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61.
62.
A simple observation about the action for geodesics in a stationary spacetime with separable geodesic equations leads to a natural class of slicings of that spacetime whose orthogonal geodesic trajectories represent the world lines of freely falling fiducial observers. The time coordinate function can then be taken to be the observer proper time, leading to a unit lapse function, although the time coordinate lines still follow Killing trajectories to retain the explicitly stationary nature of the coordinate grid. This explains some of the properties of the original Painlevé-Gullstrand coordinates on the Schwarzschild spacetime and their generalization to the Kerr-Newman family of spacetimes, reproducible also locally for the Gödel spacetime. For the static spherically symmetric case the slicing can be chosen to be intrinsically flat with spherically symmetric geodesic observers, leaving all the gravitational field information in the shift vector field. 相似文献
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64.
A finite point method for solving compressible flow problems involving moving boundaries and adaptivity is presented. The numerical methodology is based on an upwind‐biased discretization of the Euler equations, written in arbitrary Lagrangian–Eulerian form and integrated in time by means of a dual‐time steeping technique. In order to exploit the meshless potential of the method, a domain deformation approach based on the spring network analogy is implemented, and h‐adaptivity is also employed in the computations. Typical movable boundary problems in transonic flow regime are solved to assess the performance of the proposed technique. In addition, an application to a fluid–structure interaction problem involving static aeroelasticity illustrates the capability of the method to deal with practical engineering analyses. The computational cost and multi‐core performance of the proposed technique is also discussed through the examples provided. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
65.
Daiana T. Mancini Eugenio F. Souza Melissa S. Caetano Teodorico C. Ramalho 《Magnetic resonance in chemistry : MRC》2014,52(4):129-137
The phenylbenzothiazole compounds show antitumor properties and are highly selective. In this paper, the 99Tc chemical shifts based on the (99mTc)(CO)3(NNO) complex conjugated to the antitumor agent 2‐(4′‐aminophenyl)benzothiazole are reported. Thermal and solvent effects were studied computationally by quantum‐chemical methods, using the density functional theory (DFT) (DFT level BPW91/aug‐cc‐pVTZ for the Tc and BPW91/IGLO‐II for the other atoms) to compute the NMR parameters for the complex. We have calculated the 99Tc NMR chemical shifts of the complex in gas phase and solution using different solvation models (polarizable continuum model and explicit solvation). To evaluate the thermal effect, molecular dynamics simulations were carried, using the atom‐centered density matrix propagation method at the DFT level (BP86/LanL2dz). The results highlight that the 99Tc NMR spectroscopy can be a promising technique for structural investigation of biomolecules, at the molecular level, in different environments. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
66.
Leandro Augusto Gouvêa De Godoi Carla Eloísa Diniz Dos Santos Eugenio Foresti Marcelo Zaiat Márcia Helena Rissato Zamariolli Damianovic 《International journal of environmental analytical chemistry》2019,99(9):809-823
Recent developments in wastewater treatment have led to a renewed interest to obtain elemental sulphur (S°) as a by-product from bioreactors. However, practical studies are limited by the gap of adequate analytical techniques for its determination. This paper provides a statistical study and matrix effect evaluation of an adapted spectrophotometric method for routine S° analyses in aqueous samples, based on a methodology previously described by Hart (1961). Four complex matrices were tested: domestic sewage and effluent samples from three different bioreactors. Tested performance criteria included linearity, matrix effect, limit of detection and quantification and S° recovery. Results were linear (R2 = 0.99994) in the studied range (5 to 100 mg S° L?1) and no matrix effect was observed. The accuracy was based on recovery values that varied from 100% to 106%. The colloidal S° separation and extraction protocol was also considered suitable for aqueous samples, reaching more than 99.0% of S° recovery. 相似文献
67.
