High sensitive determination of trace amount of cobalt by catalytic adsorptive stripping voltammetry

A very sensitive and selective catalytic adsorptive cathodic stripping procedure for trace measurements of cobalt is presented. The method is based on adsorptive accumulation of cobalt-CCA (calcon carboxylic acid) complex onto a hanging mercury drop electrode followed by reduction of the adsorbed species by voltammetric scan using differential pulse modulation. The reduction current is enhanced catalytically by nitrite. The effect of various parameters such as pH, concentration of CCA, concentration of nitrite, accumulation potential and accumulation time on the selectivity and sensitivity were studied. The optimum condition for the analysis of cobalt, include pH 5.2 (Acetate buffer), 2.1 μM clacon carboxylic acid, 0.032 M sodium nitrite and an accumulation potential of 0.05 V (versus Ag/AgCl). Under these optimum conditions and for an accumulation time of 60 s, the measured peak current at −0.480 V is proportional to the concentration of cobalt over the entire concentration range tested 0.003–2.0 ng ml⁻¹ with a detection limit of 1 pg ml⁻¹ for an accumulation time of 60 s and 2.0–10.0 ng ml⁻¹ for an accumulation time of 40 s. The relative standard deviations for ten replicate measurement of 0.5 ng ml⁻¹ of cobalt were 3.1%. The main advantage of this new system is the microtrace Co(II) determination by ASV. The method was applied to determination of cobalt in a water sample and some analytical grade salts with satisfactory results. Published in Elektrokhimiya in Russian, 2009, Vol. 45, No. 2, pp. 221–228. The article is published in the original.     

Ultrasensitive Simultaneous Quantification of Nanomolar Level of Cd and Zn by Cathodic Adsorptive Stripping Voltammetry in Some Real Samples

A novel, simple and sensitive adsorptive stripping voltammetry method was developed for simultaneous determination of Cd and Zn using N‐Nitrozo‐N‐phenylhydroxylamine (Cupferron) as a selective complexing agent. Cadmium and zinc metals gave peaks that were distinctly separated by 450–1200 mV, allowing their determination over a wide range of concentrations. The influence of pH and the nature of supporting electrolytes, concentration of ligand, preconcentration time and applied potential were investigated. The detection limits were 0.058 ng/mL for Zn and 0.092 ng/mL for Cd, and the RSD at a concentration level of 50 ppb, were 1.8–2.1 % for both zinc and cadmium, respectively. The method was applied to the determination of cadmium and zinc in blood, drug, food and water samples with the satisfactory results.     

Phosphodiesterase‐Inhibiting Glycosides from Symplocos racemosa

Phytochemical investigation of Symplocos racemosa resulted in the isolation of two new glycosides, symploracemoside ( 1 ) and symplomoside ( 2 ), which are structurally related to the reported benzoylsalireposide ( 3 ) and salireposide ( 4 ). The structure elucidation of the isolated compounds was based primarily on 1D‐ and 2D‐NMR analysis, including COSY, NOESY, HMQC, and HMBC correlations. These glycosides showed inhibitory activity against snake‐venom phosphodiesterase I.     

One‐Pot Synthesis of New 1,5‐Disubstituted Tetrazoles Bearing 2,2‐Bis(trimethylsilyl)ethenyl Groups via The Ugi Four‐Component Condensation Reaction Catalyzed by MgBr2·2Et2O

A simple one‐pot Ugi four‐component condensation reaction has been developed for the synthesis of tetrazoles bearing 2,2‐bis(trimethylsilyl)ethenyl groups from the synthesized 4‐[2,2‐bis(trimethylsilyl) ethenyl]benzaldehyde ( 1 ), various amines, isocyanides, and trimethylsilylazide at room temperature, without solvent, and in the presence of catalytic amounts of MgBr₂·2Et₂O as catalyst.     

Electrospinning of nylon-6,6 solutions into nanofibers: Rheology and morphology relationships

The relationship between the rheological properties of nylon-6,6 solutions and the morphology of their electrospun nanofibers was established. The viscosity of nylon-6,6 in formic acid(90%) was measured in the concentration range of 5 wt%-25 wt% using a programmable viscometer. Electrospinning of nylon-6,6 solutions was carried out under controlled parameters. The chemical structure, morphology and thermal properties of the obtained nanofibers were investigated using Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and differential scanning calorimetry(DSC), respectively. Entanglement concentration(ce) was found to be 15 wt% and a power law relationship between specific viscosity and solution concentration was observed with exponents of 2.0 and 3.3 for semi-dilute unentangled(c ce) and semi-dilute entangled(c ce) regimes, respectively. The diameter and uniformity of the nanofibers were found to be dependent on the viscosity. Moreover, the average diameter of electrospun nanofibers was found to be dependent on zero shear rate viscosity and normalized concentration(c/ce) in a power law relationship with exponents of 0.298 and 0.816, respectively. For nylon-6,6 solutions, the entanglement concentration(ce = 15 wt%) provides the threshold viscosity required for the formation of a stable polymeric jet during electrospinning and producing uniform beadless fibers. For concentrations less than ce, beaded fibers with some irregularities are formed. DSC analysis showed an increase in crystallinity of all electrospun samples compared to original polymer. Furthermore, Based on FTIR spectroscopy, α phase is dominant in electrospun nanofibers and minor amount of β and γ phases is also available.     

