Electrochemical sensing of catechol using a glassy carbon electrode modified with a composite made from silver nanoparticles, polydopamine, and graphene

We report on the modification of a glassy carbon electrode with a composite consisting of silver nanoparticles (AgNPs), polydopamine, and graphene to give an electrochemical sensor for catechol. The composite was characterized by transmission electron microscopy, and the electrochemical behavior of catechol at the modified electrode was studied by cyclic voltammetry. The electrochemical response is greatly enhanced and thought to result from a combination of beneficial effects including the good conductivity and large surface area of the AgNPs, the high conductivity of graphene, the synergistic effects of the composite, and the increased quantity of catechol that is adsorbed on the surface of the electrode. Differential pulse voltammetric responses are proportional to the concentration of catechol between 0.5 and 240?μM levels of catechol, and the detection limit is 0.1?μM (S/N?=?3). The performance of the sensor was evaluated with catechol-spiked water samples, and recoveries range from 96.5 % to 103.1 %. The results indicated that the composite presented here is a promising substrate for use in electrochemical sensing.

Studies on the electrochemistry of rutin and its interaction with bovine serum albumin using a glassy carbon electrode modified with carbon-coated nickel nanoparticles

We report on a glassy carbon electrode modified with carbon-coated nickel nanoparticles (C-Ni/GCE) that can be used to study the electrochemical properties of rutin and its interaction with bovine serum albumin (BSA) via cyclic voltammetry and differential pulse voltammetry. The effects of pH value, accumulation potential, accumulation time and reaction time were optimized. A pair of reversible peaks is found in the potential range of 0 to around 0.6 V at pH?5.0. Two linear response ranges (with different slopes) are found, one in the 2 to 210 nM concentration range, the other between 0.21 and 1.72 μM. The detection limit is as low as 0.6 nM. On addition of BSA to the rutin solution, a decrease of the current is observed that is proportional to the concentration of BSA. The binding constant and stoichiometric ratio were calculated.

Ultra-sensitive electrochemical DNA biosensor based on signal amplification using gold nanoparticles modified with molybdenum disulfide,graphene and horseradish peroxidase

We have developed an ultra-sensitive electrochemical DNA biosensor by assembling probe ssDNA on a glassy carbon electrode modified with a composite made from molybdenum disulfide, graphene, chitosan and gold nanoparticles. A thiol-tagged DNA strand coupled to horseradish peroxidase conjugated to AuNP served as a tracer. The nanocomposite on the surface acts as relatively good electrical conductor for accelerating the electron transfer, while the enzyme tagged gold nanoparticles provide signal amplification. Hybridization with the target DNA was studied by measuring the electrochemical signal response of horseradish peroxidase using differential pulse voltammetry. The calibration plot is linear in the 5.0?×?10^?14 and 5.0?×?10^?9 M concentration range, and the limit of detection is 2.2?×?10^?15 M. The biosensor displays high selectivity and can differentiate between single-base mismatched and three-base mismatched sequences of DNA. The approach is deemed to provide a sensitive and reliable tool for highly specific detection of DNA.

Electrochemical immunoassay for subgroup J of avian leukosis viruses using a glassy carbon electrode modified with a film of poly (3-thiophene boronic acid), gold nanoparticles, graphene and immobilized antibody

We have modified a glassy carbon electrode (GCE) with a film of poly(3-thiophene boronic acid), gold nanoparticles and graphene, and an antibody (Ab) was immobilized on its surface through the covalent bond formed between the boronic acid group and the glycosyl groups of the Ab. Subgroup J of avian leukosis viruses (ALV-J) were electrochemically determined with the help of this electrode. There is a linear relationship between the electron transfer resistance (R _et) and the concentration of ALV-J in the range from 527 to 3,162 TCID₅₀?mL^?1 (where TCID₅₀ is the 50?% tissue culture infective dose). The detection limit is 210 TCID₅₀?mL^?1 (at an S/N of 3), and the correlation coefficient (R) is 0.9964. The electrochemical immunoassay showed good selectivity, stability and reproducibility.

Nonenzymatic glucose sensor based on glassy carbon electrode modified with a nanocomposite composed of nickel hydroxide and graphene

We report on a nonenzymatic glucose sensor based on a glassy carbon electrode that was electrochemically modified with a nanocomposite prepared from nickel hydroxide and graphene. Scanning electron microscopy revealed that the nickel hydroxide in the nanocomposite was present in the form of a nanostructure of three-dimensional spheres that were assembled by many densely arranged nanosheets. The electrocatalytic activity of the electrode toward the oxidation of glucose was investigated by chronoamperometry. The current response was linearly related to the glucose concentration in the range from 1 to 10?μM, with a sensitivity of 494?μA?mM^–1?cm^–2 and a correlation coefficient of 0.9990, and a second range (from 10 to 1000?μM with a sensitivity of 328?μA?mM^–1?cm^–2 and a correlation coefficient of 0.9990). The detection limit was 0.6?μM at a signal-to-noise ratio of 3, and the response time was as short as 2?s.

