Improvement of alternariol monomethyl ether detection at gold electrodes modified with a dodecanethiol self-assembled monolayer

The electro-oxidation of alternariol monomethyl ether (AME), one of the main metabolites of the Alternaria genus mycotoxins, is studied at 1-dodecanethiol (DDT)-modified gold electrodes, in acetonitrile (ACN) – aqueous phosphate buffer solutions of different pH values, by using cyclic (CV) and square-wave (SWV) voltammetries. The AME voltammetric response at the bare electrode suffers from two drawbacks: it appears at potentials close to the onset of gold oxide formation, and it is hampered by a fouling of the electrode surface due to the accumulation of oxidized products. These shortcomings are circumvented by the use of DDT-coated electrodes, since the intervening monolayer inhibits gold oxide formation and surface passivation by the electrochemical products, without affecting the oxidation kinetics of AME significantly. Diagnostic criteria based on the voltammetric peak parameters show that the electrochemical behavior of AME at the modified electrode is mainly controlled by reactant diffusion from solution, with a weak adsorption of both the mycotoxin and its oxidation products at monolayer defects. Calibration curves were constructed from the AME square-wave voltammetric response and a detection limit of 9.1 × 10⁻⁸ mol dm⁻³ was determined, which is about three times smaller than a previous estimate at platinum and glassy carbon electrodes, and about fifty times smaller than the limit derived from measurements carried out at a polyphenol oxidase-modified carbon paste electrode.     

Stacked graphene nanofibers doped polypyrrole nanocomposites for electrochemical sensing

This publication shows a single-step electropolymerization which has been carried out by the incorporation of an anionic stacked graphene nanofiber (SGNF) dopant into a polypyrrole (PPy) film, at a disposable screen-printed electrode. The incorporation of the SGNFs into the polymer does not affect their electrochemical properties, shown through cyclic voltammetry by the earlier oxidation of guanine, when compared with that at the graphite doped PPy electrode. The SGNF/PPy composite shows a high selectivity when used in the oxidation of guanine and hydrogen peroxide, both of which are important biomarkers used for biosensing. Disposable screen-printed electrodes provide an inexpensive, sensitive and portable substitute to glassy carbon electrodes, while giving a reproducible surface; qualities essential for effective bionsensing. The production of this single-step disposable SGNF/PPy composite electrode allows for further applications in the detection of biomedically important compounds and DNA sensing.     

Use of disposable gold working electrodes for cation chromatography-integrated pulsed amperometric detection of sulfur-containing amino acids

We have prepared disposable thin-film gold working electrodes on polymeric substrates. Our microfabrication process allows for inexpensive and reproducible mass production of such electrodes. We utilize this new type of electrode in flow-through electrochemical cells to replace the conventional non-disposable gold working electrodes for integrated pulsed amperometric detection (IPAD) of compounds separated by high-performance cation-exchange chromatography. Using two S-containing amino acids (homocysteine and cysteine) as test compounds, we have modified a previously reported waveform for optimum performance with disposable gold electrodes. With the help of the same two test substances we have characterized the analytical performance of disposable gold electrodes under the new conditions. Compared to non-disposable working electrodes, the disposable working electrodes generated equal or better results in the limit of detection, linearity of calibration and reproducibility. When used with a new IPAD waveform, the disposable electrodes functioned reproducibly for 3 days. At the end of the specified usage period of 3 days, the disposable electrodes are simply replaced. Reconditioning by polishing is thus no longer required.     

Disposable Gold Electrode Array for Simultaneous Electrochemical Studies

An efficient and inexpensive eight gold electrode array has been manufactured by a combination of screen printing and gold electrodeposition techniques. Gold electrodeposition was performed in potentiostatic and galvanostatic conditions. Different treatments, involving temperature and polishing control, led to electrodes with different roughness. The electrochemical behavior of the generated gold surface was studied by cyclic voltammetry showing the characteristic response of polycrystalline gold, in contrast with disposable gold electrodes fabricated by screen printing from gold inks. The electrodes were chemically modified through the adsorption of alkanethiols self‐assembled monolayers and the coupling of a model protein. Both reactions were followed by cyclic voltammetry and Electrochemical Impedance Spectroscopy (EIS). The electrodes have shown high reproducibility in their electrochemical behavior as well as in their modifications.     

