APP下载

蝉翼藤根中木质素苷及蔗糖酯成分研究

2017-07-13王芷杨学东査海燕郭丽娜沈丹徐丽

中国中药杂志 2017年12期

王芷+杨学东+査海燕+郭丽娜+沈丹+徐丽珍+杨世林

[摘要] 运用硅胶、MPLC和制备HPLC等柱色谱方法对蝉翼藤根的化学成分进行分离,并通过理化性质和MS、NMR波谱数据进行结构鉴定。从蝉翼藤根的95%乙醇提取物中分离鉴定了9个化合物,包括5个木质素苷acernikol-4″-O-β-D-glucopyranoside (1), (7R, 8S )-dihydrodehydrodiconiferyl alcohol 9-O-β-D-glucopyranoside (2), (7R, 8S )-dihydrodehydrodiconiferyl alcohol 4-O-β-D-glucopyranoside (3), (7R, 8S)-dihydrodehydrodiconiferyl alcohol 9′-O-β-D-glucopyranoside (4), (7R, 8S)-5-methoxydihydrodehy drodiconiferyl alcohol 4-O-β-D-glucopyranoside (5); 3个蔗糖酯3, 6′-O-diferuloylsucrose (6), 3-O-feruloyl-6′-O-sinapoylsucrose (7), sibricose A5 (8); 1个有机酸酯mehyl ferulate(9)。化合物1~5,8, 9为首次从蝉翼藤属中分离得到。采用MTT法测定了化合物对肺癌细胞株A549、宫颈癌细胞株Hela和乳腺癌细胞株MCF-7的细胞毒活性。结果表明化合物2,3和7对所测试的人源肿瘤细胞具有较弱的抑制活性。

[关键词] 蝉翼藤属; 蝉翼藤; 木质素苷; 蔗糖酯; 细胞毒活性

[Abstract] Nine compounds, including five lignan glycosides (1-5), three sucrose esters (6-8), and one organic acid ester (9), were isolated from the ethanol extract of the roots of Securidaca inappendiculata by various chromatographic methods including silica gel, MPLC and preparative HPLC. Their structures were elucidated as acernikol-4″-O-β-D-glucopyranoside (1), (7R, 8S)-dihydrodehydrodiconiferyl alcohol 9-O-β-D-glucopyranoside (2), (7R, 8S)-dihydrodehydrodiconiferyl alcohol 4-O-β-D-glucopyranoside (3), (7R, 8S)-dihydrodehydrodiconiferyl alcohol 9′-O-β-D-glucopyranoside (4), (7R, 8S)-5-methoxydihydrodehy-drodiconiferyl alcohol 4-O-β-D-glucopyranoside (5), 3, 6′-O-diferuloylsucrose (6), 3-O-feruloyl-6′-O-sinapoylsucrose (7), sibricose A5 (8), and mehyl ferulate (9) on the basis of 1H-, 13C-NMR and MS experiments. Compounds 1-5, 8, and 9 were isolated from the Securidaca genus for the first time. Compounds 2, 3, and 7 exhibited weak cytotoxic activities against Hela and MCF-7 cell lines.

[Key words] Securidaca; Securidaca inappendiculata; lignan glycosides; sucrose esters; cytotoxic activity

蟬翼藤Securidaca inappendiculata Hassk,又名五味藤,为远志科Polygalaceae蝉翼藤属的一种攀援植物,主要分布于我国的云南、广西、广东、海南及东南亚、南亚的热带地区。蝉翼藤根茎味辛、甘、苦,性微寒,有活血化瘀、消肿止痛和清热利尿的功效[1]。将其作为主药之一的广西玉林牌正骨水被2015年版《中国药典》收载,应用于跌打损伤、骨折脱位及消除运动疲劳[2]。文献报道从蝉翼藤中已分离鉴定出酮[3-4]、寡糖酯[5]、皂苷[6-7]、二苯酮[8-9]、半萜酸苷[10]、甾苷[11]、有机酸[12]等化学成分。本文在前期抗肿瘤活性皂苷类成分研究的基础上,对蝉翼藤根的95%乙醇提取物开展进一步研究,从中分离并鉴定了5个木质素苷类化合物,3个蔗糖酯化合物及1个有机酸酯化合物。化合物1~5,8,9为首次从蝉翼藤属中分离得到。在此基础上,采用MTT法测定了化合物1~3,6,7对人源肿瘤细胞A549,Hela及MCF7的细胞毒活性。

