摘要
荨麻属植物(Urtica)麻叶荨麻(Urtica cannabina L.)，在我国药用历史悠久，西北地区民间常用于治疗风湿关节炎、荨麻疹、蛇咬伤、小便不利等症。具有祛风除湿，活血解痉，抗炎消肿、利尿等功效。麻叶荨麻的同属植物异株荨麻在欧洲同样有悠久的药用历史，国外现阶段已开发出多种保健品及治疗风湿关节炎、良性前列腺增生(BPH)的药物。在国内研究已相对滞后的情况下，为充分利用西北地区丰富的植物资源，我们对麻叶荨麻的化学成分进行了比较系统的研究， 以期为进一步的研究开发奠定基础。
采用色谱技术对麻叶荨麻的乙醇提取物进行分离，得到了13个化合物。通过化学方法和光谱技术鉴定了其中10个化合物，分别为两个香豆素类化合物：6，7-二羟基香豆素(Ⅰ)，7-羟基-6—甲氧基香豆素(Ⅱ)；两个香豆素类的前体化合物：对羟基桂皮酸(Ⅲ)、对羟基桂皮酸甲酯(Ⅳ)；两个烷烃类化合物：正三十一烷(Ⅴ)正二十九烷(Ⅵ)；另外还；有3，5-二甲氧基-4-羟基苯甲醛(Ⅶ)，山奈酚7-0-鼠李糖苷(Ⅷ)， β-谷甾醇(Ⅸ)，胡萝卜苷(Ⅹ)。其中，除化合物Ⅸ、Ⅹ外，其余均首次从该植物中分离得到，化合物Ⅲ—Ⅷ，为首次从荨麻属植物中得到。
对分离过程中得到的脂肪油，通过衍生化后将其制成甲酯化物。利用GC-MS技术，从NIST谱库中检索到62个色谱峰，鉴定了其中25个脂肪酸，占出峰面积的74.04％。其中棕榈酸含量最高，达23.23％。其余含量较高的还有硬脂酸、花生酸、二十一烷酸、山嵛酸、二十四烷酸。
有机酸成分是荨麻是荨麻属植物主要抗炎活性成分之一。为研究麻叶荨麻中的有机酸成分，我们按有机酸类成分的提取方法提取总有机酸，进行甲酯化后，利用GC-MS技术从NIST谱库中共检索到60个色谱峰，鉴定了其中27个峰，占总出峰面积的71.63％。其中对羟基桂皮酸含量最大，占27.86％。其余含量超过3.00％的还有顺式乌头酸，对羟基苯甲酸，香草酸，2，5-二羟基苯甲酸，壬二酸，柠檬酸。已知对羟基桂皮酸、顺式乌头酸、对羟基苯甲酸、香草酸、柠檬酸具有抗炎活性。
肝纤维化是各种慢性肝病发展至肝硬化的一个必经共同途径，阻止肝纤维化
麻叶尊麻及活血益气汤活性部位的化学成分研究
的形成对防止肝硬化具有重要意义。活血益气方药是王健等人根据中医理论及临
床经验配伍组成的抗肝纤维化方药，由黄茂，大黄，何首乌，丹参，桃仁五味中
药组成。药效学试验表明具有较好的抗猪血清诱导的大鼠实验性肝纤维化作用，
其有效部位有两种不同的作用模式:一种是以水溶性成分为主的早期生效、具有
一定程度的剂量依赖性抑制作用、抑制效应较弱的效应模式;另一种是以脂溶性
成分为主的生效较晚、有明显的时间依赖性抑制作用、抑制效应较强的效应模式。
其中脂溶性部位Alc950/0和Alc5006在很低的剂量下，仍显示出强烈的抑制效应
为阐明活性作用的物质基础，我们对Alc95%和Alc50%的化学成分进行了研究。经
过溶剂萃取、大孔吸附树脂富集、sephadex LH一20精制、制备TLC及Semi一pre HpLC
等手段从中分离了20个化合物，利用理化性质和波谱技术(uv、工R、El/MS、Esl/MS、
，H一NMR、”C一NMR、oEPT、HMQe、HMBC)相结合鉴定了创门的结构，分别为9种葱
醒类化合物:大黄酚(Chrys。phanol)，大黄素甲醚(physeion)，大黄素(emodin)，
芦荟大黄素(aloemodin)，大黄酸(rhein)，番泻普A或B(sennoside Ao:B)，
。一经基大黄素(。一hydroxylemodin)，大黄酚一8一0一p一D一葡萄糖普
(ehrys。phan。l一8一。一口一D一glueoside)，芦荟大黄素一。一o一p一D一葡萄糖普
(aloemodin一。一0一p一D一glueoside):3种菲醒类化合物:丹参酮IIA(tanshinone
IIA)，隐丹参酮(e ryptotanshinone)，丹参酮I(tanshinonel):1种异黄酮:
7，3‘一二经基一5‘一甲氧基异黄酮(7，3‘一dihydroxy一5‘methoxyisofla-
vone)以及原儿茶醛(protoeaeehuic aldehyde)，原儿茶酸(pr。t。eaeehuic
aeid)，黄茂甲普(astragal。side Iv)，苦杏仁普(amygdazin)，z，3，s，4‘一四经
基二苯乙烯一2一o一口一D一葡萄糖普(z，3，s，4‘一tetrahydr。xylstilbene一2一。一口
