Determination of lead(II) in aqueous solution using carbon nanotubes paste electrodes modified with Amberlite IR-120

A new composite electrode is described for anodic stripping voltammetry determination of Pb(II) at trace level in aqueous solution. The electrode is based on the use of multiwalled carbon nanotubes and Amberlite IR-120. The anodic stripping voltammograms depend, to a large extent, on the composition of the modified electrode and the preconcentration conditions. Under optimum conditions, the anodic peak current at around ?0.57 V is linearly related to the concentration of Pb(II) in the range from 9.6?×?10^?8 to 1.7?×?10^?6 mol L^?1 (R?=?0.998). The detection limit is 2.1?×?10^?8 mol L^?1, and the relative standard deviation (RSD) at 0.24?×?10^?6 mol L^?1 is 1.7% (n?=?6). The modified electrode was applied to the determination of Pb(II) using the standard addition method; the results showed average relative recoveries of 95% for the samples analysed.

Evaluation of a novel composite based on functionalized multi-walled carbon nanotube and iron phthalocyanine for electroanalytical determination of isoniazid

A novel platform for electroanalysis of isoniazid based on graphene-functionalized multi-walled carbon nanotube as support for iron phthalocyanine (FePc/f-MWCNT) has been developed. The FePc/f-MWCNT composite has been dropped on glassy carbon forming FePc/f-MWCNT/GC electrode, which is sensible for isoniazid, decreasing substantially its oxidation potential to +200 mV vs Ag/AgCl. Electrochemical and electroanalytical properties of the FePc/f-MWCNT/GC-modified electrode were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, scanning electrochemical microscopy, and amperometry. The sensor presents better performance in 0.1 mol L^?1 phosphate buffer at pH 7.4. Under optimized conditions, a linear response range from 5 to 476 μmol L^?1 was obtained with a limit of detection and sensitivity of 0.56 μmol L^?1 and 0.023 μA L μmol^?1, respectively. The relative standard deviation for 10 determinations of 100 μmol L^?1 isoniazid was 2.5%. The sensor was successfully applied for isoniazid selective determination in simulated body fluids.     

Voltammetric determination of 17α-ethinylestradiol hormone in supply dam using BDD electrode

In this work, a simple method for electroanalytical determination of 17α-ethinylestradiol (EE2) hormone in natural waters was developed using a boron-doped diamond electrode (BDD). The analyses were performed using square wave voltammetry and the parameters were optimized. The results showed a well-defined irreversible oxidation peak (BR buffer 0.1 mol L^?1, pH 8.0) at +0.65 V (vs. Ag/AgCl). The voltammetric results showed also that the oxidation process is controlled by adsorption of species and indicated that there are two electrons involved. The obtained analytical curves for 17α-ethinylestradiol presented good linearity in the concentration range 9.9?×?10^?7 to 5.2?×?10^?6 mol L^?1 in utlrapure water and 7.9?×?10^?7 to 5.2?×?10^?6 mol L^?1 in natural water samples (supply dam). Detection limits (DL) obtained were between 2.4?×?10^?7 and 7.5?×?10^?7 mol L^?1 and quantification limits (QL) between 7.9?×?10^?7 and 2.5?×?10^?6 mol L^?1. The recovery experiments showed values between 86 and 114 % for spiked samples thus indicating the applicability of the electroanalytical methodology to quantify 17α-ethinylestradiol directly in natural water of supply Dam (Billings Dam in Diadema-SP. Brazil), without any preconcentration or derivatization.     

Stripping voltammetry method for determination of manganese as complex with oxine at the carbon paste electrode with and without modification with montmorillonite clay

Oxine (8-hydroxyquinoline) was used as an efficient and selective ligand for stripping voltammetry trace determination of Mn(II). A validated square-wave adsorptive cathodic stripping voltammetry method has been developed for determination of Mn(II) selectively as oxine complex using both the bare carbon paste electrode (CPE) and the modified CPE with 7 % (w/w) montmorillonite-Na clay. Modification of carbon paste with montmorillonite clay was found to greatly enhance its adsorption capacity. Limits of detection of 45 ng l^?1 (8.19?×?10^?10 mol L^?1) and 1.8 ng l^?1 (3.28?×?10^?11 mol L^?1) Mn(II) were achieved using the bare and modified CP electrodes, respectively. The achieved limits of detection of Mn(II) as oxine complex using the modified CPE are much sensitive than the detection limits obtained by most of the reported electrochemical methods. The developed stripping voltammetry method using both electrodes was successfully applied for trace determination of Mn(II) in various water samples without interferences from various organic and inorganic species.     

