Preparation and evaluation of thermally stable nano-structured self-doped polythiophene coating for analysis of phthalate ester trace levels

Nano‐structured self‐doped polythiophene (SPT) electrodeposited in the presence of fluorinated organic acid was applied as a thermally stable conductive polymer‐based solid‐phase microextraction (SPME) fiber candidate. Quantitative determination of trace levels of phthalate esters including dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and diethylhexyl phthalate (DEHP) was carried out using this novel fiber, coupling with gas chromatography‐flame ionization detector (GC‐FID). The SPT coating was proved to be stable at high temperatures (～350°C) with a high extraction capacity and long lifetime (more than 60 times). Improved temperature resistance was obtained by the presence of sulfonated groups in the backbone of polymer. Thermal stability of novel SPT was superior to common polythiophene (synthesized in LiClO₄). The extraction procedure was optimized by means of the Taguchi orthogonal array experimental design with an OA₁₆ (4⁵) matrix including extraction temperature, extraction time, salt concentration, stirring rate, and headspace volume. The good linearity was obtained for most compounds with correlation coefficients (R²) of between 0.993 and 0.995. The detection limits were lower than 0.12 ng/mL for dimethyl phthalate, DEP, dibutyl phthalate, and diethylhexyl phthalate. The method was successfully applied to the analysis of water samples with the recoveries from 90±1 to 107±1%.     

A Single-Gallery Model for the In Situ Production of Polyethylene-Clay Nanocomposites

Polyolefin-clay nanocomposites are finding many new applications because of their improved properties, such as high modulus, elevated scratch resistance and low gas permeability. Currently, these composites are produced by melt blending organically modified clay with polyolefins. The most challenging step in this process is the intercalation and exfoliation of the clay to produce a homogenously dispersed phase at the nanoscale. A promising alternative to melt blending is in-situ polymerization, where the polymer is produced between the clay layers in the polymerization reactor. In-situ polymerization of olefins with metallocene catalysts supported on clay can produce nanocomposites using conventional polymerization reactors, provided that the clay can be used as a support for the olefin polymerization catalyst. In this approach, the clay fulfills the functions of catalyst support and dispersed phase in the final nanocomposite. In this work, a mathematical model describing particle growth during in-situ polymerization of ethylene with a metallocene catalyst supported on clay will be discussed. The model expands the approach of the multi-grain model used in heterogeneous olefin polymerization to account for the layered structure of clays.     

Effect of Al2O3 nanoparticles on the steel-glass/epoxy composite joint bonded by a two-component structural acrylic adhesive

This paper reports a study on the effect of Al₂O₃ nanoparticles on the adhesion strength of steel-glass/epoxy composite joints bonded by a two-component structural acrylic adhesive. The addition of Al₂O₃ nanoparticles to the two-component acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strength of the adhesive joints increased by addition of Al₂O₃ up to 1.5 wt%, which decreased by further addition of the nanofiller. Introduction of the nanoparticles caused a reduction in the peel strength of the joints. DSC analysis revealed that the glass transition temperature (Tg) of the adhesives rose by increasing the nanofiller content. The advancing water contact angle was decreased for adhesives containing nanoparticles. SEM micrographs indicated good dispersions of the Al₂O₃ nanoparticles within the acrylic matrix in the specimens with up to 1.5 wt% Al₂O₃ and revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.     

Combined methane reforming over nano LaNiO<Subscript>3</Subscript> catalyst with modified active surface

In this study, nano catalyst LaNiO₃ with perovskite structure was synthesized using the citrate sol–gel method in the combined methane reforming with CO₂ and O₂ (CRM). The effects of increasing the surface area of the LaNiO₃ perovskite on the catalytic activity were investigated by changing the method of preparing and creating holes in the surface of the samples. Physical and chemical properties of the samples, before and after the reactor test, were determined through ICP, AA, XRD, TGA, TPR, BET, SEM, EDX and TEM techniques. The results of XRD, ICP, AA, SEM, EDX and TEM tests indicated that the citrate sol–gel method is a good way to prepare a homogeneous perovskite LaNiO₃ sample on a scale of nanometers. The results of the TPR test showed using etching in the citrate sol–gel method can produce samples with high stability. The BET results indicated that the surface area of the LaNiO₃ sample tripled with the method suggested in this paper. Changes in preparation method lead to induction time decreasing and temperature increasing. Use of etching in the citrate sol gel method had no significant effect in the results of activity tests versus time reaction at a temperature of 800 °C. TGA curves revealed no production of coke over the process for the produced samples.     

An efficient one-pot synthesis of novel 6-hydroxy-14-aryl-8H-dibenzo[a,i]xanthene-8,13(14H)-diones derived from lawsone

An efficient and convenient procedure for the synthesis of novel 6-hydroxy-14-aryl-8H-dibenzo[a,i]xanthene-8,13(14H)-dione derivatives has been developed by one-pot, three-component condensation reaction between 2-hydroxynaphthalene-1,4-dione, aromatic aldehydes and 2,3-naphthalenediol in glacial acetic acid under reflux conditions. This domino reaction implies Knoevenagel condensation, Michael addition, intramolecular cyclization and dehydration. The reaction avoids tedious workup procedure due to the direct precipitation of products from the reaction medium. The notable features of this domino transformation are operational simplicity, clean reaction, easy handling, easy purification process and high yields of the products.

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Green synthetic approach toward new chromeno[4,3-b]quinoline and chromeno[4,3-b]pyridine derivatives

Chemistry of Heterocyclic Compounds - A facile, convenient, and efficient synthesis of new chromeno[4,3-b]quinoline and chromeno[4,3-b]pyridine derivatives has been accomplished via one-pot...     

Synthesis, characterization and crystal structures of di-three-coordinated copper(I) macrocyclic Schiff base complexes

The air-stable di-copper(I) complexes Cu₂L(SCN)₂ (1) and Cu₂L(SCN)_1.86I_0.14 (2) of the N₄ macrocyclic Schiff base ligand L have been synthesized and characterized by IR, elemental analysis, UV-Vis and crystal structure determination. X-ray analysis of the complexes shows an approximate distorted trigonal planar geometry around each copper(I) ion that is constructed from one N-bonded thiocyanate (or iodide in 2) group and two imine nitrogen atoms. DFT calculations were used to determine the structural features of the Cu₂L(SCN)₂ complex, and these were consistent with the experimental data for the complex.     

Electromembrane extraction of levamisole from human biological fluids

Electromembrane extraction coupled with high-performance liquid chromatography (HPLC) and ultraviolet (UV) detection was developed for the determination of levamisole in some human biological fluids. Levamisole migrated from 4 mL of different acidized biological matrices, through a thin layer of 2-nitrophenyl octyl ether containing 5% tris-(2-ethylhexyl) phosphate immobilized in the pores of a porous hollow fiber, into a 20-μL acidic aqueous acceptor solution present inside the lumen of the fiber. The parameters influencing electromigration were investigated and optimized. Within 15 min of operation at 200 V, levamisole was extracted from different biological fluid samples with recoveries in the range of 59-65%, which corresponded to preconcentration factors in the range of 118-130. The calibration curves showed linearity in the range of 0.5-10, 0.2-10 and 0.1-10 μg/mL for plasma, urine and saliva, respectively. Limits of detection of 0.1, 0.07 and 0.05 μg/mL and limits of quantification of 0.5, 0.2 and 0.1 μg/mL were obtained for plasma, urine and saliva, respectively. The relative standard deviations of the analysis were found to be in the range of 5.6-9.7% (n = 3). Electromembrane extraction was successfully processed for determination of levamisole in plasma, urine and saliva samples.