西红花有效成分—西红花糖苷分离方法和机理的研究及应用
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摘要
本论文建立了以苯乙烯-二乙烯苯类聚合物(SZ-1吸附树脂)为柱填料的低压液相色谱分离方法分离制备西红花有效成份西红花糖苷。此分离方法以SZ-1吸附树脂为柱填料，采用甲醇-水梯度洗脱分离了20种西红花糖苷。通过纯化，10个化合物的纯度高于90％，其中西红花糖苷-1、西红花糖苷-2和西红花糖苷-3的纯度在96％以上。纯度为98.89％的西红花糖苷-1可作为西红花类药物的对照品，用以检验西红花药物的质量。对纯度高于90％的化合物进行了结构测定，确定了3个化合物的结构，并对其他化合物的结构进行了推测和初步探测。
利用各种测试方法对所用新型SZ-1吸附树脂的物理化学性能进行了测定，实验显示SZ-1吸附树脂具有较大的比表面积，良好的孔结构，较高的机械稳定性和热稳定性，较强的抗氧化能力，抗生物降解力和抗酸碱降解能力，可在pH为1-14的范围内使用。通过动态法研究了SZ-1吸附树脂的吸附性能，结果表明SZ-1吸附树脂对西红花提取物有很好的吸附效果，再生率和回收率高，可以反复使用。在此基础上，首次研究了西红花糖苷的分离机理，结果表明SZ-1吸附树脂对西红花糖苷分离机理主要是基于疏溶剂化缔合作用。
本文采用反相液相色谱法，建立了一种以西红花糖苷-1为对照品，以RPC_18为固定相，甲醇-四氢呋喃-1％乙酸水溶液为流动相的等度洗脱外标定量测定分析方法。此方法具有较宽的线性范围(0.1μg～1.16μg)和低的检出量(7ng／ml)，相关性好(R=0.9996)，回收率高(98.3％)，可作为西红花类药物的
四川大学博士学位论文
质量检测的标准方法。
本文首次将氢化物发生原子荧光法（HG－AFS）用于测定西红花中的硒含
量。此方法的检测限低（0．5 u g／mLX 回收率高（90～97％＊ 线性关系好
（R－0．9999），线性范围为 1．5叶 u g／L，在硒的痕量检测中具有广泛的应用价
值。此方法为研究西红花抗氧化作用与其硒含量的量效关系提供了有效的工
具。
A preparation method using low-pressure liquid chromatography to isolate crocins, the most abundant compounds in the saffron hydroalcoholic extract, has been developed. A material, which banded n-butane styrene-divinylbenzene polymer, has been employed as the stationary phase. The best separation is obtained by gradient elution using methanol aqueous solution as mobile phase. Yellow pigments of saffron have been separated to twenty fractions. Among them, the purity of ten compounds is as high as 90% by using a purification column respectively. The purity of crocin-1 is 98.4%. Because crocin-1 is the most abundant in yellow pigments of saffron, such high purity crocin-1 can serve as the standard sample of medical saffron. The structure of crocin-1, crocin-2 and crocin-3 has been detected by UV-Uis, IR, MS, 'HNMR and 13CNMR. The structure of other compounds has been conjectured by UV-Uis, MS.
SZ-1 adsorbent resin has not been large surface areas and excellent porous structure, but also have high mechanical strength and thermal endurance. Moreover, the adsorbent resin also has high oxidation endurance and bio-degradation endurance, as well as acidic and basic degradation. The comprehensive studies oh the adsorption properties of SZ-1 adsorbent resin were conducted in way of mobile adsorption and various effect factors were also studied. The separation mechanism was explored.
A simple sensitive and specific high-performance liquid chromatography -
UV (HPLC-UV) has been developed for quantify the major biologically active ingredient of saffron, namely crocin-1. The HPLC assay was performed on a reversed -phase C18 column using acetonitrile -tetrahy-1% aqueous acetic acid as mobile phase. Calibration was linear (R = 0.9996), with intra-and inter-day RSD of less than 9%. The assay was successfully applied to determination of four saffron samples. Result indicates that the developed HPLC assay can be readily utilized as a quality control method for crocin-containing medicinal.
