In situ Electroreduction of Graphene Oxide: Increased Sensitivity for the Determination of NADH

A novel and useful method to catalyze the electro‐oxidation of nicotinamide adenine dinucleotide (NADH) over a glassy carbon electrode (GCE) modified with graphene oxide (GO) is presented. Based on the presence of oxygen moieties in GO, which can be easily reduced, an in situ electrochemical generation of reduced graphene oxide (denoted as erGO) applying a sufficient negative potential. A potential of ?1.000 V was selected to generate the erGO/GCE as a pretreatment potential before the detection of NADH. The in situ generated erGO/GCE system produces a decrease in the overpotential of NADH oxidation from +0.720 V to +0.230 V compared with GCE. The process also produced an important increase in current signals. The modified electrode was characterized by scanning electron (SEM) and electrochemical microscopies (SECM), cyclic voltammetry and by Raman spectroscopy. Amperometric detection of NADH via this straightforward electrocatalytic method provides a wide linear range between 10 and 100 μM, a lower detection limit of 0.36 μM and an excellent sensitivity of (1.47±0.09) μA mM^?1.     

Simultaneous Detection of Dopamine and Uric Acid on Indium Tin Oxides Modified with Cost‐effective Gas‐phase Synthesized Single Walled Carbon Nanotubes

Cost‐effective gas‐phase synthesized single walled carbon nanotubes (SWCNTs) were first employed for the surface modification of indium tin oxides (ITO) via electrostatic coating of poly‐l‐lysine (PLL). Compared with control substrates of bare ITO and SWCNT‐PLL‐slide glasses, SWCNT‐PLL‐ITO, with high catalytic properties associated with large surface areas, showed significant improvement of electro catalytic activity toward the oxidation of dopamine (DA) and uric acid (UA). The cyclic voltammetric (CV) peak separation of oxidation for both DA and UA was estimated to be ∼ 0.13 V, which renders them capable of simultaneously detecting DA and UA in a mixed solution. The differential pulse voltammetry (DPV) technique was further performed to obtain a linear detection range of DA from 1.0 μM to 100 μM, and a detection limit of 1.0 μM was confirmed in the mixed solution. Furthermore, the practical analytical ability of the method was finally confirmed by selective detection of both DA and UA in human urine samples without any preliminary treatment, implying the feasibility of applying bio‐sensors in a low‐cost manner.     

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.     

A Simple and Renewable Nanoporous Gold‐based Electrochemical Sensor for Bisphenol A Detection

A sensitive and simple electrochemical sensor based on nanoporous gold (NPG) was developed for the detection of bisphenol A (BPA). NPG was prepared by the dealloying method. The NPG modified glassy carbon electrode (GCE) displayed excellent catalytic activity towards the electrooxidation of BPA. The mechanism of the electrooxidation of BPA on NPG/GCE sensor was inferred. The sensor showed a linear range from 0.1 μM to 50 μM with a detection limit of 12.1 nM BPA. Specially, a simple but effective approach was attempted to renew the used sensor. The application of the sensor for real sample analysis was demonstrated.     

Modification of the Electrode Surface by Ag Nanoparticles Decorated Nano Diamond‐graphite for Voltammetric Determination of Ceftizoxime

A modified glassy carbon electrode with a film of nano diamond? graphite nano mixture decorated with Ag nanoparticles (AgNPs? NDG/GCE) was constructed and used for sensitive voltammetric determination of ceftizoxime (CFX). Morphology of AgNPs? NDG/GCE has been examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Experimental variables such as deposited amount of the modifier suspension, pH of the supporting electrolyte and accumulation potential and time were optimized by monitoring of CV and LSV responses of CFX. The results illustrate that AgNPs? NDG/GCE exhibits an excellent electrocatalytic effect in the electro‐oxidation of CFX that leads to a considerable improvement in the corresponding anodic peak current. This also allows the development of a highly sensitive voltammetric sensor for the determination of CFX in pharmaceutical and clinical samples. Under the optimum conditions, the modified electrode showed a linear response to the concentration of CFX in the range of 0.02–7 µM with detection limit of 6 nM. The prepared modified electrode has some remarkable electrochemical properties such as simple preparation, high sensitivity, excellent repeatability and reproducibility and long‐term stability.     

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.     

Detection of NADH and Ethanol at Titanium Containing MCM‐41 with Low Overpotential

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the overvoltage of NADH oxidation reaction is observed at 0.28 V vs. SCE. The application in the amperometric biosensing of ethanol using alcohol dehydrogenase enzyme (ADH) also has been demonstrated with this material. The proposed sensor shows a highly sensitivity, an acceptable reproducibility and a good stability. The linear range of ethanol is 25–1000 μM and the detection limit is 8.0 μM. Ti‐MCM‐41 modified electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix for the construction of dehydrogenases sensor.     

