Electrochemical Behavior of 8‐Azaguanine at DNA Langmuir–Blodgett Modified Glassy Carbon Electrode and Its Analytical Application

A highly sensitive electrochemical biosensor for the detection of trace amounts of 8‐azaguanine has been designed. Double stranded (ds)DNA molecules are immobilized onto a glassy carbon electrode surface with Langmuir–Blodgett technique. The adsorptive voltammetric behaviors of 8‐azaguanine at DNA‐modified electrode were explored by means of cyclic voltammetry and square wave voltammetry. Compared with bare glassy carbon electrode (GCE), the Langmuir–Blodgett film modified electrode can greatly improve the measuring sensitivity of 8‐azaguanine. Under the optimum experimental conditions, the Langmuir–Blodgett film modified electrode in pH 3.0 Britton–Robinson buffer solutions shows a linear voltammetric response in the range of 5.0×10^?8 to 1.0×10^?5 mol L^?1 with detection limit 9.0×10^?9 mol L^?1. The method proposed was applied successfully for the determination of 8‐azaguanine in diluted human urine with wonderful satisfactory.     

A Simple Approach to Simultaneous Electroanalytical Quantification of Acetaminophen and Tramadol Using a Boron‐doped Diamond Electrode in the Existence of Sodium Dodecyl Sulfate

The present work describes the individual, selective and simultaneous quantification of acetaminophen (ACP) and tramadol hydrochloride (TRA) using a modification‐free boron‐doped diamond (BDD) electrode. Cyclic voltammetric measurements revealed that the profile of the binary mixtures of ACP and TRA were manifested by two irreversible oxidation peaks at about +1.04 V (for ACP) and +1.61 V (for TRA) in Britton‐Robinson (BR) buffer pH 3.0. TRA oxidation peak was significantly improved in the presence of anionic surfactant, sodium dodecyl sulfate (SDS), while ACP signal did not change. By employing square‐wave stripping mode in BR buffer pH 3.0 containing 8×10^?4 mol L^?1 SDS after 30 s accumulation under open‐circuit voltage, the BDD electrode could be used for quantification of ACP and TRA simultaneously in the ranges 1.0–70 μg mL^?1 (6.6×10^?6–4.6×10^?4 mol L^?1) and 1.0–70 μg mL^?1 (3.3×10^?6–2.3×10^?4 mol L^?1), with detection limits of 0.11 μg mL^?1 (7.3×10^?7 mol L^?1) and 0.13 μg mL^?1 (4.3×10^?7 mol L^?1), respectively. The practical applicability of the proposed approach was tested for the individual and simultaneous quantification of ACP and/or TRA in the pharmaceutical dosage forms.     

Voltammetric Determination of 3‐Nitrofluoranthene and 3‐Aminofluoranthene at Boron Doped Diamond Thin‐Film Electrode

The voltammetric behavior of 3‐nitrofluoranthene and 3‐aminofluoranthene was investigated in mixed methanol‐water solutions by differential pulse voltammetry (DPV) at boron doped diamond thin‐film electrode (BDDE). Optimum conditions have been found for determination of 3‐nitrofluoranthene in the concentration range of 2×10^?8–1×10^?6 mol L^?1, and for determination 3‐aminofluorathnene in the concentration range of 2×10^?7–1×10^?5 mol L^?1, respectively. Limits of determination were 3×10^?8 mol L^?1 (3‐nitrofluoranthene) and 2×10^?7 mol L^?1 (3‐aminofluoranthene).     

