Gold Electrode Modified with Self‐Assembled Monolayer of Cysteamine‐Functionalized MWCNT and Its Application in Simultaneous Determination of Dopamine and Uric Acid

The voltammetric behavior of dopamine (DA) and uric acid (UA) on a gold electrode modified with self‐assembled monolayer (SAM) of cysteamine (CA) conjugated with functionalized multiwalled carbon nanotubes (MWCNTs) was investigated. The film modifier of functionalized SAM was characterized by means of scanning electron microscopy (SEM) and also, electrochemical impedance spectroscopy (EIS) using para‐hydroquinone (PHQ) as a redox probe. For the binary mixture of DA and UA, the voltammetric signals of these two compounds can be well separated from each other, allowing simultaneous determination of DA and UA. The effect of various experimental parameters on the voltammetric responses of DA and UA was investigated. The detection limit in differential pulse voltammetric determinations was obtained as 0.02 µM and 0.1 µM for DA and UA, respectively. The prepared modified electrode indicated a stable behavior and the presence of surface COOH groups of the functionalized MWCNT avoided the passivation of the electrode surface during the electrode processes. The proposed method was successfully applied for the determination of DA and UA in urine samples with satisfactory results. The response of the gold electrode modified with MWCNT‐functionalized SAM method toward DA, UA, and ascorbic acid (AA) oxidation was compared with the response of the modified electrode prepared by the direct casting of MWCNT.     

Nanocellulose/Carbon Nanoparticles Nanocomposite Film Modified Electrode for Durable and Sensitive Electrochemical Determination of Metoclopramide

A novel electrochemical sensor based on nanocellulose‐carbon nanoparticles (NC‐CNPs) nanocomposite film modified glassy carbon electrode (GCE) is developed for the analysis of metoclopramide (MCP). Atomic force microscopy, scanning electron microscopy and electrochemical impedance spectroscopy were used to characterize the roughness, surface morphology and performance of the deposited modifier film on GCE. SEM image demonstrated that modifier nanoparticles are uniformly deposited on GCE, with an average size of less than 50 nm. The electrochemical behavior of MCP and its oxidation product is studied using linear sweep and cyclic voltammetry over a wide pH range on NC‐CNPs modified glassy carbon electrode. The results revealed that the oxidation of MCP is an irreversible and pH‐dependent process that proceeds in an adsorption‐controlled mechanism and results in the formation of a main oxidation product, which adsorbs on the surface of NC‐CNPs/ GCE. The modified electrode showed a distinctive anodic response towards MCP with a considerable enhancement (49 fold) compared to the bare GCE. Under the optimized conditions, the modified electrode exhibited a wide linear dynamic range of 0.06–2.00 µM with a detection limit of 6 nM for the voltammetric determination of MCP. The prepared modified electrode showed several advantages such as simple preparation method, high stability, reproducibility, and repetitive usability. The modified electrode is successfully applied for the accurate determination of trace amounts of MCP in pharmaceutical and clinical preparations.     

Polybenzoin Based Sensor for Determination of 2thiouracil in Biological Fluids and Pharmaceutical Formulations

A carbon paste electrode was modified by electropolymerisation of benzoin using voltammetric technique. A novel polybenzoin modified carbon paste electrode (PB‐CPE) was developed for use as a detector in cyclic voltammetry and differential pulse adsorptive stripping voltammetry for the sensitive determination of 2thiouracil (2TU). The atomic force microscopy was applied to characterize the surface morphology of PB‐CPE. The modified electrode showed excellent electrocatalytic activity for the oxidation of 2TU. The oxidation process was irreversible over the pH range studied and exhibited a diffusion controlled behavior. All experimental parameters have been optimized. The peak current for the stripping of 2TU was found to be linear over the concentration range of 0.2–1.2 µM, with a detection limit of 2.21 nM. The practical application of the PB‐CPE in the determination of 2TU in human biological fluids and pharmaceutical samples were demonstrated that it has high sensitivity and good selectivity.     

