细叶杜香的化学成分研究
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摘要
细叶杜香(Ledum palustre L. var. Angustum E. Busch)又名狭叶杜香,是杜鹃花科(Ericaceae)杜香属(ledum)植物,常绿直立小灌木,主产于我国东北(大、小兴安岭,长白山)。细叶杜香的叶又名白山苔,味苦、辛,性微寒,有活血调经,化痰止咳等功效,民间常用于治疗月经不调,不孕,胃溃疡,咳嗽痰多,气喘等症。细叶杜香的叶及花蜜有毒,其叶、枝、花和果实中含有挥发油。目前国内外对该植物的研究多集中在对挥发油的研究上,对化学成分研究得较少。为此系统研究细叶杜香的化学成分,对合理开发和利用我国丰富的细叶杜香植物资源具有重大的意义。
本论文对细叶杜香干燥的嫩枝和叶用水进行提取,收集挥发油,通过气相色谱-质谱分析,结合计算机检索和人工检索技术分离和鉴定了28种成分,其中主要成分为4-松油醇(30.23%),1-甲基-2-异丙基苯(16.58%),枯茗醛(9.85%)等。继而对该水提物的化学成分进行研究,经溶剂分步萃取,反复硅胶柱层析,有机溶剂重结晶,凝胶柱色谱等分离纯化手段,得到了12个化合物。通过理化常数测定及波谱分析方法,并辅助以其他定性方法鉴定了它们的结构,分别为:5-羟基-4′, 7-二甲氧基黄酮( 5-hydroxy-4′, 7-dimethoxyflavone, 1)、正二十八烷醇(n-octacosanol, 2)、东莨菪内酯(scopoletin, 3)、oleuropeic acid(4)、(+) (1R~*, 2R~*, 4R~*) -trihydroxy-menthane (5)、秦皮素(fraxetin, 6)、熊果酸(ursolic acid, 7)、七叶内酯(aesculetin, 8)、对羟基苯甲酸(p-hydroxybenzcic acid, 9)、对苯二酚(hydroquinone, 10)、槲皮素(quercetin, 11)、金丝桃苷(hyperoside, 12)。其中化合物2,4,5,9,10均为首次从该属植物中分离得到。
Ledum palustre L. var. Angustum E. Busch, which is also called Ledum palustre L. var. Angustum N. Busch, is widely distributed in Dongbei in the northwest of China. It is a shrub which belongs to Ericaceae family. Its leaves can be used as traditional folk medicine. It is described as bitter in taste and has functions of promoting blood circulation to restore menstrual flow and eliminating sputum to stop coughing. Its leaves and nectar are poisonous and it is rich in essential oils. So far,studies focused on the chemical constituents of Ledum palustre L. var. Angustum E. Busch were not much, most of which were concentrated on essential oils. In order to exploit and utilize the plant properly, it is very important and instructive to study the chemical constituents systematically.
In this thesis, the chemical constituents which extracted with water from the leaves and shoots of Ledum palustre L. var. Angustum E. Busch were studied. At the same time, 28 constituents were identified from the essential oils by GC-MS, of which the major constituents are known as 4-terpineol, 1-methyl-2-(1-methylethyl)- Benzene and cumaldehyde. Column chromatography with silic gel was employed to isolate and purify the ingredients. Twelve compounds were isolated from the leaves and shoots of this plant.
Their structures were elucidated by means of IR, MS, NMR and chemical methods respectively. They were elucidated as 5-hydroxy-4′, 7-dimethoxyflavone(1), n-octacosanol(2), scopoletin(3), oleuropeic acid(4), (+) (1R~*, 2R~*, 4R~*)–trihydroxy -menthane(5), fraxetin(6), ursolic acid(7), aesculetin(8), p-hydroxybenzcic acid(9), hydroquinone(10), quercetin(11) and hyperoside(12). Compounds 2, 4, 5, 9, 10 were separated from the Ledum genus for the first time.
