Electrocatalytic oxidation of NADH at mesoporous carbon modified electrodes

The electrochemical oxidation of β-nicotinamine adenine dinucleotide (NADH) was investigated at a glassy carbon electrode modified with carbon mesoporous materials (CMM). Due to the large surface area and electro-catalytic properties of CMM, the overpotential of the electrodes toward the oxidation of NADH is decreased by 595 mV in aqueous solution at neutral pH. The anodic peak currents increase steadily with the concentration of NADH in the range from 2 µM to 1.1 mM, the detection limit being 1.0 µM at pH 7.2 and a potential of +0.3 V vs. SCE. The apparent Michaelis-Menten constant is ～21.5 μM. The results enable NADH to be sensed at a low potential and are promising with respect to the design of dehydrogenase-based amperometric biosensors.     

Nanostructured nickel (II) phthalocyanine—MWCNTs as viable nanocomposite platform for electrocatalytic detection of asulam pesticide at neutral pH conditions

This work reports for the first time that nanostructured nickel (II) phthalocyanine/multiwalled carbon nanotubes composite supported on a basal plane pyrolytic electrode (NiPcNP/MWCNT-BPPGE) could potentially serve as a viable platform for the sensitive electrocatalytic detection of asulam pesticide at phosphate-buffered solution (pH 7.0 conditions). Comparative electron transfer dynamics, using ferrocyanide/ferricyanide as outer sphere redox probe, were examined and interpreted using the Davies–Compton theoretical framework dealing with voltammetry at spatially heterogeneous electrodes. The NiPcNP/MWCNT-BPPGE exhibits fast electron transport and excellent electrocatalytic behavior toward asulam, with an onset potential of about 150 mV lower than observed for the electrode without MWCNTs or bare BPPGE. Also, NiPcNP/MWCNT-BPPGE displayed good analytical performance for asulam, with a detection limit of 0.285 µM, a linear concentration range of 91–412 µM, and a sensitivity of 44.6 µA mM^?1.     

Electrocatalytic Determination of Ampicillin Using Carbon-Paste Electrode Modified with Ferrocendicarboxylic Acid

Abstract

A carbon-paste electrode spiked with ferrocenedicarboxylic acid (FDCMCPE) was constructed by incorporation of ferrocenedicarboxylic acid in a graphite powder–paraffin oil matrix. It has been shown by direct current cyclic voltammetry and double-step chronoamperometry that this electrode can catalyze the oxidation of ampicillin (AMPC) in aqueous buffered solution. It has been found that under the optimum condition (pH 10.0) in cyclic voltammetry, the oxidation of AMPC occurred at a potential of about 480 mV on the surface of the modified carbon-paste electrode. The kinetic parameters such as electron-transfer coefficient, α, and rate constant for the chemical reaction between AMPC and redox sites in FDCMCPE were also determined using electrochemical approaches. Under the optimized conditions, the electrocatalytic oxidation peak current of AMPC showed two linear dynamic ranges with a detection limit of 0.67 µmol L^?1 AMPC. The linear calibration was in the range of 2.34–30 µmol L^?1 and 40–700 µmol L^?1 AMPC using the differential pulse voltammetric method. Finally, this method was also examined as a selective, simple, and precise electrochemical sensor for the determination of AMPC in real samples such as drugs and urine.     

Room-Temperature Ionic Liquid and Multi-Walled Carbon Nanotube Composite Modified Carbon-Ceramic Electrode as a Sensitive Voltammetric Sensor for Indomethacin

The electrochemical behavior of indomethacin on the surface of a carbon-ceramic electrode modified with multi-walled carbon nanotubes and an ionic liquid composite film is reported. The results show that the nano-structured film exhibited excellent enhancement effects on the electrochemical oxidation of indomethacin. The developed sensor presented a linear response to indomethacin over the concentration range from 1 to 50 µM with a detection limit of 0.26 µM. The proposed modified electrode was employed for the determination of indomethacin in biological and pharmaceutical samples using differential pulse voltammetry.     

Electrochemical Oxidation at a Glassy Carbon Electrode of the Anti‐Arrhythmia Drug Disopyramide

Abstract

A voltammetric study of the oxidation of disopyramide has been carried out using a glassy carbon electrode. The electrochemical oxidation of disopyramide was investigated by cyclic, differential pulse, and square wave voltammetry. The oxidation of disopyramide is an irreversible, diffusion‐controlled process. The diffusion coefficient of disopyramide was calculated in pH 7.0 phosphate buffer to be D _disopyramide=3.8×10^?6 cm² s^?1. The oxidation of disopyramide is also pH dependent and for electrolytes with pH between 4 and 7 occurs with the transfer of one electron and one proton. In alkaline electrolytes, two consecutive charge transfer reactions are observed: both oxidation reactions involve the transfer of two electrons but only the first also involves the transfer of two protons. Two procedures for the analytical determination of disopyramide in pH 7.0 phosphate buffer were developed and compared and a detection limit LOD=1.27 µM was obtained.     

