功能化的无机复合体系

通过化学物理相互作用将不同组分进行复合可以形成各种各样的复合体系。如果体系中的组分均为无机物或以无机物为主则相应的复合体系称为无机复合体系。通过对组成、结构及形貌等进行设计与调控,可以赋予无机复合体系独特的性质和功能。常见的无机复合体系主要包括主-客体复合物、配位聚合物以及各种纳米复合体系等。这些无机复合体系的功能化对新材料及新能源的开发和利用具有重要意义。本文综述了各种新型无机复合体系的最新研究进展,总结了本课题组在无机复合体系及其功能化的设计与开发方面取得的最新结果,并对功能化的无机复合体系作为新型材料的应用进行了展望。     

羧酸及其衍生物的NaBH4还原体系研究进展

NaBH4还原体系可以快速、高效、选择性地还原羧酸及其衍生物。本文介绍了8类NaBH4还原体系的最近研究成果。通过对各个还原体系的分析,讨论了各类还原体系的反应机理和反应条件,并比较了不同还原体系的还原能力和适用范围。     

双极性电化学的概述及研究进展

作为近年来快速发展的一种便携、阵列、简单的电化学体系,双极性电化学在分析检测、材料制备、物质筛选等领域受到研究者的青睐。简要介绍了双极性电化学的特点,介绍了双极性电极（BPE）体系的2种主要装置：开放性BPE和封闭性BPE。并以开放性BPE体系为例,着重阐述了BPE体系的电化学原理。分别介绍了BPE的极性与驱动电极的关系、BPE体系中的电压及电流的分布,为BPE体系的研究者提供简要的理论基础。此外,还列举了BPE体系在分析检测、材料制备和物质筛选等领域的应用。     

聚乳酸共混体系的研究进展

聚乳酸是人工合成的可生物降解的热塑性脂肪族聚酯 ,是一种环境友好的材料 ,逐渐成为人们研究的热点。本文根据聚乳酸共混体系中另一组分的生物降解性 ,将聚乳酸共混体系分为完全可生物降解共混体系和部分可生物降解共混体系两类。针对体系的相容性和结晶结构以及在提高PLA的性能和降低成本等方面 .综述了聚乳酸共混体系的最新研究进展 ,并对其发展动态进行了简要介绍     

新型镝离子掺杂的三元荧光体系的构建及应用

在无水乙醇体系中构建了镝-磺基水杨酸-三正辛基氧化磷的三元配合物荧光体系,使用荧光分光光度计在激发波长305 nm,发射波长574 nm的条件下对体系进行荧光强度的检测,同时进行条件的优化,对试剂的配比和加入顺序以及反应时间进行筛选。得出了三元配合物体系中镝∶磺基水杨酸∶三正辛基氧化磷的最佳配比为2∶1∶7,最优检测时间为30 min,同时得出了最优的试剂加入顺序依次为Dy~(3+), SSA,TOPO。通过加入镧来构建新的荧光强度更为良好的发光体系。并进行了常见离子的干扰实验以及加入体系中的镧离子的条件进行了优化。在已构建的体系中加入盐酸四环素,发现体系荧光强度明显降低,并利用四环素这一荧光淬灭效应对药品中四环素含量进行检测。     

分子结构对环氧树脂性能影响的分子模拟研究

采用分子动力学方法建立了二乙基甲苯二胺/双酚A缩水甘油醚环氧树脂体系(DETDA/DGEBA体系)和间苯二胺/双酚A缩水甘油醚环氧树脂体系(mPDA/DGEBA体系)的交联模型,在此基础上,分析了固化剂分子结构的差异对树脂性能的影响,研究发现mPDA/DGEBA体系的玻璃化转变温度、模量以及阻碍水分子的扩散性能均高于DETDA/DGEBA体系。为了进一步揭示交联环氧树脂分子结构与性能之间的关系,研究了上述两体系的自由体积和内聚能密度。结果表明,与DETDA/DGEBA体系相比,mPDA/DGEBA体系具有较小的自由体积和较高的内聚能密度。较小的自由体积和较高的内聚能密度是造成mPDA/DGEBA体系玻璃化转变温度、模量以及阻碍水分子的扩散性能均高于DETDA/DGEBA体系的原因。     