Lactate biosensor based on a bionanocomposite composed of titanium oxide nanoparticles, photocatalytically reduced graphene, and lactate oxidase

We have developed a lactate biosensor based on a bionanocomposite (BNC) composed of titanium dioxide nanoparticles (TiO₂-NPs), photocatalytically reduced graphene, and lactate oxidase. Graphene oxide was photochemically reduced (without using any chemical reagents) in the presence of TiO₂-NPs to give graphene nanosheets that were characterized by atomic force microscopy, Raman and X-ray photoelectron spectroscopy. The results show the nanosheets to possess few oxygen functionalities only and to be decorated with TiO₂-NPs. These nanosheets typically are at least 1 μm long and have a thickness of 4.2 nm. A BNC was obtained by mixing lactate oxidase with the nanosheets and immobilized on the surface of a glassy carbon electrode. The resulting biosensor was applied to the determination of lactate. Compared to a sensor without TiO₂-NPs, the sensor exhibits higher sensitivity (6.0 μA mM^?1), a better detection limit (0.6 μM), a wider linear response (2.0 μM to 0.40 mM), and better reproducibility (3.2 %).

Amperometric enzyme electrodes for the determination of volatile alcohols in the headspace above fruit and vegetable juices

The surface of a glassy carbon electrode (GCE) was modified by electropolymerization of acridine red followed by drop-coating of graphene. The morphology was characterized by scanning electron microscopy. Uric acid (UA) is effectively accumulated on the surface of the modified electrode and generates a sensitive anodic peak in solutions of pH 6.5. Differential pulse voltammetry was used to evaluate the electrochemical response of the modified GCE to UA. Compared to the bare GCE, the GCE modified with acridine red, and to the graphene modified electrode, the new GCE displays high electrochemical activity in giving an oxidation peak current that is proportional to the concentration of UA in the range from 0.8 to 150?μM, with a detection limit of 0.3?μM (at an S/N of 3). The modified electrode displays excellent selectivity, sensitivity, and a wide linear range. It has been applied to the determination of UA in real samples with satisfactory results.

A glassy carbon electrode modified with a film composed of cobalt oxide nanoparticles and graphene for electrochemical sensing of H2O2

We have prepared a graphene-based hybrid nanomaterial by electrochemical deposition of cobalt oxide nanoparticles (CoO_xNPs) on the surface of electrochemically reduced graphene oxide deposited on a glassy carbon electrode (GCE). Scanning electron microscopy and cyclic voltammetry were used to characterize the immobilized nanoparticles. Electrochemical determination of H₂O₂ is demonstrated with the modified GCE at pH 7. Compared to GCEs modified with CoO_xNPs or graphene sheets only, the new electrode displays larger oxidative current response to H₂O₂, probably due to the synergistic effects between the graphene sheets and the CoO_xNPs. The sensor responds to H₂O₂ with a sensitivity of 148.6 μA mM^?1 cm^?2 and a linear response range from 5 μM to 1 mM. The detection limit is 0.2 μM at a signal to noise ratio (SNR) of three. The method was successfully applied to the determination of H₂O₂ in hydrogen peroxide samples.

Electrochemistry and voltammetric determination of L-tryptophan and L-tyrosine using a glassy carbon electrode modified with a Nafion/TiO2-graphene composite film

We describe a glassy carbon electrode (GCE) modified with a film composed of Nafion and TiO₂-graphene (TiO₂-GR) nanocomposite, and its voltammetric response to the amino acids L-tryptophane (Trp) and L-tyrosine (Tyr). The incorporation of TiO₂ nanoparticles with graphene significantly improves the electrocatalytic activity and voltammetric response compared to electrodes modified with Nafion/graphene only. The Nafion/TiO₂-GR modified electrode was used to determine Trp and Tyr with detection limits of 0.7 and 2.3 μM, and a sensitivity of 75.9 and 22.8 μA mM^?1 for Trp and Tyr, respectively.

