Sensitivity improvement of 1H-15N cross-polarization at high MAS frequency applied to NMR structural characterization of organic solids

(15)N CP/MAS solid state NMR should be a method of choice to obtain essential structural information on organic materials containing nitrogen atoms. However, the technique is generally not selected for the characterization of non-labelled chemical compounds, which represents the most common situation encountered by chemists. Actually, due to the poor sensitivity of (15)N the method is time-consuming and a very fine calibration is often a prerequisite to reach a sufficient signal/noise. The main drawback comes from the weakness of (15)N-(1)H dipolar couplings which leads to a splitting of the static Hartman Hahn condition into very narrow sideband conditions under MAS. Practically, it is more difficult to obtain a high enough CP transfer level on (15)N for the entire spectrum than on other more conventional nuclei like (13)C. An experimental investigation of the CP efficiency using the ramp and adiabatic CP transfer experiments is here proposed. Preliminary adjustments of experimental settings were first made on an (15)N-labeled substituted heterocyclic model system, and then applied to several other organic compounds. Particular attention was paid to the detection of non-protonated nitrogen atoms with a significant chemical shift anisotropy, which represented the least favourable case. It was experimentally demonstrated that, for these atoms, the adiabatic passage provided a much higher transfer level than the more conventional ramp sequence leading to an enhancement factor of up to 3.5 at a MAS frequency of 30 kHz. The resulting sensitivity rendered possible the detection of non-protonated nitrogen atoms at natural abundance with 2.5-mm rotors at 9.4 T.     

Robust suboptimal control of nonlinear systems

In this paper, we consider a nonlinear dynamic system with uncertain parameters. Our goal is to choose a control function for this system that balances two competing objectives: (i) the system should operate efficiently; and (ii) the system’s performance should be robust with respect to changes in the uncertain parameters. With this in mind, we introduce an optimal control problem with a cost function penalizing both the system cost (a function of the final state reached by the system) and the system sensitivity (the derivative of the system cost with respect to the uncertain parameters). We then show that the system sensitivity can be computed by solving an auxiliary initial value problem. This result allows one to convert the optimal control problem into a standard Mayer problem, which can be solved directly using conventional techniques. We illustrate this approach by solving two example problems using the software MISER3.     

Quantum chemical studies on the structure and detonation properties of the fused polynitrodiazoles: New high energy density molecules

In this study, we explore the possibility that fused polynitrodiazoles act as high energy density materials. Density functional theory calculations at the B3LYP/aug‐cc‐pVDZ level were performed to predict the structure, energy of explosion (≈1.68 kcal g^?1), density (≈1.98 g cm^?3), detonation velocity (≈9.50 km s^?1), and detonation pressure (≈41.50 GPa) of model molecules. The predicted properties have been found to be promising compared with 3,4,5‐trinitro‐1H‐pyrazole, 1,3,5‐trinitro‐1,3,5‐triazinane, and octahydro‐1,3,5,7‐tetranitro‐l,3,5,7‐tetraazocane. The nature of azoles of the molecule presumably determines the geometry, stability, sensitivity, density, and detonation performance. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

非均匀材料损伤破坏的多尺度耦合理论

为研究微损伤对非均匀材料宏观破坏的影响,建立了非均匀材料的三维微单元强度分布模型,在平均场模型和集团分担模型的基础上,根据模拟计算结果建立了邻近单元加权分担模型;采用细观统计的方法建立了微观损伤造成宏观破坏的概率函数及跨尺度敏感性函数.结果表明:材料的损伤分数和名义应力越大,破坏集团之间的距离越近,宏观破坏概率就越大;...     

基于拓扑优化的声学结构材料分布设计

本文针对结构的声学设计问题进行研究,通过优化两种不同的材料在结构设计域内的拓扑分 布来最小化谐振结构所产生的声场中指定参考面/参考域内的声压。在研究中假定结构为线弹性小变 形结构,材料阻尼为Rayleigh阻尼,声学介质为无粘、可压缩、小扰动流体。对结构响应采用有限 元格式进行计算,对声场采用基于Helmholtz积分的边界元格式进行计算,由于声场在无穷远自由边 界的无反射条件在边界积分中能自动得到满足,该格式特别适合于具有开放边界的声场计算。建立 了结构有限元-声场边界元格式的耦合系统拓扑优化模型,导出了耦合系统敏感度分析的一般格式及 伴随格式。数值算例验证了所提出的结构-声学耦合系统优化方法的有效性和可靠性,并揭示了基于 声学准则的拓扑优化结果的有关特性 关键词边界积分,结构声学耦合系统,拓扑优化,敏感度分析,伴随方法     

