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考虑了线性回归模型中,在Fisherian和Mahalanobis损失函数下,几乎无偏刘估计对于最小二乘估计的不可容许性;结论表明:几乎无偏刘估计在Mahalanobis损失函数下是不可容的;最后进行了数值模拟来表明结果. 相似文献
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4.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
5.
In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC4H3X ( 1 X ), SiC4H2X2 ( 2 X ), SiC4HX3 ( 3 X ), and SiC4X4 ( 4 X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔEs-t, a possible indication of stability), and band gap (ΔEH-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 X > 1 X > 3 X > 4 X . Precedence of 2 X over 1 X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 I and 4 F . The trend of divalent angle () for each X is 4 X > 1 X > 3 X > 2 X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔEs-t and ΔEH-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry. 相似文献
6.
雷电波分析与比较研究 总被引:1,自引:0,他引:1
本文对双指数雷电流模型和 IEC1 3 1 2—— 1推荐的雷电流模型进行了分析和研究 ,计算了这两种雷电流模型的雷电流参数。在此基础上 ,用 FFT方法分析了雷电流的频谱分布 相似文献
7.
Daniel L. Feldheim Del R. Lawson Charles R. Martin 《Journal of Polymer Science.Polymer Physics》1993,31(8):953-957
We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc. 相似文献
8.
Mark Webber 《Mathematical Methods in the Applied Sciences》2006,29(7):819-838
We investigate the influence of slip boundary conditions on the onset of Bénard convection in an infinite fluid layer. It is shown that the critical Rayleigh number is a decreasing function of the slip length, and therefore boundary slip is seen to have a destabilizing effect. Chebyshev‐tau and compound matrix formulations for solving the eigenvalue problem are presented. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
9.
Michael R. Caputo 《Natural Resource Modeling》1989,3(2):241-259
This paper analyzes the extent to which standard dynamic renewable resource models possess refutable implications. Both the steady state comparative static and local comparative dynamic properties of the standard model are studied. A unified framework is developed which enables one to analyze the qualitative properties of any standard renewable resource model. This is achieved by explicitly linking the local stability, steady state comparative static, and local comparative dynamic properties of the model. 相似文献
10.
水轮机水力稳定性的分析 总被引:2,自引:0,他引:2
根据收集国内外水轮机水力稳定性资料 ,分析了引起水轮机水力不稳定性的因素 ,并结合实例分析可能引起的危害 ,最后提出了解决问题的方法和建议 相似文献