The effect of electron withdrawing croups on the stability of thiabenzenes

The reactions of p-trifluoromethylphenyllithium with 2,4,6-triarylthiopyrylium perehlorates (Ar = Ph, p-CH₃OC₆H₄, p-NMe₂C₆H₄) have been studied. The initially formed thiabenzenes were not slable enough to he isolated and rearranged readily to their corresponding 4-(p-tri-fluoromethylphenyl)-2,4,6-triarylthiopyrans. The instability of the intermediate thiabenzenes reveals that, in contrast to the stabilization effect of the electron-withdrawing p-chloro- and pentalluorophcnyl groups attached to carbon atoms in sulfur ring, the electron-withdrawing p-lrilluoromethyl group on subsliluenls attached to sulfur decreases the stability of thiabenzenes.     

Polyvinylimidazole/sol–gel composite as a novel solid‐phase microextraction coating for the determination of halogenated benzenes from aqueous solutions

A polyvinylimidazole/sol–gel composite is proposed as a novel solid‐phase microextraction fiber to extract five halobenzenes from the headspace of aqueous solutions in combination with gas chromatography with mass spectrometry. The prepared fiber was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The obtained results showed that porous polyvinylimidazole/sol–gel composite was chemically deposited on fused silica fiber. The effect of important extraction parameters including extraction temperature, extraction time, and salt content were investigated. The optimum conditions were as follows: extraction temperature 25°C, extraction time 20 min, and salt concentration 30 w/v%. Detection limits and relative standard deviations of the developed method for halogenated benzenes were below 0.1 pg/mL and 15%, respectively. Repeatability of the proposed method, explained by relative standard deviation, varied between 5.48 and 9.15% (n = 5). The limits of detection (S/N = 3) ranged between 0.01 and 0.10 ng/L using gas chromatography with mass spectrometry with selected ion monitoring mode. For real sample analysis, three types of water samples with different matrices (ground, surface, and tap water) were studied. The optimized procedure was applied to extraction and method validation of halogenated benzenes in spiked water samples.     

Single quantum dot (QD) imaging of fluid flow near surfaces

We introduce the use of quantum dot (QD) nanoparticles for near-surface velocimetry and provide preliminary data to demonstrate its feasibility. Evanescent wave illumination is used to image the motion of water-soluble (CdSe)ZnS QDs with a core size of 6 nm within a region of order 100 nm of a surface . Results are presented for the two in-plane components of the velocity field.     

A novel surface cleaning method for chemical removal of fouling lead layer from chromium surfaces

Most products especially metallic surfaces require cleaning treatment to remove surface contaminations that remain after processing or usage. Lead fouling is a general problem which arises from lead fouling on the chromium surfaces of bores and other interior parts of systems which have interaction with metallic lead in high temperatures and pressures. In this study, a novel chemical solution was introduced as a cleaner reagent for removing metallic lead pollution, as a fouling metal, from chromium surfaces. The cleaner aqueous solution contains hydrogen peroxide (H₂O₂) as oxidizing agent of lead layer on the chromium surface and acetic acid (CH₃COOH) as chelating agent of lead ions. The effect of some experimental parameters such as acetic acid concentration, hydrogen peroxide concentration and temperature of the cleaner solution during the operation on the efficiency of lead cleaning procedure was investigated. The results of scanning electron microscopy (SEM) showed that using this procedure, the lead pollution layer could be completely removed from real chromium surfaces without corrosion of the original surface. Finally, the optimum conditions for the complete and fast removing of lead pollution layer from chromium surfaces were proposed. The experimental results showed that at the optimum condition (acetic acid concentration 28% (V/V), hydrogen peroxide 8% (V/V) and temperature 35 °C), only 15-min time is needed for complete removal of 3 g fouling lead from a chromium surface.     

