Multilayer structured immunosensor based on a glassy carbon electrode modified with multi-wall carbon nanotubes, polythionine, and gold nanoparticles

An immunosensor for determination of salbutamol was developed. It based on glass carbon electrode (GCE) modified with a conductive multilayer film comprised of multi-wall carbon nanotubes, polythionine and gold nanoparticles. Salbutamol antibody was immobilized on the surface of the modified GCE which then was blocked with bovine serum albumin (BSA). The stepwise self-assembly process of the immunosensor was studied by cyclic voltammetry. The detection scheme is based on competitive binding of salbutamol to the sensor surface whose differential pulse voltammetric signal decreases after competitive binding of the salbutamol-BSA conjugate and free salbutamol to the salbutamol antibody. The sensor responds to salbutamol in 5 to 150 nM concentration range, with a detection limit of 1 nM. This method was applied to the precise and sensitive determination of salbutamol in spiked feed samples.

Electrocatalytic oxidation of hydrazine at a glassy carbon electrode modified with nickel ferrite and multi-walled carbon nanotubes

A hydrothermal technique was used to synthesize nickel ferrite nanoparticles (NF-NPs) deposited on multi-walled carbon nanotubes (MWCNTs). The material was characterized by scanning electron microscopy, energy dispersive spectrometry, and X-ray powder diffraction which showed that the NF-NPs are located on the surface of the carboxylated MWCNTs. The material was used to modify a glassy carbon electrode which then was characterized via cyclic voltammetry, electrochemical impedance spectroscopy, and amperometry. The electrode displays strong electrochemical response to hydrazine. A potential hydrazine sensing scheme is suggested.

Gold nanoparticle-coated multiwall carbon nanotube-modified electrode for electrochemical determination of methyl parathion

We report on an electrochemical sensor for the determination of methyl parathion. It is based on an electrode modified with multi-walled carbon nanotubes that were covered with gold nanoparticles (Au-NPs). The vertically aligned array of MWCNTs on a tantalum substrate was coated with Au-NPs by overhead magnetron sputtering deposition. Scanning and transmission electron microscopy and XRD were used to characterize the Au-NP-MWCNTs composite. Cyclic voltammetry and differential pulse voltammetry were employed to evaluate the suitability of the new electrode for the determination of methyl parathion. Under the optimal conditions, the current response of the electrode to methyl parathion is linear in the range from 0.50 to 16.0 mg mL^-1, with a detection limit of 50 ??g mL^-1 (signal/noise = 3), and the sensitivity is 4.5 times better than that of the plain MWCNTs electrode. We conclude that this method represents a simple, rapid, effective and sensitive approach for the detection of methyl parathion.

Chronocoulometric DNA biosensor based on a glassy carbon electrode modified with gold nanoparticles, poly(dopamine) and carbon nanotubes

We describe a sensitive chronocoulometric biosensor for the sequence-specific detection of DNA. It is based on a glassy carbon electrode modified with multi-walled carbon nanotubes, polydopamine, and gold nanoparticles. The ruthenium(III)hexammine complex acts as the electrochemical indicator. Electrochemical impedance spectra and scanning electron microscopy are employed to investigate the assembly of the electrode surface. The signals of the ruthenium complex electrostatically bound to the anionic phospho groups of the DNA strands are measured by chronocoulometry before and after hybridization. The difference in signal intensity is linearly related to the logarithm of the concentration of the target DNA in the range of 1.0 nM to 10 fM with a detection limit of 3.5fM (S/N?=?3) under optimal conditions. This biosensor exhibits excellent sensitivity and selectivity and has been used for an assay of complementary target DNA in human serum sample with satisfactory results.

Electrochemiluminescent detection of the hybridization of oligonucleotides using an electrode modified with nanocomposite of carbon nanotubes and gold nanoparticles

We report on an electrochemiluminescent (ECL) sensing technique for the detection of the hybridization between oligonucleotides. A glassy carbon electrode was first functionalized with a composite prepared from gold nanoparticles and carbon nanotubes, and a sensor was then constructed by immobilizing the probing oligonucleotide. The ECL of luminol acts as the sensing signal. It is quenched, to a different degree, by the hybridized double strands of the oligonucleotide depending on the match status. The slope of the ECL response as a function of the status of hybridization drops with increasingly matched hybridization. The response is attributed to the interaction between luminol and the strands of oligomers, and also related to the reduction of reactive oxygen species.