Open‐circuit Electrochemical Polymerization for the Sensitive Detection of Phenols

We report on a novel electrochemical method for electro‐polymerizing phenols under open‐circuit conditions. The method developed here is simple, sensitive, rapid, and overcomes the well‐documented surface fouling of carbon electrodes by phenols. A pre‐charged disposable graphite pencil electrode (pCGPE) was found to be useful for both phenol sampling and sensing. The pCGPE was prepared by charging the surface of a graphite pencil electrode by applying a cyclic voltammetry electrochemical treatment in a NaOH solution. Phenol sampling was accomplished by immersing the pCGPE into a phenol solution. This method permitted phenol detection with a detection limit of 4.17 nM (0.39 ppt).     

A novel Au–Ag–Pt three-electrode microchip sensing platform for chromium(VI) determination

A simple, rapid and portable electrochemical microchip sensing platform has been successfully constructed for chromium(VI) determination. Gold–silver–platinum (Au–Ag–Pt) three-material electrodes (gold as working electrode, silver as reference electrode and platinum as counter electrode) were integrated on one poly(methyl methacrylate) (PMMA) substrate by polymer compatible photolithography process. The three-electrode microchip sensing platform was used for Cr(VI) determination for the first time, and exhibited high sensitivity and good reproducibility. A wide linear range from 2 to 200 μM with a good linear correlation (R² = 0.998) was obtained, and the detection limit was 0.9 μM. In addition, the practical analytical application of the sensing micro-platform was assessed by determination of Cr(VI) in real water samples with satisfactory results. Armed with the remarkable advantages, such as ease of use, low analyte consumption, inexpensive cost and fast response time, the microchip sensing platform may hold great potential for the high-throughput and in-field environmental monitoring Cr(VI) pollutant.     

Facilitated electrochemical oxidation of NADH and its model compound at gold electrode modified with terminally substituted electroinactive self-assembled monolayers

The electrochemical oxidation of NADH and its model compound, N-benzyl-1,4-dihydronicotinamide (DHN), has been studied at gold electrode modified with self-assembled monolayer of terminally substituted thiols/disulfide, i.e., cystamine (CYST), mercaptopropionic acid (MPA) and mercaptoethanol (ME). A substantial decrease in the overpotential (approximately 250 mV) when compared to the bare electrode has been observed for the oxidation of NADH at the monolayer-modified electrodes, containing no so-called redox mediator. The bare electrode shows an ill-defined voltammetric peak for the oxidation of DHN, whereas the monolayer-modified electrodes showed a well-defined voltammetric peak. The monolayer assembly on the gold electrode prevents the fouling of electrode surface by the oxidation products, which favors the oxidation at the less positive potential. The square-wave voltammograms showed a sharp voltammetric signal for the oxidation of NADH at all the monolayer-modified electrodes. All the monolayer-modified electrodes showed a linear current response to change in the NADH concentration in its range of 25-300 microM and their sensitivities were found to be 0.005+/-0.0003, 0.0063+/-0.0002 and 0.0052+/-0.0003 microA/microM for CYST-Au, ME-Au and MPA-Au electrodes, respectively. The hydrodynamic voltammograms obtained at the rotating CYST-Au electrode for the oxidation of NADH and DHN were used to estimate the diffusion coefficient of DHN, and the number of electrons involved in the oxidation process of NADH.     

Electrochemical sensing of silver tags labelled DNA immobilized onto disposable graphite electrodes

An electrochemical approach for the improved electrochemical sensing of DNA was developed in this study based on the oxidation signals of silver and DNA base, guanine by using disposable pencil graphite electrode (PGE) electrodes. The easy surface modification of disposable electrodes PGEs with nucleic acids was performed by passive adsorption using amino linked DNA oligonucleotide attached onto the surface of silver nanoparticles (Ag-NPs). Firstly, the microscopic characterization of silver nanoparticles was investigated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), and the electrochemical behaviour of these NPs was studied by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. Then, the overall performance of this novel electrochemical DNA sensing method based on these nanoparticles is studied and discussed in terms of optimum analytical conditions, such as; the effect of DNA concentration, NPs concentration and different buffer solutions, etc. in order to obtain silver and guanine oxidation signals in higher sensitivity and selectivity. The main features related with this electrochemical assay based on silver nanoparticles are discussed and compared with other assays reported in the literatures.     

