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小刺猴头菌子实体天然产物化学研究
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摘要
猴头菌属真菌是珍贵的药食兼用菌。小刺猴头菌隶属猴头菌属,是吉林省长白山特有的菌物资源。在前人研究的基础上,本论文对小刺猴头菌子实体的化学成分做了进一步的探讨与研究。
     猴头菌营养丰富,含有多种维生素,氨基酸及微量元素,不但有极高的营养价值,而且还有很高的药用价值。迄今为止,国内外研究报道最多的是猴头菌多糖类物质,生物学与药理学研究表明,猴头菌多糖具有很好的提高免疫力、抗肿瘤、降血糖、降血压等多种功效。对猴头菌的小分子化学成分研究报道较少且不深入。现代医学与药理学研究证明,甾醇类等小分子物质在降胆固醇、抗癌、抗氧化、抗炎、防治前列腺疾病等方面具有显著作用,而萜类物质作为神经因子促进剂可治疗老年痴呆症。因此深入开展对小刺猴头菌化学成分的研究,特别是对小分子物质的系统研究,很有现实意义。
     本论文采用有机溶剂提取,两相溶剂萃取,大孔吸附树脂层析,硅胶柱层析,结晶法等常规的植物化学方法和技术手段并结合先进的仪器设备,通过不同的提取分离路线,从小刺猴头菌中提取分离了5个单体化合物。通过物理常数,化学方法和波谱分析[核磁共振(NMR),质谱(MS)]等方法鉴定了其中2单体化合物,两个化合物都为麦角甾醇。其中化合物2为22-顺式-麦角甾-5,7,22-三烯-3-醇[Ergosta-5,7,22-trien-3-ol,(22Z)-],化合物4为22-顺式-麦角甾-5,7,22-三烯-3-醇[Ergosta-5,7,22-trien-3-ol,(22Z)-]。这两个甾醇化合物为首次从小刺猴头菌中分离得到,并且都是新的天然化合物。它们的分离为小刺猴头菌的基础研究工作增加新的内容,提供新的依据。
     此外,本研究运用超临界CO_2萃取技术结合GC/MS计算机联用技术从解析釜Ⅰ和Ⅱ中共分离、鉴定了27个化合物,这些化合物分可分为三类:硬脂肪酸酯类、烷烃类和含氮类化合物。这些化合物不但丰富了对小刺猴头菌中的化学成分的研究结果,也为以后小刺猴头菌药理学实验研究打下基础。
     综合以上研究成果,本论文初步研究分析了小刺猴头菌的化学成分,为正确评价小刺猴头菌的药用价值提供了理论依据;为扩大小刺猴头菌的药用范围及菌物界麦角甾醇的数量增添了新内容;也为小刺猴头菌的新药开发奠定了一定的基础。
The fungi in genus Hericium are valuable edible and medical fungi. H. caput-medusae(Bull.:Fr.) Pers., belonging to the genus Herieium, is a special product of Changbai Mountain inJilin Province. Based on the research achievements of the other researchers, we made a furtherstudy and probe into the chemical compositions in the fruiting body of H. caput-medusae.
     The fungi in genus Hericium are nutritious, abundant in many kinds of vitamins, amino acidsand trace elements, they are of great value not only in nutrition aspect, but also in medical aspect.Up to new, the research reports on Hericium both in domestic and abroad have focused mainly onpolysaccharides components, which have been proved by biological and pharmacologicalresearches to have the effects on improving immunity, restraining cancer, reducing blood pressureand blood sugar, and so on, while researches on their small molecular components were relativelyless and not deepgoing. Modern medical and pharmacological researches showed that smallmolecular substances as sterols have remarkable effect on deducing cholesterol, restraining cancer,arresting oxidization, resisting inflammation, prophylaxis and treatment of the prostate diseases,while terpenes as nerve factor stimulator can remedy Senile Dementia. Thus it is of great realisticsignificance to carry out deepgoing researches on chemical compositions, especially smallmolecular substances, in H. caput-medusae.
