Simultaneous determination of adenine and guanine utilizing PbO2-carbon nanotubes-ionic liquid composite film modified glassy carbon electrode

A novel and reliable electrochemical sensor based on PbO₂-carbon nanotubes-room temperature ionic liquid (i.e., 1-butyl-3-methylimidazolium hexafluorophosphate, BMIMPF6) composite film modified glassy carbon electrode (GCE) (PbO₂–MWNT–RTIL/GCE) was proposed for simultaneous and individual determination of guanine and adenine. The guanine and adenine oxidation responses were monitored by differential pulse voltammetric (DPV) measurement. Compared with the bare electrode, the PbO₂–MWNT–RTIL/GCE not only significantly enhanced the oxidation peak currents of guanine and adenine, but also lowered their oxidation overpotentials, suggesting that the synergistic effect of PbO₂, MWNT and RTIL could dramatically improve the determining sensitivity of guanine and adenine. The PbO₂–MWNT–RTIL/GCE showed good stability, high accumulation efficiency and enhanced electrocatalytic ability for the detection of guanine and adenine. Besides, the modified electrode also exhibited good behaviors in the simultaneous detection of adenine and guanine with the peak separation of 0.29 V in 0.1 M pH 7.0 phosphate buffer solution (PBS). Under the optimal conditions, the detection limit for individual determination of guanine and adenine was 6.0 × 10⁻⁹ M and 3.0 × 10⁻⁸ M (S/N = 3), respectively. The proposed method for the measurements of guanine and adenine in herring sperm DNA was successfully applied with satisfactory results.     

Fabrication of functionalized carbon nanotube modified glassy carbon electrode and its application for selective oxidation and voltammetric determination of cysteamine

The functionalized carbon nanotube electrode was fabricated by electrodeposition of 1,2-naphthoquinone-4-sulfonic acid sodium (Nq) on single-wall carbon nanotube (SWNT) modified glassy carbon electrode (GCE). This electrode was characterized by scanning electron microscopy (SEM) and the results showed that Nq can rapidly and effectively be deposited on the surface of SWNT film with high stability. The electrochemical properties of functionalized SWNT/GCE with Nq (SWNT–Nq/GCE) were studied using cyclic voltammetry, double step potential chronoamperometry and differential pulse voltammetry methods. The results indicated that SWNT could improve the electrochemical behavior of Nq and greatly enhances its redox peak currents. The SWNT–Nq/GCE exhibited a pair of well-defined redox peaks. The experimental results also demonstrated that the Nq deposited species on SWNT could catalyze cysteamine oxidation and SWNT–Nq exhibited a high performance with lowering the overpotential by more than 710 mV. The effect of pH value, number of scans and Nq concentration were investigated on the electrochemical behavior of cysteamine. The selectivity of the reaction has been assessed with no interference from tyrosine, lysine, methionine, tryptophan, alanine and glutathione. The presented method has highly selectivity for voltammetric detection of cysteamine in the dynamic range from 5.0 × 10⁻⁶ M to 2.7 × 10⁻⁴ M and with a detection of limit (3σ) 3.0 × 10⁻⁶ M.     

Voltammetric sensor based on ordered mesoporous carbon for folic acid determination

With ordered mesoporous carbon (OMC) as the modifier, a voltammetric sensor for folic acid (FA) was constructed on a glassy carbon electrode (GCE). Due to the good characteristics of OMC, FA exhibited an enhanced electrochemical response and lower reduction potential in the neutral solution. In addition, the experimental parameters such as pH values, accumulation time and potential were optimized. Using the differential pulse voltammetry (DPV) measurement, the peak current was found to be linear with FA concentration in the range from 5.0 × 10⁻¹⁰ to 1.0 × 10⁻⁷ M with a lower detection limit of 6.0 × 10⁻¹¹ M (S/N = 3). Also, in real samples analysis, the as-prepared sensor successfully gives satisfying results.     

