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81.
In this paper estimation of the probabilities of a multinomial distribution has been studied. The five estimators considered are: unrestricted estimator (UE), restricted estimator (RE) (under model ), preliminary test estimator (PTE) based on a test of the model , shrinkage estimator (SE) and the positive-rule shrinkage estimator (PRSE). Asymptotic distributions of these estimators are given under Pitman alternatives and the asymptotic risk under a quadratic loss has been evaluated. The relative performance of the five estimators is then studied with respect to their asymptotic distributional risks (ADR). It is seen that neither of the preliminary test and shrinkage estimators dominates the other, though each fares well relative to the other estimators. However, the positive rule estimator is recommended for use for dimension 3 or more while the PTE is recommended for dimension less than 3. 相似文献
82.
Fandong Meng Genhui Xu Baowei Wang Xinbin Ma. School of Chemical Engineering Technology Tianjin University Tianjin China . Luoyang Petrochemical Engineering Corporation Luoyang ChinaManuscript received March revised Apr 《天然气化学杂志》2002,(Z1)
This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and regeneration reaction are also discussed. This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation. 相似文献
83.
The extended Koopmans’ theorem is related to Fukui function, which measures the change in electron density that accompanies
electron attachment and removal. Two approaches are used, one based on the extended Koopmans’ theorem differential equation
and the other based directly on the expression of the ionized wave function from the extended Koopmans’ theorem. It is observed
that the Fukui function for electron removal can be modeled as the square of the first Dyson orbital, plus corrections. The
possibility of useful generalizations to the extended Koopmans’ theorem is considered; some of these extensions give approximations,
or even exact expressions, for the Fukui function for electron attachment. 相似文献
84.
A spot test was implemented in a flow-injection system for the spectrophotometric determination of zinc in digests of plant materials. It is based on the influence of Zn2+ on the oxidation rate of 1-naphthylethylenediamine (NED) by hexacyanoferrate(III) under acidic conditions. In order to control the precipitate formation and to maintain the resulting suspension, a micellar medium was established by adding Triton X-100. The proposed system handles about 65 samples per hour, meaning 72 μg NED and 9.0 mg K3[Fe(CN)6] per determination. Baseline drift is usually <0.01 absorbance per hour and the analytical signals for 0.5-2.5 mg l−1 Zn range within ca. 0.07-0.45 absorbance. Linearity of the analytical curve is fair (r>0.999, n=6) and detection limit was estimated as 0.2 mg l−1 Zn. Results are precise (R.S.D.<1%, n=10) and in agreement with flame atomic absorption spectrometry and with certified values of standard reference materials. 相似文献
85.
J. Voll T. Kerscher D. Geppert R. de Vivie-Riedle 《Journal of photochemistry and photobiology. A, Chemistry》2007,190(2-3):352-358
The technological needs imposed by the exponential miniaturization trend of conventional electronic devices has drawn attention towards the development of smaller and faster devices like ultrafast molecular switches. In recent years molecular switches emerge again in the focus of active and innovative research with state-of-the-art optical tools recording their dynamics in real time. Still many questions about the underlying microscopic mechanism are left open, including potential factors that effect the switching process in either way, improve or worsen it. Due to the complexity of such molecules it is difficult to obtain a global answer from experiment alone. On the other side molecular switches are generally too large for a complete quantum chemical and quantum dynamical calculation. In our group we therefore developed an ab initio based modular model to handle the laser induced quantum dynamics in molecular switches like fulgides. It enables us to study the effect of internal molecular coupling and of the molecular response to external fields. We can investigate the related wave packet dynamics, the switching efficiency and the controllability. Our results focus on the laser induced ring opening in fulgides, which equals one direction of the switching process. Presented are the influence of a conical intersection seam and of time-dependent potentials, mimicking the mean interaction with the environment. Furthermore the relation of controllability and the wave packet's momentum is studied and the influence of potential barriers on the switching dynamics is shown. 相似文献
86.
