OH functionalized Multi-Walled Carbon Nanotube modified electrode as electrochemical sensor for the detection of Aceclofenac

ABSTRACT

The rapid electrochemical determination of Aceclofenac (ACF) has been employed by cyclic voltammetry (CV), differential pulse voltammetry (DPV) using developed OH-functionalised multiwalled carbon nanotube carbon paste electrode (OH-MWCNT/CPE). Modified electrode was characterised by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDAX), X-ray diffraction spectroscopy (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The ACF exhibits two oxidation peaks at +0.4 V, +0.66 V and one reduction peak at +0.3 V. The active surface area of the bare carbon paste electrode (BCPE) and modified electrode have been characterised by using K₃[Fe(CN)₆] solution containing 0.1 M KCl. In DPV mode, variation of ACF gave the limit of detection (LOD = 3s/m) 0.246 μM over the concentration range 1.0 to 190.0 μM (R² = 0.9994). The developed electrode has good stability, reproducibility and could be successfully validated for the detection of ACF in pharmaceutical samples and biological fluids.     

Development of an Electrochemical Sensor to Detect Dopamine and Ascorbic Acid Based on Neodymium (III) Oxide and Chitosan

Neodymium (III) oxide (Nd_Ox) was dispersed in chitosan dissolution and deposited on a glassy carbon electrode (chitosan‐Nd_Ox/GCE). The surface properties of the chitosan‐Nd_Ox/GCE were evaluated with FeCN₆⁻³ solution using cyclic voltammetry and electrochemical impedance spectroscopy. The modified electrode was used in the determination of individual dopamine (DP) and ascorbic acid (AA) with square wave adsorptive voltammetry. Under optimal parameters (pH 4.0; accumulation time; t_ACC 60s and accumulation potential; E_ACC 0.10 V) for DP and (pH 3,0; t_ACC 60s and; E_ACC −0.20 V) for AA, anodic peak currents were proportional to the concentration of DP and AA between 0.90 and 17.0 μmolL⁻¹, with detection limit of 0.079 μmolL⁻¹ for DP and 0.12 μmolL⁻¹ for AA. The sensor was used in the determination of DP and AA in human urine samples and vitamin C tablets with consistent results. The new sensor is easy to develop. In addition, the sensitivity in particular for AA was improved compared with previous work.     

Novel Fe2O3@CeO2 Coreshell‐based Electrochemical Nanosensor for the Voltammetric Determination of Norepinephrine

A new selective carbon paste electrode (CPE), was applied as an electrochemical sensor for the detection of norepinephrine (NOE). The sensor was modified with 6‐amino‐4‐(3,4‐dihydroxyphenyl)‐3‐methyl‐1,4‐dihydropyrano[2,3‐c],pyrazole‐5‐carbonitrile (ADPC) assisted Fe₂O₃@CeO₂ coreshell nanoparticles (CNs) synthesized by simple method. To identify the redox properties of the modified electrode, and to examine its electrochemical properties, cyclic voltammetry (CV), chronoamperometry and differential pulse voltammetry (DPV) were conducted. Through electrochemical investigations, the coefficient of electron transfer between ADPC and the CNs/CPE (i. e. carbon paste electrode which was modified with CNs), the apparent charge transfer rate constant (k_s), and the diffusion coefficient (D) were calculated. The NOE oxidation occurred at the optimum pH of 7.0 and a potential that was about 235 mV less positive than that of the unmodified carbon paste electrode. The interaction between the two metals in the Fe₂O₃@CeO₂ coreshell led to an increase in the surface area and, consequently a sharp increase in the current. The differential pulse voltammogram of NOE showed two linear dynamic ranges an excellent detection limit (3σ) of 40 nM. In addition, NOE, AC and Trp were simultaneously determined at the modified electrode. Finally, NOE was quantitated in a number of real samples.     