Anodic Stripping Voltammetric Determination of Mercury(II) in Water Using a 4‐Tert‐Butyl‐1‐(Ethoxycarbonylmethoxy)Thiacalix[4]Arene Modified Glassy Carbon Electrode

A glassy carbon electrode coated the film of 4‐tert‐butyl‐1‐(ethoxycarbonylmethoxy)thiacalix[4]arene is designed for the determination of trace amounts of Hg²⁺. Compared with bare glassy carbon electrode, the modified electrode can improve the measuring sensitivity of Hg²⁺. Under the optimum experimental condition, the modified electrode in 0.1 mol L^?1 H₂SO₄ + 0.01 mol L^?1 KCl solution shows a linear voltammetric response in the range of 8.0 × 10^?9 ～ 3.0 × 10^?6 mol L^?1 with detection limit 5.0 × 10^?9 mol L^?1 for Hg²⁺. The high sensitivity, selectivity, and stability of modified electrode also prove its practical application for a simple, rapid and economical determination of Hg²⁺ in water samples.     

Novel sensor based on carbon paste/Nafion? modified with gold nanoparticles for the determination of glutathione

Several problems for the direct electrochemical oxidation of reduced glutathione (GSH) challenge the usage of electroanalytical techniques for its determination. In this work, the electrochemical oxidation of GSH catalyzed by gold nanoparticles electrodeposited on Nafion modified carbon paste electrode in 0.04?mol?L^?1 universal buffer solution (pH?7.4) is proved successful. The effect of various experimental parameters including pH, scan rate and stability on the voltammetric response of GSH was investigated. At the optimum conditions, the concentration of GSH was determined using differential pulse voltammetry (DPV) in two concentration ranges: 0.1?×?10^?7 to 1.6?×?10^?5?mol?L^?1 and 2.0?×?10^?5 to 2.0?×?10^?4?mol?L^?1 with correlation coefficients 0.9988, 0.9949 and the limit of detections (LOD) are 3.9?×?10^?9?mol?L^?1 and 8.2?×?10^?8?mol?L^?1, respectively, which confirmed the sensitivity of the electrode. The high sensitivity, wide linear range, good stability and reproducibility, and the minimal surface fouling make this modified electrode useful for the determination of spiked GSH in urine samples and in tablet with excellent recovery results obtained.     

Determination of Rutin in Green Tea Infusions Using Square‐Wave Voltammetry with a Rigid Carbon‐Polyurethane Composite Electrode

This paper presents a comparative study on the electrochemical behavior of the flavonoid rutin on a rigid carbon‐polyurethane composite electrode and on a glassy carbon electrode. The electrochemical oxidation reaction of rutin was found to be quasireversible and affected by adsorption on the electrode surface. A square‐wave voltammetric method was developed for determination of rutin in green tea infusion samples using the RCPE electrode and data treatment by a deconvolution procedure. The detection limit achieved in buffered solutions was 7.1×10^?9 mol L^?1 using the RCPE and 1.7×10^?8 mol L^?1 using the GC electrode the average reproducibility for five determinations being 3.5%.     

Preparation of Polypyrrole/Nuclear Fast Red Films on Gold Electrode and Its Application on the Electrocatalytic Determination of Methyl‐dopa and Ascorbic Acid

A novel voltammetric method using the Ppyox/NFR/Au (poly pyrrole – nuclear fast red – gold) modified electrode was developed for simultaneous measurement of various combinations of ascorbic acid (AA) and methyldopa (MDA). Polypyrrole film was prepared by incorporation of nuclear fast red (NFR) as doping anion, during the electropolymerization of pyrrole onto a gold (Au) electrode in aqueous solution using cyclic voltammetric (CV) method, and then it was overoxidized at constant potential. Differential pulse voltammetry was utilized for the measurement of both analytes using modified electrode. Well‐separated voltammetric peaks were observed for ascorbic acid (AA) and methyldopa at the Ppyox/NFR/Au modified electrodes with peak separation of 0.210 V. It has been found that under optimum condition (pH 3.0), the oxidation of AA and MDA at the surface of the electrode occurs at a potential about 260 and 50 mV less positive than unmodified Au electrode respectively. The current catalytic oxidation peaks showed a linear dependent on the concentration of AA and MDA in the range of 9.0×10^?6 to 1.0×10^?3 and 1.0×10^?7 to 2.0×10^?5 mol L^?1 respectively. The detection limit of 5.8×10^?6 and 5.0×10^?8 mol L^?1 (S/N=3) were obtained for AA and MDA respectively. The modified electrode was used for determination of AA and MDA in some real samples such as human serum and tablet.     

