Electrochemical Detection of Nitrite in Meat and Water Samples Using a Mesoporous Carbon Ceramic SiO2/C Electrode Modified with In Situ Generated Manganese(II) Phthalocyanine

Mesoporous carbon ceramic SiO₂/50 wt % C (S_BET=170 m² g^?1), where C is graphite, were prepared by the sol‐gel method. The materials were characterized using N₂ sorption isotherms, scanning electron microscopy, and conductivity measurements. The matrix was used as support for the in situ immobilization of Mn(II) phthalocyanine (MnPc) on their surface. XPS was used to determine the Mn/Si atomic ratios of the MnPc‐modified materials. Pressed disk electrodes were prepared with the MnPc‐modified matrix, and tested as an electrochemical sensor for nitrite oxidation. The linear response range, sensitivity, detection limit and quantification limit were 0.79–15.74 µmol L^?1, 17.31 µA L µmol^?1, 0.02 µmol L^?1 and 0.79 µmol L^?1, respectively, obtained using cyclic voltammetry. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 1.7 % for 10 measurements of a solution of 12.63 µmol L^?1 nitrite. The sensor employed to determine nitrite in sausage meat, river and lake water samples showed to be a promising tool for this purpose.     

Self-assembled sensor based on boron-doped diamond and its application in voltammetric analysis of picloram

A self-assembled sensor based on a boron-doped diamond was investigated as a sensitive tool for voltammetric analysis of a member of a pyridine herbicide family - picloram. A cyclic voltammetry and a differential pulse voltammetry were applied for investigation of the voltammetric behaviour and quantification of this herbicide. Picloram yielded one well-developed irreversible oxidation signal at a very positive potential about +1.5 V vs. Ag/AgCl/3 mol L^?1 KCl electrode in an acidic medium and 1 mol L^?1 H₂SO₄ was chosen as a suitable supporting electrolyte. Operating parameters of differential pulse voltammetry were optimized and the proposed voltammetric method provided a high repeatability (a relative standard deviation of 20 repeated measurements at a concentration level of picloram of 50 µmol L^?1 equaled to 2.58%), a linear concentration range from 2.5 to 90.9 µmol L^?1 and a low limit of detection (LD = 1.64 µmol L^?1). Practical usefulness of the ‘environmentally-green’ electrochemical sensor was verified by an analysis of spiked water samples with satisfactory recoveries.     

Determination of Oxytetracycline with a Gold Electrode Modified by Chitosan-Multiwalled Carbon Nanotube Multilayer Films and Gold Nanoparticles

A molecularly imprinted electrochemical sensor was fabricated based on a gold electrode modified by chitosan-multiwalled carbon nanotube composite (CS-MWCNTs) multilayer films and gold nanoparticles (AuNPs) for convenient and sensitive determination of oxytetracycline (OTC). The multilayer of CS-MWCNTs composites and AuNPs were used to augment electronic transmission and sensitivity. The molecularly imprinted polymers (MIPs) were synthesized using OTC as the template molecule and o-phenylenediamine (OPD) as the functional monomer. They were modified on a gold electrode by electropolymerization. The electrochemical behavior of OTC at the imprinted sensor was characterized by cyclic voltammetry (CV), scanning electron microscopy (SEM), and amperometry. The molecularly imprinted sensor showed high selectivity and excellent stability toward OTC. The linear range was from 3.0 × 10^?8 to 8.0 × 10^?5 mol/L, with a limit of detection (LOD) of 2.7 × 10^?8 mol/L (S/N = 3). The developed sensor showed good recovery in spiked samples analysis.     