Electroanalytical Oxidation of p‐Coumaric Acid

Abstract

The mechanism of the electrochemical oxidation of p‐coumaric acid on a glassy carbon electrode was investigated using cyclic, differential pulse, and square wave voltammetry at different pHs. The oxidation of p‐coumaric acid is irreversible over the whole pH range. After successive scans, the p‐coumaric acid oxidation product deposits on the electrode surface, forming a polymeric film that undergoes reversible oxidation at a lower potential than p‐coumaric acid. This polymeric film increases in thickness with the number of scans, covering the electrode surface, and impeding the diffusion of the p‐coumaric acid and its oxidation on the electrode. The oxidation of p‐coumaric acid is pH dependent up until values close to the pK_a. For pHs higher than pK_a, the p‐coumaric acid oxidation process is pH independent. An electroanalytical determination procedure of p‐coumaric in pH 8.7 0.2 M ammonium buffer was developed, and a detection limit, LOD=83 nM, and the limit of quantification, LOQ=250 nM, were obtained.     

Electrochemical determination of mesotrione and its degradation products on glassy carbon electrode

A simple, fast and sensitive analytical method was developed for the quantification of herbicide mesotrione (MES) and its degradation products: 4-(methylsulfonyl)-2-nitrobenzoic acid (MNBA) and 2-amino-4-(methylsulfonyl) benzoic acid (AMBA) using differential pulse voltammetry (DPV). Voltammetric measurements were performed using glassy carbon electrode (GCE). Potential range, pH of the electrolyte and the scan rate were optimised to achieve the lowest detection limits of analytes. The optimal conditions were obtained in a Britton–Robinson (BR) buffer at pH 4.0 for MNBA and at pH 6.0 for MES and AMBA, with the scan rate 0.08 V/s. The potential V for (1) nitro and carbonyl groups of MES, (2) nitro group of MNBA and (3) amino group of AMBA, obtained under optimised conditions, was plotted as a function of a peak current (I). The I(V) dependencies were measured for the following concentration ranges: 0.5–5.0 µM for the nitro group of MES and MNBA, 0.75–5.0 µM and 0.50–8.5 µM for the carbonyl groups of MES, and 0.25–8.5 µM for amino group of AMBA; whereas, the limit of detection was in range 0.07–0.23 µM (20–80 µg/L). The proposed method is the first one that allows the determination of both MES and its degradation products. The practical applicability of these newly developed voltammetric methods was verified by direct determination of MES and its degradation products in model samples of drinking and surface water.     

Fabrication of Silver Nanoparticles Decorated on Activated Screen Printed Carbon Electrode and Its Application for Ultrasensitive Detection of Dopamine

In the present study, we report the fabrication of silver nanoparticles (AgNPs) decorated on activated screen printed carbon electrode (ASPCE). The AgNPs were prepared by using Justicia glauca leaf extract as a reducing and stabilizing agent and the ASPCE was prepared by a simple electrochemical activation of screen printed carbon electrode (SPCE). The ASPCE/AgNPs shows a reversible electrochemical behaviour with enhanced response for DA than that of other modified SPCEs. Under optimum conditions, the electrochemical oxidation current response of DA is linear over the concentration range from 0.05 to 45.35 µM. The limit of detection is found as 0.017 µM with a high sensitivity of 7.85 µA µM^?1 cm^?2.     

Simultaneous Sensitive Determination of Dopamine and Uric Acid in the Presence of Excess Ascorbic Acid with a Magnetic Chitosan Microsphere/Thionine Modified Electrode

Magnetic chitosan microspheres (MCMS) and thionine were incorporated in a modified electrode for the simultaneous sensitive determination of dopamine (DA) and uric acid (UA). Due to the unique properties of the MCMS and the electron mediation of thionine, this modified electrode showed excellent electrocatalytic oxidation toward dopamine and uric acid with a large separation of peak potentials and a significant enhancement of peak currents. However, the electrochemical behavior of ascorbic acid may be depressed at the modified electrode. Differential pulse voltammetry was used for the simultaneous sensitive determination of dopamine and uric acid in the presence of excess ascorbic acid at this modified electrode. The current responses showed excellent linear relationships in the range of 2–30 µM and 9–100 µM for dopamine and uric acid, respectively. The detection limits were estimated to be 0.5 µM and 2.3 µM for dopamine and uric acid, respectively. In addition, this modified electrode showed excellent repeatability, good stability, and satisfactory reliability, thus indicating potential for the practical applications.     

