Simultaneous determination of levodopa, carbidopa and tryptophan using nanostructured electrochemical sensor based on novel hydroquinone and carbon nanotubes: Application to the analysis of some real samples

In the present paper, the use of a novel carbon paste electrode modified by 2, 2′-[1,2-ethanediylbis (nitriloethylidyne)]-bis-hydroquinone (EBNBH) and carbon nanotubes prepared by a simple and rapid method for the determination of levodopa (LD), carbidopa (CD) and tryptophan (Trp) was described. In the first part of the work, 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, for electron transfer between EBNBH and carbon nanotube paste electrode were calculated. In the second part of the work, the mediated oxidation of LD at the modified electrode was described. It has been found that under optimum condition (pH 7.0) in cyclic voltammetry, the oxidation of LD occurs at a potential about 460 mV less positive than that of an unmodified carbon paste electrode. The values of electron transfer coefficient (α), catalytic rate constant (k_h′) and diffusion coefficient (D) were calculated for LD, using electrochemical approaches. Differential pulse voltammetry (DPV) exhibited two linear dynamic ranges and a detection limit (3σ) of 0.094 μM for LD. In the third part of the work, simultaneous determination of LD, CD and Trp at the modified electrode was described. Finally, this method was used for the determination of LD in some real samples, using standard addition method.     

Electrocatalytic and simultaneous determination of isoproterenol, uric acid and folic acid at molybdenum (VI) complex-carbon nanotube paste electrode

This paper describes the development, electrochemical characterization and utilization of a novel modified molybdenum (VI) complex-carbon nanotube paste electrode for the electrocatalytic determination of isoproterenol (IP). The electrochemical profile of the proposed modified electrode was analyzed by cyclic voltammetry (CV) that showed a shift of the oxidation peak potential of IP at 175 mV to less positive value, compared with an unmodified carbon paste electrode. Differential pulse voltammetry (DPV) in 0.1 M phosphate buffer solution (PBS) at pH 7.0 was performed to determine IP in the range from 0.7 to 600.0 μM, with a detection limit of 35.0 nM. Then the modified electrode was used to determine IP in an excess of uric acid (UA) and folic acid (FA) by DPV. Finally, this method was used for the determination of IP in some real samples.     

Electrocatalytic oxidation of hydrazine at a Co(II) complex multi-wall carbon nanotube modified carbon paste electrode

The catalytic oxidation of hydrazine was investigated by a cobalt(II) bis (benzoylacetone) ethylenediimino multi wall carbon nanotube-modified carbon paste electrode (Co(II)BBAEDI-MWCNT-MCPE) as a highly sensitive electrochemical sensor. The effect of variables such as pH and modifier percent on cyclic voltammograms peak current was optimized. The modified electrode showed very efficient electrocatalytic activity for anodic oxidation of hydrazine in 0.1 M phosphate buffer solution (pH 7.0). Anodic peak potential of hydrazine oxidation at the surface of modified electrode shifts by about 500 mV toward negative values compared with that on the bare electrode. The diffusion coefficient and electron transfer coefficient of hydrazine were obtained using electrochemical approaches. The Co(II)BBAEDI-MWCNT-MCPE showed good reproducibility (RSD < 3.3%). The electrocatalytic current increased linearly with the hydrazine concentration in the range of 0.3–70.0 μM and detection limit was 0.1 μM. The effect of various interferences on the hydrazine peak current was studied. This method was applied to determine hydrazine in water samples.     

Electrocatalytic oxidation of hydrazine at overoxidized polypyrrole film modified glassy carbon electrode

Electrocatalytic oxidation of hydrazine (HZ) was studied on an overoxidized polypyrrole (OPPy) modified glassy carbon electrode using cyclic voltammetry and chronoamperometry techniques. The OPPy-modified glassy carbon electrode has very high catalytic ability for electrooxidation of HZ, which appeared as a reduced overpotential in a wide operational pH range of 5-10. The overall numbers of electrons involved in the catalytic oxidation of HZ, the number of electrons involved in the rate-determining and diffusion coefficient of HZ were estimated using cyclic voltammetry and chronoamperometry. It has been shown that using the OPPy-modified electrode, HZ can be determined by cyclic voltammetry and amperometry with limit of detection 36 and 3.7 μM, respectively. The results of the analysis suggest that the proposed method promises accurate results and could be employed for the routine determination of HZ.     

