Electrochemical behavior of folic acid on mercury meniscus modified silver solid amalgam electrode

Voltammetric behavior of folic acid and folates has been investigated using direct current voltammetry, differential pulse voltammetry and adsorptive stripping differential pulse voltammetry at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE). The optimum conditions have been found for their determination in a 1:9 mixture of methanol and aqueous acetate buffer, with the limit of detection about 0.5 nmol L⁻¹. RSD at this concentration level amounted to less than 4%. Practical applicability of the newly developed method was verified by analysis of three vitamin preparations and of two multivitamin juices.     

Simultaneous voltammetric determination of tramadol and acetaminophen using carbon nanoparticles modified glassy carbon electrode

A sensitive and selective electrochemical sensor was fabricated via the drop-casting of carbon nanoparticles (CNPs) suspension onto a glassy carbon electrode (GCE). The application of this sensor was investigated in simultaneous determination of acetaminophen (ACE) and tramadol (TRA) drugs in pharmaceutical dosage form and ACE determination in human plasma. In order to study the electrochemical behaviors of the drugs, cyclic and differential pulse voltammetric studies of ACE and TRA were carried out at the surfaces of the modified GCE (MGCE) and the bare GCE. The dependence of peak currents and potentials on pH, concentration and the potential scan rate were investigated for these compounds at the surface of MGCE. Atomic force microscopy (AFM) was used for the characterization of the film modifier and its morphology on the surface of GCE. The results of the electrochemical investigations showed that CNPs, via a thin layer model based on the diffusion within a porous layer, enhanced the electroactive surface area and caused a remarkable increase in the peak currents. The thin layer of the modifier showed a catalytic effect and accelerated the rate of the electron transfer process. Application of the MGCE resulted in a sensitivity enhancement and a considerable decrease in the anodic overpotential, leading to negative shifts in peak potentials. An optimum electrochemical response was obtained for the sensor in the buffered solution of pH 7.0 and using 2 μL CNPs suspension cast on the surface of GCE. Using differential pulse voltammetry, the prepared sensor showed good sensitivity and selectivity for the determination of ACE and TRA in wide linear ranges of 0.1-100 and 10-1000 μM, respectively. The resulted detection limits for ACE and TRA was 0.05 and 1 μM, respectively. The CNPs modified GCE was successfully applied for ACE and TRA determinations in pharmaceutical dosage forms and also for the determination of ACE in human plasma.     

Determination of trace selenium on hanging copper amalgam drop electrode

Hanging copper amalgam drop electrode has been applied for trace determination of selenium by cathodic stripping analysis. Detection limit for Se(IV) as low as 0.25 nM (0.02 μg L⁻¹) at deposition time (120 s) could be obtained. For seven successive determinations of Se(IV) at concentration of 5 nM relative standard deviation was 2.3% (n = 7). Interferences from selected metals and surfactant substances were examined. Absence of copper ions in sample solution causes easier optimization and makes method less vulnerable on contamination. The developed method was validated by analysis of certified reference materials (BCRs) and applied to selenium determinations in natural water samples, snow, mushrooms and ox liver.     

Flow injection amperometric determination of pyridoxine at a Prussian blue nanoparticle-modified carbon ceramic electrode

This work describes the electrocatalytic properties of a carbon composite electrode (CCE) modified with Prussian blue (PB) nanoparticles (NPs) for the electrocatalytic oxidation of pyridoxine (PN). The morphology of the PBNP-modified CCE was characterized by scanning electron microscopy (SEM). The mechanism and kinetics of the catalytic oxidation reaction of PN were monitored by cyclic voltammetry and chronoamperometry. The rate-limiting step of the charge transfer reaction was found to be a one-electron abstraction. The value of α, k, and D were calculated as 0.66, 6.7 × 10⁴ M⁻¹ s⁻¹, and 1.88 × 10⁻⁵ cm² s⁻¹, respectively. The modified electrode showed electrocatalytic activity toward the oxidation of PN and was used as an amperometric sensor. The sensor exhibited good linear response for PN over the concentration ranges 5-69 and 1-80 μM with detection limits of 0.51 and 0.87 μM, and sensitivities of 0.97 and 0.673 A M⁻¹ cm⁻² in batch and flow conditions, respectively. Some important advantages such as simple preparation, fast response, good stability, and reproducibility of the sensor for the amperometric determination of PN were achieved.     

