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31.
We consider a simplified model arising in radiation hydrodynamics which is based on the barotropic Navier–Stokes system describing the macroscopic fluid motion and a P1-approximation (see below) of the transport equation modeling the propagation of radiative intensity. We establish global-in-time existence of strong solutions for the associated Cauchy problem when initial data are close to a stable radiative equilibrium and local existence for large data with no vacuum. All our results are stated in the so-called critical Besov spaces. 相似文献
32.
Yu Shibata Haruki Nagae Shiki Sumiya Rapha?l Rochat Hayato Tsurugi Kazushi Mashima 《Chemical science》2015,6(10):5394-5399
An alkylyttrium complex supported by an N,N′-bis(2,6-diisopropylphenyl)ethylenediamido ligand, (ArNCH2CH2NAr)Y(CH2SiMe3)(THF)2 (1, Ar = 2,6-iPr2C6H3), activated an ortho-phenyl C–H bond of 2-phenylpyridine (2a) to form a (2-pyridylphenyl)yttrium complex (3a) containing a five-membered metallacycle. Subsequently, a unique C(sp2)–C(sp2) coupling of 2-phenylpyridine proceeded through a bimetallic yttrium intermediate, derived from an intramolecular shift of the yttrium center to an ortho-position of the pyridine ring in 3a, to yield a bimetallic yttrium complex (4a) bridged by two-electron reduced 6,6′-diphenyl-2,2′-bipyridyl. Aryl substituents at the ortho-position of the pyridine ring were key in order to destabilize the μ,κ2-(C,N)-pyridyldiyttrium intermediate prior to the C(sp2)–C(sp2) bond formation. 相似文献
33.
Three-dimensional models of the quantum-mechanical current density J(B) , induced in the electron cloud of the C(10)H(10) pentaprismane molecule by a magnetic field B applied along the C(5) (a C(2)) symmetry axis, orthogonal to the pentagonal (a rectangular) face, and denoted by B(‖) (B(⊥)), have been constructed. Predictions of near Hartree-Fock quality are reported for the diagonal components of magnetic tensors, magnetizability (ξ), nuclear shielding of carbon (σ(C)) and hydrogen (σ(H)), and virtual shielding at the center of mass (σ(CM)). The complicated spatial features of the induced electronic current-density field have been rationalized and compactly described via stagnation graphs that elucidate the details of its topological structure. A representation of J(B) is obtained by three-dimensional perspective plots and by planar maps visualizing phase portraits of electron flow in a series of molecular domains. Both streamline J(B) /|J(B) | and modulus |J(B) | are analyzed. These graphic tools illustrate the competition between diatropic and paratropic regimes which determine the magnitude of various components of magnetizability and magnetic shielding of hydrogen and carbon nuclei. Shielding density maps show that the differential Biot-Savart law explains magnetic shielding at hydrogen and carbon nuclei, and virtual shielding at ring and cage centers. Similarities and/or contrasting ring current effects on magnetotropicity are discussed by a comparison with triprismane C(6)H(6) and cubane C(8)H(8) . 相似文献
34.
Poiroux G Pitié M Culerrier R Ségui B Van Damme EJ Peumans WJ Bernadou J Levade T Rougé P Barre A Benoist H 《Photochemistry and photobiology》2011,87(2):370-377
Porphyrins are used as photosensitizer (PS) in photodynamic therapy in cancer treatment. Nevertheless, the development of photochemotherapy in oncology remains limited, because of the low selectivity of PSs. In order to allow PS targeting toward tumor-associated antigens, for the first time a white-light activatable porphyrin, [5-(4-(5-carboxy-1-butoxy)-phenyl)-10,15,20-tris(4-N-methyl)-pyridiniumyl)-porphyrin] (TrMPyP) was covalently linked to Morniga G (MorG), a galactose-specific binding plant lectin, known to recognize with high-affinity tumor-associated T/Tn antigen in cell-free systems. Firstly, using fluorescein-labeled MorG, the sugar-dependent binding and uptake of lectin by Tn-positive (Jurkat lymphoid leukemia) cells was demonstrated. Secondly, the TrMPyP-MorG conjugate was molecularly characterized. Cytometric and confocal microscopic analysis demonstrated that PS covalent linking to MorG preserved sugar-dependent specific binding and uptake of lectin by Jurkat leukemia lymphocytes. Thirdly, the conjugate (with a 1:1 PS:lectin ratio) that was bound and quickly (5 min) taken-up, induced greater than 90% cytotoxicity upon irradiation at 10 nm concentration, whereas the free PS was absolutely nontoxic. On the contrary, normal lymphocytes strongly resisted to the conjugate-mediated phototoxicity. Thus, owing to their binding and endocytosis capacities, plant lectins represent promising molecules for targeting of tumor glycan alteration and to enhance the efficiency of specific delivery of PSs to tumor cells. 相似文献
35.
36.
Birkel CS Kieslich G Bessas D Claudio T Branscheid R Kolb U Panthöfer M Hermann RP Tremel W 《Inorganic chemistry》2011,50(22):11807-11812
Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 M?ssbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C. 相似文献
37.
Driesschaert B Robiette R Lucaccioni F Gallez B Marchand-Brynaert J 《Chemical communications (Cambridge, England)》2011,47(16):4793-4795
We report that tetrathiatriarylmethyl (trityl) EPR probes are chiral molecules at room temperature, the two stereoisomers that differ in their helicity being configurationally stable enough to be separated and stored independently. 相似文献
38.
In this paper, we report the preparation of a series of 4(3H) quinazolinones substituted in the 2 position by a linear perfluoroalkyl-chain with RFas Cn F2n+1(n=1, 3, 5, 7).These compounds are obtained in two steps, action of F-acid chlorides on 2-aminobenzonitrile which affords the corresponding F-amides followed by cyclization of this intermediate with alkaline hydrogen peroxide. We isolated a reaction intermediate in the cyclization of N-(2-cyanophenyl) F-octanamide. All compounds were identified by the usual spectroscopic methods (IR, NMR1H, 19F, mass spectrometry). 相似文献
39.
Let p be an odd prime. For any CM number field K containing a primitive pth-root of unity, class field theory and Kummer theory put together yield the well known reflection inequality +– between the plus and minus parts of the -invariant of K. Greenbergs conjecture asserts that + is always trivial. We study here a weak form of this conjecture, namely +=– if and only if +=–=0. 相似文献
40.
Develay S Tripier R Le Baccon M Patinec V Serratrice G Handel H 《Dalton transactions (Cambridge, England : 2003)》2006,(28):3418-3426
The host-guest interaction between orthophosphate, pyrophosphate and triphosphate anions and three cyclen based macrotricyclic ligands possessing ortho- (TOC), meta- (TMC) and para-xylenyl (TPC) linkers was investigated by potentiometric measurements. The ternary species present in solution and their stability constants have been determined. The different behaviours are explained in terms of hydrogen bond formation and coulombic attraction between the organic host and the inorganic guest. The selectivity, illustrated with species distribution diagrams, is discussed. The results unambiguously showed the importance of the distance between the two cyclen cores and emphasized the increasing of the triphosphate species selectivity together with the cavity size of the ligand. A comparison of the present results with those obtained with their mono-bridged homologues is also discussed. 相似文献