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81.
Nguyen Chung Thanh Takanori Kajioka Yasunori Taga Satoshi Ogawa Yosuke Miyahara Mitsunori Oda 《Tetrahedron》2006,62(48):11227-11239
After a preliminary search of the reaction conditions for the Suzuki-Miyaura cross-coupling of haloazulenes with arylboronic acids, the title compounds were synthesized either by the direct coupling reaction between 1,3-dihaloazulene and the corresponding N,N-disubstituted 4-aminophenylboronic acids or by a two-step sequence involving the cross-coupling with 4-bromophenylboronic acid and subsequent Pd-catalyzed amination. Application of the title diamines to a hole-injecting material in organic electroluminescent devices was carried out to provide their prominent characteristics as a novel durable, non-cyanine and non-polyamine substance without color fade. The diamine derivatives, extended by an ethynyl unit between the azulenyl core and the 4-aminophenyl moiety, were also synthesized and found, unfortunately, unsuitable for vacuum deposition in preparing a multilayer composite. 相似文献
82.
Kana Kunihiro Dr. Svetlana Heyte Prof. Dr. Sébastien Paul Dr. Thierry Roisnel Prof. Dr. Jean-François Carpentier Dr. Evgueni Kirillov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(12):3997-4003
A series of in situ-prepared catalytic systems incorporating RuII precursors and bidentate phosphine ligands has been probed in the reductive carboxylation of ethylene in the presence of triethylsilane as reductant. The catalytic production of propionate and acrylate silyl esters was evidenced by high-throughput screening (HTS) and implemented in batch reactor techniques. The most promising catalyst systems identified were made of Ru(H)(Cl)(CO)(PPh3)3 and 1,4-bis(dicyclohexylphosphino)butane (DCPB) or 1,1’-ferrocene-diyl-bis(cyclohexylphosphine) (DCPF). A marked influence of water on the acrylate/propionate selectivity was noted. Turnover numbers [mol mol(Ru)−1] up to 16 for acrylate and up to 68 for propionate were reached under relatively mild conditions (20 bar, 100 °C, 0.5 mol % Ru, 40 mol % H2O vs. HSiEt3). Possible mechanisms are discussed. 相似文献
83.
Hiroshi Watanabe Tomohiro Sato Kunihiro Osaki Mutsuo Matsumoto Dobrin P. Bossev Cathy E. McNamee Masaru Nakahara 《Rheologica Acta》2000,39(2):110-121
Linear viscoelastic behavior was investigated for aqueous solutions of perfluorooctyl sulfonate (C8F17SO−
3; abbreviated as FOS) micelles having a mixture of tetraethylammonium (N+(C2H5)4; TEA) and lithium (Li+) ions as the counter-ions. The solutions had the same FOS concentration (0.1 mol l−1) and various Li+ fractions in the counter-ions, φLi = 0−0.6, and the FOS micelles in these solutions formed threads which further organized into dendritic networks. At T ≤ 15 °C,
the terminal relaxation time τ and the viscosity η, governed by thermal scission of the networks, increased with increasing
φLi up to 0.55. A further increase of φLi resulted in decreases of τ and η and in broadening of the relaxation mode distribution. These rheological changes are discussed
in relation to the role of TEA ions in thermal scission: Previous NMR studies revealed that only a fraction of TEA ions were
tightly bound to the FOS micellar surfaces and these bound ions stabilized the thread/network structures. The concentration
of non-bound TEA ions, CTEA
*, decreased and finally vanished on increasing φLi up to φLi
* ≅ 0.6, and the concentration of the bound TEA ions significantly decreased on a further increase of φLi. The non-bound TEA ions appeared to catalyze the thermal scission of the FOS threads, and the observed increases of τ and
η for φLi < 0.55 were attributed to the decrease of CTEA
*. On the other hand, the decreases of τ and η as well as the broadening of the mode distribution, found for φLi > 0.55 (where CTEA
* ≅ 0), were related to destabilization of the FOS threads/networks due to a shortage of the bound TEA ions and to the existence
of concentrated Li+ ions. Viscoelastic data of pure FOSTEA and FOSTEA/FOSLi/TEACl solutions lent support to these arguments for the role of TEA
ions in the relaxation of FOSTEA/FOSLi solutions.
Received: 12 October 1999/Accepted: 1 November 1999 相似文献
84.
Satoshi Watanabe Tatsumasa Hiratsuka Yusuke Asahi Asumi Tanaka Kazuhiro Mae Minoru T. Miyahara 《Particle & Particle Systems Characterization》2015,32(2):234-242
Gold nanoshells with tunable surface plasmon resonances are a promising material for optical and biomedical applications. They are produced through seed‐mediated growth, in which gold nanoparticles (AuNPs) are seeded on the core particle surface followed by growth of the gold seeds into a shell. However, synthetic gold nanoshell production is typically a multistep, time‐consuming batch‐type process, and a simple and scalable process remains a challenge. In the present study, a continuous flow process for the seed‐mediated growth of silica–gold nanoshells is established by exploiting the excellent mixing performance of a microreactor. In the AuNP‐seeding step, the reduction of gold ions in the presence of core particles in the microreactor enables the one‐step flow synthesis of gold‐decorated silica particles through heterogeneous nucleation. Flow shell growth is also realized using the microreactor by selecting an appropriate reducing agent. Because self‐nucleation in the bulk solution phase is suppressed in the microreactor system, no washing is needed after each step, thus enabling the connection of the microreactors for the seeding and shell growth steps into a sequential flow process to synthesize gold nanoshells. The established system is simple and robust, thus making it a promising technology for producing gold nanoshells in an industrial setting. 相似文献
85.