     Normal phytochemistry methods and technology such as organic solvent extraction, twophases solvent extraction, amberlyst chromatography, silica gel column chromatography andcrystallization, combined with advanced instruments and apparatus, were applied in thisexperiment, and five monomer compounds were extracted and isolated through different routes.On the basis of physical constants, chemical evidence and spectrum analysis [NMR, MS], twomonomer compounds were identified, both of which were ergosterins: compound 2 wasErgosta-4-en-1,3,6-triol, (22Z)- and compound 4 was Ergosta-5,7,22-trien-3-ol, (22Z)-. Thesetwo sterol compounds were the first report to be extracted and isolated form H. caput-medusaeand they were both new natural compounds. There isolation added new contents to thefundamental research and provided new foundation for it.
     In addition, we used SEF-CO_2 extraction technology, combined with GC/MS technology inthis experiment, and isolated and identified 27 compounds from Liberation kettleⅠ和Ⅱ. These compounds can be divided into three categories: stearin acid esters, diolefines and nitrogenouscompounds. These compounds not only make the chemical composition research results in H.caput-medusae more abundant, but also do the groundwork for the pharmacological researches onH. caput-medusae in the future.
     In conclusion, we did some foundamental work in studying the chemical compositions in H.caput-medusae,. Our results provide theory basis for correctly evaluate the medical value of H.caput-medusa, add to new contents to the pharmaceutical range of H. caput-medusae as well asthe number of ergosterins in nature, and make the basis for new medicine exploitation from H.caput-medusae.
引文
[1] 徐锦堂.中国药用真菌学[M].北京:医科大学和中国协和医科大学联合出版社,1997.12第一版,448
    [2] 董宜勋,奚家华.中国食用蘑菇大观[M].北京:中国旅游出版社,1986.1
    [3] 陈士瑜,陈蕙.猴头轶话[J].中国食用菌,1985,(4):40
    [4] 徐杭民,谢志慧,张尉羽,等.猴头菇多糖的免疫调节作用[J].中国中西医结合杂志,1994.14(7):427-428
    [5] 潘继红,李刚,程宝勤,等.猴头多糖的提取与鉴定[J].食用菌学报,1995,2(3):29-32
    [6] Mizuno T, Tetsuya W, Hitoshi I, et al. Antitumor active polysaccharides isolated from the fruit body of Hericium erinaceum, an edible and medical mushroom called yambushitake or houtou [J]. Biosci Biotech Biochem, 1992, 56(2): 347-348
    [7] 黄丽萍,白凤武,云战友,等.小刺猴头菌液体深层培养过程中多糖积累及其特征的研究[J].生物技术,1998,8(3):30-33
    [8] 杨焱,周昌艳,白韵琴,等.猴头菌子实体和菌丝体多糖的分离纯化与理化特征的比较[J].菌物系统,2001,20(3):397-402
    [9] 黄年来.自修食用菌学[M].南京:南京大学出版社,1987:315-318
    [10] Jia L M, Liu L, Dong Q, et al. Structural investigation of a novel rhamnog_lucogalactan isolated from the fruiting bodies of the fungus Hericium erinaceus [J]. Biosci Biotechnol Biochem, 2003, 67(6): 1292-1298