A glassy carbon electrode modified with the nickel(II)-bis(1,10-phenanthroline) complex and multi-walled carbon nanotubes, and its use as a sensor for ascorbic acid

A glassy carbon electrode (GCE) was modified with the nickel(II)-bis(1,10-phenanthroline) complex and with multi-walled carbon nanotubes (MWCNTs). The nickel complex was electrodeposited on the MWCNTs by cyclic voltammetry. The modified GCE displays excellent electrocatalytic activity to the oxidation of ascorbic acid (AA). The effects of fraction of MWCNTs, film thickness and pH values were optimized. Response to AA is linear in the 10 to 630 μM concentration range, and the detection limit is 4 μM (at a signal-to-noise ratio of 3:1). The modified electrode was applied to determine AA in vitamin C tablets and in spiked fruit juice.

Sensitive simultaneous determination of catechol and hydroquinone using a gold electrode modified with carbon nanofibers and gold nanoparticles

A highly sensitive electrochemical sensor for the simultaneous determination of catechol (CC) and hydroquinone (HQ) was fabricated by electrodeposition of gold nanoparticles onto carbon nanofiber film pre-cast on an Au electrode. Both CC and HQ cause a pair of quasi-reversible and well-defined redox peaks at the modified electrode in pH?7.0 solution. Simultaneously, the oxidation peak potentials of CC and HQ become separated by 112?mV. When simultaneously changing the concentrations of both CC and HQ, the response is linear between 9.0???M and 1.50?mM. In the presence of 0.15?mM of the respective isomer, the electrode gives a linear response in the range from 5.0 to 350???M, and from 9.0 to 500???M for CC and HQ, respectively, and detection limits are 0.36 and 0.86???M. The method was successfully examined for real sample analysis with high selectivity and sensitivity.

Disposable electrochemical immunosensor for myeloperoxidase based on the indium tin oxide electrode modified with an ionic liquid composite film containing gold nanoparticles, poly(o-phenylenediamine) and carbon nanotubes

A disposable electrochemical myeloperoxidase (MPO) immunosensor was fabricated based on the indium tin oxide electrode modified with a film composed of gold nanoparticles (AuNPs), poly(o-phenylenediamine), multi-walled carbon nanotubes and an ionic liquid. The composite film on the surface of the electrode was prepared by in situ electropolymerization using the ionic liquid as a supporting electrolyte. Negatively charged AuNPs were then adsorbed on the modified electrode via amine-gold affinity and to immobilize MPO antibody. Finally, bovine serum albumin was employed to block possible remaining active sites on the AuNPs. The modification of the electrode was studied by cyclic voltammetry and scanning electron microscopy. The factors affecting the performance of the immunosensor were investigated in detail using the hexacyanoferrate redox system. The sensor exhibited good response to MPO over two linear ranges (from 0.2 to 23.4 and from 23.4 to 300 ng.mL^?1), with a detection limit of 0.05 ng.mL^?1 (at an S/N of 3).

A sensitive and selective nitrite sensor based on a glassy carbon electrode modified with gold nanoparticles and sulfonated graphene

We describe a highly sensitive and selective amperometric sensor for the determination of nitrite. A glassy carbon electrode was modified with a composite made from gold nanoparticles (AuNPs) and sulfonated graphene (SG). The modified electrode displays excellent electrocatalytic activity in terms of nitrite oxidation by giving much higher peak currents (at even lower oxidation overpotential) than those found for the bare electrode, the AuNPs-modified electrode, and the SG-modified electrode. The sensor has a linear response in the 10 μM to 3.96 mM concentration range, a very good detection sensitivity (45.44 μA mM^?1), and a lower detection limit of 0.2 μM of nitrite. Most common ions and many environmental organic pollutants do not interfere. The sensor was successfully applied to the determination of nitrite in water samples, and the results were found to be consistent with the values obtained by spectrophotometry.

