A Polypyrrole‐Imprinted Electrochemical Sensor Based on Nano‐SnO2/Multiwalled Carbon Nanotubes Film Modified Carbon Electrode for the Determination of Oleanolic Acid

A sensitive molecularly imprinted electrochemical sensor with specific recognition ability for oleanolic acid was synthesized by modification of multiwalled carbon nanotubes (MWNTs) decorated with tin oxide nanoparticles (nano‐SnO₂/MWNTs) and polypyrrole‐imprinted polymer on a carbon electrode. The morphology and electrochemical performance of the imprinted sensor were investigated by using scanning electron microscope (SEM), X‐ray diffraction (XRD), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and amperometric i–t curve. The results showed that the imprinted sensor displayed excellent selectivity toward oleanolic acid. A linear relationship between the response currents and oleanolic acid concentrations ranging from 5.0×10^?8 g/L to 2.0×10^?5 g/L was obtained for the imprinted sensor. The limit of detection (LOD) of the imprinted sensor toward oleanolic acid was calculated as 8.6×10^?9 g/L at a signal to noise ratio (S/N) of 3. This imprinted sensor was successfully applied to the determination of oleanolic acid in Acitinidia deliciosa root samples.     

Electrochemical Fabrication of Cobalt Oxides/Nanoporous Gold Composite Electrode and its Nonenzymatic Glucose Sensing Performance

A nonenzymatic glucose sensor was successfully established by electrochemically decorating cobalt oxides (CoO_x) on a nanoporous gold electrode (NPG) using cobalt hexacyanoferrate (CoHCF) as a precursor. It exhibited high sensitivity and long‐term stability as well as satisfactory quantification of glucose concentration in human serum samples. The morphology and surface analysis of the resulting CoO_x/NPG were carefully characterized. Two detection methods, cyclic voltammetry and amperometry, were employed to evaluate the performance of CoO_x/NPG towards glucose sensing in alkaline solution. Using cyclic voltammetry, at ?0.5 V, the glucose partial oxidation peak current is linear to the glucose concentration up to 14 mM with a sensitivity of 283.7 µA mM^?1 cm^?2. A linear amperometric response at 0.55 V was obtained in the glucose concentration range from 2 µM to 2 mM with a sensitivity of 2025 µA mM^?1 cm^?2 and a response time <3 s.     

Electrochemical Behavior and Amperometric Detection of 4‐Chlorophenol on Nano‐Au Thin Films Modified Glassy Carbon Electrode

An amperometric sensor based on nano‐Au thin films was fabricated, by means of which a fast response to 4‐chlorophenol (4‐CP) can be achieved in the range of mM concentrations. The nanostructured Au thin film was prepared on glassy carbon electrodes by a template‐free, double‐potential step electrodeposition technique. Its structural feature can be controlled well by adjusting the deposition time. The amperometric detection of 4‐CP was performed at +0.85 V with a linear detection range from 0.2 to 4.8 mM and a detection limit of 0.11 mM (S/N=3). Besides, the effect of concentrations on the electrochemical behavior of 4‐CP on the Au thin film was investigated by linear sweep voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy.     

A Zinc Oxide Carbon Nanotube Based Sensor for In Situ Monitoring of Hydrogen Peroxide in Swimming Pools

Zinc oxide nanoparticles were tethered to carbon nanotubes to form an electrochemical sensing composite, which was characterized using transmission electron microscopy, and X‐ray photoelectron and attenuated total reflectance infrared spectroscopies. The sensor′s electrocatalytic response for measuring hydrogen peroxide was investigated using cyclic voltammetry and chronoamperometry in a dynamic, well defined swimming pool environment. A wide, linear response in the concentration range of 0.025–7.0 mM at a potential of ?0.360 V was shown, with rapid response time (<5 s). The sensor had excellent reproducibility, exhibited stability and selectivity, and was able to measure concentrations in a dynamic environment as they varied.     

