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51.
We prepared some taper-shaped liquid-crystalline trimers in which two phenylpyrimidine units and a 1,4-diphenyl-2,3-difluorobenzene unit are connected to 2,4-dihdroxy benzoic acid via flexible spacers. We then investigated their liquid-crystalline properties using polarised optical microscopy, differential scanning microscopy and X-ray diffraction. 6-[4–(5-Octylpyrimidin-2-yl)phenyloxy]hexyl 2-{7-{4-[4–(4-hexylphenyl)-2,3-difluorophenyl]phenyloxy}heptanoyloxy}-4-{6-[4–(5-octylpyrimidin-2-yl)phenyloxy]hexyloxy}benzoate (1) was found to exhibit a phase sequence of isotropic liquid – nematic – intercalated smectic A – intercalated anticlinic smectic C – modulated smectic C. The structure–property relation in the taper-shaped trimers reveals that the modulated phase is induced by competition between an intercalated structure stabilised by dipole–dipole interaction and a monolayer structure by packing entropy effects. Conformational change of compound 1 induced by intermolecular interactions plays an important role in the phase transition behaviour. 相似文献
52.
This Letter reviews recent advance of metallacycles with chelating Si-, Ge-, and Sn-ligands. Dehydrogenative bond-forming reactions of organosilanes, -germanes, and -stannanes promoted by Pd and Pt complexes afford four- and five-membered metallacycles composed of heavier group 14 elements. It has a couple of advantages such as easier preparation of the starting compounds and reaction procedure than the common metathesis reactions of dianions with transition metal dihalide complexes. These metallacycles are regarded as possible intermediates in catalytic dehydrocoupling polymerizations or as convenient precursors to form discrete oligomers. 相似文献
53.
Dr. Yoichi Hoshimoto Keita Ashida Yukari Sasaoka Dr. Ravindra Kumar Prof. Dr. Ken Kamikawa Prof. Dr. Xavier Verdaguer Prof. Dr. Antoni Riera Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2017,56(28):8206-8210
The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)3L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams. 相似文献
54.
Reiko Saito Yoichi Saito Hideyasu Kamoshita Yoichi Tokubuchi 《Journal of polymer science. Part A, Polymer chemistry》2012,50(16):3444-3451
Highly heterotactic poly(4‐vinyl pyridine)s (P4VPs) with the fraction of mr content (fmr) > 0.81 were synthesized by free radical polymerization of 4‐vinyl pyridine (4VP) with randomly methylated β‐cyclodextrin (β‐RMCD) in acidic aqueous media of HNO3 and CF3COOH at 40 °C. The heterotacticity of P4VP strongly depended on the neutralization of 4VP. The complete neutralization of 4VP with HNO3 or CF3COOH increased the heterotacticity of P4VP, whereas atactic P4VP was obtained in water. The partial decomposition of β‐RMCD by HCl reduced the heterotacticity of P4VP (fmr ≈ 0.74). The structures of inclusion complexed monomers were determined by Job's plot, 2D NMR with nuclear Overhauser enhancement spectroscopy analyses, and simulation by MM2. The 1:2 complex with [β‐RMCD]:[4VP] with meso placement of 4VPs in β‐RMCD was formed when 4VP was completely neutralized with acid, whereas the 1:1 complex was formed in water. The mechanism of heterospecific control by using β‐RMCD was proposed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Yoichi Makimizu Nhat Truong Nguyen Jiri Tucek Hyo-Jin Ahn JeongEun Yoo Mahshid Poornajar Imgon Hwang Stepan Kment Prof. Dr. Patrik Schmuki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(12):2685-2692
Photoelectrochemical (PEC) water splitting is a promising method for the conversion of solar energy into chemical energy stored in the form of hydrogen. Nanostructured hematite (α-Fe2O3) is one of the most attractive materials for a highly efficient charge carrier generation and collection due to its large specific surface area and the short minority carrier diffusion length. In the present work, the PEC water splitting performance of nanostructured α-Fe2O3 is investigated which was prepared by anodization followed by annealing in a low oxygen ambient (0.03 % O2 in Ar). It was found that low oxygen annealing can activate a significant PEC response of α-Fe2O3 even at a low temperature of 400 °C and provide an excellent PEC performance compared with classic air annealing. The photocurrent of the α-Fe2O3 annealed in the low oxygen at 1.5 V vs. RHE results as 0.5 mA cm−2, being 20 times higher than that of annealing in air. The obtained results show that the α-Fe2O3 annealed in low oxygen contains beneficial defects and promotes the transport of holes; it can be attributed to the improvement of conductivity due to the introduction of suitable oxygen vacancies in the α-Fe2O3. Additionally, we demonstrate the photocurrent of α-Fe2O3 annealed in low oxygen ambient can be further enhanced by Zn-Co LDH, which is a co-catalyst of oxygen evolution reaction. This indicates low oxygen annealing generates a promising method to obtain an excellent PEC water splitting performance from α-Fe2O3 photoanodes. 相似文献
58.
