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41.
Rhenium(VII) polyhydrides supported by chelating bis -phosphine ligands: DPEphos,xantphos and biphep
《Journal of Coordination Chemistry》2012,65(7):1051-1057
Three new rhenium polyhydride complexes, [ReH7(L2)], incorporating bidentate organophosphorus ligands (L2 = DPEphos, xantphos and biphep), were successfully synthesized using the corresponding [ReOCl3(L2)] complexes as precursors. The polyhydride complexes were characterized by IR, 1H and 31P NMR, and elemental analysis. 相似文献
42.
A thermodynamically consistent, large-strain, multi-phase field approach (with consequent interface stresses) is generalized for the case with anisotropic interface (gradient) energy (e.g. an energy density that depends both on the magnitude and direction of the gradients in the phase fields). Such a generalization, if done in the “usual” manner, yields a theory that can be shown to be manifestly unphysical. These theories consider the gradient energy as anisotropic in the deformed configuration, and, due to this supposition, several fundamental contradictions arise. First, the Cauchy stress tensor is non-symmetric and, consequently, violates the moment of momentum principle, in essence the Herring (thermodynamic) torque is imparting an unphysical angular momentum to the system. In addition, this non-symmetric stress implies a violation of the principle of material objectivity. These problems in the formulation can be resolved by insisting that the gradient energy is an isotropic function of the gradient of the order parameters in the deformed configuration, but depends on the direction of the gradient of the order parameters (is anisotropic) in the undeformed configuration. We find that for a propagating nonequilibrium interface, the structural part of the interfacial Cauchy stress is symmetric and reduces to a biaxial tension with the magnitude equal to the temperature- and orientation-dependent interface energy. Ginzburg–Landau equations for the evolution of the order parameters and temperature evolution equation, as well as the boundary conditions for the order parameters are derived. Small strain simplifications are presented. Remarkably, this anisotropy yields a first order correction in the Ginzburg–Landau equation for small strains, which has been neglected in prior works. The next strain-related term is third order. For concreteness, specific orientation dependencies of the gradient energy coefficients are examined, using published molecular dynamics studies of cubic crystals. In order to consider a fully specified system, a typical sixth order polynomial phase field model is considered. Analytical solutions for the propagating interface and critical nucleus are found, accounting for the influence of the anisotropic gradient energy and elucidating the distribution of components of interface stresses. The orientation-dependence of the nonequilibrium interface energy is first suitably defined and explicitly determined analytically, and the associated width is also found. The developed formalism is applicable to melting/solidification and crystal-amorphous transformation and can be generalized for martensitic and diffusive phase transformations, twinning, fracture, and grain growth, for which interface energy depends on interface orientation of crystals from either side. 相似文献
43.
《Journal of computational and graphical statistics》2013,22(4):818-837
Generalized linear mixed models (GLMMs) are often fit by computational procedures such as penalized quasi-likelihood (PQL). Special cases of GLMMs are generalized linear models (GLMs), which are often fit using algorithms like iterative weighted least squares (IWLS). High computational costs and memory space constraints make it difficult to apply these iterative procedures to datasets having a very large number of records. We propose a computationally efficient strategy based on the Gauss–Seidel algorithm that iteratively fits submodels of the GLMM to collapsed versions of the data. The strategy is applied to investigate the relationship between ischemic heart disease, socioeconomic status, and age/gender category in New South Wales, Australia, based on outcome data consisting of approximately 33 million records. For Poisson and binomial regression models, the Gauss–Seidel approach is found to substantially outperform existing methods in terms of maximum analyzable sample size. Remarkably, for both models, the average time per iteration and the total time until convergence of the Gauss–Seidel procedure are less than 0.3% of the corresponding times for the IWLS algorithm. Platform-independent pseudo-code for fitting GLMS, as well as the source code used to generate and analyze the datasets in the simulation studies, are available online as supplemental materials. 相似文献
44.
FTIR photothermal beam deflection (PBD) spectroscopy was used to record PBD spectra of IR-absorbing gases in presence of IR-absorbing and non-absorbing solids. The presence of the solid, IR-absorbing or not, causes asymmetry at the juncture of the IR and probe laser 相似文献
45.
FTIR photothermal beam deflection spectroscopy (PBDS) was used to record infrared spectra of medium-temperature carbons before and after they had been subjected to treatments with aqueous HNO3 or H2O2 solution. Changes in the functional groups present on the carbon surfaces can be clearly observed. 相似文献
46.