Static and Hydrodynamic Monitoring of Citalopram Based on its Electro-oxidation Behavior at a Glassy-Carbon Surface

Abstract

The electrooxidative behavior of citalopram (CTL) in aqueous media was studied by cyclic voltammetry (CV) and square-wave voltammetry (SWV) at a glassy-carbon electrode. The electrochemical behaviour of CTL involves two electrons and two protons in the irreversible and diffusion controlled oxidation of the tertiary amine group. The maximum analytical signal was obtained in a phosphate buffer (pH = 8.2). For analytical purposes, an SWV method and a flow-injection analysis (FIA) system with amperometric detection were developed. The optimised SWV method showed a linear range between 1.10 × 10^?5–1.20 × 10^?4 mol L^?1, with a limit of detection (LOD) of 9.5 × 10^?6 mol L^?1. Using the FIA method, a linear range between 2.00 × 10^?6–9.00 × 10^?5 mol L^?1 and an LOD of 1.9 × 10^?6 mol L^?1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products.     

Determination of Hydrogen Peroxide Using a Novel Sensor Based on Fe3O4 Magnetic Nanoparticles

Fe₃O₄ magnetic nanoparticles were synthesized by chemical co-precipitation with sodium citrate as a surfactant and were used with chitosan to construct a novel hydrogen peroxide sensor. The electrochemical behavior of hydrogen peroxide at the sensor was investigated by cyclic voltammetry. The composite film electrocatalyzed the reduction of hydrogen peroxide, and the peak current increased linearly with concentration from 1.00 × 10^?5 to 1.00 × 10^?3 mol · L^?1 (R = 0.9974) with a detection limit of 1.53 × 10^?6 mol · L^?1. This novel nonenzyme sensor provided good sensitivity, stability, and precision with potential applications.     

Electrochemical Behavior of Verapamil at Graphite–Polyurethane Composite Electrodes: Determination of Release Profiles in Pharmaceutical Samples

Abstract

A solid graphite–polyurethane composite electrode has been used to determine release profiles of verapamil, a calcium-channel blocker. The electro-oxidation process was characterized by cyclic voltammetry and electrochemical impedance spectroscopy and showed no adsorption of analyte or oxidation products, unlike at other carbon-based electrodes. Quantification gave linear ranges up to 40 µmol L^?1 with cyclic voltammetry and detection limits of 0.7 µmol L^?1 by differential pulse and square-wave voltammetry. Commercial product samples were successfully analyzed with results equal to those from spectrophotometry. Because no electrode surface renewal is needed, this electrode material has many advantages.     

Simultaneous Analysis of Sugars and Polyphenols in Tobacco by CZE with Amperometric Detection Based on a Cu2O/MWCNT-COOH Composite Electrode

A composite electrode was fabricated from Cu₂O powder, carboxyl-functionalized multi-wall carbon nanotubes (MWCNT-COOH), and paraffin oil in the proportions 51:17:32 (w/w). This composite electrode was used for amperometric detection (CZE–AD) in simultaneous capillary zone electrophoretic analysis of chlorogenic acid, rutin, sucrose, glucose, mannose, and fructose in tobacco samples. Under the optimum conditions, the six analytes could be separated in 100 mmol L^?1 NaOH buffer within 30 min. Good linearity was achieved in the range 1 × 10^?7–1 × 10^?4 mol L^?1 for the two polyphenols and 5 × 10^?6–1 × 10^?3 mol L^?1 for the four sugars. The detection limits (S/N = 3) for the polyphenols and sugars were as low as 10^?8 mol L^?1 and 10^?6 mol L^?1, respectively.     

Determination of Catechol by a Laccase Biosensor Based on Silica-Modified Zirconia Nanoparticles

A promising nanotechnological material, zirconia nanoparticles modified with SiO₂, was used as a medium for the immobilization of laccase to construct a novel biosensor that exhibits sensitive amperometric response to catechol in 0.1 mol · L^?1 phosphate buffer (pH 6.0) using cyclic voltammetry. The linear response to catechol was from 1.0 × 10^?6 to 1.0 × 10^?4 mol · L^?1 and the detection limit was 3.5 × 10^?7 mol · L^?1 at a signal-to-noise ratio of 3. The biosensor exhibited good stability, precision, and few interferences.     