Simultaneous determination of dopamine,ascorbic acid and uric acid on ordered mesoporous carbon/Nafion composite film

Here we report the selective, sensitive and simultaneous determination of dopamine (DA), ascorbic acid (AA) and uric acid (UA) on ordered mesoporous carbon (OMC)/Nafion composite film. Insoluble OMC was dispersed into ethanol in the presence of 0.5% Nafion, resulting in a stable and well-distributed OMC/Nafion suspension. After evaporation of ethanol, a uniform OMC/Nafion composite film-coated glassy carbon electrode (GCE) was achieved by simple casting deposition. The OMC/Nafion electrode shows ideal reversibility in 5 mM K₃[Fe(CN)₆] in the range of 0.02–0.50 V s⁻¹, indicating a fast electron-transfer kinetics. Moreover, due to the strong catalytic function of OMC, the overlapping voltammetric response of DA, AA and UA is well-resolved from each other with lowered oxidation potential and enhanced oxidation currents. The mechanism for the oxidation of AA, DA and UA at the OMC/Nafion film was also studied. By using differential pulse voltammetry (DPV), detection limits of 0.5, 20 and 4.0 μM were obtained for DA, AA and UA, respectively. The practical application of the electrode is successfully demonstrated for the determination of DA, AA and UA simultaneously in standard and real samples, without any preliminary treatment.     

Electrochemical determination of naltrexone on the surface of glassy carbon electrode modified with Nafion-doped carbon nanoparticles: Application to determinations in pharmaceutical and clinical preparations

A new sensitive and selective electrochemical sensor was developed for determination of naltrexone (NAL) in pharmaceutical dosage form and human plasma. Naltrexone is an opioid antagonist which is commonly used for the treatment of narcotic addiction and alcohol dependence. A voltammetric study of naltrexone has been carried out at the surface of glassy carbon electrode (GCE) modified with Nafion-doped carbon nanoparticles (CNPs). The electrochemical oxidation of naltrexone was investigated by cyclic and differential pulse voltammetric techniques. The dependence of peak currents and potentials on pH, concentration and the potential scan rate was investigated. The electrode characterization by electrochemical methods and atomic force microscopy (AFM) showed that CNPs enhanced the electroactive surface area and accelerated the rate of electron transfer. Application of the modified electrode resulted in a sensitivity enhancement of more than 20 times, relative to the bare GCE, in detection of NAL and a considerable negative shift in peak potential was achieved. Two linear dynamic ranges of 1–10 μM and 10–100 μM with a detection limit of 0.1 μM was obtained in phosphate buffer of pH = 3. Differential pulse voltammetry as a simple, rapid, sensitive and selective method was developed for the determination of NAL in dosage form and human plasma without any treatments. No electroactive interferences were found in biological fluids from the endogenous substances and additives present in capsules.     

Selective electrochemical sensing of calcium dobesilate based on an ordered mesoporous carbon-modified pyrolytic graphite electrode

Cyclic voltammetric investigation of calcium dobesilate (CD) in aqueous acid media was carried out by using an ordered mesoporous carbon-modified pyrolytic graphite electrode (OMC/PGE). A pair of well-defined redox peaks of CD was observed at the OMC/PGE, showing its good elelctrochemial response towards CD. The anodic current is linear with CD concentration in the range of 1.0 × 10⁻⁷–1.3 × 10⁻³ mol L⁻¹, with a detection limit of 4.0 × 10⁻⁸ mol L⁻¹. Meanwhile, the proposed electrode can avoid some interference coexisting with CD, such as uric acid, serotonin, and ascorbic acid. The proposed method can be potentially applied for selective electrochemical sensing of CD in physiological condition.     

Electrodeposited indigotetrasulfonate film onto glutaraldehyde-cross-linked poly-l-lysine modified glassy carbon electrode for detection of dissolved oxygen

The nano composited film of indigotetrasulfonate (ITS) electrodeposited onto poly-l-lysine (PLL)–glutaraldehyde (GA) (ITS/PLL–GA) was modified on glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. Composited of the proposed film was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), electrochemical quartz crystal microbalance (EQCM), electrochemical impedance spectroscopy (EIS), and UV–vis spectrum for the absorption at λ_max at 566 nm. For the electrocatalytic reduction of dissolved oxygen, ITS/PLL–GA film modified electrodes was determined in 0.1 M acetate buffer solution (pH 5.6) by cyclic voltammetry and rotating disk electrode voltammetry. This dissolved oxygen electrochemical sensor exhibited a linear response range (from 0 to 178.4 μM, R² = 0.9949), lowest detection limit (2.2 μM), lowest overpotential at −0.09 V, high sensitivity (906 μA mM⁻¹) and relative standard deviation (RSD) for determining dissolved oxygen (n = 3) was 4.2%. In addition, the ITS/PLL–GA/GCE was advantageous in terms of its simple preparation, specificity, stability and the ability of regeneration.     

