A new synthesis of pyrrolidines by way of an enantioselective Mannich/diastereoselective hydroamination reaction sequence

A new two-step synthesis of highly substituted pyrrolidines has been developed. Chiral silane Lewis acid promoted enantioselective Mannich reactions of silyl ketene imines with acylhydrazones may be used to access bishomoallylic benzoic hydrazides that in turn may be cyclized to pyrrolidines by way of the thermal hydroamination reaction reported recently by Beauchemin. Importantly, excellent diastereoselectivity may be realized in the hydroamination reactions.     

Variational sets: Calculus and applications to nonsmooth vector optimization

We develop elements of calculus of variational sets for set-valued mappings, which were recently introduced in Khanh and Tuan (2008) [1] and [2] to replace generalized derivatives in establishing optimality conditions in nonsmooth optimization. Most of the usual calculus rules, from chain and sum rules to rules for unions, intersections, products and other operations on mappings, are established. Direct applications in stability and optimality conditions for various vector optimization problems are provided.     

Oleanolic triterpene saponins from the roots of Panax bipinnatifidus

Ten oleanane-type saponins (1-10), including three new compounds, namely bifinosides A-C (1-3), were isolated from the roots of Panax bipinnatifidus SEEM. Their structures were elucidated on the basis of chemical and spectroscopic methods.     

Quantifying temperature and flow rate effects on the performance of a fixed-bed chromatographic reactor

Chromatographic reactors are based on coupling chemical reactions with chromatographic separation in fixed-beds. Temperature and flow rate are important parameters for the performance of such reactors. Temperature affects mainly adsorption, chemical equilibria, mass transfer and reaction kinetics, whereas flow rate influences residence time and dispersion. In order to evaluate the mentioned effects, the hydrolysis reactions of methyl formate (MF) and methyl acetate (MA) were chosen as case studies. These reactions were performed experimentally in a lab-scale fixed-bed chromatographic reactor packed with a strong acidic ion exchange resin. The chosen reactions can be considered to represent a relative fast (MF) and a relative slow (MA) reaction. The processes which take place inside the reactor were described and simulated using an isothermal equilibrium dispersive model. The essential model parameters were determined experimentally at different temperatures and flow rates. The performance of the chromatographic reactor was evaluated at several discrete constant temperature levels by quantifying product purity, productivity and yield. The work provides insight regarding the influence of temperature and flow rate on values of the model parameters and the performance criteria.     

Optical stark spectroscopy of the D1Π-X1Σ+(0,0) band of scandium monohydride

The laser induced fluorescence (LIF) spectra of the D(1)Π-X(1)Σ(+)(0,0) band of a rotationally cold (<20 K) molecular beam sample of scandium monohydride, ScH, and scandium monodeuteride, ScD, were recorded without and in the presence of a static electric field. The fine and magnetic hyperfine parameters for the X(1)Σ(+)(v=0) and D(1)Π(v=0) states of ScH and ScD were determined from the analysis of the field-free spectra. An unexpected isotopic dependence of the (45)Sc(I=7/2) magnetic hyperfine interaction was observed. The lowest J-levels of the D(1)Π( v=0) state of ScH are not perturbed, but the corresponding levels for ScD are strongly perturbed. The observed electric field induced splitting, broadenings, and shifts were analyzed to produce permanent electric dipole moments, μ(e), of 1.74 ± 0.15 and 2.177 ± 0.006 D for the X(1)Σ(+)(v=0) and D(1)Π(v=0) states, respectively. The trend in μ(e) for the 3d-metal monohydrides is discussed.     

Electronic structures, vibrational and thermochemical properties of neutral and charged niobium clusters Nb(n), n = 7-12

Geometric and electronic structures, vibrational properties, and relative stabilities of niobium clusters Nb(n), n = 7-12, are studied using both DFT (BPW91 and M06 functionals) and CCSD(T) calculations with the cc-pVnZ-PP basis set. In each cluster, various lower-lying states are very close in energy in such a way that the ground state cannot be unambiguously established by DFT computations. Nb clusters tend to prefer the lowest possible spin state as the ground state, except for Nb(12) ((3)A(g)). The optimal structure of the cluster at a certain size does not simply grow from that of the smaller one by adding an atom randomly. Instead, the Nb clusters prefer a close-packed growth behavior. Nb(10) has a spherically aromatic character, high chemical hardness and large HOMO-LUMO gap. Electron affinities, ionization energies, binding energy per atom, and the stepwise dissociation energies are evaluated. Energetic properties exhibit odd-even oscillations. Comparison with experimental values shows that both BPW91 and M06 functionals are reliable in predicting the EA and IE values, but the BPW91 is deficient in predicting the binding and dissociation energies. We re-examine in particular the experimental far IR spectra previously recorded using the IR-MPD and free electron laser spectrometric techniques and propose novel assignments for Nb(7) and Nb(9) systems. The IR spectra of the anions are also predicted.     

Local shrinkage and stress induced by thermo-oxidation in composite materials at high temperatures

The paper is concerned with the modelling, simulation and experimental characterisation of local shrinkage strains and stresses induced by thermo-oxidation phenomena in the IM7/977-2 carbon/epoxy composite material at elevated temperatures. The oxygen concentration and mechanical fields were established through a coupled model constructed from a unified multiphysical approach and the thermodynamics of irreversible processes. The model was implemented in the ABAQUS^® finite element commercial code. Simulations of thermo-oxidation-induced matrix shrinkage were run at a local scale, i.e., the scale of the elementary constituents of the composite, the fibre and the matrix. The experimental assessment was done at the same scale, and the local matrix shrinkage profiles were measured by confocal interferometric microscopy.A good agreement was found between the simulated and measured profiles, validating the unified model. The thermo-oxidation induced stress field was analysed to understand the influence of the environment on the onset of damage in composite materials at elevated temperature.     

QR methods and error analysis for computing Lyapunov and Sacker�CSell spectral intervals for linear differential-algebraic equations

In this paper, we propose and investigate numerical methods based on QR factorization for computing all or some Lyapunov or Sacker?CSell spectral intervals for linear differential-algebraic equations. Furthermore, a perturbation and error analysis for these methods is presented. We investigate how errors in the data and in the numerical integration affect the accuracy of the approximate spectral intervals. Although we need to integrate numerically some differential-algebraic systems on usually very long time-intervals, under certain assumptions, it is shown that the error of the computed spectral intervals can be controlled by the local error of numerical integration and the error in solving the algebraic constraint. Some numerical examples are presented to illustrate the theoretical results.     

A novel implicit finite difference method for the one-dimensional fractional percolation equation

In this paper, a novel implicit finite difference method for the one-dimensional fractional percolation equation is proposed. Consistency, stability and convergence of the method are established. Some numerical examples are given. The numerical results demonstrate the effectiveness of theoretical analysis.     

Primitive symmetric designs with up to 2500 points

By this article we conclude the construction of all primitive ( v, k,λ ) symmetric designs with v < 2500 , up to a few unsolved cases. Complementary to the designs with prime power number of points published previously, here we give 55 primitive symmetric designs with v ≠ p ^m , p prime and m positive integer, together with the analysis of their full automorphism groups. The research involves programming and wide‐range computations. We make use of the software package GAP and the library of primitive groups which it contains. © 2011 Wiley Periodicals, Inc. J Combin Designs 19:463‐474, 2011