王云卿1,2, 马国需3, 赵丹1,高亚茹3 ,吴桐宇3, 5,李叶丹3, 5,周兴杨3, 5,杨峻山3,袁经权1,2*,许旭东3(1. 广西师范学院化学与材料科学学院,广西南宁530001;2. 广西药用植物研究所,广西南宁 530023;3. 中国医学科学院北京协和医学院药用植物研究所,北京100193;4. 广西金秀瑶医医院,广西金秀5457084. 5. 哈尔滨商业大学 生命科学与环境科学研究中心,黑龙江 哈尔滨 150076)
摘要:目的: 对瑶药“肿瘤藤”即星毛冠盖藤Pileostegia tomentella Hand.-Mazz.藤茎的化学成分进行研究。方法: 利用各种色谱方法进行分离纯化,根据理化性质和NMR,MS等波谱技术鉴定化合物的结构。结果:从星毛冠盖藤藤茎甲醇提取物中的正丁醇萃取部位分离鉴定了13个化合物,分别为1-O-(β-D-glucosyl)-2-[2-methoxy-4-(ω-hydroxypropyl)-phenoxy]-propan-3-ol (1),(+)-lyoniresinol-3a-O-β-D-glucopyranoside (2),紫丁香苷(syingin) (3),柏松苷(coniferin) (4),二氢柏松苷(dihydroconiferin) (5),but-3-enyl-β-D-glucoside (6),4-(2,3-dihydroxy propyl)-2,6-dimethoxy phenyl-β-D-glucopyranoside (7), nikoenoside(8),原儿茶酸乙酯(protocatechuic acid ethyl ester) (9),8-甲氧基香豆素-7-O-β-D-葡萄糖(8-methoxy coumarin-7-O-β-D-glycosidase) (10),6-O-R-L-rhamnopyranosyl-β-D-glucopyranoside of methyl salicylate (11),烟酰胺(nicotinamide) (12), 3,5-二咖啡酰奎宁酸甲酯(3,5-di-O-caffeoyl quinicacid methyl ester ) (13)。结论:所有化合物均为首次从该属和该植物中分离得到。
关键词:冠盖藤;化学成分;正丁醇部位;环烯醚萜苷;香豆素。
虎耳草科(Saxifragaceae)冠盖藤属Pileostegia植物全世界仅有3种,主要分布于亚洲热带和亚热带地区,我国主要分布于长江以南各地,该属植物主要有祛风除湿,散瘀止痛,舒筋活络,消肿解毒等功效[1],为我国南方瑶族、苗族地区常用药。现代研究表明该属植物化学成分主要含有香豆素、甾体、苯并吡喃等成分,具有抗癌、消炎、镇痛等多种活性[2]。该属的星毛冠盖藤Pileostegia tomentella Hand. –Mazz.在瑶族地区被冠为为“肿瘤藤”(或称“消瘤藤”),是传统瑶医药治疗癌症的主要药材之一。但目前星毛冠盖藤的化学成分研究尚属空白,为了阐明该植物的活性物质基础,课题组对其化学成分进行了研究。从星毛冠盖藤藤茎的90%甲醇提取物的正丁醇萃取部位中分离得到了13个化合物, 通过理化性质及光谱学方法确定其结构,分别为1-O-(β-D-glucosyl)-2-[2-methoxy-4-(ω-hydroxypropyl)-phenoxy]-propan-3-ol (1),(+)-lyoniresinol-3a-O-β-D-glucopyranoside (2),紫丁香苷(syingin) (3),柏松苷(coniferin) (4),二氢柏松苷(dihydroconiferin) (5),but-3-enyl-β-D-glucoside (6),4-(2,3-dihydroxy propyl)-2,6-dimethoxy phenyl-β-D-glucopyranoside (7),nikoenoside (8),原儿茶酸乙酯(protocatechuic acid ethyl ester) (9),8-甲氧基香豆素-7-O-β-D-葡萄糖(8-methoxy coumarin-7-O-β-D-glycosidase) (10),6-O-R-L-rhamnopyranosyl-β-D-glucopyranoside of methyl salicylate (11),烟酰胺(nicotinamide) (12),3,5-二咖啡酰奎宁酸甲酯(3,5-di-O-caffeoyl quinicacid methyl ester ) (13), 上述所有化合物均为首次从该属和该植物中分离得到。
1仪器与材料
