Three-dimensional aromaticity in deltahedral boranes and carboranes

Methods derived from topology and graph theory indicate that the deltahedral boranes B _n H _n ^2– and the corresponding carboranes C₂B_n–2H _n (6 n 12) may be regarded as three-dimensional delocalized aromatic systems in which surface bonding and core bonding correspond to -bonding and -bonding, respectively, in planar polygonal two-dimensional hydrocarbons CinnH _n ^(n–6)+ (n=5/7). The two extreme types of topologies which may be used to model core bonding in deltahedral boranes and carboranes are the deltahedral (D _n ) topology based on the skeleton of the underlying deltahedron and the complete (K _n ) topology based on the corresponding complete graph. Analyses of the Hoffmann-Lipscomb LCAO extended Hückel computations, the Armstrong—Perkins—Stewart self-consistent molecular orbital computations, and SCF MOab initio GAUSSIAN-82 computations on B₆H₆ ^2– indicate that the approximation of the atomic orbitals by the sum of the molecular orbitals, as is typical in modernab initio computations, leads to significantly weaker apparent core bonding approximated more closely by deltahedral (D _n ) topology than by complete (K _n ) topology.This work was presented at the Workshop The Modern Problems of Heteroorganic Chemistry sponsored by the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (May 8–13, 1993).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1353–1360, August, 1993.     

A Background and noise elimination method for quantitative calibration of near infrared spectra

A new hybrid algorithm is proposed to eliminate the varying background and noise simultaneously for multivariate calibration of near infrared (NIR) spectral signals. The method is based on the use of multi-resolution, which is one of the main advantages provided by wavelet transform. The signals are firstly split into different frequency components, which keep the same data points of the original signals. In conjunction with a modified uninformative variable elimination (mUVE) criterion, the new method can be used to remove the low-frequency varying background and the high-frequency noise simultaneously. The method is successfully applied to simulated spectral data set and experimental NIR spectral data, resulting in more parsimonious multivariate models with higher precision. In addition, the proposed strategy can be applied to other spectral signals as well.     

Hyphenation of column liquid chromatography and Raman spectroscopy via a liquid-core waveguide: chemometrical elimination of spectral eluent background

In column liquid chromatography (LC) coupled to conventional Raman spectroscopy (RS) removal of the spectral background of the eluent is often demanding, because of the strong signals of the organic modifier. A new chemometrical method is proposed, called the eluent background subtraction (EBS) method, which can correct for small shape and intensity differences of the eluent spectra. The variations in the eluent spectra are modelled using principal component analysis (PCA). The PCA loading vectors are subsequently used for eluent background correction of the elution spectra of the analyte. The loading vectors are fitted under these spectra by an asymmetric least-squares method. This method was successfully applied under various experimental conditions and performed much better than conventional background correction methods. Analyte detectability was improved by (weighted) averaging of all elution spectra and smoothing via a p-spline function.     

Moving grid method for numerical simulation of stratified flows

We develop a second‐order accurate Navier–Stokes solver based on r‐adaptivity of the underlying numerical discretization. The motion of the mesh is based on the fluid velocity field; however, certain adjustments to the Lagrangian velocities are introduced to maintain quality of the mesh. The adjustments are based on the variational approach of energy minimization to redistribute grid points closer to the areas of rapid solution variation. To quantify the numerical diffusion inherent to each method, we monitor changes in the background potential energy, computation of which is based on the density field. We demonstrate on a standing interfacial gravity wave simulation how using our method of grid evolution decreases the rate of increase of the background potential energy compared with using the same advection scheme on the stationary grid. To further highlight the benefit of the proposed moving grid method, we apply it to the nonhydrostatic lock‐exchange flow where the evolution of the interface is more complex than in the standing wave test case. Naive grid evolution based on the fluid velocities in the lock‐exchange flow leads to grid tangling as Kelvin–Helmholtz billows develop at the interface. This is remedied by grid refinement using the variational approach. Copyright © 2012 John Wiley & Sons, Ltd.     

Novel combination of non-aqueous capillary electrophoresis and multivariate curve resolution-alternating least squares to determine phenolic acids in virgin olive oil

This paper presents the development of a non-aqueous capillary electrophoresis method coupled to UV detection combined with multivariate curve resolution-alternating least-squares (MCR-ALS) to carry out the resolution and quantitation of a mixture of six phenolic acids in virgin olive oil samples. p-Coumaric, caffeic, ferulic, 3,4-dihydroxyphenylacetic, vanillic and 4-hydroxyphenilacetic acids have been the analytes under study. All of them present different absorption spectra and overlapped time profiles with the olive oil matrix interferences and between them. The modeling strategy involves the building of a single MCR-ALS model composed of matrices augmented in the temporal mode, namely spectra remain invariant while time profiles may change from sample to sample. So MCR-ALS was used to cope with the coeluting interferences, on accounting the second order advantage inherent to this algorithm which, in addition, is able to handle data sets deviating from trilinearity, like the data herein analyzed. The method was firstly applied to resolve standard mixtures of the analytes randomly prepared in 1-propanol and, secondly, in real virgin olive oil samples, getting recovery values near to 100% in all cases. The importance and novelty of this methodology relies on the combination of non-aqueous capillary electrophoresis second-order data and MCR-ALS algorithm which allows performing the resolution of these compounds simplifying the previous sample pretreatment stages.     

基于小波高频距离像的红外小目标检测

针对远距离复杂背景下红外小目标检测问题,本文提出了一种基于小波高频距离像的方法。该方法首先将处理空间变换到小波域,通过分析残留背景、目标和噪声系数在高频子带的差异,定义基于邻域均值的子带系数表达形式,构造高频子带系数的中心向量,对小波高频图像进行综合形成距离像,得到红外复杂背景的抑制结果。在此基础上,利用恒虚警率算法将单帧背景抑制图像分割成候选目标、残留背景和噪声像素点。最后,在时间域基于目标运动的相关性,利用管道滤波实现红外小目标的最终检测。仿真实验结果表明,相对于经典算法,本文方法可以实现对红外复杂背景的有效抑制,增强目标信号的强度,准确稳定的从红外复杂背景中检测出小目标。     

一种改进的三帧差分运动目标实时检测算法

针对传统的三帧差分法提取的运动目标存在大量的噪声和空洞,提出了一种改进的三帧差分运动目标实时检测算法。该算法采用Surendra背景提取算法提取有效背景,对视频流中连续的三帧图像分别进行背景减除,得到的结果作为反馈对背景进行选择性更新,利用HSV颜色空间去除阴影后进行三帧差分,将差分结果进行“与”运行,通过将中间帧背景减除结果与“与”运算的结果进行“或”运算,这样可以得到运动目标的完整信息。实验结果表明,该算法能够快速、完整、准确地检测出运动目标,可有效应用于实时监控系统。