双氯芬酸钠在石墨烯和室温离子液体复合修饰电极上的电化学行为及其测定

运用循环伏安法研究了双氯芬酸钠(DS)在石墨烯(Gene)和室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)复合修饰电极上的电化学行为。DS在该复合电极上于0.65V处有一不可逆氧化峰。在40～200 mV/s范围内,其氧化峰电流与扫描速率平方根(v1/2)呈良好线性关系,表明电极过程是受扩散控制。测定了部分电极过程参数,优化了方波溶出伏安法(SWSV)的实验参数,DS浓度在1.0×10-7～1.0×10-4mol/L范围内与峰电流Ipa呈良好线性关系,检出限为8.0×10-8mol/L(S/N=3),加标回收率为95.7%～101.7%。     

Electrochemical oxidation of cisatracurium on carbon paste electrode and its analytical applications

The electrochemical oxidation of cisatracurium was investigated by cyclic voltammetry and differential pulse voltammetry at a carbon paste electrode and the experimental parameters have been optimized in order to obtain the optimum analytical signal. A differential pulse voltammetric method with carbon paste electrode is described for the determination of cisatracurium with detection limit of 0.38 μg/ml and quantitation limit of 1.26 μg/ml. The proposed method was applied to determine the content of cisatracurium in human urine and human serum, obtaining accurate and precise results.     

Electrochemical behavior of mesoionic sydnone derivatives at wax-impregnated carbon paste electrode

The-N=N-moiety in the mesoionic 3-phenyl sydnone and its derivatives like tolyl sydnones and anisyl sydnones undergo two-electron irreversible electrochemical reduction in Britton-Robinson (BR) buffer at wax-impregnated carbon paste electrodes. Infrared, nuclear magnetic resonance, and mass-spectral data, used to characterize the reduced product, confirm the proposed mechanism. The pasting liquid at the surface of the electrode is found to decrease the electron-transfer rate and cause a higher overpotential compared to homogeneous electrodes. The influence of variation of pH on the peak current and peak potentials is studied in the acidic range. The cathodic peak shifts to more negative potentials with increase in pH, indicating the involvement of proton in the reduction process. This could be a new method of preparation of 2,4-dihydro-3-substituted 1,2,3-oxadiazole-5-one. The substituent effect and the effect of variation of scan rate, concentration, and temperature on peak currents and peak potentials is discussed. The cathodic shift in various organic co-solvents (methanol, acetonitrile, DMF, DMSO) using BRB as the supporting electrolyte is examined. Published in Russian in Elektrokhimiya, 2006, Vol. 42; No. 7, pp. 862–868. The text was submitted by the authors in English.     

CuO-nanoparticles modified carbon paste electrode for square wave voltammetric determination of lidocaine: Comparing classical and Box–Behnken optimization methodologies

In this research, copper oxide nanoparticles modified carbon paste electrode was developed for the voltammetric determination of lidocaine. The square wave voltammogram of lidocaine solution showed a well-defined peak between +0.5 and +1.5 V. Instrumental and chemical parameters influencing voltammetric response were optimized by both one at a time and Box–Behnken model of response surface methodology. The results revealed that there was no significant difference between two methods of optimization. The linear range was 1–2500 μmol L~(-1)(Ip= 0.11 C_(LH)+ 17.38, R~2= 0.999). The LOD and LOQ based on three and ten times of the signal to noise(S/N) were 0.39 and 1.3 μmol L~(-1)(n = 10),respectively. The precision of the method was assessed for 10 replicate square wave voltammetry(SWV)determinations each of 0.05, 0.5 and 1 μmol L~(-1) of lidocaine showing relative standard deviations 4.1%,3.7% and 2.1%, respectively. The reliability of the proposed method was established by application of the method for the determination of lidocaine in two pharmaceutical preparations, namely injection and gel.     

对乙酰氨基酚在碳纳米管-离子液体糊修饰电极上的电化学行为及分析应用

制备了碳纳米管-离子液体糊修饰电极并用电化学方法对其进行了表征,研究对乙酰氨基酚在碳纳米管-离子液体糊修饰电极上的电化学行为,建立了以碳纳米管-离子液体糊修饰电极测定对乙酰氨基酚(APAP)的灵敏的电化学方法.在优化的实验条件下,对乙酰氨基酚的氧化峰电流与其浓度在1.0×10-7～1.0×10-6 mol/L和1.0×...     