Evaluation of Bismuth Modified Carbon Thread Electrode for Simultaneous and Highly Sensitive Cd (II) and Pb (II) Determination

Bismuth film modified and chemically activated carbon micro‐thread electrodes were investigated for the simultaneous determination of Cd(II) and Pb(II) using square wave anodic stripping voltammetry. The carbon thread electrode was characterised using both surface and electrochemical techniques. Electrochemical impedance spectroscopy (EIS) studies demonstrated that the H₂SO₄/IPA‐treated carbon thread electrode showed a much improved resistance response (R_ct=23 Ω) compared to the IPA‐untreated carbon thread (R_ct=8317 Ω). Furthermore, parameters such as the effect of deposition potential, deposition time and Bi(III) concentration were explored using square wave voltammetry. Detection limits (S/N=3) for Cd(II) and Pb(II) were found to be 1.08 µg L^?1 and 0.87 µg L^?1, respectively and response was found to be linear over the range 5–110 µg L^?1. The proposed Bi/IPA‐treated carbon thread electrode exhibited a high selectivity towards Cd(II) and Pb(II) even in the presence of a range of heavy metals and is capable of repetitive and reproducible measurements, being attributed to the high surface area, geometry and electrode treatment characteristics. The proposed metal ion sensor was employed to determine cadmium and lead in river water samples and % RSD was found to be 5.46 % and 5.93 % for Cd(II) and Pb(II) respectively (n=3). Such facile sensing components favour the development of cost effective portable devices for environmental sample analysis and electrochemical applications.     

An Electrochemical Sensor for L-Tryptophan Using a Molecularly Imprinted Polymer Film Produced by Copolymerization of o-Phenylenediamine and Hydroquinone

An electrochemical sensor for L-tryptophan based on a molecularly imprinted polymer was developed. The sensing film was prepared by the co-electropolymerization of o-phenylenediamine and hydroquinone on a gold electrode in the presence of L-tryptophan as the template. The performance of the L-tryptophan sensor was characterized by cyclic voltammetry, differential pulse voltammetry, and alternating current impedance. Under the optimal experimental conditions, the relative current change was linear to the concentration of L-tryptophan in the range of 1.0 × 10^?8 to 1.0 × 10^?6 mol/L and a detection limit of 0.50 × 10^?8 mol/L was obtained. The sensor showed high sensitivity and selectivity for L-tryptophan. The imprinting factor was 3.58 and selectivity factors of L-tryptophan compared to analogs were larger than 2. The sensor also demonstrated good resistance to acidic, basic, and organic environments.     

Evaluation of a Multi-Walled Carbon Nanotube-Hemin Composite for the Voltammetric Determination of Hydrogen Peroxide in Dental Products

A simple, low cost sensor was developed for the voltammetric determination of hydrogen peroxide in mouthwash and dental whitening gel based on multi-walled carbon nanotubes incorporated with hemin. The sensor showed electrocatalytic activity toward the reduction of hydrogen peroxide in 0.05 mol L^?1 Tris-HCl buffer solution (pH 7.0) using cyclic voltammetry. The optimum composition of paste was 20:10:70% (m/m/m) (multi-walled carbon nanotubes:hemin:mineral oil). A linear plot of the square root of scan rate vs. cathodic peak current showed that reduction of hydrogen peroxide is diffusion controlled. Using linear sweep voltammetry, the analytical curve ranged from 0.2 up to 1.4 mmol L^?1 (r = 0.9996) with a sensitivity of 3.62 × 10^?2 mA mol^?1 L. The limits of detection and quantification were found to be 12.5 µmol L^?1 and 41.7 µmol L^?1, respectively. The developed method was applied for hydrogen peroxide determination in dental formulations. The results were compared with a volumetric method as a reference technique. No significant differences at the 95% level (paired student t test) were observed, thus demonstrating the accuracy of the sensor for the analysis of real samples.     

