Electrochemical Behavior and Voltammetric Determination of Curcumin at Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of curcumin by using a electrochemically reduced graphene oxide (ERGO) modified glass carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The electrochemical behaviors of curcumin at ERGO/GCE were investigated by cyclic voltammetry, suggesting that the ERGO/GCE exhibits excellent electrocatalytic activity towards curcumin, compared with bare GCE and GO/GCE electrodes. The electrochemical reaction mechanisms of curcumin, demethoxycurcumin and bisdemethoxycurcumin at the ERGO/GCE were also investigated and discussed systematically. Under physiological condition, the modified electrode showed linear voltammetric response from 0.2 μM to 60.0 μM for curcumin, with the detection limit of 0.1 μm. This work demonstrates that the graphene‐modified electrode is a promising strategy for electrochemical determination of biological important phenolic compounds.     

Zinc Oxide Nanoparticle‐modified Glassy Carbon Electrode as a Highly Sensitive Electrochemical Sensor for the Detection of Caffeine

Zinc oxide nanoparticles (ZnO NPs ) were prepared by a simple, convenient, and cost‐effective wet chemical method using the biopolymer starch. The prepared ZnO NPs were characterized by X‐ray diffraction (XRD ), scanning electron microscopy (SEM ), energy‐dispersive X‐ray (EDX ), Fourier transform infrared (FT‐IR ), and UV ‐visible spectroscopic techniques. The average crystallite size calculated from XRD data using the Debye–Scherer equation was found to be 15 nm. The electrochemical behavior of caffeine (CAF ) was studied using a glassy carbon electrode (GCE ) modified with zinc oxide nanoparticles by cyclic voltammetry (CV ) and differential pulse voltammetry (DPV ). Compared to unmodified GCE , ZnO NPs‐ modified GCE (ZnO NPs MGCE ) exhibited excellent electrocatalytic activity towards CAF oxidation, which was evident from the increase in the peak current and decrease in the peak potential. Electrochemical impedance study suggested that the charge‐transfer capacity of GCE was significantly enhanced by ZnO NPs . The linear response of the peak current on the concentrations of CAF was in the range 2–100 μM . The detection limit was found to be 0.038 μM. The proposed sensor was successfully employed for the determination of CAF in commercial beverage samples.     

The Performance of Boron‐Doped Diamond Electrode for the Determination of Ramipril and its Association with Hydrochlorothiazide

The voltammetric behavior of ramipril (RMP), an angiotensin‐converting enzyme inhibitor, was investigated for the first time in the literature on a boron‐doped diamond electrode (BDDE) using cyclic (CV) and square‐wave voltammetry (SWV). Its behavior was also considered in the presence of a thiazide diuretic, hydrochlorothiazide (HCTZ), for the simultaneous determination. The performance of BDDE and glassy carbon electrode (GCE) was compared, since RMP provides a high oxidation potential. It was observed that the anodic peak potentials for HCTZ and RMP at the BDDE were 1.23 and 1.67 V (vs . Ag/AgCl (3.0 mol L^‐1 KCl)) by CV in BR buffer solution (pH 2.0), respectively. The influence of supporting electrolyte, pH and scan rate in the current response of these both drugs was examined to select optimum experimental conditions. By this way, the determination of RMP and its association with HCTZ using SWV and a BDDE was successfully applied in real samples (single and combined dosage forms), with results in close agreement at 95% confidence level with those obtained using high‐performance liquid chromatography.     

A Facile Strategy for Construction of Sensor for Detection of Ondansetron and Investigation of its Redox Behavior and Thermodynamic Parameters

A sodium dodecylsulfate‐doped polypyrrole (SDS‐PPy) film was elaborated on glassy carbon electrode (GCE) by an electrodeposition method in phosphate buffer solution (pH 2.0) containing pyrrole (Py) and sodium dodecyl sulfate (SDS). SDS‐PPy/GCE was used for the construction of sensor, which showed excellent electrochemical response for the detection of ondansetron (OND) compared to conventional PPy. The application of the square wave (SW), with the adsorptive accumulation, indicates a maximum response at 1.33 V in H₂SO₄ (0.5 M). The influence of experimental parameters on determination of OND is discussed. The adsorptive stripping technique showed to be more sensitive, giving responses twice as big as those of non‐accumulated OND. The substantial improvement of response permits the development of an electroanalytical technique with a linear concentration in the range (1.0–80 μM), low detection (0.09 μM), and quantification limits (0.3 μM), and acceptable relative standard deviations of repeatability (0.59 %), and reproducibility (1.51 %). Consequently, this electrode is promising candidate for an accurate electroanalytical determination of OND in pharmaceutical samples with high sensitivity and selectivity, good accuracy and precision. The electrooxidation of OND at SDS‐PPy/GCE at various temperatures were studied by cyclic voltammetry to evaluate both the kinetic (k_s and E_a) and thermodynamic (ΔG*, ΔH* and ΔS*) parameters.     

