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.     

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.     

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.     

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.     

Simultaneous determination of epinephrine and uric acid at a gold electrode modified by a 2-(2,3-dihydroxy phenyl)-1, 3-dithiane self-assembled monolayer

In the present paper, the use of a gold electrode modified by 2-(2,3-dihydroxy phenyl)-1,3-dithiane self-assembled monolayer (DPDSAM) for the determination of epinephrine (EP) and uric acid (UA) was described. Initially, cyclic voltammetry was used to investigate the redox properties of this modified electrode at various scan rates. The apparent charge transfer rate constant, k_s, and transfer coefficient, α, were calculated. Next, the mediated oxidation of EP at the modified electrode was described. At the optimum pH of 8.0, the oxidation of EP occurs at a potential about 155 mV less positive than that of an unmodified gold electrode. The values of electron transfer coefficients (α = 0.356), catalytic rate constant (k = 1.624 × 10⁴ M⁻¹ s⁻¹) and diffusion coefficient (D = 1.04 × 10⁻⁶ cm² s⁻¹) were calculated for EP, using electrochemical approaches. Based on differential pulse voltammetry, the oxidation of EP exhibited a dynamic range between 0.7 and 500.0 μM and a detection limit (3σ) of 0.51 μM. Furthermore, simultaneous determination of EP and UA at the modified electrode was described. Finally, this method was used for the determination of EP in EP ampoule.     

MWNT/Nafion composite modified glassy carbon electrode as the voltammetric sensor for sensitive determination of 8-hydroxyquinoline in cosmetic

In this paper, a multiwall carbon nanotube/Nafion composite modified glassy carbon electrode (MWNT/Nafion/GCE) was used as a voltammetric sensor to determine 8-hydroxyquinoline (8-HQ) in cosmetic. This voltammetric sensor exhibited strong catalytic effect toward the oxidation of 8-HQ and caused an anodic peak at 0.97 V in HAc-NaAc buffer solution (0.2 M, pH 3.6). Under the optimized condition, the anodic peak current was linear with the concentration of 8-HQ in the range of 2 × 10⁻⁸ M–1.0 × 10⁻⁵ M. The detection limit was 9 × 10⁻⁹ M. The practical application of MWNT/Nafion/GCE was carried out for determining 8-HQ in cosmetic sample with satisfactory results. The electrode reaction mechanism was studied by cyclic voltammetry and UV–vis spectra.     

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 oxidation of hydrazine using glassy carbon electrode modified with carbon nanotube and terpyridine manganese(II) complex

Here, we report a simple and extremely effective method to modify a glassy carbon (GC) electrode with carbon nanotubes (CNTs) and [Mn(CH₃COO)(CH₃OH)₂(pyterpy)]ClO₄, (pyterpy = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) complex. The kinetics of the reaction between, the terpyridine manganese(II) complex, mediator and hydrazine has been characterized using cyclic voltammetry and rotating disk electrode voltammetry. The catalytic currents were proportional to the concentration of hydrazine giving rise to calibration curves characterized by two linear segments. The linear segment over the concentration range of 1.00 × 10⁻³–1.05 mM could be used with analytical purposes to determination of hydrazine with a detection limit of 0.50 μM and a sensitivity of 0.038 μA/μM. The heterogeneous rate constant, k′ for the oxidation of hydrazine at the surface of the modified electrode was determined by rotating disk electrode voltammetry using the Koutecky–Levich plot. The transfer coefficient (α) for electrocatalytic oxidation of hydrazine and the diffusion coefficient of this substance under the experimental conditions were also investigated. The resulting modified electrode retains its initial response for at least one month if stored dry in air.     

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.     

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.     

Electrochemical sensor for trace silicic acid detection based on bismuth film electrode

A highly sensitive voltammetric detection of silicic acid (SA), the main chemical species of dissolved silica in sea water, is described. The protocol relies on a fast square-wave voltammetric measurement of the decreased molybdenum stripping signal due to the formation of silicomolybdate complex. The cathodic stripping experiments were performed at the bismuth film electrode using HCl–KCl (pH 1.6) buffer solution. Different ligands, pH, ligand concentration, deposition potential and accumulation time were evaluated. Under the optimal conditions, a linear response is observed over the 50–400 μg L⁻¹ SA concentration range with a detection limit of 2 μg L⁻¹. A highly stable response, with a relative standard deviation (RSD) of 4.8%, is observed for 10 repetitive measurements. Such an electrochemical approach offers great promise for a simple, rapid, sensitive, and on-site or in situ real-time detection of SA.     

