A low-cost,fast, disposable and sensitive biosensor study: flow injection analysis of glucose at poly-methylene blue-modified pencil graphite electrode

In this work, firstly methylene blue (MB) was electropolymerized onto pencil graphite electrode (PGE) surface for the electrocatalytic oxidation of NADH. Cyclic voltammograms show that oxidation potential of NADH at Poly-MB/PGE shifted to negative direction about 300 mV compared with bare PGE. These results indicate that Poly-MB/PGE exhibits a good electrocatalytic activity toward NADH oxidation. Then, a glucose biosensor study was performed based on the determination of enzymatically generated NADH by glucose dehydrogenase (GDH) which immobilized onto Poly-MB/PGE using glutaraldehyde cross-linking procedure. The biosensing of glucose in flow injection analysis (FIA) system was performed at GDH/Poly-MB/PGE for the first time. The electrocatalytic oxidation currents of enzymatically produced NADH obtained from FI amperometric current–time curves recorded at + 200 mV and in phosphate buffer solution at pH 7.0 containing 1.0 M KCl were linearly related to the concentration of glucose. Linear calibration plots are obtained in the concentration range from 0.01 to 1.0 mM. The limit of detection (LOD) was found to be 4.0 µM. A fast, sensitive, low-cost and disposable glucose biosensor was constructed in FIA system using GDH/Poly-MB/PGE; therefore, it might provide a new perspective for the fabrication of biosensor of other compounds such as glutamate, lactate and alcohol.     

Sensitive Detection of NADH by Ferrocenylalkanethiol Functionalized Multiwall Carbon Nanotubes Electrodes

Abstract

The 6-ferrocenylhexanethiol (FcC₆SH) functionalized multiwall carbon nanotubes (MWNTs) modified glassy carbon electrode (FcC₆SH/MWNTs/GCE) was easily fabricated and used for the sensitive detection of NADH. Cyclic voltammetric and amperometric methods were used to study the behavior of NADH on the FcC₆SH/MWNTs/GCE. A broader linear response range to the NADH concentration from 5 µM to 1.5 mM with a correlation coefficient of 0.9982 was obtained. The detection limit was 0.54 µM. The synergetic effects of FcC₆SH and MWNTs make the modified electrode highly sensitive to NADH. In addition, the modified electrode can decrease the fouling of the electrode surface.     

Electrochemical Detection of NADH,Cysteine, or Glutathione Using a Caffeic Acid Modified Glassy Carbon Electrode

A modified electrode was prepared using electrodeposition methods to immobilize caffeic acid (CAF) onto the surface of a glassy carbon electrode (GCE) to create a polymer suitable for biosensor development. The polymer film coverage of the surface bound species was further optimized using electrodeposition methods, thus increasing the surface coverage to ca. 10^?9 mol cm^?2. Using cyclic voltammetry, the modified carbon electrode was used to facilitate and observe the electrocatalytic oxidation of coenzymes such as NADH, cysteine, and glutathione at different concentrations. A calibration curve was determined in each case within the concentration range; 300 nM to 10 mM, with the limits of detection (LOD) of 246 µM, 99 µM, 2.2 µM for NADH, cysteine, and glutathione respectively.     

Voltammetric measurement of trace amount of glutathione using multiwall carbon nanotubes as a sensor and chlorpromazine as a mediator

In this work, we propose chlorpromazine as a new mediator for the rapid, sensitive, and highly selective voltammetric determination of glutathione (GSH) using multiwall carbon nanotubes paste electrode (MWCNTPE). The experimental results showed that the carbon nanotubes paste electrode has a highly electrocatalytic activity for the oxidation of GSH in the presence of chlorpromazine as a mediator. Cyclic voltammetry, double potential step chronoamperometry, and differential pulse voltammetry (DPV) are used to investigate the suitability of chlorpromazine at the surface of MWCNTPE as a mediator for the electrocatalytic oxidation of GSH in aqueous solutions. It is shown that chlorpromazine can catalyze the oxidation of GSH in an aqueous buffer solution to produce a sharp oxidation peak current at about +0.70 versus Ag/AgCl as a reference electrode. Kinetic parameters such as electron transfer coefficient and catalytic reaction rate constant, k/h, are also determined. Using DPV and under the optimum conditions at pH 4.0, the electrocatalytic oxidation peak current of GSH shows a linear dependence on GSH concentration in the GSH concentration range of 0.3 to 18.3 µM. The detection limit (3σ) is determined to be 0.16 µM. The relative standard deviation for 1.5 and 5.0 µM GSH are found to be 3.7% and 2.5%, respectively. The proposed method may, thus, also be used as a novel, selective, simple, and precise method for the voltammetric determination of GSH in such real samples as hemolyzed erythrocyte.     