Construction of a novel electrochemical sensor based on molecularly imprinted polymers for the selective determination of chlorpyrifos in real samples

We present a novel electrochemical sensor based on an electrode modified with molecularly imprinted polymers for the detection of chlorpyrifos. The modified electrode was constructed by the synthesis of molecularly imprinted polymers by a precipitation method then coated on a glassy carbon electrode. The surface morphology of the modified electrode was characterized by using field‐emission scanning electron microscopy and transmission electron microscopy. The performance of the imprinted sensor was thoroughly investigated by using cyclic voltammetry and differential pulse voltammetry. The imprinted electrochemical sensor displayed high repeatability, stability, and selectivity towards the template molecules. Under the optimal experimental conditions, the peak current response of the imprinted electrochemical sensor was linearly related to the concentration of chlorpyrifos over the range 1 × 10⁻¹⁰–1 × 10⁻⁵ mol/L with a limit of detection of 4.08 × 10⁻⁹ mol/L (signal‐to‐noise ratio = 3). Furthermore, the proposed molecularly imprinted electrochemical sensor was applied to the determination of chlorpyrifos in the complicated matrixes of real samples with satisfactory results. Therefore, the molecularly imprinted polymers based electrochemical sensor might provide a highly selective, rapid, and cost‐effective method for chlorpyrifos determination and related analysis.     

Label-Free Detection of DNA Hybridization Based on MnO2 Nanoparticles

Abstract

Nano-MnO₂/chitosan composite film modified glassy carbon electrode (MnO₂/CHIT/GCE) was fabricated and a DNA probe was immobilized on the electrode surface. The immobilization and hybridization events of DNA were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The EIS was applied to the label-free detection of the target DNA. The human immunodeficiency virus (HIV) gene fragment was successfully detected by this DNA electrochemical sensor. The dynamic detection range was from 2.0 × 10^?11 to 2.0 × 10^?6 mol/L, with a detection limit of 1.0 × 10^?12 mol/L.     

A Sensitive Sensor Based on Single‐walled Carbon Nanotubes: Its Preparation,Characterization and Application in the Electrochemical Determination of Drug Clorsulon in Milk Samples

Within this paper, a glassy carbon electrode modified with single‐walled carbon nanotubes (SWCNTs?GCE) was prepared, and employed for the determination of clorsulon (Clo), which is a frequently used veterinary drug against common liver fluke. The comprehensive topographical and electrochemical characterizations of bare GCE and SWCNTs?GCE were performed by atomic force microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. Significantly enhanced electrochemical characteristics of SWCNTs?GCE toward a ferrocyanide/ferricyanide redox couple was observed when compared to bare GCE. Further, the prepared sensor was applied for the voltammetric determination of Clo, which was electrochemically investigated for the first time in this work. Voltammetric experiments were performed using square‐wave voltammetry with optimized parameters in phosphate buffer solution, pH 6.8, which was selected as the most suitable medium for the determination of Clo. The corresponding current at approx. +1.1 V increased linearly with Clo concentration within two linear dynamic ranges of 0.75–4.00 μmol L^?1 (R²=0.9934) and 4.00–15.00 μmol L^?1 (R²=0.9942) with a sensitivity for the first calibration range of 0.76 μA L μmol^?1, a limit of detection of 0.19 μmol L^?1, and a limit of quantification of 0.64 μmol L^?1. The developed method was subsequently applied for quantitative analysis of Clo in milk samples with results proving high repeatability and recovery.     

An electrochemical sensor based on TiO2/activated carbon nanocomposite modified screen printed electrode and its performance for phenolic compounds detection in water samples

Herein, we reported a titanium oxide (TiO₂) modified activated carbon nanocomposite that showed advantageous characteristics in terms of electro-conductivity, catalytic activity and surface area. The designed nanocomposite was employed to modify the screen printed carbon electrode transducer surface in the construction of an electrochemical sensor. The electrode surface modification was characterised by cyclic voltammetry and impedimetric studies. The modified transducer surface was subsequently used for the detection of four phenolic endocrine disruptors, p-nitrophenol, hydroquinone, catechol and 1-naphtol. Under optimal conditions, TiO₂ modified activated carbon sensor was evaluated by differential pulse voltammetry showing a good linearity with correlation coefficients higher than 0.99. It showed, in parallel, a high sensitivity where the detection limits were 348 ng/L, 110.1 ng/L, 3.3 ng/L and 7.2 µg/L for the respective studied compounds (S/N = 3). Finally, we validated the method with river water samples, and good recovery values were obtained showing the potential application of the reported biosensor.     

