悬钩子属植物甜茶叶的化学成分及生物活性研究
摘要
甜茶(Rubus suavissimus S. Lee)是蔷薇科(Rosaceae)悬钩子属(Rubus L.)植物的一个新种，为多年生的有刺灌木，主要分布在我国南方丘陵地区，主产广西。在民间有悠久的应用历史，长期以来一直当茶饮用，亦用来代糖加工食品，还可入药，有清热润肺、祛痰止咳的功效，也有人用作止血消肿，是伤口生肌的良药。近年来，从甜茶中分到一种高甜低热无毒性的甜味剂，是各国科学家们普遍关注的一种蔗糖替代品，具有很高的食用和药用开发价值。
为对甜茶进行系统的药理活性和化学成分研究，以期更好地利用其药用植物资源，我们对甜茶叶的化学成分和生物活性展开研究。甜茶叶经95％乙醇回流提取后，又经50％乙醇回流提取。其中95％乙醇回流提取物，硅胶拌样，干燥后装入索氏提取器分别用石油醚，氯仿，乙酸乙酯，丙酮，乙醇(95％)，甲醇洗脱，得到6个洗脱部分(其中甲醇部分量少，将其与95％乙醇部分合并)。50％乙醇回流提取物，用水稀释经大孔树脂(D101)柱层析，分别用水，30％乙醇，60％乙醇，95％乙醇洗脱，其中水部分弃去，收集其余3个洗脱部分。对各部分分别进行降糖药理活性筛选，结果表明：30％乙醇部分和60％乙醇部分在体外对PTP1B酶均有较强的抑制作用。
本文对乙酸乙酯，丙酮和60％乙醇部分进行了系统的化学成分研究，从中分离并鉴定了27个化合物，其中有6个新化合物，并通过1D、2DNMR，IR，UV，MS及化学方法鉴定了它们的结构。包括10个二萜及其苷类成分：斯替维醇(1)，16α，17，19-三羟基贝壳杉烷(22)，3β，16α，17-三羟基贝壳杉烷(17)，16α，17二羟基贝壳杉烷-19-酸(23)，3β，16α，17，19-四羟基贝壳杉烷(24*)，7β-羟基斯替维醇(19*)，PaniculosideⅣ(27)，甜茶甙-A(26)，Sugeroside(25)，甜叶悬钩子苷(16)；7个三萜类成分：2α，3β-二羟基-乌苏-12-烯-28-酸(14)，2α，3β，23-三羟基-乌苏-12-烯-28-酸(4)，2α，3β，19α，23-四羟基-乌苏-12-烯-28-酸(6)，2α，3β，19α，23-四羟基-齐墩果-12-烯-28-酸(7)，2β，3β，19α，23，24-五羟基-乌苏-12-烯-28-酸(9*)，2，3-O-(缩丙酮)-2α，3β，19α，23-四羟基-乌苏-12-烯-28-酸(12*)，2，3-O-(缩丙酮)-2β，3β，19α，23，24-五羟基-乌苏-12-烯-28-酸(13*)；4个黄酮及其苷类成分：槲皮素(2)，槲皮素-3-O-β-D-吡喃葡萄糖苷(11)，槲皮素-3-O-α-D-核糖苷(10*)，山萘酚-3-O-β-D-6-O-(对羟基桂皮酰基)-吡喃葡萄糖苷(8)；3个木脂素类成分：(7R，8S)-dihydrodehydrodiconiferyl alcohol(18)，7，8-dihydro-Buddlenol B(赤式)(20)，7，8-dihydro-Buddlenol B(苏式)(21)；β-谷甾醇(3)，胡萝卜苷(5)，蔗糖(15)。其中，化合物9，10，12，13，19，24为新化合物；化合物4，8，7，11，14，17，18，20，21，22，23为首次从该植物中分到的已知化合物。对化合物的活性筛选结果表明，化合物19，22，23显示较强的保肝活性。
Rubus suavissimus S. Lee (Rosaceae) is a perennial frutex deciduus whichis widely distributed in Guangxi, it has been used as a potable tea and sugarin folk for a long time. In addition, it is used as a traditional medicine foreliminating phlegm by cooling, expelling phlegm to arrest coughing and hemos-tatic elimination of stagnation.
A series of pharmacological experiments and systematic analyses on the c-hemical constitutions of the leaves of Rubus suavissimus S. Lee have been co-nducted, which built a foundation for the further exploitation of Rosaceae. Thedried and powdered leaves of Rubus suavissimus S. Lee were refluxed with 95% ethanol and 50% ethanol respectively, then concentrated under reduced pre-ssure. The residue of 95% ethanol was subjected to silica-gel column chromat-ography, eluted in order with Petroleum ether, CHCl_3, EtOAc, acetone, 95%ETOH and MeOH. The residue of 50% ethanol was subjected to D101 column andwas eluted respectively by H_2O, 30%EtOH, 60%EtOH and 95%EtOH. All of t-hese portions, the EtOAc, 30%EtOH and 60%EtOH portions showed obvioushypoglycemic activities against PTP1B enzyme in the in vitro screen. Based onthe result, we studied the extract portions and tried to find the chemical comp-ounds related to above bioactivities.