Electrochemical and Photoelectrochemical Sensing of NADH and Ethanol Based on Immobilization of Electrogenerated Chlorpromazine Sulfoxide onto Graphene‐CdS Quantum Dot/Ionic Liquid Nanocomposite

Here, a simple one‐step solvothermal procedure was employed to synthesize a nanocomposite containing graphene‐nanosheets and CdS quantum dots (GNs‐CdS QDs). The electrochemical oxidation of chlorpromazine (CPZ) to chlorpromazine‐sulfoxide (CPZ‐SO) onto a GNs‐CdS QDs/ionic liquid (IL) nanocomposite modified glassy carbon (GC) electrode give rise to redox‐active products which showed excellent electrocatalytic and photoelectrocatalytic activity toward NADH oxidation at reduced overpotential. A linear response up to 200 µM was obtained for photoamperometric determination of NADH with detection limit 1 µM. Immobilizing alcohol dehydrogenase(ADH) onto the modified electrode via a simple cross linking procedure, the photoelectrochemical capability of the proposed system toward ethanol biosensing was clearly shown.     

A Simple and Effective Way to Integrate Nile Blue Covalently onto Functionalized SWCNTs Modified GC Electrodes for Sensitive and Selective Electroanalysis of NADH

A simple and new way to assemble Nile blue (NB) covalently onto the surface of functionalized single‐walled carbon nanotubes (f‐SWCNTs) modified glassy carbon (GC) electrode (NB/f‐SWCNTs/GC electrode) was described. The NB/f‐SWCNTs/GC electrode catalyzes effectively the oxidation of NADH with a remarkably decreased overpotential (ca. 700 mV) compared with that at the bare GC. The reaction was found to obey a so‐called Michaelis–Menten kinetics and the related kinetic parameters were determined. This modified electrode possesses promising characteristics as NADH sensor; a wide linear dynamic range of 0.2 to 200 µM, low detection limit of 0.18 µM, fast response time (1–2 s), high sensitivity (24 µA cm⁻² mM⁻¹), anti‐interference ability and anti‐fouling.     

Determination of Oxytetracycline in Food Using a Disposable Montmorillonite and Acetylene Black Modified Microelectrode

Oxytetracycline is a broad-spectrum antibiotic used in animal husbandry that may cause the occurrence of antibiotic residues in food-producing animals. A detailed study of the electrochemical properties of oxytetracycline was carried out at montmorillonite and acetylene black modified carbon paste microelectrode. The oxytetracycline underwent an irreversible oxidation at montmorillonite-acetylene black/carbon paste microelectrode, which was an adsorption-controlled process with one proton and one electron. Using differential normal pulse voltammetry with accumulation at a fixed potential of 0.3 V for 120 s, oxytetracycline yielded a well-defined voltammetric response at 0.6 V in pH 7.4 citric acid–Na₂HPO₄ buffer. Furthermore, the oxidation peak current of oxytetracycline at the montmorillonite–acetylene black/carbon paste microelectrode linearly increased with concentration in the range of 0.5–50 µM with a low detection limit of 87 nM (S/N = 3). This methodology was successfully applied to the determination of oxytetracycline from food samples, suggesting that it has practical applications in monitoring oxytetracycline.     

Glassy carbon electrode modified with poly-Neutral Red for photoelectrocatalytic oxidation of NADH

A new approach is described for the photoelectrocatalytic oxidation of Reduced ß-Nicotinamide Adenine Dinucleotide (NADH). It is based on a glassy carbon electrode (GCE) modified with a film of poly-Neutral Red (poly-NR) that is obtained by electropolymerization. Electrochemical measurements revealed that the modified electrode displays electrocatalytic and photo-electrocatalytic activity towards oxidation of NADH. If irradiated with a 250-W halogen lamp, the electrode yields a strongly increased electrocatalytic current compared to the current without irradiation. Amperometric and photo-amperometric detection of NADH was performed at +150 mV vs. Ag/AgCl/KCl_sat and the currents obtained are linearly related to the concentration of NADH. Linear calibration plots are obtained in the concentration range from 1.0 μM to 1.0 mM for both methods. However, the slope of the current-NADH concentration curve of the photo-electrocatalytic procedure was 2-times better than that obtained without irradiation.