Au-Pt双金属纳米颗粒在玻碳电极上的自组装

利用硼氢化钠还原HAuCl4和H2PtCl4的混合溶液, 制备了Au- Pt双金属纳米颗粒. UV- Vis、TEM、ED、XRD、XPS等研究结果表明双金属纳米颗粒为Au- Pt合金. 在玻碳电极上通过有机偶联层半胱氨酸进行了Au- Pt双金属纳米颗粒的自组装, 得到Au- Pt/半胱氨酸/玻碳电极, 并通过SEM对其表面结构进行了表征, 粒子的平均粒径为12.6 nm. 用循环伏安法对Au- Pt/半胱氨酸/玻碳电极的电化学性能进行了测试. 结果表明Au- Pt/半胱氨酸/玻碳电极具有良好的电催化甲醇氧化性能.     

Electrocatalytic Oxidation of Folic Acid on Carbon Paste Electrode Modified by Nickel Ions Dispersed into Poly(o‐anisidine) Film

Poly(o‐anisidine) (POA) was formed by successive cyclic voltammetry in monomer solution containing sodium dodecyl sulfate (SDS) at the surface of carbon paste electrode. Then Ni(II) ions were incorporated to electrode by immersion of the polymeric modified electrode having amine group in 0.1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode; a good redox behavior of Ni(OH)₂/NiOOH couple at the surface of electrode can be observed. The capability of this modified electrode for catalytic oxidation of folic acid was demonstrated. The amount of α and surface coverage (Γ*) of the redox species and catalytic chemical reaction rate constant (k) for folic acid oxidation were calculated. The catalytic oxidation peak current of folic acid was linearly dependent on its concentration and a linear calibration curve was obtained in the range of 0.1 to 5 mM with a correlation coefficient of 0.9994. The limit of detection (3σ) was determined as 0.091 mM. This electrocatalytic oxidation was used as simple, selective and precise voltammetric method for determination of folic acid in pharmaceutical preparations.     

Synthesis of Carbon Nanofibers for Mediatorless Sensitive Detection of NADH

Highly sensitive amperometric detection of dihydronicotinamide adenine dinucleotide (NADH) by using novel synthesized carbon nanofibers (CNFs) without addition of any mediator has been proposed. The CNFs were prepared by combination of electrospinning technique with thermal treatment method and were applied without any oxidation pretreatment to construct the electrochemical sensor. In amperometric detection of NADH, a linear range up to 11.45 μM with a low detection limit of 20 nM was obtained with the CNF‐modified carbon paste electrode (CNF‐CPE). Good selectivity was exhibited for the simultaneous detection of NADH and its common interferent of ascorbic acid (AA) by differential pulse voltammogram. The attractive electrochemical performance and the versatile preparation process of the CNF‐CPE made it a promising candidate for designing effective NADH sensor.     

Electrocatalytic Oxidation of 2‐Thiouracil and 2‐Thiobarbituric Acid at a Carbon‐Paste Electrode Modified with Cobalt Phthalocyanine

Voltammetric behavior of two mercaptopyrimidine derivatives (2‐thiouracil and 2‐thiobarbituric acid) has been studied by cyclic voltammetry at a cobalt phthalocyanine (CoPc)‐modified carbon‐paste electrode. The results of voltammetric determinations showed that the CoPc in the matrix of modified electrode acts as catalyst for electrooxidation of these thiols (RSH), lowering the overpotential of the reaction and significantly increasing the sensitivity for detection of thiols in neutral conditions. The results of voltammetric and polarization measurements in solutions with various pHs were used for prediction of the mechanism of electrocatalytic oxidation at the surface of modified electrode. These results showed that at the modified electrode, electrochemical oxidation of thiolate anion (RS^?) is the rate‐determining step. It was found that the modified electrode exhibits good selectivity for catalytic oxidation of mercaptopyrimidines over other biologically important mercaptans such as cysteine, glutathione and thioglycolic acid. The results demonstrate that the peak current for thiol oxidation has a linear variation with the concentration in the range of 1×10^?2–1×10^?5 M. This system can be used for sensitive and selective voltammetric detection of mercaptopyrimidine derivatives.     

