Voltammetric detection of carbofuran determination using screen-printed carbon electrodes modified with gold nanoparticles and graphene oxide.

Carbofuran is a highly toxic pesticide that is heavily used in agriculture due to its high effectiveness and low cost. Improved methods that are simpler and lower cost are needed for carbofuran detection in food and agricultural samples. Herein, we describe the development of a unique electrochemical method for carbofuran-phenol, which is the main hydrolysis product of carbofuran. We have successfully developed a highly accurate and precise method in a portable size using a screen-printed carbon electrode (SPCE) that is modified with graphene oxide (GO) and gold nanoparticles (AuNPs). Consequently, the developed electrode is highly sensitive to and selective for carbofuran. Using the central composite design (CCD) approach, we optimized the method for analysis parameters including the electrode surface loadings of GO and AuNPs as well as the working solution pH. The method exhibited a wide linear range of 1-250µM for analyte detection using differential pulse voltammetry (DPV) on AuNPs/GO-SPCE under the optimized conditions. The limits of detection and quantitation were 0.22 and 0.72µM, respectively. In addition, we also report the application of the method for carbofuran determination in real cucumber and rice samples. This sensitive and selective carbofuran detection method is very promising for simple and low cost analysis in real agricultural fields.

Determination of nickel(II) by ion-transfer to hydroxide medium using sequential injection-electrochemical analysis (SIECA).

A method for the determination of Ni(II) using ion-transfer to a hydroxide medium has been developed by the sequential injection-electrochemical analysis (SIECA), a combination between an automated flow-based analysis and electrochemical techniques with a homemade screen-printed carbon electrode (SPCE). A sample/standard solution was introduced into an electrochemical flow cell where the Ni(II) in the solution was electrochemically reduced and accumulated on the SPCE. The accumulated Ni was then oxidized to Ni(II) in a hydroxide medium, which led to the formation of nickel hydroxide (Ni(OH)2) and nickel oxyhydroxide (NiOOH) on the SPCE. The electrochemical response associated with Ni(OH)2 and NiOOH was subsequently determined by square-wave voltammetry to account for Ni(II). Under optimal conditions, the proposed method provides a low detection limit of 0.02mgmL-1. This method was further applied to determine the Ni(II) content of standard-spiked mineral water samples with satisfactory results.

Polyaniline/graphene quantum dot-modified screen-printed carbon electrode for the rapid determination of Cr(VI) using stopped-flow analysis coupled with voltammetric technique.

Polyaniline/graphene quantum dots (PANI/GQDs) were used to modify a screen-printed carbon electrode (SPCE) in a flow-based system. A method for rapidly determining the Cr(VI) concentrations by using stopped-flow analysis has been developed using an Auto-Pret system coupled with linear-sweep voltammetry using the PANI/GQD-modified SPCE. The GQDs, synthesized in a botton-up manner from citric acid, were mixed with aniline monomer in an optimized ratio. The mixture was injected into an electrochemical flow cell in which electro-polymerization of the aniline monomer occurred. Under conditions optimized for determining Cr(VI), wide linearity was obtained in the range of 0.1-10 mg L(-1), with a detection limit of 0.097 mg L(-1). For a sample volume of 0.5 m L, the modified SPCE can be used continuously with a sample-throughput of more than 90 samples per hour. In addition, this proposed method was successfully applied to mineral water samples with acceptable accuracy, and the quantitative agreement was accomplished in deteriorated Cr-plating solutions with a standard traditional method for Cr(VI) detection.

Method development for the determination of arsenic by sequential injection/anodic stripping voltammetry using long-lasting gold-modified screen-printed carbon electrode.