肝损伤是影响公众健康的重大问题之一, 已经引起了人们越来越多的关注. 而过表达的过氧化亚硝酸盐(ONOO?)在肝损伤等疾病的发病机制中起着重要作用, 被认为是一种与早期肝损伤密切相关的生物活性分子. 因此, 为了探究ONOO?在肝损伤过程中的作用, 开发可以实现肝损伤过程中ONOO?高选择性和实时检测的分析方法具有重要意义. 本文报道了一种具有大斯托克斯位移的远红光至近红外(FR-NIR)ONOO?荧光探针. 由于该探针具有大的斯托克斯位移, 可以有效消除光谱重叠和自吸收的干扰, 从而显著提高成像的信噪比. 此外, 该探针对ONOO?具有高的灵敏度(检出限为25.8 nmol/L)和良好的选择性, 被成功用于药物诱导肝损伤过程中ONOO?信号的成像检测. 相似文献
47.
Thomas Mikosch Mohsen Rezapour Olivier Wintenberger 《Stochastic Processes and their Applications》2019,129(11):4638-4662
In this paper we consider a stochastic model of perpetuity-type. In contrast to the classical affine perpetuity model of Kesten (1973) and Goldie (1991) all discount factors in the model are mutually independent. We prove that the tails of the distribution of this model are regularly varying both in the univariate and multivariate cases. Due to the additional randomness in the model the tails are not pure power laws as in the Kesten–Goldie setting but involve a logarithmic term. 相似文献
48.
This paper deals with ultrasound medical image processing, particularly to filter the noise while preserving the edges and
structures of information. The mathematical processing consists in solving by a numerical way a nonlinear evolutive boundary
value problem. Several numerical semi-implicit time marching schemes are considered and analyzed. At each time step, parallel
synchronous or asynchronous Schwarz alternating methods are used to solve the linear system and its convergence is studied.
Lastly, the results of sequential and parallel simulations are presented.
相似文献
49.
Steinar Husebye Dima Mughannam Karl W. Törnroos 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1825-1837
The complexes were synthesised by adding a hot solution of the appropriate substituted thiourea in MeOH (Br m complexes) or DMF (I m complexes) to a solution of TeO 2 dissolved in hot conc. HCl. The structures of the resulting four-coordinate square planar complexes, cis -[TeBr 2 {( i PrNH) 2 CS} 2 ] ( 1 ), cis -[TeBr 2 {( i BuNH) 2 CS} 2 ] ( 2 ), trans -[TeI 2 {( i PrNH) 2 CS} 2 ] ( 3 ), and trans -[TeI 2 {( i BuNH) 2 CS} 2 ] ( 4 ), were studied by means of X-ray crystallographic methods. The average Te-S bond length in 1 and 2 is 2.5364 Å. The corresponding average Te-Br bond length is 2.9639 Å, reflecting the stronger trans influences of the two thioureas as compared to that of bromide. In 3 and 4 where there is no trans influence affecting the Te-ligand bonds, the average Te-S and Te-I bond lengths are 2.6926 and 2.9761 Å respectively. Tetraalkyl- or arylsubstituted thioureas alone as well as bulky disubstituted thioureas together with I m ligands seem to favor formation of trans complexes. 相似文献
50.
Jiaying Yan Yaqing FengXiao Peng Yuanchao LiNuonuo Zhang Xianggao LiBao Zhang 《Tetrahedron letters》2013
Four π-extended, β,β′ aromatic ring fused porphyrins including mono- and opp-dibenzoporphyrins bearing two carboxyl groups at only one fused benzo group were synthesized. The optical results by UV–vis spectroscopy indicate that when compared with the absorption spectra of monobenzoporphyrins, greater light-harvesting capabilities can be realized for opp-dibenzoporphyrins with two benzo group at the opposite β,β′ positions of the porphyrin. The photovoltaic properties of these π-extended porphyrins were examined for the first time and the highest conversion efficiency of 1.62% was realized for opp-dibenzoporphyrin 8a-sensitized solar cell, which is ∼60% higher than that of monobenzoporphyrin 4a based solar cell indicating the effect of an extra aromatic π conjugation on the light-harvesting capabilities of π-extended porphyrins. Subsequent DFT calculation results supported our results obtained in the optical and photovoltaic studies. 相似文献