Low Background Current Research Articles

Electron Cyclotron Resonance-Sputtered Nanocarbon Film Electrode Compared with Diamond-Like Carbon and Glassy Carbon Electrodes as Regards Electrochemical Properties and Biomolecule Adsorption

The electrochemical properties and biocompatible characteristics at an electron cyclotron resonance (ECR)-sputtered nanocarbon film electrode, a diamond-like carbon (DLC) electrode and a glassy carbon (GC) electrode have been studied. The three carbon electrodes show significant current reductions with increased peak separations as a result of protein fouling before oxygen plasma treatment, but the current reductions of the ECR-sputtered nanocarbon and DLC film electrodes are smaller than that of the GC electrode due to their superior surface flatness. The oxygen plasma pretreated ECR-sputtered nanocarbon film electrode exhibits a significant improvement in anti-fouling performance with an improved electron transfer. This is because the pretreated ECR-sputtered nanocarbon film enabled the surface to introduce surface oxygen functionalities that not only improve the interaction between the analytes and the electrode surface but also make the film surface more hydrophilic, which is important for the suppression of biomolecule adsorption. At the same time, the pretreated ECR-sputtered nanocarbon film also retained an ultraflat surface even after pretreatment as a result of the low background current. This excellent performance can only be achieved with our ECR-sputtered nanocarbon film, indicating that our film is promising for application to electrochemical detectors for various biomolecular analytes.

Sensitive Determination of (−)-Epigallocatechin Gallate in Tea Infusion Using a Novel Ionic Liquid Carbon Paste Electrode

This paper investigates the electrocatalytic oxidation of (-)-epigallocatechin gallate (EGCG), the main monomer flavanol found in green tea, with a novel ionic liquid, n-octylpyridinium hexafluorophosphate (OPFP) carbon paste electrode (CPE). Due to the natural viscosity and high conductivity of OPFP, this novel OPFP-CPE exhibited very attractive properties, such as high stability and electrochemical reactivity, low background current, and wide electrochemical window. Therefore, this electrode is a very good alternative to traditional chemically modified electrodes because the electrocatalytic effect can achieved without any further electrode modification. Comparative experiments were carried out using CPE and a glassy carbon electrode (GCE). With OPFP-CPE, highly reproducible and well-defined cyclic voltammograms were obtained for EGCG. Under optimal experimental conditions, the peak current of differential pulse voltammetry (DPV) response increased linearly with EGCG concentration over the range of 5.0 × 10(-7)-1.25 × 10(-5) M. The limit of detection (LOD) and the limit of quantification (LOQ) were 1.32 × 10(-7) and 4.35 × 10(-7) M, respectively. The method was applied to the determination of EGCG in green tea infusion samples, and the recovery of the spiked EGCG to the diluted (10-fold) tea extract was from 87.62 to 99.51%.

Nickel nano-particle modified nitrogen-doped amorphous hydrogenated diamond-like carbon film for glucose sensing

Electrochemical method has been employed in this work to modify nitrogen-doped hydrogen amorphous diamond-like carbon (N-DLC) film to fabricate nickel nano-particle-modified N-DLC electrodes. The electrochemical behavior of the nickel nano-particle-modified N-DLC electrodes has been characterized at the presence of glucose in electrolyte. Meanwhile, the N-DLC film structure and the morphology of metal nano-particles on the N-DLC surface have been investigated using micro-Raman spectroscopy and atomic force microscopy. The nickel nano-particle-modified N-DLC electrode exhibits a high catalytic activity and low background current. This result shows that the nickel nano-particle deposition on N-DLC surface could be a promising method to fabricate novel electrode materials for glucose sensing.

Electrochemical Biosensor Based on Boron-Doped Diamond Electrodes with Modified Surfaces

Boron-doped diamond (BDD) thin films, as one kind of electrode materials, are superior to conventional carbon-based materials including carbon paste, porous carbon, glassy carbon (GC), carbon nanotubes in terms of high stability, wide potential window, low background current, and good biocompatibility. Electrochemical biosensor based on BDD electrodes have attracted extensive interests due to the superior properties of BDD electrodes and the merits of biosensors, such as specificity, sensitivity, and fast response. Electrochemical reactions perform at the interface between electrolyte solutions and the electrodes surfaces, so the surface structures and properties of the BDD electrodes are important for electrochemical detection. In this paper, the recent advances of BDD electrodes with different surfaces including nanostructured surface and chemically modified surface, for the construction of various electrochemical biosensors, were described.