An automated method has been developed for determining the concentration of inorganic arsenic. The technique uses sequential injection/anodic stripping voltammetry with a long-lasting gold-modified screen-printed carbon electrode. The long-lasting gold electrode was electrochemically deposited onto a screen-printed carbon electrode at a potential of -0.5 V vs. Ag/AgCl in a supporting electrolyte solution of 1M hydrochloric acid. Under optimal conditions and the applied potentials, the electrode demonstrated that it can be used for a long time without a renewal process. The linear range for the determination of arsenic(III) was 1-100 µg L(-1), and the limit of detection (LOD) in standard solutions was as low as 0.03 µg L(-1) for a deposition time of 120 s and sample volume of 1 mL. This method was used to determine the concentration of arsenic(III) in water samples with satisfactory results. The LOD in real samples was found to be 0.5 µg L(-1). In addition, speciation between arsenic(III) and arsenic(V) has been achieved with the proposed method using deposition potentials of -0.5 V and -1.5 V for the determination of the arsenic(III) concentration and the total arsenic concentration, respectively; the results were acceptable. The proposed method is an automated system that offers a less expensive alternative for determining trace amounts of inorganic arsenic.

Graphene-carbon paste electrode for cadmium and lead ion monitoring in a flow-based system.

An environment friendly electrode for determining Cd(2+) and Pb(2+) levels in an automated flow system was successfully developed. Cyclic voltammetry and square wave anodic stripping voltammetry (SWASV) coupled with sequential injection analysis (SIA) were employed to study the electrochemical behavior of the electrode. The in situ bismuth-modified graphene-carbon paste electrode (Bi-GCPE) exhibited excellent electrooxidation of Cd(2+) and Pb(2+) in the automated flow system with a significantly higher peak current for both metal ions compared with the unmodified CPE. The limits of detection from this method were 0.07 and 0.04 µg L(-1) for Cd(2+) and Pb(2+), respectively, with a linear oxidation peak current response for Cd(2+) and Pb(2+) in the range of 0.10-50.0 µg L(-1) under optimum conditions. The Bi-GCPE was also applied for the determination of Cd(2+) and Pb(2+) in low- (tap water) and high- (sea bass fish and undulated surf clam tissues) matrix complexity samples by automated flow system. The recoveries were acceptable and ranged from 70.4% to 120% for Cd(2+) and 65.8% to 113.5% for Pb(2+).

On-line preconcentration and determination of lead and cadmium by sequential injection/anodic stripping voltammetry.

The highly sensitive determination of lead (Pb(II)) and cadmium (Cd(II)) ions, with a limit of detection of 0.01µgL(-1) for Pb(II) and Cd(II), by on-line preconcentration and anodic stripping voltammetry (ASV) controlled by a sequential injection analysis (SIA) system is reported here. The SIA system consisted of a syringe pump, an 8-port selection valve and a 6-port switching valve and was incorporated with a bismuth coated screen-printed carbon nanotube electrode (Bi-SPCNTE). The preconcentration of metal ions was performed by solid phase extraction using an Analig TE-05 chelating resin mini-column on a switching valve. The metal ions collected were then eluted from the resin with 1M hydrochloric acid (HCl), deposited on the electrode surface at -1.3V vs. Ag/AgCl and then measured with ASV. The pH of the sample, eluent volume, flow rate, concentration of the bismuth plating solution and the square-wave voltammetric parameters were optimized. Under the optimum conditions, an enrichment factor of 11.9-fold and 6.6-fold for Pb(II) and Cd(II) ions, respectively, was attained. Detection of Pb(II) and Cd(II) had two different linear ranges (0.5-15µgL(-1) and 15-70µgL(-1)).

Highly sensitive determination of cadmium and lead using a low-cost electrochemical flow-through cell based on a carbon paste electrode.

A low-cost thin-layer electrochemical flow-through cell based on a carbon paste electrode (CPE), was constructed for the highly sensitive determination of cadmium(II) (Cd(2+)) and lead(II) (Pb(2+)) ions. The sensitivity of the proposed cell for Cd(2+) and Pb(2+) ion detection was improved by using the smallest channel height without the need for any complicated electrode modification. Under the optimum conditions, the detection limits of Cd(2+) and Pb(2+) ions (0.08 and 0.07 µg dm(-3), respectively) were 13.8- and 11.4-fold lower than that of a commercial flow cell (1.1 and 0.8 µg dm(-3), respectively). Moreover, the percentage recoveries of Cd(2+) and Pb(2+) for the in-house designed thin-layer flow cell were higher than those for the commercially available cell in all tested water samples, and within the acceptable range. The proposed flow cell is promising as an inexpensive and alternative one for the highly sensitive monitoring of heavy metal ions.

