Effect of solvent composition on free release static coating of capillary columns

Summary Three aspects with respect to the selection of solvents for static coating of capillary columns, i.e. coating speed, occurrence of bumping and solubility of stationary phases are discussed. Hypotheses are proposed in an attempt to explain the observed facts that mixed solvents result in much higher coating speeds than those obtained from pure solvents, that a proper choice of solvents together with a good and uniform deactivitation of the column inner wall is needed to prevent bumping. Stationary phase solubility vs. solvent composition is also briefly discussed.     

Copper(II) tetrafluoroborate as a novel and highly efficient catalyst for N-tert-butoxycarbonylation of amines under solvent-free conditions at room temperature

Commercially available copper(II) tetrafluoroborate hydrate was found to be a highly efficient catalyst for chemoselective N-tert-butoxycarbonylation of amines with di-tert-butyl dicarbonate under solvent-free conditions and at room temperature. Various aromatic amines were protected as their N-tert-butyl carbamates in high yields and in short times. No competitive side reactions such as isocyanate, urea, and N,N-di-t-Boc formation was observed. Chemoselective N-tert-butoxycarbonylation was achieved with substrates bearing OH and SH groups. Chiral α-amino acid esters afforded the corresponding N-t-Boc derivatives in excellent yields.     

Spectroscopic and Quantum Mechanical Studies of Substituted Anilines and their Charge-Transfer Complexes with Iodine in Different Solvents

Summary. Equilibrium constants and molar extinction coefficients for 1:1 charge-transfer complexes between 2-hydroxyaniline (HA), 5-chloro-2-hydroxyaniline (CHA), and 4-bromo-2,6-dimethylaniline (BMA) as donors and iodine, as a typical σ-acceptor were determined spectrophotometrically in chloroform, dichloromethane, and carbontetrachloride solutions. Spectral characteristics and formation constants are discussed in terms of donor molecular structure and solvent polarity. The stoichiometry of the complexes was established to be 1:1. For this purpose, optical data were subjected to the form of the Rose-Drago equation for 1:1 equilibria. Electronic absorption spectra of the studied anilines were measured in different solvents. Spectral data were reported and band maxima were assigned to the appropriate molecular orbital transitions (π–π^* and n–π^* electronic transition). Solvent effects on the electronic transitions were discussed. Optimized geometry of the studied anilines was obtained at B3LYP/6-31 + G(d). The effect of the electronic factors of the substituents on the geometrical parameters of the ring has been explored. Geometrical values of the ring deviate from the regular hexagonal ring. Intramolecular H-bonds in HA and CHA have been computed at B3LYP/6-31 + G(d) and MP2/6-31 + G(d) levels. The H-bonding distance was calculated to be 2.105 ? in HA and 2.127 ? in CHA. Abstracted from her M.Sc. thesis     

Efficient Oxidation of Sulfides Catalyzed by Transition Metal Salts with Molecular Oxygen in the Presence of Aldehydes

Oxidation of sulfides to sulfoxides and sulfones was achieved in moderate to high yields with a good selectivity, by using Fe₂O₃, MnO₂, Cu(OH)₂ and Cu(OAc)₂ as catalyst, with molecular oxygen in the presence of isovaleraldehyde under mild conditions.     

Silica Sulfuric Acid Catalysis the Oxidation of Organic Compounds with Sodium Bromate

Abstract

The oxidation of organic compounds by sodium bromate/silica sulfuric acid under solvent‐free conditions and in CH₂Cl₂ have been studied at room temperature.     