Cyclic voltammetric response of nicotinic acid and nicotinamide on a polycrystalline gold electrode

The oxidation of nicotinic acid and nicotinamide on a polycrystalline gold electrode occurred at almost same potentials but their reduction did at different peak potentials. The redox reaction mechanisms of nicotinic acid and nicotinamide were rationalized by the formation/disappearance of the new nitrogen-oxygen bonds in the pyridine rings by means of cyclic voltammetry and bulk electrolysis. The anodic currents of nicotinic acid and nicotinamide were controlled by diffusion, while the cathodic ones by adsorption. The difference in the cathodic peak potentials of nicotinic acid and nicotinamide on the polycrystalline gold electrode is attributed to the effect of the electron densities of remote substituents on the pyridine rings. The cathodic peak currents at about 0.20 V were linear with their concentrations in the range of 2.4 mM to 2.7 μM and 2.4 mM to 3.3 μM with detection limits of 0.27 and 0.33 μM for nicotinic acid and nicotinamide, respectively. Voltammetry was then adopted for the selective monitoring the content of nicotinic acid and nicotinamide in pharmaceuticals.     

A potentiometric and voltammetric sensor based on polypyrrole film with electrochemically induced recognition sites for detection of silver ion

Conducting polypyrrole membranes were deposited on glassy carbon electrodes by electropolymerizing pyrrole in the presence of Eriochrome Blue-Black B (EBB) as the counter anion. The electrodes were then subjected to several oxidation/reduction potential steps in pure silver nitrate solution for successive accumulation/stripping of silver species. This electrochemically mediated doping/templating generated selective recognition elements in the EBB/PPy film for silver ions. The resulting sensor exhibited a considerable enhancement in the potentiometric and voltammetric response characteristics: extending the linear dynamic range and lowering the detection limit. In the potentiometric mode, the sensor showed highly reproducible response with a Nernstian slope of 58.5 ± 0.3 mV per decade of Ag⁺ activity over a linear range spanning seven orders of magnitude (1 × 10⁻⁸ to 1 × 10⁻¹ M Ag⁺), with a detection limit of ∼6 × 10⁻⁹ M. The electrodes demonstrated high selectivity over a large number of cations including alkali, alkaline earth and several transition and heavy metal ions, and could be used over a wide pH range of 1-8.5. The EBB/PPy modified electrode was also used for preconcentration and differential pulse anodic stripping voltammetric (DPASV) measurements. The DPASV peak current was dependent on the concentration of Ag⁺ over the range 3 × 10⁻¹⁰ to 1 × 10⁻⁴ M. The presence of 1000-fold excess of Cd²⁺, Cu²⁺, Cr³⁺, Co²⁺, Mn²⁺, Fe²⁺, Fe³⁺, Ni²⁺ and Pb²⁺ can be tolerated in the determination of silver ion.     

Construction of an amperometric pyruvate oxidase enzyme electrode for determination of pyruvate and phosphate

In this study an amperometric biosensor based on pyruvate oxidase was developed for the determination of pyruvate and phosphate. For construction of the biosensor pyruvate oxidase was immobilized with gelatin and insolubilized in film by forming cross-linked bonds with glutaraldehyde. The film was fixed on a YSI type dissolved oxygen (DO) probe, covered with a teflon membrane which is high-sensitive for oxygen. The working principle of the biosensor depends on detection of consumed DO concentration related to pyruvate concentration which is used in enzymatic reaction catalyzed by pyruvate oxidase. The biosensor response shows a linearity with pyruvate concentration between 0.0025 and 0.05 μM and also response time of the biosensor is 3 min. In the optimization studies of the biosensor the most suitable enzyme activity was found as 2.5 U/cm² for pyruvate oxidase, and also phosphate buffer (pH 7.0; 50 mM) and 35 °C were established as providing the optimum working conditions. In the characterization studies of the biosensor some parameters such as reproducibility, substrate specificity, operational stability, determination of phosphate, and interference effects of some compounds on the pyruvate determination were investigated. Finally, the concentration of pyruvate was determined by using spectrophotometric method and the results obtained were compared to results obtained by the biosensor.     

Electro-oxidation and determination of gemcitabine hydrochloride,an anticancer drug at gold electrode

Electrochemical behavior of an anticancer drug, gemcitabine hydrochloride (GMB) was studied in 10.4 pH with 0.2 M phosphate buffer solution as supporting electrolyte at 25 ± 0.1 °C at gold electrode (GE) using different voltammetric techniques. The electrochemical process was observed to be diffusion controlled, irreversible and involving one-electron oxidation. Under optimal conditions, the peak current was proportional to GMB concentration in the range of 0.1–15 μM with a detection limit of 0.06 μM by differential pulse voltammetry. The method was developed for the determination of GMB in pharmaceutical formulations and urine as a real sample.     

