金边瑞香有机相提取物化学成分的分离、鉴定及其抗氧化活性研究
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摘要
金边瑞香(Daphne odora var. marginata)系瑞香科瑞香属常绿小灌木。别名睡香、瑞蓝、千里香、风流树、夺香花等。原产我国长江流域,为我国传统花卉。它不仅具有很强的观赏价值,而且还具有多种药用价值。民间传用金边瑞香叶捣烂敷患处,可治疗溃烂、无名肿痛、乳腺炎等;其花浸泡白酒后可用于治疗风湿性关节炎、类风湿性关节炎、痈、疖、痱子以及因损伤引起肿痛和各种无名肿毒。本文对金边瑞香混合有机溶剂(95%乙醇和乙酸乙酯,1:1,v／v)提取物的化学成分和抗氧化活性进行了研究,以期寻找具有生物活性或结构新颖的药物先导物,为金边瑞香的进一步开发利用提供科学依据。
第一章绪论部分,简单介绍了金边瑞香植物化学成分和药理活性研究概况；综述了两大特征成分香豆素和瑞香黄烷在瑞香属植物中的分布和生物活性研究。
第二章金边瑞香乙酸乙酯提取馏分Fr2经硅胶柱层析分离得到Fr2-B组分,并对其进行HPLC-MS分析,通过各组分保留时间、相对分子质量以及紫外光谱图等信息推测金边瑞香提取物组分Fr2-B可能含有瑞香黄烷A、C、I,双氢瑞香黄烷B, wikstro A、B、异瑞香新素以及一些新瑞香黄烷结构的化合物。提示：金边瑞香中含有大量的瑞香黄烷类化合物。
第三章选择金边瑞香混合溶剂提取物的乙醚提取馏分和乙酸乙酯提取馏分,依次采用硅胶柱,聚酰胺柱和ODS柱层析,分离得到六个单体化合物,运用UV、IR、ESI-MS、EI-MS、1HNMR和13C NMR等光谱技术以及物理化学方法鉴定,其结构分别为：瑞香黄烷B(JB-1)、瑞香黄烷C(JB-2)、瑞香黄烷I(JB-3)、双白瑞香素(JB-4)、瑞香黄烷A(JB-5)和瑞香黄烷D2(JB-6)。
第四章采用清除DPPH白由基，还原铁离子能力，总抗氧化能力(ABTS自由基)三种模型研究了四个瑞香黄烷类化合物(瑞香黄烷A, B, C、D2)和两个香豆素类化合物(瑞香素和双白瑞香素)的抗氧化活性,并探讨抗氧化活性与其结构之间的关系。结果表明：抗氧化能力与羟基所在位置有关；10”位酚羟基未成环的瑞香黄烷A、B抗氧化能力要远远强于10”位酚羟基成环的瑞香黄烷C、-D2;具有3-OH结构的瑞香黄烷B的抗氧化能力略强于瑞香黄烷A；具有7-OH结构的瑞香黄烷D2略强于瑞香黄烷C；香豆素化合物中,7-OH、8-OH邻位酚羟基结构使抗氧化活性大大增强；与对照品BHA、BHT对比发现,瑞香黄烷A、B以及瑞香素都有很强的抗氧化活性,它们有望作为安全有效的抗氧化剂或用于治疗自由基相关疾病的药物前药,值得进一步研究。
Daphne odor a var. marginata, family of Thymelaeaceae, is a famous flower and medical plant in the regions along the Yangzi River. It has been used in Chinese traditional medicine for many diseases. The leaves have been mashed up to kurashiki the affected part for the ulcerate, injury, mastitis; The flowers soaked by white spirit have been used to cure rheumatoid arthritis, rheumatism, carbuncle, furuncle, miliaria, unknown toxin and traumatic injury. In the experiment research, the chemical constituents and antioxidant activity of the extracts from Daphne odora var. marginata were studied to find lead medicinal compounds with biological activity or novel structure. Hopes would offer the theoretical foundation for the depth development and utilization of Daphne odora var. marginata.