QSPR modeling of decomposition temperature of energetic cocrystals using artificial neural network

Journal of Thermal Analysis and Calorimetry - The quantitative structure–property relationship for the decomposition temperature (Td) of energetic cocrystals was investigated. The artificial...     

Multi-photon molecular tagging velocimetry with femtosecond excitation (FemtoMTV)

We present results for first molecular tagging velocimetry (MTV) measurements in water under resonant femtosecond excitation/emission process of a phosphorescent supramolecule. Both two-photon and three-photon absorption processes are examined, and the feasibility of measurements is demonstrated by single component velocimetry in a simple jet flow. The new capabilities enabled by FemtoMTV include elimination of the need for short wavelength UV excitation source and UV optical access in flow facilities, and potential for high rep-rate flow imaging.     

In situ LIF temperature measurements in aqueous ammonium chloride solution during uni-directional solidification

We present in situ whole-field measurements of the temperature field using laser-induced fluorescence in a study of bottom-chilled uni-directional solidification of aqueous ammonium chloride. We utilize a two-color, two-dye, ratiometric approach to address the significant spatial and temporal variations of laser sheet intensity field due to refractive index variations caused by the evolving concentration and temperature fields. In our work we take advantage of two temperature sensitive fluorescent dyes with opposite temperature sensitivities in order to increase the overall sensitivity and temperature resolution of the measurements. The resulting temperature sensitivity (about 4% K⁻¹) is more than a factor of two higher than the original work of Sakakibara and Adrian (Exp Fluids 26:7–15, 1999) with a sensitivity 1.7% K⁻¹. In situ measurements of the temperature field during solidification are presented, along with temperature characteristics of some of the complex flow features, such as plumes and fingers.     

The interaction between ketamine and some crown ethers in common organic solvents studied by NMR: the effect of donating atoms and ligand structure

1H NMR spectroscopy was used to investigate the stoichiometry and stability of the drug ketamine cation complexes with some crown ethers, such as 15-crown-5 (15C5), aza-15-crown-5 (A15C5), 18-crown-6 (18C6), aza-18-crown-6 (A18C6), diaza-18-crown-6 (DA18C6), dibenzyl-diaza-18-crown-6 (DBzDA18C6) and cryptant [2,2,2] (C222) in acetonitrile (AN), dimethylsulfoxide (DMSO) and methanol (MeOH) at 27 degrees C. In order to evaluate the formation constants of the ketamine cation complexes, the CH3 protons chemical shift (on the nitrogen atom of ketamine) was measured as function of ligand/ketamine mole ratio. The formation constant of resulting complexes were calculated by the computer fitting of chemical shift versus mole ratio data to appropriate equations. A significant chemical shift variation was not observed for 15C5 and 18C6. The stoichiometry of the mono aza and diaza ligands are 1:1 and 1:2 (ligand/ketamine), respectively. In all of the solvents studied, DA18C6 formed more stable complexes than other ligands. The solvent effect on the stability of these complexes is discussed.     

A method for estimating wall friction in turbulent wall-bounded flows

We describe a simple method for estimating turbulent boundary layer wall friction using the fit of measured velocity data to a boundary layer model profile that extends the logarithmic profile all the way to the wall. Two models for the boundary layer profile are examined, the power-series interpolation scheme of Spalding and the Musker profile which is based on the eddy viscosity concept. The performance of the method is quantified using recent experimental data in zero pressure gradient flat-plate turbulent boundary layers, and favorable pressure gradient turbulent boundary layers in a pipe, for which independent measurements of wall shear are also available. Between the two model profiles tested, the Musker profile performs much better than the Spalding profile. Results show that the new procedure can provide highly accurate estimates of wall shear with a mean error of about 0.5% in friction velocity, or 1% in shear stress, an accuracy that is comparable to that from independent direct measurements of wall shear stress. An important advantage of the method is its ability to provide accurate estimates of wall shear not only based on many data points in a velocity profile but also very sparse data points in the velocity profile, including only a single data point such as that originating from a near-wall probe.