New chiral ferrocenyldiphosphine ligand for catalytic asymmetric transfer hydrogenation

New chiral ferrocenyldiphosphine ligands (R)-(S)-3 and (R)-(S)-4 were prepared. The ligands were employed in Ru(II) catalyzed asymmetric transfer hydrogenation of ketones to give corresponding secondary alcohols. Up to 99% conversion with 90% e.e. was obtained on Ru(DMSO)(4)Cl-2/4 in transfer hydrogenation of acetophenones with propan-2-ol. (C) 2003 Elsevier B.V. All rights reserved.

Assignment of absolute configuration of cyclic secondary amines by NMR techniques using Mosher's method: a general procedure exemplified with (-)-isoanabasine

A general procedure to determine the absolute configuration of cyclic secondary amines with Mosher's NMR method is demonstrated, with assignment of absolute configuration of isoanabasine as an example. Each Mosher amide can adopt two stable conformations (named rotamers) caused by hindered rotation around amide C-N bond. Via a three-step structural analysis of four rotamers, the absolute configuration of (-)-isoanabasine is deduced to be (R) on the basis of Newman projections, which makes it easy to understand and clarify the application of Mosher's method to cyclic secondary amines. Furthermore, it was observed that there was an unexpected ratio of rotamers of Mosher amide derived from (R)-isoanabasine and (R)-Mosher acid. This phenomenon implied that it is necessary to distinguish the predominant rotamer from the minor one prior to determining the absolute configuration while using this technique.

Influence of 2 secondary effects on shear failure of cantilever with attached mass block under impulsive loading

The influence of two secondary effects, rotatory inertia and presence of a crack, on the dynamic plastic shear failure of a cantilever with an attached mass block at its tip subjected to impulsive loading is investigated. It is illustrated that the consideration of the rotatory inertia of the cantilever and the presence of a crack at the upper root of the beam both increase the initial kinetic energy of the block required to cause shear failure at the interface between the beam tip and the tip mass, where the initial velocity has discontinuity Therefore, the influence of these two secondary effects on the dynamic shear failure is not negligible.

Computation of turbulent-flow in a square duct - aspects of the secondary flow and its origin

A numerical study of turbulent flow in a straight duct of square cross-section is made. An order-of-magnitude analysis of the 3-D, time-averaged Navier-Stokes equations resulted in a parabolic form of the Navier-Stokes equations. The governing equations, expressed in terms of a new vector-potential formulation, are expanded as a multi-deck structure with each deck characterized by its dominant physical forces. The resulting equations are solved using a finite-element approach with a bicubic element representation on each cross-sectional plane. The numerical integration along the streamwise direction is carried out with finite-difference approximations until a fully-developed state is reached. The computed results agree well with other numerical studies and compare very favorably with the available experimental data. One important outcome of the current investigation is the interpretation analytically that the driving force of the secondary flow in a square duct comes mainly from the second-order terms of the difference in the gradients of the normal and transverse Reynolds stresses in the axial vorticity equation.

Influence of secondary void damage in the matrix material around voids

The mechanism of ductile damage caused by secondary void damage in the matrix around primary voids is studied by large strain, finite element analysis. A cylinder embedding an initially spherical void, a plane stress cell with a circular void and plane strain cell with a cylindrical or a flat void are analysed under different loading conditions. Secondary voids of smaller scale size nucleate in the strain hardening matrix, according to the requirements of some stress/strain criteria. Their growth and coalescence, handled by the empty element technique, demonstrate distinct mechanisms of damage as circumstances change. The macroscopic stress-strain curves are decomposed and illustrated in the form of the deviatoric and the volumetric parts. Concerning the stress response and the void growth prediction, comparisons are made between the present numerical results and those of previous authors. It is shown that loading condition, void growth history and void shape effect incorporated with the interaction between two generations of voids should be accounted for besides the void volume fraction.

Sensitivity to alcohols of a planar waveguide ring resonator fabricated by a sol-gel method

A planar waveguide ring resonator was fabricated by organic-inorganic hybrid sol-gel materials; its sensitivity to ethanol vapor was experimentally investigated. It was found that dips in the transmission spectrum of the device shifted to longer wavelengths with increasing the ethanol concentration, and its sensitivity showed a linear relation with the ethanol concentration, showing a coefficient of 1.13 pm/ppm. In addition, the transmission loss of the ring resonator decreased with increasing the ethanol concentration. The measured characteristics suggest that the device may be considered as one of the candidates of alcohol vapor sensors. (c) 2006 Elsevier B.V. All rights reserved.

Primary and secondary threshold intensities of ultraviolet-laser-induced domain nucleation in nearly stoichiometric LiTaO3

The primary and secondary threshold intensities of ultraviolet-laser-induced preferential domain nucleation in nearly stoichiometric LiTaO3 is observed. The primary threshold is the minimum intensity to achieve the instantaneous preferential domain nucleation within the focus by the combined action of irradiation and electric fields. The secondary threshold is the minimum intensity to achieve the memory effect without any irradiation within the original focus. The space charge field created by the photoionization carriers is thought to be responsible for the instantaneous effect. The explanation based on the formation and transformation of extrinsic defect is presented for the memory effect. (c) 2008 American Institute of Physics.

A novel short neurotoxin, cobrotoxin c, from monocellate cobra (Naja kaouthia) venom: isolation and purification, primary and secondary structure determination, and tertiary structure modeling

A novel short neurotoxin, cobrotoxin c (CBT C) was isolated from the venom of monocellate cobra (Naja kaouthia) using a combination of ion-exchange chromatography and FPLC. Its primary structure was determined by Edman degradation. CBT C is composed of 61 amino acid residues. It differs from cobrotoxin b (CBT B) by only two amino acid substitutions, Thr/Ala11 and Arg/Thr56, which are not located on the functionally important regions by sequence similarity. However, the LD50 is 0.08 mg/g to mice, i.e. approximately five-fold higher than for CBT B. Strikingly, a structure-function relationship analysis suggests the existence of a functionally important domain on the outside of Loop III of CBT C. The functionally important basic residues on the outside of Loop III might have a pairwise interaction with alpha subunit, instead of gamma or delta subunits of the nicotinic acetylcholine receptor (nAChR). (C) 2002 Elsevier Science Inc. All rights reserved.