Functionalised multi-walled carbon nanotubes-modified electrode for sensitive determination of Diuron in seawater samples

ABSTRACT

This work was focused in to develop an electroanalytical method based on a direct modification of a glassy carbon electrode (GCE) by the deposition of successive aliquots of diluted dispersions of functionalised carbon nanotubes (MWCNT-COOH) in ethanol (0.1 mg.mL^?1) aiming the determination of Diuron into seawater samples, a common antifouling substance, using differential pulse voltammetry as electroanalytical technique. The GCE/MWCNT-COOH showed a sensitivity of 2.20 μA/μmol L^?1 about 10 times higher than the unmodified counterpart (GCE) which showed a sensitivity of 0.192 μA/μmol L^?1. The limits of detection and quantificationwere 6.88 × 10^?8 and 2.29 × 10^?7 mol L^?1 for GCE/MWCNT-COOH while for GCE were 7.87 × 10^?7 and 2.62 × 10^?6 mol L^?1, respectively. The applicability was evaluated with spiked detectable amounts of Diuron into seawater samples. The recovery results were between 76% and 119%.     

Rapid voltammetric determination of maltol in some foods and beverages using a poly(methylene blue)/graphene-modified glassy carbon electrode

A novel poly(methylene blue)/graphene composite glassy carbon electrode was fabricated and the electrochemical behavior of maltol at the modified electrode was studied by cyclic voltammetry. In phosphate-buffered solution, the modified electrode exhibited excellent electrocatalytic activity towards the electrochemical oxidation of maltol. Under optimized conditions, the oxidation peak current showed a linear relationship with the concentrations of maltol in the ranges of 8.00?×?10^?7 to 4.00?×?10^?5 and 4.00?×?10^?5 to 5.40?×?10^?4 mol L^?1, with a detection limit of 6.50?×?10^?8 mol L^?1. The performance of the developed method was validated in terms of linearity (r?=?0.9981 and 0.9955), recovery (97.0?99.3 %), reproducibility (relative standard deviations?≤?3.1 %, n?=?6), and robustness. The method shows excellent sensitivity, selectivity, and reproducibility and has been successfully applied to analyzing maltol in a wide variety of food products.     

Evaluation of the Potentialities of a Carbon Nanotubes/Silicone Rubber Composite Electrode in the Determination of Hydrochlorothiazide

A multiwall carbon nanotube/silicone rubber (MWCNT/SR) composite electrode has been used for the determination of hydrochlorothiazide (HCTZ) in pharmaceutical formulations by differential pulse voltammetry (DPV). The electro-oxidation process was evaluated by cyclic voltammetry, from which it was observed that HCTZ presents an irreversible oxidation peak at 0.82 V vs. saturated calomel electrode (SCE) in the potential range from 0.5 to 1.1 V, in Britton-Robinson buffer pH 7.0 at MWCNT/SR. HCTZ was determined by DPV using a MWCNT/SR 70% (MWCNT, m/m) composite electrode after the optimization of the experimental parameters. The linear range was from 5.0 to 70.0 µ mol L^?1, with a limit of detection (LOD) of 2.6 µ mol L^?1. The HCTZ was determined in pharmaceutical formulations using the proposed composite electrode and the results agreed with those from the official high performance liquid chromatography (HPLC) method within 95% confidence level, according to the t-Student test.     

Selective Spectrofluorimetric Method and Uncertainty Calculation for the Determination of Camptothecin in the Presence of Irinotecan and Topotecan

A selective fluorimetric method was developed to quantify camptothecin (CPT) in irinotecan (CPT-11) and in topotecan (TPT) based anti-cancer drugs. Selectivity was achieved by experimental optimization and using synchronized scanning and second-order spectral derivatization. The limits of quantification for CPT were in the order of 1 × 10^?7 mol L^?1 with a linear response up to 1 × 10^?5 mol L^?1. The combined uncertainty associated with the CPT fluorescence measurement at a 5 × 10^?7 mol L^?1 level were 10.9% and 6% of the reference level, respectively, for TPT and CPT-11 based pharmaceutical formulations. The CPT recoveries of 95 ± 12% and 91 ± 5.6% (n = 3) were achieved, respectively, in samples containing CPT-11 and TPT.     