1 材料

Bruker Avance Ⅲ核磁共振仪(600,400 MHz,瑞士Bruker公司);Agilent 6420 三重四级杆质谱仪(美国Agilent公司);J-810型圆二色光谱仪(日本Jasco公司);AUTOPOL II 型旋光仪;Dr Flash II型中压制备液相色谱仪,Cosmosil中压制备柱(50 mm×500 mm,RP-18,50 μm)(苏州利穗科技有限公司);LC3000型高效液相制备色谱仪(北京创新通恒有限公司);Cosmosil MS II C18制备色谱柱(10 mm×250 mm,5 μm),Cosmosil πNAP制备色谱柱(10 mm×250 mm,5 μm)(日本Nacalai公司);薄层色谱用硅胶(GF254,青岛海洋化工厂);柱色谱用硅胶(100~200 目,青岛海洋化工厂);分析纯乙腈(天津市康科德科技有限公司);其他分析纯试剂(天津市基准化学试剂有限公司)。

蝉翼藤根由中国科学院西双版纳热带植物园王洪于2010年采自中国云南省并鉴定为远志科蝉翼藤属植物蝉翼藤S. inappendiculata的根,该样品标本(Y201011)保存于天津大学药物科学与技术学院天然药物化学实验室。

2 提取与分离

蝉翼藤根9.85 kg粉碎后先用95%乙醇浸泡24 h,再用4倍量的95%乙醇回流提取2 h,共提取3次。提取液减压浓缩得浸膏1.25 kg。此浸膏加入适量水混悬,分别经二氯甲烷,乙酸乙酯萃取后,得到水溶液部分。水溶部分过滤后经大孔树脂D101,得到水,30%,60%,95%乙醇4个洗脱部分。60% EtOH洗脱物(180 g)硅胶拌样,进行减压柱色谱分离,氯仿-甲醇-水 (85∶15∶2,75∶20∶5,68∶24∶8,60∶32∶8,50∶42∶8,下层) 梯度洗脱后得到30个流分(C1~C30)。C10~12(4.5g)经中压制备液相色谱分离,甲醇-水(31∶69,32∶68,33∶66)梯度洗脱得到15个部分(Fr1~15)。其中,Fr11~12经制备型HPLC分离,乙腈-水(17∶83)洗脱后得到化合物 6(5 mg)和7(7 mg)。Fr10~6分别经制备型HPLC分离,流动相比例依次采用甲醇-水 31∶ 69,29∶71,27∶73,25∶75,24∶76洗脱后,分别得到化合物1(8 mg),2(11 mg),4(5 mg),5(3 mg)和3(4 mg)。Fr1~5经中压制备液相色谱分离,甲醇-水(18∶82,20∶80,24∶76)梯度洗脱,制备型HPLC纯化(甲醇-水,16∶84),得到化合物8(5 mg)。C15(0.47g)经中压制备液相色谱分离,甲醇-水(35∶65,38∶62)梯度洗脱,制备型HPLC纯化(甲醇-水,34∶66),得到化合物9(10 mg)。

