直緣烏頭地上部分非生物堿成分的研究

劉 佳 楊樹超楊崇康張 蓮羅啟鵬沈 勇*

(1.云南農(nóng)業(yè)大學(xué)農(nóng)學(xué)與生物技術(shù)學(xué)院,云南 昆明 650201;2.昆明康人生物科技有限公司,云南 昆明 650033;3.香格里拉蘭草藥業(yè),云南 迪慶 674601)

烏頭為毛茛科植物,在全世界分布很廣,我國(guó)的烏頭主要分布于西南部橫斷山區(qū),是重要的藥用植物,具有鎮(zhèn)痙、冶風(fēng)庳、風(fēng)濕神經(jīng)痛等作用[1],該屬植物雖然有毒,但也具極大的研究意義和開發(fā)利用價(jià)值。直緣烏頭Aconitum transsectum Diels 系毛茛科烏頭屬植物,該植物的二萜生物堿化學(xué)成分已有報(bào)道[2-4]。本課題組也已對(duì)該種植物的二萜生物堿[5-8]及內(nèi)生菌進(jìn)行化學(xué)成分研究[9]。本實(shí)驗(yàn)首次對(duì)直緣烏頭水溶性非生物堿部分進(jìn)行系統(tǒng)的化學(xué)成分研究。從水溶性非生物堿部分中共分離得到15 個(gè)化合物,其中化合物2～7、10、12、14～15為首次從烏頭屬植物中分離得到,15 個(gè)化合物均為首次從該植物中分離得到。

1 材料

Avance-500 MHz 核磁共振儀(瑞士Bruker 公司)；Hei-vap digital G3 旋轉(zhuǎn)蒸發(fā)儀(德國(guó)Herdorf公司)；VG Autospec 3000 質(zhì)譜儀(英國(guó)Micromass公司)；薄層色譜硅膠(臨沂市海祥化工有限公司)；柱層析硅膠(200～300 目,青島海洋化工有限公司)；Sephadex LH-20 (瑞士Pharmacia 公司)；RP-18 反相材料(德國(guó)墨克公司)。

直緣烏頭地上部分采于云南麗江玉龍縣,經(jīng)中科院昆明植物所雷立功副研究員鑒定為直緣烏頭Aconitum transsectum Diels。

2 提取與分離

將50 kg 直緣烏頭地上部分干燥粉碎后,用600 L 甲醇滲漉提取,減壓濃縮至近干。用2%HCl 水溶液溶解并過濾,濾液用5% NaOH 水溶液調(diào)pH 至9,氯仿萃取除去生物堿,水層部分用5%HCl 溶液調(diào)pH 至中性,用正丁醇萃取5 次,回收并蒸干正丁醇部分獲得水溶性非生物堿粗提物約100 g。經(jīng)硅膠柱,用氯仿-甲醇-水(8∶2∶0.1～6∶4∶0.3) 進(jìn)行梯度洗脫,經(jīng)TLC 檢查后合并得5 個(gè)流分(Fr 1-5)。其中Fr2 經(jīng)硅膠柱乙酸乙酯-甲醇-水(7∶3∶0.1),再經(jīng)Sephadex LH-20 氯仿-甲醇(1∶1),及Rp-18 反相硅膠柱甲醇-水(2∶8～5∶5) 進(jìn)行梯度洗脫反復(fù)分離純化得到化合物1(80 mg)、2 (1.20 g)、3 (26 mg)、4 (0.72 g)、5 (0.73 g)。Fr3 經(jīng)硅膠柱乙酸乙酯-甲醇-水(8∶2∶0.1)、丙酮-甲醇-水(8∶2∶0.1),再經(jīng)Sephadex LH-20 氯仿-甲醇(1∶1),Rp-18 反相硅膠柱甲醇-水(2∶8～5∶5),反復(fù)分離純化得到化合物6 (1.80 g)、7 (17 mg)、8 (15.62 g)、9 (0.64 g)、10 (23 mg)。Fr4 經(jīng)硅膠柱乙酸乙酯-甲醇-水(9∶1∶0.1)、丙酮-乙酸乙酯-水(1∶1∶0.2),再經(jīng)Sephadex LH-20 柱氯仿-甲醇(1∶1) 及Rp-18 反相硅膠柱甲醇-水(2∶8～5∶5),分離純化得到化合物11 (37 mg)、12 (40 mg)。Fr5 經(jīng)硅膠柱氯仿-甲醇-石油醚-乙酸乙酯(8∶2∶1∶1)、石油醚-丙酮-乙酸乙酯-水(1∶1∶1∶0.1),Sephadex LH-20 氯仿-甲醇(1∶1),Rp-18 反相硅膠柱甲醇-水(5∶5),分離純化得到化合物13 (20 mg)、14 (15 mg)、15 (18 mg)。