A Novel Sensitive Electrochemical Sensor Based on Nickel Chloride Solution Modified Glassy Carbon Electrode for Curcumin Determination

In this research, the high conductivity of nickel chloride solution as well as the ability of nickel ions in establishing particular bonds with curcumin was benefited to fabricate a new electrochemical sensor based on nickel chloride solution modified glassy carbon electrode (NiCl₂/GCE) for detection and measurement of curcumin in human blood serum. Atomic force microscope (AFM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) methods indicated that using nickel chloride solution for the modification of the glassy carbon electrode (GCE) surface had a significant effect on improvement of the electrode performance. Differential pulse voltammetry (DPV) was used for quantitative measurement of curcumin, which exhibited the linear response of NiCl₂/GCE toward curcumin within the concentration range of 10–600 μM and provided the detection limit of 0.109 μM for curcumin in human blood serum.     

Voltammetric Determination of Folic Acid Using Adsorption of Methylene Blue onto Electrodeposited of Reduced Graphene Oxide Film Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of folic acid by adsorbing methylene blue onto electrodeposited reduced graphene oxide film modified glassy carbon electrode (MB/ERGO/GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology of the MB/ERGO/GCE modified electrode was characterized using scanning electron microscopy, displays that both MB and ERGO distributed homogeneously on the surface of GCE. The MB/ERGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE, MB/GCE, and ERGO/GCE. The electrochemical behaviors of folic acid at MB/ERGO/GCE were investigated by cyclic voltammetry, suggesting that the modified electrode exhibited excellent electrocatalytic activity towards folic acid compared with other electrodes. Under physiological condition, the MB/ERGO/GCE modified electrode showed a linear voltammetric response from 4.0 μM to 167 μM for folic acid, and with the detection limit of 0.5 μM (S/N=3). The stability, reproducibility and anti‐interference ability of the modified electrode were examined. The developed method has been successfully applied to determination of FA in tablets with a satisfactory recovery from 96 % to 100 %. The work demonstrated that the electroactive MB adsorbing onto graphene modified electrode showed an enhanced electron transfer property and a high resolution capacity to FA.     

Stable and Sensitive Amperometric Determination of Endocrine Disruptor Bisphenol A at Residual Metal Impurities Within SWCNT

A simple and attentive method was attempted for the determination of endocrine disruptor molecule, Bisphenol A (BPA) using residual metal impurity act as a reactant present in as received SWCNT. The electrochemical behavior of BPA oxidation and its reaction mechanism was investigated by cyclic voltammetry using “as received SWCNT modified on glassy carbon electrode” (SWCNT/GCE) and the obtained results were compared with bare GCE. The SWCNT/GCE showed high electrocatalytic activity, sensitivity, stability and more importantly not much surface fouling compared with bare GCE. This is because of the formation of electroactive quinone and catechol as byproducts on SWCNT/GCE during electro‐oxidation of BPA. More interestingly, the electrochemically acid treated SWCNT/GCE not showed any characteristic oxidation and reduction peaks during electro‐oxidation of BPA which indicates that the presence of a residual metal impurity in SWCNT plays a vital role in electro‐oxidation of BPA. The amperometric detection of BPA oxidation on SWCNT/GCE showed excellent stability and good linear response from the wide range of concentration of 10–100 μM. The limit of detection and sensitivity of BPA electro‐oxidation on SWCNT/GCE is to be 7.3 μM (S/N=3) and 0.6494 μA/μM cm² respectively. Finally, the fabricated sensor using SWCNT/GCE was successfully applied for the detection of BPA in plastic water bottles with excellent recovery range from 98–102 %.     

