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301.
Hidetoshi Yamada Koki Tanigakiuchi Kohei Nagao Kotaro Okajima Tatsuya Mukae 《Tetrahedron letters》2004,45(50):9207-9209
The pyranose rings of the 2,3-bis-O-tert-butyldiphenylsilyl-α- and β-d-glucopyranoses, and of the 2,3-bis-O-tert-butyldimethylsilyl-β-d-glucopyranose were in the 1C4 form. These findings indicate that the introduction of bulky silyl protecting groups at the 2- and 3-positions can flip a pyranose ring into the axial-rich chair form. Previous such ring inversions have been carried out by the silyl protections at the 3- and 4-positions. 相似文献
302.
Electrochemical synthesis of layered manganese oxides intercalated with tetraalkylammonium ions 总被引:2,自引:0,他引:2
Nakayama M Konishi S Tagashira H Ogura K 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):354-359
Thin films of birnessite-type layered manganese oxides with various interlayer spacings have been prepared on a platinum electrode by a one-step electrochemical procedure. The process involves a potentiostatic oxidation of aqueous Mn(2+) ions at around +1.0 V (Ag/AgCl) in the presence of tetraalkylammonium cations with different alkyl chain lengths. X-ray diffraction indicates that the films deposited with tetrabutylammonium (TBA), tetrapropylammonium (TPA), and tetraethylammonium (TEA) ions are composed of a single phase where unhydrated tetraalkylammonium ions are accommodated as a monolayer between manganese oxide layers. The interlayer spacing of the products increases in an order of TEA < TPA < TBA. The film deposited with tetramethylammonium (TMA) is a mixture of two phases relating to hydrated and unhydrated guest cations, the former being predominant probably as a result of less hydrophobic property of TMA compared to that of other tetraalkylammonium ions. The TBA(+)-intercalated Mn oxide film-coated electrode exhibits a good charge/discharge property in a KCl solution between 0 and +0.8 V. In this case, TBA(+) ions between the Mn oxide layers are rapidly replaced with K(+) in solution by ion exchange, accompanying a shrinkage of the interlayer. The incorporated K(+) ions as well as protons play an important role in the electrochemical conversion between Mn(4+) and Mn(3+) in the oxide layer. In the TBACl solution, the interlayer TBA(+) ions can be excluded electrochemically during the positive-going scan, concomitant with the oxidation of Mn(3+) sites. This causes an anodic current and the accompanying shrinkage of the interlayer. On the reverse scan, however, the compressed interlayer does not allow the incorporation of bulky TBA(+) ions from the electrolyte, with virtually no cathodic current observed. Such an obvious difference in electrochemical behavior between the two electrolytes can be recognized by considering that most of the Mn oxide surface is present inside the layered structure, not on the external surface. This indicates that the layered structure is formed over the entire film. 相似文献
303.
Masakazu Nishida Haruhiko Fukaya Yoshio Hayakawa Taizo Ono Kotaro Fujii Hidehiro Uekusa 《Helvetica chimica acta》2006,89(11):2671-2685
The reagent Me3Si(C6F5) was used for the preparation of a series of perfluorinated, pentafluorophenyl‐substituted 3,6‐dihydro‐2H‐1,4‐oxazines ( 2 – 8 ), which, otherwise, would be very difficult to synthesize. Multiple pentafluorophenylation occurred not only on the heterocyclic ring of the starting compound 1 (Scheme), but also in para position of the introduced C6F5 substituent(s) leading to compounds with one to three nonafluorobiphenyl (C12F9) substituents. While the tris(pentafluorophenyl)‐substituted compound 3 could be isolated as the sole product by stoichiometric control of the reagent, the higher‐substituted compounds 5 – 8 could only be obtained as mixtures. The structures of the oligo(perfluoroaryl) compounds were confirmed by 19F‐ and 13C‐NMR, MS, and/or X‐ray crystallography. DFT simulations of the 19F‐ and 13C‐NMR chemical shifts were performed at the B3LYP‐GIAO/6‐31++G(d,p) level for geometries optimized by the B3LYP/6‐31G(d) level, a technique that proved to be very useful to accomplish full NMR assignment of these complex products. 相似文献
304.