Simultaneous Voltammetric Detection of Salsolinol and Uric Acid in the Presence of High Concentration of Ascorbic Acid with Gold Nanoparticles/Functionalized Multiwalled Carbon Nanotubes Composite Film Modified Electrode

This work demonstrates gold nanoparticles (AuNPs)/functionalized multiwalled carbon nanotubes (f‐MWCNT) composite film modified gold electrode via covalent‐bonding interaction self‐assembly technique for simultaneous determination of salsolinol (Sal) and uric Acid (UA) in the presence of high concentration of ascorbic acid (AA). In pH 7.0 PBS, the composite film modified electrode exhibits excellent voltammetric response for Sal and UA, while AA shows no voltammetric response. The oxidation peak current is linearly increased with concentrations of Sal from 0.24–11.76 μmol L^?1 and of UA from 3.36–96.36 μmol L^?1, respectively. The detection limits of Sal and UA is 3.2×10^?8 mol L^?1 and 1.7×10^?7 mol L^?1 , respectively.     

Sensitive Determination of the Diquat Herbicide in Fresh Food Samples on a Highly Boron‐Doped Diamond Electrode

The highly boron‐doped diamond electrode (HBDD) combined with square wave voltammetry (SWV) was used in the development of an analytical procedure for diquat determination in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices. Preliminary experiments realised in a medium of 0.05 mol L^?1 Na₂B₄O₇ showed the presence of two voltammetric peaks around ?0.6 V and around ?1.0 V vs. Ag/AgCl/Cl^? 3.0 mol L^?1, where the first peak could be successfully used for analytical proposes due the facility in the electrode surface renovation. After the experimental and voltammetric optimisation, the calculated detection and quantification limits were 1.6×10^?10 mol L^?1 and 5.3×10^?10 mol L^?1 (0.057 µg L^?1 and 0.192 µg L^?1, respectively), which are lower than the maximum residue limit established for fresh food samples by the Brazilian Sanitary Vigilance Agency. The proposed methodology was used to determine diquat residues in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices and the calculated recovery efficiencies indicated that the proposed procedure presents higher robustness, stability and sensitivity, good reproducibility, and is very adequate for diquat determination in complex samples.     

Square‐Wave Voltammetric Determination of Paraquat at Carbon Paste Electrode Modified with Hydroxyapatite

The voltammetric behavior of paraquat was investigated at hydroxyapatite‐modified carbon paste electrode HAP‐CPE in K₂SO₄. A method was developed for the detection of the trace of this herbicide, based on their redox reaction. The reduction peaks of paraquat were observed around ?0.70 V and ?1.00 V (vs. SCE) in square‐wave voltammetry. Experimental conditions were optimized by varying the accumulation time, apatite loading and measuring solution pH. Calibration plots were linear under the optimized parameters over the herbicide's concentration range 8–200×10^?7 mol L^?1, with a detection and quantification limits about 1.5×10^?8 mol L^?1 and 6.4 10^?8 mol L^?1, respectively.     

Voltammetric Determination of 4‐Nitrophenol and 5‐Nitrobenzimidazole Using Different Types of Silver Solid Amalgam Electrodes – A Comparative Study

