Epoxy Composite Electrode Research Articles

Indirect determination of free chlorine in seawater by cyclic voltammetry using graphite–epoxy composite electrode: Hydrogen adsorption capacity of graphite–epoxy composite is one–third of that of platinum

A new possibility of indirect determination of free chlorine using a graphite–epoxy composite(GEC) electrode instead of Pt disk electrode was suggested by interpreting the relationship between the peak current of the oxidation peak for hydrogen generated through water electrolysis in CV and the amount of the free chlorine. The linear response range of concentration was 0.06–0.2 mg∙L−1 with correlation coefficient of 0.9951 (n = 5) and the sensitivity of 1225 μA cm−2 mg−1 L. The limit of detection (LOD) calculated from the 3σ IUPAC criteria was 1.2 × 10−2 mg L−1. The relative standard deviation (RSD) to 0.06 mg L−1 was 4.65 %(n = 10). The results show that the amount of free chlorine in the disinfected seawater can be indirectly determined by using a GEC electrode without influence of interferences unlike a Pt disk electrode. On the other hand, in this paper, a new method is proposed to evaluate the relative hydrogen adsorption capacity by the sensitivity of GEC electrode compared with that of Pt disk electrode. During the investigation of the hydrogen adsorption on the surface of the working electrode, we obtained the result that the hydrogen adsorption capacity of GEC is one-third of that of platinum.

Indirect determination of free chlorine in seawater by cyclic voltammetry using graphite–epoxy composite electrode: Hydrogen adsorption capacity of graphite–epoxy composite is one–third of that of platinum

A new possibility of indirect determination of free chlorine using a graphite–epoxy composite(GEC) electrode instead of Pt disk electrode was suggested by interpreting the relationship between the peak current of the oxidation peak for hydrogen generated through water electrolysis in CV and the amount of the free chlorine. The linear response range of concentration was 0.06–0.2 mg∙L−1 with correlation coefficient of 0.9951 (n = 5) and the sensitivity of 1225 μA cm−2 mg−1 L. The limit of detection (LOD) calculated from the 3σ IUPAC criteria was 1.2 × 10−2 mg L−1. The relative standard deviation (RSD) to 0.06 mg L−1 was 4.65%(n = 10). The results show that the amount of free chlorine in the disinfected seawater can be indirectly determined by using a GEC electrode without influence of interferences unlike a Pt disk electrode. On the other hand, in this paper, a new method is proposed to evaluate the relative hydrogen adsorption capacity by the sensitivity of GEC electrode compared with that of Pt disk electrode. During the investigation of the hydrogen adsorption on the surface of the working electrode, we obtained the result that the hydrogen adsorption capacity of GEC is one-third of that of platinum.

Porous macroradical epoxy-based supercapacitors

Intrinsic p -type conductivity was observed in an otherwise aliphatic epoxy backbone through derivatization with stable radicals. The conductive potential of this combined radical-epoxy material was further investigated by prospecting for energy storage systems. This work identifies macroradical epoxy composites with 10% (w/w) conductive carbon as viable devices in supercapacitor application. In cross-linking, the appropriate selection of the diamine spacer has a profound impact on the curing and the resulting conformation of the polymer. The short-chain diamine spacer 1,2-diaminoethane exhibits the best supercapacitor performance yielding a maximum specific capacitance of 195 F g −1 at 1.0 A g −1 . The specific capacitance remains at 99% at 1.0 A g −1 after repeatedly charging and discharging 10,000 times. The observed cycling stability is rare for materials exhibiting pseudocapacitance. This better performance than a reference conventional epoxy composite is attributed to the overall contributions of the electric double layer and pseudocapacitance effect with the effective utilization of the nanoscale porous polymeric structure. Furthermore, the pseudocapacitance is significantly enhanced by using the short-chain diamine spacer due to the closer radical-to-radical interactions and the excellent dispersibility of the added conductive particles. • Macroradical epoxies have promising energy-storage prospects. • Macroradical epoxy composite electrodes are viable supercapacitors. • Superior cycling performance is observed, rare for pseudocapacitors. • Rheology and small-angle x-ray scattering correlate with electrode chemistry. • Magnets used during cross-linking are valuable in distinguishing morphology.

