Voltammetric picomolar determination of mercury, copper and cadmium using modified pencil graphite electrode with poly-L-cysteine and Fe3O4 nanoparticles.

Cost-effective simultaneous determination of mercury, copper and cadmium ions was performed by differential pulse anodic stripping voltammetry (DPASV) using a pencil graphite electrode (PGE) modified with poly-L-cysteine (P-L-Cys) and Fe3O4 nanoparticles. Electropolymerization of L-cysteine was performed by cyclic voltammetry (CV) through applying different cycles. Also, Fe3O4 was deposited in a single step by applying a constant potential on the electrode surface in the presence of ferric nitrate. To enhance the sensitivity of measurement, several parameters such as monomer concentration, scan rate, number of cycles in electropolymerization, ferric nitrate concentration, Fe3O4 electrodeposition potential and time, and pH of the sample solution were optimized. The surface morphology of the modified electrode was examined by SEM and FTIR. Electrochemical impedance spectroscopy was conducted to investigate the impedance of the electrode surface. The linear ranges for cadmium, copper and mercury were 0.001‒2500, 0.0002‒3600 and 0.0001‒2500 nM with detection limits of 6.4 × 10-13, 1.0 × 10-13 and 9.0 × 10-14 M, respectively. The stability and reproducibility of the electrode were investigated. Finally, the modified electrode was applied to determine mercury, copper and cadmium in real samples such as the groundwater, Caspian Sea and Tajan River water.

Study of Electrical Discharge Machining Parameters on Stainless Steel Using Copper Tool Electrode and Its Effect on the Structure and Electrochemical Properties.

In this work, the effect of the presence and the diffusion of the Copper from the tool electrode onto the EDMed stainless steel (SS) surface have been investigated by electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD), Quantometer analysis, and Optical microscopic observations. The Taguchi method was used to study the effects of Pulse-on time (ton), Pulse-off time (toff), discharge current (I), and overall machining time (τ) on chemical composition, microstructures, micro-cracks, and electrochemical corrosion of EDMed stainless steel workpieces. The results show that the variation of machining parameters changes the chemical composition of the workpieces. By increasing the discharge current and decreasing the Pulse-on time, the copper and the carbon diffuse onto the surface of the workpiece. Consequently, the chemical composition of the workpiece surface changes, which leads to an increment of the corrosion resistance. The XRD showed the formation of Fe2C, Cr3C2, and CuNi. In addition, at higher values of discharge current and ton/toff ratio, the micro-cracks propagate on the surface of the workpiece.

Preparation of Dawson heteropolyacid-embedded silver nanoparticles/graphene oxide nanocomposite thin film used to modify pencil graphite electrode as a sensor for trace electrochemical sensing of levodopa.

Measurement of levodopa (LD) as the most efficient treatment accessible for controlling the symptoms of Parkinson's disease was investigated. The electrocatalytic measurement of LD was performed at the surface of pencil graphite electrode (PGE) modified with graphene oxide (GO) and silver nanoparticle@Dawson heteropolyacid (AgNPs@DHPA). For this purpose, GO and the intermediate (AgNPs@DHPA) were first synthesized using a simple, cost-effective and straightforward method. The synthetic compounds, morphology, and surface characteristics of the modified sensor were evaluated. The results demonstrated that AgNPs@DHPA well-dispersed on the GO/PGE surface with a mean size of 6.27 nm and thickness of 42 nm. The electrochemical behavior of the modified PGE was also investigated. The heterogeneous charge transfer rate constant (ks) and transfer coefficient (α) for the electron transfer between AgNPs@DHPA/GO and PGE were obtained as 16.44 s-1 and 0.59, respectively. Also, the diffusion coefficient of LD for AgNPs@DHPA/GO/PGE thin film was calculated using chronoamperometric experiments (D = 9.05 × 10-6 cm2 s-1). Optimal parameters were obtained to access the best response for the measurement of LD. The results revealed that the modified PGE was able to measure the trace amounts of LD in phosphate buffer solution (pH = 6.0) in the concentration ranges from 3.0 × 10-9 to 1.0 × 10-7 M and 1.0 × 10-7 to 1.0 × 10-5 M. The calculated limit of detection was obtained 7.6 × 10-10 M which was much better than the previously reported electrochemical sensors. The modified electrode was used to measure LD in tablet, blood serum and urine.

