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991.
Zaikina JV Mori T Kovnir K Teschner D Senyshyn A Schwarz U Grin Y Shevelkov AV 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(42):12582-12589
The creation of thermoelectric materials for waste heat recovery and direct solar energy conversion is a challenge that forces the development of compounds that combine appreciable thermoelectric figure‐of‐merit with high thermal and chemical stability. Here we propose a new candidate for high‐temperature thermoelectric materials, the type‐III Si172?xPxTey cationic clathrate, in which the framework is composed of partially ordered silicon and phosphorus atoms, whereas tellurium atoms occupy guest positions. We show that the utmost stability of this clathrate (up to 1500 K) in air is ensured by the formation of a nanosized layer of phosphorus‐doped silica on the surface, which prevents further oxidation and degradation. As‐cast (non‐optimized) Si‐P‐Te clathrates display rather high values of the thermoelectric figure‐of‐merit (ZT=0.24–0.36) in the temperature range of 700–1100 K. These ZT values are comparable to the best values achieved for the properly doped transition‐metal‐oxide materials. The methods of the thermoelectric efficiency optimization are discussed. 相似文献
992.
Lesbani A Kondo H Yabusaki Y Nakai M Yamanoi Y Nishihara H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(45):13519-13527
A convenient procedure has been developed for the preparation of Group 14 compounds by integrated palladium-catalyzed cross-coupling of aromatic iodides with the corresponding Group 14 hydrides in the presence of a base. The reaction conditions can be applied to the cross-coupling of tertiary, secondary, and primary Group 14 compounds. In most cases, the desired arylated products were obtained in synthetically useful yields. Even in the case of aryl iodides containing OH, NH(2), CN, or CO(2)R groups, the reactions proceeded with good to high yields with tolerance of these reactive functional groups. A possible application of this method is the unique synthesis of a fungicidal diarylmethyl(1H-1,2,4-triazol-1-ylmethyl)silane derivative. 相似文献
993.
Hiroki Furuta Dr. Yuki Hasegawa Mariko Hase Yuji Mori Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(25):7586-7595
Gambierol was isolated as a neurotoxin from the cultured cells of the ciguatera causative dinoflagellate Gambierdiscus toxicus and classified as a member of the polycyclic ether family of marine toxins. The structure consists of a ladder‐shaped trans‐fused octacyclic ring system that includes 18 stereogenic centers, two 1,3‐diaxial dimethyl‐substituted tetrahydropyranyl rings, and a partially conjugated triene side chain. The total synthesis of gambierol has been achieved by utilizing an oxiranyl anion strategy in an iterative manner. Synthetic highlights of this route include direct carbon–carbon formation on epoxides, sulfonyl‐assisted 6‐endo cyclization, and an expansion reaction of the tetrahydropyranyl rings to oxepanes to forge the polycyclic architecture of the target molecule. 相似文献
994.
995.
Shigeru Kiryu Yusuke Inoue Kohki Yoshikawa Morio Shimada Makoto Watanabe Kuni Ohtomo 《Magnetic resonance imaging》2010
In magnetic resonance (MR) imaging of small animals, the gastrointestinal contents may give rise to intense signals on T1-weighted images. The aim of this study was to determine the optimal dietary preparation to reduce gastrointestinal signals in mice and to evaluate the usefulness of this approach. Images of the mouse trunk were obtained using a T1-weighted, three-dimensional fast low-angle shot sequence under various dietary conditions and were compared with respect to the gastrointestinal signals and image quality. The dietary preparation studied included giving alternative diets for 24 h, intestinal cleansing, and 6-h fasting. Mice with and without dietary preparation underwent MR lymphography using gadofluorine 8, and the visualization of abdominal lymph nodes was compared. In the absence of dietary preparation, hyperintense areas were conspicuous in the gastrointestinal system, whereas on the images taken from mice fed potato or sweet potato for 24 h before imaging, gastrointestinal hyperintensity was less prominent. This preparation also reduced artifactual signals and resulted in higher-quality images of the kidneys. Intestinal cleansing, which consisted of 24-h fasting and laxative intake, did not reduce the gastrointestinal signals and caused signal changes that were indicative of fatty liver development. Some of the abdominal lymph nodes of the mice that did not receive dietary preparation were visualized on MR lymphography source images but not on maximum intensity projection (MIP) images. In contrast, on the MIP images of mice fed potato, all the lymph nodes delineated on the source images were successfully visualized. In conclusion, feeding mice potato or sweet potato for 24 h before MR imaging reduces the gastrointestinal signals and image degradation due to artifacts. Appropriate dietary preparations facilitate the display of target structures on MIP images and are expected to enhance the capabilities of small animal MR imaging. 相似文献
996.