Electrochemical Behavior and Voltammetric Determination of Chloramphenicol and Doxycycline Using a Glassy Carbon Electrode Modified with Single-walled Carbon Nanohorns

We report a method for the direct and quantitative determination of chloramphenicol (CAP) and doxycycline (DOX) using a glassy carbon electrode (GCE) modified with carboxylic-group-functionalized single-walled carbon nanohorns. The modified electrode exhibits high electrocatalytic activity towards the reduction of CAP and the oxidation of DOX. It shows a linear response to CAP between 0.1 μM and 100 μM and to DOX between 0.5 μM and 100 μM. The detection limits for CAP and DOX are 0.1 μM and 0.5 μM, respectively. The modified GCE displays good sensitivity, making it suitable for the determination of CAP and DOX in real samples.     

RNA Modified Electrodes for Simultaneous Determination of Dopamine and Uric Acid in the Presence of High Amounts of Ascorbic Acid

A promising electrochemical biosensor was fabricated by electrochemical grafting of ribonucleic acid (RNA) at 1.8 V (vs. SCE) on glassy carbon electrode (GCE) (denoted as RNA/GCE), for simultaneous detection of dopamine (DA) and uric acid (UA) with coexistence of excess amount of ascorbic acid (AA). The electrode was characterized by X‐ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The RNA modified layer on GCE exhibited superior catalytic ability and anionic exclusive ability in comparison with the DNA modified electrode. Three separated anodic DPV peaks were obtained at 0.312, 0.168 and ?0.016 V for UA, DA and AA, respectively, at the RNA/GCE in pH 7.0 PBS. In the presence of 2.0 mM AA, a linear range of 0.37 to 36 μM with a detection limit of 0.2 μM for DA, and in the range of 0.74 to 73 μM with a detection limit of 0.36 μM for UA were obtained. The co‐existence of 5000 fold AA did not interfere with the detection of DA or UA. The modified electrode shows excellent selectivity, good sensitivity and good stability.     

A Boron Doped Diamond Electrode Modified with Nano‐carbon Black for the Sensitive Electrochemical Determination of Chlorogenic Acid

An electrochemical method was developed for the sensitive determination of chlorogenic acid using a boron doped diamond electrode (BDDE) modified with nano‐carbon black (nano‐CB). The active surface areas were found to be 0.059 and 0.146 cm² for the unmodified BDDE, and nano‐CB/BDDE, respectively. Compared with a BDDE, the nano‐CB/BDDE exhibited a well‐defined redox couple for chlorogenic acid. In addition, the plot of the peak current response changing from a square root to a linear dependence on scan rate is attributed to the transition from planar diffusion to surface behaviour. The anodic and cathodic peak separations (ΔE_p) were 97 mV and 14 mV at BDDE and nano‐CB/BDDE, respectively. The decrease in ΔE_p at the proposed electrode indicated that the process of chlorogenic acid was greatly accelerated. Square wave voltammetry (SWV) exhibited a dynamic range in which the current versus the concentration of chlorogenic acid were linear from 2.0×10^?8 to 2.0×10^?6 M with a LOD of 4.1×10^?9 M (based on 3S_b/m). The nano‐CB modified BDDE provided improved electrochemical behavior, high electrocatalytic activity, high sensitivity and good reproducibility.     

A Sensitive Electrochemical Sensor for Voltammetric Determination of Ganciclovir Based on Au‐ZnS Nanocomposite

An electrode modified with ZnS and gold nanoparticles (Au‐ZnS NPs) is introduced for highly sensitive voltammetric determination of ganciclovir (GCV). Surface structure and topography of the modified electrode was studied by SEM, EDX and XRD techniques. Electrochemical oxidation of GCV was investigated by cyclic (CV) and square wave voltammetry (SWV) in Briton‐Robinson buffer solution (pH 1.5). The results showed that electrochemical oxidation of GCV at the Au‐ZnS modified glassy carbon electrode (GCE) is irreversible and exhibited diffusion controlled electrode process over the pH range from 1.0 to 6.0. The oxidation potential peak and pH relationship showed that electrons and protons were transferred simultaneously over the electrochemical oxidation process. Using the proposed sensor, the linear calibration curves were obtained in the ranges of 0.04–1.50 μM and 1.5–70.0 μM with detection limit of 0.01 μM GCV by SWV technique. The modified electrode was successfully applied as a sensitive, reproducible and repeatable sensor for determination of the trace amount of GCV in human serum, urine and cymevene vials. Reasonable results were obtained from comparing the measurements of the real samples by the new sensor to high performance liquid chromatography (HPLC) as a standard method.     

