Bridgehead Bicyclo[4.4.0]boron Heterocycles: A One‐Pot Four‐Component Synthesis of Dibenzo[e,i][1,3,7,2]oxadiazaborecin‐8(7H)‐ones

A one‐pot four‐component synthesis of 6‐aryl‐6H‐dibenzo[e,i][1,3,7,2]oxadiazaborecin‐8(7H)‐ones is described. Heating a mixture of isatoic anhydride and a benzylamine afforded the corresponding anthranilamide derivative, which was condensed with a 2‐hydroxybenzaldehyde and an arylboronic acid under solvent‐free conditions to produce bridgehead bicyclo[4.4.0]‐boron heterocycles in good to excellent yields. Single‐crystal X‐ray analysis conclusively confirms the structures of the obtained bridgehead bicyclic 6–6 heterocyclic compounds.     

Theoretical calculation and prediction for experimental design to obtain spin crossover complexes

DFT methods were utilized to study SCO complexes. [Fe(2btz)₂(NCX)₂] (2btz = 2,2′‐bithiazoline, X = S ( 1 ) and Se ( 2 )), [Fe(phen)₂(NCX)₂] (phen = 1,10‐phenantroline, X = S ( 3 ) and Se ( 4 )), and [Fe(bpy)₂(NCS)₂] ( 5 ) (bpy = 2,2′‐bipyridine) compounds, which have experimentally shown SCO behavior, were calculated. B3LYP, B3LYP*, OPBE, and OLYP with 6‐31G* and 6‐311 + G** basis sets were employed to calculate the ΔE_HS/LS energy gap as a clue to find complexes with SCO behavior. It is found that calculated result by B3LYP* with c₃ = 0.14 and OPBE methods and 6‐31G* basis set are in agreement with experimentally observed SCO complexes. Then, newly designed Fe(N‐N)₂(X)₂ complexes, where N‐N are bidentate nitrogen donor chelating ligands and X= SCN^‐, SeCN^‐, Cl^‐, Br^‐, I^‐, were chosen to see their potential to be SCO compounds. ΔE_HS/LS for potential SCO complexes are estimated from 0.8 to 6.5 kcal/mol in B3LYP* and 0.6–5.7 kcal/mol in OPBE. These calculations suggest [Fe(bpy)₂(NCSe)₂], [Fe(5dmbpy)₂(NCS)₂], and [Fe(3‐BrPhen)₂(NCSe)₂] compounds have the ability to show SCO behavior. © 2016 Wiley Periodicals, Inc.     

Effects of Various Amounts of New Hepta-Ether as the Internal Donor on the Polymerization of Propylene with and without the External Donor

The new hepta-ether compound as the internal donor was synthesized using the Williamson reaction of dipentaerythritol with sodium hydride as the strong base and iodomethane as the alkyl halide. The hepta-ether compound was characterized by NMR, FTIR, and GC techniques. The MgCl₂-supported catalysts incorporated with different amounts of hepta-ether compound as the internal donor and without the internal donor were synthesized and characterized. The propylene polymerization was carried out using these catalysts in the presence of triethylaluminum as a co-catalyst and hydrogen as a chain transfer agent, with and without the external donor. The effect of a new internal donor on propylene polymerization using prepared MgCl₂-supported Ziegler-Natta catalysts was investigated.     

Exploration of the binding properties of the human serum albumin sites with neurology drugs by docking and molecular dynamics simulation

In this study, the binding properties of a set of neurology drugs to human serum albumin (HSA) were studied by docking and molecular dynamic (MD) methods. Based on the RMSD values for the MD simulation processes, the drug–protein complexes are stable. Site II of the HSA shows the best affinity for the studied drugs. Different kinds of interactions, including hydrogen bonding, π-cation interactions, and π–π interactions, are observable between ligand and protein during the MD simulation process. The MMGBSA calculations were done to evaluate the binding energy of the ligands and protein. The calculated energies are in good agreement with the previously reported experimental results. In some cases, there is a direct relation between the calculated binding energy with the half-life of the drugs, as it was expected.     

Classic Kriging <Emphasis Type="Italic">versus</Emphasis> Kriging with bootstrapping or conditional simulation: classic Kriging’s robust confidence intervals and optimization

Kriging is a popular method for estimating the global optimum of a simulated system. Kriging approximates the input/output function of the simulation model. Kriging also estimates the variances of the predictions of outputs for input combinations not yet simulated. These predictions and their variances are used by ‘efficient global optimization’ (EGO), to balance local and global search. This article focuses on two related questions: (1) How to select the next combination to be simulated when searching for the global optimum? (2) How to derive confidence intervals for outputs of input combinations not yet simulated? Classic Kriging simply plugs the estimated Kriging parameters into the formula for the predictor variance, so theoretically this variance is biased. This article concludes that practitioners may ignore this bias, because classic Kriging gives acceptable confidence intervals and estimates of the optimal input combination. This conclusion is based on bootstrapping and conditional simulation.     