本论文对细叶杜香干燥的嫩枝和叶用水进行提取,收集挥发油,通过气相色谱-质谱分析,结合计算机检索和人工检索技术分离和鉴定了28种成分,其中主要成分为4-松油醇(30.23%),1-甲基-2-异丙基苯(16.58%),枯茗醛(9.85%)等。继而对该水提物的化学成分进行研究,经溶剂分步萃取,反复硅胶柱层析,有机溶剂重结晶,凝胶柱色谱等分离纯化手段,得到了12个化合物。通过理化常数测定及波谱分析方法,并辅助以其他定性方法鉴定了它们的结构,分别为:5-羟基-4′, 7-二甲氧基黄酮( 5-hydroxy-4′, 7-dimethoxyflavone, 1)、正二十八烷醇(n-octacosanol, 2)、东莨菪内酯(scopoletin, 3)、oleuropeic acid(4)、(+) (1R~*, 2R~*, 4R~*) -trihydroxy-menthane (5)、秦皮素(fraxetin, 6)、熊果酸(ursolic acid, 7)、七叶内酯(aesculetin, 8)、对羟基苯甲酸(p-hydroxybenzcic acid, 9)、对苯二酚(hydroquinone, 10)、槲皮素(quercetin, 11)、金丝桃苷(hyperoside, 12)。其中化合物2,4,5,9,10均为首次从该属植物中分离得到。
Ledum palustre L. var. Angustum E. Busch, which is also called Ledum palustre L. var. Angustum N. Busch, is widely distributed in Dongbei in the northwest of China. It is a shrub which belongs to Ericaceae family. Its leaves can be used as traditional folk medicine. It is described as bitter in taste and has functions of promoting blood circulation to restore menstrual flow and eliminating sputum to stop coughing. Its leaves and nectar are poisonous and it is rich in essential oils. So far,studies focused on the chemical constituents of Ledum palustre L. var. Angustum E. Busch were not much, most of which were concentrated on essential oils. In order to exploit and utilize the plant properly, it is very important and instructive to study the chemical constituents systematically.
In this thesis, the chemical constituents which extracted with water from the leaves and shoots of Ledum palustre L. var. Angustum E. Busch were studied. At the same time, 28 constituents were identified from the essential oils by GC-MS, of which the major constituents are known as 4-terpineol, 1-methyl-2-(1-methylethyl)- Benzene and cumaldehyde. Column chromatography with silic gel was employed to isolate and purify the ingredients. Twelve compounds were isolated from the leaves and shoots of this plant.
Their structures were elucidated by means of IR, MS, NMR and chemical methods respectively. They were elucidated as 5-hydroxy-4′, 7-dimethoxyflavone(1), n-octacosanol(2), scopoletin(3), oleuropeic acid(4), (+) (1R~*, 2R~*, 4R~*)–trihydroxy -menthane(5), fraxetin(6), ursolic acid(7), aesculetin(8), p-hydroxybenzcic acid(9), hydroquinone(10), quercetin(11) and hyperoside(12). Compounds 2, 4, 5, 9, 10 were separated from the Ledum genus for the first time.
引文
[1] 中国科学院北京植物研究所.中国高等植物名实图鉴(第三册)[M].科学出版社, 1974:24.
[2] 《中国植物志》编辑委员会.中国植物志[M].北京:科学出版社, 2005, 57(1):004y-005a.
[3] 严永清主编. 中药辞海(第二卷)[M].北京:中国医药科技出版社, 1996.
[4] 侯宽昭编, 吴德邻等修订.中国种子植物科属词典[M].北京:科学出版社, 1982.
[5] 江苏新医学院.中药大辞典: (上册) [M].上海:上海科学技术出版社, 1977 : 696.
[6] 科诺瓦洛瓦 奥 阿. 林克勤译.杜香(Ledum Palustre L.)生物活性物质[J].国土与自然资源研究, 1995, 1:73-76.
[7] 孙秀殿, 徐连贵, 王志文.细叶杜香的栽培利用[J].特种经济动植物, 2000, 5 : 25.
[8] 赵子峰,沙伟,赵子云.我国的杜香属植物及杜香属植物的应用[J].生物学教学, 2006, 3 (14) : 8.
[9] Belova, N. V.; Shabunevich, L. E. Triterpenes in Ericaceae [J]. Khimiya Prirodnykh Soedinenii, 1967, 3(1): 62.
