【作者】 丁玉洁；

【导师】 吴海龙；

【作者基本信息】 湖南大学 ， 分析化学， 2005， 硕士

【摘要】 高效液相色谱是一种广泛应用的分析分离手段,但它的局限在于必须尽可能地避免重叠色谱峰,否则难以很好地定性定量分析,然而化学计量学可以解决这个问题。本论文概述了化学计量学多元分辨与校正这一分支的发展情况以及研究现状,重点描述了三维数据阵三线性分解算法近年来的发展和应用,在此基础上,将三线性分解算法与高效液相色谱-光二极管阵列检测器(HPLC-DAD)相结合,应用于多样品复杂多组分体系中感兴趣组分的同时定性定量分析的二阶校正研究,以解决环境污染物、药物等样品分析中由于性质相似的混合物色谱、光谱严重重叠所引起的组分分离和分析极为困难的难题,实现了化学计量学以“数学分离”代替或增强“化学分离”的构想,展示了二阶校正问题中,三维数阵三线性分解方法所具有的“二阶优势”的魅力。第一章从高效液相色谱的发展和应用简介开始,从其不足处引出化学计量学,然后概述了化学计量学多元分辨与校正这一分支在高效液相色谱中的发展情况和应用研究状况,重点描述了采用交替最小二乘原理的三维数阵三线性分解算法近年来的发展情况和应用研究状况,以及本论文工作开展的意义。第二章,利用交替三线性分解算法解决了高效液相色谱-光二极管阵列检测方法检测两种硝基苯类化合物时由于色谱和光谱峰的重叠而不能有效进行定性定量分析的问题。在背景干扰以及其它干扰共存条件下,结合利用这一算法可以进行待测各组分的同时快速定性定量分析,以“数学分离”代替或增强“化学分离”,实现测定方法的改进。同时也表明交替三线性分解算法是有效解决高效液相色谱-光二极管阵列检测中二阶校正问题的途径之一。第三章,用简单的流动相、很短的分离时间作为高效液相色谱的分离条件,然后结合交替三线性分解(ATLD)算法对尿液中两种糖皮质激素进行同时快速测定。由于这两种糖皮质激素结构相似、光谱相似、保留时间接近,因此很难使它们达到完全分离。而利用交替三线性分解算法结合高效液相色谱-光二极管阵列检测可以在尿液中同时测定这两种糖皮质激素,预测结果和实际结果接近。说明化学计量学在分析科学、生物分析和药物分析中具有广泛的应用前景。第四章是对两种麻醉剂进行快速分析,这两种麻醉剂色谱峰重叠,以考察一种新的算法:交替拟合残差(AFR)算法通过分析低分离水平下二元混合物的HPLC-DAD数据获得可分离的纯光谱、色谱以及浓度轮廓。HPLC-DAD与AFR算法相结合解决了两种局部麻醉剂在低分离水平下的色谱及光谱重叠引起的难分辨的问题,在背景干扰条件下可以进行待测各组分的同时快速定性定量分析,更多还原

【Abstract】 High performance liquid chromatography (HPLC) is one of the most useful analytical techniques. Its chief limitation lies in the need to avoid the overlap of chromatographic peaks as much as possible. However, chemometrics can solve this problem. In this thesis, the developments of multivariate resolution and calibration in chemometrics, especially the alternating trilinear decomposition algorithms for the three-way data analysis and their applications have been reviewed. The methods for three-way trilinear decomposition have been applied to the second-calibration using high performance liquid chromatography-diode array detection (HPLC-DAD). The problems arising from the serious overlapping of spectra and chromatograms are successfully resolved during the analysis of environment contamination and drugs and so on. The assume replacing or improving the “chemical separation” with “mathematical separation” and the charming of three-way data analysis from “second-order advantage” is exhibited in second-order calibration. In Chapter 1, at first, the developments and applications of HPLC have been summarized, and from its shortcoming we introduced the chemometrics. Afterward, the developments of multivariate resolution and calibration in chemometrics, especially the alternating trilinear decomposition algorithms for the three-way data analysis and their applications have been reviewed. The overlapped chromatograms and spectra system of nitrobenzenes (1-chloro-2,4-dinitrobenzene and 3,5-dinitrobenzoic acid) in the presence of 2,4-dinitrobenzoic acid were resolved by ATLD combined with HPLC-DAD in Chapter 2. It successfully solved such problem caused by overlapped chromatograms and spectra even in the presence of unknown interfering components. It uses replacing or improving the “chemical separation” with “mathematical separation”, and the analytical performances is improved. It also revealed the ATLD algorithm is one of the approaches to solve the second-order calibration problem in HPLC-DAD. In Chapter 3, we adopted simply eluting solutions and short separate time as the separate condition of HPLC-DAD and combined with ATLD algorithm to determine simultaneously and fast the two glucocorticoid drugs. Because of similarity of their physical and chemical characteristics, they have similarity spectra and adjacent elute time. In general, it is difficult to reach complete separation of them. However, ATLD method combined with HPLC-DAD can be used to determine simultaneously two glucocorticoid drugs in the presence of unknown interferences which exist in the urine. The prediction results are consistent with the actual one. It is indicated that chemometrics is a promising method to apply in analytical chemistry, biology and medicine analysis. In Chapter 4, two local anaesthetic drugs have been analyzed quickly. In the condition of overlapped chromatogram peaks, usualize a new algorithm: alternating fitting residue (AFR) method for resolving partly separated peaks into the pure chromatographic, spectral and concentration profiles even with very low levels of separation by analyzing HPLC-DAD data. The overlapped chromatograms and spectra arising from low separation level that is difficult to resolve have been settled by HPLC-DAD combining with AFR algorithm and simultaneous qualitative and quantitative analysis in the presence of unknown interfering components. It has been replace or improve the “chemical separation” with “mathematical separation”. By our treating real HPLC-DAD data sets, the results demonstrated that the proposed algorithm performs well as long as the model dimensionality chosen is not less than the number of actual components and avoid the problem of so-called two-factor degeneracy and have lower convergence rate compared with PARAFAC method. The study proved that AFR algorithm is a powder chemometric tool for solving partly separate peaks. In Chapter 5, two anti-tuberculosis drugs (isoniazid and pyrazinamide) have been determined simultaneously by using alternating fitting residue (AFR) method combined with HPLC-DAD. Comparing to alternating trilinear decomposition (ATLD) and self-weighted alternating decomposition algorithm (SWATLD), the predicted results AFR resolved is closer to actual one. The experiment showed that the proposed method can successfully solved such problem that is difficult to resolved, caused by chromatograms and spectra overlapping and quantitative analysis fast and exactly. In Chapter 6, four vitamin drugs (VB1, VB2, VB6 and VB3) have been determined simultaneously by using alternating penalty trilinear decomposition (APTLD) method combined with HPLC-DAD. The results APTLD method predicted is closer to actual one. Moreover, APTLD method has the properties of fast convergence rate and being insensitive to overestimation of the component number compared with traditional PARAFAC. The results showed this experiment can be easily performed without complicated procedures and paying out time-consumingand quantified accurately. The experiment can simultaneously determine interesting compounds in complex system and achieve direct, fast, quanlitative and quantitative analysis.更多还原