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81.
This work aims at elucidating the mechanism of solvation of a radical ion pair (RIP) in a micro‐heterogeneous binary solvent mixture using magnetically affected reaction yield (MARY) spectroscopy. For the exciplex‐forming 9,10‐dimethylanthracene/N,N‐dimethylaniline system a comparative, composition‐dependent MARY line‐broadening study is undertaken in a heterogeneous (toluene/dimethylsulfoxide) and a quasi‐homogenous (propyl acetate/butyronitrile) solvent mixture. The half‐saturation field extrapolated to zero‐quencher concentration, B1/2, and the self‐exchange rate constants are analyzed in the light of solvent dynamical properties of the mixtures and a dielectric continuum solvation model. The dependence of B1/2 on the solvent composition is explained by cluster formation giving rise to shortened RIP lifetimes. The results are in qualitative agreement with the continuum solvation model suggesting that it could serve as a theoretical basis for quantitative modeling. 相似文献
82.
《Analytical letters》2012,45(13):2485-2496
Abstract Blood samples were assayed for PSA values immediately after sampled or by standing for an assigned period. Variation of the free‐ (f), total‐ (t) values, and the free to total (f/t) ratios were determined. Mathematical models were used to interpret the phenomena of deviation. Smaller values of PSA values changed randomly with time and temperature of standings, resulting in varying f/t ratios, while larger initial PSA values were relatively unaffected to any significant extent. Model interpreted that the changes of PSA values might be caused by higher temperature and time of standings, and conformational participation was also possible. 相似文献
83.
The work continues and develops authors’ previous investigation of stability in the small for a two-layer system of inhomogeneous compressible fluids in the uniform gravity field. Here we present a solution of a similar problem in the case of arbitrary non-uniform potential gravity field. The equilibrium stratification of both density and elastic properties of the fluids is supposed arbitrary, as well as the shape of open on top reservoir filled by the fluids. The problem of stability of equilibrium is analyzed as the corresponding problem for the non-linearly elastic bodies, basing on the static energy criterion with regard for the boundary conditions at all parts of the boundary. The crucial element of the analysis is conversion of the quadratic functional of second variation of total potential energy of the system into a “canonical” form that enables to determine its sign. Making use of this canonical form, we obtain almost coinciding with each other necessary and sufficient conditions for stability (those being valid also for an arbitrary number of layers). 相似文献
84.
Eugene Kazantsev 《国际流体数值方法杂志》2011,65(10):1231-1259
A variational data assimilation technique applied to the identification of the optimal discretization of interpolation operators and derivatives in the nodes adjacent to the boundary of the domain is discussed in frames of the linear shallow water model. The advantage of controlling the discretization of operators near the boundary rather than boundary conditions is shown. Assimilating data that have been produced by the same model on a finer grid, in a model on a coarse grid, we have shown that optimal discretization allows us to correct such errors of the numerical scheme as under‐resolved boundary layer and wrong wave velocity. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
85.
In graphene in the presence of strain the elasticity theory metric naturally appears. However, this is not the one experienced by fermionic quasiparticles. Fermions propagate in curved space, whose metric is defined by expansion of the effective Hamiltonian near the topologically protected Fermi point. We discuss relation between both types of metric for different parametrizations of graphene surface. Next, we extend our consideration to the case, when the dislocations are present. We consider the situation, when the deformation is described by elasticity theory and calculate both torsion and emergent magnetic field carried by the dislocation. The dislocation carries singular torsion in addition to the quantized flux of emergent magnetic field. Both may be observed in the scattering of quasiparticles on the dislocation. Emergent magnetic field flux manifests itself in the Aharonov–Bohm effect while the torsion singularity results in Stodolsky effect. 相似文献
86.
A detailed study of the various cosmological aspects in massive gravity theory has been presented in the present work. For the homogeneous and isotropic FLRW model, the deceleration parameter has been evaluated, and, it has been examined whether there is any transition from deceleration to acceleration in recent past, or not. With the proper choice of the free parameters, it has been shown that the massive gravity theory is equivalent to Einstein gravity with a modified Newtonian gravitational constant together with a negative cosmological constant. Also, in this context, it has been examined whether the emergent scenario is possible, or not, in massive gravity theory. Finally, we have done a cosmographic analysis in massive gravity theory. 相似文献
87.
We introduce the natural lift of spacetime diffeomorphisms for conformal gravity and discuss the physical equivalence between the natural and gauge natural structure of the theory. Accordingly, we argue that conformal transformations must be introduced as gauge transformations (affecting fields but not spacetime point) and then discuss special structures implied by the splitting of the conformal group. 相似文献
88.
89.
Nobumasa Kamigata 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):667-678
Abstract The synthesis and stereochemistry of tricoordinated optically active selenium and tellurium compounds are described. Telluronium salts, telluronium imides, and seleninic acids were prepared and optically resolved by fractional recrystallization of diastereomeric mixtures or by chromatography using a chiral column of racemic mixtures. Diphenyl dichalcogenides also were optically resolved by chiral crystallization. Their absolute configurations were determined or estimated based on X-ray crystallographic analysis, specific rotations, and circular dichroism spectra. The kinetic studies and the mechanism for the racemization were also studied. 相似文献
90.
Five new optically active aromatic poly(amide-imide)s (PAIs) 5a–e were prepared from a direct polycondensation reaction of a new diacid of N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic)-bis-L-isoleucine 3 with various aromatic diamines 4a–e in a medium consisting of triphenyl phosphite (TPP), calcium chloride (CaCl2), pyridine (Py) and N-methyl-2-pyrrolidone (NMP). The polycondensation reaction produced a series of novel poly(amid-imide)s 5a–e in quantitative yields with inherent viscosities of 0.39–0.51 dL/g. The resulting polymers were fully characterized by means of 1H-NMR, FT-IR spectroscopy, elemental analyses, inherent viscosity, solubility test, specific rotation and thermal properties of them were investigated using TGA/DTG and differential scanning calorimeter (DSC). The diacid 4 was synthesized by the condensation reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6- tetracarboxylic dianhydride 1 with L-isoleucine 2 in acetic acid solution. 相似文献