Electroanalytical Determination of Paracetamol Using Pd Nanoparticles Deposited on Carboxylated Graphene Oxide Modified Glassy Carbon Electrode

The study presents a novel paracetamol (PA) sensor based on Pd nanoparticles (PdNPs) deposited on carboxylated graphene oxide (GO?COOH) and nafion (Nf) modified glassy carbon electrode (GCE). The morphologies of the as prepared composites were characterized using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and fourier transform infrared spectroscopy (FTIR). The experimental results demonstrated that Nf/GO?COOPd displayed excellent electrocatalytic response to the oxidation PA. The linear range was 0.04–800 μM for PA with limit of detection of 0.012 μM and excellent sensitivity of 232.89 μA mM^?1 cm^?2. By considering the excellent performance of Nf/GO?COOPd composite such as wider linear range, lower detection, better selectivity, repeatability, reproducibility, and storage stability, the prepared composite, especially GO?COOH support, with satisfactory electrocatalytic properties was a promising material for the modification of electrode material in electrochemical sensor and biosensor field.     

Direct and Fast Electrochemical Determination of Catechin in Tea Extracts using SWCNT‐Subphthalocyanine Hybrid Material

In this study, single walled carbon nanotubes (SWCNTs) were covalently functionalized by terminal ethynyl bearing subphthalocyanine (SubPc) to obtain a new hybrid material, viz. SWCNT‐SubPc (CS), via “click” reaction for the first time. The structural characterization and study of the electrochemical sensor properties of the CS hybrid material to catechin were carried out. A convenient and fast analytical method was offered for the determination of catechin. It was shown that the deposition of CS on the surface of a glassy carbon electrode (GCE) led to a 2.2 and 8‐fold increase in the differential pulse voltammetry (DPV) responses to catechin in Britton‐Robinson (BR) buffer solution (a pH of 3) in comparison with SWCNT‐modified and bare GCE, respectively. The dynamic range, detection and quantification limits of catechin were determined to be 0.1–1.5 μM, 13 nM and 43 nM, respectively. Selectivity of the suggested CS/GCE sensor was investigated on addition of a number of interfering metal ions, antioxidants and biomolecules. The applicability of the modified electrode for the detection of catechin in real tea samples such as green, rosehip fruit, Turkish and Indian black tea was demonstrated with the standard addition method. Along with the ease in fabrication and low prices, the proposed CS/GCE sensor was reproducible, selective, stable and sensitive to catechin in major types of tea samples.     

Electrochemical sensing of bisphenol A on single-walled carbon nanotube paper electrodes

The electrochemical detection of BPA often requires modification of electrodes to overcome BPA′s slower kinetics and higher oxidation potential. This work reports a modification-free, paper electrode based on vacuum-filtered SWCNT thin film. The prepared electrode does not need to be polished or transferred into the conducting substrates. The linear sweep voltammetric detection showed a linear response from 0.5–10 μM and 25–100 μM with the experimental LOD of 1.0 μM (S/N=3). The interference study and good recovery percentage (93–105 %) in real water samples demonstrated the method‘s selectivity. The sensor can be promising for developing a simple, low-cost, portable, and paper-based BPA monitoring system.     

金纳米粒子/碳纳米管修饰电极对4 壬基酚的电催化氧化及检测研究

制备了金纳米粒子/碳纳米管修饰玻碳电极(AuNPs-CNTs/GCE),采用循环伏安法和线性扫描伏安法研究了4-壬基酚在修饰电极上的电化学行为,并建立了一种灵敏简便地检测4-壬基酚的电化学方法。优化了pH值、扫描速率、富集时间等测定参数,并计算出pH值与氧化峰电压、扫描速率与氧化峰电流之间的数量关系。在pH 10.0的BR缓冲溶液中,4-壬基酚在AuNPs-CNTs/GCE上出现灵敏的氧化峰,氧化电位为0.51 V。与裸玻碳电极(GCE)和单一碳纳米管修饰电极(CNTs/GCE)相比,AuNPs-CNTs/GCE明显提高了4-壬基酚的氧化电流。在优化实验条件下,4-壬基酚的浓度分别在0.05～4μmol/L和6～14μmol/L范围内与氧化峰电流呈良好的线性关系,检出限为0.023μmol/L,对于实际样品测定的回收率为95%～104%。该修饰电极具有良好的重现性和稳定性,可用于环境样品中4-壬基酚的直接检测。     

Electrochemical Detection of Alloxan on Reduced Graphene Oxide Modified Glassy Carbon Electrode