A novel preparation of small TiO₂ nanoparticle and its application to dye-sensitized solar cells with binder-free paste at low temperature

TiO(2) nanoparticles with diameter <10 nm were synthesized by a facile, non-hydrothermal method at low temperature. A porous TiO(2) film electrode consisting of the obtained small TiO(2) nanoparticles and commercial TiO(2) nanoparticles without any organic binder was prepared at low temperature. The photovoltaic performance of the solar cell based on the TiO(2) electrode was investigated by the current-voltage and electrochemical impedance spectra. All the experimental results indicate that the addition amount of the small TiO(2) nanoparticles in the binder-free paste affects the photovoltaic performance of the photoelectrode greatly. The overall energy conversion efficiency of the optimized binder-free photoelectrode achieves 3.53% without high-temperature sintering. Additionally, the performance of the small particles derived from this facile method can be comparable with that of small ones obtained from traditionally hydrothermal method, indicating the small particles in our study can be applied to flexible dye-sensitized solar cells. And the present low-temperature preparation of photoelectrode containing small TiO(2) nanoparticles shows an encouraging performance on both conductive glass and plastic substrates and could be suited in the industrial and large-scale application due to its low energy cost and relatively high conversion efficiency.     

Electrocatalytic hydrazine oxidation on quinizarine modified glassy carbon electrode

The electrocatalytic oxidation of hydrazine has been studied on glassy carbon modified by electrodeposition of quinizarine, using cyclic voltammetry and chronoamperometry techniques. It has been shown that the oxidation of hydrazine to nitrogen occurs at a potential where oxidation is not observed at the bare glassy carbon electrode. The apparent charge transfer rate constant and transfer coefficient for electron transfer between the electrode surface and immobilized quinizarine were calculated as 4.44 s⁻¹ and 0.66, respectively. The heterogenous rate constant for oxidation of hydrazine at the quinizarine modified electrode surface was also determined and found to be about 4.83 × 10³ M⁻¹ s⁻¹. The diffusion coefficient of hydrazine was also estimated as 1.1 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometry.     

Novel CuO/polymethylenedisulfide nanocomposite for high performance electrocatalytic determination of hydrochlorothiazide in real samples

Journal of Porous Materials - Surface of a carbon paste electrode was modified by using copper oxide nanoparticles/polymethylenedisulfide (CuO NPs/PMDS) nanocomposite. X-ray diffraction...     

Electrochemical reduction of 2,4-dinitrophenol on nanocomposite electrodes modified with mesoporous silica and poly(vitamin B1) films

Electrochemical reduction of 2,4-dinitrophenol was investigated on a glassy carbon electrode modified with a nanocomposite Santa Barbara Amorphous silica (SBA-15) film and poly(vitamin B₁) film. For sensitive and selective detections, vanadium pentoxide and cerium oxide nanoparticles were incorporated into the matrix of SBA-15. 2,4-Dinitrophenol was reduced on the modified electrode at −0.39 and −0.25 V, corresponding to the reduction of 4-dinitrophenol and 2-dinitrophenol, respectively. Both cathodic peak currents were controlled by the diffusion of 2,4-dinitrophenol. The amplitude of the peak currents was proportional to the 2,4-dinitrophenol concentration in the range of 3.0–30 μM. The modified electrode demonstrated a long lifetime for the detection of 2,4-dinitrophenol. The detection limit of 2,4-dinitrophenol was 0.5 μM. Moreover, the modified electrode was used successfully to detect 2,4-dinitrophenol in lake water.     

Antimony powder-modified carbon paste electrodes for electrochemical stripping determination of trace heavy metals

A new type of the antimony electrode based on a carbon paste bulk-modified with antimony powder (Sb-CPE) is presented for the determination of cadmium(II) and lead(II) ions at the microgram-per-liter concentration level, when using square-wave anodic stripping voltammetric or stripping chronopotentiometric protocol. The Sb-CPE was prepared by mixing fine antimony powder, carbon powder, and silicon oil, thus combining typical features of the carbon paste material with specific electrochemical properties of antimony. Key-operational parameters, including the amount of antimony powder in the carbon paste mixture, effect of the deposition potential and deposition time, were optimized and electroanalytical performance of the Sb-CPE in nondeaerated solution of 0.01 M hydrochloric acid (pH 2) was compared with related bismuth powder-modified carbon paste electrode (Bi-CPE) and with in situ prepared antimony film carbon paste electrode (SbF-CPE). The electrode of interest exhibited well-developed signals and highly linear calibration plots for both metal ions tested. In addition, favorable limits of detection were achieved; namely: 1.4 μg L⁻¹ for Cd(II) and 0.9 μg L⁻¹ for Pb(II). The applicability of the new electrode was demonstrated on the analysis of tap water (spiked sample). Besides voltammetric measurements, the Sb-CPE was preliminary tested also under chronopotentiometric stripping mode in deoxygenated solutions, revealing also an excellent electroanalytical performance.     

