金毛狗脊化学成分研究
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摘要
本文首先综述了金毛狗脊的研究进展，包括植物资源、炮制、
化学成分、药理活性及临床应用。鉴于狗脊是常用的传统中药，其
有效成分尚未系统研究，其药理活性研究更是几乎空白。应当采用
现代科学手段对其化学成分及其药理活性进行系统研究，为金毛狗
脊的开发应用打下基础。本文首先对金毛狗脊及其混淆品进行蛋白
质电泳鉴别。采取高效毛细管电泳法对金毛狗脊及其混淆品蛋白质
进行分析，结果金毛狗脊及其混淆品蛋白质高效毛细管电泳谱图有
明显的差异，可作为金毛狗脊的生药学鉴别方法。接着对金毛狗脊
根的化学成分进行研究。先采用超临界CO_2流体萃取技术提取其精油
部分，并用GC-MS-计算机联用技术进行分离和鉴定。鉴定了其中25
个化合物。其主要成分（相对含量≥10％）按含量由高到低排列分别
为油酸、亚油酸、棕榈酸、十五碳酸、十六碳三烯酸甲酯、亚油酸
甲酯。其中γ-松油烯、桧烯、胡椒酮、杜松二烯、十六碳烯酸及其
酯、十六碳三烯酸甲酯、4-松油醇、2-异丙基-5-甲基-3-环己烯酮、
杜松萜烯、邻苯二甲酸及其酯、二十四碳烯酸甲酯、十八碳三烯醇
共12个化合物为首次从该植物中分离和鉴定。然后又对金毛狗脊中
的无机元素、磷脂、氨基酸、多糖进行分析和含量测定。再将金毛
狗脊经95％乙醇提取浸膏分别用石油醚、氯仿、乙酸乙酯、正丁醇
萃取。用GC-MS-计算机技术对金毛狗脊石油醚萃取部分的化学成分
进行分离和鉴定。结果从金毛狗脊石油醚萃取部分分离和鉴定出5
个化合物：即棕榈酸、棕榈酸甲酯、亚油酸、油酸和硬脂酸乙酯。
另外，还从乙酸乙酯萃取部分中分离和鉴定了7个化合物，分别为
对羟基乙酰苯胺（Ⅰ）、胆甾醇（Ⅱ）、蜡酸（Ⅲ）、蔗糖（Ⅳ）、原
儿茶醛（Ⅴ）、香草醛（Ⅵ）、山奈素（Ⅶ）。其中化合物Ⅰ、Ⅳ、Ⅴ
为首次从该植物中分离和鉴定。
The research survey on Cibotium barometz(L.) J. Sm was reviewed at
the beginning of this thesis, including plant source, processed chinese
medicine, chemical constituents, pharmacological activities and clinic
applications. Whereas a traditional chinese medicine, Cibotium
barometz(L.) S. Sm has not been studied on its chemical constituents and
their pharmacology systematically. So it should be done for developing
and utilizing it more.
Firstly, Cibotium barometz(L.) J. Sm and it抯 confused variety were
identified by the protein electrophoresis. The proteins in Cibotium
barometz(L.) J. Sm were analysed by high-performance capillary
electrophoresis(HPCE). The results showed that Cibotium barometz(L.) J.
Sm could be distinguished from it抯 confused variety by the protein
electrophorograms. The HPCE could be used for the pharmacognositical
identification of Cibotium baromea抸(L.) J. Sm. Secondly, the chemical
constituents in the root of Cibotium barometz(L.) J. Sm were studied. The
essential oil I and II were extracted from the root of Cibotium
barometz(L.) J. Sm with CO2 supercritical fluids by two grades isolation
and analysed by GC-MS-computer. Twenty-five compounds were
identified. The main constituents are oleic acid, linoleic acid, palmitic
acid, pentadecanoic acid, 7,10,13-hexadecatrienoic acid methyl ester,
linolemc acid methyl ester successively, every relative content of which is
over 10% respectively. Twelve compounds were identified and isolated
from this plant for the first time, which are i -terpinen, sabinen,
piperitone, cadina-1(l0)-diene, 9-hexadecenoic acid and its ester, 7,10,13-
hexadecatrienoic acid methyl ester, 4-terpineol, 2-isopropyl-5-methyl-3-
cyclohexen- 1-one, (+)- 6 -cadinene, phthalic acid and its ester, (Z)-
5,11,14,1 7-eicosatetraenoate methyl and (Z,Z,Z)-9, 12,1 5-octadecatrien- 1-
ol. At the same time, the abio-elements, phospholipids, amino acids and
polysaccharids in Cibotium barometz(L.) J. Sm were also analysed and
determinated. Finally, from the fraction extracted by acetic ester, seven
II
chemical constituents were isolated and identificated. they are
hydroxyacetanilide( I ), sucrose( II), saturated C27-fatty acids( [II),
protocatechualdehyde( IV ), ~ -sterol( V ), vanillin( VI), 3,4?5,7-
tetrahydroxyflavone(Vll), among them, I -. IV -. V were identified and
isolated from this plant for the first time.