A differential pulse voltammetric method for simultaneous determination of ascorbic acid,dopamine, and uric acid using poly (3-(5-chloro-2-hydroxyphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid) film modified glassy carbon electrode

A stable modified glassy carbon electrode based on the poly 3-(5-chloro-2-hydroxyphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (CDDA) film was prepared by electrochemical polymerization technique to investigate its electrochemical behavior by cyclic voltammetry. The properties of the electrodeposited films, during preparation under different conditions, and their stability were examined. The homogeneous rate constant, k_s, for the electron transfer between CDDA and glassy carbon electrode was calculated as 5.25(±0.20) × 10² cm s⁻¹. The modified electrode showed electrocatalytic activity toward ascorbic acid (AA), dopamine (DA), and uric acid (UA) oxidation in a buffer solution (pH 4.0) with a diminution of their overpotential of about 0.12, 0.35, and 0.50 V for AA, DA, and UA, respectively. An increase could also be observed in their peak currents. The modified glassy carbon electrode was applied to the electrocatalytic oxidation of DA, AA, and UA, which resolved the overlapping of the anodic peaks of DA, AA, and UA into three well-defined voltammetric peaks in differential pulse voltammetry (DPV). This modified electrode was quite effective not only for detecting DA, AA, and UA, but also for simultaneous determination of these species in a mixture. The separation of the oxidation peak potentials for ascorbic acid–dopamine and dopamine–uric acid were about 0.16 V and 0.17 V, respectively. The final DPV peaks potential of AA, DA and UA were 0.28, 0.44, and 0.61 V, respectively. The calibration curves for DA, AA, and UA were linear for a wide range of concentrations of each species including 5.0–240 μmol L⁻¹ AA, 5.0–280 μmol L⁻¹ DA, and 0.1–18.0 μmol L⁻¹ UA. Detection limits of 1.43 μmol L⁻¹ AA, 0.29 μmol L⁻¹ DA and 0.016 μmol L⁻¹ UA were observed at pH 4. Interference studies showed that the modified electrode exhibits excellent selectivity toward AA, DA, and UA.     

Silver nanoparticles modified carbon nanotube paste electrode for simultaneous determination of dopamine and ascorbic acid

A novel modified carbon-paste electrode was employed for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) with good selectivity and high sensitivity. Silver nanoparticle and carbon nanotube modified carbon-paste electrode (Ag/CNT–CPE) displayed excellent electrochemical catalytic activities towards dopamine (DA) and ascorbic acid (AA). The oxidation overpotentials of DA and AA were decreased significantly compared with those obtained at the bare CPE. Differential pulse voltammetry was used for the simultaneous determination of DA and AA. The peak separation between DA and AA was 67 mV. The calibration curves for DA and AA were obtained in the range of 8.0 × 10⁻⁷–6.4 × 10⁻⁵ M and 3.0 × 10⁻⁵–2.0 × 10⁻³ M, respectively. The lowest detection limits (S/N = 3) were 3.0 × 10⁻⁷ M and 1.2 × 10⁻⁵ M for DA and AA, respectively. Method was applied to the determination of DA and AA in real samples.     