Electrochemical oxidation and nanomolar detection of acetaminophen at a carbon-ceramic electrode modified by carbon nanotubes: a comparison between multi walled and single walled carbon nanotubes

Carbon-ceramic electrodes (CCE) modified with carbon nanotubes were prepared, and the electrochemical behavior towards acetaminophen (ACOP) was investigated using both a bare CCE and electrodes modified with either single walled carbon nanotubes (SWCNT) or multi walled carbon nanotubes (MWCNT) in an effort to understand which of them is the better choice in terms of electrocatalyzing the oxidation of ACOP, and thus for sensing it. The SWCNT are found to be the better material in significantly enhancing the oxidation peak current and improving the reversibility of the oxidation. Under optimal conditions, linearity between the oxidation peak current and the concentration of ACOP is obtained for the concentration range from 40?nM to 85???M, with a detection limit of 25?nM. Finally, ACOP was successfully determined with the SWCNT modified electrode in pharmaceutical samples.

Electrochemiluminescence immunoassay at a nanoporous gold leaf electrode and using CdTe quantun dots as labels

An electrochemiluminescence-based immunoassay using quantum dots (QDs) as labels for the carcinoembryonic antigen (CEA) was developed using an electrode modified with leafs of nanoporous gold. CEA was initially immobilized on the electrode via a sandwich immunoreaction, and then CdTe quantum dots capped with thioglycolic acid were used to label the second antibody. The intensity of the ECL of the QDs reflects the quantity of CEA immobilized on the electrode. Thus, in the presence of dithiopersulfate as the coreactant, the ECL serves as the signal for the determination of CEA. The intensity of the electroluminescence (ECL) of the electrode was about 5.5-fold higher than that obtained with a bare gold electrode. The relation between ECL intensity and CEA concentration is linear in the range from 0.05 to 200?ng.mL^-1, and the detection limit is 0.01?ng.mL^-1. The method has the advantages of high sensitivity, good reproducibility and long-term stability, and paves a new avenue for applying quantum dots in ECL-based bioassays.

New method for preparation of polyoxometalate-capped gold nanoparticles, and their assembly on an indium-doped tin oxide electrode

Functionalized gold nanoparticles capped with polyoxometalates were prepared by a simple photoreduction technique where phosphododecamolybdates serve as reducing reagents, photocatalysts, and as stabilizers. TEM images of the resulting gold nanoparticles show the particles to have a relative narrow size distribution. Monolayer and multilayer structures of the negatively charged capped gold nanoparticles were deposited on a poly(vinyl pyridine)-derivatized indium-doped tin oxide (ITO) electrode via the layer-by-layer technique. The surface plasmon resonance band of the gold nanoparticles displays a blue shift on the surface of the ITO electrode. This is due to the substrate-induced charge redistribution in the gold nanoparticles and a change in the electromagnetic coupling between the assembled nanoparticles. The modified electrode exhibits the characteristic electrochemical behavior of surface-confined phosphododecamolybdate and excellent electrocatalytic activity. The catalysis of the modified electrode towards the model compound iodate was systematically studied. The heterogeneous catalytic rate constant for the electrochemical reduction of iodate was determined by chronoamperometry to be ca. 1.34?×?10⁵ mol^?1·L·s^?1. The amperometric method gave a linear range from 2.5?×?10^?6 to 1.5?×?10^?3 M and a detection limit of 1.0?×?10^?6 M. We believe that the functionalized gold nanoparticles prepared by this photoreduction technique are advantageous in terms of fabrication of sensitive and stable redox electrodes.

A study on the direct electrochemistry and electrocatalysis of microperoxidase-11 immobilized on a porous network-like gold film: Sensing of hydrogen peroxide

We have prepared porous and network-like nanofilms of gold by galvanic replacement of a layer of copper particles acting as a template. The films were first characterized by scanning electron microscopy and X-ray diffraction, and then modified with cysteamine so to enable the covalent immobilization of the enzyme microperoxidase-11. The immobilized enzyme undergoes direct electron transfer to the underlying electrodes, and the electrode displays high electrocatalytic activity towards the reduction of oxygen and hydrogen peroxide, respectively, owing to the largely enhanced electroactive surface of the porous gold film. The detection limit of H₂O₂ is 0.4 μM (3 S/N).