    [11] Wang Z J, Luo D H, Liang Z Y. Structure of polysaccharides from the fruiting body of Hericium erinaceus Pers[J]. Carbohydrate Polymers, 2004, 57(3): 241-247
    [12] 李坤艳,何云庆.猴头菌丝体多糖的化学研究[J].中国中药杂志,1999,24(12):742-744
    [13] 史军花,梁忠岩,耿慧.猴头菌发酵菌丝水溶性多糖HPA的结构确定[J].分子科学学报,2003,19(6):123-126
    [14] 耿慧,梁忠岩,史军花,等.碱提猴头菌发酵菌丝体多糖的分离纯化及初步研究[J].特产研究,2003,2(1):4-6
    [15] Mizuno T, Ito H, Mori Y. Antitumor water-insoluble polysaccharide and its isolation from Hericium erinaceum[J]. Jpn. Kokai Tokkyo Koho, 1993, 4: 45-50
    [16] Mizuno T, Ito H, Mori Y. Fungal antitumor polysaccharides and their isolation[J]. Jpn. Kokai Tokkyo Koho, 1993: 4: 68-72
    [17] Inakuma T, Aizawa K , Yamauchi R, et al. Structural features of polysaccharide of Hericium erinaceum[J]. Hydrocollids, 1998, 1: 139-143
    [18] Mori H, Aizawa K, Inakuma T, et al. Structural analysis of the β-D-glucan from the fruit-body of Hericium erinaceum[J].Oyo Toshitsu Kagaku, 1998, 45(4):361-365
    [19] 孙红斌,刘梅森,陈海宴.液态发酵猴头菌多糖工艺化研究[J].食品与发酵工业,2001,27(9):30-33
    [20] Wang J C, Lee T M, Lai M N. Water-soluble polysaccharides produced by Hericium spp. with submerged culture[J]. Shipin Kexue (Taipei), 1998, 25(6):714-726
    [21] 宋慧.小刺猴头菌化学成分研究及菌种鉴定.吉林农业大学作物栽培学与耕作学博士学位论文[D],2003.6
    [22] 翟凤艳.小刺猴头菌子实体化学成分研究.吉林农业大学植物病理专业硕士学位论文[D].2004,06
    [23] 梁永波.小刺猴头菌子实体化学成分研究.吉林农业大学作物遗传育种硕士学位论文[D].2004,06
    [24] 钟建华,徐方正.植物甾醇的特性、生理功能及应用[J].食品与药品,2005,7(2):20-21
    [25] Kawagishi Y. Glycosides of regosterol derivatives from Hericium erinaceum[J]. Phytochemistry, 1991, 30(12): 4117-4120
    [26] 李洁莉,陆玲,戴传超.猴头菌醇提浸膏和水提浸膏甾醇类化合物的比较研究[J].中国中药杂志,2001,26(12):831-834
    [27] Masao H, Seiko H, Takafumi Y. Blazeispirol X and Y, two novel carbon skeletal sterols from the cultured mycelia of the fungus Agarieus blazei[J].Tetrahedron Letters, 2000, 41:5107-5110
    [28] 石磊,曹瑞敏,卢士香.榛蘑中一种新化合物的提取、分离及鉴定[J].白求恩医科大学报,1998,24(4):343
    [29] 金向群,王隶书,程东岩.大马勃的化学成分研究[J].中草药,1998,29(5):298-300
    [30] Yang S P, Xu J Y. Sterols from the Fungus Catathelasma imperiale [J].Chin Jour Chem, 2003, 21, 1390-1394
    [31] 何坚,冯孝章.桦褐孔菌化学成分的研究[J].中草药,2001,32(1):4-6
    [32] 万辉.褐圆孔牛肝菌化学成分的研究[J].中草药,2000,31(5):328-330
    [33] Yasunori Y, Kaori M, Takeyoshi I. Novel sterols and triterpenes from four edible mushrooms [J].Chem Pharm Bull, 2001, 49(5):589-594
    [34] 张静,冯孝章.亚绒盖乳菇化学成分的研究[J].中草药,1997,28(7):387-389
    [35] 高锦明,董泽军,杨雪.紫丁香蘑的化学成分[J].中草药,2002,33(5):398-401