化学成分、药理活性及临床应用。鉴于狗脊是常用的传统中药，其
有效成分尚未系统研究，其药理活性研究更是几乎空白。应当采用
现代科学手段对其化学成分及其药理活性进行系统研究，为金毛狗
脊的开发应用打下基础。本文首先对金毛狗脊及其混淆品进行蛋白
质电泳鉴别。采取高效毛细管电泳法对金毛狗脊及其混淆品蛋白质
进行分析，结果金毛狗脊及其混淆品蛋白质高效毛细管电泳谱图有
明显的差异，可作为金毛狗脊的生药学鉴别方法。接着对金毛狗脊
根的化学成分进行研究。先采用超临界CO_2流体萃取技术提取其精油
部分，并用GC-MS-计算机联用技术进行分离和鉴定。鉴定了其中25
个化合物。其主要成分（相对含量≥10％）按含量由高到低排列分别
为油酸、亚油酸、棕榈酸、十五碳酸、十六碳三烯酸甲酯、亚油酸
甲酯。其中γ-松油烯、桧烯、胡椒酮、杜松二烯、十六碳烯酸及其
酯、十六碳三烯酸甲酯、4-松油醇、2-异丙基-5-甲基-3-环己烯酮、
杜松萜烯、邻苯二甲酸及其酯、二十四碳烯酸甲酯、十八碳三烯醇
共12个化合物为首次从该植物中分离和鉴定。然后又对金毛狗脊中
的无机元素、磷脂、氨基酸、多糖进行分析和含量测定。再将金毛
狗脊经95％乙醇提取浸膏分别用石油醚、氯仿、乙酸乙酯、正丁醇
萃取。用GC-MS-计算机技术对金毛狗脊石油醚萃取部分的化学成分
进行分离和鉴定。结果从金毛狗脊石油醚萃取部分分离和鉴定出5
个化合物：即棕榈酸、棕榈酸甲酯、亚油酸、油酸和硬脂酸乙酯。
另外，还从乙酸乙酯萃取部分中分离和鉴定了7个化合物，分别为
对羟基乙酰苯胺（Ⅰ）、胆甾醇（Ⅱ）、蜡酸（Ⅲ）、蔗糖（Ⅳ）、原
儿茶醛（Ⅴ）、香草醛（Ⅵ）、山奈素（Ⅶ）。其中化合物Ⅰ、Ⅳ、Ⅴ
为首次从该植物中分离和鉴定。
The research survey on Cibotium barometz(L.) J. Sm was reviewed at
the beginning of this thesis, including plant source, processed chinese
medicine, chemical constituents, pharmacological activities and clinic
applications. Whereas a traditional chinese medicine, Cibotium
barometz(L.) S. Sm has not been studied on its chemical constituents and
their pharmacology systematically. So it should be done for developing
and utilizing it more.
Firstly, Cibotium barometz(L.) J. Sm and it抯 confused variety were
identified by the protein electrophoresis. The proteins in Cibotium
barometz(L.) J. Sm were analysed by high-performance capillary
electrophoresis(HPCE). The results showed that Cibotium barometz(L.) J.
Sm could be distinguished from it抯 confused variety by the protein
electrophorograms. The HPCE could be used for the pharmacognositical
identification of Cibotium baromea抸(L.) J. Sm. Secondly, the chemical
constituents in the root of Cibotium barometz(L.) J. Sm were studied. The
essential oil I and II were extracted from the root of Cibotium
barometz(L.) J. Sm with CO2 supercritical fluids by two grades isolation
and analysed by GC-MS-computer. Twenty-five compounds were
identified. The main constituents are oleic acid, linoleic acid, palmitic
acid, pentadecanoic acid, 7,10,13-hexadecatrienoic acid methyl ester,
linolemc acid methyl ester successively, every relative content of which is
over 10% respectively. Twelve compounds were identified and isolated
from this plant for the first time, which are i -terpinen, sabinen,
piperitone, cadina-1(l0)-diene, 9-hexadecenoic acid and its ester, 7,10,13-
hexadecatrienoic acid methyl ester, 4-terpineol, 2-isopropyl-5-methyl-3-
cyclohexen- 1-one, (+)- 6 -cadinene, phthalic acid and its ester, (Z)-
5,11,14,1 7-eicosatetraenoate methyl and (Z,Z,Z)-9, 12,1 5-octadecatrien- 1-
ol. At the same time, the abio-elements, phospholipids, amino acids and
polysaccharids in Cibotium barometz(L.) J. Sm were also analysed and
determinated. Finally, from the fraction extracted by acetic ester, seven
II
chemical constituents were isolated and identificated. they are
hydroxyacetanilide( I ), sucrose( II), saturated C27-fatty acids( [II),
protocatechualdehyde( IV ), ~ -sterol( V ), vanillin( VI), 3,4?5,7-
tetrahydroxyflavone(Vll), among them, I -. IV -. V were identified and
isolated from this plant for the first time.