3,5-二溴-2-吡啶偶氮重氮氨基偶氮苯固相萃取光度法测定银

研究了3,5-二溴-2-吡啶偶氮重氮氨基偶氮苯(3,5-DB-PDAB)与银的显色反应,在pH11.0的硼砂-氢氧化钠缓冲介质中,乳化剂-OP存在下,3,5-DB-PDAB与银反应生成2∶1稳定配合物。该配合物可用pH1~12的WatersXterraTMRP18固相萃取小柱富集,小柱上富集的配合物用含0.01mol/LpH为11.0的四氢吡咯-醋酸缓冲盐的乙醇洗脱后用光度法测定,在洗脱剂介质中λmax526nm,摩尔吸光系数1.72×105L.mol-1.cm-1,银含量0.01~1.0g/mL范围内符合比尔定律。方法用于环境水样中银的测定。     

Polyaniline Langmuir-Blodgett film modified glassy carbon electrode as a voltammetric sensor for determination of Ag ions

A highly sensitive electrochemical sensor made of a glassy carbon electrode (GCE) coated with a Langmuir-Blodgett film (LB) containing polyaniline (PAn) doped with p-toluenesulfonic acid (PTSA) (LB/PAn-PTSA/GCE) has been used for the detection of trace concentrations of Ag⁺. UV-vis absorption spectra indicated that the PAn was doped by PTSA. The surface morphology of the PAn LB film was characterized by atomic force microscopy (AFM). The electrochemical properties of this LB/PAn-PTSA/GCE were studied using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The LB/PAn-PTSA/GCE was used as a voltammetric sensor for determination of trace Ag⁺ at pH 5.0 using linear scanning stripping voltammetry. Under the optimal experimental conditions, the stripping current was proportional to the Ag⁺ concentration over the range from 6.0 × 10⁻¹⁰ mol L⁻¹ to 1.0 × 10⁻⁶ mol L⁻¹, with a detection limit of 4.0 × 10⁻¹⁰ mol L⁻¹. The high sensitivity, selectivity, and stability of this LB/PAn-PTSA/GCE also demonstrated its practical utility for simple, rapid and economical determination of Ag⁺ in water samples.     

In situ bismuth-film electrode for square-wave anodic stripping voltammetric determination of tin in biodiesel

A bismuth-film electrode (BiFE) was applied in square-wave anodic stripping voltammetry (SWASV) in order to determine Sn (IV) in biodiesel samples. In situ simultaneous deposition of tin and bismuth at −1.2 V for 90 s was carried out in a supporting electrolyte containing 0.1 mol L⁻¹ acetate buffer (pH 4.5) and 1.73 mmol L⁻¹ caffeic acid as the complexing agent. A single well-defined anodic stripping peak was observed at −0.58 V for the oxidation of Sn to Sn (II), which was used as the analytical signal. The calibration curve was obtained in the concentration range of 0.17–7.83 μmol L⁻¹ with the detection limit being 0.14 μmol L⁻¹ (r = 0.9990). Repeatability and reproducibility for the measurement of the current peak were characterized by relative standard deviations of 3.6% and 4.1%, respectively, for a 5.0 μmol L⁻¹ Sn (IV) solution (n = 10). The method was validated by comparing the results obtained with those provided by application of the atomic absorption spectroscopy technique.     

Fabrication and characterization of planar reference electrode for on-chip electroanalysis

A new method for the fabrication of a planar silver/silver chloride reference electrode for electrochemical detection is described. The film microelectrode was directly fabricated on the surface of a glass slide through a combination of electroless deposition and electroplating. Thickness of the electrode film could be easily controlled by setting the repetition times of the deposition. The whole process can be operated in ordinary chemistry laboratory at a low cost, which makes it possible for the development of disposable devices. The electrode potential showed extreme stability in 3 mol/L KCl and water during the tested period of 14 and 10 days, respectively. pH does not have a significant effect on the performance of the electrode. In both potentiometric and amperometric applications, the film Ag/AgCl electrode demonstrated to be a good reference for electroanalysis with its performance comparable to that of commercial reference electrode and the electrodes fabricated from different batches showed good reproducibility.     

Photoelectrocatalytic determination of NADH in a flow injection system with electropolymerized methylene blue

It was firstly described that a glassy carbon electrode electropolymerized with methylene blue shows an efficient photoelectrocatalytic activity towards NADH oxidation in a phosphate buffer solution (pH 7.0). In order to perform the photoelectrocatalytic determination of NADH in a flow injection analysis (FIA) system, a home-made flow electrochemical cell with a suitable transparent window for the irradiation of the electrode surface was constructed. The currents obtained from the photoamperometric measurements in the FIA system at optimum conditions (flow rate of carrier solution, 1.3 mL min⁻¹; transmission tubing length, 10 cm; injection volume, 100 μL; and constant applied potential, +150 mV vs. Ag/AgCl) were linearly dependent on the NADH concentration and linear calibration curves were obtained in the range of 1.0 × 10⁻⁷–2.0 × 10⁻⁴ M. The detection limit was found to be 4.0 × 10⁻⁸ M for photoamperometric determination of NADH.     