3 結(jié)構(gòu)鑒定

化合物1:白色粉末,C17H24O9。ESI-MS m/z:395.1 [M+Na]+。1H-NMR (500 MHz,CD3OD) δ:6.73 (2H,s,H-3,5),6.56 (1H,d,J=15.9 Hz,H-7),6.35 (1H,dd,J=11.2,5.6 Hz,H-8),4.85 (1H,d,J=7.5 Hz,H-1′),4.22 (2H,dd,J=5.6,1.5 Hz,H-9),3.85 (6H,s,-OCH3×2),3.48～3.19 (6H,m,H-2′～6′)；13C-NMR (125 MHz,CD3OD) δ:56.3 (OCH3×2),62.6 (C-6′),63.6 (C-9),71.3 (C-4′),75.7 (C-2′),77.8 (C-3′),78.4 (C-5′),105.3 (C-1′),105.4 (C-3,5),130.0 (C-7),131.3 (C-8),135.2 (C-4),135.9(C-1),154.3 (C-2,6)。以上數(shù)據(jù)與文獻(xiàn)[10]基本一致,故鑒定為丁香苷。

化合物2:淡黃色無定形粉末,C27H30O15。ESI-MS m/z:595.2 [M+H]+。1H-NMR (500 MHz,C5D5N) δ:8.42 (2H,d,J=8.8 Hz,H-2′,6′),7.22 (2H,d,J=8.7 Hz,H-3′,5′),6.92 (1H,s,H-8),6.76 (1H,d,J=2.1 Hz,H-6),6.38 (1H,d,J=7.2 Hz,Glu-H-1″),6.24 (1H,s,Rha-H-1?),1.63 (3H,d,J=6.1 Hz,Rha-H-6 ‘″)；13CNMR (125 MHz,C5D5N) δ:18.7 (Rha-C-6?),62.7 (Glu-C-6″),71.5 (Glu-C-4″),71.5 (Rha-C-5?),71.7 (Rha-C-2?),72.4 (Rha-C-3?),73.6(Rha-C-4?),76.2 (Glu-C-2″),78.6 (Glu-C-3″),79.2 (Glu-C-5″),94.9 (C-8),100.0 (C-1?),100.4 (C-6),103.7 (C-1″),106.9 (C-10),116.2(C-3′,5′),121.9 (C-1′),132.0 (C-2′,6′),135.8 (C-3),156.9 (C-9),157.4 (C-2),161.9(C-4′),162.3 (C-5),162.8 (C-7),178.9 (C-4)。以上數(shù)據(jù)與文獻(xiàn)[11]基本一致,故鑒定為山柰酚-3-O-β-D-葡萄糖-7-O-α-L-鼠李糖苷。

