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186.
Iwao Hosokawa 《Journal of statistical physics》1976,15(2):87-104
It is shown that the so-called statistical theory of turbulence, which can be exactly incorporated by the Hopf functional equation, is imperfect in that it fails to ensure the irreversible approach to a unique ultimate steady state of turbulence (for a steady boundary condition) expected from observation; and that this imperfection is removed if a stochastic random-force term is added into the Navier-Stokes equation. The ensemble mechanics for the random-forced Navier-Stokes flow is formulated by taking into account the natural random force, which has usually been neglected in the Navier-Stokes equation. 相似文献
187.
Imahori T Ojima H Yoshimura Y Takahata H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(34):10762-10771
An interesting acceleration effect of an allylic hydroxy group on ring-closing enyne metathesis has been found. Ring-closing enyne metathesis of terminal alkynes possessing an allylic hydroxy group proceeded smoothly without the ethylene atmosphere generally necessary to promote the reaction. The synthesis of (+)-isofagomine with the aid of this efficient reaction has been demonstrated. Mechanistic studies of the acceleration effect were also carried out. Results of NMR studies suggested that the reaction proceeded via an "ene-then-yne" pathway. Kinetic studies indicated switching of the rate-determining step as a consequence of the presence of an allylic hydroxy group. These results suggest acceleration of the reentry step of Ru-carbene species by the allylic hydroxy group. 相似文献
188.
Fumihiko Ozaki Dr. Shunsuke Tanaka YoungHyun Choi Dr. Wataru Osada Kozo Mukai Dr. Mitsuaki Kawamura Dr. Masahiro Fukuda Dr. Masafumi Horio Prof. Dr. Takanori Koitaya Prof. Dr. Susumu Yamamoto Prof. Dr. Iwao Matsuda Prof. Dr. Taisuke Ozaki Prof. Dr. Jun Yoshinobu 《Chemphyschem》2023,24(22):e202300477
Sulfur vacancy on an MoS2 basal plane plays a crucial role in device performance and catalytic activity; thus, an understanding of the electronic states of sulfur vacancies is still an important issue. We investigate the electronic states on an MoS2 basal plane by ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory calculations while heating the system in hydrogen. The AP-XPS results show a decrease in the intensity ratio of S 2p to Mo 3d, indicating that sulfur vacancies are formed. Furthermore, low-energy components are observed in Mo 3d and S 2p spectra. To understand the changes in the electronic states induced by sulfur vacancy formation at the atomic scale, we calculate the core-level binding energies for the model vacancy surfaces. The calculated shifts for Mo 3d and S 2p with the formation of sulfur vacancy are consistent with the experimentally observed binding energy shifts. Mulliken charge analysis indicates that this is caused by an increase in the electronic density associated with the Mo and S atoms around the sulfur vacancy as compared to the pristine surface. The present investigation provides a guideline for sulfur vacancy engineering. 相似文献
189.
The present study describes a simultaneous and highly reproducible large-scale synthesis of six (and more) colors of size-homogeneous and highly luminescent CdSe quantum dots in a single reaction, controlled by a slow-increasing temperature gradient. The described protocol allows a precise control and a synchronized isolation of aliquots of CdSe nanocrystals with defined sizes, avoiding disturbance of the growth of nanocrystals (existing in the reaction mixture) to the isolation of the next aliquot. The obtained quantum dot fractions are of high quality (in 95% size-homogeneous) and have sharp photoluminescence spectra (fwhm approximately 30 nm), quantum yields of 45-70% (in organic solvent), and a lack of aggregation in organic solvents. The method is environmentally friendly as it ensures almost complete utilization of the precursors and productive yield approximately 95%. 相似文献
190.
Sugimoto I Mitsui K Nakamura M Seyama M 《Analytical and bioanalytical chemistry》2011,399(5):1891-1899
The gas sorption capacities of sputtered carbonaceous films are evaluated with quartz crystal resonators. These films are
sensitive to 20 ppm organic vapors and exhibit structure-dependent responses. Films derived from synthetic polymers are hydrophobic,
whereas films derived from biomaterials are amphiphilic or hydrophilic. Polyethylene (PE) film has an extremely high sorption
capacity for a wide range of vapors. Transient sorption responses are investigated using a humidified carrier by employing
carboxylic acid esters, whose aliphatic groups are systematically changed. Small esters with a higher affinity to water induce negative U-shaped responses from amphiphilic films derived from biomaterials.
On the other hand, polymeric films exhibit positive exponential response curves. Even if the concentrations are decreased,
the response intensities are enhanced with the incremental expansion of carbon chains of aliphatic groups. Only fluoropolymer
film shows the opposite tendency. The modeling of quantitative structure property relationships has indicated that the sorption
capacities of the PE film to the carboxylic acid esters are fundamentally governed by electrostatic interactions. The intermolecular
attractive forces are basically attributable to interactions between the positively polarized sites in esters and the negatively
polarized/charged sites in PE film. 相似文献