Utilization of sodium montmorillonite clay-modified electrode for the determination of isoproturon and carbendazim in soil and water samples

Redox behavior of two pesticides namely isoproturon and carbendazim were investigated electrochemically using sodium montmorillonite clay-modified glassy carbon electrode in the presence and absence of a surfactant, cetyl trimethyl ammonium bromide. A solution of 0.1 M H₂SO₄ in both 50% aqueous alcohol (pH 1.0) was found to be a suitable medium for electroanalysis. Isoproturon exhibited one well-defined oxidation peak around 1.17 V along with one more oxidation and reduction peaks. Carbendazim showed only one well-defined anodic peak around 1.5 V. The main electron transfer was irreversible and the mass transfer was by diffusion for both cases. Controlled potential coulometric studies revealed 2e⁻ and 1e⁻ transfer for isoproturon and carbendazim, respectively. The surfactant had only little effect on the electrochemical properties of isoproturon and pronounced effect with carbendazim. Electroanalytical procedure for the determination of these pesticides was developed using differential pulse stripping voltammogram under their maximum current experimental conditions. Calibration plot was made for both pesticides. The determination limit and standard deviations were arrived at. The applicability of the method was also verified in a soil sample and water analyte.     

Poly(indole-6-carboxylic acid) and tetracyanoquinodimethane-modified electrode for selective oxidation of dopamine

Poly(indole-6-carboxylic acid) (PICA) was synthesized electrochemically over glassy carbon electrode (GCE) through potentiodynamic mode of polymerization. The resulting polymer was soluble in Tris-HCl buffer (pH 7.0). The processable polymer was cast over desired electrode surface along with organic redox mediator tetracyanoquinodimethane (TCNQ) as an electron transfer relay using Nafion^®. Nafion^® was used to solubilize TCNQ as well as to introduce permselectivity to the blend of polymer and TCNQ. The above blend was cast over GCE and characterized by cyclic voltammetry followed by its application in electrochemical sensing of dopamine (DA) and ascorbic acid (AA). The modified electrode was found to be selective for DA analysis. The lowest detection limit of DA sensing was found to be 4 μМ with a sensitivity of 18 μA ± 6 nA/mM of DA.     

Development of a new biosensor for mediatorless voltammetric determination of hydrogen peroxide and its application in milk samples

A new biosensor for the voltammetric detection of hydrogen peroxide was developed based on immobilization of catalase on a clinoptilolite modified carbon paste electrode using bovine serum albumin and glutaraldehyde. The biosensor response was evaluated according to electrode composition, reaction time, solution pH and temperature. The voltammetric signals were linearly in proportion to H₂O₂ concentration in the range 5.0 × 10⁻⁶–1.0 × 10⁻³ M with a correlation coefficient of 0.9975. The detection limit is 8.0 × 10⁻⁷ M and the relative standard deviation for 4.0 × 10⁻⁴ M hydrogen peroxide was 1.83% (n = 6). The biosensor exhibited high sensitivity, and it was determined that it could be used for more than 2 months. In addition, the biosensor was successfully applied for the determination of hydrogen peroxide in milk samples.     

A three-dimensional, magnetic and electroactive nanoprobe for amperometric determination of tumor biomarkers

A novel electrochemical immunosensor for tumor biomarker detection based on three-dimensional, magnetic and electroactive nanoprobes was developed in this study. To fabricate the nanoprobes, negatively charged Fe(3)O(4) nanoparticles (Fe(3)O(4) NPs) and gold nanoparticles (Au NPs) were first loaded on the surface of multiple wall carbon nanotubes (MCNTs) which were functioned with redox-active hemin and cationic polyelectrolyte poly(dimethyldiallylammonium chloride) (PDDA). Using alpha fetoprotein (AFP) as a model analyte, AFP antibody (anti-AFP) was absorbed on the surface of Au NPs, bovine serum albumin (BSA) was then used to block sites against non-specific binding, and finally formed anti-AFP/Au NPs/Fe(3)O(4)/hemin/MCNTs named anti-AFP nanoprobes. When the target antigen AFP was present, it interacted with anti-AFP and formed an antigen-antibody complex on the nanoprobe interface. This resulted in a decreased electrochemical signal of hemin for quantitative determination of AFP when immobilized onto the screen-printed working electrode (SPCE). The results showed that the nanoprobe-based electrochemical immunosensor was sensitive to AFP detection at a concentration of 0.1 to 200 ng·mL(-1) with a detection limit of 0.04 ng·mL(-1), it also demonstrated good selectivity against other interferential substances. The electroactive nanoprobes can be massively prepared, easily immobilized on the SPCE for target detection and rapidly renewed with a magnet. The proposed immunosensor is fast, simple, sensitive, stable, magnet-controlled, nontoxic, label-free and reproducible.     