An electrochemical aptasensor based on enzyme linked aptamer assay

An aptamer is an artificial functional oligonucleic acid, which can interact with its target molecule with high affinity and specificity. Enzyme linked aptamer assay (ELAA) is developed to detect cocaine using aptamer fragment/cocaine configuration based on the affinity interaction between aptamer fragments with cocaine. The aptasensor was constructed by cleaving anticocaine aptamer into two fragments: one was assembled on a gold electrode surface, while the other was modified with biotin at 3′-end, which could be further labelled with streptavidin-horseradish peroxidase (SA-HRP). Upon binding with cocaine, the HRP-labelled aptamer fragment/cocaine complex formed on the electrode would increase the reduction current of hydroquinone (HQ) in the presence of H2O2. The sensitivity and the specificity of the proposed electrochemical aptasensor were investigated by differential pulse voltammetry (DPV). The results indicated that the DPV signal change could be used to sensitively detect cocaine with the dynamic range from 0.1μM to 50μM and the detection limit down to 20nM (S/N=3). The proposed aptasensor has the advantages of high sensitivity and low background current. Furthermore, a new configuration for ELAA requiring only a single aptamer sequence is constructed, which can be generalized for detecting different kinds of targets by cleaving the aptamers into two suitable segments.

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.

Fabrication of Tiron Doped Poly-Pyrrole/Carbon Nanotubes on Low Resistance Monolayer-Modified Glassy Carbon Electrode for Selective Determination of Dopamine

In this paper, we described a novel sensor based on tiron-doped polypyrrole and carbon nanotubes (CNTs) fabricated on low resistance monolayer-modified glassy carbon electrode. First, the dodecylamine monolayer was chemically modified. Second, CNTs were controllably adsorbed onto dodecylamine. Then, tiron doped polypyrrole was electro-deposited on the CNTs film. The layer-by-layer modified electrode was sensitive to dopamine, while it made no response to even high concentration of ascorbic acid. Parameters influencing the dopamine response were optimized. High performance of the sensor was obtained, such as wide concentration range, low detection limit (3 nM), low background current, high stability, and reproducibility.

Electrochemical sensor for monitoring the photodegradation of catechol based on DNA-modified graphene oxide

We have immobilized DNA on a glassy carbon electrode (GCE) modified with graphene oxide (GO) to develop an electrochemical biosensor for catechol. Compared to carbon nanotubes, the use of GO dramatically improved the electrooxidative current of the guanine and adenine moieties in DNA but retained the low background current of unmodified GCEs. Factors such as DNA adsorption time, DNA concentration and pH of solution were investigated to optimize experimental conditions. In the presence of catechol, the voltammetric response to DNA was inhibited due to the interaction between DNA and catechol. The response to adenine is linearly proportional to the concentration of catechol in the range from 1.0 × 10−6 to 1.0 × 10−4 mol·L−1. If catechol is degraded by the combined action of UV light and hydrogen peroxide, the response to DNA is restored. Thus, the modified electrode can act as an efficient biosensor for monitoring the degradation of catechol.

PH sensing using boron doped diamond electrodes

The boron doped diamond (BDD) electrode is presented as an appropriate candidate for next generation glass-free, highly stable and accurate pH sensors. The method used in this study is based on the potential change related to the hydrogen evolution reaction following a current step, which is pH dependent. Alkali cations in the solution have no influence on the accuracy of the pH calibration curve, which provides an advantage with respect to the conventional pH glass electrode. The unwanted influence of electrochemically active compounds in solution can be avoided by adjusting the current density applied during chronopotentiometric measurements. The accuracy of the pH measurements is due to the excellent stability as well as the wide potential window and low background current of BDD electrodes. This faculty was not observed when using conventional electrode materials. The efficacy of this new type of pH sensor has been tested using tap water as a typical real sample.