Direct electrochemistry of cholesterol oxidase on MWCNTs

The direct electrochemistry of cholesterol oxidase (ChOx) was achieved on the surface of graphite electrode by immobilizing positively charged ChOx and negatively charged multi walled carbon nanotubes through electrostatic interaction using layer-by-layer technique. Two sets of well defined redox peaks were observed in cyclic voltammogram of the modified graphite electrode in phosphate buffer solution of pH 7. These peaks are corresponding to direct electron transfer of FAD/FADH₂ of ChOx and carboxylic groups of multi walled nanotubes. The modified electrode is characterized using cyclic voltammetry and electrochemical impedance spectroscopy. ChOx modified electrode was used for the determination of cholesterol. The reduction current of oxygen at the modified electrode decreases linearly with the addition of cholesterol in the concentration range of 0.2–1 mM with the lower detection limit of 30 × 10⁻⁶ M. Some common interferents like glucose, ascorbic acid, uric acid and acetaminophen did not cause any interference due to the use of a low operating potential.     

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.     

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.     

Electrochemistry of magnolol and interaction with DNA

The electrochemical behaviors of magnolol have been studied at glassy carbon electrode using cyclic voltammetry, linear sweep voltammetry and chronocoulometry. Moreover, its interaction with DNA was investigated in solution by electrochemical methods and ultraviolet–visible spectroscopy. The experiment results indicated that the electrochemical oxidation of magnolol was an irreversible process with one proton and one electron transfer. The electron transfer coefficient (α) was calculated to be 0.441 ± 0.001. At the scan rate from 100 mV/s to 450 mV/s, the electrode process was controlled by the adsorption step and at the range of 600–950 mV/s the electrochemical oxidation was diffusion controlled process. The corresponding electrochemical rate constant (k_s) was 0.0760 ± 0.0001 s⁻¹. Through chronocoulometry experiment, the diffusion coefficient (D) and the surface concentration (Γ) were obtained as (3.76 ± 0.01) × 10⁻⁷ cm²/s and (2.98 ± 0.01) × 10⁻¹⁰ mol/cm². In addition, the interaction of magnolol and DNA was ascribed to be electrostatic interaction and the calculated association constant (β) and Hill coefficient (m) were 1.14 × 10⁵ M⁻¹ and 0.973. At last a sensitive and convenient electrochemical method was proposed for the determination of magnolol.     

Sensitive electrochemical detection of hydroquinone with carbon ionogel electrode based on BMIMPF6

An ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆) based carbon ionogel electrode (CIE) was fabricated for the sensitive voltammetric sensing of hydroquinone (HQ) in this paper. Due to the specific characteristics of the prepared working electrode, HQ exhibited an enhanced electrochemical response on CIE with a pair of well-defined redox peaks appeared in pH 2.5 phosphate buffer solution. The electrochemical behaviors of HQ on CIE were investigated by different electrochemical methods such as cyclic voltammetry and differential pulse voltammetry with the electrochemical parameters calculated. Under the optimal conditions the oxidation peak currents exhibited good linear relationship with the HQ concentration in the range from 0.13 to 100.0 μmol L⁻¹ with the detection limit of 0.07 μmol L⁻¹ (3σ). The CIE showed separated electrochemical response to HQ and catechol in the mixture solution. The proposed method was successfully applied to HQ detection in artificial wastewater with the recovery in the range from 98.9% to 102.0%.     

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 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.     

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.     

A stannum/bismuth/poly(p-aminobenzene sulfonic acid) film electrode for measurement of Cd(II) using square wave anodic stripping voltammetry

In the present work, a new method for a trace analysis of metal cadmium ion has been developed on the stannum/bismuth/poly(p-aminobenzene sulfonic acid) film electrode in combination with square wave anodic stripping voltammetry. This new electrode was prepared by in situ depositing stannum, bismuth and target metal on the poly(p-aminobenzene sulfonic acid)(p-ABSA) coated glassy carbon electrode. Some key factors including the pH of measure solution, the proper proportion between Bi(III) and Sn(II), the preconcentration time and the preconcentration potential have been studied and optimized. Compared with the traditional bismuth-film electrode, the stannum/bismuth/poly(p-ABSA) film electrode displayed higher stripping current response. In addition, it has the advantages of better stability and less toxicity. Under the optimum conditions, the linear calibration graph for Cd(II) in the concentration range of 0.5–55 μg L⁻¹ was obtained and the detection limit was 0.32 μg L⁻¹. The method was applied to the analysis of cadmium ion in tap water sample with satisfactory results.