3 结构鉴定

化合物1 无色粉末;[α]22.4D-32° (c 0.15,MeOH);CD nm (Δε,MeOH):215(+1.1);ESI-MS m/z 771.9 [M+Na]+1H-NMR (CD3OD,400 MHz) δ: 7.09 (1H,d,J=8.3 Hz,H-5″),7.05 (1H,d,J=1.8Hz,H-2″),6.89 (1H,dd,J=1.8,8.4 Hz,H-6″),6.74 (1H,br s,H-6),6.72 (1H,br s,H-4),6.69 (2H,s,H-2′,6′),5.53 (1H,d,J=6.1 Hz,H-2),4.92 (1H,d,J=5.5 Hz,H-7″),4.86 (1H,d,J=7.3 Hz,H-1),4.27 (1H,m,H-8″),3.90 (1H,m,H-9″a),3.87 (3H,s,7-OCH3),3.86 (1H,m,H-3a-a),3.84 (1H,重叠,H-6b),3.83 (3H,s,3″-OCH3),3.77 (6H,s,3′,5′-OCH3),3.76 (1H,m,H-3a-b),3.63 (1H,m,H-6a),3.59 (1H,m,H-9″b),3.56 (2H,t,J=6.3 Hz,H-5c),3.48 (1H,m,H-2),3.46 (1H,m,H- 5),3.45 (1H,m,H-3),3.38 (1H,m,H-3),3.37 (1H,m,H-4),2.63 (2H,t,J=7.6 Hz,H-5a),1.81 (2H,m,H-5b);13C-NMR (CD3OD,150 MHz)δ:154.5 (C-5′),154.5 (C-3′),150.3 (C-3″),147.4 (C-7a),147.1 (C-4″),145.2 (C-7),139.6 (C-1′),137.3 (C-5),137.1 (C-1″),136.2 (C-4′),129.6 (C-4a),120.8 (C-6″),117.9 (C-4),117.3 (C-5″),114.1 (C-6),112.2 (C-2″),104.0 (C-2′,6′),102.7 (C-1),88.6 (C-2),87.0 (C-8″),78.1 (C-3),77.8 (C-5),74.9 (C-2),73.7 (C-7″),71.4 (C-4),65.0 (C-3a),62.5 (C-6),62.2 (C-5c),61.6 (C-9″),56.8 (7-OCH3),56.7 (3″-OCH3),56.6 (3′-OCH3),56.6 (5′-OCH3),55.6 (C-3),35.8 (C-5b),32.9 (C-5a)。苷元部分數据与acernikol [13]对比,在HMBC谱图上能观察到C-4″与H-1(Glc-H-1)间存在远程相关。以上数据与文献[14]报道对比,故鉴定化合物为acernikol-4″-O-β-D-glucopyranoside。

化合物2 无色粉末;[α]17.1D+10.2° (c 0.09,MeOH);CD nm (Δε,MeOH): 279(+0.36);ESI-MS m/z 545.8 [M+Na]+1H-NMR (CD3OD,600 MHz) δ: 6.99 (1H,d,J=1.6 Hz,H-2),6.85 (1H,dd,J=1.5,8.1 Hz,H-6),6.80 (1H,br s,H-2′),6.75 (1H,d,J=8.1 Hz,H-5),6.72 (1H,br s,H-6′),5.58 (1H,d,J=6.4 Hz,H-7),4.35 (1H,d,J=7.8 Hz,H-1″),4.11 (1H,dd,J=8.3,9.4 Hz,H-9a),3.87 (1H,m,H-9b),3.85 (3H,s,3′-OMe),3.84 (1H,重叠,H-6″a),3.82 (3H,s,3-OMe),3.67 (1H,m,H-6″b),3.64 (1H,m,H-8),3.56 (2H,t,J=6.4 Hz, H-9′),3.36 (1H,m,H-5″),3.29 (1H,重叠,H-3″),3.27 (1H,m,H-4″),3.22 (1H,t,J=8.0 Hz,H-2″),2.62 (2H,t,J=7.5 Hz,H-7′),1.81 (2H,m,H-8′)。13C-NMR (CD3OD,