Zhang J Vukmirovic MB Sasaki K Nilekar AU Mavrikakis M Adzic RR 《Journal of the American Chemical Society》2005,127(36):12480-12481
We have synthesized a new class of electrocatalysts for the O2 reduction reaction, consisting of a mixed monolayer of Pt and another late transition metal (Ir, Ru, Rh, Re, or Os) deposited on a Pd(111) single crystal or on carbon-supported Pd nanoparticles. Several of these mixed monolayer electrocatalysts exhibited very high activity and increased stability of Pt against oxidation, as well as a 20-fold increase in a Pt mass-specific activity, compared with state-of-the-art all-Pt electrocatalysts. Their superior activity and stability reflect a low OH coverage on Pt, caused by the lateral repulsion between the OH adsorbed on Pt and the OH or O adsorbed on neighboring, other than Pt, late transition metal atoms. The origin of this effect was identified through a combination of experimental and theoretical methods, employing electrochemical techniques, in situ X-ray absorption spectroscopy, and periodic, self-consistent density functional theory calculations. This new class of electrocatalysts promises to alleviate some major problems of existing fuel cell technology by simultaneously decreasing materials cost and enhancing performance. Our studies suggest a new way of synthesizing improved ORR catalysts through the modification and control of the surface reactivity of Pt-based mixed monolayers supported on transition metals other than Pt. In addition to improving the ORR catalysts, co-depositing oxophilic metals may be a promising possibility for improving a variety of other catalysts. 相似文献
305.
Dependence of all-optical poling efficiency on carrier-envelope phase (CEP) could be measured using photoisomerization of dye molecules which are covalently bound to a polymer main chain and have large difference in static dipole moment between the ground state and excited state. Increased chromophore density leads to an order of magnitude reduction in signal-detection time from a dye doped polymer. Analysis of all-optical poling experiments with CEP changes clearly showed the presence of polarization restoring force to zero polarization. This enables resetting of SH activity in the all-optical poling process to be used for fast response loop of CEP stabilization. Phenomenological model could explain well the difference in the growth-and-decay dynamics of poling between sample of dye doped in polymer studied previously and that grafted to a polymer main chain used in the present paper. 相似文献
306.
307.
We study a matrix model obtained by dimensionally reducing Chern–Simons theory on S3. We find that the matrix integration is decomposed into sectors classified by the representation of SU(2). We show that the N -block sectors reproduce SU(N) Yang–Mills theory on S2 as the matrix size goes to infinity. 相似文献
308.
Yuya Nishio Kotaro Yubata Yutaro Wakai Kotaro Notsu Katsumi Yamamoto Hideki Fujiwara Hiroshi Matsubara 《Tetrahedron》2019,75(10):1398-1405
Although molecular bromine (Br2) is a useful brominating reagent, it is not easy to handle. Herein, we describe the preparation of a novel air-stable bromine complex prepared from 1,3-dimethyl-2-imidazolidinone (DMI) and Br2, which was identified to be (DMI)2HBr3 by spectral and X-ray techniques. This complex was then used to brominate olefins, carbonyl compounds, and aromatics, as well as in the Hofmann rearrangement. Yields of reaction products using this complex were almost the same or superior to those using other bromine alternatives. 相似文献
309.
Miura Y Shibata T Satoh K Kamigaito M Okamoto Y 《Journal of the American Chemical Society》2006,128(50):16026-16027
Stereogradient polymers, a fundamentally new type of polymers, were prepared by the stereospecific living radical copolymerization of two monomers that have different stereospecificities and reactivities. The ruthenium-catalyzed living radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) and the silyl-capped HEMA [(tert-butyldimethylsilyl)-HEMA] (SiHEMA) in (CF3)2C(Ph)OH afforded stereogradient poly(HEMA), in which the rr content gradually increased from 62 to 77% at 0 degrees C, due to the lower reactivity and the higher syndiospecificity of SiHEMA. 相似文献
310.
Yamaguchi A Watanabe J Mahmoud MM Fujiwara R Morita K Yamashita T Amino Y Chen Y Radhakrishnan L Teramae N 《Analytica chimica acta》2006,556(1):157-163
Extraction mechanisms of charged organic dye molecules are examined for an assembly of silica-surfactant nanochannels with a channel diameter of 3.4 nm, which is formed inside the pores of an anodic alumina membrane by a surfactant-template method. Experimental results confirm that the extraction mechanism depends on the sign of a charge of the dye molecules. The extraction of the cationic rhodamine 6G is predominantly caused by an ion-pair extraction process, whereas an anion-exchange process is mainly responsible for the extraction of the anionic sulforhodamine B. These extraction mechanisms are discussed by considering the microstructures of the silica-surfactant nanochannels. 相似文献