The voltammetric behavior of two genotoxic nitro compounds (4‐nitrophenol and 5‐nitrobenzimidazole) has been investigated using direct current voltammetry (DCV) and differential pulse voltammetry (DPV) at a polished silver solid amalgam electrode (p‐AgSAE), a mercury meniscus modified silver solid amalgam electrode (m‐AgSAE), and a mercury film modified silver solid amalgam electrode (MF‐AgSAE). The optimum conditions have been evaluated for their determination in Britton‐Robinson buffer solutions. The limit of quantification (L_Q) for 5‐nitrobenzimidazole at p‐AgSAE was 0.77 µmol L^?1 (DCV) and 0.47 µmol L^?1 (DPV), at m‐AgSAE it was 0.32 µmol L^?1 (DCV) and 0.16 µmol L^?1 (DPV), and at MF‐AgSAE it was 0.97 µmol L^?1 (DCV) and 0.70 µmol L^?1 (DPV). For 4‐nitrophenol at p‐AgSAE, L_Q was 0.37 µmol L^?1 (DCV) and 0.32 µmol L^?1 (DPV), at m‐AgSAE it was 0.14 µmol L^?1 (DCV) and 0.1 µmol L^?1 (DPV), and at MF‐AgSAE, it was 0.87 µmol L^?1 (DCV) and 0.37 µmol L^?1 (DPV). Thorough comparative studies have shown that m‐AgSAE is the best sensor for voltammetric determination of the two model genotoxic compounds because it gives the lowest L_Q, is easier to prepare, and its surface can be easily renewed both chemically (by new amalgamation) and/or electrochemically (by imposition of cleaning pulses). The practical applicability of the newly developed methods was verified on model samples of drinking water.     

Amperometric Folic Acid Quantification Using a Supramolecular Tetraruthenated Nickel Porphyrin µ‐Peroxo‐Bridged Matrix Modified Electrode Associated to Batch Injection Analysis

A supramolecular Nickel (II) porphyrin complex containing four pyridyl‐bis(2,2′‐bipyridyl)chloro ruthenium meso substituents was submitted to successive voltammetric cycles in high alkaline media to produce a supramolecular matrix with Nickel centers linked by µ‐peroxo bridges, producing a highly stable thin film able to act as redox mediator for electrocatalytic oxidation of folic acid. The characterization of electrode surface material was performed by Scanning Electron Microscopy and Electrochemical Impedance Spectroscopy. The modified electrode was inserted into a batch injection electrochemical cell used for the rapid and precise quantification of folic acid in pharmaceutical products. The favorable hydrodynamic conditions provided by amperometry‐BIA association allowed a very high throughput with good linear range (1 to 200 µmol L^?1) and low detection limit (7.37×10^?7 mol L^?1). The electrochemical method was applied to the quantification of folic acid in different tablet samples. The results were comparable with values indicated by the manufacturer and those found using high HPLC according to the Brazilian Pharmacopoeia; commercial samples were submitted to a procedure in order to remove lactose of tablets, since carbohydrates act as interfering species. This procedure together with the electrochemical method showed to be simple, rapid, efficient and an appropriate alternative for quantifying this compound in real samples.     

Sensitive and Selective Detection of Dopamine Using a DNA Immobilized Ethylenedidamine/Polyglutamic Modified Electrode

DNA was attached on the surface of an ethylenedidamine/polyglutamic(En/PGA) modified glassy carbon electrode (GCE) to create a novel voltammetric sensor (DNA/En/PGA/GCE) for dopamine (DA). This modified electrode exhibited a linear voltammetric response for DA in the range from 1.0×10^?7 mol L^?1 to 1×10^?5 mol L^?1, with a detection limit of 2×10^?8 mol L^?1. The detection of DA was found to be unaffected by the presence of ascorbic acid, uric acid, serotonin and folic acid. The method proposed was applied to detect DA in pharmaceutical dosage and human blood serum with good satisfactory results.     

Nanomolar Determination of Penicillamine by Using a Novel Cobalt/Polyaniline/Carbon Paste Nanocomposite Electrode

The fabrication of cobalt/polyaniline nanocomposite was performed using a simple chemical method. It was characterized by using TEM and FTIR techniques. The nanocomposite was applied as a modifier in a carbon paste electrode for selective determination of penicillamine. Penicillamine reacts with emeraldine polyaniline by using 1,4, Michael addition reaction. It can decrease the voltammetric peak current of emeraldine polyaniline. The effects of pH and potential sweep rate on the response of the electrode were investigated. Differential pulse voltammetry was applied for quantitative determination. Dynamic linear ranges were obtained in the ranges of 1.0×10^?8–1.0×10^?7 mol L^?1 and 1.0×10^?9–1.0×10^?8 mol L^?1.     