橡胶纳米复合材料的一些新进展

近十年来出现了许多新型的橡胶纳米复合材料体系,这些体系展现出比传统体系更强的可设计性、更丰富的性能表现或者呈现功能性质。本文主要综述了橡胶基纳米复合材料的新体系设计和制备方法。基于目前研究现状,作者展望了橡胶纳米复合材料研究若干个值得关注的方向。     

缩聚反应相对分子质量的控制与计算

根据缩聚反应相对分子质量控制理论,分析了经典体系、端基封锁体系和综合体系中平均聚合度或相对分子质量的准确计算公式。     

刚性-柔性体系自组装的研究进展

刚性-柔性体系中刚柔链段间的择优取向竞争使其很容易通过自组装形成如球形、棒状、囊泡等多种形态的纳米有序结构,因此该体系的研究引起了人们广泛的关注。本文对各种不同类型的刚性-柔性体系及制备过程进行了介绍与总结,详尽总结了刚性-柔性体系在各种溶液中的不同自组装行为和相应机理,并对近年发展较为迅猛的超分子刚性-柔性复合物体系进行了重点论述。最后,对刚性-柔性体系自组装研究中存在的问题和发展前景进行了展望。     

n k(k≥4)相多体系封闭网的拼合原理

本文讨论了n k(k≥4)相多体系的某些性质,并系统提出了描述它们的标记符号。在此基础上,提出并论证了n k相多体系封闭网的拼合原理,拼合原理说:任一n k(k≥4)相多体系的封闭网,若不是该多体系所包含的某一n 3级子多体系封闭网本身,就是该多体系所包含的两个或两个以上不同的n 3级子多体系封闭网的拼合。     

Determination of vitamins in mixtures of various composition by spectrophotometry with self-modeling curve resolution

A simple and reliable method for the analysis of mixtures of water- and fat-soluble vitamins in the UV spectral region has been developed using the chemometrical algorithm of self-modeling curve resolution for the decomposition of the spectra of mixtures. The influence of various factors on the result of spectra decomposition has been investigated. The proposed method has been applied to the analysis of model vitamin mixtures as well as multivitamin preparations and energetic drinks.     

Evaluation of a spectral searching algorithm for the comparison of Raman band positions

Raman spectroscopic identification of unknown materials involves often the comparison of the spectrum of the unknown spectrum with previously recorded reference spectra or data from literature. However, when spectra with many Raman bands or spectra of mixtures are involved, searching can be quite complex. Different chemometrical approaches have been proposed, but these have some drawbacks. Therefore, in this paper a novel approach is proposed, which is based on a multivariate comparison of Raman band positions. Different similarity measures can be used and are evaluated with spectra of test samples that were recorded on different spectrometers, using different laser wavelengths. Moreover, this study evaluates the performances of this algorithm for identifying different compounds in mixtures, by using an iterative approach.     

Multi‐component analysis: blind extraction of pure components mass spectra using sparse component analysis

The paper presents sparse component analysis (SCA)‐based blind decomposition of the mixtures of mass spectra into pure components, wherein the number of mixtures is less than number of pure components. Standard solutions of the related blind source separation (BSS) problem that are published in the open literature require the number of mixtures to be greater than or equal to the unknown number of pure components. Specifically, we have demonstrated experimentally the capability of the SCA to blindly extract five pure components mass spectra from two mixtures only. Two approaches to SCA are tested: the first one based on ?₁ norm minimization implemented through linear programming and the second one implemented through multilayer hierarchical alternating least square nonnegative matrix factorization with sparseness constraints imposed on pure components spectra. In contrast to many existing blind decomposition methods no a priori information about the number of pure components is required. It is estimated from the mixtures using robust data clustering algorithm together with pure components concentration matrix. Proposed methodology can be implemented as a part of software packages used for the analysis of mass spectra and identification of chemical compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Peak alignment of urine NMR spectra using fuzzy warping

Proton nuclear magnetic resonance (1H NMR) spectroscopic analysis of mixtures has been used extensively for a variety of applications ranging from the analysis of plant extracts, wine, and food to the evaluation of toxicity in animals. For example, NMR analysis of urine samples has been used extensively for biomarker discovery and, more simply, for the construction of classification models of toxicity, disease, and biochemical phenotype. However, NMR spectra of complex mixtures typically show unwanted local peak shifts caused by matrix and instrument variability, which must be compensated for prior to statistical analysis and interpretation of the data. One approach is to align the spectral peaks across the data set. An efficient and fast warping algorithm is required as the signals typically contain ca. 32,000-64,000 data points and there can be several thousand spectra in a data set. As demonstrated in our study, the iterative fuzzy warping algorithm fulfills these requirements and can be used on-line for an alignment of the NMR spectra. Correlation coefficients between the aligned and target spectra are used as the evaluation function for the algorithm, and its performance is compared with those of other published warping methods.     