化合物3:棕黃色無定形粉末,C29H32O16。ESI-MS m/z:635.2 [M-H]-。1H-NMR (500 MHz,CD3OD) δ:8.15 (2H,d,J=8.8 Hz,H-2′,6′),6.95 (2H,d,J=8.8 Hz,H-3′,5′),6.58 (1H,d,J=1.9 Hz,H-8),6.23 (1H,d,J=1.9 Hz,H-6),5.91 (1H,d,J=7.8 Hz,H-1″),1.85 (3H,s,-CH3COO),5.49 (1H,d,J=7.8 Hz,H-1?)；13CNMR (125 MHz,CD3OD) δ:18.1 (C-6?),20.4(-CH3COO),63.3 (C-6″),72.0 (C-4″),72.0 (C-5?),72.1 (C-3?),72.4 (C-2?),74.2 (C-4?),76.4 (C-5″),78.7 (C-3″),79.1 (C-2″),96.4 (C-8),100.5 (C-6),101.5 (C-1″),104.7 (C-1?),108.2 (C-10),117.0 (C-3′,5′),123.3 (C-1′),133.2 (C-2′,6′),136.5 (C-3),158.7 (C-2),160.4 (C-9),162.5 (C-4′),163.5 (C-5),164.3(C-7),173.6 (-COOCH3),180.4 (C-4)。以上數(shù)據(jù)與文獻(xiàn)[12]基本一致,故鑒定為kaempferol-3-O-α-L-rhamnopyronosyl (1 →2) -[6-O-acetyl]-β-D-glucopyranoside。

化合物4:黃色無定形粉末,C27H30O15。ESIMS m/z:595.2 [M+H]+。1H-NMR (500 MHz,CD3OD) δ:8.06 (2H,d,J=8.8 Hz,H-2′,6′),6.87 (2H,d,J=8.8 Hz,H-3′,5′),6.74 (1H,s,H-8),6.45 (1H,s,H-6),5.55 (1H,m,H-1″),5.22 (1H,m,H-1?),1.23 (3H,d,J=6.2 Hz,H-6?)；13C-NMR (125 MHz,CD3OD) δ:18.2 (C-6?),62.7 (C-6″),71.2 (C-4″),71.3 (C-5?),71.7 (C-3?),72.1 (C-2?),73.6 (C-4?),75.7 (C-5″),78.0 (C-3″),78.3 (C-2″),95.6 (C-8),99.8 (C-6),100.7 (C-1″),104.1 (C-1?),107.5 (C-10),116.2 (C-3′,5′),122.6 (C-1′),132.4 (C-2′,6′),135.8 (C-3),158.1 (C-2),159.8 (C-9),161.8 (C-4′),162.9 (C-5),163.6 (C-7),179.7(C-4)。以上數(shù)據(jù)與文獻(xiàn)[13]基本一致,故鑒定為山柰酚-3-O-新橙皮苷。

化合物5:黃色無定形粉末,C27H30O16。ESIMS m/z:611.2 [M+H]+。1H-NMR (500 MHz,CD3OD) δ:7.73 (1H,d,J=2.2 Hz,H-2′),7.62(1H,d,J=2.2 Hz,H-6′),6.88 (1H,d,J=8.5 Hz,H-5′),6.74 (1H,d,J=2.1 Hz,H-8),6.45(1H,d,J=2.1 Hz,H-6),5.56 (1H,s,Rha-H-1″),5.35 (1H,d,J=7.6 Hz,Glu-H-1″),1.25(3H,d,J=6.2 Hz,Rha-H-6″)；13C-NMR (125 MHz,CD3OD) δ:18.4 (Rha-C-6″),62.6 (Glu-C-6″),71.3 (Glu-C-4″),71.3 (Rha-C-5″),71.7(Rha-C-3″),72.1 (Rha-C-2″),73.6 (Rha-C-4″),75.7 (Glu-C-5″),78.1 (Glu-C-3″),78.5 (Glu-C-2″),95.6 (C-8),99.9 (C-6),100.7 (Glu-C-1″),103.9 (Rha-C-1″),107.5 (C-10),116.3 (C-2′),117.7 (C-5′),123.0 (C-6′),123.4 (C-1′),135.8(C-3),146.0 (C-3′),150.1 (C-4′),158.0 (C-2),159.4 (C-9),162.8 (C-5),163.6 (C-7),179.6 (C-4)。以上數(shù)據(jù)與文獻(xiàn)[14]基本一致,故鑒定為槲皮素-3-O-β-D-吡喃葡萄糖-7-O-α-L-吡喃鼠李糖苷。