Yong Zhu Jin-lian Hu Kwok-wing Yeung Hao-jun Fan Ye-qiu 《高分子科学》2006,(2):173-186
SMPU (shape memory polyurethane) non-ionomers and ionomers, synthesized with poly(c-caprolactone) (PCL), 4, 4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (BDO), dimethylolpropionic acid (DMPA) were measured with cyclic tensile test and strain recovery test. The relations between the structure and shape memory effect of these two series were studied with respect to the ionic group content and the effect of neutralization. The resulting data indicate that, with the introduction of asymmetrical extender, the stress at 100% elongation is decreased for PU non-ionomer and ionomer series, especially lowered sharply for non-ionomer series; the fixation ratio of ionomer series is not affected obviously by the ionic group content; the total recovery ratio of ionomer series is decreased greatly. After sufficient relaxation time for samples stretched beforehand, the switching temperature is raised slightly, whereas the recovery ratio measured with strain recovery test method is lowered with increased DMPA content. The characterization with FT-IR, DSC, DMA elucidated that, the ordered hard domain of the two series is disrupted with the introduction of DMPA which causes more hard segments to dissolve in soft phase; ionic groups on hard segment enhance the cohesion between hard segments especially at high ionic group content and significantly facilitate the phase separation compared with the corresponding non-ionomer at moderate ionic group content. 相似文献
87.
The vanadium trapping effect of Mg and La containing additives in cracking catalyst contaminated with 2300 ppm Ni and 4700 ppm V has been analyzed by microactivity test (MAT) and imaging secondary ion mass spectrometry (SIMS). The results of SIMS imaging are consistent with cracking activity data and show that the La/spinel is a superior vanadium trap for the fluid catalytic cracking of hydrocarbons (FCC) operation. La/spinel serves as a dual function additive for both vanadium trap and SOx removal. The optimum amount of La/spinel added to the cracking catalyst is about 15% by weight. This results in an increased catalytic activity, an increase in gasoline yield, and a decrease in coke and gas factors. The MgAl2O4 phase of Mg/Al2O3 additive is found capable of trapping vanadium while its MgO of Mg/Al2O3 phase can migrate to zeolite particles (the active component of the FCC catalyst) that, in turn, causes a decline in the activity of that catalyst. 相似文献
88.
Antifouling coatings are the most reliable way to prevent biofouling of immersed surfaces. As concerning the high toxicity of organotin paints, the tendency is the development of coatings, which do not present environmental risks. In this work, we prepare binders from modification of acrylic copolymers containing free carboxylic acid groups. Biocides chosen are tertiary ammonium salts; alkyl chain substituents with different length are considered. The chemical modifications of resins are carried out via a single step reaction. Modification extents are monitored through proton nuclear magnetic resonance and thermogravimetric analysis and the modified resins are characterised by Fourier transform infrared spectroscopy. The glass transition temperature of the acrylate systems is assessed by dynamical mechanical analysis (pin point method) and compared with data obtained by differential scanning calorimetry. The erosion and antifouling properties of the binders are followed during an exposure to marine environment by a visual observation. 相似文献
89.
Marina DellaGreca Antonio FiorentinoMarina Isidori Lucio PreviteraFabio Temussi Armando Zarrelli 《Tetrahedron》2003,59(26):4821-4825
Investigation of the ethyl acetate extract of Juncus acutus rhizomes revealed seven benzocoumarins, probably derived from oxidation of phenanthrenes already isolated from the plant. The structures were determined by means of spectroscopic methods. The anti-algal activity of the isolated compounds tested on the green alga Pseudokirchneriella subcapitata are reported here. 相似文献
90.
The bifurcations of periodic orbits in a class of autonomous three-variable, nonlinear-differential-equation systems possessing a homoclinic orbit associated with a saddle focus with eigenvalues ( ±i,), where ¦/¦ < 1 (Sil'nikov's condition), are studied in a two-parameter space. The perturbed homoclinic systems undergo a countable set of tangent bifurcations followed by period-doubling bifurcations leading to periodic orbits which may be attractors if ¦/¦ < 1/2. The accumulation rate of the critical parameter values at the homoclinic system is exp(-2¦/¦). A global mechanism for the onset of homoclinicity in strongly contractive flows is analyzed. Cusp bifurcations with bistability and hysteresis phenomena exist locally near the onset of homoclinicity. A countable set of these cusp bifurcations with scaling properties related to the eigenvalues±i of the stationary state are shown to occur in infinitely contractive flows. In the two-parameter space, the periodic orbit attractor domain exhibits a spiral structure globally, around the set of homoclinic systems, in which all the different periodic orbits are continuously connected. 相似文献