Ultrasensitive electrochemical sensor for p-nitrophenyl organophosphates based on ordered mesoporous carbons at low potential without deoxygenization

p-Nitrophenyl organophosphates (OPs) including paraoxon, parathion and methyl parathion, etc, are highly poisonous OPs, for which sensitive and rapid detection method is most needed. In this work, an ultrasensitive electrochemical sensor for the determination of p-nitrophenyl OPs was developed based on ordered mesoporous carbons (OMCs) modified glassy carbon electrode (GCE) (OMCs/GCE). The electrochemical behavior and reaction mechanism of p-nitrophenyl OPs at OMCs/GCE was elaborated by taking paraoxon as an example. Experimental conditions such as buffer pH, preconcentration potential and time were optimized. By using differential pulse voltammetry, the current response of the sensor at −0.085 V was linear with concentration within 0.01–1.00 μM and 1.00–20 μM paraoxon. Similar linear ranges of 0.015–0.5 μM and 0.5–10 μM were found for parathion, and 0.01–0.5 μM and 0.5–10 μM for methyl parathion. The low limits of detection were evaluated to be 1.9 nM for paraoxon, 3.4 nM for parathion and 2.1 nM for methyl parathion (S/N = 3). Common interfering species had no interference to the detection of p-nitrophenyl OPs. The sensor can be applicable to real samples measurement. Therefore, a simple, sensitive, reproducible and cost-effective electrochemical sensor was proposed for the fast direct determination of trace p-nitrophenyl OPs at low potential without deoxygenization.     

Synthesis of a Dimeric Magnesium(I) Compound by an MgI/MgII Redox Reaction

The synthesis of dimeric magnesium(I) compounds of the general type RMgMgR (R=monoanionic substituent) is still a challenging synthetic task and limited to few examples with sterically demanding ligands with delocalized CN‐frameworks that all have been accessed by Na or K metal reduction of magnesium(II) halide precursors. Here we report on the synthesis of a novel diiminophosphinato magnesium(I) compound that has been synthesized by a facile redox reaction using a known magnesium(I) complex. The synthetic strategy may be applicable to other ligand systems and can help expand the class of low oxidation state magnesium complexes even if reductions with Na or K are unsuccessful. The new dimeric magnesium(I) complex has been structurally characterized and undergoes a C? C coupling reaction with tert‐butylisocyanate.     

紫草素的电化学伏安行为研究

紫草素在0.2 mol/L HAc-NaAc缓冲溶液(pH4.3)中,产生灵敏的线性扫描极谱峰,峰电位EP=-0.186 V(vs.Ag/AgCl)。峰电流与紫草素浓度在5×10-7~1×10-5mol/L范围内呈良好的线性关系。可用于紫草中紫草素含量的测定。用线性扫描和循环伏安法测试表明,该体系属具有反应物吸附性的可逆过程体系。     

Development of wavelet transform voltammetric analyzer

An on-line wavelet transform algorithm and development of voltammetric analyzer with the on-line wavelet transform (WT-voltammetric analyzer) are described. Because the on-line wavelet transform decomposes the sampled signal simultaneously with the progress of sampling, the WT-voltammetric analyzer gives all the components contained in the sampled voltammogram. Applications of the WT-voltammetric analyzer in linear sweep voltammetric analysis of mixtures of Pb(II) and Tl(I) and in square wave voltammetric analysis of mixture of Cd(II) and In(III) were investigated. Results showed that the overlapping peaks of Pb(II) and Tl(I) can be separated easily, and the peak position after the on-line wavelet transform does not change. The linearity of the calibration curves for Cd(II) and In(III) in the overlapping square wave voltammetric curves were kept after the on-line wavelet transform. Quantitative determination of Cd(II) and In(III) in mixture samples were investigated. The recoveries are between 92.5 and 107.1%.     