Fourth Moment Theorems for Markov diffusion generators

Inspired by the insightful article [4], we revisit the Nualart–Peccati criterion [13] (now known as the Fourth Moment Theorem) from the point of view of spectral theory of general Markov diffusion generators. We are not only able to drastically simplify all of its previous proofs, but also to provide new settings of diffusive generators (Laguerre, Jacobi) where such a criterion holds. Convergence towards Gamma and Beta distributions under moment conditions is also discussed.     

Solid-phase extraction and determination of ultra trace amounts of lead,mercury and cadmium in water samples using octadecyl silica membrane disks modified with 5,5′-dithiobis(2-nitrobenzoic acid) and atomic absorption spectrometry

A simple and fast method for preconcentration and determination of ultra trace amounts of lead(II), mercury(II) and cadmium(II) in water samples is presented. Lead, mercury and cadmium adsorbed quantitatively during passage of water samples (pH?=?7, flow rate?=?20 mL min^?1) through octadecyl silica membrane disks modified with 5,5′-dithiobis(2-nitrobenzoic acid). The retained lead, mercury and cadmium are then stripped from the disk with a minimal amount of 1 M hydrochloric acid solution as eluent, and determined by atomic absorption spectrometry. The influence of flow rates of the eluent and sample solution, the amount of ligand, type and least amount of eluent, pH of sample, effect of other ions and breakthrough volume are determined. The breakthrough volume of the method is greater than 2000 mL for lead and greater than 1500 mL for mercury and cadmium, which results in an enrichment factor of 200 for lead and an enrichment factor of 150 for both mercury and cadmium. The limit of detection of the proposed method is 177, 2 and 13 ng l^?1 for lead, mercury and cadmium, respectively.     

Preconcentration procedure using vortex-assisted liquid–liquid microextraction for the fast determination of trace levels of thorium in water samples

A new simple and rapid vortex-assisted liquid–liquid microextraction method was applied for the determination of thorium in water samples. In this method, chloroform used as extraction solvent was directly injected into the water sample solution. The extraction solvent was dispersed into the aqueous phase under vigorously shaking with the vortex. After centrifuging, the fine droplets of extractant phase were settled to the bottom of the conical-bottom centrifuge tube. The effect of different experimental parameters on the performance of the method were studied and discussed. Under the optimum conditions, the detection limit for Th(IV) was 7.5 ng mL^?1. The precision of the method, evaluated as the relative standard deviation obtained by analyzing of 10 replicates, was 2.8 %. The practical applicability of the developed method was examined using natural water and monazite sand samples.     

Ionic Liquid-Assisted Fabrication of Bioactive Heterogeneous Magnetic Nanocatalyst with Antioxidant and Antibacterial Activities for the Synthesis of Polyhydroquinoline Derivatives

Antibacterial materials have obtained much attention in recent years due to the presence of hazardous agents causing oxidative stress and observation of pathogens. However, materials with antioxidant and antibacterial activities can cause toxicity due to their low biocompatibility and safety profile, urging scientists to follow new ways in the synthesis of such materials. Ionic liquids have been employed as a green and environmentally solvent for the fabrication of electrically conductive polymers. In the present study, an antibacterial poly(p-phenylenediamine)@Fe₃O₄ (PpPDA@Fe₃O₄) nanocomposite was fabricated using [HPy][HSO₄] ionic liquid. The chemical preparation of PpPDA@Fe₃O₄ nanocomposite was initiated through the oxidative polymerization of p-phenylenediamine by ammonium persulfate in the presence of [HPy][HSO₄]. The PpPDA@Fe₃O₄ nanocomposite exhibited antibacterial properties against Gram-negative (Escherichia coli) and Gram-positive (Bacillus subtilis) bacteria. The PpPDA@Fe₃O₄ nanocomposite was employed as a heterogeneous nanocatalysis for one-pot synthesis of polyhydroquinoline derivatives using aromatic aldehyde, dimedone, benzyl acetoacetate, and ammonium acetate. Polyhydroquinoline derivatives were synthesized in significant yields (90–97%) without a difficult work-up procedure in short reaction times. Additionally, PpPDA@Fe₃O₄ nanocatalyst was recycled for at least five consecutive catalytic runs with a minor decrease in the catalytic activity. In this case, 11 derivatives of polyhydroquinoline showed in vitro antioxidant activity between 70–98%.