Determination of trace vanadium(V) by adsorptive anodic stripping voltammetry on an acetylene black paste electrode in the presence of alizarin violet

A sensitive and simplified voltammetric method is developed for the determination of trace amounts of vanadium(V) by adsorptive anodic stripping voltammetry using an acetylene black (AB) paste electrode. The method is based on the preconcentration of the V(V)–alizarin violet (AV) complex at open circuit while stirring the solution for 90 s in 0.15 mol dm⁻³ hexamethylenetetraamine–hydrochloric acid buffer (pH 4.4), the adsorbed complex is then oxidized, producing a response with a peak potential of 564 mV when scanning linearly from 0 to 1000 mV. For voltammetric determination of V(V), the parameters influencing the peak current have been optimized. Under the selected conditions, the peak current and concentration of V(V) accorded with linear relationship in the range of 8.0 × 10⁻¹⁰ mol dm⁻³–1.0 × 10⁻⁷ mol dm⁻³ (c_AV = 2.0 × 10⁻⁶ mol dm⁻³) and 1.0 × 10⁻⁷ mol dm⁻³–8.0 × 10⁻⁶ mol dm⁻³ (c_AV = 2.0 × 10⁻⁵ mol dm⁻³), the detection limit (three times signal to noise) was estimated to be 6.0 × 10⁻¹⁰ mol dm⁻³ for 90 s accumulation. The relative standard deviation (RSD) is 1.9% and 2.3% for V(V) concentrations of 1.0 × 10⁻⁷ mol dm⁻³ and 1.0 × 10⁻⁸ mol dm⁻³ respectively. Finally, this proposed method was successfully applied to the determination of V(V) in natural water samples.     

Preparation of poly N,N-dimethylaniline/ferrocyanide film modified carbon paste electrode: Application to electrocatalytic oxidation of l-cysteine

Functionalized poly N,N-dimethylaniline film was prepared by adsorption of ferrocyanide onto the polymer forming at the surface of carbon paste electrode (CPE) in aqueous solution. The electrocatalytic ability of poly N,N-dimethylaniline/ferrocyanide film modified carbon paste electrode (PDMA/FMCPE) was demonstrated by oxidation of l-cysteine. Cyclic voltammetry and chronoamperometry techniques were used to investigate this ability. In the optimum pH (6.00), the electrocatalytic ability about 480 mV and the catalytic reaction rate constant, (k_h), can be seen 3.08 × 10³ M⁻¹ s⁻¹. The catalytic oxidation peak current determined by cyclic voltammetry method was linearly dependent on the l-cysteine concentration and the linearity range obtained was 8.00 × 10⁻⁵ –2.25 × 10⁻³ M. Detection limit of this method was determined as 6.17 × 10⁻⁵ M (2σ). At a fixed potential under hydrodynamic conditions (stirred solution), the calibration plot was linear over the l-cysteine concentration range 7.40 × 10⁻⁶ M–1.38 × 10⁻⁴ M. The detection limit of the method was 6.38 × 10⁻⁶ M (2σ).     

Electrocatalytic activity of thianthrene toward one-electron oxidation of guanosine and DNA in a non-aqueous medium

In this study, the electrochemical behavior of thianthrene (TH) and its application toward the electrocatalytic oxidation of guanosine (Gs) and DNA in a non-aqueous solution are investigated using different voltammetric techniques. Guanosine and DNA are adsorbed on the glassy carbon electrode (GCE) by applying a positive potential to the GCE. The rate constant of catalytic reaction between DNA and TH and also between Gs and TH were evaluated using chronoamperometry which gave rate constants of 2.41 × 10⁶ cm³ mol⁻¹ s⁻¹ and 2.68 (±0.19) × 10⁶ cm³ mol⁻¹ s⁻¹, respectively. Also the diffusion coefficient of TH was obtained using hydrodynamic voltammetry (3.17 × 10⁻⁵ cm² s⁻¹). Furthermore, using hydrodynamic voltammetry, a one-electron mechanism for oxidation of Gs is suggested.     

Electrochemical detection of ethidium bromide by using pure single-walled carbon nanotube sheet as the electrode

Sheets consisted of entire single-walled carbon nanotubes (SWNTs) were used as the working electrode for electrochemical measurement of ethidium bromide by covering a glassy carbon electrode (GCE) using the SWNT-sheet. This SWNT-sheet based electrode exhibited a fast electron transfer process on the electrode surface via the cyclic voltammetry with K₄Fe(CN)₆ as electrochemical probes. This SWNT-sheet based electrode showed also a high sensitivity toward ethidium bromide, a typically harmful, aromatic backboned chemical. The SWNT-sheet based electrode was capable of accumulating ethidium bromide to a higher concentration and therefore was capable of detecting ethidium bromide with a detection limit of 1.0 × 10⁻⁸ M.     