A Simple and Sensitive Square Wave Stripping Pathway for the Analysis of Desmedipham Herbicide by Modified Carbon Paste Electrode Based on Hematite (α‐Fe2O3 Nanoparticles)

In the present study, desmedipham, used as an herbicide to control broad leaf weed in commonly sugar beet crops, was analyzed at the first time by cyclic voltammetry (CV) and square wave stripping voltammetry (SWSV) with the modified carbon paste electrode based on hematite nanoparticles (α‐Fe₂O₃?CPE). The modified α‐Fe₂O₃?CPE prepared by hematite (α‐Fe₂O₃ nanoparticles), which is very sensitive to carbon paste electrode (CPE) and glassy carbon electrode (GCE). Morphology of electrode surface detailed by scanning electron microscopy (SEM) and energy dispersive X‐ray analysis (EDX). The oxidation of desmedipham created irreversible well‐done two peaks at nearly +1.1 and +1.3 V. In order to obtain the best calibration graph, various important parameters such as pH, accumulation time, puls amplitude and frequency etc. were investigated. Under the optimum conditions, electrochemical behavior of desmedipham presented two linear working ranges at 0.15–1.20 mg/L and 1.20–4.50 mg/L. The limits of detection (LOD) for the desmedipham were calculated as 41.00 and 50.00 μg/L for the peak I and II, respectively. Furthermore, desmedipham was analyzed at high recovery in the presence of rizolex, fluometuron, teflubenzuron and some heavy metal ions. Consequently, the developed SWSV was successfully applied to evaluate desmedipham in spiked commercial strawberry juices at recoveries of 96.00–104.00 % with satisfactory relative standard deviations.     

Application of Novel Zn‐Ferrite Modified Glassy Carbon Paste Electrode as a Sensor for Determination of Cd(II) in Waste Water

This paper describes the preparation of a new sensor based on Zn‐ferrite modified glassy carbon paste electrode and its electrochemical application for the determination of trace Cd(II) ions in waste waters using differential pulse anodic stripping voltammetry (DPASV). Different Zn/Ni ferrite nanoparticles were synthesized and characterized using scanning electron microscopy (SEM) and X‐ray powder diffraction (XRPD). The prepared ferrite nanoparticles were used for the preparation of Zn‐ferrite‐modified glassy carbon paste electrode (ZnMGCPE) for determination of Cd(II) at nanomolar levels in waste water at pH 5. The different parameters such as conditions of preparation, Zn²⁺/Ni²⁺/Fe²⁺ ratio and electrochemical parameters, percentage of modifier, accumulation time, pH and accumulation potential were investigated. Besides, interference measurements were also evaluated under optimized parameters. The best voltammetric response was observed for ZnFe₂O₄ modifier, when the percentage of modifier was 3 %, accumulation time 9 min, pH of supporting electrolyte 5 and accumulation potential ?1.05 V. Thus prepared electrode displays excellent response to Cd(II) with a detection limit of 0.38 ppb, and selective detection toward Cd(II) was achieved.     

Co2O3‐NH2‐MCM‐41 Decorated Graphite as an Effective Electrode: Synthesis,Characterization and its Application for Electro‐catalytic Oxidation of Acid Red 1

The graphite electrode decorated with Co₂O₃‐NH₂‐MCM‐41 was successfully fabricated and the potential for applying this electrode for electro‐catalytic oxidation of Acid Red 1 (AR1) was investigated. The Co₂O₃‐NH₂‐MCM‐41 was characterized by Scanning Electron Microscope (SEM), Brunauer‐Emmett‐Teller (BET), X‐ray diffraction (XRD) and Fourier transform infrared spectra (FTIR). Electrochemical measurements including cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to investigate electrochemical activity of graphite anode with Co₂O₃‐NH₂‐MCM‐41. The electro‐catalytic oxidation process was carried out via varying different parameters such as voltage, electrolyte pH, electrolyte concentration, current density and interelectrode distance. The results revealed the maximum removal ratio of AR1 was 99.8 %. The AR1 solution was tested during the degradation process by CV analysis at different scan rates, UV‐Vis spectral analysis and gas chromatography−mass spectrometry (GC/MS). The linear relationship between peak current and scan rates indicated an adsorption controlled process for AR1 degradation, UV‐Vis analysis revealed that the degradation process took place through reactions such as destruction of azo groups, benzene ring, naphthalene ring and so on, GC/MS analysis demonstrated that AR1 was finally destructed to small molecules by analyzing intermediates during degradation process.     