Electrochemical oxidative determination of 4-nitrophenol based on a glassy carbon electrode modified with a hydroxyapatite nanopowder

A non-enzymatic amperometric glucose is reported that is based on an glassy carbon electrode modified with a Cu-CuO nanowire (NW) composite. The morphology and the composition of the nanowire were characterized by scanning electron microscopy and X-ray diffraction, respectively. The modified electrode efficiently catalyzes the oxidation of glucose at less-positive potential (0.30 V) in 0.10 M NaOH solution in the absence of any enzymes or redox mediators. The sensor was successfully used for the amperometric sensing of glucose. Linear response was obtained over the concentration range from 0.1 to 12 mM. The common interfering agents ascorbic acid and uric acid do not interfere with the determination of glucose. The modified electrode features high sensitivity, low working potential, excellent stability, and fast amperometric sensing of glucose. Thus it is promising for the future development of non-enzymatic glucose sensors.     

A sensitive and selective sensor‐coated molecularly imprinted sol–gel film incorporating β‐cyclodextrin‐multi‐walled carbon nanotubes and cobalt nanoparticles‐chitosan for oxacillin determination

A sensitive and selective imprinted electrochemical sensor for the determination of oxacillin was developed based on indium tin oxide electrode. The proposed sensor was decorated with imprinted sol–gel film and cobalt nanoparticles‐chitosan/β‐cyclodextrin‐multiwalled carbon nanotubes nanocomposites. The surface morphologies of the modified electrodes were characterized by scanning electron microscopy and transmission electron microscope. The stepwise assembly process and electrochemical behavior of the novel sensor were characterized by differential pulse voltammetry, cyclic voltammetry and Amperometric i‐t response. The imprinted sensor displayed excellent selectivity toward oxacillin. Meanwhile, the introduced cobalt nanoparticles‐chitosan and β‐cyclodextrin‐multi‐walled carbon nanotubes exhibited noticeable amplified electrochemical response signal. The differential voltammetric anodic peak current was linear to oxacillin concentration in the range from 2.0 × 10^?7 to 1.0 × 10^?4 mol·l^?1, and the detection limit was 6.9 × 10^?9 mol·l^?1. The proposed imprinted sensor was applied to the determination of oxacillin in human blood serum samples successfully. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication of Hierarchically Structured MOF‐Co3O4 on Well‐aligned CuO Nanowire with an Enhanced Electrocatalytic Property

Engineering appropriate shape and size of three‐dimensional inorganic nanostructures materials is of one the main critical problems in pursuing high‐performance electrode materials. Herein, we fabricate a metal‐organic framework derived cobalt oxide (Co₃O₄) are grown on copper oxide nanowire (CuO NWs) supported on the surface of 3D copper foam substrate. The highly aligned CuO NWs were prepared by using electrochemical anodization of copper foam in ambient temperature and followed by MOF Co₃O₄ was grown via a simple in situ solution deposition then consequent calcination process. The obtained binder‐free 3D CuO NWs@Co₃O₄ nanostructures were further characterized by using X‐ray diffraction, X‐ray photoelectron spectroscopy, field‐emission scanning electron microscopy, and transmission electron microscopy. Furthermore, electrochemical sensing of glucose was studied by using Cyclic Voltammetry, and chronoamperometry techniques. Interestingly, 3D CuO NWs@Co₃O₄ electrode exhibits excellent performance for the oxidation of glucose compared with individual entities. The proposed sensor shows wide linear ranges from 0.5 μM to 0.1 mM with the sensitivity of 6082 μA/μM and the lowest detection limit (LOD) of 0.23 μM was observed with the signal to noise ratio, (S/N) of 3. The superior catalytic oxidation of glucose mainly is endorsed by the excellent electrical conductivity and synergistic effect of the Co₃O₄ and CuO NWs.     