Application of surfactant modified zeolite membrane electrode towards potentiometric determination of perchlorate

Potentiometric electrodes based on the incorporation of surfactant-modified zeolite Y (SMZ) particles into poly vinyl chloride (PVC) membranes were described. The electrode characteristics were evaluated regarding the response towards perchlorate ions. PVC membranes plasticized with dioctyl phthalate and without lipophilic additives (co-exchanger) are used throughout this study. The influence of membrane composition on the electrode response was studied. The electrode exhibited a Nernstian response towards perchlorate in the concentration range of 7.9 × 10⁻⁶–8.0 × 10⁻² M with a slope of 59.7 ± 0.9 mV per decade of perchlorate concentration with a working pH range of 1.7–9.5 with a fast response time of ≤10 s. The lower and upper detection limits were 4.07 × 10⁻⁷ and 0.13 M, respectively. The electrode response to perchlorate remains constant in the temperature range of 20–40 °C and in the presence of 2.5 × 10⁻⁶–1 × 10⁻² M NaNO₃. The selectivity coefficients for perchlorate anion as test species with respect to other anions were determined. The proposed modified zeolite-PVC electrode can be used for at least 30 days without any considerable divergence in potential. It was applied as indicator electrode in water samples with satisfactory results. The results of this study and our previous work show HDTMA plays different roles according to the zeolite type and matrix, as HDTMA-zeolite Y in a carbon paste matrix showed a good Nernstian behavior towards phosphate anion.     

Graphite oxide bulk modified carbon paste electrode for the selective detection of dopamine: A voltammetric study

A novel electrochemical sensor for the selective and sensitive detection of dopamine (DA) in presence of large excess of ascorbic acid (AA) and uric acid (UA) at physiological pH was developed by the bulk modification of carbon paste electrode (CPE) with biocompatible graphite oxide (GO). Very small quantity of GO in carbon paste matrix imparted selectivity through electrostatic interactions. The modifier was characterized using infrared spectroscopy and powder X-ray diffraction. Large peak separation, good sensitivity and stability allow this modified electrode to analyze DA individually and simultaneously along with AA and UA. Applying differential pulse technique, DA could be detected even in the presence of 1000 fold excess of AA and UA. A linear dynamic range of 0.07–70 μM with detection limit of 1.5 × 10⁻⁸ M was obtained for DA. None of the bulk modified electrodes reported in the literature have shown such a low detection limit at the physiological pH. The practical application of the modified electrode was demonstrated by spiking the human blood serum and cerebral fluid with dopamine and the results obtained were satisfactory.     

Selective determination of dopamine in the presence of ascorbic acid at a multi-wall carbon nanotube-poly(3,5-dihydroxy benzoic acid) film modified electrode

A sensitive and selective method for determination of dopamine (DA) using multi-wall carbon nanotube (MWCNT)-poly(3,5-dihydroxy benzoic acid) [poly(DBA)] modified electrode is developed. The modified electrode shows excellent electrocatalytic activity toward the oxidation of dopamine in phosphate buffer solutions at pH 7.4. Using cyclic voltammetry, the linear range of 1 × 10⁻⁷–7.0 × 10⁻⁵ M in the interference of 500 μM ascorbic acid (AA) and the detection limit of 1.0 × 10⁻⁸ M were estimated for the measurement of DA in pH 7.4 phosphate buffer solutions. The value of DA current retained 98.36% of the initial response current after the modified electrode exposed to the air for one week. The interference studies showed that the modified electrode excludes effectively large excess of AA. The kinetic characteristics of the transfer of DA demonstrated that the electron propagation between DA and electrode was accelerated at MWCNT-poly(DBA) modified electrode. The work provided a valid and simple approach to selectively detect dopamine in the presence of AA in physiological environment.     

