNTs/ZLH-LP were investigated using transmission electron microscopy and scanning electron microscopy. Under optimized conditions, the MWCNTs/ZLH-LP paste electrode demonstrated an excellent electrocatalytic activity towards oxidation of PCM in the linear responses’ ranges from 7.0?×?10^?7 M to 1.0?×?10^?4 M (correlation coefficient, 0.996) with the limit of detection obtained at 8.3?×?10^?8 M. As a conclusion, the MWCNTs/ZLH-LP paste electrode revealed good repeatability, reproducibility, and stability, and was found to be applicable for use in pharmaceutical tablet samples.

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Carbon nanotube-ionic liquid nanocomposite modified carbon-ceramic electrode for determination of dopamine in real samples

Room temperature 1-butyl-3-methylimidazolium tetraflouroborate ([BMIM][BF₄]) ionic liquid was employed for dispersion of multi walled carbon nanotubes (MWCNTs) and the formation of nanocomposite on the surface of a carbon-ceramic electrode. The surface of the modified electrode was characterized using scanning electron microscopy and electrochemical impedance spectroscopy. The modified electrode exhibited excellent electrochemical activity to oxidation of dopamine (DA); whereas electro oxidation of ascorbic acid (AA) was not seen and electro oxidation of uric acid (UA) appeared at a more positive potential than DA. The multi walled carbon nanotube-ionic liquid nanocomposite modified carbon-ceramic electrode was used for the selective determination of DA in the presence of high levels of AA and UA using differential pulse voltammetry. The calibration curve for DA was linear in the range of 3.00 to 130 µM with the detection limit (S/N=3) of 0.87 µM. The present electrode was successfully applied to the determination of DA in some commercial pharmaceutical samples and human blood serum.      

Spectrophotometric study of competitive complexation equilibria involving overlapped spectral responding species: Determination of the stability constant of bismuth-pyrophosphate complex

Spectrophotometric study of competitive complex formation equilibria involving overlapped spectral responding species applying a simple and versatile algorithm was carried out. The algorithm involves multivariable regression for calculation of equilibrium concentrations from multiwavelength data and mass action law for the stability constant calculation. The used regression functions are part of common statistical software. Stability constants and complex stoichiometry of competing equilibria were simultaneously determined. The species concentration profiles at several spectral overlapping and ??-coefficient of competing reaction were obtained. Non-absorbing bismuth ?? pyrophosphate (PPh) system was studied as a competitive reaction of bismuth ?? 4-(2-Pyridylazo) resorcinol (PAR) complex. The formation of Bi-PPh complex with 1:1 stoichiometry was proved in the studied concentration region (C_Bi = 1×10^?5 mol L^?1; C_PPh = 5×10^?6 ? 1×10^?4 mol L^?1). The stability constant of the complex at pH 1 and ?? = 1.0 have been determined: log?? = 4.2±0.2.      

LC-ED with an Acetylene Black–Dihexadecyl Hydrogen Phosphate Composite Film-Modified Electrode for in Vivo Analysis of Thiols in Rat Striatal Microdialysate

Liquid chromatography with electrochemical detection (LC-ED), coupled with in vivo microdialysis sampling, has been used for analysis of thiols. An acetylene black–dihexadecyl hydrogen phosphate (AB–DHP) composite film-modified electrode was used as working electrode. The AB–DHP-modified electrode enabled efficient electrocatalytic oxidation of l-cysteine (l-Cys) and glutathione (GSH) with relatively high sensitivity, stability, and longevity. The peak currents of l-Cys and GSH were linear in the concentrations ranges 2.0 × 10^?7–2.0 × 10^?4 and 3.0 × 10^?7–5.0 × 10^?4 mol L^?1, respectively, with calculated detection limits (S/N = 3) of 1.0 × 10^?7 and 2.0 × 10^?7 mol L^?1, respectively. The method has been successfully used to measure the amounts of l-Cys and GSH in striatal microdialysate of freely moving rats.     

