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51.
Hideo Maehata Xinzhi Liu Michael Cunningham Barkev Keoshkerian 《Macromolecular rapid communications》2008,29(6):479-484
While miniemulsion polymerization has proven to be well‐suited for conducting living/controlled radical polymerizations, emulsion polymerizations have proven to be far more challenging. Ab initio emulsion polymerizations, in which monomer droplets are present during polymerization, have thus far not been successful with TEMPO‐mediated polymerizations, as a result of colloidal instability and coagulum formation. By selectively inhibiting polymerization in the monomer droplets, it is demonstrated that droplet polymerization is responsible for the formation of large (>1 µm) particles that can lead to coagulum formation. Furthermore, we show that coagulum‐free latexes can be produced using a TEMPO‐mediated ab initio emulsion polymerization by suppressing droplet polymerization.
52.
The heterotrich ciliate Blepharisma japonicum produces red pigment blepharismins, which function as self-defense toxin against predators and as a photoreceptor for step-up photonegativity. The dibenzoperylenequinone moiety of blepharismins was shown to be biosynthesized via the polyketide pathway. In this paper, the starter units of the biosynthetic pathway of blepharismins were determined to be isovaleryl-CoA and butyryl-CoA by HPLC, LC/ESI-MS, and 1H and 2H NMR analyses of the pigments obtained from feeding experiment of l-leucine or sodium butyrate in excess and deuterium-labeled l-leucine. 相似文献
53.
Izumi T Naitou Y Shimbo Y Takanishi Y Takezoe H Watanabe J 《The journal of physical chemistry. B》2006,110(47):23911-23919
The mesomorphic behavior and phase structure were examined in the mixture of two kinds of dimeric compounds, alpha,omega-bis(4-alkoxyanilinebenzylidene-4'-carbonyloxy)pentane (mOAM5AMOm), by optical microscopy, X-ray diffraction, polarization switching, and second-harmonic generation measurements. One compound is 4OAM5AMO4 with a short terminal alkyl chain that forms a single-layer smectic phase (SmCAs) with a random mixing of spacer and tail groups. Another compound is 16OAM5AMO16 with a long terminal alkyl chain that forms a chiral, anticlinic, and antiferroelectric bilayer phase (SmCAb) with the bent molecules tilted to the bilayer. By mixing these two compounds, the SmCAs phase of 4OAM5AMO4 is easily destabilized, leading to the wide content region of the bilayer phases. In the bilayer regime, three other smectic phases are newly induced. Two of them are antiferroelectric and ferroelectric phases in which the molecules lie perpendicularly with respect to the layer. The other shows no polar response to an external electric field and behaves like a smectic A. The new appearance of these bilayer phases is discussed as a mixing effect of long and short tail groups. 相似文献
54.
Yoshihiro Abe Hideo Hosono Takayuki Kamae Kouichi Kawashima 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):113-116
Abstract Protons in alkaline-earth phosphate glasses give much higher mobility than those in silicate glasses. This is caused by the difference in O-H bonding state. Protons in P-OH form a strong hydrogen bonding with oxygen anion, resulting in formation of weak O-H bond. The electrical conductivity of the glasses is proportional to the square of the proton concentration. The activation energy for the conduction is related to νOH, peak wavenumber of infrared absorption band (around~3000 cm?1), due to fundamental O-H stretching vibration. The mobility of protons increases with decreasing νOH, which depends on the species of ions included in the phosphate glasses. 相似文献
55.
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
56.
Hideo Hirai Kozo Sawada Matsuhiko Aratani Masashi Hashimoto 《Tetrahedron letters》1985,26(14):1739-1742
A stereoselective kinetic protonation of the azetidinone enolate was studied and an efficient synthesis of(cis) was achieved via aldol reaction of with acetone followed by the kinetic protonation with Ph3SnH as proton source. 相似文献
57.
A direct benzylic oxidation of alkylarenes via C-H bond abstraction was developed using alkali metal bromides and oxidants under mild conditions. This reaction proceeded with excellent selectivity by thermal oxidation or photooxidation to provide a broad range of carbonyl compounds containing electron-deficient aryl carbonyl compounds in high yields. 相似文献
58.
A tetra-n-butylammonium (TBA) salt of [H(4.5)(Ta(6)O(19))](3.5-) was synthesized by reacting hydrous tantalum oxide with TBAOH. X-ray structural analysis of TBA(3.5)[H(4.5)(Ta(6)O(19))]·2THF·5.5H(2)O (THF = tetrahydrofuran) revealed that this compound consists of a hydrogen-bonded, rod-shaped tetramer of hexatantalate that is almost 30 ? long together with TBA cations and solvent molecules of crystallization [a = 20.6354(5) ?, b = 25.5951(7) ?, c = 37.2058(8) ?, α = 77.092(1)°, β = 86.177(1)°, γ = 88.683(1)°, V = 19110.9(8) ?(3), Z = 8, and space group P ?1]. (1)H NMR spectra showed that this tetrameric structure is maintained in solution. 相似文献
59.
The behavior of a polymer chain immersed in a binary solvent mixture is investigated via a single-polymer simulation using an effective Hamiltonian, where the solvent effects are taken into account through a density-functional theory for polymer-solvent admixtures. The liquid-liquid phase separation of the binary solvent mixture is modeled as that of a Lennard-Jones binary fluid mixture with weakly attractive interactions between the different components. Two types of energetic preferences of the polymer chain for the better solvent-(A) no preferential solvophilicity and (B) strong preferential solvophilicity-are employed as polymer-solvent interaction models. The radius of gyration and the polymer-solvent radial distribution functions are determined from the simulations of various molar fractions along an isotherm slightly above the critical temperature of the liquid-liquid phase separation. These quantities near the critical point conspicuously depend on the strength of the preferential solvophilicity. In the case where the polymer exhibits a strong preferential solvophilicity, a remarkable expansion of the polymer chain is observed near the critical point. On the other hand, in the case where the polymer has no preferential solvophilicity, no characteristic variation of the polymer conformation is observed even near the critical point. These results indicate that the expansion of a polymer chain enhances the local phase separation around it, acting as a nucleus of demixing in the vicinity of the critical point. This phenomenon in binary solvents near the liquid-liquid critical point is similar to the expansion of the polymer chain in one-component supercritical solvents near the liquid-vapor critical point, which we have reported [T. Sumi and H. Sekino J. Chem. Phys. 122, 194910 (2005)]. 相似文献
60.
Ye Ji Kim Sun Min Kim Eun Jin Cho Hideo Hosono Jung Woon Yang Sung Wng Kim 《Chemical science》2015,6(6):3577-3581
A simple and highly efficient transfer hydrogenation of alkynes and alkenes by using a two-dimensional electride, dicalcium nitride ([Ca2N]+·e–), as an electron transfer agent is disclosed. Excellent yields in the transformation are attributed to the remarkable electron transfer efficiency in the electride-mediated reactions. It is clarified that an effective discharge of electrons from the [Ca2N]+·e– electride in alcoholic solvents is achieved by the decomposition of the electride via alcoholysis and the generation of ammonia and Ca(OiPr)2. We found that the choice of solvent was crucial for enhancing the electron transfer efficiency, and a maximum efficiency of 80% was achieved by using a DMF mixed isopropanol co-solvent system. This is the highest value reported to date among single electron transfer agents in the reduction of C–C multiple bonds. The observed reactivity and efficiency establish that electrides with a high density of anionic electrons can readily participate in the reduction of organic functional groups. 相似文献