Simultaneous voltammetric determination of ascorbic acid, acetaminophen and isoniazid using thionine immobilized multi-walled carbon nanotube modified carbon paste electrode

A carbon paste electrode (CPE) modified with thionine immobilized on multi-walled carbon nanotube (MWCNT), was prepared for simultaneous determination of ascorbic acid (AA) and acetaminophen (AC) in the presence of isoniazid (INZ). The electrochemical response characteristics of the modified electrode toward AA, AC and INZ were investigated by cyclic and differential pulse voltammetry (CV and DPV). The results showed an efficient catalytic role for the electro-oxidation of AA and AC, leading to a remarkable peak resolution (∼303 mV) for two compounds. On the other hand, the presence of INZ, which is considered as important drug interference for AC, does not affect the voltammetric responses of these pharmaceuticals. The mechanism of the modified electrode was analyzed by monitoring the CVs at various potential sweep rates and pHs of the buffer solutions. Under the optimum conditions, the calibration curves for AA, AC and INZ were obtained in the range of 1 × 10⁻⁶ to 1 × 10⁻⁴ M, 1 × 10⁻⁷ to 1 × 10⁻⁴ M and 1 × 10⁻⁶ to 1 × 10⁻⁴ M, respectively. The prepared modified electrode shows several advantages such as simple preparation method, high sensitivity, long-time stability, ease of preparation and regeneration of the electrode surface by simple polishing and excellent reproducibility. The proposed method was applied to determination of AA, AC and INZ in commercial drugs and in plasma samples and the obtained results were satisfactory.     

Glassy carbon electrode modified with a bilayer of multi-walled carbon nanotube and polypyrrole doped with new coccine: Application to the sensitive electrochemical determination of Sumatriptan

A promising electrochemical sensor was developed based on a layer by layer process by electro-polymerization of pyrrole in the presence of new coccine (NC) as dopant anion on the surface of the multi-walled carbon nanotubes (MWCNTs) pre-coated glassy carbon electrode (GCE). The modified electrode was used as a new and sensitive electrochemical sensor for voltammetric determination of sumatriptan (SUM). The electrochemical behavior of SUM was investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results showed a remarkable increase (∼12 times) in the anodic peak current of SUM in comparison to the bare GCE. The effect of experimental variables such as, drop size of the casted MWCNTs suspension, pH of the supporting electrolyte, accumulation conditions and the number of cycles in the electro-polymerization process on the electrode response was investigated. Under the optimum conditions, the modified electrode showed a wide linear dynamic range of 0.02–10.0 μmol L⁻¹ with a detection limit of 6 nmol L⁻¹ for the voltammetric determination of SUM. The prepared electrode showed high sensitivity, stability and good reproducibility in response to SUM. This sensor was successfully applied for the accurate determination of trace amounts of SUM in pharmaceutical and clinical preparations.     

Microfabrication, characterization and analytical application of a new thin-film silver microsensor

The present research demonstrates the microfabrication of a novel thin-film silver microelectrode based on an ion-selective PVC organic membrane. First, the gold substrate thin-film surface is treated by depositing a thin-layer of Ag electrochemically. This pretreatment step is followed by applying the organic-membrane-sensitive layer using a new nebulization technique, which gives a high stability to the organic-membrane-sensitive layer. The performance of the resulting thin-film silver microelectrode is investigated by potentiometric measurements. The microelectrode provides a linear Nernstian response of high sensitivity (58 ± 0.5 mV/decade) covering the range of 1 × 10⁻⁶-1 × 10⁻¹ mol L⁻¹ of Ag⁺ ions with a fast response time (<20 s) and a relatively long life span (>3 months). The suggested microelectrode is successfully used in the analytical evaluation of Cl⁻ ions in some real environmental samples as well as in the simultaneous determination of halides using potentiometric titration. The results obtained are compared with those obtained by the commercial silver billet electrode and the conventional bulk ion-selective electrode based on the same ionophore.