Synthesis,anti‐migration and burning rate catalytic mechanism of ferrocene‐based compounds

One of the most important components of solid rocket propellant is the burning rate catalysts (BRC) which enhance burning rate of solid composite propellant. Low‐pressure exponents and stable burning rate are the key features of an excellent solid propellant. Addition of BRC to the propellant results in the increase of burning rate of the propellant and decrease in pressure exponents. Among all BRC, ferrocene‐based BRC have attracted much attention because of their better microscopic homogeneities in distribution, ignitability of the propellants and good compatibility with organic binder. However, the main barrier for the development and practical applications of ferrocene‐based BRC is their migration property. This article reviews the field and highlights recent progress. Copyright © 2014 John Wiley & Sons, Ltd.     

Mechanism of copper underpotential deposition at Pt(<Emphasis Type="Italic">hkl</Emphasis>)-electrodes: Quantum-chemical modelling

Mechanism of copper underpotential deposition at stepped faces of platinum single crystals Pt(hkl) is studied using cyclic voltammetry, scanning probe microscopy, and quantum-chemical modelling. It is shown that the first stage of UPD is one-dimensional decoration of the (100)- or (110)-orientated steps, then copper monolayer forms at (111)-terraces. The final stage is the secondary step decoration. Quantum-chemical modelling, with the using of long-distance potentials of the Cu-Pt and Cu-Cu pair interactions, allows estimating the energy of copper adsorption at different structure elements of the substrate (steps, kinks, terraces) and revealing the succession of the adatom monolayer formation; it also provides additional information for the identifying of the nature of voltametric peaks for different stages of the copper adsorption-desorption.     

Indirect Determination of Trace Copper(II) by Adsorptive Stripping Voltammetry with Zincon at a Carbon Paste Electrode

Traces of copper(II) can be determined by adsorptive stripping voltammetry using 2‐carboxy‐2′‐hydroxy‐5′‐sulfoformazyl benzene (Zincon) as complex forming reagent. First in phosphate buffer pH 6.4, copper(II)‐Zincon complex was adsorbed on carbon paste electrode (CPE) with an accumulation potential of 0.6 V. Following this, adsorbed complex was oxidized and detected by differential pulse voltammetric (DPV) scan from 0.6 to 1.0 V. The effective parameters in sensor response were examined. The detection limit (DL) of copper(II) was 1.1 μg/L and relative standard deviations (RSDs) for 10 and 200 μg/L Cu(II) were 1.81 and 1.03%, respectively. The calibration curve was linear for 2–220 μg/L copper(II). The resulting CPE does not use mercury and therefore, has a positive environmental benefit. The method, which is reasonably sensitive and selective, has been successfully applied to the determination of trace amount of copper in water and human hair samples.     

Synthesis and characterization of novel ferrocenyl glycidyl ether polymer,ferrocenyl poly (epichlorohydrin) and ferrocenyl poly (glycidyl azide)

Poly (ferrocenyl glycidyl ether) was synthesized by polymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane (FcEpo) using toluene solution of methylaluminoxane as the catalyst. Copolymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane with epichlorohydrin was used for the synthesis of another ferrocenyl based poly (epichlorohydrin). Ferrocenyl based poly (glycidyl azide), GAP, was synthesized by treatment of sodium azide with this copolymer in DMF as solvent at room temperature. The synthesized ferrocenyl based polymers were characterized by FT-IR, ¹HNMR, UV–Vis, TGA, DSC and GPC analysis. The UV–Vis spectra of synthesized polymers show the absorption band of ferrocene moiety at about 450 nm. The TGA and DSC analysis show that poly (ferrocenyl glycidyl ether) has good thermal stability. The TGA analysis shows that the copolymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane with epichlorohydrin improved the thermal stability of the copolymer. The GPC analysis of poly (ferrocenyl glycidyl ether), ferrocenyl based poly (epichlorohydrin) and Ferrocenyl based poly (glycidyl azide) show the PDI between 1.14–1.17. The electrochemical behavior of synthesized polymers was investigated by cyclic voltammetry (CV) measurements. The CV curves of synthesized polymers show good electrochemical performance and there is one redox system with the single-electron reversible reaction that associated with ferrocene moiety in polymers structure. The anodic and cathodic peak currents increased with scan rate confirmed redox reactions in the system are kinetically fast diffusion-controlled reactions.     

核磁共振电信号内标法在人体尿液定量分析中的应用

研究了Varian谱仪核磁共振电信号内标法在人体尿液代谢物浓度测定上的应用,通过实验证明了该方法进行定量分析的可靠性.NMR电信号内标法原理上是通过Varian谱仪去耦通道在常规一维谱图上产生一个参考信号,并利用谱仪软件程序来调整该信号在频谱上的强度、频率、衰减速率等参数.避免了代谢组学中NMR定量实验需要添加已知浓度物质(例如TSP)作为内标而引起的内标物与样品相互作用、谱峰重叠、内标物不溶及弛豫时间太长等问题.研究结果表明,Varian谱仪去耦通道产生的电信号稳定可靠(标准偏差0.36%),能够用于定量分析;当样品浓度大于20 mmol/L或小于2 mmol/L时,该方法测定的相对误差分别为1%和5%.通过配制低浓度的尿液模型样品,验证了电信号内标法测量人体尿液代谢物的浓度的可行性,最后使用该方法测量真实的人体尿液中常见代谢物的浓度,测定结果与医院常用生化分析仪器的测定结果相符.