150 MHz) δ:149.0 (C-3),147.4 (C-4),147.3 (C-4′),145.1 (C-3′),137.0 (C-1′),134.6 (C-1),129.6 (C-5′),119.7 (C-6),118.1 (C-2′),116.0 (C-5),114.0 (C-6′),110.7 (C-2),104.2 (C-1″),89.2 (C-7),78.1 (C-3″),78.0 (C-5″),75.1 (C-2″),72.3 (C-9),71.6 (C-4″),62.7 (C-6″),62.2 (C-9′),56.7 (3′-OMe),56.4 (3-OMe),52.9 (C-8),35.8 (C-8′),32.8 (C-7′)。以上数据与文献[15]报道对比,故鉴定化合物2为 (7R,8S)-dihydrodehydrodiconiferyl alcohol-9-O-β-D-glucopyranoside。

化合物3 无色粉末;[α]18.9D-14.1° (c 0.14,MeOH);CD nm (Δε,MeOH):218(+10.7),228(-8.6),271.4(-4.7);ESI-MS m/z 545.1 [M+Na]+1H-NMR (CD3OD,600 MHz) δ:7.14 (1H,d,J=8.4 Hz,H-5),7.03 (1H,d,J=1.5 Hz,H-2),6.93 (1H,dd,J=1.5,8.3 Hz,H-6),6.74 (1H,br s,H-6′),6.72 (1H,br s,H-2′),5.56 (1H,d,J=5.7 Hz,H-7),4.89 (1H,d,J=8.4 Hz,H-1″),3.86 (3H,s,3-OMe),3.85 (1H,m,H-9a),3.84 (1H,m,H-6″a),3.83 (3H,s,3′-OMe),3.74 (1H,m,H-9b),3.68 (1H,dd,J=2.4,11.4 Hz,H-8),3.56 (2H,t,J=6.4 Hz,H-9′),3.50 (1H,m,H-6″b),3.47 (1H,m,H-5″),3.45 (1H,m,H-3″),3.41 (1H,m,H-4″),3.40 (1H,m,H-2″),2.62 (2H,t,J=7.6 Hz,H-7′),1.81 (2H,m,H-8′)。13C-NMR (CD3OD,150 MHz) δ:150.8 (C-3),147.5 (C-4),147.3 (C-4′),145.1 (C-3′),138.3 (C-1),137.1 (C-1′),129.5 (C-5′),119.4 (C-5),117.9 (C-6),117.8 (C-6′),114.1 (C-2′),111.1 (C-2),102.7 (C-1″),88.4 (C-7),78.0 (C-3″),77.7 (C-5″),74.8 (C-2″),71.2 (C-4″),65.0 (C-9),62.4 (C-6″),62.2 (C-9′),56.8 (3′-OMe),56.7 (3-OMe),55.5 (C-8),35.7 (C-7′),32.8 (C-8′)。以上数据与文献[16]报道对比,故鉴定化合物为(7R, 8S)-dihydrodehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside。

化合物4 无色粉末;[α]16.7D-9.2° (c 0.11,MeOH);CD nm (Δε,MeOH):234(-4.4),293(-1.6);ESI-MS m/z 545.2 [M+Na]+1H-NMR (DMSO-d6,600 MHz) δ:6.90 (1H,br s,H-2),6.74 (2H,d,J=8.8 Hz,H-5,6),6.71 (2H,s,H-2′,6′),5.40 (1H,d,J=6.7 Hz,H-7),4.11 (1H,d,J=7.7 Hz,H-1″),3.79 (1H,m,H-9′b),3.68 (1H,m,H-9b),3.66 (1H,dd,J=4.5,11.9 Hz,H-6a),3.60 (1H,m,H-9a),3.44 (1H,m,H-6b),3.40 (1H,m,H-8),3.14 (1H,m,H-4″),3.06 (2H,m,H-3″,5″),2.96 (1H,m,H-2″),2.58 (2H,t,J=7.1 Hz,H-7′),1.79 (2H,m,H-8′)。13C-NMR (DMSO-d6,150 MHz) δ:147.5 (C-3),146.3 (C-4),145.5 (C-4′),143.3 (C-3′),134.6 (C-1′),132.5 (C-1),129.0 (C-5′),118.5 (C-6),116.5 (C-6′),115.2 (C-5),112.4 (C-2′),110.2 (C-2),102.9 (C-1″),86.8 (C-7),76.8 (C-3″),76.7 (C-5″),73.4 (C-2″),70.0 (C-4″),67.8 (C-9′),62.9 (C-9),61.0 (C-6″),55.6 (3′-OCH3),55.5 (3-OCH3),53.2 (C-8),31.4 (C-7′),31.3 (C-8′)。以上數据与文献[17]报道对比,故鉴定化合物为 (7R, 8S)-dihydrodehydrodiconiferyl alcohol-9′-O-β-D-glucopyranoside。