    [36] 陈英红,姜瑞芝,高其品.安络小皮伞醇提物中镇痛成分麦角甾醇和肉桂酸的含量测定[J].中成药,2005,27(5):583-585
    [37] 陈晓梅,杨峻山,郭顺星.石斛小菇中的甾醇类化合物[J].药学学报,2000,35(5):367-369
    [38] 高锦明,张鞍灵,王晨英.耳状网褶菌的化学成分[J].西北植物学报,2002,22(2):391-395
    [39] 刘金荣,江发寿,李艳洪.药用真菌桑黄甾类成分的提取和鉴定[J].农垦医学,1998,20(3):141
    [40] Yaoita Y.Novel sterols in edible mushroom Pleurotus eryngii and Panellus serotinu[J].Chem Pharm Bull, 2002, 50(4): 551-553
    [41] 刘晓峰,李玉,孙晓波.侧耳属真菌化学成分及药用活性研究进展[J].吉林农业大学学报,1998,20(3):92-98
    [42] 高锦明,张鞍灵,姚焕英.黄鳞多孔菌的化学成分研究[J].中国中药杂志,2003,28(10):943-947
    [43] 王少芳,扬国华,季广义.桦菌芝化学成分的研究(Ⅰ)[J].中草药,1990,21(9):10-12
    [44] 黄悦,董泽军,刘吉开.高等真菌黑虎掌子实体的化学成分[J].云南植物研究,2001,23(4):125-128
    [45] 王晨英,高锦明,杨雪.黄硬皮马勃的化学成分[J].中草药,2002,33(9):778-780
    [46] 刘雅峰,潘勤.真菌竹黄中的过氧麦角甾醇的分离[J].天津中医学院学报,2004,23(1):15-16
    [47] 高锦明,董泽军,刘吉开.蓝黄红菇的化学成分[J].云南植物研究,2000,22(1):85-89
    [48] 高锦明,沈杰,杨雪.黄白红菇的化学成分[J].云南植物研究,2001,23(3):385-393
    [49] Berges R R. Randomised, placebo-controlled, double-blind clinical trial of beta-sitosterol in patients with benign prostatic hyperplasia Beta-sitosterol Study Group[J]. Lancet., 1995, 345: 1529-1532
    [50] Berges R R. Treatment of symptomatic benign prostatic hyperplasia with beta-sitosterol: an 18-month follow-up[J]. Bju lnt, 2000, 85(7): 842-846
    [51] Kassen A. Effect of beta-sitosterol on transforming growth factor-beta-1 expressionand translocation protein kinase C alpha in human prostate stromal cells in vitro[J]. EurUrol,. 2000, 37(6): 735-741
    [52] 崔建国,黄燕敏,何小玉,曾陇梅多羟基甾醇的合成(Ⅳ):20-亚甲基-4-孕烯-3β,6β-二醇的制备及其抗肿瘤活性研究[J].广西科学,2004,11(1):43-46
    [53] 何秀萍,张博润.微生物麦角甾醇研究进展[J].微生物学通报,1998,25(3):166
    [54] 胡海峰,朱宝泉,龚炳永.微生物来源的胆固醇生物合成酶抑制剂Ⅷ.抗生素sipi-8917-v的研究[J].中国抗生素杂志,1998,23(5):331
    [55] 何秀萍,张博润.微生物麦角甾醇研究进展[J].微生物学通报,1998,25(3):166
    [56] 刘梅森,陈海晏,孙红斌.猴头菌的药用价值概述[J].中国食用菌,1999,18(1):24
    [57] 高虹,谷文英,丁霄霖,谭洪卓.巴西蘑菇菌丝体中抑瘤活性甾醇的分离和结构鉴定[J].食品研究与开发,2006,127(6):52-55
    [58] Awad A B. Dietary phytosterol inhibits the growth and metastasis of MDA-MB-231 human breast cancer cells grown in SCID mice[J]. Anticancerres, 2000, 20(2A): 821-824
    [59] Mellanen P, Petanen T, Lehtimaki J, et al. Wood-derived estrogens: Studies in vitro with breast cancer cell lines and in vivo in trout[J]. Toxicol Appl Pharm, 1996, 136 (2): 381-388
    [60] Janezic S A, Rao A V. Dose-dependent effects of dietary phytosterol on epithelial-cell proliferation of the murine colon[J]. Food Chem. Toxicol, 1992, 30(7): 611-616
    [61] De Stefani E. Plant sterols and risk of stomach cancer: a case-control study in Uruguay[J]. Nutr Cancer, 2000, 37(2): 140-144