Electrochemical synthesis of a graphene sheet and gold nanoparticle-based nanocomposite, and its application to amperometric sensing of dopamine

We describe a simple, green and controllable approach for electrochemical synthesis of a nanocomposite made up from electrochemically reduced graphene oxide (ERGO) and gold nanoparticles. This material possesses the specific features of both gold nanoparticles and graphene. Its morphology was characterized by scanning electron microscopy which reveals a homogeneous distribution of gold nanoparticles on the graphene sheets. Cyclic voltammetry was used to evaluate the electrochemical properties of this nanocomposite towards dopamine by modification of it on surface of glassy carbon electrode (GCE). Compared to the bare GCE, the electrode modified with gold nanoparticles, and the electrode modified with ERGO, the one modified with the nanocomposite displays better electrocatalytic activity. Its oxidation peak current is linearly proportional to the concentration of dopamine (DA) in the range from 0.1 to 10?μM, with a detection limit of 0.04?μM (at S/N?=?3). The modified electrode also displays good storage stability, reproducibility, and selectivity.

Voltammetric study on pristine and nitrogen-doped multi-walled carbon nanotubes decorated with gold nanoparticles

Films consisting of pristine multi-walled carbon nanotubes (MWCNTs) and nitrogen-doped MWCNTs (N-MWCNTs) were fabricated by means of chemical vapor deposition and chemically decorated with gold nanoparticles (AuNPs). Optical microscopy and image analysis reveal that the deposited AuNPs have diameters of 50–200 nm and 100–400 nm, respectively. The AuNP-modified films of MWCNTs and of N-MWCNTs were initially investigated with respect to their response to the ferro/ferricyanide redox system. The N-MWCNTs/AuNPs exhibit lower detection limit (0.345 μM) for this redox system compared to that of MWCNTs/AuNPs (0.902 μM). This is probably due to the presence of nitrogen that appears to enhance the electrocatalytic activity of MWCNTs. The findings demonstrate that the electrochemical responses of both films are distinctly enhanced upon deposition of AuNPs on their surfaces. The detection limits of MWCNTs/AuNPs and N-MWCNTs/AuNPs systems are lower by about 43 % and 27 %, respectively, compared to films not modified with AuNPs. The electrocatalytic activity of the films towards the oxidation of ascorbic acid (AA), uric acid (UA), and dopamine (DA) was studied. The findings reveal that N-MWCNTs/AuNPs represent a powerful analytical tool that enables simultaneous analysis of AA, UA, and DA in a single experiment.

Electrochemical investigation of a glassy carbon electrode modified with carbon nanotubes decorated with (poly)crystalline gold

Multiwalled carbon nanotubes with nanosized sputtered gold were used to modify a glassy carbon electrode (GCE). The substrate was characterized by scanning electron microscopy (SEM), X-ray diffraction, cyclic voltammetry and amperometry. SEM micrographs indicated an uniform coverage of the carbon nanotubes with nanosized (poly)crystalline gold. Cyclic voltammetry reveals that peak separation of the unmodified GCE in the presence of 1?mM ferricyanide is 131?mV, but 60?mV only for the modified GCE. In addition, the oxidation of NADH (1?mmol?L^?1 solution) begins at negative potentials (around ?100?mV vs. Ag/AgCl), and the anodic peak potential (corresponding to the irreversible oxidation of NADH) is found at +94?mV. The effect of pH on the electrocatalytic activity was studied in the range from 5.4 to 8.0. The relationship between the anodic peak potential and the pH indicated a variation of ?33.5?mV/pH which is in agreement with a two-electron and one-proton reaction mechanism. Amperometry, performed at either ?50 or +50?mV vs. an Ag/AgCl reference electrode, indicates that the modified electrode is a viable amperometric sensor for NADH. At a working potential of +50?mV, the response to NADH is linear in the concentration range from 1 to 100???mol?L^?1, with an RSD of 6% (n?=?4).