Application of a sensitive nanocomposite-based electrochemical sensor for voltammetric determination of dicyclomine hydrochloride in real samples

In the present study a glassy carbon electrode, modified with nanocomposite of gold nanoparticles/multiwalled carbon nanotubes (GNPs/MWCNTs/GCE), was used for determination of dicyclomine hydrochloride (DcCl). The results showed that synergetic effects of GNPs and MWCNTs highly improved electrochemical response and sensitivity of the sensor. The electrochemical oxidation of DcCl was investigated by cyclic voltammetry and differential pulse voltammetry. Also, scanning electron microscopy and energy dispersive x-ray spectroscopy were used to evaluate microstructure of electrochemical sensor. The effect of various experimental parameters including pH and scan rate on the voltammetric response of DcCl were investigated. Under the optimal conditions linear response was observed in range of 1.0–1.2 × 10² µmol L^?1 for DcCl. The lower detection limit was found to be 0.40 µmol L^?1 for DcCl. The investigated method showed good stability, reproducibility and repeatability. The proposed sensor was successfully applied to the determination of DcCl in real samples.     

Alumina Polished Glassy Carbon Electrode as a Simple Electrode for Lower Potential Electrochemical Detection of Dopamine in its Sub‐micromolar Level

The electrochemical behaviour of dopamine (DA) at a cleaned and alumina polished glassy carbon electrode (GCE) was studied using cyclic voltammetry (CV). The CV studies revealed that alumina polished GCE (AGCE) shows an enhanced oxidation peak current response with 217 mV negative potential shift towards DA than that of cleaned GCE. The differential pulse voltammetry result shows that the AGCE detects the DA in the linear concentration ranges from 0.15 to 25.25 µmol L^?1. The limit of detection was calculated as 0.046 µmol L^?1 with a sensitivity of 3.74 µA µmol L^?1 cm^?2 for the determination of DA. The fabricated AGCE shows a satisfactory selectivity, practicality along with appreciable repeatability and reproducibility.     

Use of Graphite Polyurethane Composite Electrode for Imipramine Oxidation—Mechanism Proposal and Electroanalytical Determination

Abstract

This work is aimed at the elucidation of the oxidation mechanism for the tricyclic antidepressant imipramine using electrochemical and quantum chemical studies. The excellent response obtained with the use of a rigid graphite‐polyurethane composite electrode (GPU) provided the development of a new electroanalytical methodology, in 0.10 mol/L BR buffer (pH 7.0), employing square wave voltammetry. Detection and quantification limits of 4.60×10^?9 mol/L(1.5 µg L) and 3.04×10^?7 mol/L (96 µg L) were obtained. This methodology was tested in a commercial formulation of Tofranil^® and excellent recoveries were achieved by electrochemical (97.60±0.90%) and spectrophotometrical (87.10±0.90%) methods.     

A Simple and Novel Electrochemical Sensor Based on Phosphomolybdic‐Polypyrrole Film Modified Electrode for Highly Sensitive Detection of Cholic Acid

A simpe electrochemical sensor for detection of cholic acid (CA) was designed by modifying phosphomolybdate (PMo₁₂) doped polypyrrole (PPy) film on glassy carbon electrode (PMo₁₂‐PPy/GCE). The electrochemical behavior of CA on PMo₁₂‐PPy/GCE was investigated by cyclic voltammetry and 0.5 order differential voltammetry. The results indicated that CA had high inhibitory activity toward the peak currents of PMo₁₂‐PPy/GCE. The reduction peak currents were linearly related to the logarithmic value of the concentration of CA from 1.0×10^?7 to 1.0×10^?3 mol/L with a low detection limit of 1.0×10^?8 mol/L. The developed sensor exhibited excellent sensitivity, selectivity and stability for detection of CA, and it could be successfully applied to detect the level of CA in the urine samples. Moreover, the response mechanism of CA on the PMo₁₂‐PPy/GCE was discussed in detail.     