BrukerAvance III 600型核磁共振波谱仪,赛默飞世(Thermofisher) LTQ-Obitrap XL液质联用仪,柱色谱硅胶(青岛海洋化工有限公司),柱色谱薄层色谱用硅胶G,H,GF254。HW-40C凝胶(Toyopearl公司)MCI(日本三菱化学公司),常规试剂均为分析纯。
“肿瘤藤”药材由广西金秀瑶族自治县瑶医医院提供,采集于金秀瑶族自治县桐木镇,经广西中医药大学植物分类专家韦松基教授鉴定为虎耳草科冠盖藤属植物星毛冠盖藤Pileostegia tomentella Hand.- Mazz.的藤茎。
2 提取分离
15公斤冠盖藤藤茎,阴干,粉粹,以90%甲醇回流提取三次,每次3小时。过滤,提取液减压回收甲醇,并浓缩至无醇味,所得浸膏分散于水中,分别用石油醚、二氯甲烷、乙酸乙酯、正丁醇萃取,再将萃取液浓缩,得到四个部位的浸膏。取正丁醇部位220g经硅胶(100~200目)柱色谱,氯仿-甲醇(100:0~1:1)梯度洗脱得到10个流分(Fr.1~10)。Fr.6(2.0 g)用反向填料Lichroprep Rp-18 (40~63μm)柱色谱分离,得到4个组分(Fr.6-1~Fr.6-4)。Fr.6-3(50mg)经HPLC半制备色谱分离(YMC-Pack ODS-A,10 mm×250mm,5μm ,25%)得到化合物1(4.6 mg), 2(7.1mg)。Fr.7 (3.7 g)用反向材料Lichroprep Rp-18 (40~63μm)柱色谱分离,薄层色谱检测,合并相似洗脱液得到4个组分( Fr.7-1~Fr.7-4)。Fr.7-1(0.9g)经Sephadex LH-20凝胶柱色谱分离,得到化合物3(8.2mg)。Fr.7-3(0.2g),经HPLC半制备色谱分离(YMC-Pack ODS-A, 10 mm×250 mm, 5 μm, 28%甲醇)得到化合物4(3.0mg),5(3.4 mg)。Fr.8(4.2g)先后经HW-40C凝胶柱色谱分离,得到4个组分( Fr.8-1~Fr.8-4)。Fr.8-4 (0.4 g)经HPLC半制备色谱分离(Agela Technologies Innoval ODS-2,10mm×250mm,7μm, 8%甲醇)得到化合物6(1.0mg),7(2.6mg),8(1.1mg)。Fr.9(2.6 g)经HW-40C凝胶柱色谱分离,得到5个组分(Fr.9-1~Fr.9-5)。Fr.9-2(30mg)经HPLC半制备色谱分离(Agela Technologies Innoval ODS-2, 10 mm×250 mm, 7 μm,3%甲醇)得到化合物9(3.4mg),10(3.9mg)。Fr.9-4(60 mg)经HPLC半制备色谱分离(YMC-Pack ODS-A, 10 mm×250 mm, 5 μm,30%甲醇),得到化合物11(3.6 mg),Fr.9-5(0.1 g)经HPLC半制备色谱分离(YMC-Pack ODS-A, 10 mm×250 mm, 5 μm,18%甲醇)得到化合物12(2.9 mg),13 (2.4 mg)。
3结构鉴定
化合物1 无色油状,易溶于甲醇、DMSO。ESI-MS m/z: 441 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 6.97 (1H, d, J = 8.4 Hz, H-5'), 6.78 (1H, d, J = 1.8 Hz, H-3'), 6.67(1H, dd, J = 1.8, 1.2 Hz, H-6'), 4.52 (1H, t, J = 5.4 Hz, H-2), 4.19 (1H, d, J = 1.8 Hz, H-1''), 3.57 (2H, m, H-9'), 3.2–4.0 (6H, m, H-2''~H-6''), 3.39 (2H, m, H-1), 2.94 (2H, m, H-3), 2.51 (2H, t, J = 7.8 Hz, H-7'), 1.69 (2H, m, H-8'); 13C-NMR (DMSO-d6,150 MHz) δC: 149.6 (C-2'), 145.0 (C-1'), 135.5 (C-4'), 120.1 (C-5'), 116.0 (C-3'), 112.7 (C-6'), 103.4(C-1''), 78.8 (C-2), 76.9 (C-5''), 76.7(C-3''), 73.4 (C-2''), 69.9 (C-4''), 67.9 (C-1), 60.9 (C-3), 60.1 (C-6''), 60.1 (OCH3), 55.5 (C-9'), 34.4 (C-7'), 31.2 (C-8'),以上数据与文献报道数据基本一致[3],故鉴定该化合物为1-O-(β-D-glucosyl)-2-[2-methoxy-4-(ω-hydroxypropyl)-phenoxy]-propan-3-ol.