Akhil Kumar Singh Dr. Mohammad Usman Dr. Giuseppe Sciortino Prof. Dr. Eugenio Garribba Prof. Dr. Sankar Prasad Rath 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10098-10110
Metallophilic interactions between closed-shell metal ions are becoming a popular tool for a variety of applications related to high-end materials. Heavier d8 transition-metal ions are also considered to have a closed shell and can be involved in such interactions. There is no systematic investigation so far to estimate the structure and energy characteristics of metallophilic interactions in AgII/AgII (d9/d9), AgIII/AgIII (d8/d8), and mixed-valent AgII/AgIII (d9/d8) complexes, which have been demonstrated in the present study. Both interporphyrinic and intermetallic interactions were investigated on stepwise oxidation by using a rigid ethene-bridged cis silver(II) porphyrin dimer and the results compared with those for highly flexible ethane-bridged analogues. By controlling the nature of chemical oxidants and their stoichiometry, both 1e and 2e oxidations were done stepwise to generate AgII/AgIII mixed-valent and AgIII/AgIII porphyrin dimers, respectively. Unlike all other ethene-bridged metalloporphyrin dimers reported earlier, in which 2e oxidation stabilizes only the trans form, such an oxidation of silver(II) porphyrin dimer stabilizes only the cis form because of the metallophilic interaction. Besides silver(II) ⋅⋅⋅ silver(II) interactions in cis silver(II) porphyrin dimer, stepwise oxidations also enabled us to achieve various hitherto-unknown silver(II) ⋅⋅⋅ silver(III) and silver(III) ⋅⋅⋅ silver(III) interactions, which thereby allow significant modulation of their structure and properties. The strength of Ag ⋅⋅⋅ Ag interaction follows the order AgII/AgII (d9/d9)<AgII/AgIII (d9/d8)<AgIII/AgIII (d8/d8). Single-crystal XRD, X-ray photoelectron spectroscopy (XPS), 1H NMR and EPR spectroscopy, and variable-temperature magnetic investigations revealed various oxidation states of silver and metallophilic interactions, which are also well supported by computational analysis. 相似文献
68.
Roberta Seraglia Giovanni Sartore Raffaella Marin Silvia Burlina Enzo Manzato Eugenio Ragazzi Pietro Traldi Annunziata Lapolla 《Journal of mass spectrometry : JMS》2013,48(1):105-110
Increased oxidation of low density lipoprotein (LDL) is characteristic of atherosclerosis. In this frame, high density lipoproteins (HDL) play an important role, being able to remove lipid peroxides (LPOs) and cholesterol from oxidized LDL, so exhibiting a protective role against atherosclerosis. A wide range of reactive compounds lead to the oxidation of methionine (Met) residues with the formation of methionine sulphoxide (MetO) in apolipoprotein A‐I (ApoA‐I). Consequently, the determination of MetO level can give both an evaluation of oxidative stress and the reduced capability of ApoA‐I in LPOs and cholesterol transport. For these reasons, the development of analytical methods able to determine the MetO level is surely of interest, and we report here the results obtained by MALDI mass spectrometry. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
69.
Annamaria Varga Valentin Zaharia Mihály Nógrádi László Poppe 《Tetrahedron: Asymmetry》2013,24(21-22):1389-1394
Ethyl (S)-3-hydroxy-3-phenylpropionate (S)-2 was obtained by the asymmetric reduction of ethyl 3-phenyl-3-oxopropionate 1 with the yeast Saccharomyces cerevisiae (ATCC 9080). The kinetic resolution of racemic ethyl 2-acetoxy-3-phenyl-propionate rac-3 with the same microorganism, gave after hydrolysis ethyl (R)- and (S)-3-hydroxy-3-phenylpropionates (R)-2 and (S)-2 which were converted by a straightforward series of reactions to the enantiomers of 3-amino-3-phenyl-propionic acids (S)-6 and (R)-6. The asymmetric reduction and hydrolytic kinetic resolution were also tested with several other whole cell systems under a variety of conditions. 相似文献
70.
In this work, the finite point method is applied to the solution of high‐Reynolds compressible viscous flows. The aim is to explore this important field of applications focusing on two main aspects: the easiness and automation of the meshless discretization of viscous layers and the construction of a robust numerical approximation in the highly stretched clouds of points resulting in such domain areas. The flow solution scheme adopts an upwind‐biased scheme to solve the averaged Navier–Stokes equations in conjunction with an algebraic turbulence model. The numerical applications presented involve different attached boundary layer flows and are intended to show the performance of the numerical technique. The results obtained are satisfactory and indicative of the possibilities to extend the present meshless technique to more complex flow problems. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献