Sensitive voltammetric determination of baicalein at DNA Langmuir-Blodgett film modified glassy carbon electrode

The present paper describes to modify a double stranded DNA-octadecylamine (ODA) Langmuir-Blodgett film on a glassy carbon electrode (GCE) surface to develop a voltammetric sensor for the detection of trace amounts of baicalein. The electrode was characterized by atomic force microscopy (AFM) and cyclic voltammetry (CV). Electrochemical behaviour of baicalein at the modified electrode had been investigated in pH 2.87 Britton-Robinson buffer solutions by CV and square wave voltammetry (SWV). Compared with bare GCE, the electrode presented an electrocatalytic redox for baicalein. Under the optimum conditions, the modified electrode showed a linear voltammetric response for the baicalein within a concentration range of 1.0 × 10⁻⁸-2.0 × 10⁻⁶ mol L⁻¹, and a value of 6.0 × 10⁻⁹ mol L⁻¹ was calculated for the detection limit. And the modified electrode exhibited an excellent immunity from epinephrine, dopamine, glucose and ascorbic acid interference. The method was also applied successfully to detect baicalein in the medicinal tablets and spiked human blood serum samples with satisfactory results.     

Electrochemical determination of melamine using oligonucleotides modified gold electrodes

A novel and simple electrochemical method for determination of melamine is developed based on oligonucleotides film modified gold electrodes. The electrochemical probe of ferricyanide was used to investigate the interactions between oligonucleotides and melamine. Results of cyclic voltammetries, differential pulse stripping voltammetries, electrochemical impedance spectrometry and atomic force microscope, proved that melamine might interact with oligonucleotides mainly through electrostatic and hydrogen-bonding interactions. The interactions between oligonucleotides and melamine lead to the increase in the peak currents of ferricyanide, which could be used for electrochemical sensing of melamine. The redox peak currents of ferricyanide were linear with the concentration of melamine in the range from 3.9 × 10⁻⁸ to 3.3 × 10⁻⁶ M with a linear coefficiency of 0.990. The detection limit was 9.6 × 10⁻⁹ M. The proposed electrochemical biosensor is rapid, convenient and low-cost for effective sensing of melamine. Particularly, the proposed method was applied successfully to the determination of melamine in milk products, and the recovery was 95%.     

A novel method for determination of magnesium in urine and water samples with mercury film-plated carbon paste electrode

A square wave adsorptive stripping voltammetric (SWAdSV) method for the indirect determination of trace amounts of magnesium with thiopentone sodium (TPS) as an electroactive ligand, at carbon paste mercury film electrode (CP-MFE) is proposed. It is observed that the increase of the square wave voltammetric cathodic peak current of TPS, under alkaline conditions, is linear with the increase of Mg concentration. Under optimum experimental conditions viz.; pH 10.75, 3×10⁻⁵ M TPS and 0.05 M phosphate buffer (Na₂HPO₄-NaH₂PO₄), a linear relation in the range 6×10⁻⁹ to 9×10⁻⁸ M Mg²⁺ (0.14-2.16 ppb), at 60 s deposition time, is obtained. The detection limit of Mg²⁺ is 0.14 ppb for 60 s deposition time with the relative standard deviation is 0.5% (n=5). The proposed method was successfully applied to the determination of magnesium in urine and tap water samples with satisfactory results. The data obtained are compared with the standard flame atomic absorption spectrophotometric method (FAAS).     

Preconcentration and voltammetric determination of the herbicide metamitron with a silica-modified carbon paste electrode

A carbon paste electrode incorporating silica (Si-MCPE) was fabricated to accumulate Metamitron at the electrode surface. Several electroanalytical techniques were used to explore its reductive behaviour. The results indicate that the system is irreversible and fundamentally controlled by adsorption. The adsorptive stripping response has been evaluated with respect to accumulation time, deposition potential, scan rate, pH and other variables, using differential pulse voltammetry (DPV) and square wave voltammetry (SWV) as redissolution techniques. In both cases a voltammetric peak is obtained, at –0.542 V (DPV) and –0.421 V (SWV) in Britton-Robinson buffer (pH 1.9). The detection limits were 3.66 × 10^–1 M and 4.22 × 10^–9 M for AdS-DPV and AdS-SWV, respectively. Under optimum conditions the Metamitron reduction peak gave two linear regions in the range from 4.0 × 10^–9 M to 8.0 × 10^–8 M by means of AdS-DPV, with a coefficient of variation of 2.19% (n = 10) for 1 × 10^–8 M herbicide solution. A method was developed for determination of Metamitron in soils, with a recovery of 98.8% and a coefficient of variation of 5.26% (0.01 g/g of soil).     