化合物2 黄色油状,易溶于甲醇、DMSO。ESI-MS m/z:571 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 6.53 (1H, s, H-8), 6.33 (2H, s, H-2', H-6'), 4.28 (1H, d, J = 6.0 Hz, anomeric-H), 3.76 (3H, s, OCH3), 3.63 (9H, s, OCH33);13C-NMR (DMSO-d6,150 MHz) δC: 147.5 (C-3', C-5'), 146.8 (C-5), 146.5 (C-7), 137.5 (C-1'), 137.2 (C-6'), 133.2 (C-4') 128.4 (C-9), 124.9 (C-10), 106.6 (C-2'), 105.8 (C-6'), 103.4 (C-1''), 76.9 (C-3'', C-5''), 73.5 (C-2''), 70.0 (C-4''), 69.5 (C-3a), 63.9 (C-2a), 58.8 (C-6''), 56.0 (OCH32), 55.6 (OCH3), 44.3 (C-3), 40.6 (C-4), 32.4 (C-1),以上数据与文献报道数据基本一致[4],故鉴定该化合物为(+)-lyoniresinol-3a-O-β-D-glucopyranoside。
化合物3 白色粉末,易溶于甲醇、DMSO。ESI-MS m/z:395 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 6.72 (2H, s, H-2, H-6), 6.44 (1H, d, J =16.2 Hz, H-7), 6.35 (1H, dt, J = 5.4, 4.8 Hz, H-8), 4.10 (2H, s, H-9), 4.90 (1H, d, J = 3.6 Hz, H-1'), 2.99~3.60 (6H, m, Glc-H), 3.76 (6H, s, OCH32); 13C-NMR (DMSO-d6,150 MHz) δC: 152.7 (C-3, C-5), 133.7(C-1), 132.5 (C-4), 130.1 (C-7), 128.4 (C-8), 104.4 (C-2, C-6), 102.5 (C-1'),77.4 (C-5'), 76.7 (C-3'), 74.1 (C-2'), 69.9 (C-4'), 61.4 (C-9), 60.8 (C-6'), 56.3 (OCH32),以上数据与文献报道数据基本一致[5],故鉴定该化合物为紫丁香苷。
化合物4 白色粉末,易溶于甲醇、DMSO。ESI-MS m/z:365 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 6.89 (1H, dd, J = 8.4, 1.8 Hz, H-2), 7.02 (1H, d, J = 7.8 Hz, H-5), 7.19 (1H, d, J = 9.6 Hz, H-6), 6.44 (1H, br.d, J = 16.2 Hz, H-7), 6.23 (1H, dt, J = 15.6, 4.8 Hz, H-8), 4.08 (2H, t, J = 4.2 Hz, H-9), 4.88 (1H, d, J = 7.2 Hz, H-1'), 3.16~3.67 (6H, m, Glc-H), 3.87 (3H, s, OCH3); 13C-NMR (DMSO-d6,150 MHz) δC: 149.2 (C-3), 145.9 (C-4), 129.9 (C-1), 128.9 (C-7), 128.4 (C-8), 119.0 (C-6), 114.2 (C-2), 113.3 (C-5), 99.9 (C-1'), 77.0 (C-5'), 76.8 (C-3'), 73.2 (C-2'), 69.6(C-4'), 61.6 (C-9), 60.6 (C-6'), 55.6 (OCH3),以上数据与文献报道数据基本一致[6],故鉴定该化合物为柏松苷。
化合物5 白色粉末,易溶于甲醇、DMSO。ESI-MS m/z:367 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 6.79 (1H, d, J = 1.8 Hz, H-2), 6.97 (1H, d, J = 8.4 Hz, H-5), 6.66 (1H, dd, J = 8.4, 1.8 Hz, H-6), 2.54 (2H, t, J = 7.8 Hz, H-7), 1.69 (2H, m, H- 8), 3.41 (2H, m, H-9), 4.83 (1H, d, J = 7.2 Hz, H-1'), 3.15~3.65 (7H, m, Glc-H), 3.74 (3H, s, OCH3);13C-NMR (DMSO-d6,150 MHz) δC: 148.7 (C-3), 144.5 (C-4), 135.9 (C-1), 120.0 (C-6), 115.3 (C-5), 112.8 (C-2), 100.2 (C-1'), 76.9 (C-5'), 76.8 (C-3'), 73.2 (C-2'), 69.6 (C-4'), 60.6 (C-6'), 60.0 (C-9), 55.5 (OCH3), 34.4 (C-8), 31.2 (C-7),以上数据与文献报道数据基本一致[7],故鉴定该化合物为二氢柏松苷。
