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71.
One-pot synthesis of 3-fluoro-4-(trifluoromethyl)quinolines from pentafluoropropen-2-ol and their molecular modification 总被引:1,自引:0,他引:1
Pentafluoropropen-2-ol (PFP) was prepared by the reaction of hexafluoroacetone (HFA) with Mg/TMSCl. The one-pot tandem sequential reactions of PFP via Mannich addition with aldimines followed by Friedel-Crafts cyclization and aromatization afforded the title quinolines. A variety of corresponding 3-substituted quinolines were derived from the title quinoline by nucleophilic substitution of 3-fluorine with nucleophiles. A defluorinative transformation of the 4-trifluoromethyl group of the title quinoline with hydrazine afforded pyrazoloquinoline. 相似文献
72.
Yamazoe H Uemura T Tanabe T 《Langmuir : the ACS journal of surfaces and colloids》2008,24(16):8402-8404
Fabrication of micropatterned surfaces to organize and control cell adhesion and proliferation is an indispensable technique for cell-based technologies. Although several successful strategies for creating cellular micropatterns on substrates have been demonstrated, a complex multistep process and requirements for special and expensive equipment or materials limit their prevalence as a general experimental tool. To circumvent these problems, we describe here a novel facile fabrication method for a micropatterned surface for cell patterning by utilizing the UV-induced conversion of the cell adhesive property of albumin, which is the most abundant protein in blood plasma. An albumin-coated surface was prepared by cross-linking albumin with ethylene glycol diglycidyl ether and subsequent casting of the cross-linked albumin solution on the cell culture dish. While cells did not attach to the albumin surface prepared in this way, UV exposure renders the surface cell-adhesive. Thus, surface micropatterning was achieved simply by exposing the albumin-coated surface to UV light through a mask with the desired pattern. Mouse fibroblast L929 cells were inoculated on the patterned albumin substrates, and cells attached and spread in a highly selective manner according to the UV-irradiated pattern. Although detailed investigation of the molecular-level mechanism concerning the change in cell adhesiveness of the albumin-coated surface is required, the present results would give a novel facile method for the fabrication of cell micropatterned surfaces. 相似文献
73.
Miyoko Kamigauchi Kazuko Kawanishi Makiko Sugiura Hirofumi Ohishi Toshimasa Ishida 《Helvetica chimica acta》2008,91(9):1614-1624
To prevent the precipitation reaction between glycyrrhizin ( 1 ) and berberine ( 3 ) in the decoctions of Glycyrrhiza/Coptis rhizome or Glycyrrhiza/Phellodendron bark, the presence of cyclodextrin (CD) in the mixture was proven to be effective. The preventing effect decreased in the order γ‐CD>β‐CD, and no effect was observed for α‐CD. On the other hand, the extraction degree of 1 from the natural medicine Glycyrrhia was considerably increased in the presence of γ‐CD, γ‐CD being much more effective than α‐ or β‐CD. Thus, the blocking effect of CD on the precipitate formation between 1 and 3 is suggested to be primarily dependent on the stability of the inclusion complex of the CD with 1 . To establish the structure of such a preferred inclusion complex, the interactions of 1 with β‐ and γ‐CDs were investigated by 1H‐NMR spectroscopy and molecular‐dynamics (MD) calculations. The 1H‐NMR measurements showed that the increase in solubility of 1 in H2O is dependent on the degree of its inclusion into the CD, which depends on the molecular size of the CD. The MD calculations suggested that the H‐bond interactions are sufficiently strong to form a stable [ 1 /γ‐CD] complex, in which the lipophilic rings C, D, and E of 1 are fully inserted into the molecular cavity of γ‐CD, thus forming a kind of structure covered by a hydrophilic molecular capsule, while such an interaction mode is impossible for α‐ or β‐CD. 相似文献
74.
The molecular dynamics expression of heat flux, originally derived by Irving and Kirkwood [J. Chem. Phys. 18, 817 (1950)] for pairwise potentials, is generalized in this paper for systems with many-body potentials. The original formula consists of a kinetic part and a potential part, and the latter term is found in the present study to be expressible as a summation of contributions from all the many-body potentials defined in the system. The energy transfer among a set of sites for which a many-body potential is defined is discussed and evaluated by the rate of increase in the kinetic energy of each site due to the potential, and its accumulation over all the potentials in the system is shown to make up the potential part of the generalized expression. A molecular dynamics simulation for liquid n-octane was performed to demonstrate the applicability of the new expression obtained in this study to measure the heat flux and to elucidate the contributions of inter- and intramolecular potentials to heat conduction. 相似文献
75.