一D一glueoside)，(+)一儿茶素[(+)一catechin]，桂皮酸(einnamse acid)。其中
7，3’一二经基一5‘一甲氧基异黄酮是自然界中罕见的B环为间位二取代的异
黄酮类化合物，为新化合物。
采用高效液相色谱法，5 p moiamonsil一C，:分析柱，甲醇一0.1%磷酸(87:13)
洗脱，436nm检测，同时测定了Alc95%部位中5个游离葱醒的含量，结果芦荟大
黄素、大黄酸、大黄素、大黄酚、大黄素甲醚的平均回收率分别为98.30%、97.12%、
98.18%、97.66%、97.16%、RSD分别为1.64%、1.15%、0.95%、1.51%、1.64%(n二5)o
方法操作简便、准确、重现性好，可用于该活性部位的质量分析。
Studies on the chemical constituents of Urtica Cannabina L. and the active parts of the Prescription for benefited Qi to Promote flow of blood.
Urtica Cannabina L. is one species of Urtica. There are very rich plant resources in the northwest of China. The local people use U. cannabina to care rheumatism, nettle rash, wounds bited by snakes and so on. It was said to have the function of driving away wind-dampness, opening channels and collaterals, relaxing convulsions, antiinflammation and detumescence. While, Urtica dioica is another species of Urtica as same as U. Cannabina .It widely distributed in the Europe and had been used for a long time. From the 1960's to now, the foreign pharmaceutists had developed a lot of healthness protecting products and OTC drugs. Which are used for the therapy of rheumatism and benign prostate hyperplasia (BPH). In order to make full use of the plant resource in the northwest of China and the information source of foreign countries, we carried on a system research on the chemical constituents of U. Cannabina L.
By using different chromatography techniques, 13 compounds were isolated from the 80% EtOH extract. Based on modern spectroscopic analysis technique and chemical methods, the structures of 10 compounds were elucidated as esculetin, scopoletin, p-coumaric acid, methyl P-coumarate, hentriantane, nonacosane, 3,5-dimeth--oxy-4-hydroxybenzaldehyde,Kaempfero1-7-0-rhamnoside, -sitosterols and daucosterol.
This is the first report that compounds are in Urtica genus and all compounds except IX and X were first reported in Urtica cannabina L.