Alloxan is a toxic reagent that strongly induces the diabetes by destroying insulin‐producing β‐cells in the pancreas of living organisms. The reduction product of alloxan is dialuric acid, which is responsible for the intracellular generation of ROS to enhance the stress in living cells to cause kidney disease or diabetic nephropathy. Herein, we studied for the first time the electrochemical properties of alloxan on reduced graphene oxide modified glassy carbon electrode (rGO/GCE) in 0.1 M phosphate buffer solution (PBS) at pH 7. The obtained results were compared with graphene oxide modified GCE (GO/GCE) and bare GCE surfaces. The modified rGO/GCE showed well defined redox couple with 10 fold increase in both reduction as well as oxidation peak current for alloxan than that of GO/GCE and bare GCE. Differential pulse voltammetry (DPV) technique shows the linear increase in both oxidation and reduction peak current of alloxan in the range of 30 μM to 3 mM with LOD of 1.2 μM. An amperometric signal of alloxan is also increases with respect to each addition of 50 μM of alloxan on rGO/GCE at constant potential of ?0.05 V. The linear range of alloxan is observed between 50 μM to 750 μM (S/N=3). This kind of rGO/GCE surface is more suitable platform or sensor matrix for estimating unknown concentration of alloxan molecule in the real biological systems.     

A Sensitive Simultaneous Determination of Adrenalin and Paracetamol on a Glassy Carbon Electrode Coated with a Film of Chitosan/Room Temperature Ionic Liquid/Single‐Walled Carbon Nanotubes Nanocomposite

The present work demonstrates that simultaneous determination of adrenalin (AD) and paracetamol (PAR) can be performed on single‐walled carbon nanotube/chitosan/ionic liquid modified glassy carbon electrode (SWCNT‐CHIT‐IL/GCE). The electro‐oxidations of AD and PAR were investigated with cyclic voltammetry (CV), differential pulse voltammetry (DPV) and also chronoamperometry (CA) methods. DPV experiments showed that the oxidation peak currents of AD and PAR are proportional to the corresponding concentrations over the 1–580 μmol/L and 0.5–400 μmol/L ranges, respectively. The RSD at a concentration level of 15 μmol/L AD and 15 μmol/L PAR were 1.69% and 1.82%, respectively. Finally the modified electrode was used for simultaneous determination of AD and PAR in real samples with satisfactory results.     

A Novel Cerium Tungstate Nanosheets Modified Electrode for the Effective Electrochemical Detection of Carcinogenic Nitrite Ions

In this present scenario, for the first time, we propose a facile and simple wet chemical approach for the fabrication of two‐dimensional (2D) cerium tungstate (CeW₂O₉;CeW) nanosheets and evaluated as an electrochemical sensor for the detection of nitrite ions. The successful formation of CeW₂O₉ nanosheets was confirmed by various physicochemical techniques such as X‐ray diffraction, Fourier transform infrared spectroscopy, Raman, Scanning electron microscope, Transmission electron microscope and Energy dispersive X‐ray studies. The electrochemical properties of the CeW nanosheets were studied by using cyclic voltammograms (CV) and chronoamperometric techniques. As an electrochemical sensor, the CeW nanosheets modified glassy carbon electrode (GCE) showed superior electrocatalytic activity in the oxidation of nitrite in terms of higher anodic peak current and lower oxidation potential when compared with unmodified GCE. CeW nanosheets based electrochemical sensor has been fabricated which detect nitrite in wide linear response range, good sensitivity and very low detection limit of 0.02–986 μM, 2.85 μA μM⁻¹ cm⁻² and 8 nM, respectively. Moreover, the CeW nanosheets modified GCE exhibited excellent selectivity even in the presence of common metal ions and biologically co‐interfering compounds. For the practical viability of the prepared amperometric sensor has been utilized in various water samples such as tap, lake and drinking water and the obtained recoveries are appreciable.     

Biomimetic Sensor for Dobutamine Employing Nano‐ TiO2/Nafion/Carbon Nanoparticles Modified Electrode

A novel voltammetric biosensor based on nano‐TiO₂/nafion/carbon nanoparticles modified glassy carbon electrode (TiO₂/N/CNP/GCE) was developed for the determination of dobutamine (DBA). Characterization of the surface morphology and property of TiO₂/N/CNP layer was carried out by the scanning electron microscopy and atomic force microscopy. The electrochemical performance of the modified electrode was investigated by means of the cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy techniques. Effective experimental variables, such as the scan rate, pH of the supporting electrolyte, drop size of the casted modifier suspension and accumulation conditions of DBA on the surface of TiO₂/N/CNP/GCE were optimized. Under the optimized conditions, a significant electrochemical improvement was observed toward the electro‐oxidation of DBA on the surface of TiO₂/N/CNP/GCE compared to the bare GCE. Under the optimized conditions, a wide linear dynamic range (6 nM–1 µM) with a low detection limit of 2 nM for DBA was resulted. The prepared modified electrode shows high sensitivity, stability and good reproducibility in the determination of DBA concentrations. Satisfactory results were obtained for DBA analysis in the pharmaceutical and clinical preparations using TiO₂/N/CNP/GCE.     