化合物6 无色油状,易溶于甲醇、DMSO。ESI-MS m/z:405 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 7.70 (1H, d, J = 8.4 Hz, H-3), 5.13 (2H, m, H-4), 4.62 (1H, d, J = 7.8 Hz, H-1'), 3.69 (1H, s, H-1), 2.66~3.61 (6H, m, Glc-H), 2.17 (2H, t, J = 12.6 Hz, H-2);13C-NMR (DMSO-d6,150 MHz) δC: 135.2 (C-3), 115.3 (C-4), 99.0 (C-1'), 77.3 (C-5'), 76.7 (C-3'), 73.0 (C-2'), 69.9 (C-4'), 66.9 (C-1), 61.0 (C-6'), 25.4 (C-2),以上数据与文献报道数据基本一致[8],故鉴定该化合物为but-3-enyl-β-D-glucoside。
化合物7 黄色油状,易溶于甲醇、DMSO。ESI-MS m/z:413 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 6.50 (2H, s, H-2, H-6), 4.82 (1H, d, J = 3.0 Hz, H-1'), 3.71 (6H, s, OCH32), 3.68 (1H, s, H-8), 3.14 (2H, m, H-9), 2.9~3.61 (6H, m, Glc-H), 2,82 (1H, dd, J = 12.6, 5.4 Hz, H-7a), 2.67 (1H, dd, J = 12.6, 7.8 Hz);13C-NMR (DMSO-d6,150 MHz) δC: 147.6 (C-2, C-6), 133.5 (C-1), 128.2 (C-4), 102.9 (C-1'), 106.8 (C-3, C-5), 76.9 (C-3'), 76.5 (C-5'), 73.9 (C-2'), 73.2 (C-8), 70.2 (C-4'), 67.8 (C-9), 61.2 (C-6'), 55.8 (OCH32), 37.9 (C-7),以上数据与文献报道数据基本一致[9],故鉴定该化合物为4-(2,3-dihydroxypropyl)-2,6-dimethoxy phenyl-β-D-glucopyranoside。
化合物8 黄色油状物,易溶于甲醇、DMSO。ESI-MS m/z:383 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 6.76 (2H, s, H-2, H-6), 4.69 (1H, d, J = 12 Hz, H-7a), 4.66 (1H, d, J = 12.0 Hz, H-7b), 4.32 (1H, d, J = 7.2 Hz, H-1'), 3.25~3.93 (6H, m, Glc-H), 3.74 (3H, s, 4-OCH3), 3.83 (6H, s, 3,5-OCH3);13C-NMR (DMSO-d6,150 MHz) δC: 154.6 (C-3, C-5), 135.3 (C-1), 133.5 (C-4), 106.5 (C-2, C-6), 103.1 (C-1'), 78.3 (C-3'), 78.1 (C-5'), 75.3 (C-2'), 71.9 (C-4'), 71.6 (C-7), 63.0 (C-6'), 61.2 (4-OCH3), 56.7 (3,5-OCH3),以上数据与文献报道数据基本一致[10],故鉴定该化合物为nikoenoside。
化合物9 白色粉末,易溶于甲醇、DMSO。ESI-MS m/z:205 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 7.35 (1H, d, J = 1.8 Hz, H-2), 7.30 (1H, dd, J = 2.4, 6.0 Hz, H-6), 6.80 (1H, d, J = 7.8 Hz H-), 4.223 (2H, dd, J = 7.2, 7.2 Hz, H-), 1.27 (3H, t, J = 7.2 Hz, H-);13C-NMR (DMSO-d6,150 MHz) δC: 165.6 (C-7), 150.3 (C-4), 145.0 (C-3), 121.7 (C-6), 120.7 (C-1), 116.1 (C-2), 115.2 (C-5), 60.0 (C-8), 14.2 (C-9),以上数据与文献报道数据基本一致[11],故鉴定该化合物为原儿茶酸乙酯。
化合物10 白色粉末,易溶于甲醇、DMSO。ESI-MS m/z:377 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 7.90 (1H, d, J = 9.6 Hz, H-4), 7.34 (1H, d, J = 8.4 Hz, H-5), 7.23 (1H, d, J = 8.4 Hz, H-6), 6.31 (1H, d, J = 9.6 Hz, H-3), 5.07 (1H, d, J = 7.8 Hz, H-1'), 3.80 (1H, s, OCH3);13C-NMR (DMSO-d6,150 MHz) δC: 162.7 (C-2), 155.0 (C-7), 149.4 (C-9), 146.0 (C-4), 124.6 (C-5), 116.5 (C-10), 114.7 (C-3), 114.4 (C-6), 102.5 (C-1'), 78.6 (C-5'), 78.2 (C-3'),75.0 (C-2'), 71.4 (C-4'), 62.6 (C-6'), 62.3 (OCH3),以上数据与文献报道数据基本一致[12],故鉴定该化合物为8-甲氧基香豆素-7-O-β-D-葡萄糖苷。
