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1.
We report quantum mechanical calculations of cross sections and rate coefficients for rovibrational relaxation of H2 and D2 by collisions with Ar atoms over a wide range of temperatures including the ultracold limit. Limiting values of the rate coefficients for vibrational and rotational quenching at zero temperature were computed and sensitivity of the results to the choice of the interaction potential is investigated. We also demonstrate dramatic change in the behavior of the rate coefficients at low temperatures when the van der Waals potential supports a quasibound level very close to the dissociation threshold. 相似文献
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TMSOTf-catalyzed intramolecular condensation for catechin and epicatechin units are described. A potential electrophile and a nucleophile were connected with diester linkers and TMSOTf-catalyzed condensation was examined. In comparison with intermolecular catechin and catechin condensation, the intramolecular condensation required high reaction temperature and reversed 3,4-cis product was obtained. The condensed product was transformed into the natural 3,4-cis (+)-catechin-(4β→8)-(+)-catechin dimer. 相似文献
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Preparation of peptide thioester is essential for native chemical ligation and block condensation. Our novel methodology involves conversion of the carboxylic acid of a peptide into a thioester using p-toluenesulfonyl isocyanate, followed by alkylation, then thiol substitution. Our methodology can also be used for the preparation of glycopeptide thioesters. Furthermore, it is possible to carry out the reaction as a sequential peptide chemical ligation. 相似文献
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Akemi Umeyama Chihiro Ohta Yukari Shino Minori Okada Yukari Nakamura Tatsuya Hamagaki Hiroshi Imagawa Masami Tanaka Aki Ishiyama Masato Iwatsuki Kazuhiko Otoguro Satoshi Ōmura Toshihiro Hashimoto 《Tetrahedron》2014
During the search for new antitrypanosomal drug leads, three new antitrypanosomal compounds, hexatenuins A–C (1–3), were isolated from the fruiting body of Hexagonia tenuis. 1 and 3 possessed an unusual malonate half-ester functional group at C-3 position, and 1 and 2 had a spirostructure in the side-chain. Their structures were elucidated using MS analyses, extensive 2D-heteronuclear NMR data interpretation. Compounds 1–3 showed in vitro antitrypanosomal activity against Trypanosoma brucei brucei with IC50 values of 0.57, 8.60 and 5.62 μg/ml, respectively. 相似文献
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Yuetian Yan Masaaki Ubukata Robert B. Cody Timothy E. Holy Michael L. Gross 《Journal of the American Society for Mass Spectrometry》2014,25(8):1404-1411
A method for structural elucidation of biomolecules dating to the 1980s utilized high-energy collisions (~10 keV, laboratory frame) that induced charge-remote fragmentations (CRF), a class of fragmentations particularly informative for lipids, steroids, surfactants, and peptides. Unfortunately, the capability for high-energy activation has largely disappeared with the demise of magnetic sector instruments. With the latest designs of tandem time-of-flight mass spectrometers (TOF/TOF), however, this capability is now being restored to coincide with the renewed interest in metabolites and lipids, including steroid-sulfates and other steroid metabolites. For these metabolites, structure determinations are required at concentration levels below that appropriate for NMR. To meet this need, we explored CRF with TOF/TOF mass spectrometry for two groups of steroid sulfates, 3-sulfates and 21-sulfates. We demonstrated that the current generation of MALDI TOF/TOF instruments can generate charge-remote fragmentations for these materials. The resulting collision-induced dissociation (CID) spectra are useful for positional isomer differentiation and very often allow the complete structure determination of the steroid. We also propose a new nomenclature that directly indicates the cleavage sites on the steroid ring with carbon numbers. Figure
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Shigehiro Morikawa Toshiro Inubushi Kan Takahashi Hisanari Ishii Shino Shigemori 《Magnetic resonance imaging》1996,14(10):1197-1204
The relationships among tissue edema, lactate accumulation, and intracellular pH in middle cerebral artery (MCA)-occluded rats were investigated with multiecho 1H magnetic resonance imaging and spatially resolved metabolic images constructed by 1H and 31P nuclear magnetic resonance (NMR) chemical shift imaging (CSI). For the effective and sensitive detection of NMR signals from the brain, outer volume suppression (OVS), reduced k-space sampling and proton irradiation were incorporated into the CSI sequences. The consecutive three measurements of calculated T2 image, lactate image, and pH image which were required for 3.75 h were repeated for four cycles of 1–16 h after MCA occlusion. Tissue edema and lactate accumulation in the infarcted region were gradually and consistently increased during the 15-h observation period. In contrast, severe acidosis was already detected on the first pH image (2–4.7 h after MCA occlusion); thereafter, the degree of acidosis became milder and showed no further progression. The dissociation between the time courses of the lactate accumulation and pH decrease was clearly demonstrated by the NMR metabolic images. Acid-base balance in cerebral infarction might be affected not only by lactate production but also by complicated interactions with tissue edema and some other factors. 相似文献
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