Anodic Oxidation of α‐Lipoic Acid at a Glassy Carbon Electrode and Its Determination in Dietary Supplements

Abstract

Direct electrochemistry of alpha‐lipoic acid (ALA) was performed at a glassy carbon electrode using cyclic, differential pulse and square wave voltammetry over a wide range of pH. The oxidation of ALA is an irreversible process, pH independent, and involves the charge transfer of one electron. The diffusion coefficient of ALA was calculated from the results obtained at pH 6.9 in 0.1 M phosphate buffer and was shown to be D ₀=1.1×10^?5 cm² s^?1. The limits of detection (LOD) and quantification (LOQ) calculated from the results obtained at this pH are 1.8 and 6.1 µM, respectively.

The lipoic acid content in two dietary supplements samples, a syrup containing ALA and capsules of ALA, has been determined directly at the glassy carbon electrode by differential pulse voltammetry using the standard addition method.     

Electrochemical determination of picric acid based on platinum nanoparticles–reduced graphene oxide composite

Platinum nanoparticles–reduced graphene oxide composite-modified glassy carbon electrode (PtNPs–rGO/GCE) was developed as a simple, selective and sensitive electrochemical sensor for determination of picric acid (PA). Cyclic voltammogram (CV) of PA showed three well-defined irreversible reduction peaks at the potentials of ?0.43, ?0.57 and ?0.66 V versus Ag/AgCl. In this work, the interference effect of other nitrophenol compounds (NPhCs) was significantly reduced by appropriate adjusting of pH. Square wave voltammetry was used for quantification of PA in the range of 5–500 µM (1.15–115 mg L^?1) with practical detection limit of 1 µM (0.23 mg L^?1). The proposed sensor was successfully applied for the determination of PA in two natural water samples.     

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 promising electrochemical sensing platform based on copper nanoparticles-decorated polymer in carbon nanotube electrode for monitoring methimazole

In this paper, a novel and convenient electrochemical sensor for detection of methimazole (MMI) by differential pulse voltammetry is presented. This sensor was fabricated by dripping well-dispersed MWCNTs onto glassy carbon electrode (GCE) surface, and then poly-l-Arg (P-L-Arg) film was deposited on the electrode. Finally, Cu nanoparticles (CuNPs) were electrochemically deposited on the resulting film by using cyclic voltammetry to prepare CuNPs-P-L-Arg/MWCNTs/GCE. The surface morphology of the electrodes has been studied by scanning electron microscopy. Studies reveal that the irreversible oxidation of MMI was highly facile on CuNPs-P-L-Arg/MWCNTs/GCE. The dynamic detection range of this sensor to MMI was 5.2–50 µM, with the detection limit of 2 µM. A new voltammetric method for determination of MMI was erected and shows good sensitivity and selectivity, very easy surface update and good stability. The analytical application of the modified electrode is demonstrated by determining MMI in biological fluids (serum).     

Highly Selective and Sensitive Graphene Based Electrochemical Sensor for Quantification of Receptor Agonist Rizatriptan

A highly selective and sensitive electrochemical sensor has been developed by modification of a glassy carbon electrode (GCE) with graphene (GRP) for quantification of Rizatriptan. The significant increase of the peak current and the improvement of the oxidation peak potential indicate that the electrochemical sensor facilitates the electron transfer of Rizatriptan. The oxidation peak current was proportional to the Rizatriptan concentration in the range from 100 to 600 µg/mL with detection (LOD) and quantification limit (LOQ) of 36.52 and 121.73 µg/mL, respectively. The developed method was successfully employed for quantification of Rizatriptan in pharmaceutical formulations. The sensor shows great promise for simple, sensitive and quantitative detection of Rizatriptan.     

Electrochemical Behavior of Hydroquinone at Poly (Acridine Orange)–Modified Electrode and Its Separate Detection in the Presence of o‐Hydroquinone and m‐Hydroquinone

Abstract

Poly (acridine orange) (PAO) film–modified electrode was prepared by the electrooxidation of Acridine orange on a glassy carbon electrode (GCE) for the detection of hydroquinone in the presence of o‐hydroquinone and m‐hydroquinone. The electrochemical behavior of hydroquinone on the modified electrode was investigated with respect to different solution acidity, scan rate, and accumulation time. A pair of sharp and well‐defined peaks was obtained at 0.45 and 0.42 V [vs. a saturated calomel electrode (SCE)] at the PAO film–modified electrode. The potential difference between this pair of cathodic and anodic peaks was decreased to only 30 mV as compared to the 241 mV that was obtained on the bare glassy carbon electrode (GCE). As to o‐hydroquinone and m‐hydroquinone, their corresponding oxidation peaks appeared at 0.55 V and 0.89 V (vs. SCE), respectively. The oxidation potential differences between these three isomers enabled the separate detection of hydroquinone. Under the optimum experimental situation, the oxidation peak current of hydroquinone was proportional to the concentration at the range of 6.8×10^?7–9.6×10^?5 M. The detection limit was been estimated as 3×10^?7 M with 130 s accumulation. This method was applied to the hydroquinone detection in tap water samples.     

