Direct observations of freeze-etching processes of ice-embedded biomembranes by atomic force microscopy

We have fabricated a cryogenic atomic force microscope that is designed for structural investigation of freeze-fractured biological specimens. The apparatus is operated in liquid nitrogen gas at atmospheric pressure. Freeze-fracturing, freeze-etching and subsequent imaging are carried out in the same chamber, so that the surface topography of a fractured plane is easily visualized without ice contamination. A controlled superficial sublimation of volatile molecules allows us to obtain three-dimensional views of ultrastructures of biological membranes.     

N-tert-Butylbenzenesulfenamide-catalyzed oxidation of alcohols to the corresponding carbonyl compounds with N-chlorosuccinimide

N-tert-Butylbenzenesulfenamide (1)-catalyzed oxidation of various primary and secondary alcohols to the corresponding aldehydes and ketones was efficiently carried out by using N-chlorosuccinimide (NCS) in the coexistence of potassium carbonate and molecular sieves 4 Å at easy-to-control temperatures ranging from 0°C to room temperature. The present catalytic oxidation was performed without giving any damage to the functional groups in alcohols, and was particularly effective in the oxidation of alcohols that formed labile aldehydes because of its mild reaction conditions. Further, selective oxidation of primary hydroxy groups took place in 1-catalyzed oxidation of several diols. Mechanistic investigation suggested that the chlorination of the sulfenamide 1 by NCS led to the formation of a key species, N-tert-butylbenzenesulfinimidoyl chloride (2), which in turn oxidized alcohols in the presence of potassium carbonate to afford carbonyl products by accompanying regeneration of the catalyst 1.     

An improved large scale synthesis of 1,4-anhydro-4-thio-d-ribitol

An improved large scale synthesis of 1,4-anhydro-4-thio-d-ribitol (4) from d-ribose has been accomplished by combining the O-allyl and O-p-methoxybenzyl protecting groups. Compound 4 was obtained in 31% yield in eight steps with three chromatographic separations.     

Four guaianolides from Sinodielsia yunnanensis

Four new guaianolides, sinodielides A-D (1-4), were isolated from Sinodielsia yunnanensis WOLFF together with a known polyacetylene, falcarindiol, and two known coumarins, bergapten and scopoletin. Their structures were established by spectral and X-ray analyses.     

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.     

Controlled polymerization of epoxides: Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐n‐butylammonium fluoride in the presence of protic compounds

Metal‐free controlled ring‐opening polymerization of glycidyl phenyl ether (GPE) was achieved using tetra‐n‐butylammonium fluoride (Bu₄NF) as an initiator in the presence of water and ethanol as chain transfer agents (CTAs). Number‐averaged molecular weight of poly(GPE) increased with an increase of [GPE]₀/([Bu₄NF]₀ + [CTA]₀) values, showing relatively narrow molecular weight distributions. NMR spectroscopic analysis exhibited a formation of ethoxy groups as well as FCH₂ at the initiating polymer chain‐end when ethanol was used as the CTA in the polymerization. These results indicate that Bu₄NF acts as a catalyst as well as the initiator for this polymerization system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates using a phase-transfer catalyst

The catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a β-lactam derivative were synthesized.