Instant Controlled Pressure Drop technology: From a new fundamental approach of instantaneous transitory thermodynamics to large industrial applications on high performance–high controlled quality unit operations

Solvent extraction processes have been largely used in various industries. They recently were improved through new physical concepts such as CO₂ Supercritical Fluid Extraction, Ultrasound assisted process, Microwave-assisted extraction, Instant Controlled Pressure Drop DIC-assisted extraction… Systematically, a pretreatment stage of grinding takes place in order to improve the exchange surface increasing the starting accessibility. Swelling of the material structure implies an increase of the porosity thus leading to higher solvent diffusivity within the solid matrix. A new concept of expanded granule powder has recently been defined using Instant Controlled Pressure Drop DIC technology. Whatever the type of solvent is (even CO₂-SFE), such a swelled structure dramatically intensifies the kinetics through a higher specific exchange surface thanks to the open pores, while improving the solution solvent–solute diffusivity within the solid. Coupled to ultrasound, the internal transfer of solute within the pore solvent can likewise be intensified by replacing molecular diffusion within the pores by an effective convection transfer. In this work, we carried out a first approach of modeling of solvent extraction kinetics of expanded granules involving higher exchange surface and greater internal diffusion process.     

溶剂去除速度对于溶剂退火薄膜相形貌的影响

以聚苯乙烯-聚4-乙烯基吡啶(PS-b-P4VP)嵌段共聚物作为研究对象,采用DMF作为退火溶剂,以原子力显微镜(AFM)和透射电子显微镜(TEM)为表征手段,研究了溶剂退火后期溶胀薄膜中溶剂的去除速度对于薄膜相形貌的影响,发现通过改变溶剂去除速度可以有效的调控薄膜中的形貌.当薄膜厚度为35 nm时,DMF的快速挥发会导致薄膜中形成以PS为分散相的反转柱状相结构,当降低溶剂的挥发速度时,薄膜中形成了以PS为分散相的环状形貌,当进一步减缓挥发速度时,薄膜中将形成台阶状的片层结构;然而当薄膜厚度为55 nm时,溶剂退火后期薄膜中形成的是以P4VP为分散相的正常柱状相结构,在相同溶剂去除速度条件下薄膜相形貌变化较小.     

A combined approach of Kullback–Leibler divergence and background subtraction for moving object detection in thermal video

In this work, a robust method for moving object detection in thermal video frames has been proposed by including Kullback–Leibler divergence (KLD) based threshold and background subtraction (BGS) technique. A trimmed-mean based background model has been developed that is capable enough to reduce noise or dynamic component of the background. This work assumed that each pixel has normally distributed. The KLD has computed between background pixel and a current pixel with the help of Gaussian mixture model. The proposed threshold is useful enough to classify the state of each pixel. The post-processing step uses morphological tool for edge linking, and then the flood-fill algorithm has applied for hole-filling, and finally the silhouette of targeted object has generated. The proposed methods run faster and have validated over various real-time based problematic thermal video sequences. In the experimental results, the average value of F₁-score, area under the curve, the percentage of correct classification, Matthew’s correlation coefficient show higher values whereas total error and percentage of the wrong classification show minimum values. Moreover, the proposed-1 method achieved higher accuracy and execution speed with minimum false alarm rate that has been compared with proposed-2 as well as considered peer methods in the real-time thermal video.     

Macrocyclic Polyethers as Enolate Activators in Homogeneous and Heterogeneous Systems

Abstract

The ability of macrocyclic polyethers to activate enolates has been studied in the alkylation of de-oxybenzoin (1) with butyl derivatives nBuY (Y = Br, I, OMes) catalyzed by crown ether PHDB18C6 (7) or cryptand [2.2.2,C10] (8) under phase-transfer catalysis (PTC) and homogeneous (chlorobenzene) conditions. The enolate reactivity is mainly determined by the ligand (cryptand > crown ether) and solvent (increasing with the polarity, in the order: toluene < chlorobenzene < 1,2dichlorobenzene). Regioselectivity of the reaction is also remarkably affected by ligand and alkylating agent.     

Efficient Oxidation of Alcohols with KBrO 3 in the Presence of Silica Chloride and Wet SiO 2

Alcohols were oxidized to their corresponding carbonyl compounds with KBrO 3 in the presence of silica chloride and wet SiO 2 , in solution and under solvent free conditions.