Influence of NO2 attachment on the nuclear magnetic shielding tensors of N and B nuclei in C30B15N15 heterofullerene: a DFT study

Adsorption of nitrogen dioxide in three different configurations on the exterior surface of C₃₀B₁₅N₁₅ is studied using density functional theory calculations. To this end, we optimized the structures of raw C₃₀B₁₅N₁₅ and nine NO₂–C₃₀B₁₅N₁₅ complexes at the B3LYP/6-31G^* level of theory and then calculated chemical shielding (CS) tensors at the GIAO-B3LYP/6-311G^** level for the optimized structures. The calculated chemical shielding isotropy (CSI), chemical shielding anisotropy (CSA), and orientation of CS tensors (Euler angles) reveal that the adsorption configurations (nitro, trans-nitrite, and cis-nitrite) have different effects on the electronic structure of C₃₀B₁₅N₁₅. Natural atomic charges based on natural population analysis (NPA) were used to justify the changes in CSI values after gas sorption.     

Silica Gel Catalyzed Stereoselective Conversion of Dialkyl 2-(3-acetyl-4-hydroxy-1-naphthyl)-3-(triphenylphosphoranylidene) butanedioates to Dialkyl 2-(3-acetyl-4-hydroxy-1-naphthyl)-2-butenedioates in Solvent-Free Conditions

Protonation of the highly reactive 1:1 intermediates, produced in the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, by 1-hydroxy-2-acetonaphthone leads to vinyltriphenylphosphonium salts, which undergo aromatic electrophilic substitution reaction with conjugate base to produce dialkyl 2-(3-acetyl-4-hydroxy-1-naphthyl)-3-(triphenylphosphoranylidene) butanedioates. Silica gel was found to catalyze conversion of dialkyl 2-(3-acetyl-4-hydroxy-1-naphthyl)-3-(triphenylphosphoranylidene) butanedioates to dialkyl 2-(3-acetyl-4-hydroxy-1-naphthyl)-2-butenedioates in solvent-free conditions at 90°;C in fairly good yields.     

Ultrasound‐assisted emulsification microextraction combined with injection‐port derivatization for the determination of some chlorophenoxyacetic acids in water samples

An efficient method based on ultrasound‐assisted emulsification microextraction followed by injection‐port derivatization GC analysis was developed to determine 2,4‐dichlorophenoxyacetic acid (2,4‐D) and 4‐chloro‐2‐methylphenoxyacetic acid (MCPA) in natural water samples. In this procedure, 12.5 μL of 1‐undecanol was injected slowly into a 12 mL home‐designed centrifuge glass vial containing an aqueous sample of the analytes located inside an ultrasonic water bath. The resulting emulsion was centrifuged, and 1 μL of the separated organic solvent together with 1 μL of the derivatization reagent were injected into a GC equipped with a flame ionization detector. Several factors that influence the derivatization and extraction were optimized. Under the optimal conditions, the LODs were 0.33 and 1.7 μg/L for MCPA and 2,4‐D, respectively. Preconcentration factors of 670 and 836 were obtained for MCPA and 2,4‐D, respectively. The precision of the proposed method was evaluated in terms of repeatability, which was <5.7% (n = 5). The applicability of the proposed method was evaluated by extraction and determination of chlorophenoxyacetic acids from some natural waters, which indicated that the matrices of natural waters have no significant effect on the extraction and derivatization efficiency of this method.     

Application of Solid-Phase Extraction Coupled with Dispersive Liquid–Liquid Microextraction for the Determination of Benzaldehyde in Injectable Formulation Solutions

Solid-phase extraction followed by dispersive liquid–liquid microextraction (SPE-DLLME) technique has been developed as a new analytical approach for extracting, cleaning up and preconcentrating benzaldehyde, a toxic oxidation product of the widely used preservative and co-solvent benzyl alcohol, in injectable formulation solutions. SPE of benzaldehyde from samples was carried out using C₁₈ sorbent. After the elution of benzaldehyde from the sorbent by using acetonitrile, DLLME technique was performed on the obtained solution. Benzaldehyde was preconcentrated by using DLLME technique. Thus, 1.5 mL acetonitrile extract (disperser solvent) and 55.0 µL 1,2-dichloroethane (extraction solvent) were added to 5 mL ultra pure water and a DLLME technique was applied. Several variables that govern the proposed technique were studied and optimized. Under optimum conditions, the method detection limit (LOD) of benzaldehyde calculated as three times the signal-to-noise ratio (S/N) was 0.08 µg L^?1. The relative standard deviation (RSD) for four replicates was 5.8 %. The calibration graph was linear within the concentration range of 0.5–500 µg L^?1 for benzaldehyde. The proposed method has been successfully applied to the analysis of the benzaldehyde in injectable formulation solutions (diclofenac, vitamin B-complex and voltaren) and the relative recoveries were between 88 and 92 % and show that matrix has a negligible effect on the performance of the proposed method.     