Molecularly imprinted sol-gel electrochemical sensor for sildenafil based on a pencil graphite electrode modified by Preyssler heteropolyacid/gold nanoparticles/MWCNT nanocomposite.

An electrochemical sensor based on the imprinted sol-gel on pencil graphite electrode (PGE) modified with functionalized multiwalled carbon nanotube (MWCNT), gold nanoparticles (AuNPs), and Preyssler heteropolyacid (PHPA) nanohybrid was fabricated for the determination of trace amounts of sildenafil. The pencil graphite electrode was first deposited by the AuNPs@PHPA-MWCNT nanohybrids, and then, the modified electrode of MIP-sol-gel/AuNPs@PHPA-MWCNTs was prepared by the electrochemical method. The synthesized nanohybrids and prepared modified electrodes were characterized with FE-SEM, FTIR, EDX, XRD, and UV/Vis. Cyclic voltammetry, electrochemical impedance spectroscopy, and differential pulse voltammetry techniques were applied for the electrochemical analysis using the modified electrodes. By measuring the oxidation and reduction currents of the potassium ferricyanide probe, the efficiency of this sensor was evaluated for the detection of sildenafil. The anodic peak current was measured at 0.2 V vs. Ag/AgCl by differential pulse voltammetry in the potential range - 0.1 to 0.5 V (vs. Ag/AgCl). Under the optimum conditions, the current response for the detection of sildenafil was linear in two concentration ranges of 0.1-2 and 2-30 nM and the obtained limit of detection was 0.033 nM. The constructed sensor was used for the measurement of sildenafil in real samples.

Polyoxometalate/reduced graphene oxide modified pencil graphite sensor for the electrochemical trace determination of paroxetine in biological and pharmaceutical media.

Paroxetine is an effective drug for the treatment of depression and stress which has been commonly used in recent years. Because of the widespread use and therapeutic effects of paroxetine, a rapid and sensitive method is needed to determine the trace concentration of paroxetine. Herein, an electrochemical sensor was constructed for the measurement of paroxetine using a modified pencil graphite electrode (PGE). Modification of the PGE was carried out by the reduced graphene oxide/phosphotungstic acid (rGO/PWA) by potentiostatic procedure at -1.2 V for 5 min in phosphate buffer solution with pH = 7.0. Surface morphology analyzing of the modified PGE was performed by scanning electron microscopy (SEM), Raman, XRD, FTIR and electrochemical impedance spectroscopy (EIS) techniques. The kinetic parameter of electron transfer coefficient (α) was calculated for the oxidation process of paroxetine at the modified PGE. Differential pulse voltammetry (DPV) was performed for the determination of PRX. The calibration graph exhibited linear characteristics in the range of 8.0 × 10-9-1.0 × 10-6 M of PRX concentration (R2 = 0.998). The relevant limit of detection was found to be 9.0 × 10-10 M. The modified PGE was successfully performed for the determination of PRX in paroxetine tablets and real samples such as human serum and urine.

Improving stability of biosensor based on covalent immobilization of horseradish peroxidase by γ-aminobutyric acid and application in detection of H2O2.

A novel electrochemical biosensor for the determination of hydrogen peroxide (H2O2) has been fabricated through covalently immobilized horseradish peroxidase (HRP) on modified multi walled carbon nanotube (MWCNT) by γ-aminobutyric acid (GABA) on glassy carbon electrode. Using the electrochemical techniques, the electrochemical properties of the biosensor were specified. Cyclic voltammograms of the enzyme film at pH = 7.0 exhibited a pair of quasi-reversible redox peaks according to Fe(III/II) redox process of HRP. The biosensor exhibited good efficiency for finding H2O2 with a broad linear range from 2.0 × 10-7 M to 2.81 × 10-4 M and a detection limit of 0.13 µM. The surface coverage of active HRP, heterogeneous electron transfer rate constant and Michaelis-Menten constant of immobilized HRP were obtained 3.029 × 10-9 mol cm-2, 1.11 s-1, and 0.23 mM respectively. Similarly, the applicability of the suggested biosensor was examined by detecting H2O2 in human plasma samples and the average recovery was obtained as 100.50 ±â€¯0.25. Moreover, the constructed biosensor presented a high stability, reproducibility and repeatability. Finally using docking and the molecular dynamics calculations, it was determined that GABA interacts with lysine residue and it causes HRP to be placed on the electrode with a specific orientation.

