Kinetic studies on the solvolysis and axial ligand substitutions of bis-triphenylphosphine(cyclohexane-1,2-dione-dioximato)ruthenium(II) in non-aqueous solvents

Kinetic studies of ligand substitutions of the six-coordinated Ru^II pseudo-macrocyclic complex [Ru(CHDH)₂- (PPh₃)₂] (CHDH=cyclohexanedione-dioximato) have been spectrophotometrically investigated in a variety of solvents and at 70, 80, 85 and 90°C. The reactions studied are of the form:[(PPh₃)Ru(CHDH)₂(PPh₃)] + L =[(PPh₃)Ru(CHDH)₂L] + PPH₃ where L is imidazole, pyridine, piperidine or thiophene or a solvent molecule (PhCl, PhMe, MeCN, DMSO or DMF). The solvolysis reactions with chlorobenzene and toluene proceed to an equilibrium position favoring the bis-triphenylphosphine complex. All other reactions proceed to completion. From a mechanistic point of view the reactions were found to proceed through the formation of a five coordinate intermediate that possesses little or no discriminating ability towards the incoming nucleophiles. The rate data were thus interpreted in terms of a dissociative (D) or dissociative interchange (Id) mechanism. Activation parameters H and S are reported. Preliminary studies on the solvatochromic behavior of [Ru(CHDH)₂(PPh₃)₂] and the corresponding mixed complexes are discussed.     

Inhibition of Pb-Leaching from Lead Crystal Glass by Coating with Films Prepared by the Sol-Gel Method

The chemical durability of lead glass tumblers (24% PbO) in a 4% (v/v) acetic acid solution before and after coating with sol-gel derived SiO2 films was assessed to determine the extent of reduction in Pb-leaching that can be achieved. It was found that by coating the internal surface of the glass tumblers with 1 ml of 10% TEOS solutions at 100°C and densifying the coating formed at 500°C for 1 h, it was possible to reduce Pb-leaching to about one quarter of that of the uncoated glass.     

HPLC and GC Methods for Determination of Lubricants and Their Evaluation in Analysis of Real Samples of Polyethylene

High performance liquid chromatography (HPLC) and gas chromatography (GC) are introduced for analysis of polymer lubricants (stearamide, oleamide and erucamide). In the HPLC method, a reverse phase octadecylsilane (ODS) column along with acetonitrile/methanol (60:40) as a mobile phase were used. Detection of analytes was performed by a UV detector at 202 nm. The analysis time was less than 8 min. In the GC method, polar capillary column and flame ionization detector (FID) were used for separations and detection, respectively. The analysis time by GC was longer than HPLC and was about 30 min. Limits of detection, linear range and repeatability of both methods are similar, but determination of oleamide in real samples by HPLC method is difficult due to complexity of the initial part of HPLC chromatogram in polyethylene samples. That problem is not observed in the GC method. Detection limits in both methods for all analytes are lower than 0.003% which are much lower than the amount of lubricants in commercial polymers (0.05–0.2%).     

Supercritical carbon dioxide extraction of Mentha pulegium L. essential oil

The dependence of Mentha pulegium L. (pennyroyal) essential oil composition, obtained by supercritical carbon dioxide (SC-CO₂), with the following parameters: pressure, temperature, extraction time (dynamic), and modifier (methanol) was studied. The results were also compared with those obtained by conventional hydrodistillation method in laboratory conditions. Regarding the percentages of menthone (30.3%) and pulegone (52.0%), the optimum SFE results were obtained at the following experimental conditions: pressure=100 atm, T=35 °C, dynamic time=10 min, and V_modifier=0 μl. The results of hydrodistillation showed that the major components of M. pulegium L. were pulegone (37.8%), menthone (20.3%), and piperitenone (6.8%). The evaluation of the composition of each extract was performed by gas chromatography-mass spectrometry.     

