(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.     

Synthesis of Fluorescent 2,6‐Dicyano‐3,5‐Disubstituted Anilines Using Cellulose Sulfuric Acid in Aqueous Media

The synthesis of some fluorescent 2,6‐dicyano‐3,5‐disubstituted anilines using cellulose sulfuric acid (Cellulose‐SA) as an environmentally benign catalyst in H₂O is described. The one‐pot reaction of 1,3‐diketone and three equiv. of malononitrile was carried out in the presence of one equiv. of a secondary amine, Cellulose‐SA as catalyst, and H₂O as solvent. The photophysical properties (λ_Abs., λ_Flu.) of the synthesized compounds in CH₂Cl₂, MeCN, and MeOH have been measured. The emission spectra of the new compounds in the solid state are also reported.     

On the Radical Nature of Iron‐Catalyzed Cross‐Coupling Reactions

The radical nature of iron‐catalyzed cross‐coupling between Grignard reagents and alkyl halides has been studied by using a combination of competitive kinetic experiments and DFT calculations. In contrast to the corresponding coupling with aryl halides, which commences through a classical two‐electron oxidative addition/reductive elimination sequence, the presented data suggest that alkyl halides react through an atom‐transfer‐initiated radical pathway. Furthermore, a general iodine‐based quenching methodology was developed to enable the determination of highly accurate concentrations of Grignard reagents, a capability that facilitates and increases the information output of kinetic investigations based on these substrates.     

Transcendental Bernstein series for solving reaction–diffusion equations with nonlocal boundary conditions through the optimization technique

In this paper, we apply transcendental Bernstein series (TBS) for solving reaction–diffusion equations with nonlocal boundary conditions which is the novel approximation tool. To carry out the method, we firstly expand the solution of the system in the term of TBS through the operational matrix scheme. To determine the unknown free coefficients and control parameters appeared in TBS expansion, we define an optimization problem which combines the reaction–diffusion equation with its nonlocal boundary conditions. Then we use the Lagrange multipliers technique for converting the problem under study into a system of algebraic equations. High accuracy and simplicity in reducing the integral boundary conditions are some privileges of the proposed scheme. We emphasize that Bernstein polynomials is the particular case of transcendental Bernstein series. Theoretical discussion about convergence confirms the reliability of the proposed method. Some test problems are chosen to investigate the applicability and computational efficiency. The experimental results confirm that the obtained results are in good agreement with the exact solutions with high rate of convergence.     

Emulsification based dispersive liquid microextraction prior to flame atomic absorption spectrometry for the sensitive determination of Cd(II) in water samples

We report on the application of emulsification-based dispersive liquid microextraction (EB-DLME) to the preconcentration of Cd(II). This procedure not only possesses all the advantages of routine DLLME, but also results in a more stable cloudy state which is particularly useful when coupling it to FAAS. In EB-DLME, appropriate amounts of the extraction solvent (a solution of dithizone in chloroform) and an aqueous solution of sodium dodecyl sulfate (SDS; acting as a disperser) are injected into the samples. A stable cloudy microemulsion is formed and Cd(II) ion is extracted by chelation. After phase separation, the sedimented phase is subjected to FAAS. Under optimized conditions, the calibration curve for Cd(II) is linear in the range from 0.1 to 25 μg L^?1, the limit of detection (at S/N?=?3) is 30 pg L^?1, the relative standard deviations for seven replicate analyses (at 0.56 μg L^?1 of Cd(II)) is 4.6 %, and the enrichment factor is 151. EB-DLME in our opinion is a simple, efficient and rapid method for the preconcentration of Cd(II) (and most likely of many other ions) prior to FAAS determination.

Validation of Reference Genes for Silver Nanotoxicity Analysis in MCF-7 Cell Line

Following the increasing use of silver nanoparticles (AgNPs) and the growing exposure to these particles, nanotoxicity has become a general concern among researchers around the world. Although quantitative real time PCR (RT-qPCR) is the technique of choice in genotoxicity assessment, use of unconfirmed reference genes could result in data misinterpretation. GeNorm and NormFinder algorithms assist in the selection of appropriate reference genes in RT-qPCR expression analysis. Using these two algorithms, here, the stability of six reference genes’ expression including GAPDH, ACTB, UBC, TBP, HPRT-1 and YWHAZ was evaluated in MCF-7 cells treated with different concentrations (under IC50 estimated by MTT assay) of AgNP. results showed that cytotoxicity can occur in a dose dependent fashion in MCF-7 cells with IC50 value of 5.495 µg/ml. Cumulative analysis by geNorm and NormFinder programs indicated that the normalization of the RT-qPCR data under AgNPs treatment in MCF-7 cells would be greatly improved utilizing two reference genes including TBP and GAPDH. This study is the first investigation for the selection of suitable reference genes for RT-qPCR analysis in MCF-7 cells treated with different concentration of AgNPs, and could be used in future researches established to reveal mechanisms underlying nanosilver exposure.