化合物5 无色粉末;[α]16.9D-22.7° (c 0.08,MeOH);CD nm (Δε,MeOH):223(+13.4);243(-6.5),293(-4.7);ESI-MS m/z 575.0 [M+Na]+1H-NMR (CD3OD,600 MHz) δ:6.74 (1H,s,H-6 ′),6.73 (2H,s,H-2,6),6.71 (1H,s,H-2′),5.56 (1H,d,J=5.7 Hz,H-7),4.87 (1H,d,J=7.7 Hz,H-1″),3.88 (3H,s,3′-OMe),3.87 (1H,m,H-9a),3.82 (6H,s,3,5-OMe),3.77 (1H,m,H-6″a),3.75 (1H,m,H-9b),3.64 (1H,dd,J=5.3,11.9 Hz,H-6″b),3.56 (2H,t,J=6.4 Hz,H-9′),3.47 (1H,m,H-2″),3.44 (1H,m,H-8),3.40 (2H,m,H-4″,5″),3.19 (1H,m,H-3″),2.62 (2H,t,J=7.6 Hz,H-7′),1.81 (2H,m,H-8′)。13C-NMR (CD3OD,150MHz) δ:154.4 (C-3,5),147.4 (C-1),145.3 (C-3′),140.3 (C-4′),137.2 (C-1′),135.7 (C-4),129.4 (C-5′),117.9 (C-2′),114.2 (C-6′),105.2 (C-1″),104.4 (C-2,6),88.5 (C-7),78.3 (C-3″),77.8 (C-5″),75.7 (C-2″),71.3 (C-4″),65.1 (C-9),62.5 (C-6″),62.2 (C-9′),57.0 (3,5-OMe),56.8 (3′-OMe),55.8 (C-8),35.8 (C-8′),32.8 (C-7′)。以上数据与文献[18]报道对比,故鉴定化合物为 (7R, 8S)-5-methoxydihydrodehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside。