化合物11 黄色油状,易溶于甲醇、DMSO。ESI-MS m/z:483 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 7.63 (1H, dd, J = 9.6, 1.8 Hz), 7.52 (1H, m, H-5), 7.22 (1H, d, J = 8.4 Hz, H-6), 7.09 (1H, t, J = 7.2 Hz, H-4), 5.41 (1H, s, H-1'), 4.87 (1H, d, J = 7.2 Hz, H-1''), 3.43~3.86 (6H, m, Glc-H), 3.37~3.86 (5H, m, Rha-H), 1.118 (1H, d, J = 6 Hz, H-6'');13C-NMR (DMSO-d6,150 MHz) δC: 166.4 (C-7), 155.9 (C-1), 133.2 (C-5), 130.2 (C-3), 122.5 (C-4), 121.7 (C-2), 116.4 (C-6), 100.9 (C-1'), 100.7 (C-1''), 76.4 (C-5'), 75.6 (C-3'), 73.2 (C-2'), 73.0 (C-4''), 71.9 (C-2''), 70.6 (C-3''), 70.4 (C-4'), 69.9 (C-5''), 68.4 (C-6'), 56.0 (OCH3), 52.0 (C-9), 17.8 (C-6''),以上数据与文献报道数据基本一致[13],故鉴定该化合物为6-O-R-L-rhamnopyranosyl-β-D-glucopyranoside of methyl salicylate。
化合物12 无色油状,易溶于甲醇、DMSO。ESI-MS m/z:145 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 9.02 (1H, d, J = 1.8 Hz, H-2), 8.70 (1H, dd, J = 4.8, 3.6 Hz, H-6), 8.20 (1H, t, J = 1.8 Hz, H-4), 7.50 (1H, dd, J = 4.8, 0.6 Hz); 13C-NMR (DMSO-d6,150 MHz) δC: 166.4 (C-7), 151.8 (C-6), 148.6 (C-2), 135.1 (C-4), 129.6 (C-3), 123.4 (C-5),以上数据与文献报道数据基本一致[14],故鉴定该化合物为烟酰胺。
化合物13 黄色油状,易溶于甲醇、DMSO。ESI-MS m/z:575 [M + Na] +。1H-NMR (DMSO-d5, 600 MHz) δH: 7.51 (1H, d, J = 15.6 Hz, H-7'), 7.42 (1H, d, J = 15.6 Hz, H-7''), 7.03 (1H, d, J = 1.2 Hz, H-2'), 7.02 (1H, d, J = 1.2 Hz, H-2''), 7.00 (1H, d, J = 1.8 Hz, H-6'), 6.98 (1H, d, J = 1.8 Hz, H-6''), 6.97 (1H, d, J = 1.8 Hz, H-5'), 6.96 (1H, d, J = 1.8 Hz, H-5''), 6.27 (1H, d, J = 15.6 Hz, H-8'), 6..13 (1H, d, J = 15.6 Hz, H-8''), 5.25 (1H, s, H-5), 4.96 (1H, dd, J = 3.0, 9.0 Hz, H-3), 4.14 (1H, t, J = 8.4 Hz, H-4), 3.58 (3H, s, 7-OCH3), 2.24 (1H, m, H-2a), 1.99 (1H, m, H-2b);13C-NMR (DMSO-d6,150 MHz) δC: 173.3 (C-7), 165.9 (C-9'), 165.2 (C-9''), 148.7 (C-4'), 148.5 (C-4''), 145.7 (C-7'), 145.6 (C-7''), 145.6 (C-3'), 145.5 (C-3''), 125.3 (C-1'), 125.1 (C-1''), 121.4 (C-6'), 121.3 (C-6''), 115.8 (C-5'), 115.7 (C-5''),114.8 (C-2'), 114.7 (C-2''),113.7 (C-8'), 113.2 (C-8''), 72.5 (C-1, 4), 67.7 (C-5), 63.1 (C-3), 51.9 (7-OCH3),35.6 (C-6),以上数据与文献报道数据基本一致[15],故鉴定该化合物为3,5-二咖啡酰奎宁酸甲酯。
参考文献
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