Dielectric relaxation of Tripropylene glycol–water mixture using time domain reflectometry

The complex permittivity spectra of tripropylene glycol and water solutions have been obtained by time domain reflectometry (TDR) technique in the frequency range from 10 MHz to 30 GHz and the temperature range 20°C–05°C. The dielectric relaxation parameters such as static dielectric constant and relaxation time were obtained by using the non-linear least square fit method. The intermolecular hydrogen bonding of tripropylene glycol–water has been discussed using the Kirkwood correlation factor and thermodynamic parameters. The activation energy decreases with increase in water content in the mixture as expected in the Arrhenius behaviour. The dielectric constant for mixtures has been fitted to the Bruggeman mixture formula in the non-linear case.     

Theoretical approaches for predicting the color of rigid dyes in solution

Aiming at developing an affordable and easily implementable computational protocol for routine prediction of spectral properties of rigid molecular dyes, density functional theory, and time‐dependent density functional theory were used in conjunction with a vibronic coupling scheme for band shape estimate. To predict the perceived color of molecules in solution, a model has been setup linking the UV‐vis spectra predicted at ab initio level to the L *a *b * colorimetric parameters. The results show that a mixed protocol, implying the use of a global hybrid functional for the prediction of adiabatic energy differences and a range separated hybrid for the prediction of potential energy curvature, allows perceived colors to be quantitatively predicted, as demonstrated by the comparison of L *a *b * colorimetric parameters obtained from computed and experimental spectra. © 2017 Wiley Periodicals, Inc.     

[Cu6(NGuaS)6]2+ and its oxidized and reduced derivatives: Confining electrons on a torus

The hexanuclear thioguanidine mixed‐valent copper complex cation [Cu₆(NGuaS)₆]⁺² (NGuaS = o‐SC₆H₄NC(NMe₂)₂) and its oxidized/reduced states are theoretically analyzed by means of density functional theory (DFT) (TPSSh + D3BJ/def2‐TZV (p)). A detailed bonding analysis using overlap populations is performed. We find that a delocalized Cu‐based ring orbital serves as an acceptor for donated S p electrons. The formed fully delocalized orbitals give rise to a confined electron cloud within the Cu₆S₆ cage which becomes larger on reduction. The resulting strong electrostatic repulsion might prevent the fully reduced state. Experimental UV/Vis spectra are explained using time‐dependent density functional theory (TD‐DFT) and analyzed with a natural transition orbital analysis. The spectra are dominated by MLCTs within the Cu₆S₆ core over a wide range but LMCTs are also found. The experimental redshift of the reduced low energy absorption band can be explained by the clustering of the frontier orbitals. © 2017 Wiley Periodicals, Inc.     

N_2-DART-Orbitrap中的特征气相离子反应及在西药快速检测中的应用

采用实时直接分析(DART)离子源串联高分辨质谱Orbitrap技术(DART-Orbitrap MS),对8种市售常见西药进行有效成分分析,建立了一种快速、简便、准确测定西药中有效成分的方法.对DART离子源的离子化温度、扫描模式、操作气体种类、辅助溶剂种类及其酸碱性等实验条件进行了优化,得到最佳实验条件.实验结果表明,正谱条件下,采用N_2气作为操作气体时,待测组分准分子离子峰[M+H]+同样具有较高的灵敏度和谱图辨识度.因此,N2气可以替代昂贵的He气作为DART离子源的操作气体用于8种药物有效成分的现场实时检测.该方法具备成本低、快速和操作简便的特点.通过分析待测组分的特征碎片离子,发现了N2-DART离子源中的特征离子反应,包括氧化反应和重排反应.根据获得的特征碎片离子对N_2-DART-MS中发生的反应机理进行推导,并结合理论计算对其进行验证.N_2-DART-MS技术有望应用于复杂基质混合物的现场快速检测中.     

Effect of fluorination on the phase sequence,dielectric and electro-optical properties of ferroelectric and antiferroelectric mixtures

Four multicomponent room temperature mixtures were formulated using a pyrimidine-based achiral matrix as host and four terphenyl-based ester chiral compounds as dopants. Among the four mixtures, two exhibit antiferroelectric and two other exhibit ferroelectric phases at room temperature. Dopant molecules differ from each other by position and number of fluorine atom substitution at the benzoate group of the molecular rigid core. Number and location of fluorine atoms in the dopant structure show significant effect on the phase sequences as well as on different physical properties. All the mixtures found to have moderate spontaneous polarisation, high tilt angle, very fast switching time and low viscosity which are important for liquid crystal-based display applications.     

The environmental impact of lightweight HCPV modules: efficient design and effective deployment

We present a life cycle analysis of a lightweight design of high concentration photovoltaic module. The materials and processes used in construction are considered to assess the total environmental impact of the module construction in terms of the cumulative energy demand and embodied greenhouse gas emissions, which were found to be 355.3 MJ and 27.9 kgCO_2eq respectively. We consider six potential deployment locations and the system energy payback times are calculated to be 0.22–0.33 years whilst the greenhouse gas payback times are 0.29–0.88 years. The emission intensities over the lifetimes of the systems are found to be 6.5–9.8 g CO_2eq/kWh, lower than those of other HCPV, PV and CSP technologies in similar locations. Copyright © 2016 John Wiley & Sons, Ltd.     

基于支持向量回归机的陀螺漂移预测模型

为了预测某导弹陀螺漂移趋势,以该陀螺漂移角速度时间序列为对象,建立了基于支持向量回归机的预测模型。针对该预测模型的特点,提出了支持向量预选取的模型优化方法。基于ε不敏感损失函数的支持向量回归机具有稀疏性,其结构由支持向量决定。因此从训练样本集中预选出有可能成为支持向量的样本,精简样本规模是提高该类支持向量回归机训练和预测效率的有效方法。针对该类支持向量回归机从分类和回归两个角度分析了支持向量的几何特征,提出了核函数空间免疫聚类的支持向量预选取方法并用于某导弹陀螺漂移预测模型的数据预处理。仿真结果表明优化后的预测模型运算量小、建模速度快,精度高。     

随机结构非线性动力响应的概率密度演化分析

提出了随机结构非线性动力响应分析的概率密度演化方法．根据结构动力响应的随机状态方程，利用概率守恒原理，建立了随机结构非线性动力响应的概率密度演化方程．结合Newmark-Beta时程积分方法与Lax-Wendroff差分格式，提出了概率密度演化方程的数值分析方法．通过与Monte Carlo分析方法对比，表明所给出的概率密度演化方法具有良好的计算精度和较小的计算工作量．研究表明：随机结构非线性动力响应概率密度具有典型的演化特征，随着时间增长，概率密度曲线分布趋于复杂．     

Optimal Control of Deployment of a Tethered Subsatellite

One of the most important operations during a tethered satellite system mission is the deployment of a subsatellite from a space ship. We restrict tothe simple but practically important case that the system ismoving on a circular orbit around the Earth. The main problem duringdeployment due to gravity gradient is that the two satellites do not move along the straight radial relative equilibrium position which is stable for a tether of constant length. Instead, deploymentleads to an unstable motion with respect to the radial relativeequilibrium configuration. Therefore we introduce an optimal control strategy using theMaximum Principle to achieve a force controlled deployment of the tethered subsatellite from the radial relative equilibrium position close to the space ship to the radial relative equilibrium position far away from the space ship.