In the first chapter, a review was presented, in which introduced the progress of chemical constituents, pharmacological activity in Daphne odora var. marginata.The distribute and bioactivity of coumarin and daphnodorin which were characteristic components in Thymelaeaceae were reviewed, too.
In the second chapter, Fr2-B, one of the fractions eluted from Fr2 which was subjected to CC on silica gel, was analysed by HPLC-MS. Through the messages of retention time, relative molecular mass and ultraviolet spectrum, we guessed that daphnodorin A, B, C, dihydrodaphnodorin B, wikstrol A, B and isodaphneticin may have been existing in Daphne odora var. marginata. The hint:many daphnodorins have been existing in this plant.
In the third chapter, the fractions were extracted by aether, Ethyl acetate from precipitation which was from Daphne odora var. marginata extracted by mixed organic solvent(95% ethanol and Ethyl acetatel:1,v/v), and then were subjected to column chromatography on silica gel, polyamide and ODS. Six compounds were separated and purified from this plant. They were established on the basis of spectral data including UV, IR, ESI-MS, EI-MS,1H NMR, 13C NMR, physical and chemical properties, as follow:daphnodorin B (JB-1), daphnodorin C (JB-2), daphnodorin I (JB-3), daphnoretin(JB-4), daphnodorin A(JB-5) and daphnodorin D2 (JB-6).
In the fourth chapter, the pertinence relation between structural and the antioxidant activities of four daphnodorins and two coumarins was respectively studied by the total antioxidant activity, scavenging activity of DPPH radicals and reducing power. The results:the antioxidant activity mainly depends on the position and quantity of hydroxyl group; the antioxidant activity mainly depends on the position of hydroxyl group; the 2",3"-double bond and the 4"-carbonyl in the C ring contributes much to the antioxidant activity of daphnodorins; daphnodorin B with 3-OH is a little stronger than daphnodorin A; daphnodorin C is a little weaker than daphnodorin D2 with 7-OH; phenolic hydroxyl on the ortho-position is very helpful for the antioxidant activity of coumarin; compared with BHA, BHT, the antioxidant activities of daphnodorin A, daphnodorin B and daphnetin were very strong. Therefore, it is worth studying deeper to use them as safe, effective antioxidants or medicine for curing disease related to radicals.
第一章绪论部分,简单介绍了金边瑞香植物化学成分和药理活性研究概况；综述了两大特征成分香豆素和瑞香黄烷在瑞香属植物中的分布和生物活性研究。
第二章金边瑞香乙酸乙酯提取馏分Fr2经硅胶柱层析分离得到Fr2-B组分,并对其进行HPLC-MS分析,通过各组分保留时间、相对分子质量以及紫外光谱图等信息推测金边瑞香提取物组分Fr2-B可能含有瑞香黄烷A、C、I,双氢瑞香黄烷B, wikstro A、B、异瑞香新素以及一些新瑞香黄烷结构的化合物。提示：金边瑞香中含有大量的瑞香黄烷类化合物。
第三章选择金边瑞香混合溶剂提取物的乙醚提取馏分和乙酸乙酯提取馏分,依次采用硅胶柱,聚酰胺柱和ODS柱层析,分离得到六个单体化合物,运用UV、IR、ESI-MS、EI-MS、1HNMR和13C NMR等光谱技术以及物理化学方法鉴定,其结构分别为：瑞香黄烷B(JB-1)、瑞香黄烷C(JB-2)、瑞香黄烷I(JB-3)、双白瑞香素(JB-4)、瑞香黄烷A(JB-5)和瑞香黄烷D2(JB-6)。
第四章采用清除DPPH白由基，还原铁离子能力，总抗氧化能力(ABTS自由基)三种模型研究了四个瑞香黄烷类化合物(瑞香黄烷A, B, C、D2)和两个香豆素类化合物(瑞香素和双白瑞香素)的抗氧化活性,并探讨抗氧化活性与其结构之间的关系。结果表明：抗氧化能力与羟基所在位置有关；10”位酚羟基未成环的瑞香黄烷A、B抗氧化能力要远远强于10”位酚羟基成环的瑞香黄烷C、-D2;具有3-OH结构的瑞香黄烷B的抗氧化能力略强于瑞香黄烷A；具有7-OH结构的瑞香黄烷D2略强于瑞香黄烷C；香豆素化合物中,7-OH、8-OH邻位酚羟基结构使抗氧化活性大大增强；与对照品BHA、BHT对比发现,瑞香黄烷A、B以及瑞香素都有很强的抗氧化活性,它们有望作为安全有效的抗氧化剂或用于治疗自由基相关疾病的药物前药,值得进一步研究。