A method, determinate Se in saffron using AFS-230 hydride generation atomic fluorescence spectrometry (HG-AFS), was studied. The optimal analytical conditions were examined. The detection limit was 0.5 μg/L, the linear range was 1.5 - 15.0 μg/L, the correlation coefficient was 0.9999, and the recovery rate was about 90%-97%. Se of saffron in 4 regions was determined by standard curve method. The experiment results show that the developed HF-ASS assay can be readily utilized as measure for determination Se in saffron.
利用各种测试方法对所用新型SZ-1吸附树脂的物理化学性能进行了测定，实验显示SZ-1吸附树脂具有较大的比表面积，良好的孔结构，较高的机械稳定性和热稳定性，较强的抗氧化能力，抗生物降解力和抗酸碱降解能力，可在pH为1-14的范围内使用。通过动态法研究了SZ-1吸附树脂的吸附性能，结果表明SZ-1吸附树脂对西红花提取物有很好的吸附效果，再生率和回收率高，可以反复使用。在此基础上，首次研究了西红花糖苷的分离机理，结果表明SZ-1吸附树脂对西红花糖苷分离机理主要是基于疏溶剂化缔合作用。
本文采用反相液相色谱法，建立了一种以西红花糖苷-1为对照品，以RPC_18为固定相，甲醇-四氢呋喃-1％乙酸水溶液为流动相的等度洗脱外标定量测定分析方法。此方法具有较宽的线性范围(0.1μg～1.16μg)和低的检出量(7ng／ml)，相关性好(R=0.9996)，回收率高(98.3％)，可作为西红花类药物的
四川大学博士学位论文
质量检测的标准方法。
本文首次将氢化物发生原子荧光法（HG－AFS）用于测定西红花中的硒含
量。此方法的检测限低（0．5 u g／mLX 回收率高（90～97％＊ 线性关系好
（R－0．9999），线性范围为 1．5叶 u g／L，在硒的痕量检测中具有广泛的应用价
值。此方法为研究西红花抗氧化作用与其硒含量的量效关系提供了有效的工
具。
A preparation method using low-pressure liquid chromatography to isolate crocins, the most abundant compounds in the saffron hydroalcoholic extract, has been developed. A material, which banded n-butane styrene-divinylbenzene polymer, has been employed as the stationary phase. The best separation is obtained by gradient elution using methanol aqueous solution as mobile phase. Yellow pigments of saffron have been separated to twenty fractions. Among them, the purity of ten compounds is as high as 90% by using a purification column respectively. The purity of crocin-1 is 98.4%. Because crocin-1 is the most abundant in yellow pigments of saffron, such high purity crocin-1 can serve as the standard sample of medical saffron. The structure of crocin-1, crocin-2 and crocin-3 has been detected by UV-Uis, IR, MS, 'HNMR and 13CNMR. The structure of other compounds has been conjectured by UV-Uis, MS.
SZ-1 adsorbent resin has not been large surface areas and excellent porous structure, but also have high mechanical strength and thermal endurance. Moreover, the adsorbent resin also has high oxidation endurance and bio-degradation endurance, as well as acidic and basic degradation. The comprehensive studies oh the adsorption properties of SZ-1 adsorbent resin were conducted in way of mobile adsorption and various effect factors were also studied. The separation mechanism was explored.
A simple sensitive and specific high-performance liquid chromatography -
UV (HPLC-UV) has been developed for quantify the major biologically active ingredient of saffron, namely crocin-1. The HPLC assay was performed on a reversed -phase C18 column using acetonitrile -tetrahy-1% aqueous acetic acid as mobile phase. Calibration was linear (R = 0.9996), with intra-and inter-day RSD of less than 9%. The assay was successfully applied to determination of four saffron samples. Result indicates that the developed HPLC assay can be readily utilized as a quality control method for crocin-containing medicinal.
A method, determinate Se in saffron using AFS-230 hydride generation atomic fluorescence spectrometry (HG-AFS), was studied. The optimal analytical conditions were examined. The detection limit was 0.5 μg/L, the linear range was 1.5 - 15.0 μg/L, the correlation coefficient was 0.9999, and the recovery rate was about 90%-97%. Se of saffron in 4 regions was determined by standard curve method. The experiment results show that the developed HF-ASS assay can be readily utilized as measure for determination Se in saffron.
引文
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