钡离子在玫红酸钠修饰碳糊电极上电化学固相微萃取研究

本文以电化学活性的玫红酸钠修饰碳糊电极,利用玫红酸盐与钡离子的络合效应,实现钡离子的电化学固相微萃取。以循环伏安法研究了钡离子的固相微萃取及其最佳实验条件。固相微萃取的动力学符合S形曲线模型,获得表观一级反应速率常数为2.183 min-1。固相微萃取的热力学遵循Freundlich等温吸附模型,吸附常数为n=11.4,k=1.025。     

Study of an organically modified clay: selective adsorption of heavy metal ions and voltammetric determination of mercury(II)

In this work, a hydrophilic clay, Na-montmorillonite from Wyoming, USA, was rendered organophilic by exchanging the inorganic interlayer cations for hexadecyltrimethylammonium ions (HDTA), with the formulae of [(CH₃)₃N(C₁₆H₃₃)]⁺ ion. Based on fact that organo-clay has high affinities for non-ionic organic molecules, 1,3,4-thiadiazole-2,5-dithiol was loaded on the HDTA-montmorillonite surface, resulting in the 1,3,4-thiadiazole-2,5-dithiol-HDTA-montmorillonite complex (TDD-organo-clay).The following properties of TDD-organo-clay are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II).The main point of this paper is the construction of a selective sensor, a carbon paste electrode modified with TDD-organo-clay, its properties and its application to the determination of mercury(II) ions, as this element belongs to the most toxic metals. The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination.     

Determination of metformin based on amplification of its voltammetric response by a combination of molecular wire and carbon nanotubes

Molecular wires containing copper(II) (CuMW), in the form of the coordination polymer (Cu(II)₄(bpp)₄(maa)₈(H₂O)₂).2H₂O (bpp=1,3-bis(4-pyridyl)propane, maa=2-methylacrylic acid), and multiwalled carbon nanotubes (CNT) have been combined to prepare a paste electrode (CuMW/CNT/PE). The voltammetric response of the CuMW/CNT/PE to metformin (MET) was significantly greater than that of electrodes prepared from other materials, because of both the surface effect of CuMW and CNT and coordination of MET with the Cu(II) ion in the CuMW. A novel voltammetric method for determination of MET is proposed. In pH 7.2 Britton–Robinson buffer, using single sweep voltammetry, the second-order derivative peak current for oxidation of MET at 0.97 V (relative to SCE) increased linearly with MET concentration in the range 9.0 × 10⁻⁷–5.0 × 10⁻⁵ mol L⁻¹ and the detection limit was 6.5 × 10⁻⁷ mol L⁻¹. Figure When a combination of molecular wires containing copper(II) (CuMW) and multiwalled carbon nanotubes (CNT) was used to prepare a paste electrode (CuMW/CNT/PE) the voltammetric response to metformin (curve c) was significantly higher than that at a carbon/PE (curve a) or a CNT/PE (curve b), because of the amplification effect of CNT and CuMW. A novel voltammetric method is proposed for determination of MET     

Electrochemical Study of Interaction Between Clozapine and DNA and Its Analytical Application

Abstract

The interaction between clozapine (CLZ) as an orally administrated antipsychotic drug with double stranded calf thymus DNA (dsDNA) was investigated at electrode surface using differential pulse voltammetry (DPV). Activated carbon paste electrode (CPE) was modified with dsDNA and used for monitoring the changes of the characteristics peak of CLZ in 0.05 M acetate buffer (pH 4.3). The adsorptive stripping voltammetry on dsDNA‐modified carbon paste electrode (dsDNA‐CPE) was used for determination of very low concentration of CLZ. Under optimal conditions, the oxidation peak current is proportional to CLZ concentration in the range of 7×10^?9?1.2×10^?6 mol l^?1 with a detection limit of 1.5×10^?9 mol l^?1 for 180 s accumulation time by DPV. The proposed dsDNA‐CPE was successfully used for determination of CLZ in human serum samples with recovery of 97.0±2.5%.     

Differential Pulse Adsorptive Stripping Voltammetric Determination of Chlorpyrifos at a Sepiolite Modified Carbon Paste Electrode

Abstract

An adsorptive stripping voltammetric (AdSV) method for the determination of organophosphorus insecticide chlorpyrifos at a bare carbon paste electrode (CPE) and clay modified carbon paste electrode (CMCPE) was developed. A systematic study of various experimental conditions, such as the pH, accumulation variables and composition of a modifier on the adsorptive stripping response, were examined by using differential pulse voltammetry. A significant improvement was observed in the sensitivity by using the present method with CMCPE. When CMCPE was used, a linear response was obtained over the concentration range 0.0001–2.0 ppm with lower detection limit of 0.00008 ppm, at an accumulation time of 80 s. The interference from other herbicides and ions on the stripping signal of the compound was also evaluated. The described method was applied to estimate the chlorpyrifos in environmental samples.     