Swarm intelligence-based hyper-heuristic for the vehicle routing problem with prioritized customers

The vehicle routing problem (VRP) is a combinatorial optimization management problem that seeks the optimal set of routes traversed by a vehicle to deliver products to customers. A recognized problem in this domain is to serve ‘prioritized’ customers in the shortest possible time where customers with known demands are supplied by one or several depots. This problem is known as the Vehicle Routing with Prioritized Customers (VRPC). The purpose of this work is to present and compare two artificial intelligence-based novel methods that minimize the traveling distance of vehicles when moving cargo to prioritized customers. Various studies have been conducted regarding this topic; nevertheless, up to now, few studies used the Cuckoo Search-based hyper-heuristic. This paper modifies a classical mathematical model that represents the VRPC, implements and tests an evolutionary Cuckoo Search-based hyper-heuristic, and then compares the results with those of our proposed modified version of the Clarke Wright (CW) algorithm. In this modified version, the CW algorithm serves all customers per their preassigned priorities while covering the needed working hours. The results indicate that the solution selected by the Cuckoo Search-based hyper-heuristic outperformed the modified Clarke Wright algorithm while taking into consideration the customers’ priority and demands and the vehicle capacity.

     

Wet carbon-based solid acid/NaNO_3 as a mild and efficient reagent for nitration of aromatic compound under solvent free conditions

Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.     

An efficient and chemoselective method for protection of thiols catalyzed by aluminumdodecatungstophosphate (AlPW12O40), as a highly water tolerant Lewis acid catalyst

Protection of various thiols with diphenylmethanol was achieved in high yields at room temperature using catalytic amounts of AlPW₁₂O₄₀ in CH₂Cl₂. In the presence of this catalyst, protection of SH versus OH was achieved with high chemoselectivity and yields. The catalyst can be easily recovered and reused. Deprotection of DPM thioethers was also achieved using molecular iodine at reflux in CH₂Cl₂ in high yields.     

Photocatalytic ozonation degradation of ciprofloxacin using ZnO nanoparticles immobilized on the surface of stones

Ciprofloxacin is used in the treatment of bacterial infections. Because ciprofloxacin is not effectively degraded by biological processes, advanced oxidation processes such as photocatalytic ozonation are applied to remove this antibiotic from wastewater. The aim of this study was to investigate photocatalytic ozonation for the removal of ciprofloxacin from aquatic environments and optimization of the effective parameters of the process. For this purpose, ZnO nanoparticles were synthesized using the thermal method and immobilized on the surface of stones. The structural properties of the nanoparticles were determined by XRD, TEM, Photoluminescence (PL) and SEM. Experiments were carried out in a Plexiglas reactor supported with the continuous injection of ozone. The effective parameters for removal efficiency were reaction time, initial concentration of ciprofloxacin, pH, photocatalyst concentration and reaction kinetics. The highest ciprofloxacin removal efficiency occurred at the following optimal conditions: pH of 7, reaction time of 30?min, photocatalyst concentration of 3?g/L and initial ciprofloxacin concentration of 10?mg/L. Removal efficiency of 96% was obtained under these conditions. Linear kinetic models showed that the process followed pseudo-first order and Langmuir-Hinshelwood kinetics. This process had a high removal efficiency and suitable for removal of ciprofloxacin from aquatic environments.GRAPHICAL ABSTRACT     

Installation of carbon chain onto 2-cyclohexene-1,4-diol monoacetate

Alkylation of cyclohexenyl monoacetate 1 with R₂Cu(CN)(MgCl)₂ or RMgBr/CuCN (cat.) in Et₂O produced trans 1,2-isomers 4, while arylation and alkenylation of 1 was accomplished with lithium borates 5 and a nickel cat. to afford trans 1,4-isomers 3 selectively. Furthermore, several transformations of the products were carried out to demonstrate synthetic advantages of the present reactions.     

Ketoconazol‐Triiodide Ion Pair Complex as a Suitable Carrier in an Iodide Selective Membrane Electrode

A novel membrane sensor for selective monitoring of iodide, consisting of a triiodide‐ketoconazole ion pair complex dispersed in a PVC matrix, plasticized with a mixture of 2‐nitrophenyl octyl ether and dioctylphtalate with unique selectivity toward iodide ions, is described. The influence of membrane composition, pH of test solution and foreign ions on the electrode performance were investigated. The optimized membrane demonstrates a near‐Nernstian response for iodide ions over a wide linear range from 1.0 × 10^?2 to 1.0 × 10^?5 M, at 25 ± 1 °C. The electrode could be used over a wide pH range 3–10 and has the advantages of high selectivity, fast response time and good lifetime (over 4 months). It was successfully used as indicator electrode in potentiometric titrations and direct potentiometric assay of iodide ions.