Dummy Molecularly Imprinted Polymers Using DNP as a Template Molecule for Explosive Sensing and Nitroaromatic Compound Discrimination

This work reports a rapid, simple and low-cost voltammetric sensor based on a dummy molecularly imprinted polymer (MIP) that uses 2,4-dinitrophenol (DNP) as a template for the quantification of 2,4,6-trinitrotoluene (TNT) and DNP, and the identification of related substances. Once the polymer was synthesised by thermal precipitation polymerisation, it was integrated onto a graphite epoxy composite (GEC) electrode via sol–gel immobilisation. Scanning electron microscopy (SEM) was performed in order to characterise the polymer and the sensor surface. Responses towards DNP and TNT were evaluated, displaying a linear response range of 1.5 to 8.0 µmol L−1 for DNP and 1.3 to 6.5 µmol L−1 for TNT; the estimated limits of detection were 0.59 µmol L−1 and 0.29 µmol L−1, for DNP and TNT, respectively. Chemometric tools, in particular principal component analysis (PCA), demonstrated the possibilities of the MIP-modified electrodes in nitroaromatic and potential interfering species discrimination with multiple potential applications in the environmental field.

Highly Sensitive Non-Enzymatic Detection of Glucose at MWCNT-CuBTC Composite Electrode

A novel electrochemical glucose sensor was developed, based on a multiwall carbon nanotubes (MWCNTs)-copper-1,3,5-benzenetricarboxylic acid (CuBTC)-epoxy composite electrode, named MWCNT-CuBTC. The electrode nanocomposite was prepared by a two-roll mill procedure and characterized morphostructurally by scanning electron microscopy (SEM). The CuBTC formed defined crystals with a wide size distribution, which were well dispersed and embedded in the MWCNTs. Its electrical conductivity was determined by four-point probe contact (DC) conductivity measurements. The electroactive surface area, determined using cyclic voltammetry (CV), was found to be 6.9 times higher than the geometrical one. The results of the electrochemical measurements using CV, linear sweep voltammetry (LSV), differential pulse voltammetry (DPV), chronoamperometry (CA) and multiple pulse amperometry (MPA) showed that the MWCNT-CuBTC composite electrode displayed high electrocatalytic activity toward the oxidation of glucose and, as a consequence, very high sensitivity. The best sensitivity of 14,949 µAmM−1cm−1 was reached using MPA at the potential value of 0.6 V/SCE, which was much higher in comparison with other copper-based electrodes reported in the literature. The good analytical performance, low cost and simple preparation method make this novel electrode material promising for the development of an effective glucose sensor.

Voltammetric Electronic Tongue for the Simultaneous Determination of Three Benzodiazepines.

The presented manuscript reports the simultaneous detection of a ternary mixture of the benzodiazepines diazepam, lorazepam, and flunitrazepam using an array of voltammetric sensors and the electronic tongue principle. The electrodes used in the array were selected from a set of differently modified graphite epoxy composite electrodes; specifically, six electrodes were used incorporating metallic nanoparticles of Cu and Pt, oxide nanoparticles of CuO and WO3, plus pristine electrodes of epoxy-graphite and metallic Pt disk. Cyclic voltammetry was the technique used to obtain the voltammetric responses. Multivariate examination using Principal Component Analysis (PCA) justified the choice of sensors in order to get the proper discrimination of the benzodiazepines. Next, a quantitative model to predict the concentrations of mixtures of the three benzodiazepines was built employing the set of voltammograms, and was first processed with the Discrete Wavelet Transform, which fed an artificial neural network response model. The developed model successfully predicted the concentration of the three compounds with a normalized root mean square error (NRMSE) of 0.034 and 0.106 for the training and test subsets, respectively, and coefficient of correlation R ≥ 0.938 in the predicted vs. expected concentrations comparison graph.

A Voltammetric Electronic Tongue for the Resolution of Ternary Nitrophenol Mixtures.

This work reports the applicability of a voltammetric sensor array able to quantify the content of 2,4-dinitrophenol, 4-nitrophenol, and picric acid in artificial samples using the electronic tongue (ET) principles. The ET is based on cyclic voltammetry signals, obtained from an array of metal disk electrodes and a graphite epoxy composite electrode, compressed using discrete wavelet transform with chemometric tools such as artificial neural networks (ANNs). ANNs were employed to build the quantitative prediction model. In this manner, a set of standards based on a full factorial design, ranging from 0 to 300 mg·L−1, was prepared to build the model; afterward, the model was validated with a completely independent set of standards. The model successfully predicted the concentration of the three considered phenols with a normalized root mean square error of 0.030 and 0.076 for the training and test subsets, respectively, and r ≥ 0.948.

