Electrochemical Sensors based on Gold-Silver Core-Shell Nanoparticles Combined with a Graphene/PEDOT:PSS Composite Modified Glassy Carbon Electrode for Paraoxon-ethyl Detection.

Herein, a nonenzymatic detection of paraoxon-ethyl was developed by modifying a glassy carbon electrode (GCE) with gold-silver core-shell (Au-Ag) nanoparticles combined with the composite of graphene with poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS). These core-shell nanoparticles (Au-Ag) were synthesized using a seed-growth method and characterized using UV-vis spectroscopy and high-resolution transmission electron microscopy (HR-TEM) techniques. Meanwhile, the structural properties, surface morphology and topography, and electrochemical characterization of the composite of Au-Ag core-shell/graphene/PEDOT:PSS were analyzed using infrared spectroscopy, field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), and electrochemical impedance spectroscopy (EIS) techniques. Moreover, the proposed sensor for paraoxon-ethyl detection based on Au-Ag core-shell/graphene/PEDOT:PSS modified GCE demonstrates good electrochemical and electroanalytical performance when investigated with cyclic voltammetry (CV), differential pulse voltammetry (DPV), and chronoamperometry techniques. It was found that the synergistic effect between Au-Ag core-shell nanoparticles and the composite of graphene/PEDOT:PSS provides a higher conductivity and enhanced electrocatalytic activity for paraoxon-ethyl detection at an optimum pH of 7. At pH 7, the proposed sensor for paraoxon-ethyl detection shows a linear range of concentrations from 0.2 to 100 µM with a limit of detection of 10 nM and high sensitivity of 3.24 µA µM-1 cm-2. In addition, the proposed sensor for paraoxon-ethyl confirmed good reproducibility, with the possibility of being further developed as a disposable electrode. This sensor also displayed good selectivity in the presence of several interfering species such as diazinon, carbaryl, ascorbic acid, glucose, nitrite, sodium bicarbonate, and magnesium sulfate. For practical applications, this proposed sensor was employed for the determination of paraoxon-ethyl in real samples (fruits and vegetables) and showed no significant difference from the standard spectrophotometric technique. In conclusion, this proposed sensor might have a potential to be developed as a platform of electrochemical sensors for pesticide detection.

Effect of Aspect Ratio of a Gold-Nanorod-Modified Screen-Printed Carbon Electrode for Carbaryl Detection in Three Different Samples of Vegetables.

In this study, three different sizes of gold nanorods (AuNRs) were synthesized using the seed-growth method by adding various volumes of AgNO3 as 400, 600, and 800 µL into the growth solution of gold nanoparticles. Three different sizes of AuNRs were then characterized using UV-vis spectroscopy, high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) patterns, and atomic force microscopy (AFM) to investigate the surface morphology, topography, and aspect ratios of each synthesized AuNR. The aspect ratios from the histogram of size distributions of three AuNRs as 2.21, 2.53, and 2.85 can be calculated corresponding to the addition of AgNO3 volumes of 400, 600, and 800 µL. Moreover, each AuNR in three different aspect ratios was drop-cast onto the surface of a commercial screen-printed carbon electrode (SPCE) to obtain three different SPCE-modified AuNRs (SPCE-A400, SPCE-A600, and SPCE-A800, respectively). All SPCE-modified AuNRs were then evaluated for their electrochemical behavior using cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques and the highest electrochemical performance was shown as the order of magnitude of SPCE-A400 > SPCE-A600/SPCE-A800. The reason for the highest electrocatalytic activity of SPCE-A400 might be due to the smallest particle size and uniform distribution of AuNRs ∼ 2.2, which enhanced the charge transfer, thus providing the highest electroactive surface area (0.6685 cm2) compared to other electrodes. These results also confirm that the sensing mechanism for all SPCE-modified AuNRs is controlled by diffusion phenomena. In addition, the optimum pH was obtained as 4 for carbaryl detection for all SPCE-modified AuNRs with the highest current shown by SPCE-A400. Furthermore, SPCE-A400 has the highest fundamental parameters (surface coverage, catalytic rate constant, electron transfer rate constant, and adsorption capacity) for carbaryl detection, which were investigated using cyclic voltammetry and chronoamperometric techniques. The electroanalytical performances of all SPCE-modified AuNRs for carbaryl detection were also investigated with SPCE-A400 displaying the best performance among other electrodes in terms of its linearity (0.2-100 µM), limit of detection (LOD) ∼ 0.07 µM, and limit of quantification (LOQ) ∼ 0.2 µM. All SPCE-modified AuNRs were also subsequently evaluated for their stability, reproducibility, and selectivity in the presence of interfering species such as NaNO2, NH4NO3, Zn(CH3CO2)2, FeSO4, diazinon, and glucose and show reliable results as depicted from %RSD values less than 3%. At last, all SPCE-modified AuNRs have been employed for carbaryl detection using a standard addition technique in three different samples of vegetables (cabbage, cucumber, and Chinese cabbage) with its results (%recovery ≈ 100%) within the acceptable analytical range. In conclusion, this work demonstrates the great potential of a disposable device based on an AuNR-modified SPCE for rapid detection and high sensitivity in monitoring the concentration of carbaryl as a residual pesticide in vegetable samples.

Electrochemical Sensors Based on a Composite of Electrochemically Reduced Graphene Oxide and PEDOT:PSS for Hydrazine Detection.

In this study, hydrazine sensors were developed from a composite of electrochemically reduced graphene oxide (ErGO) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), deposited onto a glassy carbon electrode (GCE). The structural properties, electrochemical characterization, and surface morphologies of this hydrazine sensor were characterized by Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). In addition, the proposed hydrazine sensor also demonstrates good electrochemical and analytical performance when investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometry techniques under optimal parameters. Using these investigated parameters, DPV and amperometry were chosen as techniques for hydrazine measurements and showed a linear range of concentration in the range of 0.2-100 µM. The obtained limits of detection and limits of quantitation for hydrazine measurements were 0.01 and 0.03 µM, respectively. In addition, the proposed sensor demonstrated good reproducibility and stability in hydrazine measurements in eight consecutive days. This fabricated hydrazine sensor also exhibited good selectivity against interference from Mg2+, K+, Zn2+, Fe2+, Na+, NO2 -, CH3COO-, SO4 2-, Cl-, ascorbic acid, chlorophenol, and triclosan and combined interferences, as well as it depicted %RSD values of less than 5%. In conclusion, this proposed sensor based on GCE modified with ErGO/PEDOT:PSS displays exceptional electrochemical performance for use in hydrazine measurements and have the potential to be employed in practical applications.