Fatty acid from petroleum part was subjected to GC-MS after saponificated and methanolized. The derivative were composed of 62 components, 25 of which were identified, account for 74.04%. The content of palmitic acid was 23.23%, while stearic acid, eicosanoic acid, heneicosanoic acid, docosanic acid and tetracosanoic acid were more than 3% respectively.
Organic acid was one of anti-inflammation active component in Urtica plant. General organic acid was extracted and methanolized to be analyzed by GC-MS. 60 peaks were inspected in NIST Dictionary, 27 peaks were
identified, account for 71. 63%. The content of p-coumaric acid was 27. 86%, while cis-aconitic acid, methyl paraben, vanillic acid, 2,5-dihydroxy-benzoic acid, nonane dioic acid, citric acid were more than 3% respectively. Among them, p-coumaric acid, cis-aconitic acid, vanill ic acid, citric acid were well known antiinflammation active components. Fumaric acid, citric acid, succinic acid existed in Urtica Cannabina L. as well as in Urtica diocio.
The severe consequence of hepatic fibrosis is cirrhosis liver . Preventing hepatic fibrosis is an important target to treat cirrhosis of liver. The preseription for benefited Qi to promote flow of blood was made up by Jian Wang et al. based on Chinese Traditional Medical Principle and clinical experience, which concludes Rheum palmatum L., Salvia miltinrrhiza Bge, Astragalus membranaceus (Fisch) Bge .var. mongholicus (Bge),Hsiao, Prunus PersicacL. Batsch, Polygonum multiflorum Thunb. It shows protective effects against rat Hepatic fibrosis in vivo. Lipophilic extracts show significant inhibiting effect at very low concentration.
To further study the chemical constitutes of lipophilic active parts , we prepared Alc95% and Alc50% according to original literature. 20 compounds were isolated by using macroporous resin, silica gel, polyamide, Sephadex LH-20, Rp-18, preparative TLC and preparative HPLC chromato--graphy. The structures of them were elucidated by means of physical and chemical properties, modern spectroscopic analysis techniques桿V, IR, EI/MS,ESI/MS,1H-NMR,13C-NMR,DEPT,HMQC,HMBC. They are nine anthraquinones: chrysophanol (95-1), physcion (95-2), emodin (95-5), aloemodin (95-7), rhein (50-1) , sennoside A or B(50-6) , -hydroxylemodin (95-10) , chrysophano1-8-0-D-glucoside (95-12), aloemodin-0-D-glucoside (95-13); three phenanthaquinones: tanshinone A (95-3), cryptotanshinone (95-6) , tanshinone I (95-4); one isoflavone: 7,3' -dih
引文
1 Hegi G. "Illustrierte Floravon Mitteleuropa" ,Band Ⅲ / 1. Teil, C. Hanser Verlag, Munchen, 1958:296-303
2 Grieve M.. "A Modern Herbal" ,Vol. Ⅱ, Hafner Publishing Co., New Yorkand London, 1967:575-579
3 Tutin T. G. Heywood V.H.. Burges N. A. Valentine D.H., Walters S. M.,Webb D.A. (Eds), "Flora Europaea", VOL. 1,Cambridge University Press, Cambridge, 1964:66-68
4 权宜淑．值得开发的荨麻属植物资源．中药材，1997，20(1)：8-10，
5 贺士元．北京植物志[M]．北京：北京出版社，1984，120-123