Sensitive Voltammetric Determination of Captopril Using a Carbon Paste Electrode Modified with Nano-TiO2/Ferrocene Carboxylic Acid

A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix.The electrochemical behavior of captopril (CAP) at the surface of the modified electrode was investigated using electroanalytical methods.The modified electrode showed excellent electrocatalytic activity for the oxidation of CAP in aqueous solutions at physiological pH values.Cyclic voltammetric curves showed that the oxidation of CAP at the surface of the modified electrode reduced its overpotential by more than 290 mV.The modified electrode was used for detecting captopril using cyclic voltammetry and square wave voltammetry techniques.A calibration curve in the range of 0.03 to 2400μmol/L was obtained that had a detection limit of 0.0096 μmol/L (3σ) under the optimized conditions.The modified electrode was successfully used for the determination of captopril in pharmaceutical and biological samples.     

Electropolymerized Diphenylamine on Functionalized Multiwalled Carbon Nanotube Composite Film and Its Application to Develop a Multifunctional Biosensor

Diphenylamine (DPA) monomers have been electropolymerized on the amino‐functionalized multiwalled carbon nanotube (AFCNT) composite film modified glassy carbon electrode (GCE) by cyclic voltammetry (CV). The surface morphology of PDPA‐AFCNT was studied using field‐emission scanning electron microscopy (FE‐SEM). The interfacial electron transfer phenomenon at the modified electrode was studied using electrochemical impedance spectroscopy (EIS). The PDPA‐AFCNT/GCE represented a multifunctional sensor and showed good electrocatalytic behavior towards the oxidation of catechol and the reduction of hydrogen peroxide. Rotating‐disk electrode technique was applied to detect catechol with a sensitivity of 1360 µA mM^?1 cm^?2 and a detection limit of 0.01 mM. Amperometric determination of hydrogen peroxide at the PDPA‐AFCNT film modified electrode results in a linear range from 10 to 800 µM, a sensitivity of 487.1 µA mM^?1 cm^?2 and detection limit of 1 µM. These results show that the nano‐composite film modified electrode can be utilized to develop a multifunctional sensor.     

Amperometric Sensor for Detection of the Reduced Form of Nicotinamide Adenine Dinucleotide Using a Poly(pyronin B) Film Modified Electrode

An electrochemical method for the preparation of poly(pyronin B) film was proposed in this paper. A poly(pyronin B) (poly(PyB)) film modified glassy carbon electrode (GCE) has been fabricated via an electrochemical oxidation procedure and applied to the electrocatalytic oxidation of reduced form of nicotinamide adenine dinucleotide (NADH). The poly(PyB) film modified electrode surface has been characterized by atomic force microscope (AFM), scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), UV‐visible absorption spectrophotometry (UV‐vis) and cyclic voltammetry (CV). These studies have been used to investigate the poly(PyB) film, which demonstrates the formation of the polymer film and the excellent electroactivity of poly(PyB) in neutral and even in alkaline media. Due to its potent catalytic effects towards the electrooxidation of NADH at lower potential (0.0 V), poly(PyB) film modified electrode can be used for the selective determination of NADH in real samples because of dopamine, ascorbic acid and uric acid oxidation can be avoided at this potential. The catalytic peak currents are linearly dependent on the concentrations of NADH in the range of 1.0×10^?6 to 5.0×10^?4 mol/L with correlation coefficients of 0.999. The detection limits for NADH is 0.5×10^?6 mol/L. Poly(PyB) modified electrode also shows good stability and reproducibility due to the irreversible attachment of polymer film at GCE surface.     