Acylpyrazolone Modified Glassy Carbon Electrode Effect on the Electrochemical Behavior of Tyrosine

Abstract

This work demonstrates the electrochemical behavior of the 1-phenyl-3-methyl-4-(α-furoyl)-pyrazolone-5 (HPMαFP) modified glassy carbon electrode (HPMαFP/GCE) by a dropletting method. Tyrosine (Tyr) was detected at the HPMαFP/GCE by cyclic voltammetry. The mechanism and the best condition of electrode reaction were studied. The results indicate Tyr has an excellent electrochemical response at HPMαFP/GCE; under optimized experimental conditions, the peak current is proportional to the concentration of Tyr over a wide range. The linear regression equation at HPMαFP/GCE is I_Pa (µA) = 1.01134 + 0.96716 C (µmol · L^?1) (r = 0.99914). The low detection limit is 1.6 × 10^?7 mol · L^?1. The modified electrode exhibited high sensitivity, good selectivity, and reproducibility, and it is easy to prepare.     

Electrochemical Detection of Metals Using Thick Nanofibrous Nafion Web Modified Electrodes

In this work, GC electrodes modified with thick electrospun nanofibrous Nafion webs were characterized using scanning electron microscopy (SEM) and cyclic voltammetry (CV) and used for the extraction and electrochemical detection of cadmium by differential pulse voltammetry. Cadmium was detected after 10 min incubation at open circuit followed by anodic stripping using 60 s reduction at ?1.4 V. The electrode yielded well‐defined, undistorted and reproducible (RSD of 7.0 % based on 10 measurements) voltammetric response with two linear ranges from 0.1 to 3 µM (R²=0.994 ) and from 3 to 10 µM (R²=0.977) and a detection limit and sensitivity of 0.01 µM and 32 and 7.725 µA/µM for both linear portions of the curve respectively.     

Thionine-functionalized graphene oxide,new electrocatalyst for determination of nitrite

In this work, thionine (Th) was assembled on the surface of graphene oxide as an electron transfer mediator using diazonium reaction (Th–GO). Then, Th–GO was characterized by different methods such as scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Afterward, Th–GO was used for the modification of carbon paste electrode. Several electrochemical methods including cyclic voltammetry, differential pulse voltammetry, and hydrodynamic amperometry were used to investigate the behavior of the modified electrode. Then, the role of the modified electrode for oxidation of nitrite has been studied. For this purpose, the effect of critical experimental parameters including step potential and pulse amplitude (in differential pulse voltammetry technique), applied potential, the rotating speed of the disk (in amperometry technique), and the solution pH was investigated. Under the optimized conditions, the currents were found to be linear with the nitrite concentration in the range 0.05–33.0 and 0.5–800 µmol L^?1 with detection limits of 0.02 and 0.2 µmol L^?1 using differential pulse voltammetry and hydrodynamic amperometry, respectively. The introduced modified electrode showed good repeatability (RSD% = 3.2) and reproducibility (RSD% = 4.7). This electrochemical sensor was exerted successfully for the determination of nitrite and nitrate in real samples including water and wastewater samples.     