[10] Wollenweber, et al. Z. Naturforsch, C:Biosci, 1984, 39c (7-8), 710-713.
[11] Hopper. Shirley; chandler. R.Frank.J. Ethnopharmacol, 1984, 10, 2.
[12] 左文健, 杜香的化学成分研究[D], 沈阳药科大学, 2006.
[13] Milkhaliova. N.S , Rybalko.K.S. K Khimiya Prirodnykh Soedinenii, 1980, 2: 175-180.
[14] Milkhaliova. N.S , Rybalko.K.S. K Khimiya Prirodnykh Soedinenii, 1978, 1: 127-130.
[15] Marie. Aleth , et al. Phytochemistry, 1990, 29 (10):3367-3371.
[16] Zapesochnaya G., Pangarova T. Flavonoids of Ledum palustre L [J]. Doklady Bolgarskoi Akademii Nauk, 1980, 33 (7): 933-6.
[17] 王晓琴, 细叶杜香化学成分的研究[D], 内蒙古医学院, 2005.
[18] Uoda Hidetaka,Kondo Tamio,Kyushu Univ , et al. Essential oil of Ledum palustre var. dilatatum. I. [J]. Nippon Nogei Kagaku Kaishi, 1943, 19: 355-365.
[19] Hasebe Noboru. The essential oil of Ledum palustre L. in Saghalien. [J]. Nippon Kagaku Kaishi (1921-47), 1943, 64: 1041-1044.
[20] Von Schantz M,Widen K G,Hiltunen R. Structures of some aliphatic monoterpenoidsisolated from the essential oil of Ledum palustre L. Acta chemica Scandinavica,1973, 27 (2): 551-555.
[21] Lawrence Brian M., Terhune Stuart J., Tattje Dirk H. E. Chemical composition of the oils of Ledum palustre and Ledum groenlandicum. [J]. Int. Congr. Essent. Oils, 1974, 6, 86.
[22] Tattje.D.H.E, Bos. R. Planta Med, 1981, 41 (3): 303-307.
[23] Klokova M. V., Berezovskaya T.P., Serykh E. A. et al. Essential oils of the Ledum genus. [J]. Khimiya Prirodnykh Soedinenii, 1981, 6: 802-803.
[24] Klokova M.V.; Khan. V. A, Dubovenko. Zh. V, et al. Khimiya Prirodnykh Soedinenii. 1983, 3, 293-296.
[25] Ueyama Yoshitaka,Hashimoto Seiji, Nii Hiromichi, et al. Constituents of the essential oil from Ledum palustre L. var. angustum N. Busch. [J].Nippon Nogei Kagaku Kaishi, 1989, 63 (4): 849-851.
[26] Belousova N I, Tkachev A V, Shakirov M.M., et al. Khimiya Prirodnykh Soedinenii, 1991, 1: 24-29.
[27] Tkachev A. V.,Belousova N. I.,Khan V. A. 7-Elemenol, a new sesquiterpene alcohol from essential oil of Ledum palustre L. [J]. Khimiya Rastitel'nogo Syr'ya,1999, 3 : 39-40.
[28] Jaenson Thomas G T,Palsson Katinka,Borg-Karlson Anna-Karin. Evaluation of extracts and oils of mosquito (Diptera: Culicidae) repellent plants from Sweden and Guinea-Bissau. [J].Journal of medical entomology,2006, 43 (1) : 113-119.
[29] 林克勤, 宿佰杰. 杜香精油利用和生产工艺研究[J]. 自然资源研究, 1986, 2 : 34.
[30] 赵德修, 王华亭, 吴承顺, 等. 狭叶杜香挥发油成分的初步研究[J]. 植物学报, 1987, 29 (2) : 189-192.
[31] 江佩芬, 刘建国, 周勇, 等. 杜香植物资源开发利用的基础研究Ⅰ.杜香油化学成分的研究[J]. 天然产物研究与开发, 1993, 5 (1) : 35-38.
[32] 景治中, 王美兰, 陈涑年. 细叶杜香精油的色谱-质谱联用分析[J]. 色谱, 1993, 11 (4) : 244-245.
