Line intensities of C2H2 in the 7.7 μm spectral region

Absolute intensities of 414 lines are measured in eight bands of the 7.7 μm spectral region of the ¹²C₂H₂ molecule, with an average accuracy of 5%. Vibrational transition dipole moment squared values and empirical Herman–Wallis coefficients are obtained in order to model the rotational dependence of the transition dipole moment squared, except for some forbidden bands for which smoothed values are given. These data are used to calculate a line list for atmospheric or astrophysical applications.     

Poly(ε-caprolactone) modified by functional groups: Preparation and chemical–physical investigation

Functionalization of polymers is a particular relevant approach in the field of biodegradable polymers, where modifications are often required to allow these materials to replace more conventional, not biodegradable polymers in a wider range of applications. This article will report on functionalization of poly(ε-caprolactone) with unsaturated monomers bearing either anhydride groups (PCL-g-(MA-GMA)) or tertiary amines (PCL-g-DMAEA), obtained through radical grafting in a Brabender mixer. Crystallization kinetics parameters have been determined with several techniques (rheology, optical microscopy and differential scanning calorimetry) and the results obtained are in good agreement. It was observed that the crystallization rate significantly increases in the case of the modified polymers.     

一类单完备李代数

确定了代数Va,b.c的导子代数,其中Va.b.c是由非交换代数Ca,b,c[X±1,Y±1,Z±1]的所有内导子所张成的李代数,证明了导子代数数Va.b,c是由所有内导子和3个外导子D1,0,0,DO,1,0,D0,0,1张成的,同时还给出了一类无限维的单完备李代数.     

Ring expansion of functionalized octahydroindoles to enantiopure cis-decahydroquinolines

A new synthetic entry to enantiopure cis-decahydroquinolines is reported. Endo and exo derivatives of cis-1-benzyl-2-(hydroxymethyl)octahydroindol-6-one ethylene acetal undergo ring enlargement upon treatment with TFAA and then Et3N (thermodynamic conditions) to give enantiopure 1-benzyl-3-hydroxydecahydroquinolin-7-one derivatives in 77 and 82% yield, respectively. For 2-(1-hydroxyethyl) analogues, the best synthetic result is obtained from the (2S,1'R) endo isomer, which under kinetic reaction conditions (MsCl, THF, -20 degrees C, then AgOAc at rt ) gives the expanded product in 54% yield.     

Exploration of the Mitsunobu reaction with Tosyl- and Boc-hydrazones as nucleophilic agents

Tosyl- and Boc-hydrazones were found to be effective nucleophiles in the Mitsunobu reaction. Tosyl hydrazones reacted cleanly with primary and secondary alcohols when co-administered to a cooled DBAD/PPh3 or DEAD/PPh3 complex. Boc-hydrazones required electron-withdrawing substituents to participate in the reaction.     

基于金属卟啉的甲基磷酸二甲酯分子印迹聚合物微球的合成及性能

合成了分别以5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基锌卟啉(ZnMOTPP)和5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基钆卟啉(GdMOTPP)为功能单体, 甲基丙烯酸(MAA)为辅助功能单体的甲基磷酸二甲酯(DMMP)分子印迹聚合物微球. 扫描电子显微镜(SEM)表征结果表明, 微球平均粒径为50～100 μm, 粒度均匀. 与甲基丙烯酸作为功能单体的分子印迹聚合物微球的吸附性能和特异性进行对比发现, ZnMOTPP分子印迹微球的吸附性能优于 GdMOTPP分子印迹微球, 金属卟啉分子印迹微球的吸附性能优于仅以甲基丙烯酸作为功能单体的分子印迹微球, 并且微球对其印迹分子DMMP具有特异性吸附. Scatchard分析表明, DMMP分子印迹空穴中只存在一类结合位点, MIPMs-Zn+MAA的最大吸附量Q_max=148 μmol/g, MIPMs-Gd+MAA的Q_max=78.9 μmol/g, MIPMs-MAA的Q_max=13.57 μmol/g.     

可视交叉传感阵列对蛋白质及其热变性过程的快速识别

以卟啉及其衍生物和特异性染料为敏感化学元件, 基于交叉响应原理构建了识别蛋白质的可视6×6阵列. 该阵列以颜色差谱图显示其与蛋白质作用呈现的特异性光谱反应, 采用聚类分析、 主成分分析和欧氏距离对图谱进行了分析. 结果表明, 该阵列可以鉴别模式蛋白牛血清白蛋白(BSA)、 牛血红蛋白(BHb)和卵清白蛋白(Ova)及其混合物, 且有望实现定量分析. 此外, 阵列的高敏感性使其不仅能识别天然蛋白质和不同变性程度的蛋白质, 还能对其热变性过程进行可视化实时监控. 该阵列产生的特殊颜色变化与蛋白质的空间构型、 微环境pH值的差异及溶解度有关. 因此, 该方法不仅能实现对蛋白质的快速识别, 为蛋白质热变性机理的研究提供新途径, 而且在临床医学和食品安全等的实时快速检测方面有潜在的应用价值.     

Prandtl number effects in decaying homogeneous isotropic turbulence with a mean scalar gradient

Decaying homogeneous isotropic turbulence with an imposed mean scalar gradient is investigated numerically, thanks to a specific eddy-damped quasi-normal Markovian closure developed recently for passive scalar mixing in homogeneous anisotropic turbulence (BGC). The present modelling is compared successfully with recent direct numerical simulations and other models, for both very large and small Prandtl numbers. First, scalings for the cospectrum and scalar variance spectrum in the inertial range are recovered analytically and numerically. Then, at large Reynolds numbers, the decay and growth laws for the scalar variance and mixed velocity–scalar correlations, respectively, derived in BGC, are shown numerically to remain valid when the Prandtl number strongly departs from unity. Afterwards, the normalised correlation ρ_wθ is found to decrease in magnitude at a fixed Reynolds number when Pr either increases or decreases, in agreement with earlier predictions. Finally, the small scales return to isotropy of the scalar second-order moments is found to depend not only on the Reynolds number, but also on the Prandtl number.     

Explicit algebraic Reynolds stress model (EARSM) for compressible shear flows

We develop an explicit algebraic Reynolds stress model (EARSM) for high-speed compressible shear flows and validate the model with direct numerical simulation (DNS) data of homogeneous shear flow and experimental data of high-speed mixing-layers. Starting from a pressure–strain correlation model that incorporates compressibility effects, the weak-equilibrium assumption is invoked to derive the EARSM closure expression. The resulting closure is fully explicit and physically realizable and is a function of mean flow strain rate, rotation rate, turbulent kinetic energy, dissipation rate, and gradient Mach number. Homogeneous shear flow calculations show that the model captures the asymptotic behavior of DNS quite well. Linear EARSM calculations of a plane supersonic mixing-layer are performed, and comparison with experimental data shows good agreement. Salient results are agreement of streamwise velocity similarity profiles, mixing-layer spreading rates, and capturing the Langley curve trend.