Electrochemical Behaviors of Adenosine‐5′‐triphosphate on Molecular Wire Modified Carbon Paste Electrode and Its Sensitive Detection

A new electrochemical method was proposed for the determination of adenosine‐5′‐triphosphate (ATP) based on the electrooxidation at a molecular wire (MW) modified carbon paste electrode (CPE), which was fabricated with diphenylacetylene (DPA) as the binder. A single well‐defined irreversible oxidation peak of ATP appeared on MW‐CPE with adsorption‐controlled process and enhanced electrochemical response in a pH 3.0 Britton‐Robinson buffer solution, which was due to the presence of high conductive DPA in the electrode. The electrochemical parameters of ATP were calculated with the electron transfer coefficient (α) as 0.54, the electron transfer number (n) as 1.9, the apparent heterogeneous electron transfer rate constant (k_s) as 2.67 × 10^?5 s^?1 and the surface coverage (Γ_T) as 4.15 × 10^?10 mol cm^?2. Under the selected conditions the oxidation peak current was proportional to ATP concentration in the range from 1.0 × 10^?7 mol L^?1 to 2.0 × 10^?3 mol L^?1 with the detection limit as 1.28 × 10^?8 mol L^?1 (3σ) by sensitive differential pulse voltammetry. The proposed method showed good selectivity without the interferences of coexisting substances and was successful applied to the ATP injection samples detection.     

Simultaneous Determination of Dihydroxybenzene Isomers at MWCNTs/β‐Cyclodextrin Modified Carbon Ionic Liquid Electrode in the Presence of Cetylpyridinium Bromide

Simultaneous determination of dihydroxybenzene isomers was investigated at a multi‐wall carbon nanotubes (MWCNTs)/β‐cyclodextrin composite modified carbon ionic liquid electrode in phosphate buffer solution (pH 7.0, 1/15 mol/L) in the presence of cationic surfactant cetylpyridinium bromide (CPB). With the great enhancement of surfactant CPB, the voltammetric responses of dihydroxybenzene isomers were more sensitive and selective. The oxidation peak potential of hydroquinone was about 0.024 V, catechol was about 0.140 V and resorcinol 0.520 V in differential pulse voltammetric (DPV) measurements, which indicated that the dihydroxybenzene isomers could be separated entirely. The electrode showed wide linear behaviors in the range of 1.2×10^?7–2.2×10^?3, 7.0×10^?7–1.0×10^?3, 2.6×10^?6–9.0×10^?4 mol/L for hydroquinone, catechol and resorcinol, respectively. And the detection limits of the three dihydroxybenzene isomers were 4.0×10^?8, 8.0×10^?8, 9.0×10^?7 mol/L, respectively. The proposed method could be applied to the determination of dihydroxybenzene isomers in artificial wastewater, and the recovery was from 97.4% to 104.2%.     

Determination of ferulic acid in Chinese proprietary medicine based on a poly-glutamic acid film sensor

The poly-glutamic acid modified electrode has been prepared by direct electro-polymerization of D-glutamic acid on the surface of glassy carbon electrode. In pH 4.2, 0.1 mol L^?1 HAc-NaAc buffer solution, the film modified electrode exhibited remarkable enhancement effect to the electrochemical responses of ferulic acid. The action mechanism was preliminarily explored. In the range of 2.0 × 10^?7 to 1.0 × 10^?5 mol L^?1, and 1.0 × 10^?5 to 3.0 × 10^?4 mol L^?1, the oxidation peak current has a linear relationship to the concentration, and the detection limit was estimated to be 7.0 × 10^?8 mol L^?1. This method has been adopted to detect trace amount of ferulic acid in Chinese proprietary medicine, and the recovery was from 97.8 to 102.4%.     