    [62] Von Holtz R L. beta-Sitosterol activates the sphingomyelin cycle and induces apoptosis in LNCaP human prostate cancer cells[J]. Nutr Cancer, 1998, 32(1): 8-12
    [63] 翁良平,冯宗忱,吴万生,王淳本,等.正常人极低密度脂蛋白促进巨噬细胞胆固醇堆积及机制[J].中华心血管病杂志,1992,20(2):45-47
    [64] Blair SN. Incremental reduction of serum total cholesterol and low-density lipoprotein cholesterol with the addition of plant stanol ester-containing spread to statin therapy[J]. Am J Cardiol, 2000, 86(1): 46-52
    [65] HalliKainen M A. Plant stanol esters affect serum cholesterol concentrations of hyper cholesterolemic men and women in a dose-dependent manner[J]. J Nutr, 2000, 130(4): 767-776
    [66] Sierksma A. Spreads enriched with plant sterols, either esterified 4, 4-dimethylsterols or free 4-desmethylsterols, and plasma total- and LDL-cholesterol concentrations[J]. Br J Nutr, 1999, 82(4): 273-282
    [67] 吴时敏,吴谋成.植物甾醇的研究进展与趋向(Ⅰ)—植物甾醇的基础研究[J].中国油脂,2002,27(2):73-75
    [68] Maitani Y, Hazama M, Tojo H, et al. Effects of orally-administered liposomes with soybean-derived sterols and their glucosides on rat-body weight[J]. Biol Pharm Bull, 1995, 18 (11): 1551-1555
    [69] Eugster C, Rivara G, Biglino A, et al. Phytosterol compounds having antiviral efficacy[J]. anminerva Med., 1997, 39(1): 12-20
    [70] Bouic PJ. The effects of β-sitosterol(BSS) and β-sitosterol glucoside(BSSG) mixture on selected immune parameters of marathon runners: inhibition of post marothon immune suppression and in—flammatio[J]. Int J Sprots Med, 1999, 20(4): 258-262
    [71] Kawagishi H, Shimada A, Shiral R, et al. Erinacines A, B and C, strong stimulators of nerve growth factors(NGF) synthesis from mycelia of Hericium erinaceum. Tetrahedron Letter[J]. 1994, 35(10): 1569-1572
    [72] Kawagishi H, Simada A, Shizuki K, et al. Erinacine D, a stimulator of nerve growth factor (NGF) synthesis, from the mycelia of Hericium erinaceurn. Hetero [J]. Cycl.Commum, 1996, 2(1): 51-54
    [73] Kawagishi H, Simada A, Hosokawa S. Erinacines E, F and G, stimulators of nerve growth factor (NGF) synthesis, from the mycelia of Hericium erinaceum. [J]. Tetrahedron Lett, 1996, 37 (41): 7399-7402
    [74] Arimoto Y, Kawagishi H, Shimada A. Jpn. Kokai Tokkyo Koho [JP] 09, 235, 224 [97, 235, 224], 9 Sep 1997, Appl. 96/71, 410, 29 Feb 1996; 4 pp.(Japan)
    [75] Kawagishi H, Ando M, Mizuno T. A Novel Fatty Acid from the Mushroom Hericium erinaceum. [J]. Agrie. Biol. Chem, 1990, 54(5): 1329-1331
    [76] Kuwahara S, Morihiro E, Nemoto A. Synthesis and absolute comfiguratiom of cytotoxic fatty acid isolated from the mushroom. Hericium erinaceum[J]. Biosci. Biotecnnol Biochem, 1992, 56(9): 1417-1419