Electrooxidation of trifloxystrobin at the boron-doped diamond electrode: electrochemical mechanism,quantitative determination and degradation studies

The boron-doped diamond (BDD) presents attractive electrochemical sensing characteristics that are useful in analytical applications based on voltammetry and amperometry. It has a wide potential window in aqueous solutions enabling the quantification of the fungicide trifloxystrobin, measured at +1744 mV (versus Ag/AgCl), by square-wave anodic voltammetry in a Britton–Robinson (BR) buffer (0.04 mol L^?1; pH 4.00)/acetonitrile 70/30% v/v. The activation of the electrode was made using galvanostatic chronopotentiometry and cyclic voltammetry (CV). The linear analyte addition curve, I_p (µA) = (1.0 × 10^–1 ± 4.8 × 10^–6) C (mol L^?1) + (8.8 × 10^–2 ± 1.1 × 10^–3); R² = 0.997, was obtained using amplitude of 40 mV, frequency of 30 Hz, step potential of 20 mV. The instrumental limit of detection (LOD) was 1.4 × 10^–7 mol L^?1 (0.058 mg L^?1) and the dynamic linear range covered three decades (up to 1 × 10^–5 mol L^?1 or 4.1 mg L^?1). The samples were analysed with recoveries about 80% in orange juice samples and from 92.4% to 104.0% in water samples. A study to evaluate potential interferences was made in the presence of other fungicides. Diagnostic studies indicated that oxidation of trifloxystrobin in aqueous medium at the surface of the BDD is irreversible, involving two steps, each one with two electrons. The UV degradation of trifloxystrobin was evaluated using the proposed electrochemical method and the kinetics of degradation established with half-life of 1.07 min.     

Synergistic Effect of Graphene and Multiwalled Carbon Nanotubes on a Glassy Carbon Electrode for Simultaneous Determination of Uric Acid and Dopamine in the Presence of Ascorbic Acid

A poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotube modified glassy carbon electrode was fabricated and evaluated by cyclic voltammetry and differential pulse voltammetry. The modified electrode offered high sensitivity, selectivity, excellent long-term stability, and electrocatalytic activity for uric acid and dopamine. This sensor showed wide linear dynamic ranges of 5.0 to 350.0 µmol L^?1 for uric acid and 10.0 to 400.0 µmol L^?1 for dopamine in the presence of 500 µmol L^?1 ascorbic acid. The limits of detection were 0.13 for uric acid and 0.55 µmol L^?1 for dopamine. This functionalized electrode has potential application in bioanalysis and biomedicine.     

Detection of rutin at DNA modified carbon paste electrode based on a mixture of ionic liquid and paraffin oil as a binder

A DNA-modified carbon paste electrode (DNA-CPIE) was designed by using a mixture of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate and paraffin oil as the binder. The electrochemistry of rutin at the DNA-CPIE was investigated by cyclic voltammetry and differential pulse voltammetry. Rutin exhibits a pair of reversible redox peaks in buffer solutions of pH 3.0, and respective electrochemical parameters are established. Under the optimal conditions, the oxidative peak current is linear with the concentration of rutin in the range from 8?×?10^?9 to 1?×?10^?5 mol L^?1, and the detection limit is 1.3?×?10^?9 mol L^?1 (at S/N?=?3). The electrode exhibits higher sensitivity compared to DNA modified carbon paste electrode without ionic liquid and better selectivity comparing with electrodes without DNA. It also showed good performance, stability, and therefore represents a viable method for the determination of rutin.     

Alizarin-modified sulfonate carbon nanoparticles in vanadium sensing

The adsorption processes of alizarin onto hydrophilic carbon nanoparticles (Emperor 2000?) are investigated. The significant increase in voltammetric responses for pre-adsorbed alizarin compared with those for solution confirms high affinity of alizarin to carbon nanoparticles (possibly due to π–π stacking interaction between aromatic rings of alizarin and surface-sulfonated carbon nanoparticles). To obtain the optimum of adsorption conditions, the effects of pH, agitation rate, and adsorption time are investigated. Under square wave voltammetry conditions, the peak current for the reduction of alizarin shows a linear relationship with concentration in the range from 2.0 to 10.0 nM. The limit of detection is estimated 5.8?×?10^?9 mol L^?1. Next, alizarin is applied as a receptor for sensing of trace vanadium in acetate buffer pH 5. Linear calibration curves are obtained for vanadium in the range of 1.0?×?10^?6 to 1.0?×?10^?4 mol L^?1 and the limit of detection is estimated 9.6?×?10^?8 mol L^?1. Determination of vanadium in real samples such as sea and tap water is demonstrated.     