[33] 赵振东, 王亚玲, 杜晓光, 等. 杜香精油主要组成及利用的研究[J]. 林产化工通讯, 2001, 35 (5) : 3-6.
[34] 张凤荣, 刘莉颖, 张耀梅. 姜茁松毛细管气相色谱法测定单萜烃油及其胶丸中的对聚伞花烃含量[J]. 中草药, 2003, 34 (2) : 133.
[35] 王炎, 赵敏. 兴安岭地区细叶杜香挥发性成分的研究[J]. 色谱, 2003, 11(6) : 631.
[36] 陈其秀, 王晓琴, 陈其和, 等. 狭叶杜香挥发油提取方法的研究[J]. 内蒙古医学院学报, 2006, 28 (5) : 416.
[37] 谈华, 刘庆华. 细叶杜香挥发油抑菌和杀菌作用的研究[J]. 齐齐哈尔大学学报, 2005, 21 (3) : 33-36.
[38] 曲涛, 宋立新, 张微, 等. 细叶杜香油空气杀菌的实验研究[J]. 中医药信息, 1996, 6, 38.
[39] 马雪梅. 大兴安岭地区杜香有效成分的研究[D]. 东北林业大学, 2004.
[40] 国家中医药管理局《中华本草》编委会.《中华本草》第六分册[M]. 上海:科学技术出版社,1997,16: 5252-5253.
[41] 祝君梅, 赵树仪, 陈卫平, 等. 杜香油镇咳祛痰与急性毒性作用的实验研究[J]. 天津药学, 2001, 13 (2): 26.
[42] 朱铉, 金香花, 崔哲. 杜香萜烯对安定透皮吸收作用影响的研究[J]. 延边大学医学院学报, 1998, 21(1) : 29.
[43] 金红花, 韩慧兰, 郑桂华, 等. 杜香萜烯促进透皮吸收机理的研究[J]. 延边大学医学学报, 2001, 24(1): 25.
[44] Narimanov A A, Miakisheva S N, Kuznetsova S M. The radioprotective effect of extracts of Ardiangelica officinalis and Ledum palustre L. on mice [J]. Radeobiologiia, 1991, 31(3): 391~393.
[45] 包宪忠, 陈鸿儒. 杜香的工业原料用途[J]. 内蒙古林业调查设计, 2001, 24(增刊): 60.
[46] 韩光铉. 一种纯中药戒毒药物及其制备方法[P], 发明专利说明书, 2004.6.2.
[47] 于沈晶, 任春生, 修志龙. 天然挥发油对塑料降解和减容作用的研究[A]. 第一届全国化学工程与生物化工年会论文摘要集(下)[C], 2004.
[48] 胡秀华. 植物杜香祛斑霜的研制[J]. 高师理科学刊, 2005, 25(4): 44-45.
[49] 李景富, 吴德成, 周德本, 等. 细叶杜香资源的调查研究[J]. 国土与自然资源研究, 1987, (02):16.
[50] 张庆荣, 夏光成. 有毒中草药彩色图鉴(第 2 版)[M]. 天津: 天津科技翻译出版公司,2006: 139.
[51] 余正文, 朱海燕, 杨小生, 等.毛子草化学成分及其促 PC-12 细胞的分化作用研究 ?[J].中国中药杂志, 2005, 30(17):1335-1338.
[52] 杜彰礼, 殷志奇, 叶文才, 等. 楮叶乙醇提取物石油醚部分的化学成分研究[J]. 海峡药学, 2007, 19 (5) : 78.
[53] 陈荣,梁敬钰,卢海英,等.青橄榄叶的化学成分研究[J]. 林产化学与工业, 2007, 27(2) : 47.
[54] 段朝辉,石宝俊,吴立宏,等.长梗秦艽的化学成分[J]. 中国天然药物, 2007, 5 (6) : 418.
[55] Pellegata R, Ventura P, Villa M, et al. An improved procedure for the synthesis of oleuropeic acid. I. [J]. Synthetic Communications, 1985, 15 (2): 169.
[56] Miyazawa M, Ohsawa M. Biotransformation of α-Terpineol by the Larvae of Common Cutworm (Spodoptera litura) [J]. J. Agric. Food Chem. 2002, 50(17): 4917.