化合物6:黃色無定形粉末,C27H30O16。ESIMS m/z:611.1 [M+H]+。1H-NMR (500 MHz,DMSO-d6) δ:7.82 (1H,dd,J=2.0,8.5 Hz,H-6′),7.77 (1H,d,J=2.0 Hz,H-2′),6.88 (1H,d,J=8.5 Hz,H-5′),6.63 (1H,d,J=2.0 Hz,H-8),6.25 (1H,d,J=2.0 Hz,H-6),5.71 (1H,d,J=7.6 Hz,Glu-H-1″),5.35 (1H,s,Rha-H-1?),0.83 (3H,d,J=6.2 Hz,Rha-H-6?)；13C-NMR(125 MHz,DMSO-d6) δ:17.4 (Rha-C-6?),60.5(Glu-C-6″),68.6 (Rha-C-5?),70.0 (Glu-C-4″),70.4 (Rha-C-2?),70.7 (Rha-C-3?),72.0 (Rha-C-4?),76.8 (Glu-C-2″),77.2 (Glu-C-5″),77.4(Glu-C-3″),93.6 (C-8),98.9 (C-6),99.2 (Glu-C-1″),101.2 (Rha-C-1?),104.0 (C-10),115.8(C-2′),116.2 (C-5′),121.0 (C-6′),122.4 (C-1′),133.8 (C-3),145.0 (C-3′),148.2 (C-4′),156.3 (C-2),156.7 (C-9),161.5 (C-5),164.1(C-7),177.6 (C-4)。以上數(shù)據(jù)與文獻(xiàn)[15]基本一致,故鑒定為槲皮素-3-O-新橙皮糖苷。

化合物7:棕黃色無定形粉末,C10H12O2。ESIMS m/z:165.1 [M+H]+。1H-NMR (500 MHz,CD3OD) δ:7.05 (2H,d,J=8.4 Hz,H-2′,6′),6.75 (2H,d,J=8.4 Hz,H-3′,5′),3.05 (2H,t,J=7.4,8.1 Hz,H-3),2.82 (2H,t,J=8.1,7.4 Hz,H-4),1.90 (3H,s,H-1)；13C-NMR (125 MHz,CD3OD) δ:24.2 (C-1),34.1 (C-4),42.3(C-3),116.8 (C-3′,5′),128.6 (C-1′),130.8(C-2′,6′),157.6 (C-4′),180.2 (C-2)。以上數(shù)據(jù)與文獻(xiàn)[16]基本一致,故鑒定為4-(4′-羥基苯基) -2-丁酮。

化合物8:白色球狀結(jié)晶,C26H34O12。ESI-MS m/z:561.1 [M+Na]+。1H-NMR (500 MHz,C5D5N) δ:7.59 (1H,d,J=8.3 Hz,H-5),7.40(1H,d,J=8.3 Hz,H-5′),7.11 (1H,d,J=8.3 Hz,H-6),7.01 (1H,d,J=8.3 Hz,H-6′),5.68(1H,d,J=6.7 Hz,H-1″),5.00 (1H,d,J=8.6 Hz,H-7),4.94 (1H,d,J=8.6 Hz,H-7′)；13CNMR (125 MHz,C5D5N) δ:53.4 (C-8′),55.9(-CH3O),55.9 (-CH3O),56.5 (C-8),62.4 (C-6″),63.3 (C-9),71.0 (C-4″),71.3 (C-9′),74.9(C-2″),76.8 (C-3″),78.0 (C-7′),78.9 (C-5″),85.1 (C-7),102.3 (C-1″),111.2 (C-2′),111.8(C-2),115.9 (C-5′),116.4 (C-5),120.0 (C-6),120.3 (C-6′),134.2 (C-1),139.5 (C-1′),147.4(C-4′),147.9 (C-4),148.8 (C-3′),150.1 (C-3)。以上數(shù)據(jù)與文獻(xiàn)[17]基本一致,故鑒定為lanicepside B。

