Anionic Snieckus-Fries rearrangement: solvent effects and role of mixed aggregates

Lithiated aryl carbamates (ArLi) bearing methoxy or fluoro substituents in the meta position are generated from lithium diisopropylamide (LDA) in THF, n-BuOMe, Me2NEt, dimethoxyethane (DME), N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N'-tetramethylcyclohexanediamine (TMCDA), and hexamethylphosphoramide (HMPA). The aryllithiums are shown with (6)Li, (13)C, and (15)N NMR spectroscopies to be monomers, ArLi-LDA mixed dimers, and ArLi-LDA mixed trimers, depending on the choice of solvent. Subsequent Snieckus-Fries rearrangements afford ArOLi-LDA mixed dimers and trimers of the resulting phenolates. Rate studies of the rearrangement implicate mechanisms based on monomers, mixed dimers, and mixed trimers.     

Effect of Zn doping on electronic structure and optical properties zincblende GaN(A DFT+U insight)

The development of new materials,having exceptional properties in comparison to existing materials is highly required for bringing advancement in electronic and optoelectronic technologies.Keeping this fact,we investigated structural,electronic,and optical properties of zincblende GaN doped with selected Zn concentrations(6.25%,12.50%,and 18.70%),using the first-principle calculations based on density functional theory with GGA+U.We conducted the entire study using the WIEN2K code.In this study,we calculated various significant parametric quantities such as cohesive energies,formation energies,bulk moduli,and lattice constants along with the study of optical and electronic properties by substituting Ga atoms with Zn atoms in 1×2×2 supercell.The structural stability is confirmed by studying the phonon dispersion curves which suggest that Zn:GaN material is stable against the 6.25%and 18.70%Zn concentrations while for 12.50%,it shows instability.The Hubbard values U=0,2,4,6 eV were added to GGA and the electronic properties were improved with the U=6 eV.Optical absorption was blue shifted while the refractive index and dielectric constant were increased with increasing the Zn concentrations.Electronic properties are enhanced due to the prime contribution of cations(Zn)3ri states.The optical and electronic properties are further discussed in detail in the entire study.     

High-yield synthesis of pure ZnO nanoparticles by one-step solid-state reaction approach for enhanced photocatalytic activity

Zinc oxide (ZnO) nanostructures were synthesized via a one-step solid-state reaction approach in ammonia (NH₃) gas environment with different temperature ramp rates. The so-formed nanostructures were characterized using X-ray diffraction (XRD) for phase identification, where the typical wurtzite hexagonal structure was observed. Scanning electron microscopy (SEM) confirmed the particle size to be in the range 45–50 nm, the same as calculated by the XRD pattern for the ramp rate of 10 °C/min. Energy dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the chemical purity of the samples. The photoluminescence (PL) spectrum indicated multiple near-band-edge emissions and energy-band emissions. Then, these ZnO nanomaterials were used for the degradation of crystal violet (CV) dye under UV light irradiation. The CV solution was completely degraded in 2 hr. The initial photocatalyst and dye amounts of 0.2 g/100 ml and 0.5 mg/L, respectively, were found to be the optimum values for maximum degradation efficiency. The ZnO-based photocatalyst was stable up to three cycles of reuse. These results indicate that the high surface area and porosity of the nanomaterials are responsible for the high efficiency, which was confirmed by specific surface area analysis.     

Phosphonium-mediated cyclization of N-(2-aminophenyl)thioureas: efficient synthesis of 2-aminobenzimidazoles

BOP efficiently promoted the phosphonium-mediated cyclization of thioureas, leading to a convenient synthesis of 2-aminobenzimidazoles. Compared to conventional methods, the reactions were complete at room temperature with times ranging from a few minutes to 1 h in near quantitative yields. This method is also applicable to the synthesis of more challenging structures such as 2-akylaminobenzimidazoles and 2-(N-acyl)-aminobenzimidazoles. The methodology described herein represents a mild and efficient route to a variety of 2-aminobenzimidazoles.     