Stochastic sensitivity of attractors for a piecewise smooth neuron model

ABSTRACT

We consider a one-dimensional model of neural activity, given by a piecewise smooth discontinuous map. Fold bifurcations as well as border collision bifurcations are described in detail. Using the method of stochastic sensitivity functions, noise-induced phenomena, such as transitions within attractor and between attractors, and spike generation, are described. Statistical characteristics of interspike intervals depending on noise intensity are studied.     

Effect of partial immunity on transmission dynamics of dengue disease with optimal control

Dengue fever is one of the most dangerous vector‐borne diseases in the world in terms of death and economic cost. Hence, the modeling of dengue fever is of great significance to understand the dynamics of dengue. In this paper, we extend dengue disease transmission models by including transmit vaccinated class, in which a portion of recovered individual loses immunity and moves to the susceptibles with limited immunity and hence a less transmission probability. We obtain the threshold dynamics governed by the basic reproduction number R₀; it is shown that the disease‐free equilibrium is locally asymptotically stable if R₀ ≤ 1, and the system is uniformly persistence if R₀ > 1. We do sensitivity analysis in order to identify the key factors that greatly affect the dengue infection, and the partial rank correlation coefficient (PRCC) values for R₀ shows that the bitting rate is the most effective in lowering dengue new infections, and moreover, control of mosquito size plays an essential role in reducing equilibrium level of dengue infection. Hence, the public are highly suggested to control population size of mosquitoes and to use mosquito nets. By formulating the control objective, associated with the low infection and costs, we propose an optimal control question. By the application of optimal control theory, we analyze the existence of optimal control and obtain necessary conditions for optimal controls. Numerical simulations are carried out to show the effectiveness of control strategies; these simulations recommended that control measures such as protection from mosquito bites and mosquito eradication strategies effectively control and eradicate the dengue infections during the whole epidemic.     

基于SD-GM理论的城市交通拥堵收费模型研究

随着中国城市化建设步伐的不断加快,交通拥堵在不断地加剧。同时,因机动车污染物的排放,每年将产生大量的NO_x,从而又会引起严重的大气污染(如“雾霾”污染)。针对这些问题,本文从环境和社会的角度出发,采用系统动力学与灰色系统相结合的方法(SD-GM),构建了城市交通拥堵收费模型,并对模型中主要变量进行动态仿真和决策分析,以此来寻找缓解交通拥堵和减少机动车尾气排放的可行策略。通过现实性测试和敏感性测试,得到拥堵收费的范围不超过100元/天*辆。通过进一步的仿真和结果分析可得到以下结论:(1)在区间[25,40] 内,随着拥堵收费的提高,NO_x存量,机动车出行吸引度和交通拥堵程度都呈下降趋势,而车均道路面积呈上升趋势。(2)但并非拥堵收费越高越好, 超过40 元/天*辆,会产生相反的效果。最后,通过比较分析,得到NO_x存量,机动车出行量,机动车出行吸引度和交通拥堵程度分别下降了约33.76%,39.64%,43.26%,82.25%,而车均道路面积提高了大约65.68%,进而验证了模型的有效性和实用性。     

Modeling of Lone Star Ticks with Deer Migration to Canada

Due to climate change and an increase of favourable habitat, ticks and tick-borne diseases are reported to expand to northern areas in north America. One main factor for lone star ticks to be established in Canada is due to the migration of white-tailed deers from US. In this work, we formulate a compartmental model to study the dynamics of lone star ticks and white-tailed deers, with a focus on migration effect of white-tailed deers. The tickhost interaction and the effect of deer migration are explored analytically and numerically. The positivity of the populations in the model is proved, and the unique positive equilibrium is proved to be asymptotically stable. We conduct sensitivity analysis on a set of parameters, revealing the correlation between the parameters and equilibrium populations. Numerical results show that migration rate of white-tailed deer is one crucial parameter that increases the populations of (infected) ticks and (infected) hosts.