Determination of molecular orientation distribution of a stable paramagnetic probe in oriented 4-cyano-4’-<Emphasis Type="Italic">n</Emphasis>-pentylbiphenyl

The molecular orientation distribution function of a stable radical 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in magnetic-field oriented 4-cyano-4’-n-pentylbiphenyl was determined from the angular dependence of the ESR spectra. The preferred molecular orientation of radical species in the liquid crystal matrix was determined. The temperature evolution of the orientation distribution function was studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 2005.     

Spectral regions selection to improve prediction ability of PLS models by changeable size moving window partial least squares and searching combination moving window partial least squares

Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions.     

偏最小二乘光度法同时测定铜和铁的研究及应用

７－（１－苯偶氮）－８－羟基喹啉－５－磺酸钠在ＰＨ＝４．７５ＨＡｃ－ＮａＡｃ缓冲溶液中能与Ｃｕ（Ⅱ）和ＦＥ（Ⅲ）形成稳定的络合物，本文研究了Ｃｕ（Ⅱ）－ＰＡＨＱＳ、Ｆｅ（Ⅲ）－ＰＡＨＱＳ体系的显色条件，以偏最小二乘法处理两者重叠吸收峰，建立了光度法同时测定铜和铁的方法。     

Short Te …︁ Te bonding contacts in a new layered ternary telluride: Synthesis and crystal structure of 2D Nb3GexTe6 (x ≃ 0.9)

The new layered ternary compound Nb₃Ge_xTe₆ (x ? 0.90) was prepared by direct combination of the elements taken in the stoichiometric proportions 3 : 1 : 6, heated at 1 000 °C for 10 days in silica tubes and quenched to room temperature. The phase crystallizes in the orthorhombic symmetry, space group Pnma (#62), with the following single crystal refined parameters: a = 643.18(5) pm, b = 1391.98(11)pm and c = 1 154.07(5) pm, with Z = 4. The structure was refined to an R of 3.4% (R_w = 4.6%), with 1969 independent reflexions and 49 parameters. The structure is based on the close stacking of trigonal prismatic (TP) slabs in the AA/BB mode. The slabs can be seen as built up from face sharing biprisms, which are filled either by one or by two niobium cations situated in the middle of the trigonal prisms. The germanium is located in the middle of the common face of two prisms, leading to a rather unusual anionic square coordination. The refinements showed that this latter cation does not fill completely its square site. No cation was found in the van der Waals gap between the slabs. The mean d_{Ge? Te} distance (276.5 pm) is in agreement with Ge^II cations, while some Te …? Te distances (from 333.84 to 361.65pm) are too short for anions in a simple contact. These bonding distances, already mentionned in some MTe₂ compounds, are to be ascribed to charge transfer in the structure, with a partial oxidation state for the tellurium anions. Short Nb? Nb and Nb? Ge distances (292.0 and 281.3 pm, respectively) imply intercationic bonding within the slabs.     

Consequences of sample size, variable selection, and model validation and optimisation, for predicting classification ability from analytical data

This article discusses problems of validating classification models especially in datasets where sample sizes are small and the number of variables is large. It describes the use of percentage correctly classified (%CC) as an indicator for success of a classification model. For small datasets, %CC should not be used uncritically and its interpretation depends on sample size. It illustrates the use of a common classification method, discriminant partial least squares (D-PLS) on a randomly generated dataset of 200 samples and 200 variables.

An aim of the classifier is to determine whether the null hypothesis (there is no distinction between two classes) can be rejected. Autoprediction gives an 84.5% CC. It is shown that, if there is variable selection, it must be performed independently on the training set to obtain a CC close to 50% on the test set; otherwise, over-optimistic and false conclusions can be reached about the ability to classify samples into groups.

Finally, two aims of determining the quality of a model are frequently confused, namely optimisation (often used to determine the most appropriate number of components in a model) and independent validation; to overcome this, the data should be split into three groups.

There are often difficulties with model building if validation and optimisation have been done on different groups of samples, especially using iterative methods, each group being modelled using properties, such as a different number of components or different variables.     