New chemically modified carbon paste sensor for nanomolar concentration measurement of rifampicin in biological and pharmaceutical media.

A new carbon paste electrode for rifampicin (RIF) drug was prepared and fully characterized in terms of composition, usable pH range and temperature. The sensor is based on 2-hydroxypropyl ß-cyclodextrin as a good ionophore in the carbon paste matrix. The modified electrode showed a Nernstian slope of 59.2 mV/decade over the concentration range of 3.2 × 10-8 to 2.2 × 10-4 M with a limit of detection 2.3 × 10-8 M. The electrode has a short and stable response time of 4 s. The sensor manifested advantages of simple design, low cost, wide concentration range, excellent selectivity to rifampicin, applicable as an indicator electrode and renewability. The sensor was successfully used for determination of rifampicin in tablet and blood serum samples. Temperature dependence of the sensor potential response was examined in the temperature range of 15-55 °C. The sensor showed a very low thermal coefficient within the studied temperature range.

Ultrasound-assisted dispersive liquid-liquid microextraction followed by ion mobility spectrometry for the simultaneous determination of bendiocarb and azinphos-ethyl in water, soil, food and beverage samples.

A sensitive and fast ultrasound-assisted dispersive liquid-liquid microextraction procedure combined with ion mobility spectrometry has been developed for the simultaneous extraction and determination of bendiocarb and azinphos-ethyl. Experimental parameters affecting the analytical performance of the method were optimized: type and volume of extraction solvent (chloroform, 150 µL), pH (9.0), type and volume of buffer (ammonium buffer pH = 9.0, 4.5 mL) and extraction time (3.0 min). Under optimum conditions, the linearity was found to be in the range of 2-40 and 6-100 ng/mL and the limits of detection (LOD) were 1.04 and 1.31 ng/mL for bendiocarb and azinphos-ethyl, respectively. The method was successfully validated for the analysis of bendiocarb and azinphos-ethyl in different samples such as waters, soil, food and beverage samples.

Application of cation-modified sulfur nanoparticles as an efficient sorbent for separation and preconcentration of carbamazepine in biological and pharmaceutical samples prior to its determination by high-performance liquid chromatography.

A simple and rapid solid phase extraction procedure using a mini-column packed with modified sulfur nanoparticles as a new, efficient and reusable sorbent has been developed for the preconcentration of carbamazepine prior to its determination by high performance liquid chromatography. This method is based on the retention of carbamazepine by modified sulfur nanoparticles which are quite efficient for fast adsorption and desorption of carbamazepine. An HPLC system including C18, 250×4.6mm column, methanol-acidic water (pH=2.6 by acetic acid) (60:40) as mobile phase and UV detector (λ=276nm) was used. The effects of multiple experimental conditions such as the effect of pH, type and volume of buffer, type and volume of eluent, sample and eluent flow rate, sorbent amount and interfering ions, on the analytical performance of the method were investigated. The calibration curve was linear in the range of 0.5-200ngmL-1 and LOD of the proposed method was found to be 0.16ngmL-1. The procedure was successfully applied for the determination of carbamazepine in pharmaceutical samples, human plasma and breast milk.

Application of l-cystine modified zeolite for preconcentration and determination of ultra-trace levels of cadmium by flame atomic absorption spectrometry.

A very convenient, sensitive and precise solid phase extraction (SPE) system was developed for enrichment and determination of ultra-trace of cadmium ion in water and plant samples. This method was based on the retention of cadmium(II) ions by l-cystine adsorbed in Y-zeolite and carry out in a packed mini-column. The retained cadmium ions then were eluted and determined by flame atomic absorption spectrometry. The scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and Fourier Transform Infrared (FT-IR) spectroscopy techniques were applied for the characterization of cystine modified zeolite (CMZ). Some experimental conditions affecting the analytical performance such as pH, eluent type, concentration of sample, eluent flow rate and also the presence of interfering ions were investigated. The calibration graph was linear within the range of 0.1-7.5ngmL(-1) and limit of detection was obtained 0.04ngmL(-1) with the preconcentration factor of 400. The relative standard deviation (RSD) was obtained 1.4%, indicating the excellent reproducibility of this method. The proposed method was successfully applied for the extraction and determination of cadmium(II) ion in black tea, cigarette's tobacco and also various water samples.

