Borane-catalyzed hydroboration of substituted alkenes by lithium borohydride or sodium borohydride

In the presence of a catalytic amount of BH₃·Me₂S, TiCl₄ or Me₃SiCl, LiBH₄ or NaBH₄ are capable of hydroborating alkenes by following the unusual order of decreasing reactivity: tetramethylethylene > 1-methylcyclohexene > cyclohexene; the key step of the catalytic cycle is the exchange reaction between LiBH₄ and the mono- or dialkylboranes resulting from hydroboration of the more substituted alkenes with BH₃.     

Perhydroisoindoliniums et perhydroisoquinoliniums: Préparation et étude stéréochimique

By cyclization in aqueous media, 2-aminomethyl 1-alcynyl 1-cyclohexanols lead to perhydroisoindolinium or perhydroisoquinolinium salts. The stereochemistry of isolated diastereoisomers is elucidated. A stereoselectivity favouring trans junction of the rings is pointed out.     

Preparation and properties of two indium antimony selenides

Crystals of antimony-doped In₂Se₃ were grown by the Bridgeman method. This compound, whose composition is In_1.8Sb_0.2Se₃, appears to be isostructural with In_1.9As_0.1Se₃. The refined unit cell parameters are a = 3.97(1), c = 18.87(1) Å. Orthorhombic crystals of InSbSe₃ were grown from an isothermal melt. The refined unit cell parameters are a = 9.43(1), b = 14.02(5), and c = 3.96(1) Å. These parameters agree with those determined for α-InSbSe₃ by other studies. The observed densities measured by a hydrostatic technique are 5.98(3) g/cm³ for In_1.8Sb_0.2Se₃ and 6.07(2) g/cm³ for InSbSe₃. The room temperature dc resistivity for In_1.8Sb_0.2Se₃ has been found to be 4.4 × 10⁴ Ω-cm, whereas that of InSbSe₃ has been found to be 15.2(1) Ω-cm. A resistivity versus temperature study has beenn carried out for InSbSe₃ between 230 and 400°K. Optical studies indicate that In_1.8Sb_0.2Se₃ is an n-type semiconductor with a band gap of 1.1 eV and InSbSe₃ is a p-type semiconductor with a band gap of 0.92 eV.     

New stereoselective syntheses of cis- and trans-2-methyl-4-arylpiperidines

A stereoselective approach has been developed for the synthesis of cis- and trans-2-methyl-4-arylpiperidines from a common intermediate. The Ni-catalyzed hydrogenolysis of N-Boc-2-methyl-4-aryl-4-piperidinols, obtained by addition of organometallic reagents on N-Boc-2-methyl-4-piperidone, afforded the trans derivatives with up to 95% selectivity whereas the corresponding cis isomers were obtained in the presence of palladium catalysts.     

Quantification of veterinary antibiotics (sulfonamides and trimethoprim) in animal manure by liquid chromatography-mass spectrometry

A fast and cost effective method was developed to extract and quantify residues of veterinary antimicrobial agents (antibiotics) in animal manure by liquid-liquid extraction and liquid chromatography-mass spectrometry. The compounds investigated include six sulfonamides, one metabolite, and trimethoprim. The method was performed without sample clean up. Recoveries from spiked manure slurry samples (spike level = 1 mg/kg) were as follows: sulfaguanidine (52%), sulfadiazine (47%), sulfathiazole (64%), sulfamethazine (89%), its metabolite N4-acetyl-sulfamethazine (88%), sulfamethoxazole (84%), sulfadimethoxine (51%), and trimethoprim (64%). Relative standard deviations of the recoveries were less than 5% within the same day and less than 20% between days. The limit of quantification was below 0.1 mg/kg liquid manure slurry for all compounds and calibration curves obtained from extracts of spiked samples were linear up to a level of 5 mg/kg liquid manure, except for trimethoprim (0.01-0.5 mg/kg). Analysis of six grab samples taken in Switzerland from manure pits on farms where medicinal feed had been applied revealed total sulfonamide concentrations of up to 20 mg/kg liquid manure.     