Electroanalytical Characterization of Adenosine Mono-, Di- and Triphosphate Oxidation on Carbon Electrode

Abstract

Electrochemical oxidation of adenosine mononucleotides was characterized using a pencil graphite carbon electrode for the first time. All three adenosine mononucleotides, adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP), showed irreversible electro-activity at the carbon electrode, yielding a well-defined oxidation current response. The peak potential was highly dependent on pH. The lowest mononucleotide concentration detected was 1 µM. The electro-analytical data presented here for the oxidation of adenosine mononucleotides provides the basis for further bioanalytical investigations related to DNA-drug interactions.     

Application of a Deconvolutive Procedure to Analyze Several Chlorophenol Species in Natural Waters by Square‐Wave Voltammetry on the Boron‐Doped Diamond Electrode

Abstract

The anodic voltammetric behavior of 4‐chlorophenol (4‐CP) on a boron‐doped diamond electrode (BDD) in aqueous solution was studied by square‐wave voltammetry. After optimization of the experimental conditions, 4‐CP was determined in a Britton‐Robinson buffer solution with pH 6.0, prepared with pure water. Moreover, mixtures of some different chlorophenols were also investigated and an analytical method was developed for the simultaneous determination of these compounds in natural waters. The oxidation of 4‐CP on BDD was used for analytical purposes and quantification limits as low as 9.2 µg L^?1 were obtained. This result illustrates the advantage of using oxidation process currents on BDD electrodes as the analytical signal, even in contaminated matrices. In order to compare the results found here with the conventional methodology to determine chlorophenols, HPLC‐UV‐vis measurements were also performed and were in good agreement with the analytical values obtained by SWV.     

Determination of Levodopa in Pharmaceuticals Using a Disposable Electrochemically Activated Carbon-Paste Electrode by Linear Sweep Voltammetry

A simple disposable electrochemically activated carbon-paste electrode was developed for the determination of levodopa in pharmaceuticals and the optimal conditions for carbon-paste electrode electrochemical activation were studied. The study of the oxidation process of levodopa on the proposed electrode was performed using cyclic voltammetry and the irreversibility of levodopa with a kinetic-controlled current was established. The determination of levodopa is possible in the concentration range of 5–100?µM. The detection and quantification limits were 0.65 and 0.79?µM, respectively. The proposed procedure was satisfactorily applied in the levodopa determination in pharmaceuticals with relative standard deviation 3.4%.     

Development of carbon paste electrode modified with cadmium ion-imprinted polymer for selective voltammetric determination of Cd2+

A simple and fast voltammetric method based on a new electrode composed of carbon paste electrode/bifunctional hybrid ion imprinted polymer (CPE/IIP) was developed for the quantification of Cd²⁺ in water samples. The voltammetric measurements by Differential Pulse Voltammetry were performed by using CPE containing 11.0 mg of IIP under phosphate buffer solution at concentration 0.1 mol L^?1 and pH 6.5. The electrochemical method was carried out by Cd²⁺ preconcentration at ?1.2 V during 210 s, followed by anodic stripping. The performance of IIP towards Cd²⁺ determination was evaluated by comparison to non-imprinted polymer, whose detectability of IIP was much higher (45%). The sensitivity of the sensor was found to be 0.0105 µA/µg L^?1. The limits of detection and limits of quantification were found to be 4.95 μg L^?1 and 16.4 μg L^?1, respectively. The developed method was successfully applied to Cd²⁺ determination in mineral, tap and lake water samples, whose results are in agreement with thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) used as reference analytical technique. According to achieved results, the developed method can be used for routine analysis of quality control of water samples from different sources.     

Synthesis of a Palladium-Graphene Material and Its Application for Formaldehyde Determination

A novel electrochemical sensor for formaldehyde determination was fabricated by using the Pd-graphene nanohybrides. Pd-graphene nanohybrids were prepared via a concise chemical reduction method. Raman spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM) were used for the characterization of structure and morphology of the nanohybrids. The result showed that Pd nanoparticles were uniformly dispersed and were well-separated on the graphene sheets. The Pd-graphene nanohybrids were dissolved in Nafion and modified on the glassy carbon electrode to fabricate the electrochemical sensor. This proposed electrochemical sensor performed excellent electrocatalytic activity toward formaldehyde oxidation in alkaline medium. The peak current was linearly related to the formaldehyde concentration in the range of 7.75 µM to 62.0 µM with the detection limit of 3.15 µM. The highly sensitive and robust graphene based Pd nanohybrids sensor offers a promising and practical tool for formaldehyde sensing and chemical analysis.