Immobilization of nickel-dipicolinic acid onto a glassy carbon electrode modified with bimetallic Au-Pt inorganic-organic hybrid nanocomposite: Application to micromolar detection of fructose

This work describes the electrochemical behavior of nickel-dipicolinic acid (Ni-DPA) film immobilized on the surface of bimetallic Au-Pt inorganic-organic hybrid nanocomposite glassy carbon electrode and its electrocatalytic activity toward the oxidation of fructose. The electrode possesses a three-dimensional (3D) porous network nano architecture, in which the bimetallic Au-Pt serving as metal nano-particle based microelectrode ensembles are distributed in the matrix of interlaced 3,3′,5,5′-tetramethylbenzidine (TMB) organic nanofibers (NFs). The surface structure and composition of the sensor was characterized by scanning electron microscopy (SEM). Electrocatalytic oxidation of fructose on the surface of modified electrode was investigated with cyclic voltammetry and chronoamperometry methods and the results show that the Ni-DPA film displays excellent electrochemical catalytic activities towards fructose oxidation. The hydrodynamic amperometry at rotating modified electrode at constant potential versus reference electrode was used for detection of fructose. Under optimized conditions the calibration plots are linear in the concentration range 0.5 to 70 μM and detection limit was found to be 0.1 μM.     

Amperometric enzyme electrodes for the determination of volatile alcohols in the headspace above fruit and vegetable juices

The surface of a glassy carbon electrode (GCE) was modified by electropolymerization of acridine red followed by drop-coating of graphene. The morphology was characterized by scanning electron microscopy. Uric acid (UA) is effectively accumulated on the surface of the modified electrode and generates a sensitive anodic peak in solutions of pH 6.5. Differential pulse voltammetry was used to evaluate the electrochemical response of the modified GCE to UA. Compared to the bare GCE, the GCE modified with acridine red, and to the graphene modified electrode, the new GCE displays high electrochemical activity in giving an oxidation peak current that is proportional to the concentration of UA in the range from 0.8 to 150?μM, with a detection limit of 0.3?μM (at an S/N of 3). The modified electrode displays excellent selectivity, sensitivity, and a wide linear range. It has been applied to the determination of UA in real samples with satisfactory results.

Electrodeposition of Copper Oxide Nanoparticles on Precasted Carbon Nanoparticles Film for Electrochemical Investigation of anti‐HIV Drug Nevirapine

This work describes the development of a novel electrochemical sensor based on electrodeposition of copper oxide nanoparticles onto carbon nanoparticle (CNP) film modified electrode for the analysis of the anti‐HIV drug, nevirapine (NEV). The electrochemical experiments were performed using linear sweep and cyclic voltammetry. Atomic force microscopy was applied for surface characterization of the deposited modifier film (CuO‐CNP) on glassy carbon electrode (GCE). No oxidation peak was observed for NEV on the bare GCE, but both CNP‐GCE and CuO‐CNP‐GCE showed a distinctive anodic response towards NEV with considerable enhancement (276‐fold and 350‐fold, respectively) compared to CuO‐GCE. The mechanism of the electrocatalytic process on the modified electrode surface was investigated by cyclic and linear sweep voltammetry at various potential sweep rates and pHs of the buffer solutions. The modified electrode exhibited linear dynamic range in three concentration intervals (0.1–0.8, 1–10 and 10–100 µM) with a detection limit of 66 nM. The stability, reproducibility, and repetitive usability exhibited by the proposed modified electrode are good enough to make it a suitable sensor for the determination of NEV in real samples with complex matrices such as human blood serum.     

First Electrochemical Report for Simultaneous Determination of Norepinephrine,Tyrosine and Nicotine Using a Nanostructure Based Sensor

A carbon paste electrode was modified with ZnO nanorods and 3‐(4′‐amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic acid (3,4′AAZCPE) to cause electrocatalysis of norepinephrine oxidation. It has been found that the oxidation of norepinephrine at the surface of modified electrode occurs at a potential of about 180 mV less positive than that of an unmodified carbon paste electrode. Square wave voltammetry (SWV) exhibits linear dynamic range from 1.0×10^?7 to 8.0×10^?5 M and a detection limit of 3.9×10^?8 M for norepinephrine. In addition, this modified electrode was used for simultaneous determination of norepinephrine, tyrosine and nicotine.     

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.     

