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71.
Inmaculada Mena Miguel A. Casado Víctor Polo Pilar García‐Ordua Fernando J. Lahoz Luis A. Oro 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(36):9781-9785
In the presence of phosphanes (PR3), the amido‐bridged trinuclear complex [{Ir(μ‐NH2)(tfbb)}3] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2‐η2‐4‐κ‐C12H8F4N)(PR3)3], which are the products of the C N coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18 e− complex [Ir(Cl)(tfbb)(PMePh2)2] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule. 相似文献
72.
M. Luz Mena Verónica Carralero Araceli González-Cortés Paloma Yáñez-Sedeño 《International journal of environmental analytical chemistry》2013,93(1):57-65
The use of a robust tyrosinase biosensor, fabricated from graphite–Teflon rigid electrode matrices modified with gold nanoparticles, for the estimation of the total phenols content in olive oil mill wastewaters (OMW), is proposed. The performance of this bioelectrode using both continuous stirring and flow-injection amperometry was studied. A potential value of ?0.10?V was selected for the sensitive and stable detection of various phenolic compounds present in OMW samples: catechol, 3,4-dihydroxycinnamic acid (caffeic acid), 3,4-dihydroxyphenylacetic acid (DOPAC), 4-hydroxyphenylacetic acid, 4-hydroxyphenylethanol (tyrosol), and 4-hydroxyphenylpropionic acid. Using catechol as the target phenol, linear calibration graphs were obtained in the 1.0?×?10?8???8.0?×?10?6?mol?L?1 (batch) and 1.0?×?10?7???1.0?×?10?5?mol?L?1 (FI) concentration ranges, with slope values of 750?mA?L?mol?1 and 103?mA?L?mol?1, respectively. Batch amperometry was chosen for the analysis of real samples because of its higher sensitivity. For example, the limit of detection for caffeic acid was 80?nM. The ‘pool’ of phenolic compounds was estimated in OMW obtained from different extraction systems and containing phenols at diverse levels of concentration. A comparison of these results with those obtained by applying the Folin–Ciocalteau spectrophotometric reference method was carried out. 相似文献
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The Einstein–Straus model consists of a Schwarzschild spherical vacuole in a Friedman–Lemaître–Robertson–Walker (FLRW) dust spacetime (with or without $\Lambda $ Λ ). It constitutes the most widely accepted model to answer the question of the influence of large scale (cosmological) dynamics on local systems. The conclusion drawn by the model is that there is no influence from the cosmic background, since the spherical vacuole is static. Spherical generalizations to other interior matter models are commonly used in the construction of lumpy inhomogeneous cosmological models. On the other hand, the model has proven to be reluctant to admit non-spherical generalizations. In this review, we summarize the known uniqueness results for this model. These seem to indicate that the only reasonable and realistic non-spherical deformations of the Einstein–Straus model require perturbing the FLRW background. We review results about linear perturbations of the Einstein–Straus model, where the perturbations in the vacuole are assumed to be stationary and axially symmetric so as to describe regions (voids in particular) in which the matter has reached an equilibrium regime. 相似文献
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Numerical Algorithms - We consider differential Lyapunov and Riccati equations, and generalized versions thereof. Such equations arise in many different areas and are especially important within... 相似文献
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In this contribution, we investigate strategies to perform shock‐capturing computation of steady hypersonic flow fields by means of residual distribution schemes. The ultimate objective is the computation of flow solutions for which the correct upstream enthalpy value is recovered in the postshock region. To this end, the parallelism existing between the classical Bx scheme and the stabilized finite element techniques is exploited. The simple Lax‐Friedrichs dissipation term is leveraged to build two new residual distribution schemes. Upon testing on both inviscid and viscous steady problems, solutions obtained with one of the two schemes are shown to recover the correct upstream total enthalpy level in the postshock region. This last scheme provides also improved wall pressure and skin friction predictions; heat transfer predictions are, unfortunately, similar to those offered by the Bx scheme. A conjecture for explaining this behavior is exposed. 相似文献
80.
We study higher-dimensional gravitational collapse to topological black holes in two steps. First, we construct some (n + 2)-dimensional collapsing space–times, which include generalised Lemaître–Tolman–Bondi-like solutions, and we prove that these can be matched to static Λ-vacuum exterior space–times. We then investigate the global properties of the matched solutions which, besides black holes, may include the existence of naked singularities and wormholes. Second, we consider as interiors classes of 5-dimensional collapsing solutions built on Riemannian Bianchi IX spatial metrics matched to radiating exteriors given by the Bizoń–Chmaj–Schmidt metric. In some cases, the data at the boundary for the exterior can be chosen to be close to the data for the Schwarzschild solution. 相似文献