Electrocatalytic oxidation of methanol on carbon paste electrode modified by nickel ions dispersed into poly (1,5-diaminonaphthalene) film

Poly (1,5-diaminonaphthalene) film was prepared by using the repeated potential cycling technique in an acidic solution at the surface of carbon paste electrode. Then transition metal ions of Ni(II) were incorporated to the polymer by immersion of the modified electrode in a 1.0 M nickel chloride solution. The electrochemical characterization of this modified electrode exhibits stable redox behavior of the Ni(III)/Ni(II) couple. Also, cyclic voltammetric experiments showed that methanol electrooxidized at the surface of this Ni(II) dispersed polymeric modified carbon paste electrode [Ni/P-1,5-DAN/MCPE]. The mechanism of methanol oxidation changes from diffusion control at low concentration to a catalytic reaction at higher methanol concentration. The effects of both scan rate and methanol concentration on the anodic peak height of the methanol oxidation were discussed.     

Electrocatalytic oxidation of ascorbic acid at a 2,2′-(1,8-octanediylbisnitriloethylidine)-bis-hydroquinone modified carbon paste electrode

Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical behavior of ascorbic acid at a carbon paste electrode modified with 2,2′-(1,8-octanediylbisnitriloethylidine)-bis-hydroquinone (1,8-OBNEBHQ). The modified carbon paste electrode showed high electrocatalytic activity toward ascorbic acid; the current was enhanced significantly relative to the situation prevailing when an unmodified carbon paste electrode was used. The electrocatalytic process was highly dependent on the pH of the supporting electrolyte. The apparent charge transfer rate constant, k_s, and transfer coefficient, α, for electron transfer between 1,8-OBNEBHQ and carbon paste electrode were calculated as 20.2 ± 0.5 s⁻¹ and 0.47, respectively. Using differential pulse voltammetry, the calibration curves for AA were obtained over the range of 5–30 and 40–1,500 μM, respectively. The detection limit (kσ, k = 2) was 0.6 μM. With good selectivity and sensitivity, the present method provides a simple method for selective detection of ascorbic acid in biological samples.     

Poly(o-aminophenol) film prepared in the presence of sodium dodecyl sulfate: Application for nickel ion dispersion and the electrocatalytic oxidation of methanol and ethylene glycol

Poly(o-aminophenol) (POAP) was formed by successive cyclic voltammetry in monomer solution in the presence of sodium dodecyl sulfate (SDS) on the surface of a carbon paste electrode. The electrochemical behavior of the SDS-POAP carbon paste electrode has been investigated by cyclic voltammetry in 0.5 M HClO₄ and 5 mM K₄[Fe(CN)₆]/0.1 M KCl solutions as the supporting electrolyte and model system, respectively. Ni(II) ions were incorporated into the electrode by immersion of the polymeric modified electrode having amine groups in 0.1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode. A good redox behavior of the Ni(III)/Ni(II) couple at the surface of electrode can be observed. The electrocatalytic oxidations of methanol and ethylene glycol (EG) at the surface of the Ni/SDS-POAP electrode were studied in a 0.1 M NaOH solution. Compared to bare carbon paste and POAP-modified carbon paste electrodes, the SDS-POAP electrode significantly enhanced the catalytic efficiency of Ni ions for methanol oxidation. Finally, using a chronoamperometric method, the catalytic rate constants (k) for methanol and ethylene glycol were found to be 2.04 × 10⁵ and 1.05 × 10⁷ cm³ mol⁻¹ s⁻¹, respectively.     

