Making the liquid-phase catalytic hydrodechlorination of pce over Pd/C safer

Summary The hydrodechlorination of tetrachloroethylene in methanol (MeOH) over palladium catalysts on activated carbon (Pd/C) at 20°C and atmospheric pressure was rendered safer by using ethanol (EtOH), isopropanol (IPA) or water-alcohol mixtures as solvents. Adding water to MeOH was better than using EtOH or IPA since it resulted in a faster reaction and better stability of Pd/C, which could also be completely reactivated.     

Diastereoselective syntheses and oxygenation of silyl fulleroids

The addition of silyl diazomethane (1a-d) to fullerene C₆₀ at room temperature provided the mono-adducts, the bis- and tris-adducts of silyl fulleroid (3a-d) in moderate yields. The structures of the silyl fulleroids were characterized by mass spectroscopy, as well as ¹H and ¹³C NMR. The gated ¹H NMR and ¹³C-¹H COLOC analyses of 3a-d showed a correlation between the methine proton resonances and three fullerene carbons. These observations, as well as the ¹H NMR chemical shifts of the methine protons, suggest a remarkable diastereoselectivity, with the silyl groups located above a five-membered ring. Two transition states of the thermal nitrogen-extrusion of pyrazoline intermediate (2a) were theoretically obtained, the structures of which disclosed that the diastereoselectivity is a consequence of minimization of the repulsive interaction between the silyl groups and the N₂ moiety. The bridgehead CC double bond of the silyl fulleroid is thought to be reactive by POAV analyses. The silyl fulleroids (3a,b) were found to react with singlet oxygen to afford the silyl enol ether (9a,b) via 1,3-silyl migration of a diketone (8a,b). This is the first example of ¹O₂ oxygenation of fulleroids.     

Free-energy analysis of the molecular binding into lipid membrane with the method of energy representation

A statistical-mechanical treatment of the molecular binding into lipid membrane is presented in combination with molecular simulation. The membrane solution is viewed as an inhomogeneous, mixed solvent system, and the free energy of solvation of a solute in membrane is computed with a realistic set of potential functions by the method of energy representation. Carbon monoxide, carbon dioxide, benzene, and ethylbenzene are adopted as model solutes to analyze the binding into 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) membrane. It is shown that the membrane inside is more favorable than bulk water and that the solute distribution is diffuse throughout the membrane inside. The membrane-water partition coefficient is then constructed with the help of the Kirkwood-Buff theory from the solvation free energy obtained separately in the hydrophobic, glycerol, headgroup, and aqueous regions. To discuss the role of repulsive and attractive interactions, the solvation free energy is partitioned into the DMPC and water contributions and the effect of water to stabilize the benzene and ethylbenzene solutes within the membrane is pointed out.     

Stereoselective synthesis of c3-c12 dihydropyran portion of antitumor laulimalide using copper-catalyzed oxonium ylide formation-[2,3] shift

Copper-catalyzed oxonium ylide formation-[2,3] shift of (5S,7R)-5-allyloxy-1-diazo-8-(p-methoxybenzyloxy)-7-methyl-2-octanone (3) proceeded in tetrahydrofuran-dichloromethane (4 : 1) under reflux with an excellent stereoselectivity (97 : 3) to give (2R,6S)-2-allyl-6-[(2R)-3-(p-methoxybenzyloxy)-2-methylpropyl]-3-dihydropyranone (2) as a major isomer in 82% yield. The resultant pyranone (2) was converted to the key intermediate (1) of the Mulzer's laulimalide synthesis and its derivatives (14, 15).     

Synthesis and structure of 16 pi octaalkyltetraphenylporphyrins

The oxidized octaethyltetraphenylporphyrin (1, OETPP) and the corresponding newly prepared octaisobutyltetraphenylporphyrin (3, OisoBuTPP) could be isolated from the reaction of OETPPLi2 (or OisoBuTPPLi2) with SOCl2. The X-ray analysis and the characteristic UV-vis spectra of 1 and 3 revealed that these are the first examples of 16 pi nonaromatic porphyrins.     

X-ray photoelectron diffraction study of discommensurate Cu/Ge(111)

We have studied the atomic structure in the interior of discommensurate domains of the Cu/Ge(111) surface by using scanned-angle X-ray photoelectron diffraction (XPED). XPED patterns of Cu 2p_3/2 intensity provided direct information on the local structure in the vicinity of photoelectron emitters. It has been found that a certain number of Cu atoms are embedded within the surface layer, so that the surface has some structural similarity with the discommensurate Cu/Si(111)-‘5×5’.     

Fixed point properties for semigroup of nonexpansive mappings on Fréchet spaces

In this paper, we shall establish a fixed point property on Fréchet spaces for left reversible semitopological semigroups generalizing some classical results.     

Real-time imaging of ion uptake from root to above-ground part of the plant using conventional beta-ray emitters

We present real-time imaging of ³²P-phosphate within a living plant as well as that in culture solution toward roots. The above-ground part of the plant was irradiated with light from LED and roots were kept in dark. The plant was Lotus japonicus, cv. Miyakojima MG20 and real-time ³²P-phosphate uptake manners in young, flowering and adult phase were visualized. In the case of young plant, there was a preferential translocation of ³²P in younger leaves. When the sample was treated with phosphate deficient condition, ³²P uptake amount was much higher. In an adult phase, ³²P uptake was high at pods.     

Synthesis of proton conductive inorganic–organic hybrid membranes through copolymerization of dimethylethoxyvinylsilane with vinylphosphonic acid

Proton conductive inorganic–organic hybrid membranes were synthesized from dimethylethoxyvinylsilane (DMEVS), vinylphosphonic acid (VPA) and 3-glycidoxypropyltrimethoxysilane (GPTMS) through copolymerization followed by sol–gel process. The ratio of phosphorus to silicon in the copolymer almost corresponded to the charged molar ratio of VPA to DMEVS when the ratio of VPA to DMEVS was below 1/2. Self-standing, homogeneous, highly transparent membranes were synthesized from DMEVS–VPA copolymer and GPTMS via sol–gel condensation. Differential thermal analysis-thermogravimetry analyses indicated that these membranes were thermally stable up to 200 °C. The results of Fourier transform infrared and ¹³C NMR revealed that phosphonic acid groups of VPA were chemically bound to organosiloxane network. The copolymerization and condensation of (DMEVS–VPA)/GPTMS were confirmed by ³¹P and ²⁹Si NMR spectra. The proton conductivity of the hybrid membranes increased with phosphonic acid content. The membrane of (DMEVS–VPA)/GPTMS showed a remarkable conductivity of 6.3 × 10⁻² S cm⁻¹ at 130 °C and 100% relative humidity.