Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part II: Theoretical investigation of oxalyl chloride

The structures of the oxalyl chloride molecule (COCl)₂ in the ground and the four lowest (two singlet and two triplet) excited electronic states were investigated by means of the CASPT2(8-6)/cc-pVTZ technique. The equilibrium geometric parameters, harmonic vibrational frequencies, and adiabatic energies of the electronic transitions were determined for all states under investigation. The calculations predicted the existence of the trans- and gauche- conformers in the ground state and the trans- and cis-conformers in all excited states. For the ground electronic state, the conformer energy difference and the barriers to conformational transitions were estimated using extrapolation to the complete basis set within a Valence Focal-Point Analysis procedure. The internal rotation in the excited electronic states was found to be strongly coupled with the non-planar symmetric CCOCl wagging. Two-dimensional potential energy surface sections along internal rotation and non-planar coordinates were constructed, and the corresponding anharmonic vibrational problems for the trans-conformer were solved.     

Conservation of mass and momentum of the least-squares spectral collocation scheme for the Stokes problem

From the literature it is known that spectral least-squares schemes perform poorly with respect to mass conservation and compensate this lack by a superior conservation of momentum. This should be revised, since the here presented new least-squares spectral collocation scheme leads to an outstanding performance with respect to conservation of momentum and mass. The reasons can be found in using only a few elements, each with high polynomial degree, avoiding normal equations for solving the overdetermined linear systems of equations and by introducing the Clenshaw–Curtis quadrature rule for imposing the average pressure to be zero. Furthermore, we combined the transformation of Gordon and Hall (transfinite mapping) with our least-squares spectral collocation scheme to discretize the internal flow problems.     

Al_2O_3杂化聚酰亚胺薄膜Al含量测试方法研究

无机粒子杂化聚酰亚胺(PI)薄膜具有优良的耐电晕特性,广泛用于变频电机中,文章首先用偶联剂处理过的超细氧化铝粉掺杂聚酰胺酸(PAA)制备了不同氧化铝含量的聚酰亚胺杂化膜.通过傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、电感耦合等离子发射光谱(ICP)、重量法、热失重(TG/空气气氛)等测试方法对制备的不同Al2O3含量杂化聚酰亚胺薄膜的无机成分进行了定性和定量分析.结果表明:FTIR和XPS能很好地对杂化膜进行定性分析,FTIR主要对材料的结构进行分析从而推断出其可能的成分,而XPS则主要得到材料所含各元素信息,它具有操作简单,重复性好等优点;通过研究内层电子结合能及其氧化态的变化,XPS可以鉴别元素种类和价态、测定元素的相对含量.XPS和TG的实测值和理论值相差较大,相对标准偏差(RSD)很大,其中,XPS的RSD值大于5.0%,而TG的RSD值也都大于2.0%,只能对杂化膜进行半定量分析.而ICP和重量法的实测值和理论值相差较小且相对标准偏差(RSD)很小,它们的RSD)值均小于1.0%,能进行精确的定量分析,其中重量法的实测值最接近理论值,但只能用于单一无机组分的分析;而ICP法最精确且可以对多无机组分的复合物进行分析,它有简便、快速、灵敏度高、准确性好、可多元素同时测定,且对环境污染小等优点.由上面的结论可以得到一种分析复合材料中的无机成分的方法:首先,用FTIR和XPS对复合材料进行定性分析;然后,以XPS半定量分析结果作为参考,用重量法(单一组分)和ICP法对复合材料进行精确的定量分析.     

分析实验数据处理中的测量不确定度

在现行的分析标准中,大多未对测量不确定度提出相应的要求．本文通过对测量不确定度概念的探讨及对几种化验数据的测量不确定度分析,对检测数据出具时的规范化、标准化有重要意义．     

一种新型铷原子频标腔泡系统的光频移研究

在自行研制的一种小型化微波腔的基础上,新近研制出采用分离滤光技术的气泡型铷频标腔泡系统. 研究该种腔泡系统的光频移特性,确定了该腔泡系统的零光频移和零温度系数点. 系统的光频移系数为7.2×10^-12/10 %. 零光频移温度为68 ℃,比传统的腔泡系统低5～10 ℃. 它不依赖于吸收泡参数,可以通过改变滤光泡参数进行调整,从而简化了参数优化过程.     

气泡型铷原子频标光谱灯优化设计

铷光谱灯作为被动型铷原子频标的重要部件之一,对铷频标整机性能的影响很大. 为了满足高稳定性以及在真空、高温等特殊环境下正常工作的要求,从谱灯振荡电路稳定性、电屏蔽、热设计等方面着手,设计出一套新结构的谱灯. 文中报道了该谱灯的设计思路和初步测试结果.      

一种基于现场定标的光电图像畸变校正算法

针对CCD摄像机所采集的图像存在畸变问题,提出了一种基于现场定标法的多项式变形技术和三元卷积算法,对其进行校正.灰阶Sobel算子通过引入衰减因子对图像进行边缘检测得到不失真的灰阶边缘图,然后将灰阶边缘图进行三次样条插值处理,使标准定标图案边缘的定位达到亚像素级,提高了图像边缘检测的精度.利用建立的校正畸变的函数关系式,实现空间几何坐标变换,既保证特殊环境下的图像测量具有足够高的精度,又使光电图像几何畸变校正达到很好的效果.     

Deployment of response surface methodology to optimise recovery of grape (Vitis vinifera) stem polyphenols

A 2³-full factorial design and response surface methodology were deployed to assess some basic factors (time, % ethanol and pH) affecting profoundly the extractability of polyphenolic phytochemicals from grape (Vitis vinifera) stems. In an effort to obtain a thorough insight into the applicability of the models established, stem extracts from three different varieties were tested, by determining several indices of the polyphenolic composition, such as total polyphenol (TP), total flavanol (TFl), total flavone (TFn) and proanthocyanidin (PC) concentration. It was shown that the models generated can adequately predict the recovery levels for each polyphenol group, but the optimal conditions predicted for TP, TFl, TFn and PC recovery varied significantly. Notable differences were also seen among the different varieties. Correlation of the polyphenol indices with the antiradical activity and reducing power of the extracts indicated that the PC fraction might exert strong effects, while the influence of other groups was not apparent. Examination of the optimally obtained extracts using liquid chromatography-mass spectrometry revealed that the most prominent compounds were caftaric acid, flavanols and derivatives thereof, as well as dehydroflavonols and flavonols.     

高效液相色谱-串联质谱法测定水产品中红霉素的残留

研究了水产品中红霉素残留量测定的新方法. 该方法以红霉素同位素标记物(Erythromycin, N, N-Dimethyl-13C2)为内标物, 样品用乙腈提取、正己烷净化. 分析条件为: 以Hypersil C18为色谱分离柱, 甲醇和0.1 mmol/L 乙酸为流动相, 用带有电喷雾离子源的三重四极杆串联质谱测定, 内标法定量. 红霉素在添加量0.5～20.0 μg/kg的范围内, 回收率为87.0%～97.8%, 相对标准偏差小于10%, 方法检出限为0.5 μg/kg.     

一水合邻菲罗啉的热化学性质

用纯度为99.999%的量热基准苯甲酸标定了实验室建立的精密转动弹量热计,其能当量为18604.99±8.14J/K,测得一水合邻菲罗啉(phen·H2O)的燃烧能为-5757.45±2.53kJ/mol,换算成标准燃烧焓为-5759.93±2.53kJ/mol,进而计算出一水合邻菲罗啉的标准生成焓为-391.34±2.98kJ/mol。