Effervescence-assisted dispersive liquid-liquid microextraction based on deep eutectic solvent for preconcentration and FAAS determination of copper in aqueous samples

A new effervescence-assisted dispersive liquid-liquid microextraction, EA-DLLME, technique was developed for preconcentration and flame atomic absorption spectrometric determination of copper in aqueous samples. Effervescence assistance and DES combination for metal ion extraction was used for the first time. In the presented study, six different effervescence powders were examined to achieve maximum extraction efficiency. In addition, 1,5 diphenyl carbazide was used as complexing agent and DES prepared by mixing choline chloride and phenol was used as extraction solvent. The effect of several parameters such as pH, concentration of complexing agent, composition and volume of DES, amount of THF, composition and amount of effervescent agent were examined. Performed experiments showed that optimum pH was 6.0, the best effervesce powder composition was NaH₂PO₄:Na₂CO₃ with 2 × 10^?3:1 × 10^?3 molar ratio and the amount of effervesce powder was 0.4 g. Under optimum conditions enhancement factor, limit of detection and limit of quantification were calculated as 78, 2.9 and 9.7 μg L^?1, respectively. In addition, to prove precision of the method intra-day relative standard deviations were calculated for 10 and 50 μg L^?1 Cu²⁺ concentrations and found as 2.1% and 1.3%, respectively. The proposed method showed good linearity within the range of 10.0–100 μg L^?1. Finally, proposed method was successfully applied to determination of copper traces in aqueous samples.     

Determination of some trace metals with a new synthesized polymer resin by FAAS in various tea and herbal plants samples

In this work, a new polymer resin with a functional groups capable of holding trace metals has been synthesized. The structure of polymer resin has been examined by BET-N₂ method analyzer, IR spectrometer, scanning electron microscope (SEM) and elemental microanalyser. The synthesized polymer resin was used for the simultaneous separation and preconcentration of the trace metals from various tea and herbal plants samples. After extraction process, flame atomic absorption spectrometry (FAAS) was used to determine the trace metals. The analytical parameters and solid phase extraction (SPE) performance such as pH, sample volume, flow rates of sample, flow rates of eluent, concentration, volume and type of eluent and effect of interference ions, were investigated. The limits of detection (DL) of the SPE procedure for trace metals, were calculated to be (3s) in the range of 0.9?4.0 μg L^?1 (n = 21) and the factors of preconcentration (PF) were obtained at 200 for Cd, Co, Cu, Fe, Ni and Zn, and at 50 for Cr, Mn and Pb ions and the relative standard deviation (RSD) at ≤ 2% (n = 11).     

Microstructural properties of sintered Al–Cu–Mg–Sn alloys

A non-commercial Al4Cu0.5Mg alloy has been used for investigating the effects of the elemental Sn additions. Uniaxial die compaction response of the alloys in terms of green density was examined, and the results showed that Sn addition has no effect when compacting conducted under high pressures. In total, 93–95% green density was achieved with an applied pressure of 400 MPa. Thermal events occurring during the sintering of the emerging alloys were studied by using differential scanning calorimetry (DSC). First thermal event on the DSC analysis of the Al4Cu0.5Mg1Sn alloy is the melting of elemental Sn, whereas for Al4Cu0.5Mg alloy, it is the formation of Al–Mg liquid nearly at 450 °C. Also it is clearly seen on the DSC analysis that Sn addition led to an increase in the formation enthalpy of Al–Mg liquid phase. High Sn content and high sintering temperature (620 °C), therefore high liquid-phase content, caused decrease on the mechanical properties due to thick intergranular phases and grain coarsening. Highest transverse rupture strength and hardness values were obtained from Al4Cu0.5Mg0.1Sn alloy sintered at 600 °C and measured as 390 MPa and 73 HB, respectively.     

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%.     

