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81.
F. M. Lancas D. T. Da Silva E. Carrilho D. M. Pereira 《Journal of Radioanalytical and Nuclear Chemistry》1992,159(2):301-304
Asphaltols obtained by benzene precipitation of coal-derived liquids extracted with hot pyridine were purified by preparative liquid chromatography and X-ray irradiated to different doses. The irradiated product was analyzed using chromatographic and spectroscopic methods. The results obtained show that asphaltenes are degraded to resins. 相似文献
82.
D. Kopf K.J. Weingarten G. Zhang M. Moser M.A. Emanuel R.J. Beach J.A. Skidmore U. Keller 《Applied physics. B, Lasers and optics》1997,65(2):235-243
Received: 27 February 1997/Revised version: 14 April 1997 相似文献
83.
84.
This paper considers the inversion of experimental field data collected with light receiving systems designed to meet operational requirements. Such operational requirements include system deployment in free drifting configurations and a limited number of acoustic receivers. A well-known consequence of a reduced spatial coverage is a poor sampling of the vertical structure of the acoustic field, leading to a severe ill-conditioning of the inverse problem and data to model cost function with a massive sidelobe structure having many local extrema. This causes difficulties to meta-heuristic global search methods, such as genetic algorithms, to converge to the true model parameters. In order to cope with this difficulty, broadband high-resolution processors are proposed for their ability to significantly attenuate sidelobes, as a contribution for improving convergence. A comparative study on simulated data shows that high-resolution methods did not outperform the conventional Bartlett processor for pinpointing the true environmental parameter when using exhaustive search. However, when a meta-heuristic technique is applied for exploring a large multidimensional search space, high-resolution methods clearly improved convergence, therefore reducing the inherent uncertainty on the final estimate. These findings are supported by the results obtained on experimental field data obtained during the Maritime Rapid Environmental Assessment 2003 sea trial. 相似文献
85.
We study a coarsening process of one-dimensional cell complexes. We show that if cell boundaries move with velocities proportional to the difference in size of neighboring cells, then the average cell size grows at a prescribed exponential rate and the Poisson distribution is precisely invariant for the distribution of the whole process, rescaled in space by its average growth rate. We present numerical evidence toward the following universality conjecture: starting from any finite mean stationary renewal process, the system when rescaled by e ?2t converges to a Poisson point process. For a limited case, this makes precise what has been observed previously in experiments and simulations, and lays the foundation for a theory of universal asymptotic states of dynamical cell complexes. 相似文献
86.
In this study, affinity capillary electrophoresis (ACE) and quantum mechanical density functional theory (DFT) calculations were combined to investigate non-covalent binding interactions between the hexaarylbenzene-based receptor (R) and alkali metal ions, Rb(+) and Cs(+) , in methanol. The apparent binding (stability) constants (K(b) ) of the complexes of receptor R with alkali metal ions in the methanolic medium were determined by ACE from the dependence of effective electrophoretic mobility of the receptor R on the concentration of Rb(+) and Cs(+) ions in the BGE using a non-linear regression analysis. The receptor R formed relatively strong complexes both with rubidium (log K(b) =4.04±0.21) and cesium ions (log K(b) =3.72±0.22). The structural characteristics of the above alkali metal ion complexes with the receptor R were described by ab initio density functional theory calculations. These calculations have shown that the studied cations bind to the receptor R because they synergistically interact with the polar ethereal fence and with the central benzene ring via cation-π interaction. 相似文献
87.
88.
Emanuel Makrlík Petr Toman Petr Vaňura Rajendra Rathore 《Monatshefte für Chemie / Chemical Monthly》2011,286(1):447-451
Abstract
From extraction experiments in the two-phase water/nitrobenzene system and γ-activity measurements, the stability constant of a hexaarylbenzene-based receptor. Tl+ complex species dissolved in nitrobenzene saturated with water was determined. By using the quantum-mechanical density functional level of theory calculations, the most probable structure of this complex was derived. 相似文献89.
McKeown BA Gonzalez HE Friedfeld MR Gunnoe TB Cundari TR Sabat M 《Journal of the American Chemical Society》2011,133(47):19131-19152
Cationic platinum(II) complexes [((t)bpy)Pt(Ph)(L)](+) [(t)bpy =4,4'-di-tert-butyl-2,2'-bipyridyl; L = THF, NC(5)F(5), or NCMe] catalyze the hydrophenylation of ethylene to generate ethylbenzene and isomers of diethylbenzene. Using ethylene as the limiting reagent, an 89% yield of alkyl arene products is achieved after 4 h at 120 °C. Catalyst efficiency for ethylene hydrophenylation is diminished only slightly under aerobic conditions. Mechanistic studies support a reaction pathway that involves ethylene coordination to Pt(II), insertion of ethylene into the Pt-phenyl bond, and subsequent metal-mediated benzene C-H activation. Studies of stoichiometric benzene (C(6)H(6) or C(6)D(6)) C-H/C-D activation by [((t)bpy)Pt(Ph-d(n))(THF)](+) (n = 0 or 5) indicate a k(H)/k(D) = 1.4(1), while comparative rates of ethylene hydrophenylation using C(6)H(6) and C(6)D(6) reveal k(H)/k(D) = 1.8(4) for the overall catalytic reaction. DFT calculations suggest that the transition state for benzene C-H activation is the highest energy species along the catalytic cycle. In CD(2)Cl(2), [((t)bpy)Pt(Ph)(THF)][BAr'(4)] [Ar' = 3,5-bis(trifluoromethyl)phenyl] reacts with ethylene to generate [((t)bpy)Pt(CH(2)CH(2)Ph)(η(2)-C(2)H(4))][BAr'(4)] with k(obs) = 1.05(4) × 10(-3) s(-1) (23 °C, [C(2)H(4)] = 0.10(1) M). In the catalytic hydrophenylation of ethylene, substantial amounts of diethylbenzenes are produced, and experimental studies suggest that the selectivity for the monoalkylated arene is diminished due to a second aromatic C-H activation competing with ethylbenzene dissociation. 相似文献
90.
Molecular dynamics simulations with atomistic detail of the gel phase and melting transitions of dipalmitoyl phosphatidylcholine bilayers in water reveal the dependency of many thermodynamic and structural parameters on the initial system ordering. We quantitatively compare different methods to create a gel phase system and we observe that a very high ordering of the gel phase starting system is necessary to observe behavior which reproduces experimental data. We performed heating scans with speeds down to 0.5 K/ns and could observe sharp first order phase transitions. Also, we investigated the transition enthalpy as the natural intrinsic parameter of first order phase transitions, and obtained a quantitative match with experimental values. Furthermore, we performed systematic investigations of the statistical distribution and heating rate dependency of the microscopic phase transition temperature. 相似文献