A novel electrochemical sensor for the detection of metronidazole residues in food samples.

The widespread use and misuse of antibiotics in pharmaceuticals and animal farming has resulted in their accumulation in food sources and the environment, posing significant threats to human health, the environment, and the global economy. In this study, we have developed a hypersensitive, and ultra-selective electrochemical sensor, the first of its kind, by integrating a thermally annealed gold-silver alloy nanoporous matrix (TA-Au-Ag-ANpM) with reduced graphene oxide (r-GO) and poly(glycine) at the surface of a glassy carbon electrode (GCE). This sensor aims to detect life-threatening metronidazole (MTZ) residues in food samples. TA-Au-Ag-ANpM/r-GO/poly(glycine)/GCE was thoroughly characterized using a range of analytical techniques, including UV-Vis, FT-IR, XRD, SEM, and EDX. Furthermore, its electrochemical properties were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). The sensor exhibited outstanding performance, with a broad linear range of 2.0 pM-410 µM. The limits of detection (LOD) and quantification (LOQ) were determined to be 0.0312 pM and 0.104 pM, respectively. The TA-Au-Ag-ANpM/r-GO/poly(glycine)/GCE exhibited exceptional reproducibility, repeatability, stability, and resistance to interferences. Moreover, the sensor demonstrated outstanding performance in detecting MTZ residues in milk powder, pork, and chicken meat samples, achieving very good recoveries (96.9%-101.4%) with a relative standard deviation (RSD) below 5%. This performance highlights the potential for practical applications in food safety and quality monitoring. Therefore, the developed sensor contributes to the advancement of electrochemical sensing technology and its application in ensuring food safety and integrity by combating antibiotic residues.

Hypersensitive electrochemical sensor based on thermally annealed gold-silver alloy nanoporous matrices for the simultaneous determination of sulfathiazole and sulfamethoxazole residues in food samples.

In this study, we have developed a novel, hypersensitive, and ultraselective electrochemical sensor containing thermally annealed gold-silver alloy nanoporous matrices (TA-Au-Ag-ANpM) integrated with f-MWCNTs-CPE and poly(l-serine) nanocomposites for the simultaneous detection of sulfathiazole (SFT) and sulfamethoxazole (SFM) residues in honey, beef, and egg samples. TA-Au-Ag-ANpM/f-MWCNTs-CPE/poly(l-serine) was characterized using an extensive array of analytical (UV-Vis, FT-IR, XRD, SEM, and EDX), and electrochemical (EIS, CV and SWV) techniques. It exhibited outstanding performance over a wide linear range, from 4.0 pM to 490 µM for SFT and 4.0 pM to 520 µM for SFM, with picomolar detection and quantification limits (0.53 pM and 1.75 pM for SFT, 0.41 pM and 1.35 pM for SFM, respectively). The sensor demonstrated exceptional repeatability, reproducibility, and anti-interference capability, with percentage recovery of 95.6-102.4% in food samples and RSD below 5%. Therefore, the developed sensor is an ideal tool to address the current antibiotic residue crisis in food sources.

A cutting-edge electrochemical sensing platform for the simultaneous determination of the residues of antimicrobial drugs, rifampicin and norfloxacin, in water samples.

BACKGROUND: The widespread use and abuse of antibiotics has resulted in the pollution of water sources with antibiotic residues, posing a threat to human health, the environment, and the economy. Therefore, a highly sensitive and selective method is required for their detection in water samples. Herein, advanced ultrasensitive electrochemical sensor platform was developed by integrating gold-silver alloy nanocoral clusters (Au-Ag-ANCCs) with functionalized multi-walled carbon nanotube-carbon paste electrode (f-MWCNT-CPE) and choline chloride (ChCl) nanocomposites for simultaneously determining the residues of antimicrobial drugs, rifampicin (RAMP) and norfloxacin (NFX), in water samples. RESULTS: The developed sensor (Au-Ag-ANCCs/f-MWCNTs-CPE/ChCl) was extensively characterized using several analytical (UV-Vis, FT-IR, XRD, SEM, and EDX) and electrochemical (EIS, CV, and SWV) techniques. It exhibited outstanding performance in a wide linear range, from 14 pM to 115 µM for RAMP, and from 0.9 nM to 200 µM for NFX, with a limit of detection (LOD, 3σ/m, S/N = 3, n = 5) and a limit of quantification (LOQ, 10σ/m, S/N = 3, n = 5) values of 2.7 pM and 8.85 pM for RAMP, and 0.14 nM and 0.47 nM for NFX, respectively. The sensor also exhibited exceptional reproducibility, stability, and resistance to interference. SIGNIFICANCE: The developed sensor was effectively utilized to determine RAMP and NFX residues in hospital wastewater, river, and tap water samples, yielding recoveries within the range of 96.8-103 % and relative standard deviations below 5 %. Generally, the proposed sensor demonstrated remarkable performance in detecting the target analytes, making it an ideal tool and the first of its kind for addressing global antibiotic residue pollutants in water sources.

