Synthesis and characterization of beta-haloalkenyl-lambda3-bromanes: stereoselective Markovnikov addition of difluoro(aryl)-lambda3-bromane to terminal acetylenes

Reported here for the first time are the synthesis, isolation, and characterization of hypervalent beta-haloalkenyl-lambda3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-lambda3-bromane activated by BF3-i-Pr2O resulted in fluoro-lambda3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-beta-fluoroalkenyl-lambda3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino lambda3-bromanation-chlorine shift-fluorination or lambda3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-beta-chloroalkenyl-lambda3-bromanes stereoselectively in high yields. The beta-chloroalkenyl-lambda3-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule.     

Solid-liquid interfacial energy In Fe40at%Ni14at%P6at%B alloy glass

Based on nucleation theory, the solid-liquid interfacial energy is estimated to be about 87 ± 2 mJ/m² by the use of the nucleation frequency, supercooled liquid viscosity, and the melting point of Fe40at%Ni14at%P6at%B alloy glass. The value of this energy is found to be quite close to that estimated by means of Turnbull's assumption applied in covalent elements.     

Competition between energy and proton transfer in ultrafast excited-state dynamics of an oligomeric fluorescent protein red Kaede

We investigated femtosecond and picosecond time-resolved fluorescence dynamics of a tetrameric fluorescent protein Kaede with a red chromophore (red Kaede) to examine a relationship between the excited-state dynamics and a quaternary structure of the fluorescent protein. Red Kaede was obtained by photoconversion from green Kaede that was cloned from a stony coral Trachyphyllia geoffroyi. In common with other typical fluorescent proteins, a chromophore of red Kaede has two protonation states, the neutral and the anionic forms in equilibrium. Time-resolved fluorescence measurements clarified that excitation of the neutral form gives the anionic excited state with a time constant of 13 ps at pH 7.5. This conversion process was attributed to fluorescence resonance energy transfer (FRET) from the photoexcited neutral form to the ground-state anionic form that is located in an adjacent subunit in the tetramer. The time-resolved fluorescence data measured at different pH revealed that excited-state proton transfer (ESPT) also occurs with a time constant of 300 ps and hence that the FRET and ESPT take place simultaneously in the fluorescent protein as competing processes. The ESPT rate in red Kaede was significantly slower than the rate in Aequorea GFP, which highly likely arises from the different hydrogen bond network around the chromophore.     

Spatial arrangement of metal nanoparticles supported by porous polymer substrates studied by transmission electron microtomography

Fine metal particles (nanoparticles) stabilized on porous (polymeric) substrates can be considered as a model system of a high-performance catalyst. In the present study, the substrate was made using the periodic microphase-separated structure of a block copolymer as the template, and the Pd nanoparticles were formed inside the porous material by reduction of the Pd2+ ions with 1-propanol as the reductant. The three-dimensional morphology of such a polymer-Pd hybrid material was studied by transmission electron microtomography. The characteristic structural parameters of the hybrid, e.g., the penetration of the Pd nanoparticles into the polymer substrate, number density of the Pd nanoparticles, and size distribution of the Pd nanoparticles, were measured for the first time.     

Pressure-induced weak moment in the two-dimensional antiferromagnet (C2H5NH3)2CuCl4

Abstract

The two-dimensional Heisenberg antiferromagnet (C₂H₅NH₃)₂CuCl₄ has the ferromagnetic intralayer exchange interaction, while the extremely weak interlayer exchange interaction is antiferromagnetic. Neutron scattering experiments under high pressures have been performed on this compound. We confirm that the spin structure changes around 1～2 GPa from the collinear alignment along the a-axis to a spin-canting one. The weak moment due to the canting is parallel to the c-axis. The results indicate that the ferromagnetic intralayer and the antiferromagnetic interlayer exchange interactions are maintained up to 1～2 GPa. Why the weak ferromagnetic moment along the c-axis occurs is due to a lowering of crystal symmetry by pressure.     

Evaluation of Successive Fractions for Optimum Quantification of Bergenin and Gallic Acid in Three Industrially Important Bergenia species by High-Performance Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC -     

Precise thickness measurement within a few monolayers by X-ray diffraction from InGaAs/GaAs strained-layer superlattices

We propose a technique to measure the thickness of a GaAs layer with a precision of a few monolayers (MLs) by high-resolution X-ray diffraction (HRXRD) from InGaAs/GaAs strained-layer superlattices (SLSs) on GaAs substrates. Using this technique to monitor the GaAs growth rate, we have successfully controlled the Ga beam flux within ±1% in molecular beam epitaxy (MBE) growth for continuous 40 runs during four days by increasing the Ga cell temperature to compensate the decrease of the Ga beam flux caused by the consumption of the Ga source. Precise thickness measurements are also demonstrated in the growth on InP substrates by using InAlGaAs/InGaAs SLSs and InAlGaAs/InAlAs SLSs.     

Structure of an unsaturated fatty acid with unique vicinal dimethyl branches isolated from the Okinawan soft coral of the genus Sinularia

A new unsaturated fatty acid with unique vicinal dimethyl branches was isolated from the Okinawan soft coral of the genus Sinularia. The structure of the compound was determined based on the results of spectroscopic analysis and chemical conversion. The absolute configuration was deduced by applying the Ohrui-Akasaka method.     

Internal delivery of soft chlorine and bromine atoms: stereoselective synthesis of (E)-beta-halogenovinyl(aryl)-lambda3-iodanes through domino lambda3-iodanation-1,4-halogen shift-fluorination of alkynes

4-(Difluoroiodo)toluene-induced domino lambda(3)-iodanation-1,4-halogen shift-ring enlargement-fluorination reaction of 5-halopentynes with a four-, five-, or six-membered carbocycle afforded the ring-expanded (E)-delta-fluoro-beta-halovinyl-lambda3-iodanes stereoselectively in high yields, probably via the intermediacy of five-membered halonium ions. Use of internal alkynes makes it possible to synthesize tetrasubstituted beta-halovinyl-lambda(3)-iodanes with defined stereochemistry.