Characterization and Evaluation of Silver-Nanoparticle-Incorporated in Composite Graphite Aiming at their Application in Biosensors

Abstract Biosensors based on nanomaterial composites have been investigated for their potential to function as high sensitivity signal response devices. In the present study, we report the fabrication of silver nanoparticles (AgNPs) on a graphite epoxy composite electrode (GEC) and mixed with the polyaniline (a conductive emeraldine salt form polymer) composite electrode (AgNPs/PANI/GEC), in order to compare the performance of the generated electrochemical response signals. Cyclic voltammetry tests were conducted to compare the quality and intensity of signals from the different prepared electrodes. Tests for the AgNPs/PANI/GEC electrodes were made with and without the enzymes alcohol oxidase and horseradish peroxidase immobilized on the composite surface. The prepared AgNPs/PANI/GEC nanocomposite was evaluated by thermal analysis. Scanning electron microscopy images and EDX were obtained for characterization of the electrode surface morphology. Square wave voltammetry techniques were then employed for ethanol analysis with the AOX/HRP/AgNPs/PANI/GEC biosensor achieving good results in a range of 0.37M to 0.65 M.

Determination of pesticides using a low-temperature co-fired ceramic microfluidic platform

ABSTRACTThe aim of this work is the integration of an improved graphite–epoxy composite electrode modified with the acetylcholinesterase enzyme as a detector into a green tape ceramic microfluidic device for the online amperometric determination of pesticides. First, the operational conditions of the microfluidic system were optimized for the enzymatic substrate determination of acetylthiocholine. Good results were achieved for acetylthiocholine determination, obtaining a low detection limit and optimal sensitivity. The analytical performance of the microanalyzer was evaluated with organophosphorus and carbamate pesticides across a wide concentration range. Pesticides were determined indirectly measuring the enzymatic inhibition effect that they caused. The analysis was based on stopped-flow methodology with a three-step strategy: enzymatic substrate measurement, enzymatic inhibition by pesticide contact with the biosensor, and enzymatic substrate measurement after the inhibition process. The pesticide concentrations were determined by the percentage of inhibition produced. The microanalyzer was used for the analysis of spiked irrigation water samples using this indirect method. The low-temperature co-fired ceramic/epoxy–graphite–acetylcholinesterase microfluidic system showed low limits of detection and adequate sensitivity. The recoveries of the spiked water samples were approximately 100% with relative standard deviation values lower than 5% for three replicate measurements. All results obtained are indicative of a convenient, rapid, sensitive, and economic method for the determination of pesticides in environmental samples.

Determination of arbutin and bergenin in Bergeniae Rhizoma by capillary electrophoresis with a carbon nanotube-epoxy composite electrode

This report describes the fabrication and the application of a novel carbon nanotube (CNT)-epoxy composite electrode as a sensitive amperometric detector for the capillary electrophoresis (CE). The composite electrode was fabricated on the basis of the in situ polycondensation of a mixture of CNTs and 1,2-ethanediamine-containing bisphenol A epoxy resin in the inner bore of a piece of fused silica capillary under heat. It was coupled with CE for the separation and detection of arbutin and bergenin in Bergeniae Rhizoma, a traditional Chinese medicine, to demonstrate its feasibility and performance. The two phenolic constituents were well separated within 10min in a 45cm capillary length at a separation voltage of 12kV using a 50mM borate buffer (pH 9.2). The CNT-based detector offered higher sensitivity, significantly lower operating potential, satisfactory resistance to surface fouling, and lower expense of operation, indicating great promise for a wide range of analytical applications. It showed long-term stability and reproducibility with relative standard deviations of less than 5% for the peak current (n=15).

Crown ether-modified electrodes for the simultaneous stripping voltammetric determination of Cd(II), Pb(II) and Cu(II)

This work describes the immobilization of 4-carboxybenzo-18-crown-6 (CB-18-crown-6) and 4-carboxybenzo-15-crown-5 (CB-15-crown-5) assisted by lysine on aryl diazonium salt monolayers anchored to the surface of graphite–epoxy composite electrodes (GEC), and their use for the simultaneous determination of Cd(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetry (DPASV). These modified electrodes display a good repeatability and reproducibility with detection and quantification limits at levels of µgL−1 (ppb), confirming their suitability for the determination of Cd(II), Pb(II) and Cu(II) ions in environmental samples. The overlapped nature of the multimetal stripping measurements was resolved by employing the two-sensor array CB-15-crown-5-GEC and CB-18-crown-6-GEC, since the metal complex selectivity exhibited by the considered ligands could add some discrimination power. For the processing of the voltammograms, Discrete Wavelet Transform and Causal Index were selected as preprocessing tools for data compression coupled with an artificial neural network for the modeling of the obtained responses, allowing the resolution of mixtures of these metals with good prediction of their concentrations (correlation with expected values for an external test subset better than 0.942).

