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831.
Reactions of thioamide dianions, derived from secondary N-arylmethyl thioamides using BuLi, with thioformamides followed by the addition of iodine to yield 5-amino-2-thiazolines are described. Treatment of the 5-amino-2-thiazolines with iodine leads to a highly efficient production of 5-aminothiazoles. When N,N-diarylthioformamides are employed in this process, fluorescent 5-N,N-diarylthiazoles are obtained. 相似文献
832.
Combined with medium-pressure liquid chromatography (MPLC) and preparative high-pressure liquid chromatography (Prep-HPLC), high-speed countercurrent chromatography (HSCCC) was successfully applied for separation and purification of isoflavonoids from the extract of belamcanda. HSCCC separation was performed on a two-phase solvent system composed of methyl tert-butyl ether -ethyl acetate - n-butyl alcohol - acetonitrile -0.1% aqueous trifluoroacetic acid at a volume radio of 1:2:1:1:5. Semi-purified peak fractions from HSCCC separation were further purified by Prep-HPLC. Nine well-separated fractions were analyzed by HPLC-UV absorption spectrometry to determine their purities and characterized with ESI-MS(n). Except for peaksland VII (unknown) seven compounds were identified as apocynin (peak II), mangiferin (peak III), 7-O-methylmangiferin (peak IV), hispidulin (peak V), 3'-hydroxyltectoridin (peak VI), iristectorin B (peak VII), isoiridin (peak IX). 相似文献
833.
We have succeeded in the allylation of aromatic and olefinic C-H bonds of benzoic and acrylic acids using a rhenium catalyst, Re(2)(CO)(10). In this reaction, isomerization of the introduced allyl group to the 1-propenyl group did not occur. 相似文献
834.
Prof. Dr. Toshiaki Murai Kenta Morikawa Toshifumi Maruyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):13112-13119
The sequential addition of aromatic Grignard reagents to O‐alkyl thioformates proceeded to completion within 30 s to give aryl benzylic sulfanes in good yields. This reaction may begin with the nucleophilic attack of the Grignard reagent onto the carbon atom of the O‐alkyl thioformates, followed by the elimination of ROMgBr to generate aromatic thioaldehydes, which then react with a second molecule of the Grignard reagent at the sulfur atom to form arylsulfanyl benzylic Grignard reagents. To confirm the generation of aromatic thioaldehydes, the reaction between O‐alkyl thioformates and phenyl Grignard reagent was carried out in the presence of cyclopentadiene. As a result, hetero‐Diels–Alder adducts of the thioaldehyde and the diene were formed. The treatment of a mixture of the thioformate and phenyl Grignard reagent with iodine gave 1,2‐bis(phenylsulfanyl)‐1,2‐diphenyl ethane as a product, which indicated the formation of arylsulfanyl benzylic Grignard reagents in the reaction mixture. When electrophiles were added to the Grignard reagents that were generated in situ, four‐component coupling products, that is, O‐alkyl thioformates, two molecules of Grignard reagents, and electrophiles, were obtained in moderate‐to‐good yields. The use of silyl chloride or allylic bromides gave the adducts within 5 min, whereas the reaction with benzylic halides required more than 30 min. The addition to carbonyl compounds was complete within 1 min and the use of lithium bromide as an additive enhanced the yields of the four‐component coupling products. Finally, oxiranes and imines also participated in the coupling reaction. 相似文献
835.
We consider the problem of a one-dimensional elastic filament immersed in a two-dimensional steady Stokes fluid. Immersed boundary problems in which a thin elastic structure interacts with a surrounding fluid are prevalent in science and engineering, a class of problems for which Peskin has made pioneering contributions. Using boundary integrals, we first reduce the fluid equations to an evolution equation solely for the immersed filament configuration. We then establish local well-posedness for this equation with initial data in low-regularity Hölder spaces. This is accomplished by first extracting the principal linear evolution by a small-scale decomposition and then establishing precise smoothing estimates on the nonlinear remainder. Higher regularity of these solutions is established via commutator estimates with error terms generated by an explicit class of integral kernels. Furthermore, we show that the set of equilibria consists of uniformly parametrized circles and prove nonlinear stability of these equilibria with explicit exponential decay estimates, the optimality of which we verify numerically. Finally, we identify a quantity that respects the symmetries of the problem and controls global-in-time behavior of the system. © 2018 Wiley Periodicals, Inc. 相似文献
836.
Dibenzophosphole oxides were obtained from secondary hydrophosphine oxides with a biphenyl group by dehydrogenation via phosphine-hydrogen and carbon-hydrogen bond cleavage in the presence of a catalytic amount of palladium(II) acetate, Pd(OAc)(2). By using this reaction, a ladder-type dibenzophosphole oxide could also be synthesized by double intramolecular dehydrogenative cyclization. 相似文献
837.