86.
Tanaka K Toda F Mochizuki E Yasui N Kai Y Miyahara I Hirotsu K 《Angewandte Chemie (International ed. in English)》1999,38(23):3523-3525
An intermolecular enantioselective photoreaction by a single-crystal-to-single-crystal transformation has been carried out for the first time, as is evident from X-ray structure analysis and X-ray powder diffractometric studies. This reaction, the dimerization of the title compound to cyclobutane derivative 1 (X=O, S), provides a good example for studying the mechanism of topochemical reactions in the crystal. 相似文献
87.
Y Nishihara M Iwata K Ikawa M Püttmann L W Robertson M Miyahara H Terada K Utsumi 《Chemical & pharmaceutical bulletin》1992,40(10):2769-2774
The actions of three hexachlorobiphenyls (HCBs) 2,3,4,2',3',4'-, 2,3,4,3',4',5'- and 3,4,5,3',4',5'-HCBs, on the respiration of rat liver mitochondria with succinate as the substrate were compared, and the effect of chloro-substitution sites in HCB on the respiration was examined. 2,3,4,2',3',4'-HCB strongly inhibited both state 3 and 2,4-dinitrophenol (DNP)-stimulated respiration with 50% inhibition dose of 52 and 54 microM for state 3 and DNP-stimulated respiration, respectively. The inhibitory action of 2,3,4,3',4',5'-HCB on both respiration was approximately half as potent as that of 2,3,4,2',3',4'-HCB. On the other hand, 3,4,5,3',4',5'-HCB did not inhibit any respiration at all. These results indicate that both inside (ortho) and outside (meta or para) positions in each phenyl ring of the biphenyl molecule should be replaced with chlorines for HCB to be an effective inhibitor. Either the actual position of chloro-substituent or steric conformation caused by its substitution or both can be considered as factors affecting the inhibition. On the basis of the conformational energy, calculated by AM1 (Austin model 1) method, with increases in chlorine number in ortho position, HCB molecule became angulated. Furthermore, calculated probability of the conformation distribution for HCB indicated that the probability of nonplanarity was higher for effective HCB than for less effective HCB. These structural features suggest the significance of steric conformation as well as chloro-substituent sites in determining the inhibitory ability of HCB.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献
88.
Ajayan Vinu Mani Karthik Masahiko Miyahara Velayudam Murugesan Katsuhiko Ariga 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):151-157
CoAl-MCM-41 (X) catalysts with X = nSi/(nCo + nAl) various ratios were synthesized and ethylation of phenol with ethanol was studied in vapor-phase at temperatures between 250 and 450 °C. The products obtained were O-alkylated product (ethyl phenyl ether), C-alkylated products (2-ethylphenol and 4-ethylphenol), and C-/O-alkylated products (ethyl ethylphenyl ether). The phenol conversion increased significantly with reaction temperature over all the catalysts. The activity of the catalysts followed the order CoAl-MCM-41 (20) > CoAl-MCM-41 (50) > CoAl-MCM-41 (80). Selectivity between the C-alkylation and the O-alkylation depended on the factors such as acidity of the catalyst and the reaction temperature. CoAl-MCM-41 (20) catalyst displayed a phenol conversion of 40% and a selectivity of more than 80% for 2-ethylphenol under the optimized reaction condition. The ethanol to phenol ratios and the reactant flow rate are also influential for both activity and selectivity of CoAl-MCM-41 catalysts. 相似文献
89.
The recognition of cellular nucleic acids by synthetic oligonucleotides is a versatile strategy for regulating biological processes. The vast majority of published studies have focused on antisense oligonucleotides that target mRNA, but it is also possible to design antigene oligonucleotides that are complementary to chromosomal DNA. Antigene oligomers could be used to inhibit the expression of any gene or analyze promoter structure and the mechanisms governing gene regulation. Other potential applications of antigene oligomers include activation of expression of chosen genes or the introduction of mutations to correct genetic disease. Peptide nucleic acid (PNA) is a nonionic DNA/RNA mimic that possesses outstanding potential for recognition of duplex DNA. Here we describe properties of PNAs and the challenges for their development as robust antigene agents. 相似文献
90.
Kunihiro Ichimura 《Journal of polymer science. Part A, Polymer chemistry》1984,22(11):2817-2828
A method to immobilize enzymes photochemically with use of photocrosslinkable poly(vinylalcohol) bearing stilbazolium groups is described. Irradiation of a film of the photosensitive polymer containing enzyme gave water-insoluble, cellophane-like transparent film demonstrating high enzyme activity. The dissolution of enzymes from the film was dependent upon the molecular weight of the proteins and the content of the photocrosslinking unit. It was found that various enzymes are sufficiently entrapped in the photocrosslinked polymer matrix when the content of the photosensitive group is more than about 1.0 mol%. 相似文献