Electrochemical detection of fluoroquinolone antibiotics in milk using a magneto immunosensor.

An amperometric magneto-immunosensor (AMIS) for the detection of residues of fluoroquinolone antibiotics in milk samples is described for the first time. The immunosensor presented combines magnetic beads biomodified with an antibody with a broad recognition profile of fluoroquinolones, a haptenized enzyme and a magnetic graphite–epoxy composite (m-GEC) electrode. After the immunochemical reaction with specific enzyme tracer, the antibody biomodified magnetic beads are easily captured by an electrode made of graphite-epoxy composite containing a magnet, which also acts as transducer for the electrochemical detection. In spite of the complexity of milk, the use of magnetic beads allows elimination of potential interferences caused by the matrix components; hence the AMIS could perform quantitative measurements, directly in these samples, without any additional sample cleanup or extraction step. The immunosensor is able to detect up to seven different fluoroquinolones far below the MRLs defined by the UE for milk; for example ciprofloxacin is detected directly in milk with an IC50 of 0.74 μg/L and a LOD of 0.009 μg/L. This strategy offers great promise for rapid, simple, cost-effective, and on-site analysis fluoroquinolones in complex samples.

Compressed multiwall carbon nanotube composite electrodes provide enhanced electroanalytical performance for determination of serotonin

Serotonin (5-HT) is an important neurochemical that is present in high concentrations within the intestinal tract. Carbon fibre and boron-doped diamond based electrodes have been widely used to date for monitoring 5-HT, however these electrodes are prone to fouling and are difficult to fabricate in certain sizes and geometries. Carbon nanotubes have shown potential as a suitable material for electroanalytical monitoring of 5-HT but can be difficult to manipulate into a suitable form. The fabrication of composite electrodes is an approach that can shape conductive materials into practical electrode geometries suitable for biological environments. This work investigated how compression of multiwall carbon nanotubes (MWCNTs) epoxy composite electrodes can influence their electroanalytical performance. Highly compressed composite electrodes displayed significant improvements in their electrochemical properties along with decreased internal and charge transfer resistance, reproducible behaviour and improved batch to batch variability when compared to non-compressed composite electrodes. Compression of MWCNT epoxy composite electrodes resulted in an increased current response for potassium ferricyanide, ruthenium hexaammine and dopamine, by preferentially removing the epoxy during compression and increasing the electrochemical active surface of the final electrode. For the detection of serotonin, compressed electrodes have a lower limit of detection and improved sensitivity compared to non-compressed electrodes. Fouling studies were carried out in 10μM serotonin where the MWCNT compressed electrodes were shown to be less prone to fouling than non-compressed electrodes. This work indicates that the compression of MWCNT carbon-epoxy can result in a highly conductive material that can be moulded to various geometries, thus providing scope for electroanalytical measurements and the production of a wide range of analytical devices for a variety of systems.

Array of peptide-modified electrodes for the simultaneous determination of Pb(II), Cd(II) and Zn(II)

This paper reports the development of three peptide modified sensors in which glutathione (GSH) and its fragments Cys–Gly and γ-Glu–Cys were immobilized respectively through aryl diazonium electrochemical grafting onto the surface of graphite–epoxy composite electrodes (GEC), and used for the simultaneous determination of Cd(II), Pb(II) and Zn(II). The concentration interval ranged from 0.1 to 1.5μmolL−1 for each metal, and the technique used was differential pulse adsorptive stripping voltammetry. This study aimed to the comparison of the information provided by one single modified electrode at both fixed and multiple pH values (pH 6.8, 7.5 and 8.2) for the simultaneous determination of the three metals, with those supplied by the three-sensor array at multiple pH values. For the processing of the voltammograms, the fast Fourier transform was selected as the preprocessing tool for data compression coupled with an artificial neural network for the modeling of the obtained responses.

Electrochemical detection of sulphide in water/seawater using nanostructured carbon–epoxy composite electrodes

Detection results obtained for sulphide detection in real water using a CNF electrode by square-wave voltammetry.