Electrodeposition of dendritic gold/silver nanaoparticles on disposable screen‐printed carbon electrode and its application of 4‐mercaptopyridine in in situ electrochemical surface‐enhanced Raman scattering

Column electrodes pretreated through oxidation–reduction cycles were traditionally used in electrochemical surface‐enhanced Raman scattering (SERS). In this study, a disposable screen‐printed carbon electrode was introduced into in situ electrochemical SERS through the electrodeposition of dendritic gold/silver nanoparticles (Au/AgNPs) onto the surface of the carbon working electrode to induce the SERS enhancement effect on the electrode. Scanning electron microscopy images showed that dendritic Au/AgNPs nanostructures could be fabricated under appropriate electrodeposition conditions and could present a minimum SERS factor of 4.25 × 10⁵. Furthermore, the absorbed behavior of 4‐mercaptopyridine was investigated under different potentials. The adsorption configuration was inferred to transform from ‘vertical’ to ‘lying‐flat’. The proposed new electrode combined with a portable Raman spectrometer could be useful in the identifying products or intermediates during electrochemical synthesis or electrochemical catalysis in in situ electrochemical SERS. Copyright © 2016 John Wiley & Sons, Ltd.     

Incorporation of Disposable Screen‐Printed Electrodes for Use in Capillary Electrophoresis End‐Column Amperometric Detection System

The development and performance of an end‐column amperometric detection system integrated with disposable screen‐printed electrodes for capillary electrophoresis is presented. In this system, the electrode and capillary can be easily replaced and the capillary/electrode alignment procedure is straightforward. The use of easily replaceable screen‐printed electrodes offers a tremendous benefit for capillary electrophoresis applications requiring frequent replacement of the working electrode due to fouling. This simple and convenient system is very attractive for routine analyses by capillary electrophoresis with electrochemical detection. The separation and determination of uric acid in human urine is presented.     

Disposable paper-based electrochemical sensor based on stacked gold nanoparticles supported carbon nanotubes for the determination of bisphenol A

This work reports a new type of disposable electrochemical sensor for the determination of bisphenol A (BPA). The working electrodes were fabricated by sputtering gold nanoparticles on commercial art paper and then modifying the gold layer with multi-walled carbon nanotubes (MWCNTs). The electrode in their intermediated and final stage was characterized by atomic force microscope, scanning electron microscope and electrochemical techniques. To perform electrochemical analysis, the resulting electrode was integrated with a homemade paper-based analytical device, which could also ensure the immobilization of MWCNTs on the electrode surface without any functionalization. The determination of BPA was investigated by linear sweep voltammetry (LSV). A wide linearity in the range from 0.2 to 20 mg/L with a detection limit of 0.03 mg/L (S/N = 3) was obtained. The between-sensor reproducibility was 5.7% (n = 8) for 0.5 mg/L BPA. The proposed sensor showed good resistance against interferences and was applied to detect BPA leached from real plastic samples with satisfying results. This disposable sensor is readily mass-produced and has been verified to serve as an attractive alternative to screen-printed electrodes for practical applications.     

Novel reagentless paper-based screen-printed electrochemical sensor to detect phosphate

Herein we describe a novel reagentless paper-based electrochemical phosphate sensor, manufactured with a simple and inexpensive approach. By following three easy steps, consisting of wax patterning, paper chemical modification, and electrode screen-printing, the filter paper provides an effective electroanalytical platform to sense phosphate ions in standard solutions and real samples (river water). The electrochemical properties of the paper-based platform were evaluated, firstly, by using ferricyanide as a redox mediator, proving no analyte-entrapment due to the cellulose lattice. Then, the reference colorimetric method for phosphate ions, which is based on the formation of phosphomolybdic complex, was successfully adapted to a reagentless electrochemically paper-based platform. This novel and highly sustainable configuration readily allows for the determination of phosphate ions with high reproducibility and long storage stability, achieving a detection limit of 4 μM over a wide linear range up to 300 μM. This in-house approach would be able to generically develop an affordable in situ and user-friendly sensing device without the addition of any reagent, to be applied for a broad range of analytes.     