Akio Kawai Shuichi Mori Kazuhide Tsuji Kazuhiko Shibuya 《Applied magnetic resonance》2010,38(2):205-216
Quenching of the triplet excited state of molecular tryptophan by nitroxide radical in 1,4-dioxane and water solutions was
investigated by means of time-resolved electron paramagnetic resonance (EPR) and Fourier-transform (FT)-EPR. The chemically
induced dynamic electron polarization (CIDEP) signals with net emissive phase were recorded at these quenching events and
were analyzed through radical-triplet pair mechanism. The CIDEP time profiles were well reproduced by Bloch and kinetic equations,
assuming radical-triplet pair mechanism with the appropriate quenching rate constants. From a comparison of the simulation
and the experiment, CIDEP enhancement factor in 1,4-dioxane was determined to be −30 × P
eq, where P
eq is the spin polarization of nitroxide at thermal equilibrium. Net emissive CIDEP was also observed by FT-EPR measurements
on the nitroxide quenching of the triplet excited state of tryptophan residue in α-lactalbumin. Magnitude of CIDEP created
in α-lactalbumin/nitroxide system depends on the pH condition of α-lactalbumin solution, which is related to protein folding
dynamics. We argue the CIDEP mechanism at the α-lactalbumin surface and propose a possibility of a novel CIDEP method to probe
a protein surface and structural changes. 相似文献
997.
Yusuke Yamauchi Norihiro Suzuki Logudurai Radhakrishnan Liang Wang 《Chemical record (New York, N.Y.)》2009,9(6):321-339
Currently, ordered mesoporous materials prepared through the self‐assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic‐based materials, for example, transition‐metal oxides, carbons, inorganic‐organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant‐based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation‐mediated direct templating (EDIT), spray‐dried techniques, and collaboration with hard‐templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic‐scale controls of mesochannels are important for innovative applications such as molecular‐scale devices and electrodes with enhanced diffusions of guest species. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 321–339; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900022 相似文献
998.
Compostella F Ronchi S Panza L Mariotti S Mori L De Libero G Ronchetti F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(21):5587-5595
CD1a protein binds sulfatide (3-O-sulfo-beta-D-galactosylceramide) to form an antigen complex that interacts with T cell receptors and activates T cells. To assess the role of the position of the sulfate in T cell activation, the synthesis of three beta-D-galactosylceramides, variously bearing a sulfate at position 2, 4, or 6 of galactose, has been planned and carried out. The compounds were synthesized by an orthogonal sulfation strategy from a common beta-D-galactosylceramide scaffold, which was in turn obtained through an efficient glycosylation reaction between a fully orthogonally protected galactosyl imidate and 3-O-benzoylazidosphingosine. Immunological evaluation of the three sulfated compounds in CD1a-mediated T cell activation, in comparison with natural sulfatide, provided evidence of the influence of the sulfate position in the recognition event between the antigen, the CD1 protein and the T cell receptor. 相似文献
999.
Miyazaki M Yamashita T Suzuki Y Saito Y Soeta S Taira H Suzuki A 《Chemistry & biology》2006,13(10):1071-1079
Domestic cats spray urine with species-specific odor for territorial marking. Felinine (2-amino-7-hydroxy-5,5-dimethyl-4-thiaheptanoic acid), a putative pheromone precursor, is excreted in cat urine. Here, we report that cauxin, a carboxylesterase excreted as a major urinary component, regulates felinine production. In vitro enzyme assays indicated that cauxin hydrolyzed the felinine precursor 3-methylbutanol-cysteinylglycine to felinine and glycine. Cauxin and felinine were excreted age dependently after 3 months of age. The age-dependent increases in cauxin and felinine excretion were significantly correlated. In mature cats, cauxin and felinine levels were sex-dependently correlated and were higher in males than in females. In headspace gas of cat urine, 3-mercapto-3-methyl-1-butanol, 3-mercapto-3-methylbutyl formate, 3-methyl-3-methylthio-1-butanol, and 3-methyl-3-(2-methyldisulfanyl)-1-butanol were identified as candidates for felinine derivatives. These findings demonstrate that cauxin-dependent felinine production is a cat-specific metabolic pathway, and they provide information for the biosynthetic mechanisms of species-specific molecules in mammals. 相似文献
1000.
A new ionization method, electrospray droplet impact ionization (EDI), has been developed for matrix-free secondary-ion mass spectrometry (SIMS). The charged droplets formed by electrospraying 1 M acetic acid aqueous solution are sampled through an orifice with a diameter of 400 microm into the first vacuum chamber, transported into a quadrupole ion guide, and accelerated by 10 kV after exiting the ion guide. The droplets impact on a dry solid sample (no matrix used) deposited on a stainless steel substrate. The secondary ions formed by the impact are transported to a second quadrupole ion guide and mass-analyzed by an orthogonal time-of-flight mass spectrometer (TOF-MS). Ten pmol of gramicidin S could be detected with the presence of as much as 10 nmol of NaCl. The ion signal for arginine disappeared with decrease in the substrate temperature below 150 K owing to the formation of ice film over the sample surface. While 10 fmol of gramicidin S could be detected for 30 min, the ionization/desorption efficiency for EDI becomes smaller with an increase in the molecular weight (MW) of a biological sample. The largest protein samples detected to date are cytochrome c and lysozyme. The high sensitivity for EDI is due to the fact that samples only a few monolayers thick are subject to desorption/ionization by EDI, with little fragmentation. A coherent phonon excitation may be the main mechanism for the desorption/ionization of the solid sample. 相似文献