A chiral chelating diene as a new type of chiral ligand for transition metal catalysts: its preparation and use for the rhodium-catalyzed asymmetric 1,4-addition

As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.     

A convenient synthesis of the beraprost intermediate: a useful method for introducing a C3 unit at the benzyl position

[reaction: see text] The Heck reaction is a more efficient and reliable method than previous ones for introducing a C3 unit at the benzyl position for the synthesis of Beraprost. Especially, trialkylated long-chain amines such as (n-C(8)H(17))(3)N and (n-C(12)H(25))(3)N resulted in good yields. This development will be used for the industrial synthesis of Beraprost.     

Boundedness of integral operators on generalized Morrey spaces and its application to Schrödinger operators

In this paper, we study boundedness of integral operators on generalized Morrey spaces and its application to estimates in Morrey spaces for the Schrödinger operator with nonnegative (reverse Hölder class) and small perturbed potentials .

     

The surjectivity of the canonical homomorphism from singular homology to Cech homology

Let be a locally -connected compact metric space. Then, the canonical homomorphism from the singular homology group to the Cech homology group is surjective. Consequently, if a compact metric space is locally connected, then the canonical homomorphism from to is surjective.

     

Adsorption and structure of methyl mercaptoacetate on Cu(1 1 1) surface by XPS and NEXAFS spectroscopy

Methyl mercaptoacetate (MA) on Cu(1 1 1) surface was investigated using synchrotron radiation-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. MA adsorbs on the surface via thiolate formation and weak interaction of the carbonyl group with the surface. Two different adsorption states previously reported for methanethiolate and ethanethiolate were confirmed, besides atomic sulfur. NEXAFS measurements support gauche-type conformation of MA whose skeleton lies on the surface.     

An effective noise removal technique for recovering the shapes of diamond abrasive grains in SLM images degraded by clustered spike noise

A new noise-removal technique is applied to scanning laser microscopic (SLM) images to remove clustered spike noise in the images and to recover the shapes of diamond abrasive grains degraded by the noise. For achievement of this purpose, noise points in the SLM image are accurately detected by taking advantage of their properties in the space and spatial-frequency regions. The noise points are removed by a method of smoothing that is based on linear interpolation; that is, their pixel values are replaced by the interpolated values of their non-noise neighboring points. Noise-point information in the space region is acquired from image segmentation based on pixel classification, while noise-point information in the frequency region is derived from redundant wavelet decomposition for the SLM image. Fisher's linear discriminant method is used to yield the two noise-point images. The degraded grain shapes in the SLM images at different noise levels are satisfactorily recovered with a single iteration of smoothing without losses in sharp edges although a single smoothing needed four interpolations. Thus, the present noise-removal technique is shown to be effective for recovering the original shapes of the grains in every SLM image.     

On the efficient application of weighted essentially nonoscillatory scheme

In this paper, the efficient application of high‐order weighted essentially nonoscillatory (WENO) reconstruction to the subsonic and transonic engineering problems is studied. On the basis of the physical considerations, two techniques are proposed to enhance the accuracy and efficiency of the WENO reconstruction. First, it is observed that the WENO scheme using characteristic variable has better accuracy and convergence speed than the scheme using primitive variable. For engineering problems with shock of moderate amplitude, on the basis of the Rankine–Hugoniot conditions, a simplified characteristic‐variable‐based WENO is developed. The simplified version significantly reduces the cost overhead without sacrificing the shock‐capturing capability. Second, in this work, it is found for viscous case that it is better to include the viscous effect. On the basis of a simple analysis, the viscous correction to the parameter ε in the WENO reconstruction is proposed. Numerical results indicate, with the proposed simplified characteristic‐variable‐based reconstruction and the viscous correction, that the nonlinear WENO interpolation is sharply activated in the region of shock jump, whereas in the shockless area, the WENO interpolation weights are tuned towards the designed optimal value for better accuracy. Compared with the original characteristic‐variable‐based WENO, the current implementation has similar accuracy and reduced cost. At the same time, compared with the primitive variable‐based WENO, better accuracy and convergence speed are obtained at marginal cost overhead. Several practical cases are calculated to demonstrate the accuracy and efficiency of the current methodology. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and fluorescent properties of model compounds for conjugated polymer containing maleimide units at the main chain

2,3‐Diaryl substituted maleimides as model compounds of conjugated maleimide polymers [poly(RMI‐alt‐Ar) and poly(RMI‐co‐Ar)] were synthesized from 2,3‐dibromo‐N‐substituted maleimide (DBrRMI) [R= cyclohexyl (DBrCHMI) and n‐hexyl (DBrHMI)] and aryl boronic acid using palladium catalysts. To clarify structures of conjugated polymer containing maleimide units at the main chain, ¹³C NMR spectra of 2‐aryl or 2,3‐diaryl substituted maleimides were compared with those of N‐substituted maleimide polymers. Copolymers obtained with DBrRMI via Suzuki‐Miyaura cross‐coupling polymerizations or Yamamoto coupling polymerizations were dehalogenated structures at the terminal end. This dehalogenation may contribute to the low polymerizability of DBrRMIs. On the other hand, the π‐conjugated compounds showed high solubility in common organic solvents. The N‐substituents of maleimide cannot significantly affect the photoluminescence spectra of 2,3‐diaryl substituted maleimides derivatives. The fluorescence spectra of poly(RMI‐alt‐Ar) and poly(RMI‐co‐Ar) varied with N‐substituents of the maleimide ring. When exposed to ultraviolet light of wavelength 352 nm, a series of 1,4‐phenylene‐ and/or 2,5‐thienylene‐based copolymers containing N‐substituted maleimide derivatives fluoresced in a yellow to blue color. It was found that photoluminescence emissions and electronic state of π‐conjugated maleimide derivatives were controlled by aryl‐ and N‐substituents, and maleimide sequences of copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Limitation of immunoaffinity column for the removal of abundant proteins from plasma in quantitative plasma proteomics

In plasma proteomics, before a proteome analysis, it is essential to prepare protein samples without high‐abundance proteins, including albumin, via specific preparation techniques, such as immunoaffinity capture. However, our preliminary experiments suggested that functional changes with use alter the ability of the immunoaffinity column. Thus, in this study, to evaluate the changes of the removal ability of abundant proteins from plasma by the immunoaffinity column, plasma proteome analysis was performed for the long‐term test for the reproducibility of the affinity column using the fluorogenic derivatization–liquid chromatography–tandem mass spectrometry method combined with an IgY column. The specific adsorption for albumin decreased with an increase in the number of the column usage before its expiration date. Moreover, it was demonstrated that hydrophobic high molecular weight compounds in plasma adsorbed onto the column materials surface contributed to the functional changes from specific immunoaffinity adsorption into hydrophobic interaction. These results suggested that, in quantitative plasma proteomics studies, it is important to keep in mind the risk of not only the nonselective loss but also the changes in the adsorption ability of the immunoafinity column. Copyright © 2008 John Wiley & Sons, Ltd.