引文
1 陈绍基．狗脊的炮制．中药通报．1987，(6)：2911-13
2 甑汉深，黄家智．狗脊炮制历史沿革的研究．中药材．1991，14(8)：31-33
3 阴健．中药现代研究与临床应用(3)．北京：中医古籍出版社，1997：182
4 中科院药物所．中药志(第二册)．北京：人民卫生出版社，1982：436
5 王永山，许益民，徐燕，等．荧光薄层扫描法测定中药中磷脂酰胆碱含量．中成药．1997，19(12)：34-35
6 贾主柱，李军，解世全，等．狗脊及其炮制品挥发油成分的比较研究．中国中药杂志．1996，21(4)：216-217
7 原忠，苏世元，江泽荣，等．中药狗脊化学成分的研究．中草药．1996，27(2)：76
8 Logan K J, Thomas B A. Distribution of lignin deterivatives in plants. New Phytol. 1985,99(4):571-573
9 Takao M, Toshiko S, Katsumi N, et al. Pterosin derivate aus der familie Pteridaceae. Phytochemistry. 1980, 19:1743-46
10 Saito K, NagaoT, Matoba M, et al. Chemical assay of ptaguiloside, the carcinogen of Pteridium aquilium, and the distribution of related compounds in the Pteridaceae. Phytochemistry. 1989, 28(6):1605-08
11 周汝俊．金狗毛枯矾散用于拔牙创伤止血等的临床观察．中西医结合杂志．1985，5(8)：483-484
12 Li Jun (李军), JiaTianzhu (贾天柱), Du Guangli(杜光力), et al. Studies on the basic principles for the processing of Rhizoma Cibotii: Part Ⅰ influence of Rhizoma Cibotii and its processed samples on thrombin induced rabbit platelet aggregation. Chinese Traditional and Herbal Drugs. 2000,31(9):678-680
13 李广勋．中药药理毒理与临床．天津：天津科技翻译出版公司，1992：396
14．辛效毅，王魁亮，安莉萍．中医药治疗骨质疏松症60例．四川中医．1997，15(7)：46-47
15 古凤江，孙瑞涛，朱笑飞．泌炎宝冲剂治疗肾盂肾炎68例疗效观察．长春中医学院学报．1997，13(1)：30-31
16 贾存恩．颈安散治疗颈椎病100例．吉林中医药．1997，17(3)：25-26
17 陈瑞俊．加味补肾安胎饮治疗肾虚胎动不安38例．福建中医药．1997，28(3)：12-13
18 中国医科院药物所．中药志(第二册)．北京：人民卫生出版社，1982：439
19 李红旗，沈忠耀．高效毛细管电泳在蛋白质分析上的应用．生物工程进展．1995，15(6)：40-42
20 胡平，罗国安，王如骥，等．中药菟丝子的高效毛细管电泳法鉴别．药学学报．1997，32(7)：549-551
21 张朝晖，范国荣，徐国钧，等．12种海马、海龙类药材高效毛细管电泳鉴别．中国中药杂志．1998，23(5)：259-260
22 Steven B, Hawthorne, David J Miller, et al. Coupled SFE-GC:A Rapid and Simple Technique for Extracting, Identifying, and Quantitating organic Analytes from Solids and Sorbent Resins. J Chromatogr Sci. 1989,27(7):347-351
23 King JW. Fundamentals and applications of supercritical fluid extraction in chromatographic science. J Chromatogr Sci. 1989,27:355-359
24 陈渊卿，顾健人，蒋惠秋，等．钴的螯合对象对争光霉素亲肿瘤的作用．上海医学．1980，3(5)：16-17
25 Gunby Phil. Selenium may act as cancer inhibitor. JAWA. 1981,46:1510-12
26 徐兵河，孙燕．微量元素硒的防癌抗癌作用．中国新药杂志．1998，7(3)：176-177
27 吴建梅，陈大为，孙波．天然活性成分磷脂复合物药学研究概述．中国药学杂志．1998，33(1)：9-11
28 顾学裘．抗衰老、抗癌中药的研究及展望．中国中医药科技出版社，1989：22
29 曹锦花，李华．多糖免疫调节作用的研究进展．中国生化药物杂志．1999，20(2)：104-106
30 李建恒，张杏红．抗肿瘤中药多糖研究进展．中医药学报．1998，26(4)：46-48