化合物6 黄色粉末;ESI-MS m/z 717.3 [M+Na]+1H-NMR (CD3OD,400 MHz) δ:7.69 (1H,d,J=15.8 Hz,H-7″),7.61 (1H,d,J=15.8 Hz,H-7 ),7.23 (1H,d,J=1.7 Hz,H-2),7.21 (1H,d,J=1.7 Hz,H-2″),7.11 (1H,dd,J=1.8,8.2 Hz,H-6″),7.05 (1H,dd,J=1.8,8.2 Hz,H-6 ),6.80 (1H,d,J=8.1 Hz,H-5 ),6.78 (1H,d,J=8.1 Hz,H-5″),6.44 (1H,d,J=15.9 Hz,H-8),6.43 (1H,d,J=15.9 Hz,H-8″),5.49 (1H,d,J=3.5 Hz,H-1′),5.48 (1H,d,J=8.1 Hz,H-3),4.63 (1H,m,H-6′a),4.47 (1H,t,J=7.3 Hz,H-4),4.24 (1H,m,H-5′),4.24 (1H,m,H -6′b),3.97 (1H,td,J=3.0,7.3 Hz,H-5),3.90 (3H,s,3″-OCH3),3.89(1H,m,H-6a),3.87 (3H,s,3-OCH3),3.82 (1H,dd,J=3.0,11.8 Hz,H-6b),3.67 (1H,t,J=8.0 Hz,H-3′),3.64 (1H,重叠,H-1a),3.61 (1H,重叠,H-1b),3.47 (1H,dd,J=3.8,9.7 Hz,H-2′),3.32 (1H,m,H-4′);13C-NMR (CD3OD,100 MHz) δ:169.2 (C-9),168.3 (C-9″),150.7 (C-3″),150.7 (C-3),149.4 (C-4),149.4 (C-4″),147.7 (C-7″),147.1 (C-7),127.6 (C-1″),127.6 (C-1),124.3 (C-6),124.2 (C-6″),116.4 (C-5),116.3 (C-5″),115.3 (C-8 ),115.0 (C-8″),112.0 (C-2 ),111.5 (C-2″),104.8 (C-2),92.7 (C-1′),84.3 (C-5),79.4 (C-3),75.0 (C-3′),74.1 (C-4),73.1 (C-2′),72.4 (C-5′),71.9 (C-4′),65.6 (C-6′),65.4 (C-1),63.8 (C-6),56.5 (C-10″OCH3),56.4 (C-10OCH3)。以上數据与文献[19]报道对比,故鉴定化合物为3,6′ -O-diferuloylsucrose。

化合物7 黄色粉末;ESI-MS m/z 725.8 [M+H]+1H-NMR (DMSO-d6,400 MHz) δ:7.60 (1H,d,J=15.8 Hz,H-7″),7.54 (1H,d,J=15.8 Hz,H-7),7.26 (1H,d,J=1.3 Hz,H-2″),7.14 (1H,dd,J=1.4,8.2 Hz,H-6″),7.00 (2H,s,H-2,6),6.79 (1H,d,J=8.1 Hz,H-5″),6.52 (1H,d,J=15.8 Hz,H-8),6.41 (1H,d,J=15.8 Hz,H-8″),5.39(1H,d,J=8.1Hz,H-3),5.28(1H,d,J=3.4 Hz,H-1′),4.87(1 H,t,J=8.0 Hz,H-4),4.65(1 H,m,H-6′b),4.44 (1H,d,J=11.3 Hz,H-5′),4.23 (1H,m,H-6′a),4.15 (1H,m,H-5),4.08 (1H,m,H-6b),3.81 (3H,s,3″-OCH3),3.77 (6H,s,3,6-OCH3),3.68 (1H,m,H-6a),3.63 (1H,m,H-3′),3.49 (1H,m,H-1a),3.40 (1H,m,H-1b),3.31 (1H,m,H-2′),3.16 (1H,m,H-4′);13C-NMR (DMSO-d6,150 MHz) δ:166.7 (C-9),165.7 (C-9″),148.1 (C-4″),148.0 (C-3″),148.0 (C- 5),148.0 (C-3),145.6 (C-7″),145.4 (C-7),125.5 (C-4),124.4 (C-1″),122.9 (C-1),115.6 (C-6″),114.8 (C-5″),114.2 (C-8),111.6 (C-8″),108.0 (C-2″),106.2 (C-2,6),103.1 (C-2),91.0 (C-1′),82.9 (C-5),77.2 (C-3),73.1 (C-3′),72.6 (C-4),71.4 (C-2′),70.6 (C-5′),70.2 (C-4′),64.2 (C-1),63.6 (C-6′),62.3 (C-6),56.1 (3,5-OMe),55.7 (3″-OMe)。以上数据与文献[20]报道对比,故鉴定化合物为3-O-feruloyl-6′-O-sinapoylsucrose。

