Reversed‐phase vortex‐assisted liquid–liquid microextraction: A new sample preparation method for the determination of amygdalin in oil and kernel samples

A novel, simple, and rapid reversed‐phase vortex‐assisted liquid–liquid microextraction coupled with high‐performance liquid chromatography has been introduced for the extraction, clean‐up, and preconcentration of amygdalin in oil and kernel samples. In this technique, deionized water was used as the extracting solvent. Unlike the reversed‐phase dispersive liquid–liquid microextraction, dispersive solvent was eliminated in the proposed method. Various parameters that affected the extraction efficiency, such as extracting solvent volume and its pH, vortex, and centrifuging times were evaluated and optimized. The calibration curve shows good linearity (r² = 0.9955) and precision (RSD < 5.2%) in the range of 0.07–20 μg/mL. The limit of detection and limit of quantitation were 0.02 and 0.07 μg/mL, respectively. The recoveries were in the range of 96.0–102.0% with relative standard deviation values ranging from 4.0 to 5.1%. Unlike the conventional extraction methods for plant extracts, no evaporative and re‐solubilizing operations were needed in the proposed technique.     

(2‐Aminopyrimidine‐κN1)aqua(pyridine‐2,6‐dicarboxylato‐κ3O2,N,O6)copper(II): X‐ray and DFT calculated structure

In the title compound, [Cu(C₇H₃N₂O₄)(C₄H₅N₂)(H₂O)], (I), pyridine‐2,6‐dicarboxylate (pydc²⁻), 2‐aminopyrimidine and aqua ligands coordinate the Cu^II centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc²⁻ ligand. Because of the presence of Cu...X_bridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the Cu^II centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment.     

Corrosion and biological behavior of nanostructured 316L stainless steel processed by severe plastic deformation

Nanostructured metals have different mechanical, chemical, and physical behaviors in comparison with the microstructured ones. Numerous research studies demonstrated that the biological behavior of nanostructured metallic implants was improved significantly. Concerning the nanostructured metals, decreasing the corrosion rate and the releasing of hazardous ions from metallic implants, and thus increasing the biocompatibility of implants are due to improving the native oxide layer. In the present study, nanostructured 316L stainless steel (biomedical grade) was manufactured via equal channel angular pressing (ECAP) method. To do so, the 316L stainless steel (SS) was exposed to the ECAP operation for eight passes. The impact of the ECAP process on corrosion behavior of SS samples was evaluated through performing the electrochemical polarization corrosion tests in Ringer's solution. Scanning electron microscopy was employed to study the surface morphology of common SS and ECAPed SS sample after the electrochemical polarization tests. Moreover, the biological behavior of the samples was evaluated via cell culture using fibroblast cells. The corrosion test results revealed a substantial decrease of corrosion rate from 3.12 (coarse‐grained sample) to 0.42 μA cm^?2 (for nanostructured). Furthermore, the cell proliferation in the interface of nanostructured sample and cell culture medium enhanced dramatically compared with the coarse‐grained one. The much better biological behavior of nanostructured SS sample in comparison with the coarse‐grained one is mostly due to the significant decrease of corrosion rate on the surface of SS samples, and the presence of much more chrome oxide on the surface of SS sample. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media

An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodepo-sition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.     

Improved hydrogen evolution on glassy carbon electrode modified with novel Pt/cetyltrimethylammonium bromide nanoscale aggregates

A novel, cost‐effective, and simple electrocatalyst based on a Pt‐modified glassy carbon electrode (GCE), using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, is reported. Am‐phiphilic...     

Magnetically nano core–shell Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@Cu(OH)<Subscript>x</Subscript>: a highly efficient and reusable catalyst for rapid and green reduction of nitro compounds

Magnetically separable nano core–shell Fe₃O₄@Cu(OH)_x with 22 % Cu content was prepared by the addition of sodium hydroxide to a mixture of CuCl₂·2H₂O and nano Fe₃O₄ in water. Characterization of the impregnated copper hydroxide was carried out by X-ray fluorescence (XRF), X-ray diffraction (XRD) atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM), value stream mapping (VSM) and Brunauer–Emmett–Teller (BET) analysis. The core–shell nanocatalyst exhibited the excellent catalytic activity toward reduction of various nitro compounds to the corresponding amines with NaBH₄. All reactions were carried out in H₂O (55–60 °C) within 3–15 min to afford amines in high to excellent yields. Reusability of core–shell Cu(OH)_x catalyst was examined 9 times without significant loss of its catalytic activity.     