6 Benigni R., Capra C., Cattorini P.E.. "Piante Medicinali-Chimica, Farmacologia e Teraia". Vol. 2, Inverni & della Beffa, Milano, 1964,: 1056-1063
7 Madaus G.. "Lehrbuch der biologischen Heilmittel" Band Ⅲ. 2nd ed., Olms Verlag, Hildesheim- New York, 1979,: 2746-2754
8 侯宽昭．中国种子植物科属辞典(修订版)，北京：科学出版社，1982
9 王梦月，卫莹芳．荨麻属植物在民间的药用情况调查．中国民族民间医药杂志，2001，总53期：345-346
10 E. Bomba., P. Mora., Urtica dioica L.. Fitoterapia, 1997, LXⅧ (151): 390
11 Franck Bakke I. L., Thorsen E., Nordal A.. Medd. Norsk. Farm. Selsk.,1987, 40:181
12 Beschia M., Leonte A.. Bul. Univ. Galati, Fasc, 1982, 6:59
13 Budzianowski J.. Caffeic acid Esters from Urtica dioica and Urtica urens, Planta Med., 1991, 57:507
14 Kraus R., Spiteller G.,Barstsch W., (10E-12Z)-9-aydroxy-10,12-octadeca-diensaure, ein Aromstase-nernmstoff aus dern Warzelextrakt von Urtica dioica. Liebigs Ann. Chem., 1991:335
15 Gan β er D., Spiteller G., Aromatase Inhibitors from Urtica dioica Roots, Planta Med. 1995, 61:138
16 Kraus R., Spiteller G., Phenolic Compounds from roots of Urtica Dioica, Phytochemistry, 1990 29:1653
17 ChaurasiaN., WichtlM.,Flavonol Glucosides fromUrtica dioica, Planta Med., 1987, 53:432
18 ELLnain Wojtaszek M., Bylka W.,Kowalewski Z, Herba Polonica, 1986, 32:131
19 Matthias Schottmer, Josef Reiner, Francis S.K. Tayman,(+)—Neo—Olivil From Roots of Urtica Dioica, Phytochemistry, 1997, 46 (6): 1107-1109
20 Matthias Schottmer, Dietmar Ganger, Gerhard Spiteller, Lignans from the Roots of Urtica dioica and their Metabolites Bind to Human Sex Hormone Binding Globulin (SHBG), Planta Medica, 1997, 63:529-532
21 Chaurasia N, Witchtl M., Phenylpropane und Lignane aus der Wurzel von Urtica dioica L., Dtsch. hpoth. Ztg 1986, 126:1559
22 Kraus R., Spiteller G., Lignanglucosideaus Wurzeln von Urtica dioica, Liebigs Ann. Chem., 1990, 1205-1213
23 Neer Chaurasia, Max Wichtl, Flavonolglykoside aus Urtica dioica, Planta Med, 1987, 432-433
24 SolveigAndersen, Jens K. Wold, Water-soluble Glycoprotein from Urtica dioica leaves, Phytochemistry, 1978, 17:1875-1877
25 Schilcher H., Effenberger S., Zur Standardisierung von Brennesselwurzel, Scopoletin und β-Sitosterol-zwei geeignete Leitsubstanzen fur Urtecae radix, Dtsch. hpoth. Ztg, 1986, 126:79
26 ChaurasiaN., WichtlM., Scopoletin, 3-β-Sitosterin und Sitosterin-3β-D-Glucosidaus Brennesselwurzel (Urticae radix), Dtsch. hpoth. Ztg, 1986, 126:81
27 Johannes J. L., Carola M., The Inhibiting Effects of Urtica dioica Root Extracts on Experimentally Induced Prostatic Huperplasia in the Mouse, Plarta Med., 1997, 63:307
28 Blaim K, Major histocompatibility class I molecules present Urtica dioica agglutinin, a superantigen of vegetal origin to T lymphocytes Flora(Jena), 1962, 152:171
29 Chaurasia N., Wichtl M., Sterols and steryl glycoside from Urtica Dioca, J. Nat. Prod., 1987, 50:881-885
30 Hirans T., Homma M., Kitato O., Effects of Stinging Nettle Root Extracts and their Steroidal Components on the Na~+, K~+-ATPase of the Benign Prostatic Hyperplasia, Planta Med, 1994, 60: 30