Simultaneous trace-levels determination of Hg(II) and Pb(II) ions in various samples using a modified carbon paste electrode based on multi-walled carbon nanotubes and a new synthesized Schiff base

A modified carbon paste electrode based on multi-walled carbon nanotubes (MWCNTs) and 3-(4-methoxybenzylideneamino)-2-thioxothiazolodin-4-one as a new synthesized Schiff base was constructed for the simultaneous determination of trace amounts of Hg(II) and Pb(II) by square wave anodic stripping voltammetry. The modified electrode showed an excellent selectivity and stability for Hg(II) and Pb(II) determinations and for accelerated electron transfer between the electrode and the analytes. The electrochemical properties and applications of the modified electrode were studied. Operational parameters such as pH, deposition potential and deposition time were optimized for the purpose of determination of traces of metal ions at pH 3.0. Under optimal conditions the limits of detection, based on three times the background noise, were 9.0 × 10⁻⁴ and 6.0 × 10⁻⁴ μmol L⁻¹ for Hg(II) and Pb(II) with a 90 s preconcentration, respectively. In addition, the modified electrode displayed a good reproducibility and selectivity, making it suitable for the simultaneous determination of Hg(II) and Pb(II) in real samples such as sea water, waste water, tobacco, marine and human teeth samples.     

氧氟沙星在乙炔黑修饰电极上的电化学行为及测定

本文制备了一种乙炔黑修饰电极,研究了氧氟沙星(OFL)在该修饰电极上的循环伏安行为。结果表明,在pH=5的PBS缓冲液中,氧氟沙星在该修饰电极上出现一不可逆的氧化峰,在40～360 mV/s扫速范围内,氧化峰电流与扫速呈线性关系,表明该电极过程受吸附控制。计算了电极过程的部分动力学参数:反应电子数为2,电极有效面积为0.067 cm2。讨论了修饰剂用量、缓冲液种类、溶液pH值对测定的影响。用方波溶出伏安法对OFL进行测定,在2.5×10-6～2.5×10-4mol.L-1的浓度范围内与氧化峰电流(Ipa)呈线性关系,Ipa(μA)=-1.6148+0.2169c(10-6 mol.L-1),相关系数为0.9951,检出限为1.332×10-7 mol.L-1,回收率为90.40%～101.06%。     

离子液体BMIMPF6修饰碳糊电极电化学测定维生素E

用疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸([BMIM]PF6)作粘合剂制备了离子液体修饰碳糊电极(IL/CPE)。采用循环伏安法(CV)研究了维生素E(vitamin E,VE)的氧化产物生育酚红在IL/CPE和未修饰碳糊电极(CPE)上的电化学行为,结果表明生育酚红在IL/CPE上氧化过程更易于进行,峰电流响应ip也明显增加,表明IL/CPE对生育酚红的氧化还原反应具有良好的电催化作用。同时测定了电极过程的动力学参数:电荷转移系数α=0.8746,扩散系数D=1.65×10-3cm2/s,电极反应速率常数kf=6.64×10-2cm/s。采用方波伏安法(SWV)发现生育酚红氧化峰电流与其浓度在1.53×10-4mol/L～8.39×10-7mol/L范围内呈线性关系,检出限为1.58×10-8mol/L。该法可用于VE实际样品的分析测定。     

Electrochemical modification of a carbon paste electrode with poly (1,5-diaminonaphthalene) and copper-cobalt nanostructures for the determination of thioctic acid in real samples

This study used square-wave voltammetry and cyclic voltammetry to investigate the electrochemical oxidation of Thioctic Acid (TA) on a Carbon Paste Electrode (CPE) modified with copper-cobalt nanostructures and poly (1,5-Diaminonaphthalene). The voltammetric sensor was sensitive to the oxidation of TA. In addition, we optimized the effects of multiple cycles of deposition of Cu-Co nanostructures, and electro-polymerization of monomer 1,5-DAN, scan rate, and pH. The sensor showed good identification capabilities for TA. The linear responses obtained ranged from 0.6 μM to 150 μM with a detection limit of 0.48 μM for the modified CPE. The adsorption process controlled the oxidation of TA. We used the proposed sensor and method to determine TA in real samples.     

Electrochemical determination of lead(II) using a montmorillonite calcium-modified carbon paste electrode

Utilizing the fascinating properties of montmorillonite calcium (MMT-Ca), such as huge cationic exchange capacity, strong adsorptive ability, high chemical and mechanical stability, an MMT-Ca modified carbon paste electrode (CPE) was constructed for the sensitive determination of Pb²⁺. In 0.01 mol·L⁻¹ HCl, Pb²⁺ was firstly exchanged and accumulated on an MMT-Ca modified CPE surface and secondly reduced to Pb at −0.90 V. In the following potential sweep from −0.90 to −0.50 V, reduced Pb was oxidized, resulting in an obvious stripping peak at −0.58 V. After optimizing the parameters, such as determining medium, content of MMT-Ca, accumulation potential and time, an electrochemical method was developed for the analysis of Pb²⁺. Compared with bare CPE, the MMT-Ca modified CPE significantly enhances the sensitivity of Pb²⁺ analysis. The limit of detection is evaluated to be 6.0 × 10⁻⁹ mol L⁻¹ Pb²⁺. Finally, this method was successfully employed to determine trace levels of Pb²⁺ in water samples. The first two authors contribute equally do this work     