Daphne odor a var. marginata, family of Thymelaeaceae, is a famous flower and medical plant in the regions along the Yangzi River. It has been used in Chinese traditional medicine for many diseases. The leaves have been mashed up to kurashiki the affected part for the ulcerate, injury, mastitis; The flowers soaked by white spirit have been used to cure rheumatoid arthritis, rheumatism, carbuncle, furuncle, miliaria, unknown toxin and traumatic injury. In the experiment research, the chemical constituents and antioxidant activity of the extracts from Daphne odora var. marginata were studied to find lead medicinal compounds with biological activity or novel structure. Hopes would offer the theoretical foundation for the depth development and utilization of Daphne odora var. marginata.
In the first chapter, a review was presented, in which introduced the progress of chemical constituents, pharmacological activity in Daphne odora var. marginata.The distribute and bioactivity of coumarin and daphnodorin which were characteristic components in Thymelaeaceae were reviewed, too.
In the second chapter, Fr2-B, one of the fractions eluted from Fr2 which was subjected to CC on silica gel, was analysed by HPLC-MS. Through the messages of retention time, relative molecular mass and ultraviolet spectrum, we guessed that daphnodorin A, B, C, dihydrodaphnodorin B, wikstrol A, B and isodaphneticin may have been existing in Daphne odora var. marginata. The hint:many daphnodorins have been existing in this plant.
In the third chapter, the fractions were extracted by aether, Ethyl acetate from precipitation which was from Daphne odora var. marginata extracted by mixed organic solvent(95% ethanol and Ethyl acetatel:1,v/v), and then were subjected to column chromatography on silica gel, polyamide and ODS. Six compounds were separated and purified from this plant. They were established on the basis of spectral data including UV, IR, ESI-MS, EI-MS,1H NMR, 13C NMR, physical and chemical properties, as follow:daphnodorin B (JB-1), daphnodorin C (JB-2), daphnodorin I (JB-3), daphnoretin(JB-4), daphnodorin A(JB-5) and daphnodorin D2 (JB-6).
In the fourth chapter, the pertinence relation between structural and the antioxidant activities of four daphnodorins and two coumarins was respectively studied by the total antioxidant activity, scavenging activity of DPPH radicals and reducing power. The results:the antioxidant activity mainly depends on the position and quantity of hydroxyl group; the antioxidant activity mainly depends on the position of hydroxyl group; the 2",3"-double bond and the 4"-carbonyl in the C ring contributes much to the antioxidant activity of daphnodorins; daphnodorin B with 3-OH is a little stronger than daphnodorin A; daphnodorin C is a little weaker than daphnodorin D2 with 7-OH; phenolic hydroxyl on the ortho-position is very helpful for the antioxidant activity of coumarin; compared with BHA, BHT, the antioxidant activities of daphnodorin A, daphnodorin B and daphnetin were very strong. Therefore, it is worth studying deeper to use them as safe, effective antioxidants or medicine for curing disease related to radicals.
引文
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