Vertically aligned carbon nanofiber electrode arrays for nucleic acid detection

We present electrochemical detection of DNA targets that corresponds to Escherichia coli O157:H7 16S rRNA gene using a nanoelectrode array consisting of vertically aligned carbon nanofiber (VACNF) electrodes. Parylene C is used as gap filling ‘matrix’ material to avoid high temperature processing in electrode construction. This easy to deposit film of several micron heights provides a conformal coating between the high aspect ratio VACNFs with negligible pin-holes. The low background currents show the potential of this approach for ultra-sensitive detection. Consistent and reproducible electrochemical-signals are achieved using a simple electrode preparation. This simple, reliable and low-cost approach is a forward step in developing practical sensors for applications like pathogen detection, early cancer diagnosis and environmental monitoring.

Pt-polyaniline nanocomposite on boron-doped diamond electrode for amperometic biosensor with low detection limit

Boron-doped diamond electrodes covered with a nanostructured Pt nanoparticle-polyaniline composite have been fabricated and employed as sensitive amperometric sensors with low detection limit. A highly conductive boron-doped diamond thin film (BDD) was prepared by chemical vapor deposition, and its morphology was characterized by scanning electron microscopy and transmission electron microscopy. The nanostructured composite layer was grown on the BDD electrode by electrochemical deposition of polyaniline and Pt nanoparticles. Glucose oxidase (GOx) was then adsorptively immobilized on the modified BDD electrode. The biosensor displays a large surface area, high catalytic activity of the Pt nanoparticles, efficient electron mediation through the conducting polymer, and low background current of the electrode. The biosensor exhibits an excellent response to glucose, with a broad linear range from 5.9 μM to 0.51 mM, a sensitivity of 5.5 μA·mM−1, a correlation coefficient (R) of 0.9947, and a detection limit of 0.10 μM. The apparent Michaelis-Menten constant (KMapp) and the maximum current density of the electrode are 4.1 mM and 0.021 mA, respectively. This suggests that the immobilized GOx possesses a higher affinity for glucose at the lower KMapp, and that the enzymatic reaction rate constitutes the rate-limiting step of the response.

Ionic liquid–graphene composite for ultratrace explosive trinitrotoluene detection

A new ionic liquid (IL)–graphene composite prepared by combining IL and a three-dimensional graphene material with large specific surface area and pronounced mesoporosity was used for ultratrace trinitrotoluene detection, showing low background current, high sensitivity of 1.65 μA cm − 2 per ppb, low detection limit of 0.5 ppb and good reproducibility, which is much superior to that demonstrated by the IL–CNT and IL–graphite composites. The preparation of IL–graphene composite expands the scope of IL-based electrochemical devices.

Fast coating of ultramicroelectrodes with boron-doped nanocrystalline diamond

The present work is focused on the deposition of thin boron-doped nanocrystalline diamond (B-NCD) films on electrochemically etched tungsten wires by the hot filament assisted CVD method. The goal is the manufacturing of robust inert ultramicroelectrodes (UMEs) with a superior performance to be used for localised electrochemical analysis. The conductive diamond films can confer high stability of chemical and physical properties as well as low background current. Filament and substrate temperatures were kept constant at 2350 °C and 670 °C, respectively. The total system pressure was equal to 50 mbar and the CH 4/H 2 gas flow ratio was 0.07. Boron was used as the doping agent by solving B 2O 3 in ethanol, with a B/C content of 15000 ppm, and the solution was then dragged with argon gas flowing through a bubbler. The (Ar+B)/H 2 ratio values varied within the range of 0.06–0.21. The film growth rate decreases with the boron content increasing, but larger (Ar+B)/H 2 ratios result in smoother surfaces. UMEs insulation was carried out with epoxy resin in a home built device. The production of very sharp tungsten tips fully coated with B-NCD after just 30 min, for a (Ar+B)/H 2 ratio of 0.21, is one of the main outcomes of this work. The cyclic voltammetry showed a stable behavior with a wide electrochemical window of ~ 2.25 V in a 0.05 M NaCl solution proving the applicability of the developed UME for localized electroanalytical studies in biomedical and corrosion applications.