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.     

Electrochemical Sensor Based on Multi‐walled Carbon Nanotube/Gold Nanoparticle Modified Glassy Carbon Electrode for Detection of Estradiol in Environmental Samples

We report a rapid and simple method for sensing estradiol by electro‐oxidation on a multi‐walled carbon nanotube (MWCNT) and gold nanoparticle (AuNP) modified glassy carbon electrode (GCE). Compared with a bare GCE, AuNP/GCE and MWCNT/GCE, the composite modified GCE shows an enhanced response to estradiol in 0.1 M phosphate buffer solution. Experimental parameters, including pH and accumulation time for estradiol determination were optimised at AuNP/MWCNT/GCE. A pH of 7.0 was found to be optimum pH with an accumulation time of 5 minutes. Estradiol was determined by linear sweep voltammetry over a dynamic range up to 20 %mol L^?1 and the limit of detection was estimated to be 7.0×10^?8 mol L^?1. The sensor was successfully applied to estradiol determination in tap water and waste water.     

Fabrication of Co3O4 nanoparticles-decorated graphene composite for determination of L-tryptophan

A novel Co(3)O(4) nanoparticles-decorated graphene (GR) composite was synthesized by electro-deposition and characterized by scanning electron micrographs, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy. Then, amperometric biosensors based on a Co(3)O(4) nanoparticles-decorated GR composite modified glassy carbon electrode (GCE) were developed for the sensitive determination of L-tryptophan (Trp). The direct electrooxidation behaviors of Trp on the Co(3)O(4)/GR/Nafion/GCE were carefully investigated by cyclic voltammetry and square wave voltammetry. The results indicated that Trp showed an increase of the oxidation peak current with a negative shift of the oxidation peak potential compared with that on the bare GCE. Under optimum conditions, the proposed biosensor can be applied to the quantification analysis of Trp with a wide linear range covering 0.05-10 μM (R = 0.996) and a low detection limit of 0.01 μM. The experimental results also showed that the sensor exhibited good reproducibility, long-term stability as well as high selectivity. Moreover, the novel biosensor for the detection of Trp in a real amino acid sample with satisfactory results has been proved.     

Ferrocene Decorated N-doped Carbon Modified Electrode with Enhanced Electrocatalytic Activity towards Non-enzymatic Glucose Detection

The nitrogen doped carbon (NDCN) have been synthesized by flame synthetic method to prepare ferrocene decorated NDCN. The hydrolysis product (FC-SH) of ferrocene benzyne derivative (FC-SAc) was immobilized onto NDCN modified GCE and used for glucose detection with high sensitivity. Cyclic voltammetric analysis reveal that FC-S-NDCN/GCE exhibit excellent activity for glucose oxidation when compared to FC/GCE. The FC-S-NDCN/GCE with wide linear responses range from 0.001 to 0.01 mM with the regression co-efficient of 0.998. The FC-S-NDCN/GCE show low detection limit (LOD) of 0.08 μM and exhibit sensitivity of 1580 μA mM⁻¹ cm⁻². The FC-S-NDCN glucose sensor exhibit wide linear range, high sensitivity and lower detection limit on determination of glucose.     

Electrochemical determination of nitrite using a gold nanoparticles-modified glassy carbon electrode prepared by the seed-mediated growth technique.

Seed-mediated growth of gold nanoparticles on glassy carbon (GC) surfaces was developed. The field emission scanning electron microscopy (FE-SEM) and electrochemical characterization confirmed the effective attachment of gold nanoparticles on GC surface with such a wet-chemical method. The as-prepared gold nanoparticles attached glassy carbon electrode (Au/GCE) presented excellent catalytic ability toward the oxidation of nitrite. Compared with bare GCE and planar gold electrode, the Au/GCE obviously decreased the overpotential of nitrite oxidation and improved the peak current. The catalytic current was found to be linearly proportional to the nitrite concentration in the range of 1 x 10(-5) - 5 x 10(-3) M, with a detection limit of 2.4 x 10(-6) M. The Au/GCE was successfully applied to the electrochemical determination of nitrite in a real wastewater sample, showing excellent stability and anti-interference ability.