Ru(III), Cr(III), Fe(III) complexes of Schiff base ligands bearing phenoxy Groups: Application as catalysts in the synthesis of vitamin K3

Two polydentade Schiff base ligands and their Ru(III), Cr(III) and Fe(III) complexes were synthesized and characterized by elemental analysis (C, H, N), UV/Vis, FT IR, ¹H and ¹³C NMR, LC–MS/MS, molar conductivity and magnetic susceptibility techniques. The absorption bands in the electronic spectra and magnetic moment measurements verified an octahedral environment around the metal ions in the complexes. The thermal stabilities were investigated using TGA. The synthesized complexes were used in the catalytic oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone; vitamin K₃, menadione, 2MNQ; using hydrogen peroxide, acetic acid and sulfuric acid. L₁-Fe(III) complex showed very efficient catalytic activity with 58.54% selectivity in the conversions of 79.11%.     

Transfer hydrogenation of aryl ketones with homogeneous ruthenium catalysts containing diazafluorene ligands

Novel cationic ruthenium(II) complexes bearing a 4,5‐diazafluorene unit and p‐cymene as ligands have been synthesised. The complexes were characterised based on elemental analysis and Fourier transform infrared and nuclear magnetic resonance spectroscopies. The synthesised Ru(II) complexes were employed as pre‐catalysts for the transfer hydrogenation of aromatic ketones using 2‐propanol as both hydrogen source and solvent in the presence of NaOH. All complexes showed high catalytic activity as catalysts in the reduction of substituted acetophenones to corresponding secondary alcohols. The products of catalysis were obtained with conversion rates of between 80 and 99%. Among the seven new complexes investigated, the most efficient catalyst showed turnover frequencies in the range 255–291 h^?1 corresponding to 85 to 97% conversion, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Investigation of the aqueous salt solutions of some first and second group metals at various pressures

In the scope of this study, boiling points of aqueous solutions of NaCl, DCl, CaCl₂, BaCl₂, KNO₃ and Ca(NO₃)₂ salts with salt concentrations between 0.5335 and 6.5935 mol kg⁻¹ within 21.332–101.325 kPa pressure range have been determined. Duhring diagrams have been plotted for each solution. In cases, where Raoult's law applied to non-dilute solutions, the deviations from these were determined.     

Silver Nanoparticle Thin Films with Nanocavities for Surface‐Enhanced Raman Scattering

The formation of nanometer‐sized gaps between silver nanoparticles is critically important for optimal enhancement in surface‐enhanced Raman scattering (SERS). A simple approach is developed to generate nanometer‐sized cavities in a silver nanoparticle thin film for use as a SERS substrate with extremely high enhancement. In this method, a submicroliter volume of concentrated silver colloidal suspension stabilized with cetyltrimethylammonium bromide (CTAB) is spotted on hydrophobic glass surfaces prepared by the exposure of the glass to dichloromethysilane vapors. The use of a hydrophobic surface helps the formation of a more uniform silver nanoparticle thin film, and CTAB acts as a molecular spacer to keep the silver nanoparticles at a distance. A series of CTAB concentrations is investigated to optimize the interparticle distance and aggregation status. The silver nanoparticle thin films prepared on regular and hydrophobic surfaces are compared. Rhodamine 6G is used as a probe to characterize the thin films as SERS substrates. SERS enhancement without the contribution of the resonance of the thin film prepared on the hydrophobic surface is calculated as 2×10⁷ for rhodamine 6G, which is about one order of magnitude greater than that of the silver nanoparticle aggregates prepared with CTAB on regular glass surfaces and two orders of magnitude greater than that of the silver nanoparticle aggregates prepared without CTAB on regular glass surfaces. A hydrophobic surface and the presence of CTAB have an increased effect on the charge‐transfer component of the SERS enhancement mechanism. The limit of detection for rhodamine 6G is estimated as 1.0×10^?8 M . Scanning electron microscopy and atomic force microscopy are used for the characterization of the prepared substrate.     

Determination of selected polychlorinated biphenyls in water samples by ultrasound-assisted emulsification-microextraction and gas chromatography-mass-selective detection

Ultrasound-assisted emulsification-microextraction (USAEME) procedure was developed for the determination of selected polychlorinated biphenyls (PCBs) in 10 mL of water samples by gas chromatography-mass-selective detection. After determination of the most suitable solvent and extraction time, several other parameters including solvent volume, centrifugation time and ionic strength of the sample were optimized using a 2³ factorial experimental design. The optimized USAEME procedure used 200 μL of chloroform as extraction solvent, 10 min of extraction with no ionic strength adjustment at 25 °C and 5 min of centrifugation at 4000 rpm. The limits of detection ranged from 14 ng L⁻¹ (for PCB153) to 30 ng L⁻¹ (for PCB101). Recoveries of PCBs from fortified distilled water are over 80% for three different fortification levels between 0.1 and 5 μg L⁻¹ and relative standard deviations of the recoveries are below 10%. The performance of the proposed method was compared with those involving traditional liquid-liquid extraction (LLE) and solid phase extraction (SPE) on the real water samples (i.e., tap and well water as well as domestic and industrial wastewaters, etc.) and comparable efficiencies were obtained. The proposed USAEME procedure has been demonstrated to be viable, simple, rapid and easy to use for residue analysis of PCBs in water samples.     

