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991.
Hide-Ki Ishida Hiromune Ando Hiromi Ito Hideharu Ishida Makoto Kiso Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(4-5):413-428
Abstract A first total synthesis of gangliosides GD1c and GT1a containing Neu5Acα(2→8) Neu5Acα(2→3)Gal residue in their non-reducing terminal is described. Condensation of methyl O-[methyl 5-acetamido-8-O-(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylono-11,9-lactone) -4,7- di-O-acetyl-3,5-dideoxy-D-glycero-α-D-galcto-2-nonulopyranosyranosylanate]-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-D-gala-ctopyranoside (1) with 2-(trimethylsilyl)ethyl O-(2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranosyl)- (1→4) -O -(2,3,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (2) or 2-(trimethylsilyl)ethyl O-(2-acetamido-6-O-benzyl-2-deoxy-β-D-galactopyranosyl)-(1→4)-(9-[methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)]-O-(2,6-di-O-benzyl-β-D-galactopyranosyl) - (1→4) - 2,3,6-tri-O-benzyl-β-D-glucopyranoside (3) in the presence of dimethyl(methylthio)sulfonium triflate (DMTST) gave the corresponding hexa-and heptasaccharide derivatives 4 and 5, respectively. These oligosaccharides were converted into the α-trichloroacetimidates 10 and 11 via reductive removal of the benzyl groups and/or benzylidene group, O-acetylation, selective removal of the 2-(trimethylsilyl)ethyl group and treatment with trichloroacetonitrile, which, on coupling with 2-azidosphingosine derivatives 12 or 13, gave the β-glycosides 14 and 15, respectively. Finally, 14 and 15 were transformed, via selective reduction of the azido group, coupling with octadecanoic acid and removal of all protecting groups, into the title gangliosides GD1c 18 and GT1a 19. 相似文献
992.
Makoto Ito 《Few-Body Systems》2013,54(1-4):527-530
The generalized two-center cluster model (GTCM), which can handle various single particle configurations in general two center systems, is applied to the light neutron-rich system, 12 Be = α + α +4N. We discuss the change of the neutrons’ configuration around two α as a variation of an excitation energy. The covalent, ionic and atomic configurations coexists with the degenerate feature above the α +8 He g.s. particle-decay threshold. We find the strong enhancement in the monopole excitation from the ground state to the excited states. The GTCM calculation is also applied to even Be isotopes, and the systematics on the structural changes from bound region to continuum is discussed. 相似文献
993.
Keisuke Sekine Dai Akaishi Kakeru Konagaya Prof. Dr. Shigekazu Ito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200657
Optically active cyclopropanes have been widely investigated especially from the views of pharmaceutical and agrochemical industries, and substituting one of the methylenes with the difluoromethylene unit should be promising for developing novel biologically relevant compounds and functional materials. In this paper, the copper-catalyzed enantioselective hydrosilylation of gem-difluorocyclopropenes to provide the corresponding chiral gem-difluorocyclopropanes is presented. The use of copper(I) chloride, chiral ligands including bidentate BINAPs and monodentate phosphoramidites, and silylborane Me2PhSi-Bpin accompanying sodium tert-butoxide in methanol was appropriate for the enantioselective hydrosilylation of the strained C=C double bond, and the resultant chiral difluorinated three-membered ring was unambiguously characterized. Subsequent activation of the silyl groups in enantio-enriched gem-difluorocyclopropanes showed substantial reduction of the enantiopurity, indicating cleavage of the distal C−C bond leading to the transient acyclic intermediates. 相似文献
994.
In this paper, we give an algebro-geometric characterization of Cayley polytopes. As a special case, we also characterize lattice polytopes with lattice width one by using Seshadri constants. 相似文献
995.
Liquid‐Crystalline Biomacromolecular Templates for the Formation of Oriented Thin‐Film Hybrids Composed of Ordered Chitin and Alkaline‐Earth Carbonate 下载免费PDF全文
Dr. Tatsuya Nishimura Ken Toyoda Takahiro Ito Dr. Yuya Oaki Yukiko Namatame Prof. Takashi Kato 《化学:亚洲杂志》2015,10(11):2356-2360
Macroscopically ordered inorganic thin films have been formed on unidirectionally oriented, liquid‐crystalline chitin matrices. In the presence of poly(acrylic acid) (PAA), unidirectionally oriented chitin films act as templates for the formation of oriented thin‐film crystals of alkaline‐earth carbonates such as SrCO3 and BaCO3. The morphology and orientation of crystals are dependent on the metal ion concentration. For SrCO3 crystallization, unidirectional thin films and hexagonal‐shaped thin films have been deposited from 200 and 25 mm concentration strontium solutions, respectively. 相似文献
996.