Modified Graphite Paste Electrode with Lewatit FO36 Nanoresin/Multi-Walled Carbon Nanotubes for Determination of Quercetin

In the present study, the electrochemical oxidation of quercetin (QUR) was investigated using a graphite paste electrode (GPE) modified with multi-walled carbon nanotube and Lewatit FO36 nanoresin (LFONR-MWCNT/GPE). LFONR-MWCNT/GPE could effectively a sensitive anodic peak at around 0.23 V (vs. SCE) in a 0.10 M phosphate buffer solution. Modified electrode revealed that activated with multiwalled carbon nanotube and LFONR was capable of facilitating electron transfer and increasing surface area. The electrochemical oxidation of QUR was studied using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). Some kinetic parameters for electrochemical oxidation of QUR including total number of electrons (n) and standard heterogeneous rate constant (k_s) were also determined. The calibration graph consisted of two linear segments of 1.8–25.0 μM, and 25.0–570.0 μM with a detection limit of 0.213 μM (based on 3S_b). The applicability of the method to juice of peach, red grape, sour cherry and Gincora tablets analysis was also evaluated.     

Electrocatalytic Oxidation and Voltammetric Determination of Hydrazine on the Tetrabromo‐p‐Benzoquinone Modified Carbon Paste Electrode

The electrochemical properties of hydrazine studied at the surface of a carbon paste electrode spiked with p‐bromanil (tetrabromo‐p‐benzoquinone) using cyclic voltammetry (CV), double potential‐step chronoamperometry and differential pulse voltammetry (DPV) in aqueous media. The results show this quinone derivative modified carbon paste electrode, can catalyze the hydrazine oxidation in an aqueous buffered solution. It has been found that under the optimum conditions (pH 10.00), the oxidation of hydrazine at the surface of this carbon paste modified electrode occurs at a potential of about 550 mV less positive than that of a bar carbon paste electrode. The electrocatalytic oxidation peak current of hydrazine showed a linear dependent on the hydrazine concentrations and linear analytical curves were obtained in the ranges of 6.00×10^?5 M–8.00×10^?3 M and 7.00×10^?6 M–8.00×10^?4 M of hydrazine concentration with CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (3σ) were determined as 3.6×10^?5 M and 5.2×10^?6 M by CV and DPV methods. This method was also used for the determination of hydrazine in the real sample (waste water of the Mazandaran wood and paper factory) by standard addition method.     

Determination of hydroxylamine using a carbon paste electrode modified with graphene oxide nano sheets

A carbon paste electrode that was chemically modified with 3-(4'-amino-3'-hydroxy-biphenyl-4-yl)-acrylic acid (3,4-AA) was used as a selective electrochemical sensor for the detection of hydroxylamine. Cyclic voltammetry (CV), choronoamperometry (CHA) and square wave voltammetry (SWV) were used to investigate oxidation of hydroxylamine in aqueous solution. Under optimized concentration the electrocatalytic oxidation current peak for hydroxylamine increased linearly with concentration in the range of 0.025–10.0 μM. The detection limits for hydroxylamine was 0.012 μM. Finally, the modified electrode was applied to detection hydroxylamine in water samples.     

