Enantioselective benzylic hydroxylation of indan and tetralin with Pseudomonas monteilii TA-5

A set of 22 toluene- and ethylbenzene-degrading strains were screened for the enantioselective benzylic hydroxylation of indan and tetralin, and Pseudomonas monteilii TA-5 was discovered as an active and selective biocatalyst for such hydroxylations. Cells of P. monteilii TA-5 can be easily grown to a high density and demonstrated a specific hydroxylation activity of 24 U/g cdw (cell dry weight). Conditions for the hydroxylation of indan 1a and tetralin 1b with resting cells of this strain were optimized, to give the corresponding (R)-1-indanol 2a and (R)-1-tetralol 2b in 99% ee and 62–67% yields, respectively. No significant product inhibition was observed, and biohydroxylation with cell-free extracts suggested that the responsible hydroxylase is a soluble enzyme depending on either NADH or NADPH. Preparative biohydroxylation was demonstrated with resting cells as biocatalysts, affording (R)-2a in 99% ee and 65% yield, and (R)-2b in 99% ee and in 63% yield, respectively.     

Luminescent mesogen jacketed poly(1‐alkyne) bearing lateral terphenyl with hexyloxy tail

Mesogen jacketed liquid crystalline poly(1‐alkyne) and poly(1‐phenyl‐1‐alkyne) linked pendants of terphenyl mesogens with hexyloxy tails at the waist position (? {RC?C? [(CH₂)₃OOC‐terpheyl‐(OC₆H₁₃)₂]}_n? , where R?H, PHATP(OC6)2 ; R?C₆H₅, PPATP(OC6)2 ) were synthesized. The influences of structural variations on the thermal, mesomorphic, and luminescent properties were investigated. Polymerizations of all monomers are carried out by WCl₆‐Ph₄Sn catalysts successfully. The polymers are stable (T_d ≥ 340 °C) and soluble in common solvents. The monomers and polymers show enantiotropic SmA phases in the heating and cooling processes, and the lateral side chains of the mesogenic units are perpendicular to the main chain. The “jacket effect” of chromophoric terphenyl core “shell” around the main chain also contributes to polymers with high photoluminescence, and the pendant‐to‐backbone energy transfer path is involved in the luminescence process of this polymers. In comparison with monosubstituted polyacetylene PHATP(OC6)2 , the disubstituted polyacetylene PPATP(OC6)2 shows better photoluminescence in both THF solution and film, and exhibited about 40 nm red‐shifted than PHATP(OC6)2 , indicating that the “jacket effect” of terphenyl mesogens forces poly(1‐phenyl‐1‐alkyne) backbone to extend in a more planar conformation with a better conjugation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Sur les racines d'une équation fondamentale

Sans résumé Les théorèmes I et II de la présente note ont été déjà publiés dans un mémoire portant ce même titre et communiqué à l'académie des sciences à Stockholm le 14 nov. 1900.     

有机物添加剂对碱性锌电极的影响

通过腐蚀实验,测量了锌在碱性溶液中的腐蚀速度,比较了几种有机物添加剂的缓蚀效果 用恒电位极化的方法研究了锌的沉积电流随时间的变化企图用该方法考查一些有机物添加剂对二次碱性锌电极枝晶生长的抑制作用 测量了多孔锌电极在含有各种有机物添加剂的碱液中的阴,阳极极化曲线结果发现,季胺盐型有机表面活性剂 Ｃ Ｔ Ｍ Ｂ在碱性溶液中对锌具有一定的缓蚀作用还可以抑制二次锌电极上枝晶的生长 又不会严重影响锌电极的阳极放电行为为碱性电池中锌电极代汞缓蚀剂的研究提供了一种新的途径     

A Dimensional Splitting Method for Quasilinear Hyperbolic Equations with Variable Coefficients

A numerical method is presented for the variable coefficient, nonlinear hyperbolic equation u _t + _i=1 ^d V _i(x, t)f _i(u) _{x i} = 0 in arbitrary space dimension for bounded velocities that are Lipschitz continuous in the x variable. The method is based on dimensional splitting and uses a recent front tracking method to solve the resulting one-dimensional non-conservative equations. The method is unconditionally stable, and it produces a subsequence that converges to the entropy solution as the discretization of time and space tends to zero. Four numerical examples are presented; numerical error mechanisms are illustrated for two linear equations, the efficiency of the method compared with a high-resolution TVD method is discussed for a nonlinear problem, and finally, applications to reservoir simulation are presented.     

Elastic constants of layers in isotropic laminates

The individual laminae elastic constants in multilayer laminates composed of dissimilar isotropic layers were determined using ultrasonic-resonance spectroscopy and the linear theory of elasticity. Ultrasonic resonance allows one to measure the free-vibration response spectrum of a traction-free solid under periodic vibration. These frequencies depend on pointwise density, laminate dimensions, layer thickness, and layer elastic constants. Given a material with known mass but unknown constitution, this method allows one to extract the elastic constants and density of the constituent layers. This is accomplished by measuring the frequencies and then minimizing the differences between these and those calculated using the theory of elasticity for layered media to select the constants that best replicate the frequency-response spectrum. This approach is applied to a three-layer, unsymmetric laminate of WpCu, and very good agreement is found with the elastic constants of the two constituent materials.     

尼龙6/高岭土界面相互作用对其复合材料力学性能和流变行为的影响

<正> 无机填料填充复合材料的性能,除了依赖于聚合物基体和填料固有的内在性质外,很大程度上依赖于它们之间的界面性质。因此,研究聚合物/填料界面相互作用,对合理地设计具有优良性能的复合材料具有十分重要的意义。 目前,还很难对粉末填料与聚合物基体之间界面相互作用进行定量的研究,而且关于这方面的报道也较少。本文利用接触角法测定了高岭土填料和尼龙6基体的表面自由能、界面张力、粘附功等热力学参数,对高岭土与尼龙6之间界面相互作用与复合材料力学性能、流变行为的关系进行了分析和探讨。     

Enantioselective Michael addition to vinyl phosphonates via hydrogen bond-enhanced halogen bond catalysis

An asymmetric Michael addition of malononitrile to vinyl phosphonates was accomplished by hydrogen bond-enhanced bifunctional halogen bond (XB) catalysis. NMR titration experiments were used to demonstrate that halogen bonding, with the support of hydrogen-bonding, played a key role in the activation of the Michael acceptors through the phosphonate group. This is the first example of the use of XBs for the activation of organophosphorus compounds in synthesis. In addition, the iodo-perfluorophenyl group proved to be a better directing unit than different iodo- and nitro-substituted phenyl groups. The developed approach afforded products with up to excellent yields and diastereoselectivities and up to good enantioselectivities.

An asymmetric Michael addition of malononitrile to vinyl phosphonates was accomplished by hydrogen bond-enhanced bifunctional halogen bond (XB) catalysis.