    [77] Stadler M, Mayer A, Anke H. Fatty Acids and Other Compounds withNematicidal Activity from Cultures of Basidiomycetes[J]. Planta Med, 1994, 60: 128-132
    [78] 曹瑞敏.猴头菌中部分脂肪酸和微量元素分析[J].白求恩医科大学学报,1996,22(3):243-244
    [79] 李胜奇,熊正英,田振军.野生猴头菌主要营养成分的测定与评价[J].陕西师范大学学报(自然科学版),1998,1:21-23
    [80] 李洁莉,陆玲,仓一华,等.猴头菌及其提取物有关甾醇类化合物初探[J].中国生化药物杂志,2001,22(3):124-126
    [81] 何燕.甘露醇生产与应用[J].精细化工原料及中间体,2003,1:15-18
    [82] 周日尤.多元醇的国内外市场和发展(上)[J].江苏化工,2003,31(4):9-13
    [83] 黎颖.甘露醇的性质、生产与发展建议[J].广西化工,1999,28(4):29-33
    [84] 钱伏刚,徐光漪,杜上鉴,等.猴头菌培养物中二个新吡喃酮化合物的分离与鉴定[J].药学学报,1990,25(7):522-525
    [85] Kawagishi H. Erinapyrones A and B from cultured mycelia of Hericium erinaceum[J]. chem Lett, 1992, 12: 2475-2476
    [86] Kawagishi H, Ando M, Mizuno T. Hericenone A and B as cytotoxic principles from the mushroom Hericium erinaceum[J]. Tetrahedron Letter, 1990, 31(3): 373-376
    [87] Kawagishi H, Ando M, Sakamoto H. Hericenones C, D and E Stimulator of nerve growth factors synthesis from the mushroom of Hericium erinaceum[J]. Tetrahedron Letter, 1991, 32(35): 4561-4563
    [88] 李敬轩,张敬贤.从猴头菌得到的2种新的生理活性物质[J].吉林农业大学学报,1998,20(增刊):35-39
    [89] Kimura Y, Nishibe M, Nakajima H. Hericerin, a new pollen growth inhibitor from the mushroom Hericium erinaceum[J]. Agaric Biol Chem, 1991, 55(10): 2673-2674
    [90] Stump H. Ger. Offen. DE [P] 19, 612, 807, 2 Oct 1997, Appl. 19, 612, 807, 1 Apr 1996; 6pp
    [91] 李洁莉,陆玲,陈坤,等.猴头菌及其药物制品腺苷等药效成分分析[J].中国食用菌,2002.21(3):32-34
    [92] 梁宝钻,李菁,梁卫萍,等.亚东乌头总生物碱的超临界CO_2萃取及含量测定[J].中药材.2002,25(5):332-333
    [93] 曹优明,郑仕远.茶多酚制备新方法[J].应用化工,2002,31(5):8-10
    [94] 廖传华.超临界CO_2萃取β-胡萝卜素的实验研究[J].精细化工,2002,19(6):365-366
    [95] 李新社,王志兴.溶剂提取和超临界流体萃取百合中的秋水仙碱[J].中南大学学报(自然科学版),2004,35(2):244-248
    [96] 游海,陶秉莹,张立麒超临界萃取法从银杏叶中提取黄酮类化合物、萜内酯的工艺研究[J].南昌大学学报(工科版),2000,22(4):34-38
    [97] 葛发欢,谢健鸣,李菁,等.超临界CO2从柴胡中萃取挥发油及其皂甙的研究[J].中国中药杂志,2000,25(3):149-153
    [98] 刘灿明,黄高山,刘祥华.超临界CO_2萃取百合花挥发油的工艺研究[J].天然产物研究与开发,2005,17(4):485-487
    [99] 夏开元.二氧化碳超临界流体萃取研究进展[J].中成药,1997,19(5):87-89
    [100] 孙英杰,徐迪民,刘辉.超临界水氧化技术研究与应用进展[J].中国给水排水,2002,18(2):35-37
    [101] 丁军委,陈峰秋,吴素芳,等.超临界水氧化法处理含酚废水[J].环境污染与防治,2000,22(1):1-3
    [102] 陈武,李凡修,梅平.超临界流体技术在环境保护中的应用[J].环境污染治理技术与设备,2003,4(2):59-62
    [103] 孙爱友,贾士儒,杨扬.超临界流体技术在生物工程中的应用[J].天津轻工业学院学报,2001,4(39):14-17
    [104] 陈惠晴,杨基础.超临界CO_2的溶剂特性对脂肪酶催化反应的影响[J].清华大学学报(自然科学版,1999,39(6):31-34
    [105] 侯玉翠,张毅民,刘克文,等.超临界流体技术的研究进展[J].化学工业与工程,2002,19(5):384-380

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