A novel and simple biosensor based on poly(indoleacetic acid) film and its application for simultaneous electrochemical determination of dopamine and epinephrine in the presence of ascorbic acid

A novel and simple biosensor based on poly(indoleacetic acid) film-modified electrode (PIAA/CPE) was fabricated by electrochemical polymerization of indoleacetic acid on a carbon paste electrode (CPE) through cyclic voltammetry. The resulting electrode was characterized by scanning electron microscopy, and the electrochemical behaviors of dopamine (DA) and epinephrine (EP) at the electrode were studied. It was illustrated that PIAA/CPE had excellent electrochemical catalytic activities toward DA and EP. The anodic peak currents (I _pa) were dramatically enhanced by about seven-fold for DA and ten times for EP at PIAA/CPE. Thus, the determinations of DA and EP were carried out using PIAA/CPE successfully. The linear responses were obtained in the range of 3.0?×?10^?7～7.0?×?10^?4 and 1.0?×?10^?6 ～8.0?×?10^?4 mol L^?1 with the detection limits (3σ) of 1?×?10^?7 and 4?×?10^?7 mol L^?1 corresponding with DA and EP, respectively. Moreover, the cathodic peaks of DA and EP were well-separated with a potential difference about 325 mV in pH 5.3 phosphate-buffered saline, so simultaneous determination of DA and EP was carried out in this paper. Additionally, the interference studies showed that the PIAA/CPE exhibited excellent selectivity in the presence of ascorbic acid (AA). With good selectivity and sensitivity, the present method has been successfully applied to the determination of DA and EP in pharmaceutical samples.     

Ionic silsesquioxane film immobilized on silica applied in the development of carbon paste electrode for determination of methyl parathion

A mesoporous silica-based hybrid material composed of silica xerogel modified with an ionic silsesquioxane, which contains the 1,4-diazoniabicyclo[2.2.2]octane chloride group, was obtained. The silsesquioxane film is highly dispersed on the surface. This hybrid material was utilized to develop a carbon paste electrode (CPE) for determination of methyl parathion. Transmission FTIR, elemental analysis and N₂ adsorption–desorption isotherms were used for characterization of the material. The electrochemical behavior of methyl parathion was evaluated by cyclic voltammetry and differential pulse voltammetry. It was observed a linear response to methyl parathion in the concentration range from 1.25 × 10^?7 to 2.56 × 10^?6 mol L^?1 by employing the carbon paste electrode, in Britton–Robinson buffer solution (pH 6). The achieved detection limit (3 SD of the blank divided by the slope of calibration curve) was 0.013 µmol L^?1 and sensitivity was 6.3 µA µmol L^?1. This result shows the potentiality of this electrode for application as electrochemical sensor for methyl parathion.     

Self-assembled sensor based on boron-doped diamond and its application in voltammetric analysis of picloram

A self-assembled sensor based on a boron-doped diamond was investigated as a sensitive tool for voltammetric analysis of a member of a pyridine herbicide family - picloram. A cyclic voltammetry and a differential pulse voltammetry were applied for investigation of the voltammetric behaviour and quantification of this herbicide. Picloram yielded one well-developed irreversible oxidation signal at a very positive potential about +1.5 V vs. Ag/AgCl/3 mol L^?1 KCl electrode in an acidic medium and 1 mol L^?1 H₂SO₄ was chosen as a suitable supporting electrolyte. Operating parameters of differential pulse voltammetry were optimized and the proposed voltammetric method provided a high repeatability (a relative standard deviation of 20 repeated measurements at a concentration level of picloram of 50 µmol L^?1 equaled to 2.58%), a linear concentration range from 2.5 to 90.9 µmol L^?1 and a low limit of detection (LD = 1.64 µmol L^?1). Practical usefulness of the ‘environmentally-green’ electrochemical sensor was verified by an analysis of spiked water samples with satisfactory recoveries.