Rofeamor P. Obena Mei-Chun Tseng Indah Primadona Jun Hsiao I-Che Li Rey Y. Capangpangan Hsiu-Fong Lu Wan-Sheung Li Ito Chao Chun-Cheng Lin Yu-Ju Chen 《Chemical science》2015,6(8):4790-4800
The structure-specific fragmentation of gas-phase ions in tandem mass spectrometry among other techniques provides an efficient analytical method for confirming unknown analytes or for elucidating chemical structures. Using concentration-dependent UV-absorbing matrix-functionalized magnetic nanoparticles and matrix-assisted laser desorption-ionization mass spectrometry (MALDI MS), we developed a single-step pseudo-MS/MS approach for tunable ionization and fragmentation to facilitate structure determination. Without chemical derivatization, we have demonstrated that this approach successfully distinguished isomeric sets of di-, tri- and tetrasaccharides. Low concentration of nanomatrix provided an enhanced signal for accurate mass determination of the intact molecular ions of analytes present in the sample. In contrast, high concentration of nanomatrix induced extensive and unique fragmentation, including high-energy facile bond breakage (A- and X-type cross-ring cleavages), which facilitated the linkage and sequence characterization of oligosaccharides without conventional tandem mass spectrometric instrumentation. The practicality of this approach for complex sample analysis was evaluated by an oligosaccharide mixture, wherein molecular ions are unambiguously observed and signature product ions are distinguishable enough for molecular identification and isomer differentiation by this simple tunable approach. By probing the roles of the multilayer nanomatrix components: matrix (energy absorption), silane-coating (energy pooling and dissipation) and core Fe3O4 (fragmentation), a plausible energy transfer mechanism was proposed based on a computational study and photoelectron experiments. The differentiation of tri- and tetra-oligosaccharide shown in this study not only demonstrated the first step toward glycan characterization by nanoparticle-assisted MALDI-MS, but also shed some insight on the nanoparticle-mediated energy transfer dynamics behind our approach. 相似文献
997.
Tomohiro Seki Taichi Ozaki Takuma Okura Kiyotaka Asakura Aya Sakon Hidehiro Uekusa Hajime Ito 《Chemical science》2015,6(4):2187-false
In this study, we report the interconvertible tetracolored solid state photoluminescence of gold(i) isocyanide complex 2 upon various external stimuli through solid state structural changes. Soaking complex 2 in acetone yields blue emission as a result of the formation of 2B. The subsequent removal of acetone yields 2G through a crystal-to-crystal phase transition, which exhibits green emission. This green-emitting solid 2G exhibits stepwise emission color changes to yellow and then to orange upon mechanical stimulation by ball-milling, which corresponds to the formation of 2Y and 2O, respectively. 2B could be recovered upon the addition of acetone to 2G, 2Y, and 2O. Thus, these four emitting solid states of 2 can be switched between repeatedly by means of acetone soaking and the application of mechanical stimulation. Importantly, single crystal and powder X-ray diffraction (PXRD) studies fully show the detailed molecular arrangements of 2B, 2G, and 2Y. This is the first mechanochromic compound to show interconvertible four color emission in the solid state. We also present the first example of using PXRD measurements and the Rietveld refinement technique for the structural analysis of a ground powder in a luminescence mechanochromism study. We obtained complete molecular-level structural information of the crystalline states of 2B, 2G, 2Y, and 2O. In comparison with a more solvophobic analogue 1, we suggest that the weak interaction of 2 with acetone in the solid state would allow a solvent inclusion/release mode, which is an important structural factor for the unprecedented multicolor mechanochromic luminescence. 相似文献
998.
Ito T Masuda Y Abe N Oyama M Sawa R Takahashi Y Chelladurai V Iinuma M 《Chemical & pharmaceutical bulletin》2010,58(10):1369-1378
Comprehensive re-investigation of the chemical constituents in the leaves of Vateria indica (Dipterocarpaceae) resulted in the isolation of a novel resveratrol dimeric dimer having a C(2)-symmetric structure, vateriaphenol F (1), and two new O-glucosides of resveratrol oligomers, vateriosides A (2) (resveratrol dimer) and B (4) (resveratrol tetramer), along with a new natural compound (3) and 33 known compounds including 26 resveratrol derivatives. The absolute structures were elucidated by spectroscopic analysis, including two dimensional NMR and circular dichroism (CD) spectra. 相似文献
999.
The solubilities and selectivities for CO2, N2 and CH4 in ionic liquid were predicted using a COSMO based activity coefficient model, COSMO-SAC method. The 1-alkyl-3-methylimidazolium cations were focused in this work. The anion species include tetrafluoroborate [BF4], hexafluorophosphate [PF6], triflate [OTf], dicyanamide [dca] and bis(trifluoromethane)-sulfonimide [Tf2N]. The predicted results of the solubilities of CO2 in the ionic liquids by COSMO-SAC method are in agreement with the experimental data within the averaged deviation of 0.0017 in mole fraction. The predicted results of selectivities for CO2/N2 and CO2/CH4 represent the effects of anion species qualitatively. Permeability through supported liquid membrane can be presented by solubility and diffusion coefficients in the liquid. The permeabilities of CO2 through the ionic liquid membranes were also predicted by a solution-diffusion model with COSMO-SAC method. The predicted results of the CO2 permeabilities through the ionic liquids represent the experimental data within the order of the permeabilities. 相似文献
1000.
Thermoelectric NaxCo2O4/Ag composites were synthesized by citric acid complex (CAC) method and Ag precipitation from CH3COOAg aqueous solution on the NaxCo2O4 powders. Effects of the synthesis process on microstructure and thermoelectric performance of NaxCo2O4/Ag composites were investigated. When the NaxCo2O4 CAC powders were dipped in CH3COOAg aqueous solution and dried, fine Ag particles less than around 300 nm in size were precipitated on the surface of NaxCo2O4 powders. After the subsequent sintering process, the flaky Ag phase, the length and thickness of which were up to 5 and 1 μm,
respectively, existed along interfaces between NaxCo2O4 grains. The sizes of Ag particles obtained in this study were found to be smaller than those of the conventionally prepared
NaxCo2O4/Ag composites. The fine dispersion of Ag grains was effective for suppressing the increase in thermal conductivity due to
the addition of metallic phase, Ag, and for improving the thermoelectric performance of NaxCo2O4/Ag composites, suggesting that the synthesis technique composed of the CAC method and Ag precipitation from CH3COOAg aqueous solution is significantly important process for thermoelectric NaxCo2O4/Ag composites. 相似文献