Electrocatalytic oxidation and detection of hydrazine at carbon nanotube-supported palladium nanoparticles in strong acidic solution conditions

Pd nanoparticle catalysts supported by multiwall carbon nanotubes (Pd/MWNTs) prepared using a complexation–reduction method are used in this study for the electrochemical determination of hydrazine. The physico-chemical properties of the Pd/MWNT catalyst were characterized by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM) and scanning electron microscopy physico-chemical (SEM). These structural analyses reveal that the Pd/MWNTs-modified glassy carbon electrode possesses a three-dimensional network structure in which the Pd nanoparticles, with an average size of 5 nm, are uniformly distributed on the surface of the MWNTs. After Nafion solution was coated on the surface of the Pd/MWNT layer, the resulting Pd/MWNT–Nafion modified electrode retained the three-dimensional network structure. Electrochemical measurements show that the oxidation peak current of hydrazine decreases with increasing pH. Under optimum conditions, the Pd/MWNT–Nafion-based hydrazine sensor exhibits a broad linear calibration range (2.5–700 μM) and a low detection limit of 1.0 μM for hydrazine.     

TiO2-Pt/Mm（Ni3.4Mn0.4Al0.3Co0.7）电极的可助光充电

1～8 nm的Pt微粒通过光催化分解法沉积在20～50 nm的TiO₂微粒表面,然后把所制备的TiO₂-Pt纳米微粒修饰到富La的贮氢合金电极的表面,形成可助光充电的TiO₂-Pt/Mm（Ni_3.4Mn_0.4Al_0.3Co_0.7）电极（TPM电极）,研究了TPM电极的光电化学、可助光充电行为。结果表明：微小的电流对TPM电极的光充电效应有较强的辅助作用。当TPM电极只被光照时,放出的电量较小;而在光照的同时加上一个微弱的电流,可显著改善其光充电性能。通过交流阻抗谱和循环伏安实验研究了其光充电机理。     

Green bio-synthesis of Ni/montmorillonite nanocomposite using extract of Allium jesdianum as the nano-catalyst for electrocatalytic oxidation of methanol

In this work, synthesis of Ni nanoparticles was carried out successfully by water extract of Allium jesdianum as a biochemical reducing agent in the presence of montmorillonite clay (MMT) as a natural solid support for the first time. Then the electrochemical activity of the synthesized nanocomposite was investigated in methanol electrocatalytic oxidation. MMT with high cation exchange capacity and nano layer structure was exposed to ion exchange conditions in nickel solution. Then Ni²⁺ ion exchanged form was used in this process as a source of ions and also capping agent. Water extract of Allium jesdianum used as a reducing agent due to abundant availability of phenolic and flavonoid contents. The synthesized Ni/MMT nanocomposite was characterized using UV-Vis spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM) and Energy-dispersive X-ray spectroscopy (EDX). The surface of prepared modified electrode has been characterized using SEM to evaluate the morphology, showing uniform dispersion of Ni nanoparticles with mean diameter of 12 to 20 nm. The modified carbon paste electrode was then used in methanol electrocatalytic oxidation reaction. Methanol oxidation on the proposed modified electrode surface occurs at 0.6 V and 0.3 V in alkaline and acidic medium respectively. Also, the results showed the better performance of modified electrode toward methanol electrocatalytic oxidation in comparison with carbon paste electrode that is modified by ion exchanged MMT. Charge transfer coefficients and apparent charge transfer rate constant for the modified electrode in the absence of methanol in alkaline medium were respectively found as: α_a = 0.53, α_c = 0.37 and k_s = 1.6×10^-1 s^-1. Also, the average value of catalytic rate constant for the electrocatalytic oxidation of methanol by the prepared nano-catalyst was estimated to be about 0.9 L·mol^-1·s^-1 by chronoamperometry technique. The prepared electrode was also effective for electrocatalytic oxidation of ethanol and formaldehyde in alkaline medium.     

Direct electrochemistry of catalase at amine-functionalized graphene/gold nanoparticles composite film for hydrogen peroxide sensor

Direct electrochemistry and electrocatalysis of catalase (Cat) was studied based on a nano-composite film consisting of amine functionalized graphene and gold nanoparticles (AuNPs) modified glassy carbon electrode. Graphene was synthesized chemically by Hummers and Offeman method and then was functionalized with amino groups via chemical modification of carboxyl groups introduced on the graphene surface. The nano-composite film showed an obvious promotion of the direct electron transfer between Cat and the underlying electrode, which attributed to the synergistic effect of graphene-NH₂ and AuNPs. The resultant bioelectrode retained its biocatalytic activity and offered fast and sensitive H₂O₂ quantification. Under the optimized experimental conditions, hydrogen peroxide was detected in the concentration range from 0.3 to 600 μM with a detection limit of 50 nM at S/N = 3. The biosensor exhibited some advantages, such as short time respond (2 s), high sensitivity (13.4 μA/mM) and good reproducibility (RSD = 5.8%).     