[57] Ahmed A. Mahmoud, Ahmed A. Ahmed. α -Pinene-type monoterpenes and other constituents from Artemisia suksdorfii[J]. Phytochemistry, 2006, 67:2103-2109.
[58] 石心红, 陈华贺, 孔令义. 沙戟化学成分的研究[J]. 中国药学杂志, 2007, 42(4) :253.
[59] 付晓丽. 满山红叶中化学成分的研究[D]. 山西医科大学, 2006 : 48.
[60] 高广春, 吴萍, 曹洪麟, 等.金钟藤中酚类化合物的研究[J].热带亚热带植物学报, 2006, 14(3) : 234.
[61] 于德泉, 杨峻山.分析化学手册:第七分册[M].北京:化学工业出版社, 1999:449-839.
[62] 曾宪仪, 方乍浦, 吴永忠, 等.蔓荆子化学成分研究[J]. 中国中药杂志,1996,21(3):167.
[63] 李蕾, 罗氘芸, 刘勇. 云南琵琶甲抗菌活性成分研究[J]. 中草药, 2001, 32 (3):198.
[64] 吴立军.天然药物化学:第 4 版[M].北京:人民卫生出版社, 2003:196-206.
[65] 杨书慧, 田瑄.秀雅杜鹃化学成分的研究[J].西北植物学报, 2007, 27(2):366.
[66] 何华, 余江南, 倪坤仪. 现代色谱分析[M]. 北京:化学工业出版社, 2004: 167-189.
[2] 《中国植物志》编辑委员会.中国植物志[M].北京:科学出版社, 2005, 57(1):004y-005a.
[3] 严永清主编. 中药辞海(第二卷)[M].北京:中国医药科技出版社, 1996.
[4] 侯宽昭编, 吴德邻等修订.中国种子植物科属词典[M].北京:科学出版社, 1982.
[5] 江苏新医学院.中药大辞典: (上册) [M].上海:上海科学技术出版社, 1977 : 696.
[6] 科诺瓦洛瓦 奥 阿. 林克勤译.杜香(Ledum Palustre L.)生物活性物质[J].国土与自然资源研究, 1995, 1:73-76.
[7] 孙秀殿, 徐连贵, 王志文.细叶杜香的栽培利用[J].特种经济动植物, 2000, 5 : 25.
[8] 赵子峰,沙伟,赵子云.我国的杜香属植物及杜香属植物的应用[J].生物学教学, 2006, 3 (14) : 8.
[9] Belova, N. V.; Shabunevich, L. E. Triterpenes in Ericaceae [J]. Khimiya Prirodnykh Soedinenii, 1967, 3(1): 62.
[10] Wollenweber, et al. Z. Naturforsch, C:Biosci, 1984, 39c (7-8), 710-713.
[11] Hopper. Shirley; chandler. R.Frank.J. Ethnopharmacol, 1984, 10, 2.
[12] 左文健, 杜香的化学成分研究[D], 沈阳药科大学, 2006.
[13] Milkhaliova. N.S , Rybalko.K.S. K Khimiya Prirodnykh Soedinenii, 1980, 2: 175-180.
[14] Milkhaliova. N.S , Rybalko.K.S. K Khimiya Prirodnykh Soedinenii, 1978, 1: 127-130.
[15] Marie. Aleth , et al. Phytochemistry, 1990, 29 (10):3367-3371.
[16] Zapesochnaya G., Pangarova T. Flavonoids of Ledum palustre L [J]. Doklady Bolgarskoi Akademii Nauk, 1980, 33 (7): 933-6.
[17] 王晓琴, 细叶杜香化学成分的研究[D], 内蒙古医学院, 2005.
[18] Uoda Hidetaka,Kondo Tamio,Kyushu Univ , et al. Essential oil of Ledum palustre var. dilatatum. I. [J]. Nippon Nogei Kagaku Kaishi, 1943, 19: 355-365.
[19] Hasebe Noboru. The essential oil of Ledum palustre L. in Saghalien. [J]. Nippon Kagaku Kaishi (1921-47), 1943, 64: 1041-1044.
