Copper‐Catalyzed Trifluoromethylation of Aliphatic N‐Arylhydrazones: A Concise Synthetic Entry to 2‐Trifluoromethylindoles from Simple Aldehydes

The copper‐catalyzed C(sp²) H trifluoromethylation of N,N‐disubstituted hydrazones using the Togni reagent is demonstrated to proceed efficiently for aliphatic aldehyde‐derived substrates. The success of the reactions relied on the choice of the N,N‐diphenylamino group as the terminal hydrazone amino group where N,N‐dialkylamino groups were preferred for (hetero)aromatic aldehyde‐derived substrates. In addition, the trifluoromethylated N‐arylhydrazones are shown to be ideal substrates for Fischer indole synthesis allowing a straightforward, three‐step access to 2‐trifluoromethylindole derivatives from simple aldehydes.

     

Large-scale production of a hypoallergenic preparation of F(ab′)2 fragments from bovine colostrum

A method for the production of bovine colostral F(ab′)₂ fragments at pilot-plant scale was developed. Optimum yield of immunoglobulins in colostral whey was obtained after rennet treatment of first milking colostrum. Pepsin digestion was carried out directly on the colostral whey at pH 3·8 for 4 h, which led to the complete digestion of immunoglobulins into F(ab′)₂ fragments. Elimination of β-lactoglobulin, the main immunogenic protein, was achieved by anion exchange on Duolite A560 at pH 6·0. The preparation was diafiltered with a 5000 Da membrane and the retentate spray-dried. The powder obtained contained approximately 34% F(ab′)₂ fragments, with an antibody activity three times higher than the initial colostrum.     

Retrogradation Kinetics of Eight Starches

Retrogradation rate and extent were determined by differential scanning calorimetry and rheology measurements on 40% dry matter gels made from pea, modified waxy maize, rice, waxy rice, wheat, manioc, potato and microwaved irradiated potato starches. As a result, each starch retrogrades differently, depending also on the measurement technique. Nevertheless, potato and pea starches seem to be the most sensitive and the waxy and modified waxy types are the least sensitive to retrogradation.     

Polysilazane derived micro/nano Si3N4/SiC composites

The pyrolised polysilazanes poly(hydridomethyl)silazane NCP 200 and poly(urea)silazane CERASET derived Si–C–N amorphous powders were used for preparation of micro/nano Si₃N₄/SiC composites by hot pressing. Y₂O₃–Al₂O₃ and Y₂O₃–Yb₂O₃ were used, as sintering aids. The resulting ceramic composites of all compositions were dense and polycrystalline with fine microstructure of average grain size <1 μm of both Si₃N₄ and SiC phases. The fine SiC nano-inclusions were identified within the Si₃N₄ micrograins. Phase composition of both composites consist of , β modifications of Si₃N₄ and SiC. High weight loss was observed during the hot pressing cycle, 12 and 19 wt.% for NCP 200 and CERASET precursors, respectively. The fracture toughness of both nanocomposites (NCP 2000 and CERASET derived) was not different. Indentation method measured values are from 5 to 6 MPa m^1/2, with respect to the sintering additive system. Fracture toughness is slightly sensitive to the SiC content of the nanocomposite. Hardness increases with the content of SiC in the nanocomposite. The highest hardness was achieved for pyrolysed CERASET precursor with 2 wt.% Y₂O₃ and 6 wt.% Yb₂O₃, HV 23 GPa. This is a consequence of the highest SiC content as well as the chemical composition of additives.     

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one‐component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42759.     

基于Livermore模型CT图片构建人体躯干数字体模及其在肺部计数器虚拟刻度中的应用

基于Livermore 人体躯干物理模型CT图片构建数字体模,并结合蒙特卡罗程序MCNP对一套由四个宽能高纯锗探测器(BEGe)构成的肺部计数器进行了虚拟刻度.首先,利用点源(241Am,137Cs,60Co,54Mn,57Co,109Cd) 实验数据,对高纯锗晶体尺寸进行调整以获得正确的探测器几何参数,在γ射线能量13.9 keV～1332.5 keV范围内,调整后四个探测器全能峰效率实验测量的平均值与蒙特卡罗计算值的差别在±10%范围内.之后,对不同胸壁厚度(CWT=19 mm, 25 mm, 30 mm, 43 mm)躯干体模进行CT扫描获得其CT图片,利用Dosigray软件对CT图片进行分割后,连同探测器几何描述文件输入到OEDIPE软件,生成数字体模虚拟刻度用MCNP输入程序.最后,利用241Am、152Eu肺部源对数字体模虚拟刻度结果进行了实验验证,结果表明:在59.5 keV～1408 keV能量范围内,虚拟刻度结果与实验结果的差别在±10%之间;对于17.5 keV能量,差别在±30%之间.     

The heat treatment and the gelation are strong determinants of the kinetics of milk proteins digestion and of the peripheral availability of amino acids

This study aimed to determine the kinetics of milk protein digestion and amino acid absorption after ingestion of four dairy matrices by six minipigs: unheated or heated skim milk and corresponding rennet gels. Digestive contents and plasma samples were collected over a 7 h-period after meal ingestion. Gelation of milk slowed down the outflow of the meal from the stomach and the subsequent absorption of amino acids, and decreased their bioavailability in peripheral blood. The gelled rennet matrices also led to low levels of milk proteins at the duodenum. Caseins and β-lactoglobulin, respectively, were sensitive and resistant to hydrolysis in the stomach with the unheated matrices, but showed similar digestion with the heated matrices, with a heat-induced susceptibility to hydrolysis for β-lactoglobulin. These results suggest a significant influence of the meal microstructure (resulting from heat treatment) and macrostructure (resulting from gelation process) on the different steps of milk proteins digestion.     

Effect of dehydroxylation on the specific heat of simple clay mixtures

Specific heats of four clays (standard reference kaolins, commercial kaolin and montmorillonite) before and after dehydroxylation have been measured. The results were compared with handbook data for the thermal chemical properties of solids. Good agreement has been obtained for the reference kaolin before any thermal treatment. Then, following thermal treatments at 500 °C, 600 °C and 700 °C, dehydroxylation leads to a progressive decrease of heat capacity per unit mass. After dehydroxylation, heat capacity values for all the studied materials are rather similar and agree closely with those estimated by the rule of mixtures. Finally, an empirical relation describing the specific heat capacity (C) in J kg⁻¹ K⁻¹ of dehydroxylated kaolin from 40 °C to 1100 °C is proposed: C = 1128 + 0.102T − 36 × 10⁶T⁻² where T is in K.