化合物9:粉紅色無定形粉末,C12H13NO3。ESI-MS m/z:220.1 [M+H]+,242 [M+Na]+。1HNMR (500 MHz,CDCl3) δ:8.68 (1H,s,OH-8),8.45 (1H,s,OH-9),7.02 (1H,s,H-10),6.97(1H,s,H-7),4.52 (1H,d,J=7.7 Hz,H-10b),4.32 (1H,m,H-5),2.88 (1H,m,H-5),2.70(2H,m,H-6),2.40 (1H,m,H-2),2.32 (1H,m,H-2),1.65 (1H,m,H-1)；13C-NMR (125 MHz,CDCl3) δ:28.1 (C-6),28.2 (C-1),32.0(C-2),37.5 (C-5),56.5 (C-10b),112.8 (C-10),116.6 (C-7),124.8 (C-6a),129.4 (C-10a),146.2 (C-8),146.4 (C-9),172.7 (C-3)。以上數(shù)據(jù)與文獻(xiàn) [18]基本一致,故鑒定為馬齒莧酰胺E。

化合物10:淡黃色針狀結(jié)晶,C20H18O10。ESIMS m/z:419.1 [M+H]+。1H-NMR (500 MHz,C5D5N) δ:8.08 (2H,q,H-2′,6′),6.92 (2H,q,H-3′,5′),6.76 (1H,d,J=2.1 Hz,H-8),6.38(1H,d,J=2.2 Hz,H-6),5.30 (1H,d,J=7.2 Hz,Ara-H-1″)；13C-NMR (125 MHz,C5D5N) δ:65.9 (Xyl-C-5″),67.5 (Xyl-C-4″),70.0 (Xyl-C-2″),72.4 (Xyl-C-3″),94.2 (C-8),98.8 (C-6),100.2 (Xyl-C-1″),104.6 (C-10),115.5 (C-3′,5′),121.6 (C-1′),129.7 (C-2′,6′),136.1 (C-3),147.5 (C-9),155.8 (C-2),159.4 (C-4′),160.3 (C-5),162.6 (C-7),176.1 (C-4)。以上數(shù)據(jù)與文獻(xiàn)[19]基本一致,故鑒定為kaempferol-3-O-β-D-xylopyranosyloside。

化合物11:白色粉末,C26H34O12。ESI-MS m/z:561.1 [M+Na]+。1H-NMR (500 MHz,C5D5N) δ:7.13 (1H,d,J=8.3 Hz,H-5′),7.06 (1H,d,J=1.9 Hz,H-2′),6.93 (1H,d,J=1.9 Hz,H-2),6.76 (1H,dd,J=1.9,6.7 Hz,H-6),4.85 (1H,d,J=6.7 Hz,H-1″),4.53 (1H,d,J=8.5 Hz,H-7′)；13C-NMR (125 MHz,C5D5N) δ:52.7 (C-8′),55.8 (-CH3O),56.4 (-CH3O),56.7 (C-8),62.5(C-6″),63.2 (C-9),71.1 (C-4″),71.3 (C-9′),74.9 (C-2″),77.3 (C-3″),77.8 (C-7′),78.2 (C-5″),85.8 (C-7),102.8 (C-1″),111.2 (C-2),112.2 (C-2′),116.0 (C-5),117.5 (C-5′),120.6(C-6′),120.7 (C-6),134.0 (C-1′),139.6 (C-1),147.4 (C-4),147.6 (C-4′),149.1 (C-3),150.8 (C-3′)。以上數(shù)據(jù)與文獻(xiàn)[17]基本一致,故鑒定為lanicepside A。