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.     

Prussian Blue Nanoparticles Self Assembling on Electrochemically Reduced Graphene Oxide Modified GC Electrode for Sensitive Hydrogen Peroxide Detection

A facile, fast, and convenient route was suggested for the fabrication of Prussian blue nano particles (PBNPs) assembled on reduced graphene oxide (RGO) modified glassy carbon electrode (PBNPs|RGO|GCE). RGO was electrodeposited on the surface of GCE and the prepared RGO|GCE was immersed into a ferric‐hexacyanoferrate(III) solution and PBNPs were assembled on the RGO|GCE for a certain period of time. The PBNPs film thickness can be easily controlled by adjusting the assembling duration. The developed PBNPs|RGO|GCE was successfully used for determining hydrogen peroxide, with a linear response over the concentration range 0.5‐400 μM, a good accuracy and precision, detection limit 0.44 μM, and sensitivity 1168 mA M^?1 cm^?2.     

Highly Sensitive Electrochemical Sensor Based on Pt Doped NiO Nanoparticles/MWCNTs Nanocomposite Modified Electrode for Simultaneous Sensing of Piroxicam and Amlodipine

In this paper, a high‐sensitivity electrochemical sensor based on platinum (Pt) doped nickel oxide (NiO) nanoparticles and multi‐walled carbon nanotubes (MWCNTs) modified glassy carbon electrode (Pt?NiO/MWCNTs/GCE) has been developed to determine piroxicam (PIR) and amlodipine (AML) simultaneously. The electrochemical behavior of PIR and AML at the proposed sensor has been investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry (CA) methods. Pt doped NiO nanoparticles were synthesized by the sol‐gel procedure and were investigated using X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDX) and field emission scanning electron microscopy (FESEM) techniques. DPV responses of PIR and AML increased linearly with their concentration in wide linear dynamic ranges of 0.6–320.0 μM and 1.0–250.0 μM, respectively. The limits of detection were 0.061 μM for PIR and 0.092 μM for AML. The excellent analytical figure of merits of the proposed modified electrode leads to application of it promising electrochemical sensor to determine PIR and AML in human serum and urine with satisfactory results.     

Graphene Nanocomposites Based Electrochemical Sensing Platform for Simultaneous Detection of Multi-drugs

Three reduced graphene oxide nanocomposites were employed to achieve the simultaneous electrochemical determination of multi-drugs including acetaminophen (ACTM), carbendazim (CB) and ciprofloxacin (CFX). All nanocomposite modified electrodes showed improved current responses for three drugs. Notably cauliflower-like platinum nanoparticles decorated reduced graphene oxide modified electrode (or Pt−RGO/GCE) exhibited the best performance in terms of electrochemical stability. Using Pt−RGO/GCE, the linear detect ranges of 30–120 μM, 25–115 μM and 10–25 μM, and detection limit values of 3.49, 2.96, and 1.53 μM were achieved for ACTM, CB and CFX respectively. The electrode was further used for the successful determination of above drugs in tap and river water using differential pulse voltammetry. From the obtained results, we believe that Pt-RGO/GCE is highly promising for the fabrication of robust electrochemical sensors for simultaneously determining ACTM, CB and CFX or similar types of drugs in the future.     

Facile Synthesis of Reduced Graphene Oxide-octahedral Mn3O4 Nanocomposites as a Platform for the Electrochemical Determination of Metronidazole and Sulfamonomethoxine

A facile synthesis strategy of reduced graphene oxide (RGO)-octahedral Mn₃O₄ (oct-Mn₃O₄) nanocomposites using in situ one-pot hydrothermal reaction was reported. The RGO-oct-Mn₃O₄ nanocomposites were drop-casted onto the surface of glassy carbon electrode (GCE) to obtain RGO-oct-Mn₃O₄/GCE. DPV results revealed that the performance of RGO-oct-Mn₃O₄/GCE towards metronidazole displayed a linear ranging from 0.1 to 9.5 μM with a detection limit of 0.037 μM. For sulfamonomethoxine, it exhibited a linear ranging from 1 to 95 μM with a detection limit of 0.27 μM. Moreover, the proposed sensor had good anti-interference capability, high stability, satisfactory reproducibility, and was successfully applied in real samples.     