Simultaneous Determination of Isoproterenol,Acetaminophen and Folic Acid Using a Novel Nanostructure‐Based Electrochemical Sensor

In this study, a carbon paste electrode modified with (E)‐2‐((2‐chlorophenylimino)methyl)benzene‐1,4‐diol (CD) and titanium dioxide nanoparticles (TiO₂) was used to prepare a novel electrochemical sensor. The objective of this novel electrode modification was to seek new electrochemical performances for the detection of isoproterenol (IP) in the presence of acetaminophen (AC) and folic acid (FA). Initially, cyclic voltammetry (CV) was used to investigate the redox properties of this modified electrode at various scan rates. In the following, the mediated oxidation of IP at the modified electrode was described. The results showed an efficient catalytic activity of the electrode for the electrooxidation of IP, which leads to a reduction in its overpotential by more than 235 mV. The value of the electron transfer coefficient (α), catalytic rate constant (k_h) and diffusion coefficient (D) were calculated for IP, using electrochemical approaches. Based on differential pulse voltammetry (DPV), the oxidation of IP exhibited a dynamic range between 0.5 and 1000 µM and a detection limit (3σ) of 0.47 µM. DPV was used for simultaneous determination of IP, AC and FA at the modified electrode. Finally, this method was used for the determination of IP in real samples, using standard addition method.     

Fabrication of highly sensitive and selective nanocomposite film based on CuNPs/fullerene-C60/MWCNTs: An electrochemical nanosensor for trace recognition of paracetamol

Designing an electrochemical sensor for versatile clinical applications is a sophisticated task and how dedicatedly functionalized composite materials can perform on this stage is a challenge for today and tomorrow's Nanoscience and Nanotechnology. In the present work, we demonstrate a new strategy for the development of novel electrochemical sensor based on catalytic nanocomposite film. Fullerene-C₆₀ and multi-walled carbon nanotubes (MWCNTs) were dropped on the pre-treated carbon paste electrode (CPE) and copper nanoparticles (CuNPs) electrochemically deposited on the modified CPE to form nanocomposite film of CuNPs/C₆₀/MWCNTs/CPE. In this work, an electrochemical method based on square wave voltammetry (SWV) employing CuNPs/C₆₀/MWCNTs/CPE has been presented for the recognition and determination of paracetamol (PT). Developed electrochemical sensor was characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronocoulometry. The composite film made the fabricated sensor to display high sensitivity and good selectivity for PT detection. The influence of the optimization parameters such as pH, accumulation time, deposition potential, scan rate and effect of loading of composite mixture of C₆₀-MWCNTs and CuNPs on the electrochemical performance of the sensor were evaluated. A linear range from 4.0 × 10⁻⁹ to 4.0 × 10⁻⁷ M for PT detection was obtained with a detection limit of 7.3 × 10⁻¹¹ M. The fabricated sensor was successfully applied to the detection of PT in biological samples with good recovery ranging from 99.21 to 103%.     

Boron Nitride Nanosheet Modified Electrode: Preparation and Application to Direct Electrochemistry of Myoglobin

An ionic liquid modified carbon paste electrode (CILE) was prepared with 1‐hexylpyridine hexafluorophosphate (HPPF₆) and used as a substrate electrode. Then hexagonal boron nitride (BN) nanosheet, myoglobin (Mb) and Nafion were fixed on the electrode surface by coating method to get a new‐style chemically modified electrode (Nafion/Mb/BN/CILE). The morphology and crystal phase of BN nanosheet were characterized by SEM, TEM and XRD. UV‐Vis and FT‐IR results showed that Mb retained its original conformation in the composite modified film. In phosphate buffer solutions (PBS) with pH 3.0, cyclic voltammetry (CV) was performed to investigate the direct electrochemical behaviour of Mb. A pair of quasi‐reversible redox reaction peaks was obtained on the CV curve, proving that BN nanosheet had good biocompatibility and could accelerate electron transfer between Mb and electrode surface. Electrocatalytic reduction of trichloroacetic acid (TCA) was investigated, which was further applied to TCA detection. The catalytic reduction peak current at ?0.355 V depended linearly on the TCA concentration in the range of 0.2～30.0 mmol/L with the equation of Ipc (μA)=6.340 C (mmol/L)+0.305 (r=0.998), and the detection limit was 0.05 mmol/L (3 σ).     