化合物8 黄色粉末;ESI-MS m/z 541.1 [M+Na]+1H-NMR (CD3OD,400 MHz) δ:7.71 (1H,d,J=15.9 Hz,H-7″),7.23 (1H,d,J=1.7 Hz,H-2″),7.13 (1H,dd,J=1.8,8.2 Hz,H-6″),6.80 (1H,d,J=8.1 Hz,H-5″),6.43 (1H,d,J=15.9 Hz,H-8″),5.46 (1H,d,J=7.8 Hz,H-3),5.43 (1H,d,J=3.6 Hz,H-1′),4.37 (1H,t,J=7.9 Hz,H-4),3.93 (1H,m,H-5),3.92 (1H,m,H-5′),3.90 (3H,s,3″-OCH3),3.83 (1H,m,H-6a),3.83 (1H,m,H-6b),3.79 (1H,m,H-6′a),3.75 (1H,m,H-6′b),3.66 (1H,t,J=9.2 Hz,H-3′),3.65 (1H,d,J=12.2 Hz,H-1b),3.59 (1H,d,J=12.2 Hz,H-1a),3.43 (1H,dd,J=3.5,6.2 Hz,H-2′),3.40 (1H,m,H-4′);13C-NMR (CD3OD,100 MHz) δ:168.3 (C-9″),150.9 (C-4″),149.4 (C-3″),147.7 (C-7″),127.5 (C-1″),124.2 (C-6″),116.5 (C-5″),114.9 (C-8″),112.1 (C-2″),104.8 (C-2),93.3 (C-1′),84.1 (C-5),79.6 (C-3),74.9 (C-3′),74.5 (C-4),73.8 (C-5′),73.1 (C-2′),71.2 (C-4′),65.3 (C-1),62.9 (C-6),62.3 (C-6′),56.5 (3″-OCH3)。以上数据与文献[21]报道对比,故鉴定化合物为sibiricose A5。

化合物9 白色粉末;ESI-MS m/z 231.2 [M+Na]+1H-NMR (CDCl3,400 MHz) δ:7.62 (1H,d,J=15.9 Hz,H-7),7.07 (1H,dd,J=1.7,8.1 Hz,H-6),7.02 (1H,d,J=1.7 Hz,H-2),6.92 (1H,d,J=8.1 Hz,H-5),6.29 (1H,d,J=15.9 Hz,H-8),3.92 (3H,s,3-OCH3),3.79 (3H,s,9-OCH3);13C-NMR (CDCl3,100MHz) δ:167.9 (C-9),148.1 (C-4),146.8 (C-3),145.1 (C-7),127.0 (C-1),123.1 (C-6),115.2 (C-5),114.8 (C-8),109.4 (C-2),56.0 (3-OCH3),51.7 (9-OCH3)。以上數据与文献[22]报道对比,故鉴定化合物为mehyl ferulate。

4 细胞毒活性

采用MTT [23] 法测定化合物1~3,6,7对人源肿瘤细胞A549,Hela及MCF7的细胞毒活性,以顺铂为阳性对照,其IC50分别为16.74,16.74,19.83 μmol·L-1。化合物2对Hela和MCF7的IC50分别为87.21,89.75 μmol·L-1;化合物3对Hela和MCF7的IC50分别为79.95,59.98 μmol·L-1;化合物7对MCF7的IC50为88.41 μmol·L-1。结果表明,化合物2,3,7对所测试的人源肿瘤细胞具有较弱的抑制活性。

[参考文献]

[1] 常银霞,陈业高. 蝉翼藤属药用植物的研究进展[J]. 山西师范大学学报:自然科学版,2005, 19 (1):95.

[2] 中国药典. 一部[S]. 2015: 421.

[3] Yang X D, Xu L Z, Yang S L. Xanthones from the stems of Securidaca inappendiculata[J]. Phytochemistry, 2001, 58 (8):1245

[4] Zuo J, Mao K J, Yuan F, et al. Xanthones with anti-tumor activity isolated from Securidaca inappendiculata[J]. Med Chem Res, 2014, 23 (11):4865.