最小一乘稳健多元分析校正

本文论述最小一乘求解的多元分析校正算法，探讨了最小一乘较常规最小二乘法及其他隐健算法的优点。用计算机数值模拟及实际多组分光谱体系对方法进行了检验，展示了最小一乘法在分析化学计量学中实际应用的可行性。     

方波伏安法测定酚酞片含量

研究了酚酞在0.5 mol/L氨水-氯化铵缓冲溶液(pH 10)介质中汞膜电极上的电化学行为,并依此建立了酚酞含量的方波伏安法测定.酚酞于-0.98 V(VS.Ag/AgCl)处出现一灵敏的阴极还原峰,峰高与酚酞的浓度在3.0×10-7-5.0×10-5mol/L范围内有良好的线性关系.方法的最低检出限为1.0×10-7mol/L,方法用于酚酞片中酚酞含量的测定,结果满意.     

基于SVR和k-近邻群的组合预测在QSAR中的应用

为提高定量构效关系(QSAR)研究的预测精度,发展了一种新的基于支持向量机回归(SVR)非线性筛选分子结构描述符、基于k-近邻群的非线性组合预测方法.首先以均方误差(MSE)最小为原则,以留一法通过多轮末尾淘汰实施分子结构描述符的非线性SVR汰选并给出最优核函数和相应保留描述符;其次基于待测样本与训练样本保留描述符向量的欧氏距离,以不同k-近邻群子模型双重留一法预测值反映样本集的异质性;然后基于MSE最小,以留一法通过多轮末尾淘汰实施近邻群子模型的非线性SVR汰选并给出最优核函数和相应保留子模型;最后基于保留子模型以双重留一法实施组合预测.以取代苯胺和苯酚类化合物对大型溞的QSAR实例验证表明:新方法在所有参比模型中预测精度最高,且能更精细地反映描述符与化合物毒性间的非线性关系,具结构风险最小、非线性、适于小样本,能有效克服过拟合、维数灾和局极小,非线性筛选描述符和子模型,非线性组合预测,自动选择最优核函数及其相应参数,泛化推广能力优异、预测精度高等诸多优点,在QSAR研究中有广泛应用前景.     

Chemometric data analysis of pollutants in wastewater—a case study

In this study, chemometric techniques such as cluster analysis (CA), discriminant analysis (DA), principal component analysis (PCA) and partial least squares (PLS) were used to analyse the wastewater dataset to identify the factors which affect the composition of sewage of domestic origin, spatial and temporal variations, similarity/dissimilarity among the wastewater characteristics of cis- and trans-drains and discriminating variables. Samples collected from 24 wastewater drains in Lucknow city and from three sites on Gomti river in the month of January/February, May, August and November during the period of 5 years (1994-1999) were characterized for 32 parameters. The multivariate techniques successfully described the similarities/dissimilarities among the sewage drains on the basis of their wastewater characteristics and sources signifying the effect of routine domestic/commercial activities in respective drainage areas. Spatial and seasonal variations in wastewater composition were also determined successfully. CA generated six groups of drains on the basis of similar wastewater characteristic. PCA provided information on seasonal influence and compositional differences in sewage generated by domestic and industrial waste dominated drains and showed that drains influenced by mixed industrial effluents have high organic pollution load. DA rendered six variables (TDS, alkalinity, F, TKN, Cd and Cr) discriminating between cis- and trans-drains. PLS-DA showed dominance of Cd, Cr, NO₃, PO₄ and F in cis-drains wastewater. The results suggest that biological-process based STPs could treat wastewater both from the cis- as well as trans-drains, however, prior removal of toxic metals will be required from the cis-drains sewage. Further, seasonal variations in wastewater composition and pollution load could be the guiding factor for determining the STPs design parameters. The information generated would be useful in selection of process type and in designing of the proposed sewage treatment plants (STPs) for safe disposal of wastewater.     

径向基-偏最小二乘-贝叶斯方法及其在化学模式分类中的应用

提出一种用于模式分类的RBF-PLS—Bayes方法。它集成地应用径向基(RBF)变换与偏最小二乘(PLS)方法，从原有模式中提取出分类能力甚强的成分，然后进行贝叶斯(Bayes)判别。这种集成方法尤其适用于复杂化学信息的模式分类，本文将其应用于两种类型的化学模式分类问题，均取得了令人满意的效果。与经典的判别分析方法和单纯的神经网络方法相比，具有明显的优越性。