【作者】 赵春霞；

【导师】 何潮洪；

【作者基本信息】 浙江大学 ， 化学工程， 2007， 博士

【摘要】 多层螺旋管行星式离心仪又称高速逆流色谱仪，是一种新型的液液分配色谱技术。与传统色谱相比，高速逆流色谱不使用固相载体作固定相，克服了固相载体带来的样品吸附、损失和污染等缺点，因此广泛应用于各种天然产物、合成物质的分离和分析。高速逆流色谱采用了一种特殊的行星式运动使两相溶剂在螺旋管内形成单向性动力学分布，可以保证在较高的流动相流量条件下，实现较高的固定相保留及两相溶剂高效率的混合分离，从而使样品在两相溶剂中得到充分的分配，达到高效率的分离。本文第一章对高速逆流色谱的研究进展进行了综述，包括逆流色谱的发展、高速逆流色谱的单向动力学平衡机理、高速逆流色谱的应用、溶剂系统的选择、洗脱模式、固定相保留值、高速逆流色谱仪器的发展以及逆流色谱的放大研究等。本文第二章研究了高速逆流色谱的固定相保留值。根据高速逆流色谱螺旋管内两相流体流动的两种基本情形：(1)层流流动，(2)液滴流流动，建立了描述操作参数(流量、转速)、两相系统的物性参数(两相密度差、粘度和界面张力)和仪器参数(螺旋管内径、公转半径)对固定相保留值影响的数学模型。通过分析固定相保留值的实验数据确定了模型参数以及两种流型转变的临界参数，并采用文献中不同的实验体系对模型进行了验证，包括制备型、半制备型和分析型、不同管材包括聚四氟乙烯和不锈钢，共计十六种溶剂系统的固定相保留值。本文第三章考察了高速逆流色谱分离中各种参数之间的关系，包括流量、转速对色谱峰保留时间和峰宽的影响；色谱峰峰宽和色谱峰保留时间之间的关系。根据这些参数之间的关系，可以估算分离度和分离效率。本文第四章研究了制备型高速逆流色谱中上样量的影响。根据Van Deemter的包括进样量影响的塔板理论，研究了进样量包括进样体积、浓度以及进样质量对色谱峰高和峰宽的影响，考察了Van Deemter理论在高速逆流色谱中的适用性，讨论了限制上样量的因素，包括分离度、分配等温线以及样品的溶解度等。本文第五章研究了高速逆流色谱中的传质特性和色谱洗脱峰模型。通常高速逆流色谱中物质的保留行为只与两相的分配有关，而且轴向扩散和相间传质是造成色谱峰展宽的主要原因。基于这两点假设本文建立了高速逆流色谱的传质-扩散模型，其中包括两个模型参数：轴向扩散系数和相间传质系数，并通过辨识色谱流出曲线得到了轴向扩散系数和相间体积传质系数的普遍关联式。在已知物质分配系数和固定相保留值的情况下，采用本文建立的色谱洗脱峰模型可以对色谱峰进行较准确的预测。本文第六章将高速逆流色谱应用于中药白术中有效成分苍术酮和白术内酯Ⅲ的分离。首先优化了白术挥发油的提取工艺，继而对高速逆流色谱分离条件包括溶剂系统、流量、转速、温度、进样量和洗脱模式进行了优化，并在优化条件下实现了白术挥发油中苍术酮和白术内酯Ⅲ的一步分离。最后，对本文的研究内容进行了总结，并对高速逆流色谱的进一步研究提出了一些建议。更多还原

【Abstract】 Multilayer coil planet centrifuge, also called high-speed countercurrent chromatography (HSCCC), is a new type of liquid-liquid partition chromatography. HSCCC provides an advantage over the conventional column chromatography by eliminating the use of a solid support where dangers of irreversible adsorption from the support, loss and contamination of the sample are inevitably present. So far, it has been widely applied to analytical and preparative scale separations of natural product and other chemical substances. HSCCC utilizes a special synchronous planet motion which produces a unique unilateral hydrodynamic motion of the two solvent phases, and the special motion can guarantee the retention of the stationary phase and efficient mixing and settling of the two-phase solvent system against the flow of the mobile phase to produce excellent peak resolution, and provides the efficient partition and separation of the sample.Chapter 1 of the dissertation gives the literature review about the high-speed countercurrent chromatography, including development of CC-C, unilateral hydrodynamic equilibrium mechanism of HSCCC, application of HSCCC, selection of the two-phase solvent system, elution mode, retention of the stationary phase, development of HSCCC apparatus and its scale-up.Chapter 2 deals with the retention of the stationary phase. A mathematical model was proposed to describe the influences of operation conditions (flow rate, rotation speed), physical properties (density difference, viscosity and interfacial tension) and instrument parameters (tube diameter, revolution radius) on the retention of the stationary phase, by building on the flow behavior of the two phases in the coiled column, laminar flow or droplet flow. The model parameters, together with the critical value at which the transition between the laminar flow and droplet flow occurs, were determined by the analysis of experimental data of the retention of the stationary phase measured in this work. Furthermore, the proposed model wastested to predict the literature data of retention of the stationary phase for seven HSCCC apparatuses including preparative, semi-preparative and analytical types, with the coiled column material of polytetrafluorethylene (PTFE) and stainless steel, and for 16 two-phase systems.Chapter 3 explores the relationships between the operational variables affecting HSCCC, such as the influence of flow rate, rotation speed on the peaks retention time, peaks width, the relationship between the peaks width and peaks retention time. According to these relationships, resolution and efficiency can be estimated.Chapter 4 deals with the sample capacity of preparative HSCCC. Based on the plate theory of Van Deemter, the effects of the sample load including the sample volume, concentrantion and sample mass on the peak retention time and peak width were investigated in a preparative HSCCC, and the theory of Van Deemter was verified in preparative high-speed countercurrent chromatography. Furthermore, the factors limiting the mass load including the resolution between the peaks, the partition isotherm and the sample solubility were also discussed.Chapter 5 deals with the mass transfer and the elution profile model of HSCCC. A transfer-dispersive model was proposed to describe the effluent concentration profile, based on the assumption that retention of a peak is caused by partitioning over two phases, and peak broadening is caused by axial dispersion and mass transfer limitation. The model parameters of axial dispersion coefficient and volumetric mass-transfer coefficient were obtained by comparing model simulations to experimental data. Two correlations about axial dispersion and mass transfer coefficient were obtained. The model presented in this chapter can predict the effluent concentration profiles accurately with the known partition coefficient and the retention of the stationary phase.Chapter 6 deals with the application of preparative HSCCC in separation and purification of two main bioactive components, namely, atractylon and atractylenolide III from the traditional Chinese medicine Atractylodes macrocephala. First, the extraction process of essential oil of Atractylodes macrocephala wasoptimized, and then the HSCCC separation conditions including two-phase solvent system, flow rate, rotation speed, temperature, sample load and elution mode were also optimized. Under the optimized condition, one-step preparative separation of atractylon and atractylenolide III from essential oil of Atractylodes macrocephala was achieved.In Chapter 7, the final section, the research contents of this dissertation were summarized, and several aspects concerning the further investigations of HSCCC are suggested.更多还原