Electroanalytical Characterization of Adenosine Mono-, Di- and Triphosphate Oxidation on Carbon Electrode

Abstract

Electrochemical oxidation of adenosine mononucleotides was characterized using a pencil graphite carbon electrode for the first time. All three adenosine mononucleotides, adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP), showed irreversible electro-activity at the carbon electrode, yielding a well-defined oxidation current response. The peak potential was highly dependent on pH. The lowest mononucleotide concentration detected was 1 µM. The electro-analytical data presented here for the oxidation of adenosine mononucleotides provides the basis for further bioanalytical investigations related to DNA-drug interactions.     

Sensitive and Selective Determination of Phenylhydrazine in the Presence of Hydrazine at a Ferrocene Monocarboxylic Acid Modified Carbon Nanotube Paste Electrode

In the present paper, the use of a carbon paste electrode modified by ferrocene monocarboxylic acid (FMC) and carbon nanotubes prepared by a simple and rapid method was described. The modified electrode showed an excellent character for electrocatalytic oxidization of phenylhydrazine (PHZ) and hydrazine (HZ) with a 300 mV separation of both peaks. Differential pulse voltammetric peak currents of PHZ and HZ increased linearly with their concentrations at the range of 0.8 µM to 700 µM and 16 µM to 800 µM and the detection limits (3σ) were determined to be 0.42 µM and 14 µM, respectively.     

Lead-doped carbon ceramic electrode as a renewable surface composite electrode for the preparation of lead dioxide film and detection of <Emphasis Type="SmallCaps">l</Emphasis>-tyrosine

Lead-doped carbon ceramic electrode as a new type of renewable composite electrode was prepared by mixing the lead powder with electrode matrix before gelation. Pb on the electrode surface was then converted to lead dioxide by the potential scanning of the composite electrode in 0.1 M NaOH solution in the range of ? 0.3 to 0.7 V versus SCE. The composition and morphology of the electrodes were studied by energy dispersive X-ray spectrometry, scanning electron microscopy, and atomic force microscopy techniques. Cyclic voltammetry and chronoamperometry techniques were also used to study the electrocatalytic activity of the modified electrode toward the oxidation of the l-tyrosine. The best results were obtained at a working potential of 0.45 V (vs. SCE) in 0.1 M NaOH solution. The sensor exhibited a good linear response in the range of 5–1458 µM with a coefficient of determination of 0.9963. The detection limit was 0.77 µM, and sensitivity was 37.4 μA mM^?1. In addition, the modified electrode showed high stability and interference-free response for to detection of the l-tyrosine.     

Copper hydroxide nanostructure-modified carbon ionic liquid electrode as an efficient voltammetric sensor for detection of metformin: a theoretical and experimental study

The electrocatalytic oxidation of metformin (MET) was investigated at Cu(OH)₂ nanoparticle-modified carbon ionic liquid electrode (Cu(OH)₂/CILE). This electrode exhibited excellent characteristic for the electrocatalytic oxidation of metformin at the potential of +0.6 V with good sensitivity and selectivity. The presence of Cu(OH)₂ nanostructures in the composite electrode leads to the appearance of oxidation peak of MET. Under optimal experimental conditions, the peak current response increased linearly with metformin concentration over the range of 1 µM–4 mM. The detection limit of the method is 0.5 µM. Moreover, the closer look was taken at the electronic properties of MET and its Cu (II) complexes such as frontier molecular orbital (HOMO and LUMO) and binding interaction energies using density functional theory. Effect of pH was also investigated at B3LYP/6-311++g** level. Theoretical results confirmed the experimental evidences of Cu (II) complexation. Therefore, Ease of preparation, wide linear range, low overpotential, high sensitivity and selectivity provide the possibility of applying this method for the detection of MET in biological samples.     

