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四种植物化学与生物活性研究
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摘要
本论文共由四章组成。第一章对华丽芒毛苣苔、具斑芒毛苣苔,椭圆线柱苣苔的化学成分进行研究。第二章对华丽芒毛苣苔、具斑芒毛苣苔和椭圆线柱苣苔的各提取部位及单体化合物进行了体外抑制α-葡萄糖苷酶、体外抗氧化和抗菌活性筛选。第三章,综述了苦苣苔科植物的应用、化学成分、药理活性和分类学研究现状,以期对其进行更好的开发利用。第四章对海州常山花的挥发性成分进行了研究。
     第一章华丽芒毛苣苔、具斑芒毛苣苔和椭圆线柱苣苔化学成分研究
     采用柱色谱方法对华丽芒毛苣苔的地上部分进行系统的化学成分研究。从华丽芒毛苣苔地上部分的乙酸乙酯和甲醇部位中分离鉴定了12个化合物。分别为β-谷甾醇(1),羽扇豆醇(2),carissol (3),3-hydroxy-20(29)-lupen-28-oic acid (4),3-hydroxy-5,12-oleanadien-28-oic-acid (5),芹菜素(6),5,7,4'-三羟基-6-甲氧基黄酮(7),熊果酸(8),β-胡萝卜苷(9),2,6-二甲基-4-甲氧基-5-羟基苯甲酸(10)和3,24-dihdroxy-12-oleanen-28-oicacid (11)和3,24-dihdroxy-12-ursen-28-oic acid (12)。化合物1~12为首次从该植物中分离得到;8~12为首次从该属中分离得到;2、3、5、6、7、10、11和12为首次从该科植物中得到。
     采用柱色谱方法对具斑芒毛苣苔的地上部分进行了系统的化学成分研究。从具斑芒毛苣苔地上部分的乙酸乙酯和甲醇部位中分离得到11个化合物,鉴定了其中的10个,分别为羽扇豆醇(1),豆甾醇(2),熊果酸(3),豆甾-5,22(E)-二烯-3β-醇(4),β-胡萝卜苷(5),3-hydroxy-12-taraxasten-28-oic-acid (6),齐墩果酸(8),12-乌苏酸-3-O-β-D-葡萄糖苷(9),12-齐墩果酸-28-O-β-D-葡萄糖苷(10),12-齐墩果酸-3-O-β-D-葡萄糖苷(11)。化合物1~11为首次从该植物中分离得到,6,9,10,11为首次从该科中分离得到,6,8,9,10,11为首次从该属植物中分离得到。
     采用柱色谱方法对椭圆线柱苣苔的地上部分进行了系统的化学成分研究。从椭圆线柱苣苔地上部分的乙酸乙酯和甲醇部位中分离得到8个化合物,鉴定了其中的6个,分别为β-谷甾醇(1),熊果酸(2),豆甾醇(3),齐墩果烷-3-O-β-D-葡萄糖苷(4),β-胡萝卜苷(5),正十八烷酸(6)。化合物1~6为首次从该植物中分离得到,且为首次从该属中分离得到。
     第二章华丽芒毛苣苔、具斑芒毛苣苔和椭圆线柱苣苔生物活性研究
     采用96微孔板法对华丽芒毛苣苔、具斑芒毛苣苔和椭圆线柱苣苔不同溶剂提取物及部分分离得到的化合物进行体外α-葡萄糖苷酶抑制活性研究。结果显示华丽芒毛苣苔石油醚部位,具斑芒毛苣苔的石油醚部位、乙酸乙酯部位和甲醇部位,椭圆线柱苣苔的石油醚部位、乙酸乙酯部位有较好的体外α-葡萄糖苷酶抑制活性。且活性顺序为椭圆线柱苣苔石油醚部位>具斑芒毛苣苔石油醚部位>华丽芒毛苣苔石油醚部位>椭圆线柱苣苔乙酸乙酯部位>具斑芒毛苣苔乙酸乙酯部位>具斑芒毛苣苔甲醇部位。化合物羽扇豆醇、carissol、5,7,4'-三羟基-6-甲氧基黄酮、熊果酸、豆甾-5,22(E)-二烯-3β-醇、3-hydroxy-12-taraxasten-28-oic-acid和齐墩果酸也具有好的体外α-葡萄糖苷酶抑制活性。
     采用DPPH、ABTS和FRAP3种方法综合评价华丽芒毛苣苔、具斑芒毛苣苔和椭圆线柱苣苔三种苦苣苔科植物不同溶剂提取物及分离得到的化合物体外抗氧化活性。华丽芒毛苣苔乙酸乙酯部位、甲醇部位和具斑芒毛苣苔乙酸乙酯部位、甲醇部位的抗氧化活性较好,且三种植物的提取物对DPPH自由基、ABTS自由基的清除能力及对Fe~(3+)的还原能力,均有一定的剂量依赖性。
     对华丽芒毛苣苔、具斑芒毛苣苔和椭圆线柱苣苔三种苦苣苔科植物总甲醇提取物及部分单体化合物的体外抗菌活性研究。三种植物总甲醇提取物对SA均有抑制作用,单体无活性。
     第三章苦苣苔科植物研究进展
     从植物系统分类学、园林应用、化学成分和药理作用等方面对苦苣苔科植物的研究现状进行了综述,以期对该科植物进行更好的开发利用。
     第四章海州常山花的挥发性成分研究
     采用顶空固相微萃取和气质联用技术(HS-SPME-GC-MS),分析了海州常山花的挥发性成分。从海州常山花中共鉴定出了27个化合物,占挥发油成分总峰面积的94.10%,主要有烷烃、醛、醇和酸类。其中含量较高的成分有2,6,10,14-四甲基十六烷(17.25%)、棕榈醛(10.57%)、1-辛烯-3-醇(6.78%)、苯甲醛(6.10%)和棕榈酸(4.85%)。
This dissertation is composed of four chapters. The first chapter included the isolation andidentification of compounds from Aeschynanthus superbus, Aeschynanthus maculatus, and Rhyncho-techum ellipticum. The second chapter studied the antioxidant, α-glucosidase inhibitory and anti-bacteriasactivity of different extracts and compounds from A.superbus, A. maculatus, and R.ellipticum werereported. The third chapter summarized the progress of landscape application, chemical constituent,pharmaceutical activity and taxonomy of the Gesneriaceae family.The four chapter studied the volatilesfrom the flowers of Clerodendron trichotomum Thunb.