2 甑汉深，黄家智．狗脊炮制历史沿革的研究．中药材．1991，14(8)：31-33
3 阴健．中药现代研究与临床应用(3)．北京：中医古籍出版社，1997：182
4 中科院药物所．中药志(第二册)．北京：人民卫生出版社，1982：436
5 王永山，许益民，徐燕，等．荧光薄层扫描法测定中药中磷脂酰胆碱含量．中成药．1997，19(12)：34-35
6 贾主柱，李军，解世全，等．狗脊及其炮制品挥发油成分的比较研究．中国中药杂志．1996，21(4)：216-217
7 原忠，苏世元，江泽荣，等．中药狗脊化学成分的研究．中草药．1996，27(2)：76
8 Logan K J, Thomas B A. Distribution of lignin deterivatives in plants. New Phytol. 1985,99(4):571-573
9 Takao M, Toshiko S, Katsumi N, et al. Pterosin derivate aus der familie Pteridaceae. Phytochemistry. 1980, 19:1743-46
10 Saito K, NagaoT, Matoba M, et al. Chemical assay of ptaguiloside, the carcinogen of Pteridium aquilium, and the distribution of related compounds in the Pteridaceae. Phytochemistry. 1989, 28(6):1605-08
11 周汝俊．金狗毛枯矾散用于拔牙创伤止血等的临床观察．中西医结合杂志．1985，5(8)：483-484
12 Li Jun (李军), JiaTianzhu (贾天柱), Du Guangli(杜光力), et al. Studies on the basic principles for the processing of Rhizoma Cibotii: Part Ⅰ influence of Rhizoma Cibotii and its processed samples on thrombin induced rabbit platelet aggregation. Chinese Traditional and Herbal Drugs. 2000,31(9):678-680
13 李广勋．中药药理毒理与临床．天津：天津科技翻译出版公司，1992：396
14．辛效毅，王魁亮，安莉萍．中医药治疗骨质疏松症60例．四川中医．1997，15(7)：46-47
15 古凤江，孙瑞涛，朱笑飞．泌炎宝冲剂治疗肾盂肾炎68例疗效观察．长春中医学院学报．1997，13(1)：30-31
16 贾存恩．颈安散治疗颈椎病100例．吉林中医药．1997，17(3)：25-26
17 陈瑞俊．加味补肾安胎饮治疗肾虚胎动不安38例．福建中医药．1997，28(3)：12-13
18 中国医科院药物所．中药志(第二册)．北京：人民卫生出版社，1982：439
19 李红旗，沈忠耀．高效毛细管电泳在蛋白质分析上的应用．生物工程进展．1995，15(6)：40-42
20 胡平，罗国安，王如骥，等．中药菟丝子的高效毛细管电泳法鉴别．药学学报．1997，32(7)：549-551
21 张朝晖，范国荣，徐国钧，等．12种海马、海龙类药材高效毛细管电泳鉴别．中国中药杂志．1998，23(5)：259-260
22 Steven B, Hawthorne, David J Miller, et al. Coupled SFE-GC:A Rapid and Simple Technique for Extracting, Identifying, and Quantitating organic Analytes from Solids and Sorbent Resins. J Chromatogr Sci. 1989,27(7):347-351
23 King JW. Fundamentals and applications of supercritical fluid extraction in chromatographic science. J Chromatogr Sci. 1989,27:355-359
24 陈渊卿，顾健人，蒋惠秋，等．钴的螯合对象对争光霉素亲肿瘤的作用．上海医学．1980，3(5)：16-17
25 Gunby Phil. Selenium may act as cancer inhibitor. JAWA. 1981,46:1510-12
26 徐兵河，孙燕．微量元素硒的防癌抗癌作用．中国新药杂志．1998，7(3)：176-177
27 吴建梅，陈大为，孙波．天然活性成分磷脂复合物药学研究概述．中国药学杂志．1998，33(1)：9-11
28 顾学裘．抗衰老、抗癌中药的研究及展望．中国中医药科技出版社，1989：22
29 曹锦花，李华．多糖免疫调节作用的研究进展．中国生化药物杂志．1999，20(2)：104-106
30 李建恒，张杏红．抗肿瘤中药多糖研究进展．中医药学报．1998，26(4)：46-48