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.

Graphene/polyvinylpyrrolidone/polyaniline nanocomposite-modified electrode for simultaneous determination of parabens by high performance liquid chromatography.

A nanocomposite of graphene (G), polyvinylpyrrolidone (PVP) and polyaniline (PANI) modified onto screen-printed carbon electrode (SPCE) using an electrospraying technique was developed for simultaneous determination of five parabens in beverages and cosmetic products by high performance liquid chromatography. PVP and PANI were used as the dispersing agents of graphene, and also for the enhancement of electrochemical conductivity of the electrode. The electrochemical behavior of each paraben was investigated using the G/PVP/PANI nanocomposite-modified SPCE, compared to the unmodified SPCE. Using HPLC along with amperometric detection at a controlled potential of +1.2V vs Ag/AgCl, the chromatogram of five parabens obtained from the modified SPCE exhibits well defined peaks and higher current response than those of its unmodified counterpart. Under the optimal conditions, the calibration curves of five parabens similarly provide a linear range between 0.1 and 30 µg mL(-1) with the detection limits of 0.01 µg mL(-1) for methyl paraben (MP), ethyl paraben (EP) and propyl paraben (PP), 0.02 and 0.03 µg mL(-1) for isobutyl paraben (IBP) and butyl paraben (BP), respectively. Furthermore, this proposed method was applied for the simultaneous determination of five parabens in real samples including a soft drink and a cosmetic product with satisfactory results, yielding the recovery in the range of 90.4-105.0%.

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+).