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The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献
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Dr. Liat Avram Dr. Václav Havel Ronit Shusterman-Krush Dr. Mark A. Iron Dr. Moritz Zaiss Prof. Vladimír Šindelář Dr. Amnon Bar-Shir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1687-1690
The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF4− are mediated by the side chains on the receptor (100 s−1<kex<5000 s−1), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method. 相似文献
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We give a sheaf theoretic interpretation of Potts models with external magnetic field, in terms of constructible sheaves and their Euler characteristics. We show that the polynomial countability question for the hypersurfaces defined by the vanishing of the partition function is affected by changes in the magnetic field: elementary examples suffice to see non-polynomially countable cases that become polynomially countable after a perturbation of the magnetic field. The same recursive formula for the Grothendieck classes, under edge-doubling operations, holds as in the case without magnetic field, but the closed formulae for specific examples like banana graphs differ in the presence of magnetic field. We give examples of computation of the Euler characteristic with compact support, for the set of real zeros, and find a similar exponential growth with the size of the graph. This can be viewed as a measure of topological and algorithmic complexity. We also consider the computational complexity question for evaluations of the polynomial, and show both tractable and NP-hard examples, using dynamic programming. 相似文献
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In this paper, we consider a viscoelastic wave equation of variable coefficients in the presence of past history with nonlinear damping and delay in the internal feedback and dynamic boundary conditions. Under suitable assumptions, we establish an explicit and general decay rate result without imposing restrictive assumption on the behavior of the relaxation function at infinity by Riemannian geometry method and Lyapunov functional method. 相似文献
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With the proliferation of mobile computing technologies, location based services have been identified as one of the most promising
target application. We classify mobile information service domains based on feature characteristics of the information sources
and different patterns of mobile information access. By carefully examining the service requirements, we identify the dynamic
data management problem that must be addressed for effective location based services in mobile environments. We then devise
a general architecture and cost model for servicing both location independent and location dependent data. Based on the architecture
and cost model, we propose a set of dynamic data management strategies that employs judicious caching, proactive server pushing
and neighborhood replication to reduce service cost and improve response time under changing user mobility and access patterns.
Detail behavior analysis helps us in precisely capturing when and how to apply these strategies. Simulation results suggest
that different strategies are effective for different types of data in response to different patterns of movement and information
access.
Shiow-yang Wu is an associate professor of the Department of Computer Science and Information Engineering at National Dong Hwa University,
Hualien, Taiwan, R.O.C. He received the BS and MS degrees in computer engineering from National Chiao Tung University, Hsinchu,
Taiwan, ROC, and the PhD degree in computer science from the University of Texas at Austin in 1984, 1986, and 1995, respectively.
His research interests include data/knowledge bases, mobile computing, distributed processing, intelligence information systems,
and electronic commerce.
Kun-Ta Wu was born in Taipei, Taiwan, R.O.C., in 1976. He received the B.S. degree in computer science from Soochow University, Taipei,
Taiwan, R.O.C., in 1999 and the M.S. degree in computer science and information engineering from National Dong Hwa University,
Hualien, Taiwan, R.O.C., in 2001.
Currently, he is an Assistant Researcher in the Domestic Division at Science and Technology Information Center, National Science
Council, R.O.C., as a member of Information Gathering and Analysis Group of National Information and Communication Security
Taskforce. His research interests include mobile computing, wireless network and information security. 相似文献
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目标RCS动态数据的分布特征研究 总被引:1,自引:0,他引:1
复杂目标在不同视向的RCS分布特征是不同的,传统模型对此都没有给出详细的结果。文中以某歼击机和直升机为对象,应用X^2。分布、对数正态分布和瑞利分布模型,以及Kolmogomv拟合优度检验方法,研究其RCS动态测量数据的统计分布特征,得到了在一定显著性水平下,两种目标在不同视向角下对三种模型的拟合效果,同时得到应用X^2。分布拟合时模型半自由度随视向角的分布情况。在显著性水平为0.05时,对于在较短时间内录得的复杂目标动态RCS数据,应用X^2分布可以取得较好的拟合效果。文中结果精确地描述了目标RCS的起伏特征,能够为目标回波的精确模拟与检测提供可靠的依据。 相似文献