Simultaneous spectrophotometric determination of iron and vanadium by H-point standard addition method and partial least squares regression in micellar medium

Simultaneous determination of total iron and vanadium by H-point standard addition method (HPSAM) and partial least squares (PLS) is described. Gallic acid (GA) in a cationic micellar solution of CTAB was used for determination of iron and vanadium in different oxidation states at pH 5. The presence of a micellar system enables total iron and vanadium to be determined with improved sensitivities. The total relative standard error for applying the PLS method to 15 synthetic samples in the ranges 0.20–15.00 μg ml⁻¹ iron and 0.20–8.00 μg ml⁻¹ vanadium was 2.2%. The results of applying the H-point standard addition method showed that iron and vanadium can be determined simultaneously with the concentration ratios of iron to vanadium from 10:1 to 1:20 in the mixed sample. Both HPSAM and PLS methods showed suitable abilities to resolve accurately overlapped absorption spectra of the compounds. Both proposed methods were successfully applied to the determination of Fe and V in several synthetic alloy solutions.     

Characteristics of the two frontier orbital interactions in the Diels-Alder cycloaddition

Two electron-deficient dienes were reacted with a series of twelve electron-poor and electron-rich dienophiles to give, in some cases, the corresponding Diels-Alder adducts. Clear differences in the roles played by the two frontier orbital interactions emerged. It was demonstrated that in the case of normal Diels-Alder cycloadditions, the FMO theory could predict the relative reactivities between dienophiles, while in the case of inverse-electron demand Diels-Alder reactions, it could not. It was shown that the dissymmetry in electron-rich dienophiles increases their reactivities.     

L‐Cysteine Voltammetry at a Carbon Paste Electrode Bulk‐Modified with Ferrocenedicarboxylic Acid

The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH 8.00) in cyclic voltammetry, the oxidation of L ‐cysteine occurs at a potential about 200 mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, k_h were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10^?5 M–2.2×10^?3 M and 1.5×10^?5 M–3.2×10^?3 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 2.6×10^?5 M and 1.4×10^?6 M by CV and DPV methods.     

Semi-suspension polymerization process

A novel heterogeneous polymerization process for synthesizing particulate with a wide range of properties has been developed. This process, which is called semi - suspension polymerization (SSP), consists of two steps. In the first step a mixture of monomer, polymer, initiator, and other required ingredients is prepared by means of a non- suspension polymerization process. In the second step, this mixture is suspended in the continuous phase and is polymerized to complete conversion. The properties of the semi-polymerized mixture prepared in the first step as well as the rate of polymerization in the second step can be used to control inter-droplet and/or intra-particle mass transfer. This unique capability allows control of the mass transfer between and within particles during the suspension polymerization, thereby enabling synthesis of particulate with a wide range of molecular properties and morphologies unattainable by conventional suspension polymerization. The characteristics of this process and its advantages/limitations will be discussed.     

Finite element and experimental method for analyzing the effects of martensite morphologies on the formability of DP steels

Abstract

In this article, we investigated the effect of martensite morphology on the mechanical properties and formability of dual phase steels. At first, three heat treatment cycles were subjected to a low-carbon steel to produce ferrite–martensite microstructure with martensite morphology of blocky-shaped, continuous, and fibrous. Tensile tests were then carried out so as to study mechanical properties, particularly the strength and strain hardening behavior of dual phase steels. In order to study the formability of dual phase samples, Forming Limit Diagram was obtained experimentally and numerically. Experimental forming limit diagram was obtained using Nakazima forming test, while Finite Element Method was utilized to numerically predict the forming limit diagram. The results indicated that the dual phase samples with fibrous martensite morphology had the highest tensile properties and strain rate hardening out of the three different microstructures. Blocky-shaped martensite morphology, on the other hand, had the worst mechanical properties. The study of the strain hardening behavior of dual phase sample by Kocks–Mecking-type plots, evinced two stages of strain hardening for all specimens with different microstructures: stages III and IV. The forming limit diagram of dual phase steels also proved that samples with fibrous martensite morphology had the best formability compared to other two microstructures. The simulated forming limit diagram manifested that there is a good agreement between experimental results and those obtained by FEM.     

Expeditious enyne construction from alkynes via oxidative Pd(II)-catalyzed Heck-type coupling

The enyne, ubiquitous in natural products, can be a challenge to generate since these moieties require many synthetic transformations to assemble them. We developed a simpler protocol to construct enynes while we found that this oxidative reaction was tolerant in substrate scope. In addition, the utility of this reaction was demonstrated through the attempt in synthesizing antifungal agent Lamisil^™.     

Electrochemical behavior of ascorbic acid at a 2,2'-[3,6-Dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone carbon paste electrode

Electrocatalytic oxidation of ascorbic acid (AA) at a carbon paste electrode, chemically modified 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone, was thoroughly investigated. The results of cyclic voltammetry, double potential-step chronoamperometry, linear sweep voltammetry and differential pulse voltammetry (DPV) studies were used for the prediction of the mechanism of electrochemical oxidation of AA mediated with 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone at the surface of the modified electrode. The diffusion coefficient (D = 2.45 x 10(-5) cm(2) s(-1)) and the kinetic parameters such as the electron transfer coefficient (alpha = 0.34) were also determined. The results of DPV using the 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone-modified electrode were applied in a highly sensitive determination of AA in drug samples. A linear range of 3.0 x 10(-6) - 1.2 x 10(-4) M and the detection limit (3sigma) 3.8 x 10(-7) M were obtained for DPV determination of AA in buffered pH 7.00 solutions (0.1 M phosphate buffer).     

A tandem highly stereoselective FeCl3-promoted synthesis of a bisindoline: synthetic utility of radical cations in heterocyclic construction

A conceptually distinctive stereoselective construction of the novel dimer, N-[N′-acetyl-7,7′-bis-(3,4-dimethoxy-phenyl)-7,8,7′,8′-tetrahydro-N′H-[8,8′]biindolyl-N-yl]-ethanone 25 (bisindoline) is described below. These structures, which include 7-(3,4-dimethoxyphenyl)-indoline 24 (veratryl indoline), were obtained by the tactical combination of palladium-catalysed coupling which produced 10-acetamido-3,4-dimethoxystilbene 9, followed by FeCl₃ induced oxidative cyclization/dimerization. All new structures were fully characterized by 1- and 2D NMR spectroscopy, (proton, carbon-13, COSY, HMBC, HMQC) and mass spectrometry. Configurational assignments were further supported by semi-empirical AM1 calculations. Mechanistic interpretations, consistent with our results, are discussed.     

A quadrature free convergent method for the numerical solution of linear Fredholm integral equations based on Hermite-spline interpolation

In this paper we use the Hermite-spline interpolation in a special form for the numerical solution of linear Fredholm integral equations. We prove the convergence of this method as a main part of the paper. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)