[20] Von Schantz M,Widen K G,Hiltunen R. Structures of some aliphatic monoterpenoidsisolated from the essential oil of Ledum palustre L. Acta chemica Scandinavica,1973, 27 (2): 551-555.
[21] Lawrence Brian M., Terhune Stuart J., Tattje Dirk H. E. Chemical composition of the oils of Ledum palustre and Ledum groenlandicum. [J]. Int. Congr. Essent. Oils, 1974, 6, 86.
[22] Tattje.D.H.E, Bos. R. Planta Med, 1981, 41 (3): 303-307.
[23] Klokova M. V., Berezovskaya T.P., Serykh E. A. et al. Essential oils of the Ledum genus. [J]. Khimiya Prirodnykh Soedinenii, 1981, 6: 802-803.
[24] Klokova M.V.; Khan. V. A, Dubovenko. Zh. V, et al. Khimiya Prirodnykh Soedinenii. 1983, 3, 293-296.
[25] Ueyama Yoshitaka,Hashimoto Seiji, Nii Hiromichi, et al. Constituents of the essential oil from Ledum palustre L. var. angustum N. Busch. [J].Nippon Nogei Kagaku Kaishi, 1989, 63 (4): 849-851.
[26] Belousova N I, Tkachev A V, Shakirov M.M., et al. Khimiya Prirodnykh Soedinenii, 1991, 1: 24-29.
[27] Tkachev A. V.,Belousova N. I.,Khan V. A. 7-Elemenol, a new sesquiterpene alcohol from essential oil of Ledum palustre L. [J]. Khimiya Rastitel'nogo Syr'ya,1999, 3 : 39-40.
[28] Jaenson Thomas G T,Palsson Katinka,Borg-Karlson Anna-Karin. Evaluation of extracts and oils of mosquito (Diptera: Culicidae) repellent plants from Sweden and Guinea-Bissau. [J].Journal of medical entomology,2006, 43 (1) : 113-119.
[29] 林克勤, 宿佰杰. 杜香精油利用和生产工艺研究[J]. 自然资源研究, 1986, 2 : 34.
[30] 赵德修, 王华亭, 吴承顺, 等. 狭叶杜香挥发油成分的初步研究[J]. 植物学报, 1987, 29 (2) : 189-192.
[31] 江佩芬, 刘建国, 周勇, 等. 杜香植物资源开发利用的基础研究Ⅰ.杜香油化学成分的研究[J]. 天然产物研究与开发, 1993, 5 (1) : 35-38.
[32] 景治中, 王美兰, 陈涑年. 细叶杜香精油的色谱-质谱联用分析[J]. 色谱, 1993, 11 (4) : 244-245.
[33] 赵振东, 王亚玲, 杜晓光, 等. 杜香精油主要组成及利用的研究[J]. 林产化工通讯, 2001, 35 (5) : 3-6.
[34] 张凤荣, 刘莉颖, 张耀梅. 姜茁松毛细管气相色谱法测定单萜烃油及其胶丸中的对聚伞花烃含量[J]. 中草药, 2003, 34 (2) : 133.
[35] 王炎, 赵敏. 兴安岭地区细叶杜香挥发性成分的研究[J]. 色谱, 2003, 11(6) : 631.
[36] 陈其秀, 王晓琴, 陈其和, 等. 狭叶杜香挥发油提取方法的研究[J]. 内蒙古医学院学报, 2006, 28 (5) : 416.
[37] 谈华, 刘庆华. 细叶杜香挥发油抑菌和杀菌作用的研究[J]. 齐齐哈尔大学学报, 2005, 21 (3) : 33-36.
[38] 曲涛, 宋立新, 张微, 等. 细叶杜香油空气杀菌的实验研究[J]. 中医药信息, 1996, 6, 38.
[39] 马雪梅. 大兴安岭地区杜香有效成分的研究[D]. 东北林业大学, 2004.
[40] 国家中医药管理局《中华本草》编委会.《中华本草》第六分册[M]. 上海:科学技术出版社,1997,16: 5252-5253.
[41] 祝君梅, 赵树仪, 陈卫平, 等. 杜香油镇咳祛痰与急性毒性作用的实验研究[J]. 天津药学, 2001, 13 (2): 26.
