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51.
The concise synthesis of Amaryllidaceae alkaloids, such as anhydrolycorinone, anhydrolycorin-7-one, assoanine, and oxoassoanine, which have a pyrrolophenanthridine skeleton, was achieved in moderate yield using the Pd-mediated biaryl coupling reaction of 1-(2-halobenzyl)-2,3-dihydroindole, which applied the regioselective C-H activation method with intramolecular coordination of the benzylamino group to Pd. 相似文献
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Ozeki H Nomoto A Ogawa K Kobuke Y Murakami M Hosoda K Ohtani M Nakashima S Miyasaka H Okada T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6393-6401
We synthesized special-pair/electron-acceptor systems consisting of a complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin, bearing pyromellitdiimide as the electron acceptor. In the case of the dimer, the first and second oxidation potentials were split into a total of four peaks in the differential pulse voltammetry measurement. Furthermore, the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were almost half of those observed for the monomer. These results indicate that the radical cation is delocalized over the whole pi system of the dimer. Time-resolved transient absorption measurements revealed that, relative to the corresponding monomer, the dimer accelerated the charge separation rate, but decelerated the charge recombination rate. The smaller reorganization energy of the slipped cofacial dimer relative to that of the monomeric system demonstrates the significance of the special-pair arrangement for efficient charge separation in photosynthesis. 相似文献
54.
Sasanuma Y Nishimura F Wakabayashi H Suzuki A 《Langmuir : the ACS journal of surfaces and colloids》2004,20(3):665-672
Conformational characteristics of 1-butanol incorporated not only in hexagonal and lamellar aggregates formed by a lyotropic liquid crystal composed of sodium octanoate, 1-butanol, and water but also in a thermotropic liquid crystal, 4'-methoxybenzylidene-4-n-butylaniline (MBBA), have been investigated from 2H NMR quadrupolar splittings of the perdeuterated and partially deuterated compounds. In the lyotropic phases, 1-butanol shows strong trans preferences and renders itself extended, and octanoate decreases the trans fraction toward the methyl terminal to fill the inner space of the aggregate on behalf of 1-butanol. In MBBA, 1-butanol prefers globular conformations. This tendency was also indicated from the phase behaviors of 1-butanol/MBBA and 1-decanol/MBBA systems. In the nematic field, two successive C-C bonds of 1-butanol mostly adopt g+/-g+/- conformations, which are formed in the vicinity of the headgroup of 1-decanol in the lamella of the sodium octanoate/1-decanol/water system. A large degree ofconformational freedom near the hydroxyl group of alcohols, being shown by ab initio molecular orbital calculations at the Gaussian-2 level, permits them to change conformation for each environment. 相似文献
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Toshiyuki Fujii Frédéric Moynier Arnaud Agranier Emmanuel Ponzevera Minori Abe Akihiro Uehara Hajimu Yamana 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(1):261-265
Environmental transport of Tl is affected by redox reaction between Tl(I) and Tl(III) and ligand exchange reactions of them. In order to deepen the knowledge of Tl chemistry, we investigated fractionation of Tl stable isotopes (203Tl and 205Tl) in a chemical exchange system. Tl isotopes were fractionated in a liquid–liquid extraction system, in which aqueous and organic phases are hydrochloric acid solution and dichloroethane including a crown ether, respectively. After purification by ion-exchange chemistry, the isotope ratio of 205Tl/203Tl in equilibrated aqueous phase was measured precisely by multiple-collector–inductively-coupled-plasma–mass-spectrometry. A large isotope fractionation >1 ‰ was found. Electronic structures of possible Tl species (hydrated Tl+, Tl3+, and Tl chlorides) were calculated by ab initio methods, and the isotope fractionation factor was theoretically obtained. The isotope fractionation via intramolecular vibrations was calculated to be much smaller than the experimental result. The isotope fractionation via isotopic change in nuclear volume, named the nuclear field shift effect, was calculated to be >1 ‰ in Tl(I)–Tl(III) redox systems and/or ligand exchange systems of Tl(III). The nuclear field shift effect was found to be the major origin of Tl isotope fractionation. 相似文献
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We report a novel methodology for rapid and quantitative screening of O-glycosylation reactions of application to the analysis of parallel reaction systems. Our system exploits perdeuterated benzyl (Bn-d7) ether, and stereoselectivity and yield are evaluated by 1H NMR and MALDI-TOF MS, respectively. This paper summarizes over 240 screenings of 1 → 3 linkage formation between glucose residues targeting the α-isomer in high yield. 相似文献
59.
Hara K Wang ZS Sato T Furube A Katoh R Sugihara H Dan-Oh Y Kasada C Shinpo A Suga S 《The journal of physical chemistry. B》2005,109(32):15476-15482
We have developed oligothiophene-containing coumarin dyes fully functionalized for dye-sensitized nanocrystalline TiO(2) solar cells (DSSCs). DSSCs based on the dyes gave good performance in terms of incident photon-to-current conversion efficiency (IPCE) in the range of 400-800 nm. A solar energy-to-electricity conversion efficiency (eta) of 7.4% was obtained with a DSSC based on 2-cyano-3-[5'-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-[2,2']bithiophenyl-5-yl]acrylic acid (NKX-2677) under simulated AM 1.5G irradiation (100 mW cm(-2)) with a mask: short-circuit current density (J(sc)) = 13.5 mA cm(-2); open-circuit voltage (V(oc)) = 0.71 V; fill factor (FF) = 0.77. Transient absorption spectroscopy measurements indicated that electron injection from NKX-2677 to the conduction band of TiO(2) is very rapid (<100 fs), which is much faster than the emission lifetime of the dye (1.0 ns), giving a highly efficient electron injection yield of near unity. 相似文献
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