Voltammetric determination of pyridoxine (Vitamin B6) at a carbon paste electrode modified with vanadyl(IV)-Salen complex

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicylideneiminato)oxovanadium(IV) complex [VO(Salen)] as well as its behavior in relation to the oxidation of pyridoxine (Vitamin B₆) are described. The electrochemical behavior of the modified electrode and the electrooxidation of pyridoxine were investigated using cyclic voltammetry. The best voltammetric response was obtained for an electrode composition of 15% (m/m) [VO(Salen)] in the paste, KCl solution of pH 5.5-8.0 and scan rate of 25 mV s⁻¹. A sensitive linear voltammetric response for pyridoxine was obtained in the concentration range of 4.5×10⁻⁴ to 3.3×10⁻³ mol l⁻¹ with a slope of 42.5 μA mmol⁻¹ l, and a detection limit (3σ/slope) of 3.7×10⁻⁵ mol l⁻¹ using linear sweep voltammetry. Among several compounds tested only Vitamin B₁ seems to interfere in the analyte signal. The concentrations of pyridoxine in pharmaceutical formulations using the proposed electrode and an official spectrophotometric method based in the reaction with N,N-diethyl-p-phenylenediamine are in agreement at the 95% confidence level and within an acceptable range of error.     

The recognition of similarities in trace elements content in medicinal plants using MLP and RBF neural networks

The objective of the paper was to verify if the content of some elements provides enough information for proper classification of the medicinal plant raw materials. Such information could be helpful in standardization process of herbal products. Four elements—zinc, copper, lead and cadmium were determined using inverse voltammetry in commercially available medicinal herbal raw materials. Initially, principal component analysis (PCA) was employed to investigate the relationships among the analyzed trace elements. In the next stage of the study, two different types of feed-forward artificial neural networks (FANNs)—multilayer perceptron (MLP) and radial basis function (RBF) were applied. The concentrations of the elements were used as input variables to neural networks models, which were to recognize the taxonomy of the plant and the anatomical part it originated from. Although full recognition of the samples with use of FANNs on the basis of some trace elements content was not achieved, it was possible to identify two elements—cadmium and lead as the most important in the classification analysis of medicinal plants.     

A TTF–TCNQ Electrode as a Voltammetric Analogue of an Ion‐Selective Electrode

A TTF‐TCNQ/PVC composite electrode is proposed as a voltammetric cation and anion sensor. The electrode relies on the principle that, during redox processes involving the TCNQ^0/? couple for cations and the TTF^+/0 couple for anions, electrolyte ions are included into lattice sites in the charge neutralization process. This voltammetric ion‐sensor provides results that are similar to those of sensors based on two electrodes (viz. one modified with TCNQ for cations and another modified with TTF for anions) but with some practical advantages over them.     

高效液相色谱分离催化伏安检测微量稀土元素——钆、铽、镝、钬、铒

本文提出用Ag(Hg)-Pt-Ag三电极流动微电解池检测高效液相色谱柱流出液中痕量稀土的浓度。用Apple-Ⅱ微电脑采集伏安信号,再转换成色谱流出曲线。稀土元素的检测限可达0.5μg。     

A Note on Similarity Reductions of Barotropic and Quasi-geostrophic Potential Vorticity Equation

Applying the classical Lie symmetry approach to the barotropic and quasi-geostrophic potential vorticity equation without forcing and dissipation on a β-plane channel, we find a new symmetry, which is not presented in a previous work [F. Huang, Commun. Theor. Phys. （Beijing, China） 42 （2004） 903]. A general finite transformation group is obtained based on the full Lie point symmetry, Furthermore, two new types of similarity reduction solutions are obtained.     

Solutions and continuum limits to nonlocal discrete sine-Gordon equations: Bilinearization reduction method

In this paper, we investigate local and nonlocal reductions of a discrete negative order Ablowitz–Kaup–Newell–Segur equation. By the bilinearization reduction method, we construct exact solutions in double Casoratian form to the reduced nonlocal discrete sine-Gordon equations. Then, nonlocal semidiscrete sine-Gordon equations and their solutions are obtained through the continuum limits. The dynamics of soliton solutions are analyzed and illustrated by asymptotic analysis. The research ideas and methods in this paper can be generalized to other nonlocal discrete integrable systems.