New bis(1-ferrocenylethyl)amine-derived monodentate phosphoramidite ligands for highly enantioselective copper-catalyzed 1,4-conjugate addition

A new family of chiral bis(1-ferrocenylethyl)amine-derived monodentate phosphoramidite ligands has been prepared and successfully applied in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to a variety of α,β-unsaturated compounds, in which up to 99% ee was obtained for nitroalkenes at ?78 °C and >98% ee for cyclohexenone at ?30 °C, comparable to or higher than those obtained with the most efficient monophosphoramidite ligands reported so far.     

Theoretical study of the [Si,C, P,O] potential energy surface

The structures, energetics, spectroscopies and stability of the doublet [Si, C, P, O] radical are explored at the density functional theory and ab initio levels. Eighteen isomers connected by 22 interconversion transition states are located at the DFT/B3LYP/6-311G(d) level. The structures of the kinetically stable isomers and the relevant transition states are further optimized at the QCISD/6-311G(d) level followed by CCSD(T)/6-311 + G(2df) single-point energy calculations. At the QCISD/6-311G(d) level, the lowest-lying isomer is the cyclic O-cCSiP 8 (0.0 kcal/mol) with considerable kinetic stability of 22.0 kcal/mol. In addition, two bent isomers OSiCP 1 (7.3 kcal/mol) and SiCPO 3 (34.7 kcal/mol) also possess considerable kinetic stability (more than 10.0 kcal/mol). As a result, three isomers 1, 3 and 8 are predicted to be possible candidates for future experimental and astrophysical detection. The bonding nature of the three isomers is analysed. The calculated results are compared with those of the analogous radical [Si, C, N, O]. Implications in the laboratory and interstellar space are also discussed. The predicted structures and spectroscopic properties are expected to be informative for the identification of [Si, C, P, O] in the laboratory and space.     

Flow of dilute to semi-dilute polystyrene solutions through a benchmark 8:1 planar abrupt micro-contraction

We have studied the flow of thermodynamically ideal solutions of a high molecular weight (M_w = 6.9 MDa) atactic polystyrene in the θ solvent dioctyl phthalate (aPS in DOP) through a micro-fabricated 8:1 planar abrupt contraction geometry. The channel is much deeper than most micro-scale geometries, providing an aspect ratio of 16:1 and a good approximation to 2D flow in the narrow channel. The solutions span a range of concentration 0.03 wt.% < c < 0.6 wt.%, encompassing the dilute to semi-dilute regimes and providing a range of fluid viscosities and relaxation times such that we achieve a range of Weissenberg numbers (8.7 < Wi < 1562) and Reynolds numbers (0.07 < Re < 11.2), giving elasticity numbers between 31 < El < 295. We study the flow using a combination of micro-particle image velocimetry (μ-PIV) to characterize the flow field, pressure measurements to evaluate the non-Newtonian viscosity, and birefringence measurements to assess macromolecular strain. Flow field observations reveal three broad flow regimes characterized by Newtonian-like flow, unstable flow and vortex growth in the upstream salient corners. Transitions between the flow regimes scale with Wi, independent of El, indicating the dominance of elastic over inertial effects in all the fluids. Transitions in the flow field are also reflected by transitions in the relative viscosity (determined from the pressure drop) and the macromolecular strain (determined from birefringence measurements). The strain through the 8:1 contraction saturates at a value of ～4–5 at high Wi. The results of these experiments broaden the limited set of literature on flow through micro-fluidic planar contractions and should be of significant value for optimizing lab-on-a-chip design and for comparison with modeling studies with elasticity dominated fluids.     

一类四项指数和的四次均值

本文利用三角和的性质以及同余方程解的个数研究了一类四项指数和的四次均值的计算问题，并给出两个精确的计算公式.     

Readily available chiral phosphine–aminophosphine ligands derived from 1-phenylethylamine for Rh-catalyzed enantioselective hydrogenations

A series of new chiral phosphine–aminophosphine ligands have been prepared via a two- or three-step transformation from commercially available and inexpensive (S)-1-phenylethylamine, and successfully used in the rhodium-catalyzed asymmetric hydrogenation of various enamides, β-dehydroamino acid esters, and dimethyl itaconate. The results show that the ligand structure plays an important influence on both the reactivity and enantioselectivity. Ligand 2d bearing a N–H proton and two F-atoms on the 3,5-positions of the phenyl ring of the aminophosphino moiety was most effective for the hydrogenation of enamides and (Z)-β-aryl-β-(acylamino)acrylates, whereas ligand 1b showed the highest enantioselectivities in the hydrogenation of (Z)-β-alkyl-β-(acylamino)acrylates and dimethyl itaconate.     

中国上市公司股权集中度、董事会独立性和公司绩效——基于结构方程模型的研究

股权集中度与公司绩效的关系，董事会独立性与公司绩效的关系是公司治理中的重要内容。以往的实证研究仅检验这两个直接关系。实际上公司董事会独立性，股权集中度，和公司绩效存在三角关系。本文研究此三角关系，以我国沪深300指数成分股上市公司数据为样本应用结构方程模型进行实证检验。结果发现，股权集中度与董事会独立性为负向关系，董事会独立性与公司绩效为负向关系，股权集中度对公司绩效不但有直接影响而且通过董事会独立性产生间接影响。     

SOI波导反射模式的古斯-汉欣空间位移效应及其数字式热光开关

借助波导转角镜结构,利用古斯-汉欣空间位移和热光效应折射率调制的有效组合,提出了波导反射模式数字式热光开关结构。在给定入射角的条件下优化了空间古斯-汉欣位移,在具有古斯-汉欣效应的本征态下,反射光束出现了较大的跳跃。在1.0μm厚硅膜的绝缘体上硅平台上,单模输入波导和多模干涉波导结构之间的导模本征态匹配,验证了1×3数字式光开关功能。实验中,器件结构引起的光损耗为0.3 dB,开关功率为130~150 mW,开关时间约为50μs,相邻输出端之间隔离度为15 dB。与马赫-曾德尔干涉仪型的2×2热光开关和等离子体效应热光开关的最新结果进行比较证明了该数字式热光开关的先进性。     

Amine-functionalized lanthanide-doped zirconia nanoparticles: optical spectroscopy, time-resolved fluorescence resonance energy transfer biodetection, and targeted imaging

Ultrasmall inorganic oxide nanoparticles doped with trivalent lanthanide ions (Ln(3+)), a new and huge family of luminescent bioprobes, remain nearly untouched. Currently it is a challenge to synthesize biocompatible ultrasmall oxide bioprobes. Herein, we report a new inorganic oxide bioprobe based on sub-5 nm amine-functionalized tetragonal ZrO(2)-Ln(3+) nanoparticles synthesized via a facile solvothermal method and ligand exchange. By utilizing the long-lived luminescence of Ln(3+), we demonstrate its application as a sensitive time-resolved fluorescence resonance energy transfer (FRET) bioprobe to detect avidin with a record-low detection limit of 3.0 nM. The oxide nanoparticles also exhibit specific recognition of cancer cells overexpressed with urokinase plasminogen activator receptor (uPAR, an important marker of tumor biology and metastasis) and thus may have great potentials in targeted bioimaging.