[42] 朱铉, 金香花, 崔哲. 杜香萜烯对安定透皮吸收作用影响的研究[J]. 延边大学医学院学报, 1998, 21(1) : 29.
[43] 金红花, 韩慧兰, 郑桂华, 等. 杜香萜烯促进透皮吸收机理的研究[J]. 延边大学医学学报, 2001, 24(1): 25.
[44] Narimanov A A, Miakisheva S N, Kuznetsova S M. The radioprotective effect of extracts of Ardiangelica officinalis and Ledum palustre L. on mice [J]. Radeobiologiia, 1991, 31(3): 391~393.
[45] 包宪忠, 陈鸿儒. 杜香的工业原料用途[J]. 内蒙古林业调查设计, 2001, 24(增刊): 60.
[46] 韩光铉. 一种纯中药戒毒药物及其制备方法[P], 发明专利说明书, 2004.6.2.
[47] 于沈晶, 任春生, 修志龙. 天然挥发油对塑料降解和减容作用的研究[A]. 第一届全国化学工程与生物化工年会论文摘要集(下)[C], 2004.
[48] 胡秀华. 植物杜香祛斑霜的研制[J]. 高师理科学刊, 2005, 25(4): 44-45.
[49] 李景富, 吴德成, 周德本, 等. 细叶杜香资源的调查研究[J]. 国土与自然资源研究, 1987, (02):16.
[50] 张庆荣, 夏光成. 有毒中草药彩色图鉴(第 2 版)[M]. 天津: 天津科技翻译出版公司,2006: 139.
[51] 余正文, 朱海燕, 杨小生, 等.毛子草化学成分及其促 PC-12 细胞的分化作用研究 ?[J].中国中药杂志, 2005, 30(17):1335-1338.
[52] 杜彰礼, 殷志奇, 叶文才, 等. 楮叶乙醇提取物石油醚部分的化学成分研究[J]. 海峡药学, 2007, 19 (5) : 78.
[53] 陈荣,梁敬钰,卢海英,等.青橄榄叶的化学成分研究[J]. 林产化学与工业, 2007, 27(2) : 47.
[54] 段朝辉,石宝俊,吴立宏,等.长梗秦艽的化学成分[J]. 中国天然药物, 2007, 5 (6) : 418.
[55] Pellegata R, Ventura P, Villa M, et al. An improved procedure for the synthesis of oleuropeic acid. I. [J]. Synthetic Communications, 1985, 15 (2): 169.
[56] Miyazawa M, Ohsawa M. Biotransformation of α-Terpineol by the Larvae of Common Cutworm (Spodoptera litura) [J]. J. Agric. Food Chem. 2002, 50(17): 4917.
[57] Ahmed A. Mahmoud, Ahmed A. Ahmed. α -Pinene-type monoterpenes and other constituents from Artemisia suksdorfii[J]. Phytochemistry, 2006, 67:2103-2109.
[58] 石心红, 陈华贺, 孔令义. 沙戟化学成分的研究[J]. 中国药学杂志, 2007, 42(4) :253.
[59] 付晓丽. 满山红叶中化学成分的研究[D]. 山西医科大学, 2006 : 48.
[60] 高广春, 吴萍, 曹洪麟, 等.金钟藤中酚类化合物的研究[J].热带亚热带植物学报, 2006, 14(3) : 234.
[61] 于德泉, 杨峻山.分析化学手册:第七分册[M].北京:化学工业出版社, 1999:449-839.
[62] 曾宪仪, 方乍浦, 吴永忠, 等.蔓荆子化学成分研究[J]. 中国中药杂志,1996,21(3):167.
[63] 李蕾, 罗氘芸, 刘勇. 云南琵琶甲抗菌活性成分研究[J]. 中草药, 2001, 32 (3):198.
[64] 吴立军.天然药物化学:第 4 版[M].北京:人民卫生出版社, 2003:196-206.
[65] 杨书慧, 田瑄.秀雅杜鹃化学成分的研究[J].西北植物学报, 2007, 27(2):366.
[66] 何华, 余江南, 倪坤仪. 现代色谱分析[M]. 北京:化学工业出版社, 2004: 167-189.