Development of a novel carbon paste sensor for determination of micromolar amounts of sulfaquinoxaline in pharmaceutical and biological samples.

A potentiometric carbon paste sensor was fabricated for determination of sulfaquinoxaline (SQX) based on the use of ion-association complex of sulfaquinoxaline sodium with 2,3,5-triphenyltetrazolium chloride. The proposed sensor exhibited Nernstian slope of 58.4 ± 0.3 mV per decade for sulfaquinoxaline over a wide concentration range of 5.0 × 10(-6) to 1.0 × 10(-2)M, with a low detection limit of 3.0 × 10(-6)M. The sensor manifested advantages of fast response time, satisfactory reproducibility, long life time, high thermal stability and, most importantly, excellent selectivities for sulfaquinoxaline relative to a wide variety of common foreign inorganic cations, anions, sugars and amino acids. The sensor was successfully used for determination of sulfaquinoxaline in pharmaceutical solution, blood serum, urine and milk samples. The isothermal coefficient of the electrode was calculated by the investigation of temperature effects on the electrode potential response.

Synthesis, crystal structure, fluorescence and electrochemical studies of a new tridentate Schiff base ligand and its nickel(II) and palladium(II) complexes.

A new unsymmetrical tridentate Schiff base ligand was derived from the 1:1M condensation of ortho-vanillin with 2-mercaptoethylamine. Nickel and palladium complexes were obtained by the reaction of the tridentate Schiff base ligand with nickel(II) acetate tetrahydrate and palladium(II) acetate in 2:1M ratio. In nickel and palladium complexes the ligand was coordinated to metals via the imine N and enolic O atoms. The S groups of Schiff bases were not coordinated to the metals and S-S coupling was occured. The complexes have been found to possess 1:2 Metal:Ligand stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The complexes exhibited octahedral coordination geometry. The emission spectra of the ligand and its complexes were studied in methanol. Electrochemical properties of the ligand and its metal complexes were investigated in the CH3CN solvent at the 100 mV s(-1) scan rate. The ligand and metal complexes showed both reversible and quasi-reversible processes at this scan rate. The Schiff base and its complexes have been characterized by IR, (1)H NMR, UV/Vis, elemental analyses and conductometry. The crystal structure of nickel complex has been determined by single crystal X-ray diffraction.

Development of a new chemically modified carbon paste electrode for selective determination of urinary and serum oxalate concentration.

The construction and evaluation of a novel modified carbon paste electrode with high selectivity toward oxalate ion are described. The constructed carbon paste potentiometric sensor for oxalate ion is based on the use of a zirconium salan complex as a good ionophore in the carbon paste matrix. The electrode exhibits a Nernstian slope of 29.1 mV/decade to oxalate ion over a wide concentration range from 1.5×10(-6) to 3.9 ×10(-2) mol L(-1) with a low detection limit of 7.0×10(-7) mol L(-1). The electrode possesses fast response time, satisfactory reproducibility, appropriate lifetime, and most importantly, good selectivity toward C2O4(2-) relative to a variety of common anions. The potentiometric response of the electrode is independent of the pH of the test solution in the pH range 2.5-8.0. The modified carbon paste electrode was successfully applied as an indicator electrode in potentiometric titration and potentiometric determination of oxalate ion in mineral water, blood serum and urine samples.

Uranyl-selective PVC membrane electrodes based on some recently synthesized benzo-substituted macrocyclic diamides.

Four different recently synthesized macrocyclic diamides were studied to characterize their abilities as uranyl ion carriers in PVC membrane electrodes. The electrodes based on macrocycle 1,18-diaza-3,4;15,16-dibenzo-5,8,11,14,21,24-hexaoxacyclohexaeicosane-2,17-dione resulted in a Nernstian response for UO(2)(2+) ion over wide concentration ranges. The linear concentration range for the polymeric membrane electrode (PME) is 3.0x10(-6)-8.2x10(-3) M with a detection limit of 2.2x10(-6) and that for the coated graphite electrode (CGE) is 5.0x10(-7)-1.5x10(-3) M with a detection limit of 3.5x10(-7) M. The electrodes manifest advantages of low resistance, very fast response and, most importantly, good selectivities relative to a wide variety of other cations.