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61.
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63.
Oligomeric Alkoxysilanes with Cagelike Hybrids as Cores: Designed Precursors of Nanohybrid Materials
Hideki Kuge Yoshiaki Hagiwara Atsushi Shimojima Dr. Kazuyuki Kuroda Prof. 《化学:亚洲杂志》2008,3(3):600-606
Well‐defined alkoxysilane oligomers containing a cagelike carbosiloxane core were synthesized and used as novel building blocks for the formation of siloxane‐based hybrid networks. These oligomers were synthesized from the cagelike trimer derived from bis(triethoxysilyl)methane by silylation with mono‐, di‐, and triethoxychlorosilanes ((EtO)nMe3?nSiCl, n=1, 2, and 3). Hybrid xerogels were prepared by hydrolysis and polycondensation of these oligomers under acidic conditions. The structures of the products varied depending on the number of alkoxy groups (n). When n=2 and 3, microporous xerogels (BET surface areas of 820 and 510 m2 g?1, respectively) were obtained, whereas a nonporous xerogel was obtained when n=1. 29Si NMR spectroscopic analysis suggested that partial rearrangement of the siloxane networks, which accompanied the cleavage of the Si–O–Si linkages, occurred during the polycondensation processes. By using an amphiphilic triblock copolymer surfactant as a structure‐directing agent, hybrid thin films with a 2D hexagonal mesostructure were obtained when n=2 and 3. These results provide important insight into the rational synthesis of molecularly designed hybrid materials by sol–gel chemistry. 相似文献
64.
The concise enantioselective total synthesis of C(2)-asymmetrical (-)-deoxocuscohygrine and (-)-dihydrocuscohygrine are described. Double-diastereoselective additions of normal Grignard reagent to bis(1,3-oxazolidine) have been deployed to construct chiral diamine fragments as a key step. 相似文献
65.
Preparation and mechanical properties of bacterial cellulose nanocomposites loaded with silica nanoparticles 总被引:3,自引:0,他引:3
Shoichiro Yano Hideaki Maeda Megumi Nakajima Toshiki Hagiwara Takashi Sawaguchi 《Cellulose (London, England)》2008,15(1):111-120
Bacterial cellulose (BC), which is produced by Gluconacetobacter xylinus (Ga. xylinus) in culture, is made up of a three-dimensional network of ribbon-shaped bundles of cellulose microfibrils. In the current
studies, we used two processes to prepare nanocomposites of BC filled with silica particles. In Process I, Ga. xylinus was incubated in medium containing silica sol Snowtex 0 (ST 0, pH 2–4) or Snowtex 20 (ST 20, pH 9.5–10.0). The elastic modulus
at 20 °C was improved by keeping the amount of silica in the nanocomposites below 4% when ST 20 was used and below 8.7% when
ST 0 was used. This process allowed incorporation of 50% silica in BC. Inclusion of higher amounts of silica reduced the modulus
at 20 °C and the strength of the nanocomposites below that of BC. X-ray diffraction measurements revealed that the silica
particles disturb the formation of ribbon-shaped fibrils and affect the preferential orientation of the (
) plane. We also produced BC-silica nanocomposites by Process II, wherein the BC hydrogel was immersed in different concentrations
of silica sols, allowing silica particles to diffuse into the BC hydrogel and lodge in the spaces between the ribbon-shaped
fibrils. This method increased the modulus at 20°C and the strength compared to the BC matrix, but it was difficult to load
the BC with more than 10% silica in this way. 相似文献
66.
Kohara S Takata M Matsumoto K Hagiwara R Suzuya K Morita H Siewenie JE Benmore CJ 《The Journal of chemical physics》2008,129(1):014512
The structure of liquid Cs(FH)(2.3)F was revealed using a combination of high-energy x-ray and neutron diffraction measurements. We found that the strongest intermolecular H-F hydrogen bonds at an average distance of 1.36 A are accompanied by the formation of a high degree of bending of the oligomer chain in the melt, with [angle]FHF=150 degrees . A reverse Monte Carlo simulation showed that the average number of atoms per chain is 4.4. A detailed chain analysis of the atomic configuration revealed that (FH)(2)F(-) oligomer chains are the major entities in the liquid, and asymmetrical FHF(-) are formed owing to the strong H-F hydrogen bonds. The results suggest that an average of one or two HF molecules bond to each of the 11 fluorine atoms surrounding a cesium ion. 相似文献
67.
Application to Photocatalytic H2 Production of a Whole‐Cell Reaction by Recombinant Escherichia coli Cells Expressing [FeFe]‐Hydrogenase and Maturases Genes
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Dr. Yuki Honda Prof. Hidehisa Hagiwara Prof. Shintaro Ida Prof. Tatsumi Ishihara 《Angewandte Chemie (International ed. in English)》2016,55(28):8045-8048
A photocatalytic H2 production system using an inorganic–bio hybrid photocatalyst could contribute to the efficient utilization of solar energy, but would require the development of a new approach for preparing a H2‐forming biocatalyst. In the present study, we constructed a recombinant strain of Escherichia coli expressing the genes encoding the [FeFe]‐hydrogenase and relevant maturases from Clostridium acetobutylicum NBRC 13948 for use as a biocatalyst. We investigated the direct application of a whole‐cell of the recombinant E. coli. The combination of TiO2, methylviologen, and the recombinant E. coli formed H2 under light irradiation, demonstrating that whole cells of the recombinant E. coli could be employed for photocatalytic H2 production without any time‐consuming and costly manipulations (for example, enzyme purification). This is the first report of the direct application of a whole‐cell reaction of recombinant E. coli to photocatalytic H2 production. 相似文献
68.
Natural enantiomers of unique tricyclic sesquiterpenoids, valeriananoids A-C 1-3, have been synthesized starting from bicyclo[2.2.2]octane-2,5-dione derivative 11, which was obtained by diastereoselective catalytic domino Michael reaction of oxophorone 5 with 8-phenylmenthyl acrylate 10 by LDA or silica-gel-base (NMAP-Li). The tricyclic ring was closed selectively by intramolecular 6-endo-trig mode cyclization of the ketyl radical, which was generated from keto-allylether 25 by either lithium or sodium naphthalenide. 相似文献
69.
70.
Satoru Amou Shin Nishimura Akio Takahashi Tokio Hagiwara Hiroshi Hamana Tadashi Narita 《Journal of polymer science. Part A, Polymer chemistry》1999,37(3):341-347
N‐(4‐Tetrahydropyranyl‐oxy‐phenyl)maleimide (THPMI) was prepared and polymerized by radical or anionic initiators. THPMI could be polymerized by 2,2′‐azobis(isobutyronitrile) (AIBN) and potassium tert‐butoxide. Radical polymers (poly(THPMI)r) were obtained in 15–50% yields for AIBN in THF at 65°C after 2–5 h. The yield of anionic polymers (poly(THPMI)a) obtained from potassium tert‐butoxide in THF at 0°C after 20 h was 91%. The molecular weights of poly(THPMI)r and poly(THPMI)a were Mn = 2750–3300 (Mw/Mn = 1.2–3.3) and Mn = 11300 (Mw/Mn = 6.0), respectively. The difference in molecular weights of the polymers was due to the differences in the termination mechanism of polymerization and the solubility of these polymers in THF. The thermal decomposition temperatures were 205 and 365°C. The first decomposition step was based on elimination of the tetrahydropyranyl group from the poly(THPMI). Positive image patterns were obtained by chemical amplification of positive photoresist composed of poly(THPMI) and 4‐morpholinophenyl diazonium trifluoromethanesulfonate used as an acid generator. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 341–347, 1999 相似文献