Selective Electrochemical Determination of Dopamine with Molecularly Imprinted Poly(Carbazole‐co‐Aniline) Electrode Decorated with Gold Nanoparticles

Dopamine (DA) is a significant neurotransmitter in the central nervous system, coexisting with uric acid (UA) and ascorbic acid (AA). UA and AA are easily oxidizable compounds having potentials close to that of DA for electrochemical analysis, resulting in overlapping voltammetric response. In this work, a novel molecularly imprinted (MI) electrochemical sensor was proposed for selective determination of DA (in the presence of up to 80‐fold excess of UA and AA), relying on gold nanoparticles (Au_nano)‐decorated glassy carbon (GC) electrode coated with poly(carbazole (Cz)‐co‐aniline (ANI)) copolymer film incorporating DA as template (DA imprinted‐GC/P(Cz‐co‐ANI)‐Au_nano electrode, DA‐MIP‐Au_nano electrode). The DA recognizing sensor electrode showed great electroactivity for analyte oxidation in 0.2 mol L^?1 pH 7 phosphate buffer. Square wave voltammetry (SWV) was performed within 10^?4–10^?5 mol L^?1 of DA, of which the oxidation peak potential was observed at 0.16 V. The limit of detection (LOD) and limit of quantification (LOQ) were 2.0×10^?6 and 6.7×10^?6 mol L^?1, respectively. Binary and ternary synthetic mixtures of DA‐UA, DA‐AA and DA‐UA‐AA yielded excellent recoveries for DA. Additionally, DA was quantitatively recovered from a real sample of bovine serum spiked with DA, and determined in concentrated dopamine injection solution. The developed SWV method was statistically validated against a literature potentiodynamic method using a caffeic acid modified‐GC electrode.     

The New Application of Boron Doped Diamond Electrode Modified with Nafion and Lead Films for Simultaneous Voltammetric Determination of Dopamine and Paracetamol

A new voltammetric procedure for the simultaneous determination of dopamine (DA) and paracetamol (PA) using boron doped diamond electrode modified with Nafion and lead films (PbF/Nafion/BDDE) was investigated. The use of this electrode resolved the overlapped voltammetric waves of DA and PA into well‐defined peaks with peak to peak separation of about 320 mV. Under the optimized experimental conditions in differential pulse voltammetric technique, DA and PA gave a linear response over the ranges 2.0×10^?7–1.0×10^?4 mol L^?1*(R²=0.9996) and 5.0×10^?7–1.0×10^?3 mol L^?1 (R²=0.9979), respectively. The detection limits were found to be 5.4×10^?8 mol L^?1 for DA and 1.4×10^?7 mol L^?1 for PA. They are lower, comparable or in some cases a little bit higher than those obtained using other electrochemical sensors. However, the proposed procedure of the sensor preparation is much simpler than procedures described in the literature with a lower detection limit. The proposed procedure was successfully applied to the determination of PA in some commercial pharmaceuticals as well as to the simultaneous determination of DA and PA in human urine, whole blood and serum samples directly without any separation steps.     

Voltammetric Determination of Proguanil in Malarone and Spiked Urine with a Renewable Silver Amalgam Film Electrode

Electrochemical properties of proguanil were investigated by a voltammetric method (SWV) using a renewable silver amalgam film electrode. The influence of buffer pH as well as potential amplitude, frequency, and step potential was studied. The repeatability, precision and recovery of the developed method were examined. The reduction peak current was used for proguanil voltammetric determination in the range 1×10^?7–6×10^?6 mol L^?1, LOD=2.9×10^?8 mol L^?1, LOQ=9.7×10^?8 mol L^?1. The standard addition method was used to determine proguanil in a commercial formulation (Malarone) and in spiked urine.