31 Kraus R., Spiteller G., Terpene diol and Terpene diol glucosides from roots of Urtica dioica, Phytochemistry, 1991, 30:1203-1205
32 Wagner H., Willer F., Kreher B., Biologisch active Verbindungen aus dem Wasserextrakt yon Urtica dioica, Planta Med.,1989, 55:452
33 Wagner H., Willer F., Samtlegen R., Boos G., Phytomedicine, 1994, 1: 213
34 PeumansW. J., De Ley M., An unusual lectin from stinging nettle (Urtica dioica) rhizomes, FEBS Lett., 1984, 177:99
35 Radunz, Alfons. Z. Naturforsch., C: Biosci, 1976, 31C (9-10): 589
36 Kraus R., Spiteller G., Biol. Mass Spectr., 1991, 20:53
37 Kraus R., Spiteller G., Ceramides from Ortica dioica Roots, Liebigs Ann. Chem., 1991, 36:125
38 Andersen S., Wold j. K.. Water -soluble glucoprotein from Urtica dioica leaves. Phytochemistry, 1978, 17:1875
39 覃凌，康书华，袁阿兴．裂叶荨麻的化学成分．中草药，1989，20(6)：9
40 新疆中草药，新疆人民出版社，1975：115
41 Vishnevskii O. V., Proshunina D. V., Urtica dioica hgglutinin, Farm. Zh., 1989, 2:50
42 庄根林．荨麻叶浸膏治疗风湿的临床效果．国外医药·植物药分册，1996，11(2)：66-67
43 王梦月，刘瑛，卫莹芳．川产荨麻药理作用的初步研究．中国民族民间医药杂志，2001，总51：229-231
44 Obertreis B., Giller K., Teucher T., Antiphlogistdsche Effekte yon Extractum Urtica dioica floiorum im vergleich zu kaffeoulapfelsamre. Arzneim-Forsch/Drug Res. 1996, 46 (I): 52
45 王洁，刘湘．大荨麻根用于治疗前列腺疾病．国外医药·植物药分册，1996，11(4)：162-163
46 Rovira P., Buckle M. I. Delineation of two lumphocyte subsets. J. Immunol, 1999, 29:1571
47 Le Moal M. A., Colle J. H., Galelli A. Mouse T-lympphocyte activation by Urtica dioica agglutin. Res. Immunol, 1992, 143:691
48 秦元满，全洪吉．荨麻对小鼠凝血时间和出血时间的影响．中医药学报，2001，29(3)：65-66
49 Henderson D., J. Phytomedicine Research in Germany. Steroid Biochem, 1987, 27(4-6): 905
50 EL EtrebyM. F., J. Atamestane:An aromatase inhibitor for the treatment of Benign prostatic Hyperplasia a short Revien. Steroid Biochem. Molec. Biol, 1993, 44(4-6): 565
51 Thompson E. A., Jr., Siiteri P. K., The use of Glutaraldehyde-Treated Eruthrocytes for Assaying the Agglutinating activity of Letin. Biol Chem, 1974, 249:5364
52 Thompson E. A., Jr., Siiteri P. K., Randomized controlled trial of nettle
sting for treatment of base-of-thumb pain. Biol Chem, 1974, 249: 5373
53 Johannes J. L., Heiner R., Wolfgang B., The Inhibiting Effects of Components of Stinging Nettle Roots on Experimentally Induced Proststic Uyperplasia in Mice, Planta Med., 1999, 65:666
54 Lutz Konrad, Uans-HelgeMuller, CorinnaLenz, Antiproliferative Effect on Human Prostate Cancer Ceils by a Stinging Nettle Roots (Urtica dioica) Extract, Planta Medica., 2000, 66:44-47
55 Kristina R., Bert B., Klaus S. O., Plant extracts from stinging nettle (Urticadioica), an antirheumatic remedy, inhibit the proinflammatory transcription factor NF-Kb, FEBS Letters, 1999, 442:1:89-94
56 Rosner W., Hryb D. J., Khan M. S. Sex Hormone-Binding globulin: Anatomy and physiology of a new regulatory system. Steroid Biochem. Molec. Biol., 1991, 4:813