A Study of Adsorption of Water Vapour on Wool under Static and Dynamic Conditions

Adsorption of water vapour on wool provides not only textile comfort, but also convenience in transportation due to increase in its bulk density. The adsorption and desorption isotherms of water vapour for wool were determined by both volumetric technique using a Coulter Omnisorp 100CX instrument and gravimetric method employing a Cahn 2000 electronic microbalance. Adsorption isotherm fitting to B.E.T. model and hysteresis on desorption was observed. The average effective diffusion coefficient of water in wool was found to be 8.4 × 10^-14 m²s^-1 at 25°C from gravimetric data. The effects of packing height and air velocity on the breakthrough curves were also investigated in the wool packed columns. For pseudo first order model, k values changing between 0.33 × 10^-6 – 69 × 10^-6 s^-1 was obtained for 2.2–6.4 cm s^-1 air velocity and 0.05–0.20 m packing height ranges.     

Nonoscillation and asymptotic behaviour for third order nonlinear differential equations

In this paper we consider the equation y +q(t)y + p(t)h(y)=0, where p, q are real valued continuous functions on [0, ) such that q(t) 0, p(t) 0 and h(y) is continuous in (–, ) such that h(y)y > 0 for y 0. We obtain sufficient conditions for solutions of the considered equation to be nonoscillatory. Furthermore, the asymptotic behaviour of these nonoscillatory solutions is studied.     

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.     

The Influence of Malathion and Its Decomposition Products on Free and Immobilized Acetylcholinesterase1

The influence of malathion and its four main degradation products found in irradiated solutions (malaoxon, isomalathion, diethyl maleate and O,O-dimethyl phosphate) on acetylcholinesterase (AChE) of free and immobilized bovine erythrocytes was investigated. The concentration-dependent responses to malathion and related organophosphates, malaoxon and isomalathion, of both AChE bioassays used were obtained. The IC ₅₀ values for free and immobilized AChE (3.7 ± 0.2) × 10⁻⁴ M/(1.6 ± 0.1) × 10⁻⁴, (2.4 ± 0.3) × 10⁻⁶/(3.4 ± 0.1) × 10⁻⁶ M, and (3.2 ± 0.3) × 10⁻⁶ M/(2.7 ± 0.2) × 10⁻⁶ M were obtained in the presence of malathion, malaoxon and isomalathion, respectively. However, diethyl maleate inhibited AChE activity at concentrations ≥ 10 mM, while O,O-dimethyl phosphate did not noticeably affect enzyme activity at all investigated concentrations. The relation between the structure of the compounds and their ability to inhibit enzyme activity was discussed. The article is published in the original.     

On the Modeling of CO2 EUA and CER Prices of EU‐ETS for the 2008–2012 Period

Increased consumption of fossil fuels in industrial production has led to a significant elevation in the emission of greenhouse gases and to global warming. The most effective international action against global warming is the Kyoto Protocol, which aims to reduce carbon emissions to desired levels in a certain time span. Carbon trading is one of the mechanisms used to achieve the desired reductions. One of the most important implications of carbon trading for industrial systems is the risk of uncertainty about the prices of carbon allowance permits traded in the carbon markets. In this paper, we consider stochastic and time series modeling of carbon market prices and provide estimates of the model parameters involved, based on the European Union emissions trading scheme carbon allowances data obtained for 2008–2012 period. In particular, we consider fractional Brownian motion and autoregressive moving average–generalized autoregressive conditional heteroskedastic modeling of the European Union emissions trading scheme data and provide comparisons with benchmark models. Our analysis reveals evidence for structural changes in the underlying models in the span of the years 2008–2012. Data‐driven methods for identifying possible change‐points in the underlying models are employed, and a detailed analysis is provided. Our analysis indicated change‐points in the European Union Allowance (EUA) prices in the first half of 2009 and in the second half of 2011, whereas in the Certified Emissions Reduction (CER) prices three change‐points have appeared, in the first half of 2009, the middle of 2011, and in the second half of 2012. These change‐points seem to parallel the global economic indicators as well. Copyright © 2016 John Wiley & Sons, Ltd.