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101.
102.
We consider a single free spin- 1 / 2 particle. The reduced density matrix for its spin is not covariant under Lorentz transformations. The spin entropy is not a relativistic scalar and has no invariant meaning. 相似文献
103.
In situ generation of CuH ligated by Takasago's new nonracemic ligand, DTBM-SEGPHOS, leads to an especially reactive reagent capable of effecting asymmetric hydrosilylation of heteroaromatic (H) ketones under very mild conditions. PMHS serves as an inexpensive source of hydride. Substrate-to-ligand ratios on the order of 2000:1 are employed. [reaction: see text] 相似文献
104.
105.
Asymmetric hydrosilylation of aryl ketones catalyzed by copper hydride complexed by nonracemic biphenyl bis-phosphine ligands 总被引:1,自引:0,他引:1
Lipshutz BH Noson K Chrisman W Lower A 《Journal of the American Chemical Society》2003,125(29):8779-8789
When complexed by selected ligands in either the BIPHEP or the SEGPHOS series, CuH is an extremely reactive catalyst capable of effecting asymmetric hydrosilylations of aromatic ketones at temperatures between -50 and -78 degrees C. Inexpensive silanes serve as stoichiometric sources of hydride. Substrate-to-ligand ratios exceeding 100000:1 have been documented. The level of induction is usually in the >90% ee category. The nature of the reagent has been investigated using spectroscopic and chemical means, although its composition remains unclear. 相似文献
106.
We developed an intelligent polymerized crystalline colloidal array (IPCCA) photonic crystal sensing material which reversibly
senses the organophosphate compound methyl paraoxon at micromolar concentrations in aqueous solutions. A periodic array of
colloidal particles is embedded in a poly-2-hydroxyethylacrylate hydrogel. The particle lattice spacing is such that the array
Bragg-diffracts visible light. We utilize a bimodular sensing approach in which the enzyme organophosphorus hydrolase (OPH)
catalyzes the hydrolysis of methyl paraoxon at basic pH, producing p-nitrophenolate, dimethylphosphate, and two protons. The protons lower the pH and create a steady-state pH gradient. Protonation
of the phenolates attached to the hydrogel makes the free energy of mixing of the hydrogel less favorable, which causes the
hydrogel to shrink. The IPCCA’s lattice constant decreases, which blueshifts the diffracted light. The magnitude of the steady-state
diffraction blueshift is proportional to the concentration of methyl paraoxon. The current detection limit is 0.2 μmol methyl
paraoxon per liter. 相似文献
107.
We study the connection between the phase and the amplitude of the wave function and the conditions under which this relationship exists. For this we use the model of particle in a box. We have shown that the amplitude can be calculated from the phase and vice versa if the log analytical uncertainty relations are satisfied. 相似文献
108.
Acoustic performance characteristics of catalysts in the exhaust system are important in the development of predictive tools for the breathing system of internal combustion engines. To understand the wave attenuation behavior of these elements with firing engines, dynamometer experiments are conducted on a 3.0L V-6 engine with two different exhaust systems: one with the catalysts on the cross-over pipe, and the other that replaces the catalysts with equal length straight pipes. The instantaneous crank-angle resolved pressure data are acquired at wide open throttle and 500 rpm intervals over the operating range of the engine (from 1000 to 5000 rpm) at various locations in both exhaust systems. The effect of the catalyst is then isolated and discussed in terms of insertion loss at critical locations in the exhaust system. The analysis is presented both in terms of time-domain and order-domain. The predictive capability of a finite-difference based time-domain nonlinear approach is also demonstrated as applied to large amplitude waves in the exhaust system of firing engines. 相似文献
109.
Asher Yahalom 《Entropy (Basel, Switzerland)》2022,24(12)
An electron moving at velocities much lower that the speed of light with a spin, is described by a wave function which is a solution of Pauli’s equation. It has been demonstrated that this system can be viewed as a vortical fluid which has remarkable similarities but also differences with classical ideal flows. In this respect, it was shown that the internal energy of the Pauli fluid can be interpreted, to some degree, as Fisher Information. In previous work on this subject, electromagnetic fields which are represented by a vector potential were ignored, here we remove this limitation and study the system under general electromagnetic interaction. 相似文献
110.
Mikhonin AV Bykov SV Myshakina NS Asher SA 《The journal of physical chemistry. B》2006,110(4):1928-1943
We used UV resonance Raman (UVRR) spectroscopy to quantitatively correlate the peptide bond AmIII3 frequency to its Psi Ramachandran angle and to the number and types of amide hydrogen bonds at different temperatures. This information allows us to develop a family of relationships to directly estimate the Psi Ramachandran angle from measured UVRR AmIII3 frequencies for peptide bonds (PBs) with known hydrogen bonding (HB). These relationships ignore the more modest Phi Ramachandran angle dependence and allow determination of the Psi angle with a standard error of +/-8 degrees , if the HB state of a PB is known. This is normally the case if a known secondary structure motif is studied. Further, if the HB state of a PB in water is unknown, the extreme alterations in such a state could additionally bias the Psi angle by +/-6 degrees . The resulting ability to measure Psi spectroscopically will enable new incisive protein conformational studies, especially in the field of protein folding. This is because any attempt to understand reaction mechanisms requires elucidation of the relevant reaction coordinate(s). The Psi angle is precisely the reaction coordinate that determines secondary structure changes. As shown elsewhere (Mikhonin et al. J. Am. Chem. Soc. 2005, 127, 7712), this correlation can be used to determine portions of the energy landscape along the Psi reaction coordinate. 相似文献