Potential‐driven peptide extractions across supported liquid membranes: Investigation of principal operational parameters

Fundamental experiments on electromembrane extraction were performed to increase the basic knowledge about the current and the mass transfer of target peptides and background electrolyte ions. Three peptides (angiotensin 2, bradykinin, and enkephalin) were extracted from 500 microL aqueous donor solution (1 mM HCl, positive electrode), through a 200 microm supported liquid membrane (SLM) of 1-octanol/di-isobutylketon/di-(2-ethylhexyl) phosphate (55:35:10 w/w/w) sustained in the pores of a porous hollow fiber, and into 25 microL aqueous acceptor solution (50 mM HCl, negative electrode) present inside the lumen of the fiber by the application of an electrical potential (50 V) and agitation (1050 rpm). Recoveries were typically in the range of 55-65% after 5 min of extraction and were principally determined by the chemical composition of the SLM and by the applied voltage. The electrical current in the system was measured during the extraction and was close to 350 microA. The current arose to some extent from mass transfer of the target peptides, but the major contribution was due to a background current from di-(2-ethylhexyl) phosphate in the SLM and from mass transfer of background electrolytes. Operation at relatively low background current was important to maintain a stable system.

Design and Characterization of Liquid Crystal−Graphite Composite Electrodes

Thermotropic ionic liquid crystals (ILCs), 1,1′-dialkyl-4,4′-bipyridinium bis(triflimide)s have been used as binders to fabricate new carbon composite electrodes. ILC compounds possess an ordered molecular orientation, and upon mixing with graphite, ILCs retain their liquid crystal characteristics and thus their ordered arrangement. The electrochemical performances of these composite electrodes were evaluated by using different electrochemical probes. The resulting electrodes offer high electrochemical reactivity, low background current, improved signal-to-noise ratio, greater stability, excellent mechanical strength, and very good antifouling effects. It is believed that the higher conductivity of ILCs as well as the ordered orientation of these thermotropic ILCs which cause an increase in the edge-plane sites of these composite electrodes are responsible for the promotion of their electrocatalytic activities and antifouling effects. Such characteristics make these composite electrodes ideal for use in d...

Strategies for the optimization of carbon nanotube/polymer ratio in composite materials: Applications as voltammetric sensors

Multiwall carbon nanotubes and resin epoxy have been used to fabricate a composite electrode for electroanalytical purposes. The optimum composite proportions for high electrode sensitivity, low limit of detection and fast response were investigated. Compositions were characterized by percolation theory, electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, atomic force microscopy and chronoamperometry. We found that around the optimum composite proportion, the electrode performance is less affected by small variations in the composition of the composite. These composite electrodes provide easy surface renewal, low background current, an efficient mass transport and are suitable for chemical modification. The potentiality of this approach in terms of electroanalytical response is demonstrated by means of the amperometric detection of ascorbic acid in water solution.

Microelectrode-array of IrO 2 prepared by thermal treatment of pure Ir

In this paper, the IrO 2 electrode preparation technique consisting in thermal treatment of pure Ir in air was used in order to produce an IrO 2-based microelectrode-array (TOIROF-MEA) with low capacitive background current. The TOIROF-MEA was characterized using Fe ( CN ) 6 4 - / 3 - as model redox couple. It was found that very low concentrations can be detected; this feature makes TOIROF-MEA suitable for analytical applications.

Ultrasensitive Detection of DNA in Diluted Serum Using NaBH4 Electrooxidation Mediated by [Ru(NH3)6]3+ at Indium−Tin Oxide Electrodes