[5] 杨学东, 刘江云, 许莉,等. 蝉翼藤茎中蔗糖酯成分研究[J]. 高等学校化学学报, 2003, 24 (1):61.

[6] Zha H, Wang Z, Yang X, et al. New acylated triterpene saponins from the roots of Securidaca inappendiculata Hassk[J]. Phytochem Lett, 2015, 13:108.

[7] 查海燕,杨学东,张丽杰,等. 蝉翼藤根中的皂苷类成分及其肿瘤细胞毒活性[J]. 中国中药杂志, 2015, 40 (14):2849.

[8] Yang X D,Xu L Z, Yang S L. A new benzophenone from Securidaca inappendiculata[J]. Chin Chem Lett,2003,14 (9):930.

[9] 张丽杰, 张琳, 徐丽珍,等. 蝉翼藤根中的一个新二苯酮[J]. 药学学报, 2005, 40 (6):536.

[10] 杨学东, 徐丽珍, 杨世林. 蝉翼藤茎化学成分研究[J]. 药学学报, 2002, 37 (5):348.

[11] Zhang L J, Yang X D, Xu L Z, et al. A new sterol glycoside from Securidaca inappendiculata.[J]. J Asian Nat Prod Res,2005,7 (4):649.

[12] 杨学东,徐丽珍, 杨世林. 蝉翼藤茎中有机酸成分的研究[J]. 中国中药杂志, 2001, 26 (4):258.

[13] Morikawa T,Tao J,Ueda K, et al. Medicinal foodstuffs. ⅩⅩⅪ. Structures of new aromatic constituents and inhibitors of degranulation in RBL-2H3 cells from a Japanese folk medicine,the stem bark of Acer nikoense[J]. Chem Pharm Bull, 2003, 51(1):62.

[14] Gao P Y, Li L Z, Peng Y, et al. Monoterpene and lignan glycosides in the leaves of Crataegus pinnatifida[J]. Biochem Syst Ecol, 2010, 38(5):988.

[15] Wang C,Jia Z. Lignan,phenylpropanoid and iridoid glycosides from Pedicularis torta[J]. Phytochemistry, 1997, 45(45):159.

[16] Matsuda N, Sato H, Yaoita Y, et al. Isolation and absolute structures of the neolignan glycosides with the enantimetric aglycones from the leaves of Viburnum awabuki K. KOCH[J]. Chem Pharm Bull, 1996, 44(5):1122.

[17] Takeda Y, Mima C,Masuda T,et al. Glochidioboside, a glucoside of (7 S, 8 R)-dihydrodehydrodiconiferyl alcohol from leaves of Glochidion obovatum[J]. Phytochemistry, 1998, 49(7):2137.

[18] Takara K,Matsui D,Wada K, et al. New phenolic compounds from Kokuto, non-centrifuged cane sugar [J].Biosci Biotechnol Biochem, 2003, 67(2):376.

[19] Choudhary M I, Begum A,Abbaskhan A,et al. Cinnamate derivatives of fructo-oligosaccharides from Lindelofia stylosa[J]. Carbohydr Res, 2006, 341(14):2398.

[20] Miyase T,Ueno A. Sucrose derivatives from the roots of Polygala tenuifolia[J]. Japa J Pharmacog, 1993, 47(3):267.

[21] Miyase T, Noguchi H, Chen X M. Sucrose esters and xanthone C-glycosides from the roots of Polygala sibirica[J]. J Nat Prod, 1999, 62(7):993.

[22] Yu B C,Yang M C, Lee K H,et al. Two new phenolic constituents of Humulus japonicus and their cytotoxicity test in vitro[J]. Arch Pharmacal Res, 2007, 30(11):1471.

[23] Mosmann T. Rapid colorimetric assay for cellular growth and survival: Application to proliferation and cytotoxicity assays[J]. J Immunol Methods, 1983, 65(1/2):55.

[責任编辑 丁广治]