Determination of vitamin B6 (pyridoxine hydrochloride) based on a novel BZ oscillating reaction system catalyzed by a macrocyclic complex

This paper reports a new method for determination of VB₆ (pyridoxine hydrochloride) by its perturbation effects on a novel Belousov-Zhabotinskii (BZ) oscillating system. This novel BZ system, in which malic acid serves as the substrate, contains an enzyme-like complex, macrocyclic complex {[CuL](ClO₄)₂}, as catalyst. The ligand L in the complex is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. Results show that the addition of pyridoxine hydrochloride can perturb the oscillation amplitude and period, and the change of the oscillation amplitude is linearly proportional to the concentration of pyridoxine hydrochloride in the range of 5×10^?7?2.5×10^?4 M. The obtained RSD with seven samples is 3.073%. An assay of pharmaceutical tablets of vitamin B₆ was evaluated. Some foreign ions were studied with respect to their possible influence on the determination of pyridoxine hydrochloride. The factors which influence this reaction include the concentration of reactant, the temperature of the reaction, property of catalyst, etc. Furthermore, the possible reaction mechanism has been proposed using the Field-Körös-Noyes (FKN) model.      

Reactions of ligands from BT(B)P family with solvated electrons and benzophenone ketyl radicals in 1-octanol solutions. Pulse radiolysis study

Pulse radiolysis involving reactions of solvated electrons and benzophenone ketyl radicals in 1-octanol with selected compounds from bis-triazinyl pyridines and bis-triazinyl bipyridines, BT(B)P family, developed for extraction of trivalent actinides have been studied. The designated ligands were: 2,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4]triazin-3-yl)pyridine, 6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4-]triazin-3-yl)-[2,2′]bipyridine, 6,6′-bis(5,6-diethyl-[1,2,4]triazin-3-yl)-[2,2′]bipyridine and 6,6′-bis(5,6-dipentyl-[1,2,4]triazin-3-yl)-[2,2′]bipyridine. Reactions of the ligands with solvated electrons in 1-octanol are fast. The rate constants were determined as equal to: $ k_{{{\text{CyMe}}_{4} {\text{BTP}}}} . $  = (2.4 ± 0.2) × 10⁹ dm³ mol^?1 s^?1, $ k_{{{\text{CyMe}}_{ 4} {\text{BTBP}}}} $  = (1.7 ± 0.3) × 10⁹ dm³ mol^?1 s^?1, $ k_{{{\text{C}}_{ 2} {\text{BTBP}}}} $  = (1.3 ± 0.3) × 10⁹ dm³ mol^?1 s^?1 and $ k_{{{\text{C}}_{ 5} {\text{BTBP}}}} $  = (1.7 ± 0.3) × 10⁹ dm³ mol^?1 s^?1. Reactions of the ligands with benzophenone ketyl radicals are much slower and the measured rate constants were as follows: $ k_{{{\text{CyMe}}_{ 4} {\text{BTP}}}} $  = 6.7 × 10⁷ dm³ mol^?1 s^?1 and $ k_{{{\text{CyMe}}_{ 4} {\text{BTBP}}}} $  = 3.2 × 10⁷ dm³ mol^?1 s^?1.     

A thin poly(acridine orange) film containing reduced graphene oxide for voltammetric simultaneous sensing of ascorbic acid and uric acid

We have fabricated, in a single step, carbon ceramic electrodes modified with a poly(acridine orange) film containing reduced graphene oxide. They display electrocatalytic activity to ascorbic acid (AA) and uric acid (UA) at pH 4.5. The anodic peak potentials of AA and UA are separated by 276 mV so that they can be well resolved in cyclic voltammetry. UA and AA were simultaneously determined in a mixture at working potentials of 170 and 400 mV, respectively. Under optimized conditions, the calibration curves for AA and UA cover the 0.8–5,000 μM and 0.6–900 μM concentration range, respectively, while detection limits are 0.3 μM and 0.2 μM. The electrode was applied to determine AA and UA in urine samples.

Sensitive and fast determination of papaverine by adsorptive stripping voltammetry on renewable mercury film electrode

The renewable mercury film electrode, applied for the determination of papaverine traces using differential pulse adsorptive stripping voltammetry (DP AdSV) is presented. The calibration graph obtained for papaverine is linear from 1.25 nM (0.42 µg L^?1) to 95 nM (32.2 µg L^?1) for a preconcentration time of 60 s, with correlation coefficient of 0.998. For the renewable mercury electrode (Hg(Ag)FE) with a surface area of 9.1 mm² the detection limit for a preconcentration time of 60 s is 0.7 nM (0.24 µg L^?1). The repeatability of the method at a concentration level of the analyte as low as 17 µg L^?1, expressed as RSD is 3.3% (n=5). The proposed method was successfully applied and validated by studying the recovery of papaverine from drugs, urine and synthetic solution.