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111.
The problem of homoaromaticity in mono-, di- and polyfluorinated- homotropylium cations is addressed by the B3LYP/6-311++G** DFT method. The energetic, structural and magnetic criteria are used for this purpose. They convincingly show that the ground state equilibrium species are aromatic, or in other words that the homoaromaticity is preserved by the (poly)fluorination. In contrast, a considerable decrease in the aromatic stabilization is observed in the transition structures (TS). According to the NICS(0) index, they vary form strongly antiaromatic, via weakly and non-aromatic to slightly aromatic transition states. However, the hierarchy of the aromaticity in fluorinated homotropylium ions predicted by NICS(0) is completely unrelated to that obtained by using the energy criterion assuming a kinetic definition of aromaticity. On the other hand the latter is closely related to geometric parameters of the equilibrium and transition structures. 相似文献
112.
Michaël Ternon 《Tetrahedron》2004,60(39):8721-8728
FRET based systems are some of the best methods available to detect and monitor proteolytic activity. To enhance fluorescent signals and hence assay sensitivity, two different systems were developed using two different dendrimeric constructs. In the first case, a triple branched dendrimer bearing three dansyl groups was used to enhance assay sensitivity and showed a significant enhancement of fluorescence following enzymatic cleavage. In another example, a tris-fluorescein probe, that undergoes self-quenching, was utilized in a combinatorial library synthesis to map the substrate specificity of proteases. 相似文献
113.
A porphyrazine based supramolecule with a nonanuclear structure has been prepared by the ready coordination of pyridine donor sites in octakis(4-pyridoxyethylthio)porphyrazinatomagnesium with vanadyl bis(acetylacetonate) and characterized by EPR spectroscopy. 相似文献
114.
115.
Inés CarrancoJosé Luis D?&#x;az Oscar JiménezRodolfo Lavilla 《Tetrahedron letters》2003,44(46):8449-8452
The Lewis acid-catalyzed interaction of dihydropyridines with ethyl glyoxalate and primary aliphatic amines yields, depending on the reaction conditions, bicyclic aminals or rearranged tetrahydropyridines in one-pot multicomponent reactions. 相似文献
116.
Gravimetric measurements of thermodesorption of n-hexane and n-heptane were performed under quasi-equilibrium conditions. Differential thermodesorption profiles for ZSM-5 and ZSM-11 showed two peaks, but for Y zeolites, only one thermodesorption peak was observed. A model function, derived from the Langmiur adsorption model, was fitted to the experimental data, and the model parameters (the adsorption entropy and enthalpy) were estimated. The two-step desorption profiles observed for ZSM-5 and ZSM-11 were attributed to the commensurate freezing effect, i.e. a transition in the adsorbed phase resulting in ordering of the adsorbed molecules in the zeolite channels. The results observed for ZSM-11 indicate that the zigzag channels typical for ZSM-5 micropore system are not necessary for this transition to occur. 相似文献
117.
R. Ochoa-Land?&#x;n M. Flores-Acosta R. Ram?&#x;rez-Bon H. Arizpe-Chávez F.F. Castillón-Barraza 《Journal of Physics and Chemistry of Solids》2003,64(11):2245-2251
CdS clusters were synthesized in A type zeolite by reaction in alkaline aqueous solution at temperatures from 30 to 70 °C. The optical properties of the samples were studied by diffuse reflectance and photoluminescence spectroscopy. Their crystalline structure and morphology were studied by X-ray diffraction and by transmission and scanning electron microscopy. We found that at lower temperatures the CdS clusters are encapsulated in the zeolite cages. We compared the properties of these clusters with those encapsulated in the cages of zeolites X and Y, prepared by similar methods. CdS clusters smaller than the CdS exciton diameter are also formed outside the cages in the zeolite matrix. The size of these clusters increases with temperature producing a red-shift of the absorption edge in the optical absorption spectra. 相似文献
118.
Mihai Tib?r 《Topology》2003,42(3):629-639
We show that the complex link of a large class of space germs (X,x0) is characterized by its “simplicity”, among the Milnor fibres of functions with isolated singularity on X. This amounts to the minimality of the Milnor number, whenever this number is defined. Such a phenomenon has been first pointed out in case (X,x0) is an isolated hypersurface singularity, by Teissier (Cycles évanescents, sections planes et conditions de Whitney, in: Singularités à Cargèse 1972, Asterisque, Nos. 7 et 8, Soc. Math. France, Paris, 1973, pp. 285-362). 相似文献
119.
Ruili?ZhangEmail author Jianming?Dai Wenhai?Song Yongqing?Ma Jie?Yang Yuping?Sun 《中国科学G辑(英文版)》2004,47(1):113-120
It is helpful to study the photo-induced effect in the perovskite manganites not only for elucidating the mechanism of colossal
magnetoresistance (CMR) effect but also for potential applications in technology. The laser-induced effect in the Co doping
layered perovskite manganites La1.2Sr1.8Mn1.8Co0.2O7, is studied in this paper and the obtained results are also compared with that gained in the Nd-doping manganites with cubic
perovskite structure. 相似文献
120.
The effect of hydrostatic pressure on the ferroelectric phase transition temperature in [NH2(CH3)2]3[Sb2Cl9] (DMACA) has been studied by electric permittivity measurements at pressures up to 400 MPa. The pressure-temperature phase diagram is given. The phase transition temperature (Tc) increases with increasing pressure up to 150 MPa, passes through a maximum and then decreases with a further increase of pressure. The unexpected nonlinear decrease in Tc with pressure increasing above 150 MPa suggests that the mechanism of ferroelectric phase transition in DMACA is different from hitherto assumed. 相似文献