A Novel Biomimetic Hydrogen Peroxide Biosensor Based on Pt Flowers‐decorated Fe3O4/Graphene Nanocomposite

A sensitive and selective amperometric H₂O₂ biosensor was obtained by utilizing the electrodeposition of Pt flowers on iron oxide‐reduced graphene oxide (Fe₃O₄/rGO) nanocomposite modified glassy carbon electrode (GCE). The morphology of Fe₃O₄/rGO and Pt/Fe₃O₄/rGO was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. The step‐wise modification and the electrochemical characteristics of the resulting biosensor were characterized by cyclic voltammetry (CV) and chronoamperometry methods. Thanks to the fast electron transfer at the Pt/Fe₃O₄/rGO electrode interface, the developed biosensor exhibits a fast and linear amperometric response upon H₂O₂. The linear range of Pt/Fe₃O₄/rGO is 0.1∼2.4 mM (R²=0.998), with a sensitivity of 6.875 μA/mM and a detection limit of 1.58 μM (S/N=3). In addition, the prepared biosensor also provides good anti‐interferent ability and long‐term stability due to the favorable biocompatibility of the electrode interface. The proposed sensor will become a reliable and effective tool for monitoring and sensing the H₂O₂ in complicate environment.     

A Novel Flexible Electrochemical Ascorbic Acid Sensor Constructed by Ferrocene Methanol doped Multi-walled Carbon Nanotube Yarn

An ascorbic acid (AA) electrochemical sensor was fabricated by ferrocene methanol (Fc−OH) modified multi-walled carbon nanotube yarn (CNTY). The prepared sensor (Fc−OH/CNTY) exhibited outstanding flexibility, highly stretchability, excellent bendability and obviously electrocatalytic activity for oxidation of ascorbic acid. The morphology of Fc−OH/CNTY was evaluated by scanning electron microscope. The electrochemical behaviour of Fc−OH/CNTY sensor was studied by cyclic voltammetry and amperometry measurements. Moreover, the influence of Fc−OH concentration, applied potential and electrolyte solution pH were also investigated to obtain the best sensor performance. The prepared sensor exhibited a wide linear range from 3 μM to 3.0 mM toward AA, and a detection limit of 1.32 μM (S/N=3). It also possessed a good lifetime and a fast response speed (2.83 s). In addition, the Fc−OH/CNTY sensor remained 90 % and 60 % of its initial activity after 100 and 500 times bending, respectively, which indicated a potential application on flexible, implantable and/or wearable electrochemical sensors.     

Dispersed Nickel Nanoparticles on Flower‐like Layered Nickel‐Cobalt Double Hydroxides for Non‐enzymic Amperometric Sensing of Glucose

The article describes the preparation of supported nickel nanoparticles (NiNPs) by partial reduction of Ni,Co‐layered double hydroxide (NiCo‐LDH). The nanocomposites were characterized by X‐ray diffraction and their morphology and composition were characterized by scanning electron microscopy and transmission electron microscopy. The electrochemical properties of the nanocomposite were explored by cyclic voltammetry and amperometry, which revealed significant electrocatalytic behavior towards the oxidation of glucose. The resulted non‐enzymatic glucose sensor has a linear response to glucose in the 5.0 μM to 14.8 mM concentration range, a low detection limit of 1.6 μM, high sensitivity, and excellent selectivity.     

Addition of porous cuprous oxide to a Nafion film strongly improves the performance of a nonenzymatic glucose sensor

The direct electrocatalytic oxidation of glucose in alkaline medium at an electrode modified with microcubes of porous cuprous oxide is reported. Compared to the glassy carbon electrode, a substantial increase in the efficiency of the electrocatalytic oxidation of glucose is observed starting at around +0.20 V (vs. Ag/AgCl). The pH dependence of the response was examined by cyclic voltammetry. This non-enzymatic amperometric sensor may be used for non-enzymatic detection of glucose with a high and reproducible sensitivity of 10.95 μA per mM at a potential of +0.40 V, with response times of <3 s, a linear range from 2.0 to 350 μM, and a detection limit of 1.3 μM. The porous microcubes are conveniently prepared, and display high sensitivity and repeatability.     

