Crystallographic report: Bis{µ‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]1κ:S,2κ:S‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]‐1κ2S,S′}dicadmium(II)

The centrosymmetric title compound, [Cd₂{CH₃OC₆H₄P(OC₅H₉)S₂}₄], features an eight‐membered [? Cd? S? P? S? ]₂ ring owing to the presence of bridging dithiolate ligands. Tetrahedral coordination geometries for cadmium are completed by chelating ligands. Copyright © 2004 John Wiley & Sons, Ltd.     

Preconcentration and separation of copper(II), cadmium(II) and chromium(III) in a syringe filled with 3-aminopropyltriethoxysilane supported on silica gel

In this study, a syringe was filled with silica gel loaded with 3-aminopropyltriethoxysilane, for the separation and preconcentration of copper, cadmium and chromium prior to their determination by graphite furnace atomic absorption spectrometry (GFAAS) in seawater. For this purpose, a syringe was filled with 0.5 g of modified silica gel and the sample solution was drawn into the syringe and ejected back again. The analyte elements were quantitatively retained at pH 5. Then, the elements sorbed by the silica gel were eluted with 2.0 M of HCl and determined by GFAAS. At optimum conditions, the recovery of Cu, Cd and Cr were 96-98%. Detection limits (3delta) were 6.6, 7.5 and 6.0 micro g L(-1) for Cu, Cd and Cr, respectively. The elements could be concentrated by drawing and discharging several portions of sample successively but eluting only once. Cu, Cd and Cr added to a seawater sample were quantitatively recovered (>95%) in the range of the 95% confidence level. The method proposed in this paper was compared with a column technique. Optimum experimental conditions, reproducibility, precision and recoveries of both techniques are the same, but the syringe technique is much faster, easier and more practical than the column technique. It is a portable system and allows one to make the sorption process in the source of sample. In addition, the risk of contamination is less than in the column technique.     

Lyotropic Liquid Crystal to Soft Mesocrystal Transformation in Hydrated Salt–Surfactant Mixtures

Hydrated CaCl₂, LiI, and MgCl₂ salts induce self‐assembly in nonionic surfactants (such as C₁₂H₂₅(OCH₂CH₂)₁₀OH) to form lyotropic liquid‐crystalline (LLC) mesophases that undergo a phase transition to a new type of soft mesocrystal (SMC) under ambient conditions. The SMC samples can be obtained by aging the LLC samples, which were prepared as thin films by spin‐coating, dip‐coating, or drop‐casting of a clear homogenized solution of water, salt, and surfactant over a substrate surface. The LLC mesophase exists up to a salt/surfactant mole ratio of 8, 10, and 4 (corresponding to 59, 68, and 40 wt % salt/surfactant) in the CaCl₂, LiI, and MgCl₂ mesophases, respectively. The SMC phase can transform back to a LLC mesophase at a higher relative humidity. The phase transformations have been monitored using powder X‐ray diffraction (PXRD), polarized optical microscopy (POM), and FTIR techniques. The LLC mesophases only diffract at small angles, but the SMCs diffract at both small and wide angles. The broad surfactant features in the FTIR spectra of the LLC mesophases become sharp and well resolved upon SMC formation. The unit cell of the mesophases expands upon SMC transformation, in which the expansion is largest in the MgCl₂ and smallest in the CaCl₂ systems. The POM images of the SMCs display birefringent textures with well‐defined edges, similar to crystals. However, the surface of the crystals is highly patterned, like buckling patterns, which indicates that these crystals are quite soft. This unusual phase behavior could be beneficial in designing new soft materials in the fields of phase‐changing materials and mesostructured materials, and it demonstrates the richness of the phase behavior in the salt–surfactant mesophases.     

New Methacrylate Copolymers Based on the Benzofurane Ring: Synthesis,Characterization, Monomer Reactivity Ratios and Biological Activity

The free radical copolymerization of (5-bromo-1-Benzofuran-2-yl)(phenyl)-O-methacrylketoxime (BPMKO) with 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA) has been carried out in 1, 4-dioxane at 65°C ± 1 and was analyzed by Fourier transform infrared, ¹H-NMR, ¹³C-NMR and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of BPMKO and AOEMA in the copolymers. The monomer–reactivity ratios were calculated according to the general copolymerization equation using Kelen-Tüdõs and Finemann-Ross linearization methods. The reactivity ratios indicated a tendency toward random copolymerization. The polydispersity indices of the polymers were determined by gel permeation chromatography and suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperature of the copolymers increased with increasing BPMKO content in the copolymers. All the products showed moderate activity against different strains of bacteria and fungi.     

Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite

The adsorption of two dyes, namely, Acid Red 57 (AR57) and Acid Blue 294 (AB294), onto acid-activated bentonite in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. Acidic pH was favorable for the adsorption of these dyes. The surface characterization of acid-activated bentonite was performed using the FTIR technique. The pseudo-first-order and pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamic data fitted the pseudo-second-order kinetic model well and also followed the intraparticle diffusion model up to 90 min, but diffusion is not the only rate controlling step. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The Freundlich model agrees very well with experimental data. The activation energies of adsorption were also evaluated for the adsorption of AR57 and AB294 onto activated bentonite.     

Mathematical models for job-shop scheduling problems with routing and process plan flexibility

As a result of rapid developments in production technologies in recent years, flexible job-shop scheduling problems have become increasingly significant. This paper deals with two NP-hard optimization problems: flexible job-shop scheduling problems (FJSPs) that encompass routing and sequencing sub-problems, and the FJSPs with process plan flexibility (FJSP-PPFs) that additionally include the process plan selection sub-problem. The study is carried out in two steps. In the first step, a mixed-integer linear programming model (MILP-1) is developed for FJSPs and compared to an alternative model in the literature (Model F) in terms of computational efficiency. In the second step, one other mixed-integer linear programming model, a modification of MILP-1, for the FJSP-PPFs is presented along with its computational results on hypothetically generated test problems.     

Determination of lead, copper and manganese by graphite furnace atomic absorption spectrometry after separation/concentration using a water-soluble polymer

In this study, a water-soluble polymer, polyvinylpyrrolidinone (PVP) having chelating functionalities was used for the preconcentration and separation of traces of Pb, Cu, Ve and Mn prior to their determination by graphite furnace atomic absorption spectrometry. For this purpose, the sample and the PVP solutions were mixed and the metal bound polymer was precipitated by adding the mixture onto acetone. The precipitate was separated by decantation and dissolved with water. By increasing the ratio of the volumes of sample to water used in dissolving the precipitate, the analyte elements were concentrated as needed. The concentration of trace elements was determined using graphite furnace atomic absorption spectrometry. The analyte elements in matrix free aqueous solutions were quantitatively recovered. The validity of the proposed method was checked with a standard reference material (NIST SRM 1577b bovine liver) and spiked fruit juice, sea water and mineral water samples. The analytical results were found to be in good agreement with certified and added values. Detection limits (3δ) were 1.7, 3.6 and 4.1 μg l⁻¹ for Pb, Cu and Mn, respectively, using 10 μl of sample volume. The method is novel and can be characterized by rapidity, simplicity, quantitative recovery and high reproducibility.     

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

In situ photoelastic‐modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the cross‐linked film. This high water activity at the interface leads to a reversible wet de‐adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S–Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross‐linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.