邻仲丁基苯酚在玻碳电极上的电化学行为

通过循环伏安法(CV)研究了玻碳电极上邻仲丁基苯酚(OSBP)的电化学行为.结果显示:在pH=8.0的磷酸盐缓冲液中,OSBP在玻碳电极上发生的氧化反应是受扩散控制的不可逆等电子、质子转移过程,且氧化产物部分被还原.氧化峰电流与浓度在5.0×10~(-6)～2.0×10~(-4)mol·L~(-1)之间呈良好的线性关系,检出限(S/N=3)为6.60×10~7mol·L~(-1).重复测定的相对标准偏差(RSD)为4.48%(n=7),加标回收率为86.2%～100.5%.结果令人满意.     

Voltammetric sensor for glutathione determination based on ferrocene-modified carbon paste electrode

The electrocatalytic oxidation of glutathione (GSH) has been studied at the surface of ferrocene-modified carbon paste electrode (FMCPE). Cyclic voltammetry (CV), double potential step chronoamperometry, and differential pulse voltammetry (DPV) techniques were used to investigate the suitability of incorporation of ferrocene into FMCPE as a mediator for the electrocatalytic oxidation of GSH in buffered aqueous solution. Results showed that pH 7.00 is the most suitable for this purpose. In the optimum condition (pH 7.00), the electrocatalytic ability of about 480 mV can be found and the heterogeneous rate constant of catalytic reaction was calculated as . Also, the diffusion coefficient of glutathione, D, was found to be 3.61 × 10^–5 cm² s⁻¹. The electrocatalytic oxidation peak current of glutathione at the surface of this modified electrode was linearly dependent on the GSH concentration and the linear analytical curves were obtained in the ranges of 3.2 × 10^–5 M–1.6 × 10^–3 M and 2.2 × 10^–6 M–3.5 × 10^–3 M with cyclic voltammetry and differential pulse voltammetry methods, respectively. The detection limits (3σ) were determined as 1.8 × 10^–5 M and 2.1 × 10^–6 M using CV and DPV, respectively. Finally, the electrocatalytic oxidation of GSH at the surface of this modified electrode can be employed as a new method for the voltammetric determination of glutathione in real samples such as human plasma.     

Application of multi-walled carbon nanotubes modified carbon ionic liquid electrode for electrocatalytic oxidation of dopamine

A simple, sensitive, and reliable method based on a multi-walled carbon nanotubes (MWNTs) modified carbon ionic liquid electrode (CILE) has been successfully developed for determination of dopamine (DA) in the presence of ascorbic acid (AA). The acid-treated MWNTs with carboxylic acid functional groups could promote the electron-transfer reaction of DA and inhibit the voltammetric response of AA. Due to the good performance of the ionic liquid, the electrochemical response of DA on the MWNTs/CILE was better than that of other MWNTs modified electrodes. Under the optimum conditions a linear calibration plot was obtained in the range 5.0×10(-8) to 2.0×10(-4) mol L(-1) and the detection limit was 1.0×10(-8) mol L(-1).     

Electrochemical response of a carbon paste electrode containing an adsorbed species on incorporated alumina

The electrochemical response of carbon paste electrode was investigated containing an inorganic and a non-electroactive compound on which an electro- active organic molecule was adsorbed. Alizarin S was chosen as the test molecule adsorbed on 150 m²/g of alumina, because this molecule is either easily reduced or oxidized on carbon. The electrode response was found to be linear for low amounts of alumina containing a known amount of Alizarin S. The electrical yield was never higher than 50%, but was reproducible. An increasing alumina amount in the paste increased the response, but lowered the electrical yield.     

Modified glassy carbon electrode by electropolymerization of tetrakis-(2-aminopheny)porphyrin for the determination of norepinephrine in the presence of ascorbic acid

A glassy carbon electrode (GCE) was modified with electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin (TAPP) in acetonitrile by cyclic voltammetry (CV). The voltammetric behavior of norepinephrine (NE) in the presence of excess ascorbic acid (AA) was investigated at the modified electrode by cyclic and square wave voltammetry (SWV) in phosphate buffer solution. The modified electrode gave higher selectivity and highly effective electroactivity to NE oxidation in voltammetric measurements of NE in the presence of AA and epinephrine. In pH 7.4 phosphate buffer solution, the peak current increased linearly with the concentration of NE in two concentration ranges of 1.0×10⁻⁶ to 5.0×10⁻⁵ mol dm⁻³.