Manabu Ishifune Ryuhei Suzuki Mikio Yamane Hiroyuki Tanabe Yuki Nakagawa Kumao Uchida 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(7):523-528
Acrylamide (AAm) was found to polymerize in a solution of poly(N‐isopropylacrylamide) (PNIPAAm) in water at around its lower critical solution temperature (LCST) (32°C) without any initiators. This phenomenon was specifically observed in aqueous solutions of the polymers having LCST such as PNIPAAm and poly(methylvinylether) (PMVE). AAm polymerized only when PNIPAAm and AAm were dissolved in water below LCST of PNIPAAm and then the solution was warmed up to the polymerization temperature (40°C). On the other hand, the polymerization of AAm did not proceed when AAm was added into aqueous PNIPAAm solution during and after the phase separation above 32°C. Furthermore the polymerizability of AAm was remarkably affected by the concentration and molecular weight of the PNIPAAm additives. Under the condition of lower PNIPAAm concentration (0.30 mol/L), the increase in the molecular weight of PNIPAAm considerably increased the molecular weight of the resulting PAAm but decreased the yield of PAAm. Under the condition of higher PNIPAAm concentration (0.60 mol/L) the polymerizability was not so affected by the molecular weight of PNIPAAm, while the molecular weight of PAAm formed by using higher molecular weight PNIPAAm was higher than those of PAAm formed by using lower molecular weight PNIPAAm. Moreover, the molecular weight of PAAm formed by the PNIPAAm induced polymerization of AAm was much higher than that of the polymer obtained by the radical polymerization using AIBN in THF or VA‐ 061 in water. 相似文献
59.
Yoichi Ishibai Takashi Nishikawa Shigeyoshi Miyagishi 《Journal of Dispersion Science and Technology》2013,34(8):1093-1098
Nano‐sized TiO2 sol was prepared through a wet synthesis process. The synthesis procedure involved hydrolysis of TiCl4, acid treatment, and a SiO2 surface‐modifying process. Before surface modification, the TiO2 suspension was treated with acid to remove Na ions, soluble TiO2, and other impurities. The acid treatment of a TiO2 suspension at a higher temperature was proved to be useful for effective SiO2 modification. The colloidal sol provided high transparency in visible light as well as excellent UV‐shielding properties. Surface modification of TiO2 particles with SiO2 greatly improved both the dispersing stability in neutral pH and the photostability of TiO2 colloidal sol. 相似文献
60.
Katsufumi Tanaka Takatoshi Morina Yuichiro Tanabe Ryuichi Akiyama 《Liquid crystals》2013,40(9):1019-1028
The concentration dependences of dielectric properties measured at 105 Hz and 106 Hz are reported for aqueous solutions of hydroxypropyl cellulose. Phase behaviour of the solutions was also observed with a polarizing optical microscope. For solutions with concentrations well above 40 wt %, polydomain textures, including the banded texture, were observed after a prehistory of deformation. No significant discontinuous changes in the dielectric constant, εr′, and loss factor, εr″, were found at the concentrations around the onset of the isotropic–cholesteric phase transition and in the biphasic region. In contrast, the steeper changes in εr′ and εr″ were found at the critical concentration for the fully developed cholesteric phase transition with the polydomain textures. 相似文献