An Efficient Novel Electrochemical Sensor for Simultaneous Determination of Vitamin C and Aspirin Based on a PMR/Zn-Al LDH/GCE

A sensitive, low-cost, and simple electrochemical sensor based on Zn−Al layered double hydroxide (Zn−Al LDH) combined with a polymer film of methyl red (PMR) to modify a GCE has been created for the first time. Using cyclic voltammetry (CV), the electrochemical characteristics of the newly fabricated sensor were investigated. The characterised PMR/Zn−Al LDH/GCE shows high electro-catalytic activity towards the vitamin C (AA) and aspirin (ASA) oxidation. Schematic fabrication of PMR/Zn−Al LDH/GCE for the determination of AA or ASA was presented. The new sensor demonstrated superior analytical efficiency for the simultaneous identification of AA and ASA traces in well-spaced anodic peaks, even in the presence of certain intervening species. According to experimental results, the fabricated sensor represented two well-separated oxidation peaks for AA and ASA oxidation with potential difference of 799 mV (vs. Ag/AgCl). The linear dependences of the anodic peak currents of AA and ASA on their concentrations in the ranges of 0.10–53.17 μM are good. The detection limits of AA and ASA at the PMR/Zn−Al LDH/GCE were found to be 1.26 and 1.27 μM, respectively. Meanwhile, the quantification limits of AA and ASA were calculated as 4.21 and 4.25 μM, respectively. On other hand, the limit of detection (LODs) of AA and ASA oxidation were determined to be 0.47 and 0.21 μM, respectively, according to DPV method. The effect of scan rate (100 to 800 mV/s) on the anodic peak currents of AA and ASA was examined. A sensing model mechanism has been suggested and discussed in detail. Finally, the proposed sensor displayed a good reproducibility, stability and selectivity. The developed sensor was eventually used to successfully detect AA and ASA in urine samples.     

Preparation and Characterization of Bhant Leaves‐derived Nitrogen‐doped Carbon and its Use as an Electrocatalyst for Detecting Ketoconazole

In this study, the electrocatalytic characteristics of nitrogen‐doped carbon (NDC) prepared from Clerodendrum Infortunatum L leaves on a glassy carbon electrode (GCE) surface was evaluated with regards to its ability to detect the electroactive drug ketoconazole (KCZ). The NDC was prepared by carrying out a simple pyrolysis of dry powder of the leaves at 850 °C. The prepared NDC was characterized using field‐emission scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy and Brunauer‐Emmett‐Teller analysis, and was then used as an electrode material. The performance of the electrochemical KCZ sensor with the NDC‐modified glassy carbon electrode (NDC/GCE) was found to be optimal when using PBS buffer at pH 3 and a concentration of 0.1 mg/ml of NDC in the conjugate with Nafion polymer. Under these conditions, the NDC/GCE displayed a KCZ detection limit of 3 μM and a linear dependence of its response on KCZ concentration over a wide range of KCZ concentrations from 47 μM to 752 μM (R²=0.9742). These results confirmed the potential of NDC as an electrocatalyst.     

A Facile Fabrication of Poly-ethionine Film on Glassy Carbon Electrode for Simultaneous and Sensitive Detection of Dopamine and Paracetamol

An electrochemical sensor based on poly-ethionine (Poly-ET) film modified glassy carbon electrode was developed for sensitive and simultaneous sensing of dopamine (DA) and paracetamol (PA). The electropolymerization of ethionine monomer was carried out to modify the electrode. The modified electrode was characterized by using scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The Poly-ET/GCE exhibited excellent electrocatalysis towards the sensing of DA and PA. Poly-ET/GCE showed a linear increase of current response with increase concentration of DA and PA ranging from 0.1 μM–60 μM and 0.1 μM–180 μM, respectively. The LODs were found to be 7 nM and 18 nM (S/N=3) for DA and PA, respectively. This electrochemical sensor was successfully utilized for the detection of DA and PA in pharmaceutical samples.     

Voltammetric Determination of Phenoxybenzyl‐Type Insecticides at Chemically Modified Conducting Polymer‐Carbon Nanotubes Coated Electrodes

The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M₁) and polypyrrole (herein called as modifier M₂) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L^?1 and 0.05–100 mg L^?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M₁)‐GCE respectively. The MWCNT(M₂)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L^?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L^?1, 0.9 μg L^?1 and 0.1 μg L^?1 for CYP, DEL and FEN respectively on MWCNT(M₂)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.