1-C-Alkyl imino-d-xylitol and -l-arabinitol derivatives obtained via nucleophilic addition to pentose-derived N-tert-butanesulfinyl imines: sugar- versus chiral auxiliary-induced stereoselectivity

The stereoselective synthesis of 1-C-alkyl iminosugars in the d-xylo and l-arabino series as potential drugs for the treatment of lysosomal diseases has been achieved. The key step involves nucleophilic addition to pentodialdofuranose-derived imines generated using enantiopure tert-butanesulfinamide. Depending on the pentofuranose configuration and structure, the stereoselectivity of this reaction was found to be controlled either by the sugar moiety or by the stereogenic sulfur center.     

Surface crystallization of rapamycin on stents using a temperature induced process

Metallic drug eluting stents (DES) are usually prepared by coating with a drug-polymer matrix as a rate controlling diffusion barrier. However, coating materials may display numerous problems, thus carrier-free DES are desired, yet releasing drug over long period of time. For this, we are reporting a novel temperature induced (TI) crystallization process for coating rapamycin on stents. Rapamycin crystals with a defined morphology and target drug load were applied from supersaturated solution. This method enables fabrication of controllable and homogeneous crystalline coatings on stent scaffolds and allowing the drug to release for several weeks.     

Monte Carlo modelling for the in vivo lung monitoring of enriched uranium: Results of an international comparison

In order to assess the reliability of Monte Carlo (MC)-based numerical calibration of in vivo counting systems the EURADOS network supported a comparison of MC simulation of well-defined experiments. This action also provided training for the use of voxel phantoms. In vivo measurements of enriched uranium in a thoracic phantom have been carried out and the needed information to simulate these measurements was distributed to 17 participants. About half of the participants managed to simulate the measured counting efficiency without support from the organisers. Following additional support all participants managed to simulate the counting efficiencies within a typical agreement of ±5% with experiment.     

Enhancement effect of CdTe quantum dots-IgG bioconjugates on chemiluminescence of luminol-H2O2 system

In this paper we developed an entirely new and highly sensitive luminol-H₂O₂ flow injection chemiluminescence system using the enhancement effect of CdTe quantum dots-IgG bioconjugates. Immunoglobulin G (IgG) as a kind of bio-molecule was conjugated to different sized CdTe semiconductor quantum dots (QDs). Using PL spectra and CL intensity profiles, it was found that chemiluminescence resonance energy transfer (CRET) was possibly occurring between CdTe-IgG bioconjugate and luminol. Under optimum conditions, increase of IgG concentration in CdTe-IgG bioconjugate resulted enhancing effect on CL intensity of luminol-H₂O₂ system. Moreover quenching effects on CL intensity by addition of different proteases can construct turn off biosensor for these proteases with low detection limits and wide linear range. Furthermore, the effects of various organic and inorganic species on CdTe-IgG bioconjugates enhanced luminol-H₂O₂ CL system were also studied in this paper.     

Aurones and Analogues: Promising Heterocyclic Scaffolds for Development of Antioxidant and Antimicrobial Agents

Russian Journal of General Chemistry - Synthesis of some new multi-functional analogues of 2′-hydroxy chalcone containing isoxazole and pyrazole functions were synthesized, and their...     

pH-Metric study of gamma-irradiated table sugar for dosimetry purpose

Table sugar has been studied for a long time as a dosimeter in radiation accident and in high-dose dosimetry by using different analytical techniques especially electron paramagnetic resonance (EPR) and optical absorption spectrometry (OA). In this work, we report the results obtained by pH-metry on gamma-irradiated sugar. Table sugar samples were exposed to gamma radiation with doses of 0.1–58 kGy. Aqueous solutions of sugar were prepared with different concentrations ranged from 1% to 60% (w/w). It was found that sugar solutions showed strong decrease of pH up to concentration of 10% (w/w) followed by a slow decrease for the concentrations between 10 and 60% (w/w). Two possible mechanisms are proposed to explain the acidity increasing of the sugar solutions based on the existence of a carbonyl radical induced by gamma irradiation in solid table sugar with an open ring structure. Results for radiation response, post-irradiation change, reading temperature, dose-rate effect and repeatability are presented in this study. The results showed that pH-metric/sugar solution is an adequate high-dose dosimetric system in the dose range of 0.1–10 kGy.