Signal amplification for thrombin impedimetric aptasensor: Sandwich protocol and use of gold-streptavidin nanoparticles

In this work, we report a highly specific amplification strategy demonstrated for the ultrasensitive biosensing of thrombin with the use of gold-streptavidin nanoparticles (strep-AuNPs) and silver reduction enhancement. The biotinylated aptamer of thrombin was immobilized onto an avidin-graphite epoxy composite (AvGEC) electrode surface by affinity interaction between biotin and avidin; electrochemical impedance measurements were performed in a solution containing the redox marker ferrocyanide/ferricyanide. The change in interfacial charge transfer resistance (Rct) experimented by the redox marker, was recorded to confirm aptamer complex formation with target protein, thrombin (Thr), in a label-free first stage. A biotinylated second thrombin aptamer, with complementary recognition properties was then used in a sandwich approach. The addition of strep-AuNPs and silver enhancement treatment led to a further increment of Rct thus obtaining significant signal amplification. The AptThrBio1-Thr-AptThrBio2 sandwich formation was inspected by confocal microcopy after incubation with streptavidin quantum dots. In order to visualize the presence of gold nanoparticles, the same silver enhancement treatment was applied to electrodes already modified with the nanoparticle-sandwich conjugate, allowing direct observation by scanning electron microscopy (SEM). Results showed high sensitivity and selectivity for thrombin detection, with an improvement from ca. 4.7pM in a simple assay to 0.3pM in the amplified reported scheme.

Graphene–epoxy composite electrode fabricated by in situ polycondensation for enhanced amperometric detection in capillary electrophoresis

This report describes the development and application of a novel graphene–epoxy composite electrode as a sensitive amperometric detector of capillary electrophoresis. The composite electrode was fabricated on the basis of the in situ polycondensation of a mixture of graphene and 1,2-ethanediamine-containing bisphenol A epoxy resin in the inner bore of a piece of fused silica capillary under heat. The structure of the material was investigated by scanning electron microscopy, thermogravimetric analysis, X-ray diffraction, and Fourier transform infrared spectroscopy. The results indicated that graphene sheets were well dispersed and interconnected throughout the composite to form an electrically conductive network. The performance of this unique electrode was demonstrated by separating and detecting two naturally occurring phenolic compounds in rosemary in combination with capillary electrophoresis. The graphene-based detector offered significantly lower operating potentials, higher sensitivity, satisfactory resistance to surface fouling, and lower expense of operation, indicating great promise for a wide range of applications.

Use of non-native phenazines to improve the performance of Pseudomonas aeruginosa MTCC 2474 catalysed fuel cells

One of the bottlenecks to performance of microbial fuel cells (MFC) has been the low electron transfer from bacterial cell membrane or membrane organelle to anode. In this study, the effect of phenazines, a class of secondary metabolites was examined on the power generation in Pseudomonas aeruginosa MTCC 2474 catalysed MFC with graphite electrodes. Different metal salt-doped graphite epoxy composite electrodes (MS-GECE) were tested in phenazine supplemented MFC. With Cu2+-GECE as anode in oxychloraphin and tubermycin supplemented MFC, power density generated was 7831±112.5 and 2096.5±11.8μW/m2 respectively. However, the addition of native phenazines (pyocyanin and pyorubin) which are normally produced by the bacteria was not very helpful in performance of the MFC. Also, the addition of these phenazines inhibited the growth of bacteria as well. Thus, choice of an appropriate secondary metabolite can have a positive influence as a mediator of electron transfer in the working of MFCs.

Biotin determination in food supplements by an electrochemical magneto biosensor

An electrochemical magneto biosensor for the rapid determination of biotin in food samples is reported. The affinity reaction was performed on streptavidin-modified magnetic microbeads as a solid support in a direct competitive format. The biotinylated horseradish peroxidase enzyme (biotin-HRP) competes with free biotin in the sample for the binding sites of streptavidin on the magnetic microbeads. The modified magnetic beads were then easily captured by a magneto graphite–epoxy composite electrode and the electrochemical signal was based on the enzymatic activity of the HRP enzyme under the addition of H2O2 as the substrate and o-phenilendiamine as cosubstrate. The response was electrochemically detected by square wave voltammetry. The limit of detection was 8.4×10−8molL−−1 of biotin (20μgL−−1) with a dynamic range from 0.94 to 2.4×10−7molL−−1. Biotin-fortified commercial dietary supplement and infant formula samples were evaluated obtaining good performances in the results. Total time of analysis was 40min per 20 assays.

Reproducible Fabrication of Robust, Renewable Vertically Aligned Multiwalled Carbon Nanotube/Epoxy Composite Electrodes

We describe the reproducible fabrication of robust, vertically aligned multiwalled carbon nanotube (VACNT)/epoxy composite electrodes. The electrodes are characterized by cyclic voltammetry, impedance spectroscopy, and scanning electron and atomic force microscopies. Low background currents are obtained at the electrodes, and common redox probe molecules and NADH show excellent voltammetric behavior. When electrode performance deteriorates due to fouling, the electrode surfaces can be reproducibly renewed by mechanical polishing followed by O(2) plasma treatment. The electrochemical performance of the electrodes is maintained after more than 100 cycles of use and renewal.