Development of a carbon nanotubes paste electrode modified with crosslinked chitosan for cadmium(II) and mercury(II) determination

A functionalized carbon nanotubes paste electrode modified with cross-linked chitosan for the determination of trace amounts of cadmium(II) and mercury(II) by linear anodic stripping voltammetry is described. Under optimal experimental conditions, the peak current was linear in the Cd(II) concentration range from 5.9 × 10⁻⁸ to 1.5 × 10⁻⁶ mol L⁻¹ with a detection limit of 9.8 × 10⁻⁹ mol L⁻¹ and, for Hg(II) from 6.7 × 10⁻⁹ to 8.3 × 10⁻⁸ mol L⁻¹with a detection limit of 2.4 × 10⁻⁹ mol L⁻¹. The proposed method was successfully applied for the determination of Hg(II) in natural and industrial wastewater samples, and Cd(II) in sediments, human urine, natural, and industrial wastewater samples.     

Electrochemical layer-by-layer modified imprinted sensor based on multi-walled carbon nanotubes and sol–gel materials for sensitive determination of thymidine

A novel electrochemical sol–gel imprinted sensor for sensitive and convenient determination of thymidine was developed. Thin film of molecularly imprinted sol–gel polymers with specific binding sites for thymidine was cast on carbon electrode by electrochemical deposition. Multi-walled carbon nanotubes (MWCNTs) were introduced for the enhancement of electronic transmission and sensitivity. The morphology and performance of the imprinted film was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV) and amperometric measurements (i–t) in detail. The results showed that the imprinted film exhibited high selectivity toward thymidine. The linear range is over the range from 2 to 22 μmol L⁻¹, and the linear regression equation for thymidine is I = 0.867C + 0.232 with the detection limit of 1.6 × 10⁻⁹ mol L⁻¹(S/N = 3). The imprinted sensor was successfully employed to detect thymidine in some zidovudine-tablet samples.     

Crown ether-dendrimer based potentiometric Na sensor electrode

Poly(vinyl chloride) (PVC)-based membranes of silacrown end grafted carbosilane dendrimer (I) with sodium tetraphenylborate (NaTPB) as an anion inhibitor and dibutylphthalate (DBP), dioctylphthalate (DOP), dibutyl (butyl) phosphonate (DBBP) and 1-chloronaphthalene (CN) as plasticizing solvent mediators were prepared and used as Na⁺-selective electrodes. Optimum performance was observed with the membrane having I–PVC–NaTPB–DOP in the ratio 1:33:1:65 (w/w). The electrode works well over a wide concentration range 1.5 × 10⁻⁶–1.0 × 10⁻¹ M with Nernstian compliance 56.0 mV/decade between pH 5.8 and 9.2 with a fast response time of about 15 s. The selectivity relative to alkali, alkaline earth and transition heavy metal ions is good. The selectivity coefficient values towards potassium ions have been calculated to be 2.3 × 10⁻⁴ by utilizing Fixed Interference Method. The proposed electrode could be used for at least 2 months without considerable alteration in its potential. The effect of nonionic surfactants Tween 20, Tween 80, Triton X 100, Span 20 and Span 60 on the potentiometric properties of the sodium selective membrane was also studied.     

Electrochemical impedimetry of electrodeposited poly(propylene imine) dendrimer monolayer

Voltammetric and electrochemical impedance spectroscopic (EIS) studies of generation one poly(propylene imine) (G1 PPI) dendrimer as an electroactive and catalytic nanomaterials both in solution and as an electrode modifier based on a simple one step electrodeposition method is presented. The G1 PPI exhibited a reversible one electron redox behaviour at E^0′ ca 210 mV in phosphate buffer pH 7.2 with diffusion coefficient and Warburg coefficient of 7.5 × 10⁻¹⁰ cm² s⁻¹ and 8.87 × 10⁻⁴ Ω s^−1/2 respectively. Cyclic voltammetric electrodeposition of a monolayer of G1 PPI on glassy carbon electrode was carried out between −100 mV and 1100 mV for 10 cycles. The nanoelectrode was electroactive in PBS at E^0′ ca 220 mV. Kinetic profiles such as time constant (4.64 × 10⁻⁵ s rad⁻¹), exchange current (1.55 × 10⁻⁴ A) and heterogeneous rate constant (4.52 × 10⁻³ cm s⁻¹) obtained from EIS showed that the dendrimer layer catalysed the redox reaction of Fe^2+/3+ in [Fe(CN)₆]^3−/4− redox probe.