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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   
3.
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   
4.
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   
5.
电路过渡过程所列方程是微分方程,本文中采用的是方框图模型分析法,即将微分方程的复杂示解分解成最基本的加(减)、乘(除)、积分(微分)、增益等运算,采用VB设计用户界面产进行计算,并给出了一算例。  相似文献   
6.
We discuss an error estimation procedure for the global error of collocation schemes applied to solve singular boundary value problems with a singularity of the first kind. This a posteriori estimate of the global error was proposed by Stetter in 1978 and is based on the idea of Defect Correction, originally due to Zadunaisky. Here, we present a new, carefully designed modification of this error estimate which not only results in less computational work but also appears to perform satisfactorily for singular problems. We give a full analytical justification for the asymptotical correctness of the error estimate when it is applied to a general nonlinear regular problem. For the singular case, we are presently only able to provide computational evidence for the full convergence order, the related analysis is still work in progress. This global estimate is the basis for a grid selection routine in which the grid is modified with the aim to equidistribute the global error. This procedure yields meshes suitable for an efficient numerical solution. Most importantly, we observe that the grid is refined in a way reflecting only the behavior of the solution and remains unaffected by the unsmooth direction field close to the singular point.  相似文献   
7.
根据生产任务选择加工设备进行制造资源重组是实现可重构制造系统的关键问题之一,由于设备的选择涉及到多种因素,既有定量指标,又有定性指标,传统的依靠人工经验的方法显得力不从心。本文首先结合实际情况,提出了一套设备选择评价体系,通过对模糊判断矩阵采用最小对数二乘法确定各评价因素的权重系数,针对定性指标和定量指标采用不同的方法确定其性能指标值,通过模糊积分对评判指标进行综合评判,最后进行了实例研究。所提出的方法有效地简化了决策过程,为可重构制造系统设备选择提供了一套行之有效的方法。  相似文献   
8.
We consider a resource management problem in which the management objective is to minimize fluctuations in resource stocks. Stabilizing management policies constitute the designing of memoryless state feedback control strategies for a discrete time resource model which contains unknown but bounded fluctuations. We also show that the problem of maximizing sustainable yield in an uncertain fishery can be considered as the problem of stabilizing of the stock level.The paper corresponds to an invited talk at the 14th Symposium on Operations Research, Ulm, September 6–8, 1989.The support by Yrjö Jahnsson Foundation is gratefully acknowledged.This work was supported by NSF and AFOSR under grant ECS 8602524.  相似文献   
9.
Papert's (1978) appeal to reconsider the power and possibilities of the aesthetic in mathematics learning is often ignored in mathematics education research. This paper begins with the premise, put forth by Dewey (1934), that the aesthetic structures many dimensions of inquiry and experience. In the same way that using particular paintings, musical compositions, or even everyday experiences has been instrumental to attempts by philosophers to understand the aesthetic dimensions of meaning and experience in artistic domains, I propose that analysing a particular encounter with mathematics may help reveal the nature and role of the often nebulous responses of elegance, beauty, and `fit' to which mathematicians lay claim in their mathematical activity. To achieve this, I draw on and adapt the defining features of the aesthetic character of experience set forth by the aesthetician Beardsley (1982). This, in turn, sheds light on the role thataesthetics can play in mathematical inquiry and experience, and provides initial categories and conjectures that can be used to investigate the potential roles of aesthetics in mathematics learning contexts.This revised version was published online in September 2005 with corrections to the Cover Date.  相似文献   
10.
韩力  卢杰  李莉 《物理实验》2006,26(4):39-40,43
基于夫琅禾费衍射理论和巴比涅互补原理,提出了利用激光衍射对细丝直径进行动态测量的方法.该方法具有测量精度高、速度快、非接触、使用方便且易于微机联接实现自动化测量等优点.  相似文献   
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