Synthesis of New Ligand 1,2-Bis{di[（R,R）-1,3,2-oxzaphosphlidine]phosphino}ethane with C_2-symmetric Axis and Application in Rh-catalyzed Asymmetric Hydrogenation

New ligand 1,2-bis{di[（R,R）-1,3,2-oxzaphosphlidine]phosphino}ethane [（R,R）-BDOPPEs 1,2,3 and 4] with C2-symmetric axis and bearing nitrogen and oxygen were synthesized from readily available optically active amino alcohols.Rh complexes with these ligands were highly enantioselective catalysts for asymmetric hydrogenation of N-benzoyldehydroamino acid derivatives and α-functionalized ketones in 99%e.e.and 98%e.e.,respectively.This new class of（R,R）-BDOPPEs 1,2,3 and 4 gave much more effectivity and enantionselectivity than their corresponding non-C2-asymmetric aminophosphine phosphinite.     

Tetrathiafulvalene crowns: redox-switchable ligands

A series of redox-responsive ligands that associate the electroactive tetrathiafulvalene core with polyether subunits of various lengths has been synthesized. X-ray structures are provided for each of the free ligands. The requisite structural criteria for reaching switchable ligands are satisfied for the largest macrocycles, that is, planarity of the 1,1',3,3'-tetrathiafulvalene (TTF) pi system and correctly oriented coordinating atoms. The ability of these ligands to recognize various metal cations as a function of the cavity size has been investigated by various techniques (LSIMS, 1H NMR, and UV/Vis spectroscopy, cyclic voltammetry). These systems exhibit an unprecedented high coordination ability among TTF crown ethers. Their switchable ligating properties have been confirmed by cyclic voltammetry, and metal-cation complexation has been illustrated by X-ray structures of three of the corresponding metal complexes (Pb2+, Sr2+, and Ba2+). Solid-state structures of these complexes display original packing modes with channel-like arrangements.     

吸附理论的研究进展及其在吸附分离中的应用

综述了吸附理论的进展及其在吸附分离中的应用,并介绍了对气体分离过程至关重要的混合气的吸附模型或关联式。     

Quantifying uncertainty with ensembles of surrogates for blackbox optimization

Blackbox optimization tackles problems where the functions are expensive to evaluate and where no analytical information is available. In this context, a tried and tested technique is to build surrogates of the objective and the constraints in order to conduct the optimization at a cheaper computational cost. This work introduces an extension to a specific type of surrogates: ensembles of surrogates, enabling them to quantify the uncertainty on the predictions they produce. The resulting extended ensembles of surrogates behave as stochastic models and allow the use of efficient Bayesian optimization tools. The method is incorporated in the search step of the mesh adaptive direct search (MADS) algorithm to improve the exploration of the search space. Computational experiments are conducted on seven analytical problems, two multi-disciplinary optimization problems and two simulation problems. The results show that the proposed approach solves expensive simulation-based problems at a greater precision and with a lower computational effort than stochastic models.

     

A High-Order Finite Difference Scheme for 3D Unsteady Convection Diffusion Reaction Equations北大核心CSCD

针对三维非稳态对流扩散反应方程,构造了一种高精度紧致有限差分格式,对空间的离散采用四阶紧致差分方法,对时间的离散采用Taylor级数展开和余项修正技术,所提格式在时间上的精度为二阶、在空间上的精度为四阶。利用Fourier稳定性分析法证明了该格式是无条件稳定的。最后给出数值算例验证了理论结果。     

Magnetic penetration depth in V3Si and LiTi2O4 measured by μSR

Muon spin relaxation (SR) studies have been performed in the normal spinel LiTi₂O₄ and the A-15 superconductor V₃Si to measure the magnetic penetration depth . The relaxation rate(T) 1/² in field-cooled measurements shows a sharp increase belowT _c followed by saturation at low temperatures in both systems. This feature implies an isotropic energy gap without anomalous zeros, and most likelys-wave pairing. The low temperature penetration depth (T 0) is determined to be 2100Å for LiTi₂O₄ and 1300Å for V₃Si respectively. Assuming a clean limit relation ^–2 n _s /m ^*, we derive the Fermi temperatureT _F n _s/ ^2/3 m ^* from the relaxation rate and the Sommerfeld constant asT _F ^3/4–1/4. Unlike conventional superconductors, both LiTi₂O₄ and V₃Si have a large ratio ofT _c /T _F 0.01, only slightly smaller than those ratios in more exotic superconductors.We thank C. Ballard and K. Hoyle for technical assistance. Work at Columbia University is supported by NSF Grant No. DMR-89-13784 and Packard Foundation (YJU). Ames Laboratory is operated for the U. S. Department of Energy by Iowa State University under Contract No. W-7405-Eng-82. Work at Ames was supported by the Director for Energy Research, Office of Basic Energy Sciences.