Multicomponent analysis in luminescence spectroscopy

Multicomponent analysis of absorption spectra (infrared or electronic spectra) by factor analysis is a suitable method to use. The algorithm of factor analysis is now available for luminescence spectroscopy. The first possibility, as in absorption spectroscopy, is to determine pure components emission spectra for a unique set of spectra of mixtures in overdetermined conditions. On the other hand, it is also possible to extract pure components emission and excitation spectra of the only data corresponding to the 3D fluorescent spectrum of a single mixture. The results are evaluated in respect to noise level and concentrations ratio on both simulated and real spectra.     

Multicomponent analysis in luminescence spectroscopy

Multicomponent analysis of absorption spectra (infrared or electronic spectra) by factor analysis is a suitable method to use. The algorithm of factor analysis is now available for luminescence spectroscopy. The first possibility, as in absorption spectroscopy, is to determine pure components emission spectra for a unique set of spectra of mixtures in overdetermined conditions. On the other hand, it is also possible to extract pure components emission and excitation spectra of the only data corresponding to the 3D fluorescent spectrum of a single mixture. The results are evaluated in respect to noise level and concentrations ratio on both simulated and real spectra.     

A correlation method in library search

The identification of unknown pure compounds or mixtures by means of mass spectral library search can be improved by partly resolving the spectra of the individual components within the spectrum of the measured unknown. This is accomplished by investigating sequential spectra in series of spectra; masses with highly correlating sequential intensities are clustered into individual groups. On the assumption that correlated masses belong to the same component spectrum, a filtering algorithm is developed to exclude spectra of non-identical compounds. The basic ideas, methods, examples and experiences gained with applications are reported.     

Kalman filter quantitative resolution of shifted ESCA spectra after optimal alignment by simulated annealing

Summary The quantitative separation of overlapped responses accomplished by the Kalman filter algorithm is deteriorated by the errors in the model due to shifts of the component peaks. This is particularly true for spectral resolution in Electron Spectroscopy for Chemical Analysis (ESCA). A computational approach for the quantitative resolution of overlapping ESCA spectra when there is loss of collinearity between the pure component peaks and the mixture peak, has been developed. The procedure makes itera tive use of the Kalman filter for resolving the mixture spectrum with the component spectra aligned according to some values of the position parameters, and of the simulated annealing algorithm to find the optimal alignment. The performance of simulated annealing in pursuing this task, has been compared with those of simplex and steepest descent, by analyzing a set of overlapped synthetic spectra and some ESCA spectra of powder mixtures of lead compounds.     

Analysis of multicomponent mass spectra applying Bayesian probability theory

In this paper we develop a method for the decomposition of mass spectra of gas mixtures, together with the relevant calibration measurements. The method is based on Bayesian probability theory. Given a set of spectra, the algorithm returns the relative concentrations and the associated margin of confidence for each component of the mixture. In addition to the concentrations, such a data set enables the derivation of improved values of the cracking coefficients of all contributing species, even for those components for which the set does not contain a calibration measurement. This latter feature also allows one to analyze mixtures that contain radicals in addition to stable molecules. As an example, we analyze and discuss the mass spectra obtained from the pyrolysis of azomethane, which contain the radical CH3 apart from nitrogen and C1- and C2-hydrocarbons.     

熵最小算法解析中药挥发油GC-MS谱中同分异构体的研究

采用以熵最小算法为基本原理的化学计量学方法,结合气相色谱-质谱联用分析法,对玫瑰精油及茉莉花挥发油中的2对同分异构体重叠峰进行重建分析,并分别得到各组分的重建质谱,同时采用NIST数据库相似度检索、质谱碎片信息比对及程序升温指数对分析得到的各组分进行定性分析。通过分析,分别从玫瑰精油和茉莉花挥发油的GC-MS重叠峰中分离得到1对同分异构体。分析结果显示,采用熵最小算法可以成功地对重叠峰中的各组分进行定性分析。该研究为类似同分异构体混合物中各组分的测定提供了参考。