     Chapter1. The chemical constituents of Aeschynanthus superbus, Aeschynanthusmaculatus and Rhynchotechum ellipticum.
     1. The chemical constituents from the A. superbus were studied by column chromatography.Twelve compounds were isolated and identified as β-sitosterol (1), lupeol (2), carissol (3),3-hydroxy-20(29)-lupen-28-oic acid (4),3β-hydroxy-5,12-oleanadien-28-oic-acid (5), apigenin (6),5,7,4'-trihydroxy-6-methoxyflavone (7), ursolic acid (8), β-daucosterol (9),2,6,-dimethyl-4-methoxy-5-hydroxy benzoic acid(10), mixture of3,24-dihdroxy-12-oleanen-28-oic acid (11) and3,24-dihdroxy-12-ursen-28-oic acid (12).Compound1~12were isolated from this plant for the first time. Compound8~12were isolated fromAeschynanthus genus for the first time. Compound2~7,10~12were isolated from this family for the firsttime.
     2. The chemical constituents from the A. maculatus were studied by column chromatography.Ten compounds were isolated and identified from the A. maculatus as lupeol (1), stigmasterol (2), ursolicacid (3), stigmast-5,22(E)-diene-3β-ol (4), β-daucosterol (5),3-hydroxy-12-taraxasten-28-oic-acid (6),oleanolic acid (7),3-hydroxy-12-ursen-28-oic acid,3-O-β-D-glucopyranoside (8),3-hydroxy-12-oleanen-28-oic acid,28-O-β-D-glucopyranoside (10) and3-hydroxy-12-oleanen-28-oic acid,3-O-β-D-glucop-yranoside (11). Compound1~11were isolated from this plant for the first time. Compound6~11wasisolated from Aeschynanthus genus for the first time. Compound6~11were isolated from this family forthe first time.
     3. The chemical constituents from the R. ellipticum were studied by column chromatography. Sixcompounds were isolated and identified as β-sitosterol (1), ursolic acid (2), stigmasterol (3),3-hydroxy-12-oleanane-3-O-β-D-glucopyranoside (4), β-daucosterol (5) and octadecanoic acid (6). Compound1~6were isolated from this plant for the first time. And also were isolated from the Rhynchotechum Jack forthe first time.
     Chapter2. The biological activity of Aeschynanthus superbus, Aeschynanthus maculatus,and Rhynchotechum ellipticum.
     1. The inhibitory effect against α-glucosidase of different extracts and compounds from A.superbus, A. maculatus and R. ellipticum were screened in a96-well plate. Petroleum ether extracts of thethree plants and EtOAC extracts of A. maculatus and R. ellipticum showed stronger inhibitory effectagainst a-glucosidase, and were much higher than that of acarbose (IC50=1103.01μg·mL-1). Compoundslupeol, carissol,5,7,4'-trihydroxy-6-methoxyflavone, ursolic acid, stigmast-5,22(E)-diene-3β-ol,3-hydroxy -12-taraxasten-28-oic-acid and oleanolic acid also exhibited stronger inhibitory activity.
     2. DPPH, ABTS, and FRAP assays were used to screen the antioxidant activity of differentextracts and compounds from A. superbus, A. maculatus, and R. ellipticum. EtOAC and the MeOH extractsfrom A. superbus and A. maculatus showed better antioxidant activity.
     3. Antibacterial activity against Staphylococcus aureus (SA), methicillin-resistant Staphylococcusaureus (MRSA) and β-lactamase positive Staphylococcus aureus (ESBLs-SA) of total methol extracts andcompounds from A. superbus, A. maculatus and R. ellipticum were assayed. Three total methol extractsexhibited antibacterial activity of SA. The compounds displayed no activity.
     Chapter3. The study progress of the Gesneriaceae
     The study progress of systematic taxonomy, landscape application, chemical constituent andpharmaceutical of the Gesneriaceae were summarized.
     Chapter4. The volatiles in the Clerodendron trichotomum Thunb.
     The volatiles from the flowers of Clerodendron trichotomum Thunb. were analyzed byhead-space solid micro-extraction, coupled with GC-MS for the first time.27compounds were identifiedfrom the C. trichotomum and account for94.10%of the total volatiles. Hydrocarbons, aldehydes, alcoholsand acids were dominant in the flowers. The main compounds were2,6,10,14-tetramethyl-hexadecane(17.25%), hexadecanal (10.57%),1-octen-3-ol (6.78%), benzaldehyde (6.10%) and n-hexadecanoic acid(4.85%).
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