In this thesis, twenty-seven compounds were obtained from the EtOAc, ac-etone portions of the 95% ethanolic extract and 60% ethanolic portion of the50% ethanolic extract, in which six compounds are new compounds. Their str-uctures were elucidated by spectroscopic methods including IR, UV, MS, HRMS, 1D and 2DNMR and chemical methods. As a result, there are 10 diterpeno-ids (1, 16-17, 19, 22-27), 7 triterpenoids (4, 6-7, 9, 12-14), 4 flavonoids (2, 8,10-11), 3 lignans (18, 20-21), 3 other compounds (3, 5, 15). These compoundswere identified respectively as follows: Steviol (1), Quercetin (2),β-sitosterol (3),2α,3β,23-trihydroxy-urs-12-en-28-oic acid (4), Daucosterin (5), 2α,3β,19α,23-tet-rahydroxy-urs-12-en-28-oic acid (6), 2α,3β,19α,23-tetrahydroxy-olean-12-en-28-oicacid (7), kaempferol-3-O-(7-O-trans-p-coumaryol)-β-D-glucopyranoside (8), 2β,3β,19a,23,24-pentahydroxy-urs-12-en-28-oic acid (9), Quercetin-3-O-α-D-ribopyra-noside (10), Quercetin-3-O-β-D-glucopyranoside (11), 2,3-O-acetonide-2α,3β,19α,23- tetrahydroxy-urs-12-en-28-oic acid (12), 2,3-O-acetonide-2β,3β,19α,23,24-pentahy-droxy-urs-12-en-28-oic acid (13), 2α,3β-dihydroxy-urs-12-en-28-oic acid (14), Su-crose (15), Rubusoside (16), 3β,16α,17-trihydroxy-ent-kaurane (17), (7R,8S)-dih-ydrodehydrodiconiferyl alcohol (18), 7β-hydroxy-setviol (19), 7,8-dihydro-Buddle-nol B(erythro) (20), 7,8-dihydro-Buddlenol B (threo)(21), 16α,17,19-trihydroxy-ent-kaurane (22), ent-16α,17-dihydroxy-kauran-19-oic acid (23), 3β,16α,17,19-te-trahydroxy-ent-kaurane (24), Sugeroside (25), Suavioside A (26), PaniculosideⅣ(27). Among them, 9, 10, 12, 13, 19and 24 are new compounds; 4, 7, 8,11, 14, 17, 18, 20, 21, 22 and 23 are isolated from this plant for the fristtime.We also explored the pharmacological activities about the compounds iso-lated from Rubus suavissimus S. Lee. As a result, compound 19, 22 and 23 s-howed potent hepatoprotective activity.
为对甜茶进行系统的药理活性和化学成分研究，以期更好地利用其药用植物资源，我们对甜茶叶的化学成分和生物活性展开研究。甜茶叶经95％乙醇回流提取后，又经50％乙醇回流提取。其中95％乙醇回流提取物，硅胶拌样，干燥后装入索氏提取器分别用石油醚，氯仿，乙酸乙酯，丙酮，乙醇(95％)，甲醇洗脱，得到6个洗脱部分(其中甲醇部分量少，将其与95％乙醇部分合并)。50％乙醇回流提取物，用水稀释经大孔树脂(D101)柱层析，分别用水，30％乙醇，60％乙醇，95％乙醇洗脱，其中水部分弃去，收集其余3个洗脱部分。对各部分分别进行降糖药理活性筛选，结果表明：30％乙醇部分和60％乙醇部分在体外对PTP1B酶均有较强的抑制作用。
本文对乙酸乙酯，丙酮和60％乙醇部分进行了系统的化学成分研究，从中分离并鉴定了27个化合物，其中有6个新化合物，并通过1D、2DNMR，IR，UV，MS及化学方法鉴定了它们的结构。包括10个二萜及其苷类成分：斯替维醇(1)，16α，17，19-三羟基贝壳杉烷(22)，3β，16α，17-三羟基贝壳杉烷(17)，16α，17二羟基贝壳杉烷-19-酸(23)，3β，16α，17，19-四羟基贝壳杉烷(24*)，7β-羟基斯替维醇(19*)，PaniculosideⅣ(27)，甜茶甙-A(26)，Sugeroside(25)，甜叶悬钩子苷(16)；7个三萜类成分：2α，3β-二羟基-乌苏-12-烯-28-酸(14)，2α，3β，23-三羟基-乌苏-12-烯-28-酸(4)，2α，3β，19α，23-四羟基-乌苏-12-烯-28-酸(6)，2α，3β，19α，23-四羟基-齐墩果-12-烯-28-酸(7)，2β，3β，19α，23，24-五羟基-乌苏-12-烯-28-酸(9*)，2，3-O-(缩丙酮)-2α，3β，19α，23-四羟基-乌苏-12-烯-28-酸(12*)，2，3-O-(缩丙酮)-2β，3β，19α，23，24-五羟基-乌苏-12-烯-28-酸(13*)；4个黄酮及其苷类成分：槲皮素(2)，槲皮素-3-O-β-D-吡喃葡萄糖苷(11)，槲皮素-3-O-α-D-核糖苷(10*)，山萘酚-3-O-β-D-6-O-(对羟基桂皮酰基)-吡喃葡萄糖苷(8)；3个木脂素类成分：(7R，8S)-dihydrodehydrodiconiferyl alcohol(18)，7，8-dihydro-Buddlenol B(赤式)(20)，7，8-dihydro-Buddlenol B(苏式)(21)；β-谷甾醇(3)，胡萝卜苷(5)，蔗糖(15)。其中，化合物9，10，12，13，19，24为新化合物；化合物4，8，7，11，14，17，18，20，21，22，23为首次从该植物中分到的已知化合物。对化合物的活性筛选结果表明，化合物19，22，23显示较强的保肝活性。
Rubus suavissimus S. Lee (Rosaceae) is a perennial frutex deciduus whichis widely distributed in Guangxi, it has been used as a potable tea and sugarin folk for a long time. In addition, it is used as a traditional medicine foreliminating phlegm by cooling, expelling phlegm to arrest coughing and hemos-tatic elimination of stagnation.