Determination of trace heavy metals by sequential injection-anodic stripping voltammetry using bismuth film screen-printed printed carbon electrode.

A sequential injection-square-wave anodic stripping voltammetry (SIA-SWASV) is proposed for the simultaneous determination of Pb(II), Cd(II) and Zn(II), employing an in situ plated bismuth film screen-printed carbon electrode (Bi-SPCE) as a working electrode and hydrochloric acid as a supporting electrolyte. Bi(III) and analyte metal ions were on-line deposited onto a SPCE at -1.4 V vs. Ag/AgCl for 180 s. At a stopped flow, a square-wave voltammogram was recorded from -1.3 to 0 V vs. Ag/AgCl. The experimental conditions were optimized. Under the optimum conditions, the linear ranges were 0 - 70 microg L(-1) for Pb(II) and Cd(II), and 75 - 200 microg L(-1) for Zn(II). The limits of detection (S/N = 3) were obtained at concentrations as low as 0.89 microg L(-1) for Pb(II) and 0.69 microg L(-1) for Cd(II) for a 180-s deposition time. The proposed method was applied to the determination of Pb(II), Cd(II) and Zn(II) in water samples with satisfactory results.

Electrochemical analysis of chloramphenicol using boron-doped diamond electrode applied to a flow-injection system.

The electrochemical properties of chloramphenicol at a boron-doped diamond thin-film (BDD) electrode were studied using cyclic voltammetry. The highest current response of chloramphenicol was obtained with phosphate buffer, pH 6 (0.1 M) in 1% ethanol. The relationship between the concentration of chloramphenicol and the current response was linear over the range of 0.1-10 mM (R2=0.9990). The amount of chloramphenicol was analyzed by flow-injection analysis. A thin-layer flow cell equipped with a BDD electrode was used as an amperometric detector, and experiments were carried out at -0.7 V (vs. Ag/AgCl). The linear relationship between the current response and the concentration of chloramphenicol in the range of 0.1-50 microM (R2=0.9948) and the limit of detection of 0.03 microM (S/N=3) were obtained. This method has been successfully applied to the determination of chloramphenicol in sterile eye drops and milk sample by the standard addition method. The average recoveries of chloramphenicol in eye drops were 98.0%, and the average recoveries of chloramphenicol from spiked milk were 93.9-103%.

Cost-effective flow cell for the determination of malachite green and leucomalachite green at a boron-doped diamond thin-film electrode.

An electrooxidation and a cost-effective flow-based analysis of malachite green (MG) and leucomalachite green (LMG) were investigated at a boron-doped diamond thin-film (BDD) electrode. Cyclic voltammetry as a function of the pH of the supporting electrolyte solution was studied. Comparison experiments were performed with a glassy carbon electrode. A well-defined cyclic voltammogram, providing the highest peak current, was obtained when using phosphate buffer at pH 2. The potential sweep-rate dependence of MG and LMG oxidation (peak currents for 1 mM MG and LMG linearly proportional to v 1/2, within the range of 0.01 to 0.3 V/s) indicates that the oxidation current is a diffusion-controlled process on the BDD surface. In addition, hydrodynamic voltammetry and amperometric detection using the BDD electrode combined with a flow injection analysis system was also studied. A homemade flow cell was used, and the results were compared with a commercial flow cell. A detection potential of 0.85 V was selected when using a commercial flow cell, at which MG and LMG exhibited the highest signal-to-background ratios. For the homemade flow cell, a detection potential of 1.1 V was chosen because MG and LMG exhibited a steady response. The flow analysis results showed linear concentration ranges of 1-100 microM and 4-80 microM for MG and LMG, respectively. The detection limit for both compounds was 50 nM.

Use of nickel implanted boron-doped diamond thin film electrode coupled to HPLC system for the determination of tetracyclines.