A nanoporous ruthenium oxide framework for amperometric sensing of glucose and potentiometric sensing of pH

We report on a carbon ionic liquid electrode modified with a composite made from Nafion, graphene oxide and ionic liquid, and its application to the sensitive determination of rutin. The modified electrode was characterized by cyclic voltammetry and electrochemical impedance spectroscopy. It shows excellent cyclic voltammetric and differential pulse voltammetric performance due to the presence of nanoscale graphene oxide and the ionic liquid, and their interaction. A pair of well-defined redox peaks of rutin appears at pH 3.0, and the reduction peak current is linearly related to its concentration in the range from 0.08 μM to 0.1 mM with a detection limit of 0.016 μM (at 3σ). The modified electrode displays excellent selectivity and good stability, and was successfully applied to the determination of rutin in tablets with good recovery.

Label-free electrochemical immunosensor for the carcinoembryonic antigen using a glassy carbon electrode modified with electrodeposited Prussian Blue, a graphene and carbon nanotube assembly and an antibody immobilized on gold nanoparticles

We described a sensitive, label-free electrochemical immunosensor for the detection of carcinoembryonic antigen. It is based on the use of a glassy carbon electrode (GCE) modified with a multi-layer films made from Prussian Blue (PB), graphene and carbon nanotubes by electrodeposition and assembling techniques. Gold nanoparticles were electrostatically absorbed on the surface of the film and used for the immobilization of antibody, while PB acts as signaling molecule. The stepwise assembly process was investigated by differential pulse voltammetry and scanning electron microscopy. It is found that the formation of antibody-antigen complexes partially inhibits the electron transfer of PB and decreased its peak current. Under the optimal conditions, the decrease of intensity of the peak current of PB is linearly related to the concentration of carcinoembryonic antigen in two ranges (0.2–1.0, and 1.0–40.0 ng·mL^?1), with a detection limit of 60 pg·mL^?1 (S/N?=?3). The immunosensor was applied to analyze five clinical samples, and the results obtained were in agreement with clinical data. In addition, the immunosensor exhibited good precision, acceptable stability and reproducibility.

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.

Direct electron transfer and biocatalytic activity of iron storage protein molecules immobilized on electrodeposited cobalt oxide nanoparticles

Ferritin was immobilized on a glassy carbon electrode with electrodeposited cobalt oxide nanoparticles, and its direct electron transfer behavior was studied. It exhibits a pair of redox peaks due to direct electron transfer between ferritin and the nanoparticles. Electrochemical parameters including the formal potential (E^0??), the charge transfer coefficient (??), and the apparent heterogeneous electron transfer rate constant (k_s) were determined. The sensor displays excellent biocatalytic activity in terms of reduction of hydrogen peroxide, and this was applied to electrochemical sensing of hydrogen peroxide.

Voltammetric determination of bisphenol A in food package by a glassy carbon electrode modified with carboxylated multi-walled carbon nanotubes

A highly sensitive and mercury-free method for determination of bisphenol A (BPA) was established using a glassy carbon electrode that was modified with carboxylated multi-walled carbon nanotubes. A sensitive oxidation peak is found at 550?mV in linear sweep voltammograms at pH?7. Based on this finding, trace levels of bisphenol A can be determined over a concentration range that is linear from 10?nM to 10⁴?nM, the correlation coefficient being 0.9983, and the detection limit (S/N?=?3) being 5.0?nM. The method was successfully applied to the determination of BPA in food package.

Electrochemical oxidation behavior of guanosine-5��-monophosphate on a glassy carbon electrode modified with a composite film of graphene and multi-walled carbon nanotubes, and its amperometric determination

The electrochemical oxidation of guanosine-5??-monophosphate (GMP) was studied with a glassy carbon electrode modified with a composite made from graphene and multi-walled carbon nanotubes. GMP undergoes an irreversible oxidation process at an oxidation peak potential of 987?mV in phosphate buffer solution. Compared to other electrodes, the oxidation peak current of GMP with this electrode was significantly increased, and the corresponding oxidation peak potential negatively shifted, thereby indicating that the modified material exhibited electrochemical catalytic activity towards GMP. Chronocoulometry demonstrates that the material also effectively increases the surface area of the electrode and increases the amount of GMP adsorbed. Under the optimum conditions, the oxidation current is proportional to the GMP concentration in the range from 0.1 to 59.7???M with a correlation coefficient of 0.9991. The detection limit is 0.025???M (at S/N?=?3).