Simultaneous Determination of Mineral Nutrients and Toxic Metals in M. stenopetala from Southern Ethiopia: A Comparative Study of Three Cultivating Areas Using MP-AES.

In this study, for the first time, the levels of thirteen micro- and macromineral nutrients in the leaves, seeds, and supportive soil of Moringa stenopetala (M. stenopetala) were simultaneously determined using microwave plasma atomic emission spectroscopy (MP-AES). The samples were collected during the arid season, in 2019 from the three main M. stenopetala growing areas in southern Ethiopia (Chano Mile Kebele, Nechisar Kebele, and Konso Special Woreda). A novel digestion method for leaf and seed samples was developed using an optimized acid mixture (2.5 : 0.75 : 0.5 of HNO3, HClO4, and H2O2) at 240°C for 2 hrs and 30 min, resulting in clear and colorless solutions. The method makes the digestion process more efficient by minimizing the reagent volume, reducing digestion temperature and time, and simplifying the overall procedure. The efficiency of the optimized procedure was validated by spiking experiments, and the percentage recovery ranged between 94 and 110%. Under optimized experimental conditions, higher concentrations of essential minerals (K, Na, Ca, and Mg) were observed in the plant leaf and seed samples from the three areas. In addition, significant amounts of trace elements (Fe, Mn, Zn, and Cu) were also found. Importantly, no traces of the toxic elements (Cd and Pb) were detected in any of the analyzed samples, suggesting that the leaves and seeds of M. stenopetala are valuable sources of both micro- and macromineral nutrients and are safe from toxic metals. From a dietary perspective, the seed contains almost comparable concentrations of minerals as the leaves. As a result, the seeds of M. stenopetala can serve as an alternative source of minerals and play a role in overcoming the current global food crisis, particularly in the dry season. Analysis of variance at a 95% confidence level revealed significant differences in the levels of all mineral nutrients between the three sample means except K, Ca, Co, and Cu. Generally, the developed method includes an innovative digestion procedure that minimizes reagent consumption, operates at lower temperatures, and requires shorter digestion times, thereby optimizing resource utilization and maintaining analytical accuracy. Notably, the absence of toxic elements in the MP-AES procedure highlights the safety and reliability of M. stenopetala leaves and seeds as valuable, contamination-free sources of essential nutrients.

Electrochemical determination of zinc(II) using N1-hydroxy-N1,N2-diphenylbenzamidine and multi-walled carbon nanotubes modified carbon paste electrode.

In this study, a new carbon paste electrode modified with a laboratory-synthesized ligand, N1-hydroxy-N1,N2-diphenylbenzamidine (HDPBA) and multi-walled carbon nanotubes (MWCNTs) (HDPBA‒MWCNTs/CPE) has been developed. The modified electrode was applied for preconcentration and voltammetric determination of zinc ions (Zn(II)) by square wave anodic stripping voltammetry (SWASV). The preconcentration of Zn(II) on the electrode surface was performed in 0.1 M Brinton Robinson (B-R) buffer solution (pH 6) at an applied potential of -1.30 V versus Ag/AgCl for 120 s, followed by stripping in the positive potential scan of the SWASV after a quit time of 10 s. Under optimized experimental conditions, the proposed electrode exhibited a wider linear dynamic response for Zn(II) in a concentration range of 0.02-10.00 µM with a detection limit of 2.48 nM. This is due to the excellent metal-chelation property of the ligand, and the good conductivity and large surface area of MWCNTs which significantly improved the sensing performance of the nanocomposite modified electrode. The selectivity of the electrode was studied by evaluating the interference effects of various foreign ions on the peak current of Zn(II). The method exhibited high reproducibility with a relative standard deviation (RSD) of 3.1%. The present method was applied for the determination of zinc ions in water samples. The recovery values in the tested samples were found to be 98.50-106.0%, indicating a good accuracy of the proposed electrode. Furthermore, the electrochemical behavior of HDPBA in acetonitrile and aqueous solutions has been studied.

Stripping voltammetric determination of pyridine-2-aldoxime methochloride at the iron(III) doped zeolite modified glassy carbon electrode.

