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181.
A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones. 相似文献
182.
Yuki Goto Masahiro Shiosaki Takeshi Hanamoto Masato Yoshida Hideo Sawada 《Colloid and polymer science》2013,291(5):1211-1217
Fluoro(silyl)acetylenes, which were prepared by reaction of 1,1-difluoroethylene with silyl chlorides, reacted with triethylamine to give dark-brown colored polyfluoro(silyl)acetylene powders in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated acetylene was unable to react with triethylamine at all to afford poly(silyl)acetylene under similar conditions. Polyfluoro(silyl)acetylenes thus obtained were nanometer size-controlled cubic fine particles with a good dispersibility and stability in a variety of solvents. These polyfluoro(silyl)acetylene nanoparticles exhibited clear absorption and emission spectra related to the conjugated units in polymer main chain. Furthermore, these polyfluoro(silyl)acetylene nanoparticles were applied to the surface modification of poly(methyl methacrylate) [PMMA] film to exhibit a higher oleophobicity imparted by fluorine on their surface, compared to that on the reverse side. Figure
New polyfluoro(silyl)acetylenes were prepared by reaction of the creesponding fluoro(silyl)acetylenes with triethylamine in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated silylacetylene was unable to give poly(silyl)acetylene under similar conditions. These polyfluoro(silyl)acetylenes thus obtained can form the nanometer size-controlled cubic fine particles (within 100 nm) in a variety of solvents. 相似文献
183.
Mari Iizuka Shoju Fukushima Yuki Goto Masaaki Okazaki Hideo Sawada Masato Yoshida 《Colloid and polymer science》2013,291(3):595-601
Head-to-head-type styrene and substituted styrene dimers bearing two fluoroalkyl end-groups have been efficiently synthesized by a simple reaction of perfluoroalkyl iodide with styrene under radical conditions as a mixture of meso and racemic forms. The meso form obtained from the mixture by recrystallization gave a crystal suitable for X-ray diffraction study and the crystal structure was found to be based on π-stacking of benzene rings and aggregation of fluoroalkyl chains. Dynamic light scattering measurements showed that meso-styrene dimers bearing two fluoroalkyl end-groups can form the nanometer size-controlled self-assemblies through the intermolecular π-stacking of benzene rings and aggregation of end-capped fluoroalkyl groups in methanol. Figure
Self-assembled meso-perfluorohexylated styrene dimer [C6F13–CH2CHPh–CHPh–CH2–C6F13] based on π-stacking of benzene rings and aggregation of fluoroalkyl chains: Fluorous domains are constructed by self-assembly of fluoroalkyl chains. 相似文献
184.
Masami Sakamoto Kazuya Yoshiwara Fumitoshi Yagishita Wataru Yoshida Takashi Mino Tsutomu Fujita 《Research on Chemical Intermediates》2013,39(1):385-395
The irradiation of methyl 2- and 3-chromonecarboxylate in the presence of various alkenes afforded cyclobutane type adducts, whose structures were established by X-ray structural analysis. Methyl 2-chromonecarboxylate showed higher photochemical reactivity than methyl 3-chromonecarboxylate, in which endo adducts were yielded as major products. 相似文献
185.
Dr. Emi Uchida Dr. Kouji Sakaki Dr. Yumiko Nakamura Dr. Reiko Azumi Dr. Yuki Hirai Dr. Haruhisa Akiyama Dr. Masaru Yoshida Dr. Yasuo Norikane 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(51):17391-17397
Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups ( 1 ) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal–isotropic phase–crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be ?0.84. Heating enhances the thermal cis‐to‐trans isomerization and subsequent cooling returned crystals of the trans/trans isomer. 相似文献
186.
187.
The pigment, tecophilin, in blue flowers of Tecophilaea cyanocrocus was isolated and the structure was determined to be 3-O-(6-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-7-O-(6-O-(4-O-(2-O-(4-O-β-d-glucopyranosyl-(E)-caffeoyl)-6-O-(4-O-β-d-glucopyranosyl-(E)-caffeoyl)-β-d-glucopyranosyl)-(E)-caffeoyl)-β-d-glucopyranosyl)delphinidin. The reproduction experiment of the same color as petals according to the results of chemical analysis and measurement of vacuolar pH of blue cells clarified that the blue color solely develops by tecophilin without interaction of metal ions nor co-pigments. 1H NMR analysis and CD spectrum indicate the co-existence of clockwise intermolecular self-association of the delphinidin nuclei and intramolecular π–π stacking between the chromophore and caffeoyl residues to derive bathochromic shift of the absorption spectrum and stabilize the color by preventing hydration reaction. 相似文献
188.
Measuring the electron affinity of organic solids: an indispensable new tool for organic electronics
Hiroyuki Yoshida 《Analytical and bioanalytical chemistry》2014,406(9-10):2231-2237
Electron affinity is a fundamental energy parameter of materials. In organic semiconductors, the electron affinity is closely related to electron conduction. It is not only important to understand fundamental electronic processes in organic solids, but it is also indispensable for research and development of organic semiconductor devices such as organic light-emitting diodes and organic photovoltaic cells. However, there has been no experimental technique for examining the electron affinity of organic materials that meets the requirements of such research. Recently, a new method, called low-energy inverse-photoemission spectroscopy, has been developed. A beam of low-energy electrons is focused onto the sample surface, and photons emitted owing to the radiative transition to unoccupied states are then detected. From the onset of the spectral intensity, the electron affinity is determined within an uncertainty of 0.1 eV. Unlike in conventional inverse-photoemission spectroscopy, sample damage is negligible and the resolution is improved by a factor of 2. The principle of the method and several applications are reported. Figure
Energy level diagram of low-energy inverse photoemission spectroscopy, LEIPS (left). A beam of low-energy electrons with the kinetic energy E k is focused onto the sample surface, and photons hν emitted owing to the radiative transition to unoccupied states are detected. From the onset of the spectral intensity, the electron affinity E A is determined. The electron affinities of typical organic semiconductors determined using LEIPS (right). 相似文献
189.
Yusuke Shiraki Kazuhiro Tsuruta Junpei Morimoto Chihiro Ohba Akifumi Kawamura Ryo Yoshida Ryuji Kawano Tadashi Uragami Takashi Miyata 《Macromolecular rapid communications》2015,36(6):515-519
Microdevices designed for practical environmental pollution monitoring need to detect specific pollutants such as dioxins. Bisphenol A (BPA) has been widely used as a monomer for the synthesis of polycarbonate and epoxy resins. However, the recent discovery of its high potential ability to disrupt human endocrine systems has made the development of smart systems and microdevices for its detection and removal necessary. Molecule‐responsive microsized hydrogels with β‐cycrodextrin (β‐CD) as ligands are prepared by photopolymerization using a fluorescence microscope. The molecule‐responsive micro‐hydrogels show ultra‐quick shrinkage in response to target BPA. Furthermore, the flow rate of a microchannel is autonomously regulated by the molecule‐responsive shrinking of their hydrogels as smart microvalves.
190.
Yoshida Keiichiro Ishizuka Tomohiro Mizushima Chiharu Nishidate Izumi Kawauchi Satoko Sato Shunichi Sato Manabu 《Optical Review》2015,22(2):374-384
Optical Review - To evaluate multi-spectral images of the absorption and scattering properties in the cerebral cortex of rat brain, we investigated spectral reflectance images estimated by the... 相似文献