A Novel Electrochemical Sensor Based on Poly(1,5-diaminonaphthalene) and Poly(1,2-diaminoanthraquinone) Core-shell Composite Electrodes for Effective Voltammetric Determination of Nitrite

In this article, poly(1,2-diaminoanthraquinone) (pDAAQ) and poly(1,5-diaminonaphthalene) (pDAN) were electrochemically deposited layer by layer on a glassy carbon electrode (GCE) to generate pDAAQ/pDAN@GCE and pDAN/pDAAQ@GCE composite electrodes, respectively. The morphology and characteristics of the modified electrodes were investigated via electrochemical impedance spectroscopy)EIS), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy)SEM). The obtained results reveal the outstanding performance of the pDAN/pDAAQ@GCE electrode for electrochemical nitrite sensing where pDAAQ plays a vital role as the inner layer. Cyclic voltammetry (CV), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV) measurements revealed that the oxidation peak current of nitrite was proportional to its concentration. The best LSV results were obtained in a concentration range of 10–150 μM, with a limit of detection of 1.2 μM. Furthermore, the pDAN/pDAAQ@GCE composite electrode was used to determine nitrite ions in real water samples with good results.     

Disposable Electrochemical Aptasensor for Ultrasensitive Determination of Aflatoxin B1 Using Copper Nanoparticles as Probes

An electrochemical aptasensor for aflatoxin B1 (AFB1) detection was constructed based on the copper nanoparticles (CuNPs) and gold nanoflowers modified screen-printed carbon electrodes as electrochemical probes and substrates, respectively. In the range of 100 aM to 100 pM, a good linear relationship between oxidation peak current of CuNPs and concentration of AFB1 was obtained. The high sensitivity could be ascribed to the amplified electrochemical signals by CuNPs. The high affinity of AFB1 with aptamer endowed its high selectivity. The above advantages and disposable traits made this aptasensor as an ideal platform for evaluation of AFB1 level in food samples.     

Highly selective sensing of dopamine using carbon nanotube ink doped with anionic surfactant modified disposable paper electrode

An unconventional, flexible, disposable paper-based selective sensing platform for dopamine in the presence of ascorbic acid, suitable for wearable electronics, has been described for the first time in this work. The carbon nanotube ink-modified paper (CNIMP) in the presence of an anionic surfactant was able to discriminate effectively between dopamine and ascorbic acid thereby alleviating the difficulties associated with the sensing of dopamine in the presence of high concentration of ascorbic acid which undergoes oxidation at similar potential. The CNIMP electrode provided a large surface area in addition to its flexibility and disposability which was 25 times higher compared to a glassy carbon electrode of the same geometric area. The conductivity of the CNIMP electrodes as measured by four probe conductivity measurements was reasonably high of the order of 1.7 × 10^?2 S cm^?1 facilitating its usefulness for the development of flexible sensors. The microscopic features of the electrodes showed the dense coverage and even distribution of carbon nanotubes on the surface with the surfactant molecules uniformly encapsulated on the surface.     

Dual detection strategy for electrochemical analysis of glucose and nitrite using a partitionally modified electrode

A dual-region modified electrode was designed and fabricated by means of partitioned electrodeposition of gold and platinum nanoparticles on an indium tin oxide (ITO) conductive glass for dual-component electrochemical detection. The two differently modified regions were assigned to detect two analytes, separately and simultaneously. The gold nanoparticle modified ITO region (AuNPs/ITO) was used for glucose detection while the platinum nanoparticle modified ITO region (PtNPs/ITO) for nitrite detection. The glucose oxidation peak current at 0.10 V on AuNPs/ITO exhibited a linear dependence on the concentration of glucose and was used to determine the concentration of glucose in dual-detection. The nitrite reduction peak current at PtNPs/ITO showed a nonlinear dependence on the concentration of nitrite. A theoretical model combining the adsorption-controlled and the mass-transfer-controlled kinetics was proposed to quantitatively describe the nonlinear behavior. Though the presence of glucose interfered with the electrochemical detection of nitrite, it was demonstrated that the influence of glucose on nitrite detection can be corrected. On the basis of the proposed theoretical model, the simultaneous dual-detection of glucose and nitrite was accomplished at ITO electrodes partitionally modified with AuNPs and PtNPs.     