57 Wagner H., Geiger W. N., New method for quantitative determinaion of Uronic Acids. Phytomedicine, 1995, 4:287
58 CPI (B)1994, (9411): 97
59 Abdelhafid T., Sabah y., Abdelkhaleq L., Acute diuretic, natriuretic and hypotensive effects of a continuous perfusion of aqueous extract of Urtica dioica in the rat, J. Ethnopharmacology, 2000, 73:95-100
60 D. J. Hryb, M. S. Khan, N. A. Romas, The Effect of Extracts of the Roots of the stinging nettle (Urtica dioica) on the Interaction of SHBGwith its Receptor on Human Prostatic Membranes, Planta Med., 1995, 61: 31-32
61 Balzarini J., Neyts J., Schols D., The mannose-specific plant lectine from Cymbidium hubrid and Epipatis helleborine and the (N-autylglucosamine)_n-Specific plant lectin from Urtica dioica are potent and selective inhibitors of human immunodeficiency virus and cytomegaloverus replication in vitro. Antiviral Res., 1992, 18:191
62 Suh N., Luyengi L., Fong H. H. S., Discovery of Natural Product Chemopreventive Agents utilizing HL-60 Cell differentiation as a modle. Anticancer Res., 1995, 15:233
63 Koch E., in "Phytopharmaka in Forschung und klinischer Anvendund", D., Loew. N. Rietbrock (Eds), D. Steindopff VERlag, Darmstadt. 1995, 57-79.
64 R. Petlevski, M. Hadzija, M. Slijepcevic, Effectof "antidiabetis" herbal preparation on serum glucose and fructosam in NOD mice, J. Ethnopharmacology, 2001, 75:181-184
65 Geiger W. N., Haak G., Wanger H., 2nd International Congress on Phytomedicine and 7th Congress of the German Society of Phytotherapy, Munich, Germany, September 11-14, 1996 Abstract SL-106
66 Samtleben R., Boos G., Wagner H., 2nd International Congress on Phytomedicine and 7th Congress of the German Society of Phytotherapy, Munich, Germany, September 11-14, 1996 Abstract SL-107
67 Gelia B., Broncano F. j., Investigation of the Bicinchoninic Acid Protein Assay: Identification of the Groups Responsible for Color Formation. An. Bromatol. 1984, 35:99
68 张杰，柳云溪．大荨麻对急性关节炎的抗风湿作用，国外医药．植物药分册，1998，13(2)：86-87
69 Randall C, Randall H, Dobbs F, Randomized controlled trial or nettle sting for treatment of base-of-thumb pain, J. R. Soc Med 2000 Jun, 93 (6): 305-309
70 Vontobel H. P. Herzog R., Rutishauser G. Kres G., Urologe [B], 1985, 24:49
71 Friesen A., Benigne Prostatahyperplasie Ⅱ-Klin., Exp. Urol., 1988, 19:121
72 Feiber H., Benigne Prostatahyperplasie Ⅱ-Klin., Exp. Urol., 1988, 19:75
73 Sokeland J., Albrecht J., 2ndI nternational Congress on Phytomedicine and 7th Congress of the German Society of Phytotherapy, Munich, Germany, September 11-14, 1996 Abstract SL-105
74 Sonnenschein R., Urologe [B], 1987, 27:232
75 Brandstadter L., The synthesis of acetulcholine by plants Therapiewoche, 1987, 37:1918
76 Belaiche P., Llievoux O., Combined sabal and urtica extract compared with finasteride in men with benign prostatic hyperplasia: analysis of prostate volume and therapeutic outcome. Phytotherapy, 1991, Res. 5: 267
77 李光辉．荨麻合剂治疗慢性肾炎尿毒症12例．湖南中医杂志，1991，第5期：38