An iron(III) doped zeolite modified glassy carbon electrode was constructed for the determination of pyridine-2-aldoxime methochloride. X-ray diffraction and chemical analysis were utilized to determine the optimum pH and chemical content for doping zeolite. Cyclic voltammetry was used to characterize the modified electrode and study the kinetics of the acid treated and untreated modified electrode. Acid treatment of the modified electrode showed a better electrochemical behavior compared to the untreated iron(III) doped zeolite modified electrode. Square wave anodic stripping voltammetry was employed to investigate the working pH and preconcentration time. The analytical performance of the modified electrode was evaluated, and a linear anodic stripping response for pyridine-2-aldoxime methochloride in the concentration range of 0.5-100.0 µM with a detection limit of 1.61 × 10(-7) M was obtained. Finally, the developed method was successfully applied for the determination of pyridine-2-aldoxime methochloride in a biological sample.

Polymer-modified glassy carbon electrode for the electrochemical detection of quinine in human urine and pharmaceutical formulations.

Glassy carbon electrode was modified by electropolymerization of 4-amino-3-hydroxynaphthalene sulfonic acid. Cyclic voltammetric study of quinine showed higher current response at the modified electrode compared to the bare and activated glassy carbon electrodes in pH 7.0 phosphate buffer solution. Under optimized conditions, a calibration curve was obtained by square wave voltammetry at the modified electrode. The linear relationship between the peak current and the concentration of quinine in the range of 1.0 × 10(-7) to 1.0 × 10(-5) M was I (pa) (in microamperes) = 6.26C (in micromolars) + 0.2997 (R (2) = 0.999). The detection limit calculated (S/N = 3) was 1.42 × 10(-8) M, which is much lower than similar reports. The method was successfully applied for the determination of quinine in spiked human urine, and pharmaceutical formulations and recovery values >90 % were obtained.

A Novel Carbon Paste Electrode Modified with N1-Hydroxy-N1,N2-Diphenylbenzamidine for the Electrochemical Determination of Cadmium(II) in Environmental Samples.

The present study introduces a novel electrode for rapid, highly sensitive, and selective electrochemical sensor for cadmium(II) using 5% N1-hydroxy-N1,N2-diphenylbenzamidine (HDPBA) modified carbon paste electrode (CPE) (HDPBA‒CPE). Surface characterizations and structural analysis of the proposed HDPBA‒CPE were performed using several analytical techniques. The voltammetric measurements of Cd(II) were conducted by cyclic voltammetry (CV) and square wave anodic stripping voltammetry (SWASV). Several experimental conditions such as composition and pH of buffer solutions, HDPBA composition, accumulation potential and time, and other voltammetric conditions were optimized. Cd(II) was preconcentrated on the modified electrode surface for 270 s using Britton Robinson (B-R) buffer (0.1 M, pH 4) at -1.0 V versus Ag/AgCl, followed by electrochemical oxidation of the accumulated Cd(II) in the positive scan of SWASV after a quiet time of 10 s. Under optimized parameters, the proposed method showed a linear range of 0.3-100 nM Cd(II) with a detection limit of 0.032 nM. The fabricated HDPBA-modified carbon paste electrode exhibited excellent sensitivity, selectivity, stability, and reproducibility (with RSD of 3.8%). The developed HDPBA‒CPE was used for the quantification of Cd(II) in tobacco and environmental water samples, and it was found to be applicable for the determination of different types of real samples.

Development of a new electrochemical method for the determination of copper(ii) at trace levels in environmental and food samples.

This paper presents the fabrication of a new modified carbon paste electrode (CPE) with N 1-hydroxy-N 1,N 2-diphenylbenzamidine (HDPBA) and functionalized multi-walled carbon nanotubes (MWCNTs) (HDPBA-MWCNTs/CPE) for highly sensitive and selective determination of Cu(ii) using the square wave anodic stripping voltammetry (SWASV) technique. The fabricated electrode was characterized using various spectroscopic techniques to study its morphological, structural, and electrochemical properties. The accumulation of Cu(ii) on the surface of HDPBA-MWCNTs/CPE was done in 0.1 M ammonium chloride (NH4Cl, pH 5) solution at an applied potential of -0.70 V versus Ag/AgCl for 180 s, followed by electrochemical stripping in the positive scan of the voltammetry after a resting time of 10 s. The developed HDPBA-MWCNTs/CPE was found to be highly selective, sensitive and reproducible. At optimal conditions of the experiment, the proposed method exhibited a very low limit of detection (0.0048 nM Cu(ii)), a wide linear dynamic range (0.00007-1.5000 µM Cu(ii)), and good reproducibility with relative standard deviation (RSD) value of 3.7%. The effect of various foreign ions on the voltammetric response of Cu(ii) was investigated and the electrode was found to be highly selective to Cu(ii). The practical applicability of the proposed HDPBA-MWCNTs/CPE was studied by applying the electrode for the quantification of Cu(ii) contents in environmental water (wastewater and tap water), soft drink (Fanta and Sprite), and food supplement (commercially available multi-mineral/vitamin tablets) samples. The present method was validated with atomic absorption spectrometry (AAS). The results found from the two methods are in good agreement with a 95% confidence level.