A Polypyrrole‐Imprinted Electrochemical Sensor Based on Nano‐SnO2/Multiwalled Carbon Nanotubes Film Modified Carbon Electrode for the Determination of Oleanolic Acid

A sensitive molecularly imprinted electrochemical sensor with specific recognition ability for oleanolic acid was synthesized by modification of multiwalled carbon nanotubes (MWNTs) decorated with tin oxide nanoparticles (nano‐SnO₂/MWNTs) and polypyrrole‐imprinted polymer on a carbon electrode. The morphology and electrochemical performance of the imprinted sensor were investigated by using scanning electron microscope (SEM), X‐ray diffraction (XRD), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and amperometric i–t curve. The results showed that the imprinted sensor displayed excellent selectivity toward oleanolic acid. A linear relationship between the response currents and oleanolic acid concentrations ranging from 5.0×10^?8 g/L to 2.0×10^?5 g/L was obtained for the imprinted sensor. The limit of detection (LOD) of the imprinted sensor toward oleanolic acid was calculated as 8.6×10^?9 g/L at a signal to noise ratio (S/N) of 3. This imprinted sensor was successfully applied to the determination of oleanolic acid in Acitinidia deliciosa root samples.     

Very sensitive differential pulse adsorptive stripping voltammetric determination of 4-nitrophenol at poly (diphenylamine)/multi-walled carbon nanotube-β-cyclodextrin-modified glassy carbon electrode

In this work, a glassy carbon electrode (GCE) modified with poly (diphenylamine)/multi-walled carbon nanotubes-β-cyclodextrin (PDPA/MWCNT-β-CD) film was constructed and used for the determination of 4-nitrophenol (4-NP). Diphenylamine was successfully electropolymerised onto MWCNT-β-CD-modified GCE by cyclic voltammetry in monomer solution and 5 mol L^?1 H₂SO₄. The surface morphology of PDPA/MWCNT-β-CD film was characterised using scanning electron microscopy and electrochemical impedance spectroscopy. After adsorption of 4-NP on PDPA/MWCNT-β-CD at 0.2 V for 150 s, it showed a well-defined reduction peak in phosphate buffer solution at pH = 7. The PDPA/MWCNT-β-CD film enhanced the reduction peak current due to the complex formation between β-CD and 4-NP, presence of conductive polymer film as electron transfer mediator and also ability of MWCNTs for strong adsorptive and catalytic effect. Peak current increased linearly with 4-NP concentration in the range of 0.1 to 13.9 µg L^?1. The detection limit was obtained as 0.02 µg L^?1, which is better than other reported detection limits for the determination of 4-NP. The results showed that modified electrode has good sensitivity and selectivity. This sensor was used for the determination of 4-NP in water samples.     

Electrochemical study and voltammetric determination of sodium diethyldithiocarbamate using silver nanoparticles solid amalgam electrode

We report in this work, for the first time, the voltammetric study and the development of an electroanalytical method for the determination of sodium diethyldithiocarbamate (Na-DDC) using solid amalgam electrode fabricated with silver nanoparticles. The experimental parameters were studied and the best voltammetric response was reached when using 0.02 mol L^–1 Britton–Robinson buffer (pH = 5.5). Cyclic voltammograms of the substance presented two voltammetric signals: one cathodic peak at E_p = – 0.55 V and one anodic peak at E_p = – 0.49 V. The redox process of Na-DDC showed itself as an adsorption-controlled and quasi-reversible system. A mechanism for this electrochemical reaction was proposed. The analytical studies employed square-wave adsorptive stripping voltammetry (SWAdSV) and were based on the cathodic signal given by Na-DDC. Good linearity was observed in the concentration range from 2.83 × 10^–7 mol L^–1 to 6.89 × 10^–6 mol L^–1. The obtained limit of detection was 7.26 × 10^–8 mol L^–1. The electroanalytical approach described here was successfully employed for the determination of Na-DDC in river water at levels of concentration from 1.46 × 10^–7 mol L^–1 to 1.46 × 10^–6 mol L^–1 with good repeatability and reproducibility (RSD values of 4.2% and 5.9%, respectively). The values found during these determinations presented good concordance when compared with the expected values. According to the data presented here, the solid amalgam electrode fabricated with silver nanoparticles may be seen as an effective and green tool for the electrochemical analysis of Na-DDC and also other reducible compounds that usually require mercury-based electrode surfaces.