Design of a New Carbon Paste Electrode Modified with TiO2 Nanoparticles to Use in an Electrochemical Study of Codeine and Simultaneous Determination of Codeine and Acetaminophen in Human Plasma Serum Samples

A new electrochemical sensor was fabricated via TiO₂ nanoparticles onto a carbon paste electrode. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) studied the response of the modified electrode toward codeine. The effects of pH, modifier amount, pulse amplitude, and scan rate of potential have been examined. Using DPV, we could measure simultaneously codeine and acetaminophen in one mixture. The detection limits of 0.018 and 0.050 µmol L^?1 were achieved for codeine and acetaminophen, respectively. The electrooxidation pathway, transfer coefficient, and standard rate constant, are estimated. The proposed voltammetric sensor was successfully applied to determination of codeine and acetaminophen in human plasma serum samples.     

Voltammetric Determination of Metronidazole Using a Sensor Based on Electropolymerization of α‐Cyclodextrin over a Carbon Paste Electrode

An electrochemical sensor for metronidazole (MTZ) was built via the surface modification of a carbon paste electrode (CPE) by a film obtained through electropolymerization of α‐cyclodextrin (CPE_α‐CD). The CPE_α‐CD was characterized by cyclic voltammetry (CV) and atomic force microscopy (AFM), by both techniques was demonstrated that the polymer film is coating the electrode surface. The electroreduction behaviour of MTZ in HClO₄ media as a supporting electrolyte was studied by differential‐pulse voltammetric (DPV) technique. The DPV electrochemical process was observed to be diffusion controlled and irreversible. Under optimal conditions, the peak current was proportional to MTZ concentration in the range of 0.5 to 103.0 μM with a detection limit of 0.28±0.02 μM. The method was successfully applied to quantify of MTZ in pharmaceutical formulations. In addition, this proposed MTZ sensor exhibited good reproducibility, long‐term stability and fast current response.     

Simultaneous Electrochemical Determination of Paracetamol and Allura Red in Pharmaceutical Doses and Food Using a Mo(VI) Oxide-Carbon Paste Microcomposite

This work presents a new application for MoO₃ combined with carbon paste to prepare a microcomposite electrode (Mo(VI)_Ox/CPE) for the simultaneous determination of paracetamol (PCM) and Allure Red (AR) by square-wave voltammetry (SWV). The anodic peak currents for PCM and AR were 70.0 and 80.0 % high compared with an unmodified carbon paste electrode. The surface areas of Mo(VI)_Ox/CPE and CPE were evaluated by cyclic voltammetry. The detection limit were 0.14 and 0.38 μmol/L for PCM and AR respectively. The relative standard deviations (RSDs) were 2.0 % (n=7). Stability, shelf life and possible interferences were also evaluated with very acceptable results.     

Electrodeposition of Cobalt Oxide Nanostructure on the Glassy Carbon Electrode for Electrocatalytic Determination of para‐Nitrophenol

Cobalt oxide nanostructure (CoO_xNS) deposited on the glassy carbon (GC) electrode surface is proposed as a novel electrocatalytic system for the reduction of para‐Nitrophenol. Cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and scanning electron microscopy were used for characterization of deposited CoO_xNS. CoO_xNS deposited by cycling at positive potentials (0 to +1.3 V) show less charge‐transfer resistance (Rct) and more catalytic activity for the electroreduction of p‐nitrophenol compared to those CoO_xNS obtained by scanning the applied potential throughout a negative V range. The GC/CoO_xNS electrode showed good electrocatalytic activity toward the reduction of p‐nitrophenol at different pH values.     