Electrochemical Sensing of Paracetamol Using 3D Porous Laser Scribed Graphene Platform

This work presents a novel disposable electrochemical sensor for paracetamol (PCM). The sensing platform is based on graphene, manufactured via laser-scribing technology (LSG) to produce a 3D-porous structure that offers a large surface area. The analytical performances of LSG electrodes were greatly enhanced due to the high catalytic activity of graphene produced by LSG technology compared to conventional carbon electrodes. Moreover, the results showed an outstanding adsorption feature towards PCM, allowing its detection at nanomolar level from 5 nM to 100 nM through pre-concentration. The proposed sensing strategy was successfully applied for the determination of PCM in human urine samples.     

Electroanalytical sensing of chromium(III) and (VI) utilising gold screen printed macro electrodes

We report the fabrication of gold screen printed macro electrodes which are electrochemically characterised and contrasted to polycrystalline gold macroelectrodes with their potential analytical application towards the sensing of chromium(III) and (VI) critically explored. It is found that while these gold screen printed macro electrodes have electrode kinetics typically one order of magnitude lower than polycrystalline gold macroelectrodes as is measured via a standard redox probe, in terms of analytical sensing, these gold screen printed macro electrodes mimic polycrystalline gold in terms of their analytical performance towards the sensing of chromium(III) and (VI), whilst boasting additional advantages over the macro electrode due to their disposable one-shot nature and the ease of mass production. An additional advantage of these gold screen printed macro electrodes compared to polycrystalline gold is the alleviation of the requirement to potential cycle the latter to form the required gold oxide which aids in the simplification of the analytical protocol. We demonstrate that gold screen printed macro electrodes allow the low micro-molar sensing of chromium(VI) in aqueous solutions over the range 10 to 1600 μM with a limit of detection (3σ) of 4.4 μM. The feasibility of the analytical protocol is also tested through chromium(VI) detection in environmental samples.     

Analytical Application of Pyramidal,Rodlike, and Spherical Gold Nanostructures: Simultaneous Detection of Ascorbic Acid and Uric Acid

Simultaneous detection of ascorbic (AA) and uric acid (UA) is developed at pyramidal (NP), rodlike (NR), and spherical (NS) gold nanostructures, due to their high electrocatalytic activities toward the oxidation of AA and UA. Unlike at bare gold electrode, the fouling resulted from the oxidized product of AA is eliminated at the nanostructured gold electrode. The voltammetric signals of AA and UA are completely separated with a potential difference of 216 mV, 158 mV and 195 mV, respectively, at the pyramidal, rodlike, and spherical gold surfaces. The experimental results reveal that solution pH effects the peak separation of AA and UA, acidic solution is more favorable for the simultaneous determination of AA and UA than neutral one, than alkaline one. The coexistence of a large excess of AA does not interfere with the voltammetric sensing of UA, vice versa. All the three kinds of nanostructured gold electrodes show excellent sensitivity, stability, selectivity, low detection limit, quick response and wide linear range in the repeated detection of AA and UA. The practical utility of the present nanostructured gold electrodes is demonstrating by determining the concentration of AA in fruit juice and UA in urine sample.     

Electorchemical Studies of Cytochrome c on Electodes Modified by Single—Wall Carbon Naotubes

Single-wall carbon nanotubes(SWNTs) modified gold electrodes were prepared by using two different methods.The electrochemical behavior of cytochrome c on the modified gold electrodes was investigated.The first kind of SWNT-modified electrode (noted as SWNT/Au electrode)was prepared by the adsorption of carboxylterminated SWNTs from DMF dispersion on the gold electrode.The oxidatively processed SWNT tips were covalently modified by coupling with amines (AET) to form amide linkage.Via Au-S chemical bonding,the self-assembled monolayer of thiol-unctionalized nanotubes on gold surface was fabricated so as to prepare the others SWNT-modified electrode (noted as SWNT/AET/Au electrode).It was shown from cyclic voltammetry cxperiments that cytochrome c exhibited direct electrochemical responses on the both electrodes, but only the current of controlled diffusion existed on the SWNT/Au electrode while both the currents of controlled diffusion and adsorption of cytochrome c occurred on the SWNT/AET/Au electrode.Photoelastic Modulation Infared Reflection Absorpthion Spectroscopy (PEM-IRRAS) and Quartz Crystal Microbalance (QCM) were employed to verify the adsorption of SWNTs on the gold electrodes.The results proved that SWNTs could enhance the direct electron transfer proecss between the electrodes and redox proteins.