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61.
62.
Near-infrared fluorescent silica-porphyrin hybrid nanotubes (HNTs) were successfully synthesized by π-π stacking, electrostatic interaction and a sol-gel reaction. The HNTs-labeled macrophages were detected in vivo, and the minimum detectable number of cells was 200. Furthermore, the biodistribution of HNTs-labeled macrophages was tracked by fluorescence imaging. 相似文献
63.
Takahashi K Hasegawa Y Sakamoto R Nishikawa M Kume S Nishibori E Nishihara H 《Inorganic chemistry》2012,51(9):5188-5198
We previously reported that an Fe(II) complex ligated by two (Z)-2,6-di(1H-pyrazol-1-yl)-4-styrylpyridine ligands (Z-H) presented a solid state ligand-driven light-induced spin change (LD-LISC) upon one-way Z-to-E photoisomerization, although modulation of the magnetism was trivial at ambient temperatures (Chem. Commun.2011, 47, 6846). Here, we report the synthesis of new derivatives of Z-H, Z-CN and Z-NO(2), in which electron-withdrawing cyano and nitro substituents are introduced at the 4-position of the styryl group to attain a more profound photomagnetism at ambient temperatures. Z-CN and Z-NO(2) undergo quantitative one-way Z-to-E photochromism upon excitation of the charge transfer band both in acetonitrile and in the solid state, similar to the behavior observed for Z-H. In solution, these substituents stabilized the low-spin (LS) states of Z-CN and Z-NO(2), and the behavior was quantitatively analyzed according to the Evans equation. The photomagnetic properties in the solid state, on the other hand, cannot be explained in terms of the substituent effect alone. Z-CN displayed photomagnetic properties almost identical to those of Z-H. Z-CN preferred the high-spin (HS) state at all temperatures tested, whereas photoirradiated Z-CN yielded a lower χ(M)T at ambient temperatures. The behavior of Z-NO(2) was counterintuitive, and the material displayed surprising photomagnetic properties in the solid state. Z-NO(2) occupied the LS state at low temperatures and underwent thermal spin crossover (SCO) with a T(1/2) of about 270 K. The photoirradiated Z-NO(2) displayed a higher value of χ(M)T and the modulation of χ(M)T exceeded that of Z-H or Z-CN. Z-NO(2)·acetone, in which acetone molecules were incorporated into the crystal lattice, further stabilized the LS state (T(1/2) > 300 K), thereby promoting large modulations of the χ(M)T values (87% at 273 K and 64% at 300 K) upon Z-to-E photoisomerization. Single crystal X-ray structure analysis revealed that structural factors played a vital role in the photomagnetic properties in the solid state. Z-H and Z-CN favored intermolecular π-π stacking among the ligand molecules. The coordination sphere around the Fe(II) nucleus was distorted, which stabilized the HS state. In contrast, Z-NO(2)·acetone was liberated from such intermolecular π-π stacking and coordination distortion, resulting in the stabilization of the LS state. 相似文献
64.
Kanno M Nakamura K Kanai E Hoki K Kono H Tanaka M 《The journal of physical chemistry. A》2012,116(9):2177-2183
There have been a growing number of articles that report dramatic improvements in the experimental performance of chemical reactions by microwave irradiation compared to that under conventional heating conditions. We theoretically examined whether nonthermal microwave effects on intramolecular reactions exist or not, in particular, on Newman-Kwart rearrangements and intramolecular Diels-Alder reactions. The reaction rates of the former calculated by the transition state theory, which consider only the thermal effects of microwaves, agree quantitatively with experimental data, and thus, the increases in reaction rates can be ascribed to dielectric heating of the solvent by microwaves. In contrast, for the latter, the temperature dependence of reaction rates can be explained qualitatively by thermal effects but the possibility of nonthermal effects still remains regardless of whether competitive processes are present or not. The effective intramolecular potential energy surface in the presence of a microwave field suggests that nonthermal effects arising from potential distortion are vanishingly small in intramolecular reactions. It is useful in the elucidation of the reaction mechanisms of microwave synthesis to apply the present theoretical approach with reference to the experiments where thermal and nonthermal effects are separated by screening microwave fields. 相似文献
65.
Michihiro Hirayama 《Journal of statistical physics》2005,118(1-2):103-118
Consider basic set for Axiom A diffeomorphism on compact surface.We derive second variational formulae for the dimension spectra of equilibrium state on the basic set with respect to the perturbations of both the potential and\break the dynamical system.In particular we obtain a second variational formula for the Hausdorff dimension of the basic set.These results will find their use in the study of a quadratic extremal problem for multifrcatal analysis. 相似文献
66.
67.
Electrical conductivity and Seebeck coefficient for the Bi2−xYxRu2O7 pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y2Ru2O7 indicated the thermal activation-type behavior of the holes, while that for the Bi2−xYxRu2O7 with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t2g and O2p orbitals, but the mixing of Bi6s, 6p states at EF may not be ruled out. The thermoelectric power factors for the Bi2−xYxRu2O7 with x=1.5 and 2.0 were lower than 10−5 W m−1 K−2 and those with x=0.0,0.5,1.0 were around 1-3×10−5 W m−1 K−2. 相似文献
68.
The modulated point vortex model associated with the Hasegawa-Mima equation is used to study the dynamical behavior of drift wave vortices in a bounded region. When a circle is taken as the boundary of the region, the potential for the vortices can be constructed with the aid of the circle theorem which replaces the boundary by the mirror images of the vortices inside the circle and ensures that the potential for the vortices is zero on the boundary. Periodic, aperiodic and chaotic motions are realized depending on the number of vortices and the magnitude of the value of the diamagnetic drift which breaks the rotational symmetry and has a tendency to drive vortices into chaotic motion. 相似文献
69.
70.