A dinuclear uranium(IV) complex of the chelating ligand 1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­diene

The ligand 1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­diene (cp*py) forms a dinuclear complex with U^IV, i.e. di‐μ‐oxo‐bis­{chloro­(diethyl ether‐κO)[(η⁵,κN)‐1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­dienyl]uranium(IV)}, [U₂Cl₂O₂(C₁₄H₁₆N)₂(C₄H₁₀O)₂], in which cp*py acts as a chelating ligand, being bound to the metal atom by the cyclo­penta­dienyl unit and also by the N atom of the pyridyl ring.     

正己烷在Pt-Ce促进的氧化硅担载的杂多酸金属氧酸盐上的异构化

制备了用于正己烷临氢异构化的氧化硅担载的Keggin型杂多酸和还原态Pt-Ce氧化物催化剂.这些混合氧化物催化剂或单独使用,或与氧化硅担载的杂多酸催化剂一起使用.用X射线衍射、傅里叶变换红外光谱、傅里叶变换拉曼光谱、热重和N2物理吸附等方法表征在氧化、还原态和催化实验后的催化剂状态.本文的目的是在最佳反应条件(反应温度、还原温度和流量等)下,筛选出具有最好异构化收率的催化剂.结果表明,还原氧化物的存在不但有利于消除积炭,而且在反应期间能有效地维持氧化硅担载杂多酸的结构.从这些催化剂样品中,可以找到具有更好异构化活性和选择性的催化剂.     

Gravity-induced convective flow in microfluidic systems: electrochemical characterization and application to enzyme-linked immunosorbent assay tests

A way of using gravity flow to induce a linear convection within a microfluidic system is presented. It is shown and mathematically supported that tilting a 1 cm long covered microchannel is enough to generate flow rates up to 1000 nL.min(-1), which represents a linear velocity of 2.4 mm.s(-1). This paper also presents a method to monitor the microfluidic events occurring in a covered microchannel when a difference of pressure is applied to force a solution to flow in said covered microchannel, thanks to electrodes inserted in the microfluidic device. Gravity-induced flow monitored electrochemically is applied to the performance of a parallel-microchannel enzyme-linked immunosorbent assay (ELISA) of the thyroid-stimulating hormone (TSH) with electrochemical detection. A simple method for generating and monitoring fluid flows is described, which can, for instance, be used for controlling parallel assays in microsystems.     

Biomimetic zinc funnel complexes based on calix[6]N3ArO ligands: an acid-base switch for guest binding

The coordination chemistry of Zn in an N(3)ArOH environment has been explored. The ligands are based on calix[6]arenes that present two imidazole arms and an amino phenol moiety at the narrow rim. Three different types of complexes have been characterized. One is dicationic with Zn(2+) coordinated to the three nitrogen atoms and to the oxygen of the phenol group of the calix[6]ligand. This complex is very sensitive to exogenous coordinating molecules and exists as a 5-coordinate species due to the endo-complexation of a guest. The second species is a monocationic complex for which the phenol group has been deprotonated. The resulting N(3)ArOZn complex can also bind a guest ligand albeit with a lower affinity than the dicationic complex. The third species is neutral. It can be obtained upon reaction with a base to yield a hydroxo complex or with an anion such as a chloride that coordinates the metal center from the outside of the calixarene cavity. The simultaneous binding of two anionic donors decreases the Zn Lewis acidity, allowing an impressive conformational reorganization of the system. One imidazole arm is released by the metal center. The other one undergoes self-inclusion into the pi-basic calixarene cavity because the low affinity of the metal center for neutral ligand does not allow the endo-coordination of an exogenous guest. Hence, the calix[6]N(3)ArOH-based Zn complexes act as an acid-base switch for guest binding. Several aspects of this system appear reminiscent of Zn-peptidases of the astacin and serralisin families.