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71.
Genki Namba Yuki Mimura Prof. Yoshitane Imai Dr. Ryo Inoue Prof. Yasuhiro Morisaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14871-14877
Optically active X-shaped molecules based on the planar chiral [2.2]paracyclophane building block were prepared, in which di(methoxy)terphenyl units were stacked on the central benzene rings. At 25 °C, anisolyl rings freely rotate in solution, while in the crystal form, they are fixed by intramolecular CH–π interactions, thereby leading to the expression of the axial chirality, i.e., propeller chirality was exhibited by the planar chiral [2.2]paracyclophane moiety. The X-shaped molecule exhibited good circularly polarized luminescence (CPL) profiles with moderate ΦPL and a large glum value in the order of 10−3 at 25 °C, in solution. In contrast, at −120 °C, dual CPL emission with opposite signs was observed. According to the theoretical studies, the rotary motion of the anisolyl units is suppressed in the excited states, and so emission from two isomers could be observed. These results demonstrate that the axial chirality was controlled by the planar chirality, leading ultimately to propeller chirality. 相似文献
72.
Dr. Yuki Ohishi Kentaro Masuda Kazuki Kudo Prof. Dr. Hajime Abe Prof. Dr. Masahiko Inouye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):785-793
Generally, cage-shaped hosts for saccharides can bind strongly to guest molecules because of the three-dimensional preorganized hydrogen-bonding sites. However, the preparation of cage molecules is often difficult because of the low yield of the macrocyclization step. Here, we report a three-arm-shaped molecule possessing pyridine-acetylene-phenol units as a new kind of host having a preorganized three-dimensional hydrogen-bonding site. This three-arm-shaped host was readily prepared compared to a cage-shaped analogue. This host associated with lipophilic glycosides to form chiral complexes, and the association constants were sufficiently high as to be comparable to those of the cage-shaped analogue. Furthermore, this host extracted native monosaccharides into a lipophilic solvent. 相似文献
73.
Underground fluids are important natural sources of drinking water, geothermal energy, and oil-based fuels. To facilitate the surveying of such underground fluids, a novel microchannel extraction device was investigated for in-line continuous analysis and flow injection analysis of sulfide levels in water and in oil. Of the four designs investigated, the honeycomb-patterned microchannel extraction (HMCE) device was found to offer the most effective liquid–liquid extraction. In the HMCE device, a thin silicone membrane was sandwiched between two polydimethylsiloxane plates in which honeycomb-patterned microchannels had been fabricated. The identical patterns on the two plates were accurately aligned. The extracted sulfide was detected by quenching monitoring of fluorescein mercuric acetate (FMA). The sulfide extraction efficiencies from water and oil samples of the HMCE device and of three other designs (two annular and one rectangular channel) were examined theoretically and experimentally. The best performance was obtained with the HMCE device because of its thin sample layer (small diffusion distance) and large interface area. Quantitative extraction from both water and oil could be obtained using the HMCE device. The estimated limit of detection for continuous monitoring was 0.05 μM, and sulfide concentrations in the range of 0.15–10 μM could be determined when the acceptor was 5 μM FMA alkaline solution. The method was applied to natural water analysis using flow injection mode, and the data agreed with those obtained using headspace gas chromatography-flame photometric detection. The analysis of hydrogen sulfide levels in prepared oil samples was also performed. The proposed device is expected to be used for real time survey of oil wells and groundwater wells. 相似文献
74.
Masayuki Kirihara Takuya Noguchi Nobuhiro Okajima Sayuri Naito Yuki Ishizuka Aiko Harano Hiroyuki Tsukiji Ryu Takizawa 《Tetrahedron》2012,68(5):1515-1520
The reaction of dithioacetals with 30% hydrogen peroxide in the presence of catalytic amounts of tantalum(V) and iodide ion effectively produced carbonyl compounds in high yields. Dithioacetals also can be deprotected using the niobium(V) catalyzed oxidation of iodide ion by hydrogen peroxide under mild conditions. 相似文献
75.
76.
Masami Kuriyama Satoko Tanigawa Yuki Kubo Yosuke Demizu Osamu Onomura 《Tetrahedron: Asymmetry》2010,21(11-12):1370-1373
A facile synthetic method toward optically active 3,3-disubstituted oxindoles with excellent enantioselectivity was achieved using chiral copper-catalyzed desymmetrization of prochiral 1,3-diols. The monotosylated product was transformed into oxindole derivatives efficiently. 相似文献
77.