化合物12:白色粉末,C36H44O15。ESI-MS m/z:715.3 [M-H]-。1H-NMR (500 MHz,CD3OD) δ:7.13 (1H,s,H2″),6.99 (1H,s,H-2),6.94(1H,s,H-2′),6.87 (1H,d,J=8.3 Hz,H-5),6.81 (2H,d,J=8.3 Hz,H-6,6′),6.76 (2H,d,J=8.3 Hz,H-5′,5″),6.06 (1H,d,J=1.1 Hz,H-7),5.79 (1H,d,J=6.3 Hz,H-8),4.85 (1H,d,J=3.8 Hz,H-7),4.70 (1H,d,J=4.1 Hz,H-7′),4.46 (1H,d,J=4.3 Hz,H-8″),4.33 (1H,q,J=5.3,1.1 Hz,H-9),4.22 (2H,d,J=6.6 Hz,H-9,9′),4.17 (1H,d,J=7.3 Hz,H-1?),4.05 (1H,m,H-3),3.85 (1H,dd,J=11.6,6.0 Hz,H-9″),3.56 (1H,dd,J=11.6,6.0 Hz,H-9″),1.76(2H,m,H-4),1.63 (1H,d,J=12.1 Hz,H-2),1.44 (1H,d,J=2.0 Hz,H-2),1.26 (3H,d,J=5.5 Hz,H-10),1.12 (3H,s,H-13),0.87 (3H,s,H-12)；13C-NMR (125 MHz,CD3OD) δ:55.8(C-8),55.9 (C-8′),56.3 (-CH3O),56.4 (-CH3O),56.5 (-CH3O),62.3 (C-9″),62.5 (C-6?),71.2 (C-4?),71.3 (C-9),71.3 (C-9′),74.9 (C-2?),77.1 (C-3?),78.2 (C-5?),78.2(C-7″),85.8 (C-8″),86.3 (C-7),87.2 (C-7′),102.8 (C-1?),111.2 (C-2′),111.2 (C-2),111.2(C-2″),115.8 (C-5″),116.0 (C-5′),118.7 (C-5),120.2 (C-6),120.3 (C-6′),120.5 (C-6″),131.0 (C-1″),134.1 (C-1′),137.0 (C-1),147.4(C-4′),147.6 (C-4″),148.7 (C-3″),148.9 (C-3′),149.1 (C-4),151.7 (C-3)。以上數(shù)據(jù)與文獻(xiàn)[20]基本一致,故鑒定為mananthoside K。

化合物13:白色粉末,C13H24O4。ESI-MS m/z:243.2 [M-H]-。1H-NMR (500 MHz,CD3OD) δ:6.06 (1H,d,J=1.1 Hz,H-7),5.79 (1H,d,J=6.3 Hz,H-8),4.33 (1H,t,J=5.3,1.1 Hz,H-9),4.05 (1H,m,H-3),1.76 (2H,m,H-4),1.63 (1H,d,J=12.1 Hz,H-2),1.44 (1H,d,J=2.0 Hz,H-2),1.26 (3H,d,J=5.5 Hz,H-10),1.12 (3H,s,H-13),0.87 (3H,s,H-12)；13C-NMR (125 MHz,CD3OD) δ:24.2 (C-10),26.2 (C-12),27.1 (C-13),27.5 (C-11),40.7(C-1),45.7 (C-4),46.4 (C-2),65.3 (C-3),69.6 (C-9),77.8 (C-5),78.9 (C-6),131.2 (C-7),136.1 (C-8)。以上數(shù)據(jù)與文獻(xiàn)[21]基本一致,故鑒定為megastigmane。