Sensitive and selective determination of vitamin B2 in non-alcoholic beverage and milk samples at poly (glutamic acid)/zinc oxide nanoparticles modified carbon paste electrode.

BACKGROUND: The deficiency of vitamin B2 can lead to many health problems. Therefore, it is necessary to develop a sensitive, selective and fast method for the determination of vitamin B2 in food samples. In this work, a sensitive, selective and low-cost electrochemical sensor was developed using poly (glutamic acid) and Zinc oxide nanoparticles (ZnO NPs) for vitamin B2 in non-alcoholic beverage and milk samples. METHODS: The modification of the electrode surface was carried out by electropolymerization of glutamic acid on ZnO NPs-carbon paste electrode (ZnO NPS-CPE). The prepared electrodes were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and X-Ray diffraction (XRD). CV and square wave voltammetry (SWV) were used to investigate the electrochemical behavior of vitamin B2 at the modified electrode. The effect of various parameters such as amount of ZnO NPs, polymerization cycle, concentration of the monomer, pH, scan rate and accumulation time were optimized to obtain maximum sensitivity at the modified electrode. RESULTS: The developed sensor showed high electrocatalytic activity towards vitamin B2. Under the optimized conditions, the developed sensor showed a linear response in the range 0.005-10 µM with a low detection limit of (LOD) 0.0007 ± 0.00001 µM and high sensitivity of 21.53 µA/µM. CONCLUSIONS: A reproducible, repeatable, stable and selective sensor was successfully applied for the quantification of vitamin B2 in beverage and milk samples with acceptable recoveries in the range of 88-101%.

Voltammetric determination of uric acid using multiwall carbon nanotubes coated-poly(4-amino-3-hydroxy naphthalene sulfonic acid) modified glassy carbon electrode.

In this study, an electrochemical sensor based multiwalled carbon nanotubes (MWCNTs)-poly (4-amino-3-hydroxy naphthalene sulfonic acid) modified glassy carbon electrode (MWCNTs/poly (AHNSA)/GCE) was developed for the determination of uric acid (UA). The composite electrode was prepared first by electropolymerization of the monomer (AHNSA) on GCE using cyclic voltammetry within the potential range of -0.8 V to +2.0 V vs Ag/AgCl for 15 cycles followed by drop coating of MWCNTs solution on the surface of poly (AHNSA)/GCE. Under optimal conditions, MWCNTs/poly (AHNSA)/GCE showed a linear current response with UA concentrations in the range of 1 × 10-6 to 1 × 10-4 M with R2 = 0.9972. The sensor exhibited low detection limit with a value of 0.024 µM. The sensors have been applied to successfully quantify UA in urine samples.

Electrochemical application of cobalt nanoparticles-polypyrrole composite modified electrode for the determination of phoxim.

In this study, cobalt nanoparticles (CoNPs) were synthesized and cobalt nanoparticles modified glassy carbon electrode (CoNPs/GCE) was prepared by drop coating the nanoparticles on glassy carbon electrode. After preparing polypyrrole modified glassy carbon electrode (PPy/GCE) using electropolymerization of pyrrole in LiClO4 solution, cobalt nanoparticles-polypyrrole composite modified glassy carbon electrode (CoNPs/PPy/GCE) was fabricated by drop coating the CoNPs on the PPy/GCE. Different characterization techniques such as scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, FTIR spectroscopy, electrochemical impedance spectroscopy and cyclic voltammetry were used to study the morphological structure and electrochemical behavior of the sensors. The results demonstrated that PPy chains interacted with CoNPs through donor-acceptor bonds. Among all the electrodes, CoNPs/PPy/GCE exhibited highest electroactive surface area and lowest electron transfer resistance towards phoxim. Under the optimal conditions, the sensor showed linear relationship between the reduction peak current and the concentration of phoxim in the range of 0.025 µM-12 µM with the detection limit as 4.5 nM. Besides, the composite electrode demonstrated excellent reproducibility, good stability and selectivity towards the possible interfering substances. All of these properties made CoNPs/PPy/GCE a suitable electrochemical sensor for the electrochemical determination of phoxim in water samples using square wave voltammetry.