Abstract The grafting of poly(organophosphazenes) onto carbon black surface by the reaction of poly(dichlorophosphazene) (PDCP) with carbon black having sodium phenoxide groups was investigated. PDCP was prepared by the ring-opening polymerization of hexachlorocyclotriphos-phazene in solution using sulfamic acid as a catalyst. The introduction of sodium phenoxide groups onto carbon black was achieved by treatment of phenolic hydroxyl groups on the surface with sodium hydroxide in methanol. Poly(diphenoxyphosphazene) (PDPP) was successfully grafted onto carbon black by the reaction of PDCP with sodium phenoxide groups introduced onto the surface followed by the replacement of chlorine atoms in PDCP with phenoxy groups. The percentage of grafting onto carbon black increased to 206% at 30°C after 12 h. It was found that only 1.4% of sodium phenoxide groups on carbon black surface was used for the grafting of PDCP because of the blocking of the surface by grafted polymer chains. Poly(diaminophenylphosphazene) and poly-(diethoxyphosphazene) were also grafted onto carbon black surface by the treatment of PDCP-grafted carbon black with aniline and sodium ethoxide, respectively. Poly(organophosphazenes)-grafted carbon blacks produced stable colloidal dispersions in good solvents for grafted polymers. Furthermore, thermogravimetric analysis indicated that poly-(organophosphazenes)-grafted carbon blacks were stable in air about 300°C. 相似文献
78.
Eishun Tsuchida 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):545-571
Construction of artificial oxygen carriers by use of iron or cobalt complexes bound to synthetic polymers was attempted. Radical copolymerization of porphyrin vinyl monomers with styrene gave the metalloporphyrins covalently bonded to a polymer chain at low concentration. For these metalloporphyrin polymers, irreversible oxidation via dimerization was prevented in aprotic solvents and reversible oxygenation was observed. The chemical environment around the oxygen-binding site was presumed to play an important role on the stability of oxygenated complex as in the case of the tetraamide groups on the porphyrin plane. When ethylenebis(salicylideniminato)cobalt chelate coordinated to a polymer-ligand, it formed a stable oxygenated complex at room temperature. Rotational motion of the chelate was decreased markedly by the polymer chain to enhance the coordinate bond between the metal ion and the bound oxygen molecule. Furthermore, the iron porphyrin with bulky substituents was oxygenated even in homogeneous aqueous solutions by combining it with the rigid, hydrophobic domain of a water-soluble block copolymer. 相似文献
79.
Tae Seok Kwon Sadanori Kumazawa Shuji Kondo† Koji Takagi Hideo Kunisada Yasuo Yuki 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):1895-1913
Abstract 1,4-Bis(p-tert-butylphenylselenomethyl) benzene was synthesized, and used as a bifunctional photoiniferter for the polymerization of styrene. Both the polymer yields and the number average of molecular weights (n) of polymers increased with the polymerization. The polymerization of styrene by this iniferter permitted telechelic polystyrene containing arylseleno groups at both chain ends, and the degree of functionality was 1.9. The seleno groups of both chain ends of polystyrene were reduced quantitatively by tri-n-butyltin hydride. These seleno groups in polystyrene were also eliminated by treatment with hydrogen peroxide to give telechelic polystyrene with carbon-carbon double bond at both chain ends. Further, polystyrene with double bonds was converted to telechelic polystyrene carrying terminal functional groups as epoxy, hydroxy, and iodide group, respectively. 相似文献
80.
Dieter Wohrle Jörg Gitzel Gerhard Krawczyk Eishun Tsuchida Hiroyoki Ohno Ichiro Okura 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10-11):1227-1254
Metal complexes of covalently bound porphyrins are used as sensitive probes for several investigations. Substituted derivatives of tetraphenyl-porphin, phthalocyanine, and naphthalocyanine are synthesized at positively and negatively charged as well as uncharged polymers. The photo-redox activities were studied under irradiation with visible light in the presence of a donor and an acceptor. The triplet life times of covalently bound porphyrin moieties are strongly enhanced compared with the analogous monomeric porphyrins. In addition, the polymer binding results in higher photocatalytic activity. The electron-transfer reactions of Mn(III)-containing porphyrins using the reducing agent dithionite are strongly influenced by the polymer environment. In contrast to monomeric Mn(III)-porphyrins, the porphyrins containing polymers exhibit a two-step reduction which may be due to the change of the conformation of the polymer coil. The catalytic epoxidation of 2,5-dihydrofuran with hypochlorite with formation of 3,4-epoxytetrahydrofuran occurs with water-soluble porphyrins in water. No influence of the polymer environment exists. The different reactions require reaction times from milliseconds up to hours. 相似文献