化合物14:白色粉末,C20H26O7。ESI-MS m/z:379.2 [M+H]+。1H-NMR (500 MHz,CD3OD) δ:6.90 (1H,d,H-2),6.88 (1H,d,H-2′),6.81(1H,d,J=2.6 Hz,H-6),6.79 (1H,d,J=2.6 Hz,H-6′),3.85 (1H,d,J=9.1 Hz,H-1),3.62(1H,m,H-4),3.30 (1H,m,H-2),1.12 (1H,m,H-3)；13C-NMR (125 MHz,CD3OD) δ:43.8 (C-3),45.9 (C-2),55.8 (-CH3O),56.4 (-CH3O),56.7 (C-8),62.5 (C-6″),63.2 (C-9),71.1 (C-4″),71.3 (C-9′),74.9 (C-2″),77.3 (C-3″),77.8 (C-7′),78.2 (C-5″),85.8 (C-7),102.8 (C-1″),111.2 (C-2),112.2 (C-2′),116.0 (C-5),117.5 (C-5′),120.6 (C-6′),120.7 (C-6),134.0(C-1′),139.6 (C-1),147.4 (C-4),147.6 (C-4′),149.1 (C-3),150.8 (C-3′)。以上數(shù)據(jù)與文獻(xiàn)[22]基本一致,故鑒定此化合物為4-(3′-hydroxy-4′-methoxyphenyl) -4-(4″-hydroxy-3″-methoxyphenyl) -2,3-di (hydroxymethyl) butan-1-ol。

化合物15:無色油狀,C38H36O11。ESI-MS m/z:691.3 [M+Na]+。1H-NMR (500 MHz,CD3CD) δ:6.70～7.02 (20H,m,H-2,H-5,H-6,H-2′,H-5′,H-6′,H-3″,H-5″,H-3?,and H-5?),4.87 (2H,m,H-7),4.84 (2H,m,H-9′),4.51 (2H,m,H-8),4.43 (2H,m,H-9),3.82 (3H,s,-CH3O),3.79 (3H,s,-CH3O)；13C-NMR (125 MHz,CD3OD) δ:56.4 (-CH3O),56.5 (-CH3O),63.2(C-9),65.3 (C-9′),74.1 (C-7),85.8 (C-8),111.4 (C-2),111.7 (C-2′),115.6 (C-8″),115.8(C-8?),115.8 (C-5),115.9 (C-5′),116.0 (C-3″,5″),116.0 (C-3?,5?),118.5 (C-2),118.7(C-2′),120.6 (C-6),120.6 (C-6′),120.6 (C-8′),127.0 (C-1″),127.1 (C-1?),131.2 (C-2″,6″),131.2 (C-2?,6?),133.8 (C-1),134.0 (C-1′),134.1 (C-7′),147.0 (C-7″),147.1 (C-7?),147.4 (C-3),147.8 (C-4),148.6 (C-4′),148.8(C-3′),160.3 (C-4″),160.6 (C-4?),167.4 (C-9″),167.6 (C-9?)。以上數(shù)據(jù)與文獻(xiàn)[23]基本一致,故鑒定為dadahol B。

4 討論

烏頭葉作為《中國(guó)藥典》 收錄品種,也是蒙醫(yī)藥里的一味重要藥材,據(jù)調(diào)查,蒙醫(yī)藥近300 種常用成方之中,應(yīng)用草烏葉的就有20 余種[24]。然而近年來,烏頭的地上部分沒有得到很好的開發(fā)利用,種出的烏頭地上部分絕大多數(shù)都是焚燒丟棄的。如果能在烏頭地上部分發(fā)現(xiàn)一些活性成分,將可以將烏頭葉加以利用,變廢為寶。

烏頭屬植物雖然有毒,但幾千年來民間仍有煮食烏頭的習(xí)慣,這足以說明其具有增強(qiáng)體質(zhì)、預(yù)防疾病的作用。煮食烏頭的溶劑是水,用水煮提的成分除了部分中弱極性的二萜生物堿外,還存在很多強(qiáng)極性成分,而烏頭的強(qiáng)極性成分一直以來很少被關(guān)注。本實(shí)驗(yàn)從中分離得到了1 個(gè)生物堿、6 個(gè)黃酮苷、8 個(gè)酚酸及酚苷類化合物,表明直緣烏頭的主要成分除了生物堿,還有黃酮及黃酮苷、酚酸及酚苷類,這兩大類成分在近年來的很多研究表明,有很強(qiáng)的藥理活性[25-28]。基于此,下一步課題組將針對(duì)這兩大類成分進(jìn)行系統(tǒng)的藥理活性研究,以期發(fā)掘其獨(dú)特的活性成分。