Simultaneous determination of caffeine and paracetamol by square wave voltammetry at poly(4-amino-3-hydroxynaphthalene sulfonic acid)-modified glassy carbon electrode.

Poly(4-amino-3-hydroxynaphthalene sulfonic acid)-modified glassy carbon electrode (poly(AHNSA)/GCE) was prepared for simultaneous determination of caffeine and paracetamol using square-wave voltammetry. The method was used to study the effects of pH and scan rate on the voltammetric response of caffeine and paracetamol. Linear calibration curves in the range of 10-125µM were obtained for both caffeine and paracetamol in acetate buffer solution of pH 4.5 with a correlation coefficient of 0.9989 and 0.9986, respectively. The calculated detection limits (S/N=3) were 0.79µM for caffeine and 0.45µM for paracetamol. The effects of some interfering substances in the determination of caffeine and paracetamol were also studied and their interferences were found to be negligible which proved the selectivity of the modified electrode. The method was successfully applied for the quantitative determination of caffeine and paracetamol in Coca-Cola, Pepsi-Cola and tea samples.

Electrochemical Characterization and Determination of Phenol and Chlorophenols by Voltammetry at Single Wall Carbon Nanotube/Poly(3,4-ethylenedioxythiophene) Modified Screen Printed Carbon Electrode.

Screen printed carbon electrode (SPCE) has been modified with single wall carbon nanotube/poly(3,4-ethylenedioxythiophene) (SWCNT/PEDOT) composites for the determination of phenol and chlorophenols (phenol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol). The effect of the modifiers on the electrode characteristics was evaluated and the responses were optimized for the voltammetric determination of phenol and chlorophenols. The parameters affecting the responses such as pH, scan rate, and stability were studied. The analytical performance of the SWCNT/PEDOT/SPCE using cyclic voltammetry was tested and found to be impressive. Under these conditions, the designed electrode showed a good performance for the voltammetric measurements of the phenolic compounds. The modified SPCE, when it is compared with other enzymatic and nonenzymatic sensors, showed a wider dynamic range for the detection of the phenolic compounds. The modified SPCE was used for the quantification of phenol in water samples. The results suggest that the method is quite useful for analyzing and monitoring phenols and chlorophenols.

Simultaneous determination of N-acetyl-p-aminophenol and p-aminophenol with poly(3,4-ethylenedioxythiophene) modified glassy carbon electrode.

A sensitive and selective method was developed for the determination of N-acetyl-p-aminophenol (APAP) and p-aminophenol (PAP) using poly(3,4-ethylenedioxythiophene) (PEDOT)-modified glassy carbon electrode (GCE). Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical reaction of APAP and PAP at the modified electrode. Both APAP and PAP showed quasireversible redox reactions with formal potentials of 367 mV and 101 mV (vs. Ag/AgCl), respectively, in phosphate buffer solution of pH 7.0. The significant peak potential difference (266 mV) between APAP and PAP enabled the simultaneous determination both species based on differential pulse voltammetry. The voltammetric responses gave linear ranges of 1.0×10(-6)-1.0×10(-4) mol L(-1) and 4.0×10(-6)-3.2×10(-4) mol L(-1), with detection limits of 4.0×10(-7) mol L(-1) and 1.2×10(-6) mol L(-1) for APAP and PAP, respectively. The method was successfully applied for the determination of APAP and PAP in pharmaceutical formulations and biological samples.

Indirect voltammetric determination of caffeine content in coffee using 1,4-benzoquinone modified carbon paste electrode.

In this paper a simple and highly sensitive electroanalytical method for the determination of caffeine content using 1,4-benzoquinone modified carbon paste electrode is presented. The method is based on suppression of 1,4-benzoquinone peak current on addition of caffeine. Square-wave and cyclic voltammetric techniques were utilised for the investigation. The 1,4-benzoquinone modified electrode exhibited a well-defined peak with reproducible peak current values for repetitive measurements; and showed a decrease in peak current value with an increase in caffeine content. The result revealed two linear range regions between 0 mmol L(-1) and 0.5 mmol L(-1) and 0.5 mmol L(-1) and 8.0 mmol L(-1), with detection limits of 0.3 micromol L(-1) and 5.1 micromol L(-1), respectively. The method was then successfully applied to the determination of caffeine content in coffee samples. The effects of pH, electrode composition, step potential, pulse amplitude and square-wave frequency on the voltammetric responses were also investigated.