There is a crucial need for simple and highly sensitive techniques to detect DNA in complicated biological samples such as serum. Here we present an ultrasensitive electrochemical DNA sensor using (i) single DNA hybridization with peptide nucleic acid (PNA), (ii) selective binding of [Ru(NH(3))(6)](3+) to hybridized DNA, (iii) fast NaBH(4) electrooxidation mediated by [Ru(NH(3))(6)](3+), and (iv) low background currents of NaBH(4) at indium-tin oxide (ITO) electrodes. The [Ru(III)(NH(3))(5)NH(2)](2+) formed from [Ru(III)(NH(3))(6)](3+) in borate buffer (pH 11.0) is readily electrooxidized to both [Ru(IV)(NH(3))(5)NH(2)](3+) and Ru complex with a higher oxidation state. In the absence of [Ru(NH(3))(6)](3+) bound to the DNA-sensing ITO electrodes, the oxidation currents of NaBH(4) are very low. However, in the presence of [Ru(NH(3))(6)](3+), the oxidation currents of NaBH(4) are highly enhanced due to electron mediation of the oxidized Ru complexes. The significant enhancement in the electrocatalytic activity of sensing electrodes after [Ru(NH(3))(6)](3+) binding facilitates to obtain high signal-to-background ratios. PNA and ethylenediamine on DNA-sensing electrodes significantly decrease [Ru(NH(3))(6)](3+) binding, also allowing for high signal-to-background ratios. The oxidation charges of NaBH(4) obtained from chronocoulometry are highly reproducible. All combined effects enable the detection of DNA with a detection limit of 1 fM in ten-fold diluted human serum. The simple and fast detection procedure and the ultrasensitivity make this approach highly promising for practical DNA detection.

Boron-Doped Diamond Microelectrodes Reveal Reduced Serotonin Uptake Rates in Lymphocytes from Adult Rhesus Monkeys Carrying the Short Allele of the 5-HTTLPR

Uptake resolved by high-speed chronoamperometry on a second-by-second basis has revealed important differences in brain serotonin transporter function associated with genetic variability. Here, we use chronoamperometry to investigate variations in serotonin transport in primary lymphocytes associated with the rhesus serotonin transporter gene-linked polymorphism (rh5-HTTLPR), a promoter polymorphism whose orthologs occur only in higher order primates including humans. Serotonin clearance by lymphocytes is Na(+)-dependent and inhibited by the serotonin-selective reuptake inhibitor paroxetine (Paxil®), indicative of active uptake by serotonin transporters. Moreover, reductions in serotonin uptake rates are evident in lymphocytes from monkeys with one or two copies of the short 's' allele of the rh5-HTTLPR (s/s<s/l<l/l). These findings illustrate that rh5-HTTLPR-related alterations in serotonin uptake are present during adulthood in peripheral blood cells natively expressing serotonin transporters. Moreover, they suggest that lymphocytes can be used as peripheral biomarkers for investigating genetic or pharmacologic alterations in serotonin transporter function. Use of boron-doped diamond microelectrodes for measuring serotonin uptake, in contrast to carbon fiber microelectrodes used previously in the brain, enabled these high-sensitivity and high-resolution measurements. Boron-doped diamond microelectrodes show excellent signal-to-noise and signal-to-background ratios due mainly to low background currents and are highly resistant to fouling when exposed to lymphocytes or high concentrations of serotonin.

Preparation of a sol–gel-derived carbon nanotube ceramic electrode by microwave irradiation and its application for the determination of adenine and guanine

In this study, microwave irradiation was used for the fast preparation (min) of a sol–gel-derived carbon nanotube ceramic electrode (MW-CNCE). For confirmation of the preparation of the ceramic by MW irradiation, Fourier transform infrared, X-ray diffraction spectra and scanning electron microscopy images of the produced ceramic were compared with those of conventional ceramic (which is produced by drying the ceramic in air for 48 h). The electrochemical behavior of MW-CNCE in nicotinamide adenine dinucleotide, l-cysteine, adenine and guanine was compared with that of a conventional sol–gel-derived carbon nanotube ceramic electrode (CNCE). In all systems, similar peak potentials and lower background currents were obtained with respect to CNCE. Finally, the MW-CNCE was used for the simultaneous determination of adenine and guanine using differential pulse voltammetry. The linear ranges of 0.1–10 and 0.1–20 μM were obtained for adenine and guanine, respectively. These results are comparable with some modified electrodes that have recently been reported for the determination of adenine and guanine, with the advantage that the proposed electrode did not contain modifier. In addition, the proposed electrode was successfully used for the oxidation of adenine and guanine in DNA, and the detection limit for this measurement was 0.05 μg mL −1 DNA.