【作者】 李博岩；

【导师】 梁逸曾；

【作者基本信息】 湖南大学 ， 分析化学， 2002， 硕士

【摘要】 基于现代分析化学分析手段的仪器化与信息量测的多样化的特征，联用仪器及相关化学计量学方法的发展为复杂化学体系的分析提供了强有力的手段和广阔的前景。本论文以多组分体系为研究目标，利用化学计量学分辨技术实现对实际样本的快速定性定量分析。 论文的第一章总结了近年来化学计量学基于矩阵分辨而发展的诸多算法，其中一些成熟的算法充分利用了联用色谱的色谱分离能力与光谱表征能力，借助数学手段解决化学问题，给分析科学注入新的活力，推动了分析科学的发展。 第二章系统地阐述了原油样本中非烃化合物的分离富集以及对实际二阶数据进行分辨的全过程。含氮化合物是非烃化合物的重要组成部分，其结构复杂、种类繁多，而且相对含量较小，是原油非烃组分分析的难点。研究该类化合物目的是要摸索出能够简捷、快速、较准确地分离分析重质原油中的含氮化物的方法，尽可能多地获取有关氮化物的组成、结构、物理化学特性等多方面的信息。为深入研究原油重馏分的加氢脱氮反应提供依据，不仅有重要的理论意义，而且在实践中，对原油的勘探和开发有重要的参考价值。联用色谱优良的分离性能可将分析体系沿色谱方向分解为一系列相对简单的子体系，从而实现二阶数据的唯一分辨，在很大程度上很好地解决了色谱重叠与混合质谱检索问题。 第三章将二维数据分析技术用于复杂样本—中药体系的解析。熟地黄为玄参科植物地黄的根茎的炮制加工品，由于其独特的药理药效，在临床上得以广泛地应用。本章针对熟地黄石油醚酸性提取物的甲酯化产物进行解析和鉴定，进而考察熟地黄所含有的化学成分，为熟地黄或者在处方中含有熟地黄的中成药的质量控制和综合评价提供可靠的指标，具有一定的实用价值和意义。同时为提高GC-MS数据中小组分定性的准确度，提出了局部平滑化合物确认方法。根据分析信号与随机噪声的质量色谱峰宽度不同，通过滤除质谱中的随机噪声，较为准确地得到化合物分子离子或准分子离子的信息，可显著地改善定性分析的准确性。 第四章基于相同的化学物质具有相同的光谱，提出了光谱相关色谱的新概念。利用联用色谱的光谱信息与色谱信息，实现复杂中药色谱指纹图谱中的组分相关性判断和不同实验条件下所得中药色谱指纹图谱仪器的系统误差的化学计量学校准，为客观表征和评价中药色谱指纹图谱打下了基础。光谱相关色谱分析为中药化学特征指纹图谱的整体模糊综合分析提供了实用、方便、可靠、有力手段。更多还原

【Abstract】 The basic feature of modern analytical chemistry is instrumentation of measurement and diversification of information. With the development of modern hyphenated apparatus and related chemometric methods,a powerful technique and extensive prospect is provided for complex chemical systems to be dealt with. This research aims at real multicomponent samples in order to analyze rapidly them qualitatively and quantitatively using chemometric resolution methods.In the first chapter of this thesis,many algorithms,which were developed on the basis of matrix resolution in recent years,are reviewed and summarized. Some consummation of them makes good use of both ability of chromatographic separation and ability of spectral characterization of hyphenated chromatography. With the help of mathematics and statistics,some difficult problems in analytical chemistry can be solved elegantly. They not only pour vitality into analytical science but also advance it.The second chapter elaborates preparative separation and enrichment of non-hydrocarbons in crude oil as well as a complete process of resolving real two-dimensional data. Organic nitrogen compounds are principal chemical classes of non-hydrocarbons,whose complicated structures,multifarious types and presentation in poorly low quantities result in the difficulty of analysis. We study them with the purpose of seeking an effective method to separate and analyze nitrogen compounds in high-boiling petroleum,concisely,rapidly and exactly,and getting as maximal information as possible about their constitutes,structures and physical chemistry characteristics and so on. It is significant to provide hydrogenation and denitrogenation in farther processes with a theory. What’s more,it is of great referenced value to direct practical petroleum exploration and exploitation. Excellent separating behavior of hyphenated chromatography can divide the whole investigated system into a series of subsystems in the chromatography direction so as to resolve two-dimensional data uniquely,which cope with overlapping chromatography and mixed spectra to a great extent.In chapter 3,two-dimensional data resolution algorithm is applied to acomplex traditional Chinese medicine system. Radix Rehmanniae Preparata(RRP),as a prepared root of a medicinal plant Rehmannia glutinosa Libosch. (family Scrophulariaceae),has been prescribed and utilized popularly in the clinic due to its pharmacology and pharmacodynamics (e.g. hematopoietics,tonics or antipyretics etc.). Chemical constituents of RRP are intimated by analyzing methylesterification products of the acidic fraction after petroleum ether extract from RRP through resolution and identification. With such obtained information at hand,quality control and comprehensive evaluation upon RRP or some Chinese medicine formula containing RRP can be done reliably. At the same time,a novel method,say local smoothing for component identification method,is proposed to enhance qualitative analysis of low content components of the data. It is based on the assumption that analytical signals differ from random noise in the chromatographic peak width. The information of the molecular ion or pseudo-molecular ion about the analytes can be obtained. Consequently,the resolved mass spectra are refined and qualitative results are improved evidently.In chapter 4,spectral correlation chromatography,as a new concept,is proposed to determine correctly component correlation of complicated chromatographic fingerprints of traditional Chinese medicines by dint of the information both from spectra and from chromatographies obtained from hyphenated instruments,since the same chemical should has the same spectrum in common. Based on the results from the spectral correlation chromatography,fingerprints of traditional Chinese medicines under different experimental conditions can then be characterized and evaluated objectively. It is a practical,convenient and powerful means to the analysis of characteristic chemical fingerprints of traditional Chinese medicines.更多还原