Nonenzymatic sensing of glucose at neutral pH values using a glassy carbon electrode modified with graphene nanosheets and Pt-Pd bimetallic nanocubes

We report on a nonenzymatic method for the determination of glucose using an electrode covered with graphene nanosheets (GNs) modified with Pt-Pd nanocubes (PtPdNCs). The latter were prepared on GNs by using N,N-dimethylformamide as a bifunctional solvent for the reduction of both metallic precursors and graphene oxide, and for confining the growth of PtPdNCs on the surface. The modified electrode displays strong and sensitive current response to the electrooxidation of glucose, notably at pH 7. The sensitivities increase in the order of Pt₁Pd₅NCs< Pt₁Pd₃NCs< Pt₅Pd₁NCs< Pt₃Pd₁NCs< Pt₁Pd₁NCs. At an applied potential of +0.25 V, the electrode responds linearly (R?=?0.9987) to glucose in up to 24.5 mM concentration, with a sensitivity of 1.4 μA cm^?2 M^?1. The sensor is not poisoned by chloride, and not interfered by ascorbic acid, uric acid and p-acetamidophenol under normal physiological conditions. The modified electrode also displays a wide linear range, good stability and fast amperometric response, thereby indicating the potential of the bimetallic materials for nonenzymatic sensing of glucose.

Sensitive detection of hydrogen peroxide in foodstuff using an organic�Cinorganic hybrid multilayer-functionalized graphene biosensing platform

We report on a new electrochemical biosensing strategy for the sensitive detection of hydrogen peroxide (H₂O₂) in foodstuff samples. It is based on a gold electrode modified with layer of graphene patterned with a multilayer made from an organic?Cinorganic hybrid nanomaterial. Initially, a layer of thionine (Th) was assembled on the surface of the graphene nanosheets, and these were then cast on the surface of the electrode for the alternate assembly of gold nanoparticles and horseradish peroxidase. The large surface-to-volume ratio and high conductivity of the nanosheets provides a benign microenvironment for the construction of the biosensor. The use of such a multilayer not only shortens the electron transfer pathway of the active center of the enzyme due to the presence of gold nanoparticles, but also enhances the electrocatalytic efficiency of the biosensor toward the reduction of H₂O₂. The electrochemical characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The number of layers, the operating potential, and the pH of the supporting electrolyte were optimized. Linear response is obtained for the range from 0.5???M to 1.8?mM of H₂O₂, the detection limit is 10 nM (at S/N?=?3), and 95% of the steady-state current is reached within 2?s. The method was applied to sense H₂O₂ in spiked sterilized milk and correlated excellently with the permanganate titration method.

Electrochemical synthesis of a novel platinum nanostructure on a glassy carbon electrode, and its application to the electrooxidation of methanol

We show that the addition of white dextrin during the electrochemical deposition of platinum nanostructures (nano-Pt) on a glassy carbon electrode (GCE) results in an electrochemically active surface that is much larger than that of platinum microparticles prepared by the same procedure but in the absence of dextrin. The nano-Pt deposits are characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy, and electrochemical methods. The SEM images reveal deposits composed of mainly nanoparticles and short nanorods. The GCE was applied as a novel and cost-effective catalyst for methanol oxidation. The use of nano-Pt improves the electrocatalytic activity and the stability of the electrodes.

Dopamine sensor based on a glassy carbon electrode modified with a reduced graphene oxide and palladium nanoparticles composite

We report on a sensitive electrochemical sensor for dopamine (DA) based on a glassy carbon electrode that was modified with a nanocomposite containing electrochemically reduced graphene oxide (RGO) and palladium nanoparticles (Pd-NPs). The composite was characterized by scanning electron microscopy, energy dispersive spectroscopy, and electrochemical impendence spectroscopy. The electrode can oxidize DA at lower potential (234 mV vs Ag/AgCl) than electrodes modified with RGO or Pd-NPs only. The response of the sensor to DA is linear in the 1–150 μM concentration range, and the detection limit is 0.233 μM. The sensor was applied to the determination of DA in commercial DA injection solutions.

A graphene-based electrochemical sensor for sensitive and selective determination of hydroquinone

Graphene was prepared by electrochemical reduction of exfoliated graphite oxide at cathodic potentials, and used to fabricate a graphene-modified glassy carbon electrode (GCE) which was applied in a sensor for highly sensitive and selective voltammetric determination of hydroquinone (HQ). Compared to a bare (conventional) GCE, the redox peak current for HQ in pH 5.7 acetate buffer solution is significantly increased, indicating that graphene possesses electrocatalytic activity towards HQ. In addition, the peak-to-peak separation is significantly improved. The modified electrode enables sensing of HQ without interference by catechol or resorcinol. Under optimal conditions, the sensor exhibits excellent performance for detecting HQ with a detection limit of 0.8?μM, a reproducibility of 2.5% (expressed as the RSD), and a recoveries from 98.4 to 101.2%.