Shitao Wang Dr. Tomohisa Sawada Dr. Kazuaki Ohara Prof. Dr. Kentaro Yamaguchi Prof. Dr. Makoto Fujita 《Angewandte Chemie (International ed. in English)》2016,55(6):2063-2066
Guest‐induced M18L6–M24L8 capsule–capsule conversion is reported. Both capsules are composed of PdII ethylenediamine units (M) and 1,3,5‐tris(3,5‐pyrimidyl)pyrimidine (L), and form trigonal bipyramidal (M18L6) and octahedral (M24L8) closed‐shell structures with huge hydrophobic inner spaces. The M18L6 trigonal bipyramid is converted to the M24L8 octahedron through encapsulation of large aromatic guests, with the latter capsule possessing a cavity volume three times larger than the former. Despite the dynamic properties of the capsule host, the encapsulated guests are difficult to extract and are thus isolated from the external environment. 相似文献
76.
A simple and rapid detection method of oligosaccharides using high-performance liquid chromatography with a charged aerosol detection (HPLC-CAD) was studied. The direct detection of a sialylglycopeptide (SGP) derived from egg yolk was accomplished by HPLC-CAD using an amido-silica column, and its limit of detection was 0.40 pmol [signal-to-noise ratio (S/N) = 3]. The sensitivity of this method was lower than that of the fluorescence detection; however, the method showed approximately 5 times higher sensitivity than that using the conventional UV absorbance detection. Furthermore, this method was used for the analysis of the acid hydrolysis products of SGP. Monosialo- and asialo-oligosaccharides as well as free sialic acid were detected without using fluorescent derivatization. These results indicate that the present method is a new tool for the analysis of oligosaccharides. 相似文献
77.
Mitsuhashi S Fukushima T Tomiya M Santa T Imai K Toyo'oka T 《Analytica chimica acta》2007,584(2):315-321
Kynurenine (KYN), a tryptophan metabolite, is a crucial compound for modulating neurotransmission because it can be metabolized in vivo into both quinolinic acid and kynurenic acid, which are the agonist and antagonist, respectively, of N-methyl-d-aspartate receptor. For the highly sensitive detection of KYN by high-performance liquid chromatography (HPLC), a fluorescence derivatization of KYN with a benzofurazan-type fluorogenic reagent, 4-N,N-dimethylaminosulfonyl-7-fluoro-2,1,3-benzoxadiazole (DBD-F) was investigated in the present study. KYN was derivatized with DBD-F (DBD-KYN) at 60 °C for 30 min, and separated on an octadecylsilica column with a gradient elution of the mobile phase, which consists of 0.1% formic acid in acetonitrile/methanol/water. DBD-KYN was detected fluorimetrically at 553 nm with an excitation wavelength of 431 nm. The limits of detection and quantification were approximately 0.30 pmol [signal-to-noise ratio (S/N) 3] and 1.0 pmol (S/N, 10) on column, respectively. Plasma KYN levels were successfully determined using 10 μL of rat plasma with satisfactory precision and accuracy. Intra- and inter-day precisions and accuracies were 1.7-6.8%, and −10 to 9.6%, respectively. KYN levels in plasma of male Sprague-Dawley rats (7 weeks old) were approximately 2.4 ± 0.32 μmol L−1 (n = 4). The proposed HPLC method was applied to determine KYN levels in the plasma of ketamine-treated rats—the animal model of schizophrenia. 相似文献
78.
Toshimasa Fujisawa Wilfred G. van der Wiel Leo P. Kouwenhoven 《Physica E: Low-dimensional Systems and Nanostructures》2000,7(3-4)
Coupling a quantum system to a bosonic environment always give rise to inelastic processes, which reduce the coherency of the system. We measure energy-dependent rates for inelastic tunneling processes in a fully controllable two-level system of a double quantum dot. The emission and absorption rates are well reproduced by Einstein's coefficients, which relate to the spontaneous emission rate. The inelastic tunneling rate can be comparable to the elastic tunneling rate if the boson occupation number becomes large. In the specific semiconductor double dot, the energy dependence of the inelastic rate suggests that acoustic phonons are coupled to the double dot piezoelectrically. 相似文献
79.
80.
Let be a simple undirected graph with a set V of vertices and a set E of edges. Each vertex has a demand , and a cost , where and denote the set of nonnegative integers and the set of nonnegative reals, respectively. The source location problem with vertex-connectivity requirements in a given graph G asks to find a set S of vertices minimizing such that there are at least pairwise vertex-disjoint paths from S to v for each vertex . It is known that the problem is not approximable within a ratio of , unless NP has an -time deterministic algorithm. Also, it is known that even if every vertex has a uniform cost and holds, then the problem is NP-hard, where .In this paper, we consider the problem in the case where every vertex has uniform cost. We propose a simple greedy algorithm for providing a -approximate solution to the problem in time, while we also show that there exists an instance for which it provides no better than a -approximate solution. Especially, in the case of , we give a tight analysis to show that it achieves an approximation ratio of 3. We also show the APX-hardness of the problem even restricted to . 相似文献