Nanostructured Base Electrochemical Sensor for Simultaneous Quantification and Voltammetric Studies of Levodopa and Carbidopa in Pharmaceutical Products and Biological Samples

A novel carbon paste electrode modified with carbon nanotubes and 5‐amino‐2′‐ethyl‐biphenyl‐2‐ol (5AEB) was fabricated. The electrochemical study of the modified electrode, as well as its efficiency for electrocatalytic oxidation of levodopa (LD) and carbidopa (CD), is described. Cyclic voltammetry (CV) was used to investigate the redox properties of this modified electrode at various scan rates. The apparent charge transfer rate constant, k_s, and transfer coefficient, a, for electron transfer between 5AEB and CPE were calculated as 17.3 s^?1 and 0.5, respectively. Square wave voltammetry (SWV) exhibits a linear dynamic range from 2.5×10^?7 to 2.0×10^?4 M and a detection limit of 9.0×10^?8 M for LD.     

Detection of dopamine in the pharmacy with a carbon nanotube paste electrode using voltammetry

A simply prepared DNA immobilized on a carbon nanotube paste electrode (CNTPE) was utilized to monitor dopamine ion concentration using the cyclic voltammetry (CV) and square-wave (SW) stripping voltammetry methods. The optimum analytical conditions were sought. The result obtained was a very low detection limit compared to other common voltammetry methods. The optimal parameters were found to be as follows: 3.5 pH, 0.48 V SW amplitude, 71 Hz frequency, 5 s accumulation time, 0.01 V increment potential, and -1.3 V (anodic-*-) and 1.2 V (cathodic-o-) accumulation potentials. Given these conditions, the linear working range was observed to be within 0.01-0.11 microg L(-1) (SW anodic and CV). The analytical detection limit was determined to be SW anodic and CV: 4.0 microg L(-1) (2.1 x 10(-11) mol L(-1)) dopamin, and the relative standard deviation at the dopamine concentration of SW anodic 0.05 microg L(-1) was 0.02% (n=15) at the optimum conditions.     

L‐Cysteine Voltammetry at a Carbon Paste Electrode Bulk‐Modified with Ferrocenedicarboxylic Acid

The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH 8.00) in cyclic voltammetry, the oxidation of L ‐cysteine occurs at a potential about 200 mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, k_h were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10^?5 M–2.2×10^?3 M and 1.5×10^?5 M–3.2×10^?3 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 2.6×10^?5 M and 1.4×10^?6 M by CV and DPV methods.     

Biomass valorization of walnut shell into biochar as a resource for electrochemical simultaneous detection of heavy metal ions in water and soil samples: Preparation,characterization, and applications

Lately, due to its accessibility and eco-friendliness, walnut shell biochar (WS-BC) is gaining attention as an electrode material component in the electrochemical detection of water pollutants. The overall performance of WS-BC is reliant on the nature of raw biomass and the production methods as well. In our concept, biochar, prepared from raw walnut shell (WS) by pyrolysis, was added to a carbon paste electrode (CPE), and poly-tyrosine (p-Tyr) was electrodeposited on the surface of the BC-doped electrode. The conditions of the elaboration of the electrode, such as pH, potential, and the number of deposition cycles, pH were optimized. The obtained p-Tyr-BC-CPE platform was tested for the determination of cadmium, lead, copper, and mercury ions in water and soil samples, using square wave voltammetry (SWV). The raw WS biomass and its BC were examined by thermal analysis (TG-DSC), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDX) techniques. The synergistic effects of the coexistence of the WS-BC and the thin film of p-Tyr, for the detection of traces of heavy metal ions were investigated by electrochemical tests. The electrochemical characterization of the unmodified and modified electrodes was performed using the cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods, while the Cd²⁺, Pb²⁺, Cu^2+, and Hg²⁺ detection experiments were studied using the CV and SWV techniques. The optimized experimental conditions for the p-Tyr-BC-CPE platform were evaluated. The obtained electrochemical results showed that the p-Tyr-BC-CPE platform produced excellent sensitivity toward the heavy metal ions: LOD of 0.086, 0.175, 0.246, and 0.383 nM for Cd(II), Pb(II), Cu(II) and Hg(II), respectively. The modified electrode platform displayed high selectivity, stability, and good reproducibility.