CuO Nanostructures Based Electrochemical Sensor for Simultaneous Determination of Hydroquinone and Ascorbic Acid

A simple, sensitive and reliable electrochemical sensor has been developed based on CuO nanostructures modified glassy carbon electrode for simultaneous determination of hydroquinone (HQ) and ascorbic acid (AA). The CuO nano material was synthesized by aqueous chemical growth method using different sources of OH. The characterization of nano material was performed by Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy and energy dispersive X‐ray spectroscopy. The glassy carbon electrode was modified by CuO nano material using drop cast method and studied by cyclic voltammetry. The CuO/GCE exhibited excellent electrocatalytic activity towards the oxidations of HQ and AA in borate buffer solution (pH 8.0) and the corresponding electrochemical signals have appeared as two well resolved oxidation peaks with significant peak potential differences of (0.21V vs. Ag/AgCl). Differential pulse voltammetry was used for simultaneous determination of HQ and AA using the CuO/GCE. At the optimum conditions, for simultaneous determination by synchronous change of the analyte concentrations, the linear response ranges were between 0.0003–0.355 mM for HQ and 0.0001–0.30 mM for AA respectively. Furthermore, CuO/GCE was successfully applied for the independent determination of AA in fruit juices as well as for the simultaneous determination of HQ and AA in cosmetic samples.     

Fabrication of Trimetallic Pt−Pd−Co Porous Nanostructures on Reduced Graphene Oxide by Galvanic Replacement: Application to Electrocatalytic Oxidation of Ethylene Glycol

In present work, reduced graphene oxide nanosheets (rGO) decorated with trimetallic three‐dimensional (3D) Pt−Pd−Co porous nanostructures was fabricated on glassy carbon electrode (Pt−Pd−Co/rGO/GCE). First, GO suspension was drop‐casted on the electrode surface, then GO film reduction was carried out by cycling the potential in negative direction to form the rGO film modified GCE (rGO/GCE). Then, electrodeposition of the cobalt nanoparticles (CoNPs) as sacrificial seeds was performed onto the rGO/GCE by using cyclic voltammetry. Afterward, Pt−Pd−Co 3D porous nanostructures fabrication occurs through galvanic replacement (GR) method based on a spontaneous redox process between PtCl₂, PdCl_2, and CoNPs. The morphology and structure of the Pt−Pd−Co/rGO porous nanostructure film was characterized by scanning electron microscopy, energy dispersive spectroscopy and X‐ray diffraction method. The performance of the prepared electrode was investigated by various electrochemical methods including, cyclic voltammetry and electrochemical impedance spectroscopy. The electrocatalytic activity of the as‐prepared modified electrode with high surface areas was evaluated in anodic oxidation of ethylene glycol. The study on electrocatalytic performances revealed that, in comparison to various metal combinations in modified electrodes, trimetallic Pt−Pd−Co/rGO/GCE exhibit a lower onset potential, significantly higher peak current density, high durability and stability for the anodic oxidation of ethylene glycol. The excellent performances are attributed to the rGO as catalysts support and resulting synergistic effects of the trimetallic and appropriate characteristics of the resulted 3D porous nanostructures. Moreover, the influence of various concentrations of ethylene glycol, the potential scan rate and switching potential on the electrode reaction, in addition, long‐term stability have been studied by chronoamperometric and cyclic voltammetric methods.     

Free‐standing and Flexible MoS2/rGO Paper Electrode for Amperometric Detection of Folic Acid