Determination of hydrazine by polyNi(II) complex modified electrodes with a wide linear calibration range

Polymeric [Ni^II(teta)]²⁺ (poly(Ni); teta = C-meso-(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane)) modified glassy carbon and Nafion (Nf)-coated glassy carbon electrodes (GC/poly(Ni) and GC/Nf/poly(Ni), respectively) were used for the efficient electrocatalytic oxidation of hydrazine (HZ) in 0.1 M NaOH. The catalytic currents were proportional to the concentration of HZ with a wide linear calibration range (LCR). GC/poly(Ni) had a LCR from 1.0 μM to 10.0 mM, whereas that of GC/Nf/poly(Ni) ranged from 1.0 μM to 100.0 mM. The latter is the widest LCR reported to date. The presence of the Nf film (i.e., in GC/Nf/poly(Ni)) not only increased the stability of the poly(Ni) film but also widened the LCR. The electrocatalytic oxidation of HZ obeyed first-order kinetics with respect to HZ concentration. The kinetic parameters were investigated by cyclic voltammetry and chronoamperometry.     

吸附伏安法测定抗坏血酸实验条件的确定

采用吸附伏安法,在纳米介孔二氧化硅修饰碳糊电极上测定抗坏血酸,讨论了支持电解质溶液、pH值、富集电位、富集时间以及扫描速率对检测峰电流的影响,确定出当支持电解质为PBS缓冲溶液,pH值为5．5,开路富集时间为120s,扫描速率为50mV／s时,可获得最大检测峰电流。     

A simple and sensitive electroanalytical determination of anxiolytic buspirone hydrochloride drug based on multiwalled carbon nanotubes modified electrode

In the present study, a simple and sensitive buspirone hydrochloride (BPH) sensor was developed based on multiwalled carbon nanotubes (MWCNT) modified electrode. The modified electrode was characterized using transmission electron microscopy and electrochemical impedance spectroscopy. The MWCNT modified electrode showed an enhanced oxidation peak current response toward BPH than unmodified electrode. The oxidation peak potential of BPH at modified electrode was 0.85, which was quite lower than that of bare electrode (0.88 V). The BPH was successfully determined at modified electrode using different electrochemical methods, such as cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometry. The good sensitivity and linear range response of BPH were obtained using amperometry when compared with other methods employed in this study (CV and DPV). The modified electrode displayed the electro-oxidation of BPH in the linear response from 0.5 to 99.5 μM with the sensitivity of 16.49 μA μM^?1 cm^?2. The limit of detection was calculated as 0.22 μM. In addition, the modified electrode exhibited a good repeatability and repeatability with acceptable stability.     

Electrochemical behavior and simultaneous determination of dihydroxybenzene isomers at a functionalized SBA-15 mesoporous silica modified carbon paste electrode

The simultaneous voltammetric determination of dihydroxybenzene isomers was investigated using cyclic and differential pulse voltammetries at the amino-functionalized SBA-15 mesoporous silica-modified carbon paste electrode (NH₂-SBA15/CPE) in phosphate buffer solution (pH 6.0). The NH₂-SBA15/CPE showed a larger peak current and higher selectivity for the dihydroxybenzene isomers in comparison with the bare carbon paste electrode (CPE) and SBA-15 mesoporous silica-modified carbon paste electrode (SBA15/CPE). The oxidation peak potential difference between hydroquinone (HQ) and catechol (CC) was 115 mV and was 396 mV between catechol and resorcinol (RC). This indicated that catechol, resorcinol and hydroquinone could be identified entirely at the NH₂-SBA15/CPE. Under the optimized conditions, the amperometric currents were linear over ranges from the following: 0.8–160 μmol L⁻¹ for hydroquinone, 1.0–140 μmol L⁻¹ for catechol and 2.0–160 μmol L⁻¹ for resorcinol. The detection limits were 0.3, 0.5 and 0.8 μmol L⁻¹, respectively. The proposed electrode can be applied to the simultaneous determination of dihydroxybenzene isomers in mixtures without previous chemical or physical separations.