A series of pharmacological experiments and systematic analyses on the c-hemical constitutions of the leaves of Rubus suavissimus S. Lee have been co-nducted, which built a foundation for the further exploitation of Rosaceae. Thedried and powdered leaves of Rubus suavissimus S. Lee were refluxed with 95% ethanol and 50% ethanol respectively, then concentrated under reduced pre-ssure. The residue of 95% ethanol was subjected to silica-gel column chromat-ography, eluted in order with Petroleum ether, CHCl_3, EtOAc, acetone, 95%ETOH and MeOH. The residue of 50% ethanol was subjected to D101 column andwas eluted respectively by H_2O, 30%EtOH, 60%EtOH and 95%EtOH. All of t-hese portions, the EtOAc, 30%EtOH and 60%EtOH portions showed obvioushypoglycemic activities against PTP1B enzyme in the in vitro screen. Based onthe result, we studied the extract portions and tried to find the chemical comp-ounds related to above bioactivities.
In this thesis, twenty-seven compounds were obtained from the EtOAc, ac-etone portions of the 95% ethanolic extract and 60% ethanolic portion of the50% ethanolic extract, in which six compounds are new compounds. Their str-uctures were elucidated by spectroscopic methods including IR, UV, MS, HRMS, 1D and 2DNMR and chemical methods. As a result, there are 10 diterpeno-ids (1, 16-17, 19, 22-27), 7 triterpenoids (4, 6-7, 9, 12-14), 4 flavonoids (2, 8,10-11), 3 lignans (18, 20-21), 3 other compounds (3, 5, 15). These compoundswere identified respectively as follows: Steviol (1), Quercetin (2),β-sitosterol (3),2α,3β,23-trihydroxy-urs-12-en-28-oic acid (4), Daucosterin (5), 2α,3β,19α,23-tet-rahydroxy-urs-12-en-28-oic acid (6), 2α,3β,19α,23-tetrahydroxy-olean-12-en-28-oicacid (7), kaempferol-3-O-(7-O-trans-p-coumaryol)-β-D-glucopyranoside (8), 2β,3β,19a,23,24-pentahydroxy-urs-12-en-28-oic acid (9), Quercetin-3-O-α-D-ribopyra-noside (10), Quercetin-3-O-β-D-glucopyranoside (11), 2,3-O-acetonide-2α,3β,19α,23- tetrahydroxy-urs-12-en-28-oic acid (12), 2,3-O-acetonide-2β,3β,19α,23,24-pentahy-droxy-urs-12-en-28-oic acid (13), 2α,3β-dihydroxy-urs-12-en-28-oic acid (14), Su-crose (15), Rubusoside (16), 3β,16α,17-trihydroxy-ent-kaurane (17), (7R,8S)-dih-ydrodehydrodiconiferyl alcohol (18), 7β-hydroxy-setviol (19), 7,8-dihydro-Buddle-nol B(erythro) (20), 7,8-dihydro-Buddlenol B (threo)(21), 16α,17,19-trihydroxy-ent-kaurane (22), ent-16α,17-dihydroxy-kauran-19-oic acid (23), 3β,16α,17,19-te-trahydroxy-ent-kaurane (24), Sugeroside (25), Suavioside A (26), PaniculosideⅣ(27). Among them, 9, 10, 12, 13, 19and 24 are new compounds; 4, 7, 8,11, 14, 17, 18, 20, 21, 22 and 23 are isolated from this plant for the fristtime.We also explored the pharmacological activities about the compounds iso-lated from Rubus suavissimus S. Lee. As a result, compound 19, 22 and 23 s-howed potent hepatoprotective activity.
引文
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