The development of flexible electrodes is of considerable current interest because of the increasing demand for modern electronics, portable medical products, and compact devices. We report a new type of flexible electrochemical sensor fabricated by integrating graphene and MoS₂ nanosheets. A highly flexible and free‐standing conductive MoS₂ nanosheets/reduced graphene oxide (MoS₂/rGO) paper was prepared by a two‐step process: vacuum filtration and chemical reduction treatment. The MoS₂/graphene oxide (MoS₂/GO) paper obtained by a simple filtration method was transformed into MoS₂/rGO paper after a chemical reduction process. The obtained MoS₂/rGO paper was characterized by scanning electron microscopy, X‐ray diffraction spectroscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy, electrochemical impedance spectroscopy. The electrochemical behavior of folic acid (FA) on MoS₂/rGO paper electrode was investigated by cyclic voltammetry and amperometry. Electrochemical experiments indicated that flexible MoS₂/rGO composite paper electrode exhibited excellent electrocatalytic activity toward the FA, which can be attributed to excellent electrical conductivity and high specific surface area of the MoS₂/rGO paper. The resulting biosensor showed highly sensitive amperometric response to FA with a wide linear range.     

Electrodeposition of Cobalt Oxides on Carbon Nanotubes for Sensitive Bromhexine Sensing

We develop an electrochemical sensor for the determination of bromhexine hydrochloride (BHC), a widely use mucolytic drug. The sensor is prepared by electrodeposition of cobalt oxides (CoO_x) on a glassy carbon electrode modified with carboxylated single-walled carbon nanotubes (SWCNT). A synergistic effect between CoO_x and SWCNT is observed, leading to a significant improvement in the BHC electrooxidation current. Based on cyclic voltammetry studies at varying scan rates, we conclude that the electrochemical oxidation of BHC is under mixed diffusion–adsorption control. The proposed sensor allows the amperometric determination of BHC in a linear range of 10–500 µM with a low applied voltage of 0.75 V. The designed sensor provides reproducible measurements, is not affected by common interfering substances, and shows excellent performance for the analysis of BHC in pharmaceutical preparations.     

Free‐standing Graphene/Poly(methylene blue)/AgNPs Composite Paper for Electrochemical Sensing of NADH

Highly flexible graphene/poly(methylene blue)/AgNPs composite paper was successfully prepared for amperometric biosensing of NADH. For this purpose, a dispersion including graphene oxide (GO), methylene blue (MB) and silver nanoparticles (AgNPs) was prepared and GO/MB/AgNPs paper was acquired by vacuum‐filtration of this dispersion through a suitable membrane. After peeling it off from membrane, it was transformed to rGO/MB/AgNPs paper by performing reduction with hydriodic acid. In a three‐electrode cell, which is containing 0.1 M phosphate buffer solution (pH: 9.0), rGO/MB/AgNPs paper was used as working electrode and rGO/poly(MB)/AgNPs composite paper was generated by surface‐confined electropolymerization of MB using successive cyclic voltammetry approach in a suitable potential window. Characterization of this composite paper was carried out by using scanning electron microscopy, scanning tunneling microscopy, X‐ray photoelectron spectroscopy, powder X‐ray diffraction spectroscopy, Raman spectroscopy, four‐point probe conductivity measurement and cyclic voltammetry techniques. Flexible rGO/poly(MB)/AgNPs composite paper has demonstrated high sensitivity, wide linear range and low detection limit for amperometric quantification of NADH.     

Amperometric Glucose Biosensor on Layer by Layer Assembled Carbon Nanotube and Polypyrrole Multilayer Film

An amperometric glucose biosensor on layer by layer assembled carbon nanotube and polypyrrole multilayer film has been reported in the present investigation. Homogeneous and stable single wall carbon nanotubes (SWNTs) and polypyrrole (PPy) multilayer films were alternately assembled on platinum coated Polyvinylidene fluoride (PVDF) membrane. Since conducting polypyrrole has excellent anti‐interference ability, protection ability in favor of increasing the amount of the SWNTs on platinum coated PVDF membrane and superior transducing ability, a layer by layer approach of polypyrrole and carbon nanotubes has provided an excellent matrix for the immobilization of enzyme. The layer‐by‐layer assembled SWNTs and PPy‐modified platinum coated PVDF membrane is shown to be an excellent amperometric sensor over a wide range of concentrations of glucose. The glucose oxidase (GOx) was immobilized on layer by layer assembled film by a physical adsorption method by cross linking through Glutaraldehyde. The glucose biosensor exhibited a linear response range from 1 mM to 50 mM of glucose concentration with excellent sensitivity of 7.06 μA/mM.     