Voltammetric sensing of paracetamol, dopamine and 4-aminophenol at a glassy carbon electrode coated with gold nanoparticles and an organophillic layered double hydroxide

A differential pulse voltammetric method was developed for the simultaneous determination of paracetamol, 4-aminophenol and dopamine at pH 7.0 using a glassy carbon electrode (GCE) coated with gold nanoparticles (AuNPs) and a layered double hydroxide sodium modified with dodecyl sulfate (SDS-LDH). The modified electrode displays excellent redox activity towards paracetamol, and the redox current is increased (and the corresponding over-potential decreased) compared to those of the bare GCE, the AuNPs-modified GCE, and the SDS-LDH-modified GCE. The modified electrode enables the determination of paracetamol in the concentration range from 0.5 to 400???M, with a detection limit of 0.13???M (at an S/N of 3). The sensor was successfully applied to the stimultaneous determination of paracetamol and dopamine, and of paracetamol and 4-aminophenol, respectively, in pharmaceutical tablets and in spiked human serum samples.

Hydrogen peroxide sensor based on a stainless steel electrode coated with multi-walled carbon nanotubes modified with magnetite nanoparticles

Multi-walled carbon nanotubes (MWCNTs) were decorated with magnetite (Fe₃O₄) nanoparticles and then used to modify a stainless steel electrode. The Fe₃O₄/MWCNTs composite was characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction patterns. Electrochemical properties of the modified electrode revealed a substantial catalytic activity for the reduction of hydrogen peroxide. The relationship between peak current and the concentration of hydrogen peroxide was linear in the range from 0.06?mmol?L^?1 to 0.36?mmol?L^?1, and the lowest detectable concentration is 0.01?mmol·L^?1 (S/N?=?3). The modified stainless steel electrode displays excellent stability.

Direct electron transfer of glucose oxidase promoted by carbon nanotubes is without value in certain mediator-free applications

We have investigated the direct electron transfer (DET) promoted by carbon nanotubes (CNTs) on an electrode containing immobilized glucose oxidase (GOx) with the aim to develop a third-generation glucose biosensor and a mediator-free glucose biofuel cell anode. GOx was immobilized via chitosan (CS) on a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs). Cyclic voltammetric revealed that the GOx on the surface of such an electrode is unable to simultaneously demonstrate DET with the electrode and to retain its catalytic activity towards glucose, although the MWCNTs alone can promote electron transfer between GOx and electrode. This is interpreted in terms of two types of GOx on the surface, the distribution and properties of which are quite different. The first type exhibits DET capability that results from the collaboration of MWCNTs and metal impurities, but is unable to catalyze the oxidation of glucose. The second type maintains its glucose-specific catalytic capability in the presence of a mediator, which can be enhanced by MWCNTs, but cannot undergo DET with the electrode. As a result, the MWCNTs are capable of promoting the electron transfer, but this is without value in some mediator-free applications such as in third-generation glucose biosensors and in mediator-free anodes for glucose biofuel cells.

Amperometric hydrogen peroxide biosensor based on a glassy carbon electrode modified with polythionine and gold nanoparticles

We report on a novel hydrogen peroxide biosensor that was fabricated by the layer-by-layer deposition method. Thionine was first deposited on a glassy carbon electrode by two-step electropolymerization to form a positively charged surface. The negatively charged gold nanoparticles and positively charged horseradish peroxidase were then immobilized onto the electrode via electrostatic adsorption. The sequential deposition process was characterized using electrochemical impedance spectroscopy by monitoring the impedance change of the electrode surface during the construction process. The electrochemical behaviour of the modified electrode and its response to hydrogen peroxide were studied by cyclic voltammetry. The effects of the experimental variables on the amperometric determination of H₂O₂ such as solution pH and applied potential were investigated for optimum analytical performance. Under the optimized conditions, the biosensor exhibited linear response to H₂O₂ in the concentration ranges from 0.20 to 1.6?mM and 1.6 to 4.0?mM, with a detection limit of 0.067?mM (at an S/N of 3). In addition, the stability and reproducibility of this biosensor was also evaluated and gave satisfactory results.