PVDF/PU blend membrane separator for lithium-ion batteries via non-solvent-induced phase separation (NIPS)

Membrane separator based on the polyvinylidene fluoride (PVDF) is prepared via the non-solvent-induced phase separation (NIPS) method with water and ethanol as non-solvent and a mixture of dimethylformamide (DMF) and acetone as solvent. The effect of various acetone/DMF ratios and non-solvent material on the physical and electrochemical properties of the separator is studied by FE-SEM, tensile strength, electrochemical AC-impedance spectroscopy (EIS), thermal stability, and linear sweep voltammetry (LSV). The charge-discharge studies are carried out by fabricating a lithium foil/polymer electrolyte membrane/LiFePO4 cell. The results show that with the change of solvent and non-solvent, the structure and morphology of the separator change and its physical and electrochemical properties. The results indicate that the membrane sample with non-solvent ethanol, acetone/DMF: 80/20 (wt/wt), and PVDF/PU: 95/5 (wt/wt) shows high porosity (66.3%) and high ionic conductivity (1.34 mS/cm) as well as excellent thermal stability.

     

Naked magnetite nanoparticles for both clean-up and solid-phase extraction-trace determination of mercury

A new solid-phase extraction method was developed for trace determination of Hg(II) by using a small amount of naked magnetite nanoparticles as an adsorbent. The magnetite nanoparticles were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The adsorbed Hg(II)-dithizone complex was eluted with 1.0 mL aliquot of an acidic 1-propanol solution prior to electrothermal atomic absorption spectrometry. A huge positive effect was found on the mercury adsorption by ionic strength. Under optimized condition, a linear calibration curve was obtained for mercury in the range of 0.2–50 ng mL^?1 with relative standard deviation in the range of 0.5–2.0%. The limit of detection and enrichment factor were 0.01 ng mL^?1 and 98.3, respectively. The effects of coexisting ions were studied extensively, and a new clean-up procedure was used to remove the matrix effects by using a simple sample pretreatment step using a little amount of magnetite nanoparticles. The method was successfully applied to the determination of Hg(II) in different water and human urine samples and a commercial sodium nitrate.     

Polymerization of β‐cyclodextrin in the presence of bentonite clay to produce polymer nanocomposites for removal of heavy metals from drinking water

New hybrid organic–inorganic nanocomposites consist of β‐cyclodextrin (β‐CD)/epichlorohydrin (ECH), and bentonite clay were prepared by direct intercalation through one step emulsion polymerization. The structure and thermal stability of prepared nanocomposites were investigated by Fourier‐transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), field emission‐scanning electron microscopy (FE‐SEM), energy dispersive X‐ray analysis (EDAX), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), differential of differential scanning calorimetry (DDSC), thermogravimetric analysis (TGA) and differential thermogravimetric (DTG) analyses. The observed results show that the β‐CD polymer/clay nanocomposites (β‐CD–ECH polymer/clay) with higher thermal stability than β‐CD–ECH polymer were successfully prepared. The removal of heavy metals such as Cu(II), Zn(II) and Co(II) ions from drinking water was studied using a batch method at ambient temperature. The removal percentage and distribution coefficients (Kd) were determined for the adsorption system. It was found that the β‐CD–ECH polymer/clay nanocomposites showed higher removal capacity for Co²⁺, Cu²⁺ and Zn²⁺ ions in comparison with β‐CD–ECH polymer. The selectivity order could be given as Zn²⁺ > Cu²⁺ > Co²⁺. Copyright © 2016 John Wiley & Sons, Ltd.     

A study on the two binding sites of hexokinase on brain mitochondria

Background  

Type I hexokinase (HK-I) constitutes the predominant form of the enzyme in the brain, a major portion of which is associated with the outer mitochondrial membrane involving two sets of binding sites. In addition to the glucose-6-phosphate (G6P)-sensitive site (Type A), the enzyme is bound on a second set of sites (Type B) which are, while insensitive to G6P, totally releasable by use of high concentrations of chaotropic salts such as KSCN. Results obtained on release of HK-I from these "sites" suggested the possibility for the existence of distinct populations of the bound enzyme, differing in susceptibility to release by G6P.     

Diastereoselective Synthesis of Novel Pyrrolidine or Pyrrolizine‐Fused Benzo‐δ‐sultams via 1,3‐Dipolar Cycloadditions

The synthesis of novel pyrrolidine or pyrrolizine‐fused benzosultams is described. A number of (E)‐N‐(2‐formylphenyl)‐N‐alkyl‐2‐phenylethenesulfonamides derivatives were synthesized and subjected to intramolecular [3 + 2] cycloaddition with azomethine ylides derived in situ from the reaction with sarcosine, phenylglycine, and L‐proline.     

Sonochemically synthesis of pyrazolones using reusable catalyst CuI nanoparticles that was prepared by sonication

A simple and green process to prepare copper iodide in nano scale via sonication was carried out. Subsequently, this nanoparticles was used as an efficient catalyst for the synthesis of 2-aryl-5-methyl-2,3-dihydro-1H-3-pyrazolones via four-component reaction of hydrazine, ethyl acetoacetate, aldehyde and β-naphthol in water under ultrasound irradiation. The combinatorial synthesis was attained for this procedure with applying ultrasound irradiation while making use of water as green ambient. Simple work-up, excellent yield of products and short reaction times are some of the important features of this protocol. Notably, this catalyst could be recycled and reused for five times without noticeably decreasing the catalytic activity.