Semi-automated salt-assisted liquid–liquid extraction coupled to high-performance liquid chromatography to determine three aromatic hydrocarbons in aqueous samples

In this study, a new device for semi-automated salt-assisted liquid–liquid extraction was designed and coupled with high-performance liquid chromatography (HPLC) to determine three aromatic hydrocarbons in aqueous samples. In order to evaluate the performance of the designed device, three aromatic hydrocarbons including 2-naphthol, naphthalene and anthracene were selected as model analytes. Sample solution, extraction solvent and salt solution using separate channels were transferred to a sample holder, respectively. These three components were mixed using a magnetic stirrer. After stirrer stopping, the aqueous and organic phases were separated and organic layer transferred to the injection loop of HPLC system. Optimization process was achieved using response surface methodology by Design-Expert software. A central composite design was used to optimize the main parameters including pH (A), stirrer time (B), organic solvent volume (C) and salt concentration (D). The limit of quantitation for 2-naphthol, naphthalene and anthracene was 15.0, 25.0 and 1.0 ng mL^?1, respectively. Under the optimum conditions, obtained recoveries for three analytes were in the range of 76.0–96.2% with relative standard deviation less than 8.2%. The salt-assisted liquid–liquid extraction method using the proposed device has been successfully used for the analysis of real samples containing studied analytes in various matrices.     

Bounded complexes of cotorsion sheaves

We provide a necessary and su?cient condition which ensure that every flat quasi-coherent sheaf has finite cotorsion dimension. Also, we will show that every locally noetherian scheme with a dualizing complex has this requirement.     

Density functional studies of influences of Ni triad metals and solvents on oxidative addition of MeI to [M(CH3)2(NH3)2] complexes and C-C reductive elimination from [M(CH3)3(NH3)2I] complexes

Three metal square planar complexes of the type [M(CH₃)₂(NH₃)₂] (M = Ni, Pd, Pt), with a systematic variation in the metals, are chosen to investigating their S_N2-type oxidative addition reactions with methyl iodide by using the B3LYP levels of theory. The oxidative addition was found to take place via a transition state with a nearly linear arrangement of the I-CH₃-M moiety. Solvation effects in these oxidative addition reactions were also investigated. Considering the nature of the metal centre and solvation effects, the following conclusions emerge: (i) addition of MeI is exothermic for all three metals, and Pt is predicted to react with a much lower barrier than either Pd or Ni. The results describe that the MeI addition would be expected to be more favourable with the complex bearing the third-row metal (platinum) as compared to the other triad metals, nickel or palladium, in which case a more strongly bound MeI adduct is formed with a lower activation barriers and the reaction being more exothermic; (ii) the reaction is very difficult to occur in low polar solvents, such as benzene, due to the high barrier which is induced by dissociation of iodide anion from methyl group, but the reaction easily occurs in polar solvents, such as acetonitrile; this is attributed to the ability of polar solvents to solvate and therefore stabilize the related polar intermediate ion pair. Ethane reductive elimination from the M(VI) complexes fac-[M(CH₃)₃(NH₃)₂I] were also studied, indicating that the Ni(IV) and Pd(IV) complexes are very prone to undergo the reductive elimination while the Pt(IV) analogous is less reactive towards the reductive elimination. The results indicate that in contrast to the Me-Me reductive elimination, the S_N2 oxidative addition reaction of MeI to M(II) is much less sensitive to the nature of the metal centre, suggesting that the nucleophilicity of M(II) in [M(CH₃)₂(NH₃)₂] does not change significantly as one moves from M = Ni to Pt.     

Competition of methyltrioxorhenium (MTO) with osmium tetroxide (OsO4) for pyridines binding: Ligand binding assay

Competition of methyltrioxorhenium (MTO) with osmium tetroxide (OsO₄) toward L = pyridine and its derivatives, based on the equilibrium constant for the reaction OsO₄·L + MTO = MTO·L + OsO₄, has been measured. A successful correlation of log K_eq with the Hammett σ constants of the substituents on the ligands was realized. A negative reaction constant, obtained for the reactions, shows that a more positive charge expands on the pyridine nitrogen in the complex MTO·L as compared with the complex OsO₄·L. So, the rhenium center acts as a better electron acceptor than osmium center. The thermodynamic parameters have been obtained and an excellent linear relationship was observed between the enthalpy and entropy of the reactions.