Wang H Koshi Y Minato D Nonaka H Kiyonaka S Mori Y Tsukiji S Hamachi I 《Journal of the American Chemical Society》2011,133(31):12220-12228
Catalysts hold promise as tools for chemical protein modification. However, the application of catalysts or catalyst-mediated reactions to proteins has only recently begun to be addressed, mainly in in vitro systems. By radically improving the affinity-guided DMAP (4-dimethylaminopyridine) (AGD) catalysts that we previously reported (Koshi, Y.; Nakata, E.; Miyagawa, M.; Tsukiji, S.; Ogawa, T.; Hamachi, I. J. Am. Chem. Soc. 2008, 130, 245.), here we have developed a new organocatalyst-based approach that allows specific chemical acylation of a receptor protein on the surface of live cells. The catalysts consist of a set of 'multivalent' DMAP groups (the acyl transfer catalyst) fused to a ligand specific to the target protein. It was clearly demonstrated by in vitro experiments that the catalyst multivalency enables remarkable enhancement of protein acylation efficiency in the labeling of three different proteins: congerin II, a Src homology 2 (SH2) domain, and FKBP12. Using a multivalent AGD catalyst and optimized acyl donors containing a chosen probe, we successfully achieved selective chemical labeling of bradykinin B(2) receptor (B(2)R), a G-protein coupled receptor, on the live cell-surface. Furthermore, the present tool allowed us to construct a membrane protein (B(2)R)-based fluorescent biosensor, the fluorescence of which is enhanced (tuned on) in response to the antagonist ligand binding. The biosensor should be applicable to rapid and quantitative screening and assay of potent drug candidates in the cellular context. The design concept of the affinity-guided, multivalent catalysts should facilitate further development of diverse catalyst-based protein modification tools, providing new opportunities for organic chemistry in biological research. 相似文献
838.
We report quasi-ballistic conduction in single-walled carbon nanotube (SWNT) fibers at room temperature, with a measured mean free path of 1.0–2.6 μm. The dynamic submersion of vertical SWNT fibers into liquid mercury (Hg) electrode shows plateaus and steps indicative of quasi-ballistic electron transport. This response is described with a newly developed network model that uses surface impurities to simplify the parallel conducting channels. The quasi-ballistic SWNT fibers exhibit a resistance per unit length of 2.5–6.5 kΩ/μm and a mean free path exceeding 1 μm, a length longer than typical via dimensions in existing Si-chip technologies. These results highlight that SWNT fiber conductivity can be enhanced by increasing the metallic to semiconducting SWNT ratio and reducing the surface impurities. 相似文献
839.
Cheng-Jun Xia Toshiki Maruyama Ang Li Bao Yuan Sun Wen-Hui Long Ying-Xun Zhang 《理论物理通讯》2022,74(9):95303
In the framework of the Thomas-Fermi approximation, we systematically study the EOSs and microscopic structures of neutron star matter in a vast density range with nb ≈ 10−10-2 fm−3, where various covariant density functionals are adopted, i.e., those with nonlinear self couplings (NL3, PK1, TM1, GM1, MTVTC) and density-dependent couplings (DD-LZ1, DDME-X, PKDD, DD-ME2, DD2, TW99). It is found that the EOSs generally coincide with each other at nb ≲ 10−4 fm−3 and 0.1 fm−3 ≲ nb ≲ 0.3 fm−3, while in other density regions they are sensitive to the effective interactions between nucleons. By adopting functionals with a larger slope of symmetry energy L, the curvature parameter Ksym and neutron drip density generally increases, while the droplet size, proton number of nucleus, core-crust transition density, and onset density of non-spherical nuclei, decrease. All functionals predict neutron stars with maximum masses exceeding the two-solar-mass limit, while those of DD2, DD-LZ1, DD-ME2, and DDME-X predict optimum neutron star radii according to the observational constraints. Nevertheless, the corresponding skewness coefficients J are much larger than expected, while only the functionals MTVTC and TW99 meet the start-of-art constraints on J. More accurate measurements on the radius of PSR J0740 + 6620 and the maximum mass of neutron stars are thus essential to identify the functional that satisfies all constraints from nuclear physics and astrophysical observations. Approximate linear correlations between neutron stars' radii at M = 1.4M⊙ and 2M⊙, the slope L and curvature parameter Ksym of symmetry energy are observed as well, which are mainly attributed to the curvature-slope correlations in the functionals adopted here. The results presented here are applicable for investigations of the structures and evolutions of compact stars in a unified manner. 相似文献
840.
Experimental results and analytical results are presented on chaotic vibrations of a shallow double-curved shell-panel subjected to gravity and periodic excitation. Modal interactions in the chaotic responses are discussed. The shell-panel with square boundary is simply supported for deflection. In-plane displacement at the boundary is elastically constrained. In the experiment, time histories of the chaotic responses at the spatial multiple positions of the shell-panel are measured for the inspection of modal interaction. In the analysis, the shallow shell-panel is assumed to have constant curvatures along to orthogonal directions and geometric initial imperfection. The Donnell-Mushtari-Vlasov type equation is used as governing equation with lateral inertia force. Assuming deflection with multiple modes of vibration, the governing equation is reduced to a set of nonlinear ordinary differential equations by the Bubnov-Galerkin procedure. Chaotic responses are integrated numerically. The chaotic responses, which are obtained by the experiment and the analysis, are inspected with the Fourier spectra, the Poincaré projections, the maximum Lyapunov exponents and the Lyapunov dimension. Contribution of modes of vibration to the chaotic responses is analyzed by the principal component analysis, i.e., Karhunen-Loève transformation. 相似文献