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101.
Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems
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Dawei Zhang Dr. Bastien Chatelet Eloisa Serrano Dr. Olivier Perraud Dr. Jean‐Pierre Dutasta Prof. Dr. Vincent Robert Prof. Dr. Alexandre Martinez 《Chemphyschem》2015,16(14):2931-2935
The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions. 相似文献
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Ganesh P. Sanganwar Ram B. Gupta Alexandre Ermoline James V. Scicolone Rajesh N. Dave 《Journal of nanoparticle research》2009,11(2):405-419
Due to the increased use of nanocomposites, mixing at nanoscale has become important. Current mixing techniques can be classified
into: (a) dry mixing (mechanical mixing), (b) wet mixing, and (c) simultaneous production of mixed nanoparticles (when possible).
Dry mixing is in general not effective in achieving desired mixing at nanoscale, whereas wet mixing suffers from different
disadvantages like nanomaterial of interest should be insoluble, has to wet the liquid, and involves additional steps of filtration
and drying. This paper examines the use of pressurized carbon dioxide having high density and low viscosity to replace the
liquids (e.g., n-hexane, toluene). Ultrasound is applied to the suspension of nanopowders in gaseous and supercritical carbon dioxide where
high impact collisions during sonication help mixing and the final mixture is obtained by simple depressurization. The method
is tested for binary mixture of alumina/silica, silica/titania, MWNT (multiwalled carbon nanotubes)/silica, and MWNT/titania.
The effects of sonication intensity and pressure on the degree of mixing are studied. Comparative study is also done with
liquid n-hexane as a mixing media. Quantitative characterization (e.g., mean composition standard deviation, intensity of segregation)
of mixing of alumina/silica and silica/titania is done with energy-dispersive X-ray spectroscopy, and that of MWNT/silica
and MWNT/titania is done using field-emission scanning electron microscopy and day-light illumination spectrophotometry. Results
show that mixing in carbon dioxide at higher ultrasound amplitudes is as good as in liquid n-hexane, and the final mixed product does not contain any residual media as in the case of liquid n-hexane. 相似文献
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Hawking radiation is studied for arbitrary scalars, fermions and spin-1 bosons, using a tunneling approach, to every order in ? but ignoring back-reaction effects. It is shown that the additional quantum terms yield no new contribution to the Hawking temperature. Indeed, it is found that the limit of small ? in the standard quantum WKB approximation is replaced by the near-horizon limit in the gravitational WKB approach. 相似文献
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Larisa Petrovna Demyanova Viaseslav S. Rimkevich Alexandre S. Buynovskiy 《Journal of fluorine chemistry》2011,132(12):1067-1071
A method of elaboration of nanometric amorphous silica is proposed using a rational processing of quartz-based ores with the help of a fluorination method. The different steps of the process are described, including the kinetics of the interaction mechanism of ammonium bifluoride with the initial raw materials, the sublimation of ammonium fluorosilicate and the formation of nanometric amorphous silica. Rate constants and activation energy of the chemical reactions are calculated. 相似文献
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