Synthesis, characterization, catalytic, electrochemical and thermal properties of tetradentate Schiff base complexes

In this study, the Schiff base ligands H₂L¹–H₂L³ and their Cu^II, Co^II, Ni^II, Fe^III Ru^III and VO^IV complexes have been prepared and characterized by spectroscopic and analytical techniques. All the complexes are mononuclear. Keto-enol tautomeric forms of the ligands have been investigated in polar and apolar solvents. The ligands favor the keto-form in the C₇H₈ and C₆H₁₄. The C–C coupling reaction of the 2,6-di-t-butylphenol has been investigated by the Co^II and Cu^II complexes. Thermal properties of the complexes have been assessed using thermal techniques and similar properties were found. In the Fe^III and Ru^III complexes, firstly, the coordinated water molecule is lost from the complex; in the second step, the chloride ion leaves the molecule in the 300–350 °C temperature range. Finally, the complexes decompose to the appropriate metal oxide at the higher temperature ranges. The electrochemical properties of the complexes have been studied in the two different solvents (DMF and CH₃CN).     

Occupational prolonged organic solvent exposure in shoemakers: brain MR spectroscopy findings

Our purpose was to investigate, by magnetic resonance (MR) spectroscopy, the metabolite changes in the brains of subjects in the shoemaking industry who had been chronically exposed to organic solvents. A total of 49 male subjects and 30 age-matched healthy volunteers underwent detailed neurological and psychiatric examinations. All subjects had long-echo [repetition time (TR) 2000 ms, echo time (TE) 136 ms] single-voxel MR spectroscopy. Voxels (15 x 15 x 15 mm(3)) were placed in the parietal white matter, thalamus, and basal ganglia. N-acetylaspartate (NAA)/creatine (Cr) and choline (Cho)/Cr ratios were calculated. There was no significant difference between the study subjects and the control group in NAA/Cr ratios obtained from thalamus, basal ganglia, and parietal white matter. Cho/Cr ratios in thalamus, basal ganglia, and parietal white matter were found to be significantly increased compared to controls. There was a positive correlation between basal ganglia Cho/Cr ratio and duration of exposure (r = 0.63). MR spectroscopy should be performed to reveal metabolite changes and determine the degree of brain involvement in solvent-related industry workers.     

Simultaneous determination of aliphatic and aromatic amines in water and sediment samples by ion-pair extraction and gas chromatography-mass spectrometry

A gas chromatography-mass spectrometry (GC-MS) method has been proposed for the determination of aliphatic and aromatic amines in a variety of environmental samples including wastewater, river water, sea water and sediment samples. The method includes ion-pair extraction with bis-2-ethylhexylphosphate (BEHPA), derivatisation of compounds with isobutyl chloroformate (IBCF) and their GC-MS analysis. Aliphatic and aromatic amines were isolated from aqueous samples using BEHPA as ion-pair reagent and derivatised with IBCF for their chromatographic analysis. Solid-liquid extraction of aliphatic and aromatic amines in sediment samples were performed in Soxhlet apparatus with acidic MeOH and ion-pair extraction with BEHPA were carried out for the isolation of amines followed by derivatisation with IBCF. Aliphatic and aromatic amines were then analysed with GC-MS in both electron impact (EI) and positive and negative ion chemical ionisation (PNICI) mode as their isobutyloxycarbonyl (isoBOC) derivatives. The obtained recoveries ranged from 81.0 to 98.0% and the precision of this method, as indicated by the relative standard deviations (RSDs) was within the range of 0.5 and 4.3%. The detection limits obtained from calculations by using GC-MS results based on S/N = 3 were within the range from 0.07 to 0.50 ng/l.     

Sensitive Determination of Terbutaline Using a Platform Based on Nanoparticles of Europium Oxide and Carbon Nanotubes

This study presents a sensitive voltammetric determination of terbutaline (TER) on a platform based on carbon nanotubes (CNTs) and europium oxide nanoparticles (Eu₂O₃NPs) coated glassy carbon electrodes (GCEs). An ultrasonic bath was performed for the preparation of composite material. The material was characterized by energy dispersive X‐ray spectroscopy (EDX), X‐ray diffraction method (XRD) and scanning electron microscopy (SEM). The Eu₂O₃NPs/CNTs/GCE system was assessed for the oxidation of terbutaline (TER). A broad oxidation peak was appeared at 0.71 V using a bare GCE. However, the voltammetry of TER has been improved at a GCE coated with CNTs and a well‐defined anodic peak exhibited at 0.61 V. Furthermore, the nanoparticles of Eu₂O₃ and CNTs coated GCE has greatly improved the electrochemical behaviour of TER and a sharp peak was appeared at 0.59 V. Cyclic voltammetry at Eu₂O₃NPs/CNTs/GCE also reveals a high catalytic effect for the oxidation of TER with an oxidation peak that is distinctly enhanced compared to GCE and CNTs/GCE. Eu₂O₃ nanoparticles were utilized to enhance the surface area of GCE and then improve the sensitivity of the procedure. The response of TER was linear over a concentration range of 2.0×10^?8 M ?9.5×10^?6 M with an LOD of 3.7×10^?9 M. Square wave voltammetric analysis of tablets by Eu₂O₃NPs/CNTs/GCE yielded a recovery of 99.2 % with an RSD% of 3.2. The modified electrode (EuO₂NPs/CNTs/GCE) provides accuracy and precision to the analysis of samples.