Room-Temperature Ionic Liquid and Multi-Walled Carbon Nanotube Composite Modified Carbon-Ceramic Electrode as a Sensitive Voltammetric Sensor for Indomethacin

The electrochemical behavior of indomethacin on the surface of a carbon-ceramic electrode modified with multi-walled carbon nanotubes and an ionic liquid composite film is reported. The results show that the nano-structured film exhibited excellent enhancement effects on the electrochemical oxidation of indomethacin. The developed sensor presented a linear response to indomethacin over the concentration range from 1 to 50 µM with a detection limit of 0.26 µM. The proposed modified electrode was employed for the determination of indomethacin in biological and pharmaceutical samples using differential pulse voltammetry.     

First electrochemical investigation of organophosphorus pesticide azametiphos and its quantification using electroanalytical approach

ABSTRACT

In this work, the electrochemical behaviour and the subsequent development of an analytical procedure for quantification of pesticide azamethiphos, using boron-doped diamond (BDD) electrode are reported for the first time. It was found that azamethiphos electrochemical behaviour is irreversible oxidation at the potential of around 1.70 V, in 1 M nitric acid (pH 0). Also, it was found that potential of this oxidation was not pH dependent which can be attributed to the no proton involvement in electrochemical reaction on the electrode surface. The square wave voltammetric method was most appropriate for azamethiphos quantification. Under optimised experimental conditions, linear working range from 2 to 100 µM was estimated with the detection limit of 0.45 µM. Negligible effect of the possible interfering compound was observed. The obtained results show that the developed analytical methodology can be an adequate replacement for the, up to date, used methods for detection of organophosphorous pesticide.     

Simultaneous Sensitive Determination of Dopamine and Uric Acid in the Presence of Excess Ascorbic Acid with a Magnetic Chitosan Microsphere/Thionine Modified Electrode

Magnetic chitosan microspheres (MCMS) and thionine were incorporated in a modified electrode for the simultaneous sensitive determination of dopamine (DA) and uric acid (UA). Due to the unique properties of the MCMS and the electron mediation of thionine, this modified electrode showed excellent electrocatalytic oxidation toward dopamine and uric acid with a large separation of peak potentials and a significant enhancement of peak currents. However, the electrochemical behavior of ascorbic acid may be depressed at the modified electrode. Differential pulse voltammetry was used for the simultaneous sensitive determination of dopamine and uric acid in the presence of excess ascorbic acid at this modified electrode. The current responses showed excellent linear relationships in the range of 2–30 µM and 9–100 µM for dopamine and uric acid, respectively. The detection limits were estimated to be 0.5 µM and 2.3 µM for dopamine and uric acid, respectively. In addition, this modified electrode showed excellent repeatability, good stability, and satisfactory reliability, thus indicating potential for the practical applications.     

The NADH Electrochemical Detection Performed at Carbon Nanofibers Modified Glassy Carbon Electrode

In this work, the capability of carbon nanofibers to be used for the design of catalytic electrochemical biosensors is demonstrated. The direct electrochemistry of NADH was studied at a glassy carbon electrode modified using carbon nanofibers. A decrease of the oxidation potential of NADH by more than 300 mV is observed in the case of the assembled carbon nanofiber‐glassy carbon electrode comparing with a bare glassy carbon electrode. The carbon nanofiber‐modified electrode exhibited a wide linear response range of 3×10^?5 to 2.1×10^?3 mol L^?1 with a correlation coefficient of 0.997 for the detection of NADH, a high specific sensitivity of 3637.65 (μA/M cm²), a low detection of limit (LOD=3σ) of 11 μM, and a fast response time (3 s). These results have confirmed the fact that the carbon nanofibers represent a promising material to assemble electrochemical sensors and biosensors.     

Graphene oxides/multi-walled carbon nanotubes hybrid-modified carbon electrodes for fast and sensitive voltammetric determination of the anticancer drug 5-fluorouracil in spiked human plasma samples

The electrochemical oxidation of anticancer drug 5-fluorouracil (5-FU) at graphene oxides (GOs)/carbon nanotubes (CNTs) nanohybrid-modified screen-printed carbon and glassy carbon electrodes was studied by voltammetric techniques. The modified electrodes showed better performance toward the electro-oxidation and determination of 5-FU compared to CNTs-modified or GOs-modified electrodes. The oxidation peak current obtained at about + 1.156 V (vs. Ag/AgCl) from square wave voltammetry was linearly dependent on the 5-FU concentration in the ranges of 0.05–5 and 5–1200 µM in phosphate buffer solution of pH 7.0. The developed method was applied successfully to the electrochemical sensing of 5-FU in human plasma samples at micro-molar concentration levels with satisfactory results. It is hopeful that the developed method in the future can be used for the simple and fast determination of 5-FU in clinical test and pharmacokinetics.     