Electrochemical Sensor Based on Oxidation of 2,8‐Dihydroxyadenine to Monitor DNA Damage in Calf Thymus DNA

A novel and reliable direct electrochemical method has been established to monitor DNA damage in acid hydrolyzed calf thymus DNA, based on the determination of 2,8‐dihydroxyadenine (2,8‐DHA). A single‐wall carbon nanotubes (SWCNT) modified edge plane pyrolytic graphite electrode (EPPGE) has been used as a sensor to monitor the DNA damage. 2,8‐DHA the main in vivo adenine oxidation product undergoes oxidation at ～395 mV at SWCNT modified EPPGE using square wave voltammetry (SWV). The sensor exhibits potent and persistent electron‐mediating behavior. A well‐defined oxidation peak for the oxidation of 2,8‐DHA was observed at modified electrode with lowering of peak potential and increase in peak current as compared to bare EPPGE. At optimal experimental conditions, the catalytic oxidative peak current was responsive with the 2,8‐DHA concentrations ranging from 0.05 nM to 100 nM. The detection limit was 3.8×10^?11 M and limit of quantification was 1.27×10^?10 M. The modified electrode exhibited high stability and reproducibility.     

Amperometric sensor for the determination of ascorbic acid based on Cobalt hexacyanoferrate modified electrode fabricated through a new route

A new approach was attempted to prepare a chemically modified electrode using Cobalt hexacyanoferrate (CoHCF) as the redox mediator and to study its stability and electrocatalytic activity for ascorbic acid (AA) oxidation. The basic principle underlying the electrode modification is the coordination of cobalt ion with the amino nitrogen of aniline adsorbed on the surface of a graphite rod. This surface was subsequently derivatized with ferrocyanide to get CoHCF film on the electrode surface. The CoHCF modified electrode as prepared above was characterized using cyclic voltammetry. The effect of scan rate, supporting electrolyte and pH of the medium on the performance of the modified electrode was investigated. The CoHCF modified electrode exhibited good electrocatalytic activity towards the oxidation of ascorbic acid and gave a linear response from 5.52 x 10(-5) M to 3.23 x 10(-2) M with a correlation coefficient of 0.9929. The detection limit was found to be 3.33 x 10(-5) M. Hydrodynamic voltammetry and chronoamperometry studies for the oxidation of ascorbic acid were also carried out. The electrode was highly stable and exhibited good reproducibility. This modified electrode was also applied for the determination of ascorbic acid in commercial 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.     

铜氮杂配合物修饰金电极对抗坏血酸的分析测定

本实验制备了一种新型的氮杂铜配合物修饰金电极,该电极可用于抗坏血酸的测定。采用循环伏安法和扫描电化学显微镜技术对电极进行了表征。该修饰电极可催化氧化抗坏血酸,相对于裸电极抗坏血酸在修饰电极上氧化电位移动了250mV,并且氧化电流在抗坏血酸的浓度为5.0×10−7 to 4.0×10−5 mol/L时呈线性关系,检测限为4.8×10-8 mol/L。用此方法测定抗坏血酸与文献报道的测定结果一致,这表明该电极可用作抗坏血酸测定的电化学传感器。     

Selective Detection of Uric Acid in the Presence of Ascorbic Acid and Dopamine Using Polymerized Luminol Film Modified Glassy Carbon Electrode

Electrochemically polymerized luminol film on a glassy carbon electrode (GCE) surface has been used as a sensor for selective detection of uric acid (UA) in the presence of ascorbic acid (AA) and dopamine (DA). Cyclic voltammetry was used to evaluate the electrochemical properties of the poly(luminol) film modified electrode. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) have been used for surface characterizations. The bare GCE failed to distinguish the oxidation peaks of AA, DA and UA in phosphate buffer solution (pH 7.0), while the poly(luminol) modified electrode could separate them efficiently. In differential pulse voltammetric (DPV) measurements, the modified GCE could separate AA and DA signals from UA, allowing the selective determination of UA. Using DPV, the linear range (3.0×10^?5 to 1.0×10^?3 M) and the detection limit (2.0×10^?6 M) were estimated for measurement of UA in physiological condition. The applicability of the prepared electrode was demonstrated by measuring UA in human urine samples.