The electrochemical analysis of tetracyclines was investigated using nickel-implanted boron-doped diamond thin film electrode (Ni-DIA) by cyclic voltammetry and high performance liquid chromatographic with amperometry. Cyclic voltammetry was used to study the electrochemical oxidation of tetracyclines. Comparison experiments were carried out utilizing as-deposited BDD and glassy carbon electrodes. Ni-DIA electrode provided well-resolved oxidative irreversible cyclic voltammograms and the highest current signals among the electrode studied. High performance liquid chromatography (HPLC) with amperometric detection was also studied. The chromatography was performed using a commercially available Inertsil C18 column, with the mobile phase being: 80% phosphate buffer (pH 2.5)-20% acetonitrile and detected at 1.55V. The methods were validated over the concentration range 0.05-100ppm with the overall average recoveries from 83.3 to 102.5% and R.S.D. of less than 10%. The proposed method was further applied to analyse shrimp samples.

Electroanalysis of sulfonamides by flow injection system/high-performance liquid chromatography coupled with amperometric detection using boron-doped diamond electrode.

Sulfonamides (SAs) were electrochemically investigated using cyclic voltammetry at a boron-doped diamond (BDD) electrode. Comparison experiments were carried out using a glassy carbon electrode. The BDD electrode provided well-resolved oxidation, irreversible cyclic voltammograms and higher current signals when compared to the glassy carbon electrode. Results obtained from using the BDD electrode in a flow injection system coupled with amperometric detection were illustrated. The optimum potential from a hydrodynamic voltammogram was found to be 1100mV versus Ag/AgCl, which was chosen for the HPLC-amperometric system. Excellent results of linear range and detection limit were obtained. This method was also used for determination of sulfonamides in egg samples. The standard solutions of 5, 10, and 15ppm were spiked in a real sample, and percentage of recoveries was found to be between 90.0 and 107.7.

Electroanalysis of tetracycline using nickel-implanted boron-doped diamond thin film electrode applied to flow injection system.

The electrochemical analysis of tetracycline was investigated using nickel-implanted boron-doped diamond thin film electrode by cyclic voltammetry and amperometry with a flow injection system. Cyclic voltammetry was used to study the electrochemical oxidation of tetracycline. Comparison experiments were carried out using as-deposited boron-doped diamond thin film electrode (BDD). Nickel-implanted boron-doped diamond thin film electrode (Ni-DIA) provided well-resolved oxidation irreversible cyclic voltammograms. The current signals were higher than those obtained using the as-deposited BDD electrode. Results using nickel-implanted boron-doped diamond thin film electrode in flow injection system coupled with amperometric detection are presented. The optimum potential for tetracycline was 1.55 V versus Ag/AgCl. The linear range of 1.0 to 100 microM and the detection limit of 10 nM were obtained. In addition, the application for drug formulation was also investigated.

Analysis of tetracycline antibiotics using HPLC with pulsed amperometric detection.

The analysis of tetracycline, oxytetracyline, chlortetracycline and doxycycline by high-performance liquid chromatography with pulsed amperometric detection using an anodized boron-doped diamond thin film (BDD) electrode is originally reported. The analyses were carried out using the mobile phase, phosphate buffer (0.01 M, pH 2.5)-acetonitrile (80:20; v/v), on a C18 column (250 x 4.6 mm i.d., 5 microm) at a flow rate of 1.0 mL/min. The optimal PAD waveform parameters at the anodized BDD were 1.5 V (versus Ag/AgCl) detection potential (E(det)) for 290 ms (200 ms delay time and 90 ms integration time), 2.0 V (versus Ag/AgCl) oxidation potential (E(oxd)) for 200 ms oxidation time (t(oxd)) and 0.4 V (versus Ag/AgCI) reduction potential (E(red)) for 200 ms reduction time (t(red)). The proposed method showed the simultaneous determination of tetracycline, oxytetracyline, chlortetracycline and doxycycline with a linear range of 0.1 - 100 microg/mL, detection limits of 0.05 - 0.1 microg/mL and recoveries of 70.8 - 96.0%. The application of this method to real samples was demonstrated and validated using a shrimp sample.