Modification of carbon ceramic electrode prepared with sol-gel technique by a thin film of chlorogenic acid: application to amperometric detection of NADH

The carbon ceramic electrode prepared with sol-gel technique is modified by a thin film of chlorogenic acid (CGA). By immersing the carbon ceramic electrode in aqueous solution of chlorogenic acid at less than 2 s a thin film of chlorogenic acid adsorbed strongly and irreversibly on the surface of electrode. The cyclic voltammetry of the resulting modified CCE prepared at optimum conditions shows a well-defined stable reversible redox couple due to hydroquinone/quinone system in both acidic and basic solutions. The modified electrode showed excellent electrocatalytic activity toward NADH oxidation and it also showed a high analytical performance for amperometric detection of NADH. The catalytic rate constant of the modified carbon ceramic electrode for the oxidation of NADH is determined by cyclic voltammetry measurement. Under the optimised conditions the calibration curve is linear in the concentration range 1-120 μm. The detection limit (S/N = 3) and sensitivity are 0.2 μM and 25 nA μM⁻¹.The results of six successive measurement-regeneration cycles show relative standard deviations of 2.5% for electrolyte solution containing 1 mM NADH, indicating that the electrode renewal gives a good reproducible and antifouling surface. The advantages of this amperometric detector are: high sensitivity, excellent catalytic activity, short response time t < 2 s, remarkable long-term stability, simplicity of preparation at short time and good reproducibility.     

Amperometric biosensors based on the immobilization of oxidases in a Prussian blue film by electrochemical codeposition

Prussian blue has been formed by cyclic voltammetry onto the basal pyrolytic graphite surface to prepare a chemically modified electrode which provides excellent electrocatalysis for both oxidation and reduction of hydrogen peroxide. It is found for the first time that glucose oxidase or -amino oxidase can be incorporated into a Prussian blue film during its electrochemical growth process. Two amperometric biosensors were fabricated by electrochemical codeposition, and the resulting sensors were protected by coverage with a thin film of Nafion. The influence of various experimental conditions was examined for optimum analytical performance. The glucose sensor responds rapidly to substrates with a detection limit of 2 × 10⁻⁶ M and a linear concentration range of 0.01–3 mM. There was no interference from 2 mM ascorbic acid or uric acid. Another ( -amino acid) sensor gave a detection limit of 3 × 10⁻⁵ M -alanine, injected with a linear concentration range of 7.0 × 10⁻⁵-1.4 × 10⁻² M. Glucose and -amino acid sensors remain relatively stable for 20 and 15 days, respectively. There is no obvious interference from anion electroactive species due to a low operating potential and excellent permselectivity of Nafion.     

Ultra‐sensitive Amperometric Hydrazine Sensing via Dimethyl Glyoxomat Derived NiO Nanostructures

Here we report the synthesis of NiO nanostructures via glyoxomat assisted precipitation protocol using hydrothermal route under the influence of ammonia followed by annealing at 450 ^oC. These nanostructures were characterized via Scanning Electron Microscopy (SEM) and X‐ray Diffraction (XRD) method. The morphological investigation of the finally prepared NiO revealed foam‐like porous nanostructures. These NiO nanostructures were immobilized onto glassy carbon electrode (GCE) with nafion as binding material and used as highly sensitive and selective sensor for determining hydrazine in the range of 100–500 nM and 600–1600 nM with a calculated limit of detection (LOD) equal to 5 nM. The as prepared sensor was tested for the presence of various interfering species such as Na⁺, Cu²⁺, uric acid, hydrogen peroxide and glucose in the presence of equimolar concentration of hydrazine and negligible interference was noticed. The sensor was further tested for hydrazine detection using square wave voltammetry (SWV) however it only worked in the range of 50–1200 μM. Finally the sensor was successfully implemented for hydrazine determination in real water samples using amperometric protocol.