Electro-oxidative polymerization of phenothiazine dyes into a multilayer-containing carbon nanotube on a glassy carbon electrode for the sensitive and low-potential detection of NADH

An electrochemical sensing platform was developed for the amperometric detection of β-nicotinamide adenine dinucleotide (NADH) through the integration of a multi-walled carbon nanotube (MWCNT) into electropolymerized phenothiazine dyes. The composite containing MWCNT and poly(phenothiazine) was prepared by electro-oxidative polymerization of phenothiazine derivatives, Azure B, Azure A and thionine, into an MWCNT/ poly(diallyldimethylammonium chloride) (PDDA) multilayer, which was constructed by electrostatic layer-by-layer assembly on a glassy carbon electrode. The three phenothiazine monomers used in this study exhibited similar electrochemical behaviors. Azure B was used extensively as a model monomer for the investigation. Electrochemical techniques and scanning electron microscopy were used to demonstrate that the porous composite was formed and that the carbon nanotube served as a nano-sized backbone for the loading of polymeric phenothiazine. The electrocatalytic current for NADH oxidation was enhanced as the number of layers increased, implying that the increase of NADH-accessible poly(phenothiazine) and the three-dimensional arrangement of the poly(phenothiazine)-coated MWCNT in the composite facilitated electron and NADH transfer. Under optimal conditions, the detection limit for NADH decreases to 7.0 × 10^?8?M at a potential of 0.1 V (versus Ag/AgCl) using a {MWCNT/PDDA}₈?poly(Azure B) composite modified glassy carbon electrode, with a response time of about 5 s. This work demonstrates that the electropolymerization of the phenothiazine monomer into a pre-formed multilayer containing MWCNT can be used for the controllable preparation of stable MWCNT/poly(phenothiazine) composites on electrode surfaces, which have the potential to provide a platform for electrochemical biosensors based on NAD⁺-dependent dehydrogenase enzymes.     

Electropolymerization of Thin Film Conducting Polymer and Its Application for Simultaneous Determination of Ascorbic Acid,Dopamine and Uric Acid

In this paper electropolymerization of a thin film of para‐phenylenediamine (PPD) is studied at glassy carbon electrode (GCE) in sulfuric acid media by cyclic voltammetry. The results showed that this polymer was conducting and had a reproducible redox couple in the potential region from 0.0 to 0.4 V in phosphate buffer solution. This modified GCE (p‐PPD‐GCE) was applied for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) using differential pulse voltammetry (DPV). The p‐PPD‐GCE in 0.1 M phosphate buffer solution (pH 5.0) separated the DPV signals of AA, DA and UA with sufficient potential differences between AA–DA and DA–UA and also enhanced their oxidation peak currents. The oxidation currents were increased from 2.0 to 2000.0 µM for AA, 10.0 to 1250.0 µM for DA and 50.0 to 1600.0 µM for UA. The detection limits were evaluated as 0.4, 1.0 and 2.5 µM for AA, DA and UA, respectively (S/N=3).     

Au‐TiO2/Graphene Nanocomposite Film for Electrochemical Sensing of Hydrogen Peroxide and NADH

We describe a simple method for preparing Au‐TiO₂/graphene (GR) nanocomposite by deposition of Au nanoparticles (NPs) on TiO₂/GR substrates. The as‐prepared Au‐TiO₂/GR was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The presence of Au NPs on TiO₂/GR surface remarkably improves the electrocatalytic activity towards the oxidation of hydrogen peroxide (H₂O₂) and β‐nicotinamide adenine dinucleotide (NADH). The Au‐TiO₂/GR modified glassy carbon (GC) electrode exhibits good amperometric response to H₂O₂ and NADH, with linear range from 10 to 200 µM and 10 to 240 µM, and detection limit of 0.7 and 0.2 µM, respectively.