Determination of Ascorbic Acid in the Presence of Uric Acid and Folic Acid by a Nanostructured Electrochemical Sensor Based on a TiO2 Nanoparticle Carbon Paste Electrode

A carbon paste electrode (CPE), modified with novel hydroquinone/TiO₂ nanoparticles, was designed and used for simultaneous determination of ascorbic acid (AA), uric acid (UA) and folic acid (FA). The magnitude of the peak current for modified TiO₂-nanoparticle CPE (MTNCPE) increased sharply in the presence of ascorbic acid and was proportional to its concentration. A dynamic range of 1.0–1400.0 μM, with the detection limit of 6.4 × 10^?7 M for AA, was obtained using the DPV technique (pH = 7.0). The prepared electrode was successfully applied for the determination of AA, UA, and FA in real samples.     

Adsorptive/Extractive Stripping Voltammetry of 1,2,3,4-Tetrahydrocarbazole

Abstract

Adsorptive/extractive accumulation of 1,2,3,4-tetrahydrocarbazole at a carbon paste electrode is used to improve the subsequent voltammetric measurement with respect to sensitivity and selectivity. By simply immersing the electrode in the 1,2,3,4-tetrahydrocarbazole solution for a given period of time, and then transferring it to a blank solution, high degree of selectivity is achieved. After 10 min preconcentration, a detection limit near 1.4×10^-8M 1,2,3,4-tetrahydrocarbazole is obtained. Cyclic voltammetry is used to aid understanding the nature of the accumulation process. Applicability to measurements of other indole alkaloids and to analysis of urine samples is illustrated.     

Determination of Bisphenol A Using an Electrochemical Sensor Based on a Molecularly Imprinted Polymer-Modified Multiwalled Carbon Nanotube Paste Electrode

A novel electrochemical sensor for bisphenol A was developed through the combination of a molecular imprinting technique with a multiwalled carbon nanotube paste electrode. A molecularly imprinted polymer and nonimprinted polymer were synthesized in the presence and absence of bisphenol A, and then used to prepare the electrode. The bisphenol A imprinted polymer was applied as a selective recognition element in the electrochemical sensor. Differential pulse voltammetry was used to characterize the electrochemical behavior of bisphenol A at the modified electrodes. The results showed that the imprinted sensor had highest response for bisphenol A. Parameters including the carbon paste composition, pH, and adsorption time for the imprinted sensor were optimized. Under the optimized conditions, the differential pulse voltammetry peak current was linear with the concentration of bisphenol A from 0.08 to 100.0 µM, with a detection limit of 0.022 µM. The imprinted sensor for bisphenol A exhibited good selectivity, stability, and reproducibility. This sensor was successfully used for the determination of bisphenol A in real water samples.     

Sensing System Integrating Lanthanum Hydroxide Nanowires with Copper(II) Ion for Uracil and its Application

Abstract

A sensing system for uracil was constituted by using lanthanum hydroxide nanowires (LNW) as a modifier to obtain LNW modified carbon paste electrode (LNW/CPE) and by introducing copper(II) ion into supporting electrolyte to transform electroinactive uracil to electroactive uracil‐Cu(II) complex. The voltammetric behaviors of uracil in the presence of Cu(II) ion at LNW/CPE were investigated. A reduction peak of the uracil‐Cu(II) complex at ?0.18 V was the two‐electron reduction of Cu(II) ion in the uracil‐Cu(II) complex; while a new oxidation peak at 0.22 V was the one‐electron oxidation of the uracil‐Cu(I) complex. Additionally, the voltammetric responses of all the complexes at LNW/CPE were more sensitive than that at carbon and multiwall carbon nanotube paste electrodes, which resulted from both the large surface effect of LNW and the chemical coordination of uracil with La(III) ion in LNW. With the sensitive oxidation peak of the uracil‐Cu(I) complex at LNW/CPE, a linear range of 4.0×10^?9?3.0×10^?8 mol/l for uracil was obtained along with a detection limit of 2.0×10^?10 mol/l. The proposed system was evaluated by the determination of uracil derivatives, anticancer drug 5‐flurouracil, in pharmaceutical preparations.