小刺猴头菌子实体化学成分研究
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摘要
猴头菌属(Hericium)真菌是珍贵的食药用菌，利用该属内小刺猴头菌发酵液浸膏制成的药物在临床上治疗胃炎、胃溃疡等消化系统疾病取得了显著的疗效。此外，现代医学和药理学的很多研究表明，猴头菌在提高机体免疫力、抗癌抑瘤、降血压、降血糖等多方面均有一定的疗效。因此，近年来对猴头菌化学成分的研究越来越引起人们的重视。
国内外对猴头菌属的研究范围主要局限于多糖、脂肪酸及其衍生物和一些营养成分如蛋白质、氨基酸及微量元素等方面，对小分子有机化学成分的研究很少。小刺猴头菌[Hericium caput-medusae(Bull.:Fr.)Pers.]作为猴头菌属的一个主要种，其化学成分的研究很少，弄清其化学成分组成，进而研究其药用价值，具有重要意义。
本论文采用有机溶剂浸提法提取小刺猴头菌子实体中化学成分。将小刺猴头菌子实体干品粉碎成粉末，室温下用95％医用乙醇多次进行浸泡提取，合并提取液，在40℃条件下减压浓缩，得到乙醇提取液浓缩液。浓缩液在室温下自然放置分为四层，过滤后继续浓缩至浸膏。预试验结果显示：甾醇类化合物定性实验现象比较明显，呈阳性。
采用系统溶剂分离法、萃取法、层析法、结晶及重结晶等多种方法和不同的分离工艺路线，对小刺猴头菌子实体乙醇提取浓缩液浸膏进行逐级分离纯化，得到结晶型化合物X、Y和Z。通过物理常数、化学方法和波谱分析[核磁共振(NMR)和质谱(MS)]等方法对化合物X、Y和Z进行了结构鉴定。分析结果表明化合物X为豆甾醇，化合物Z为甾醇类化合物，分子式为C_(29)H_(48)O_2，分子量为428，其母核与豆甾醇相同，为首次发现，并命名为28ξ-羟基-豆甾-4-烯-3-醇。
本研究从小刺猴头菌子实体中首次提取分离得到的甾醇类化合物，且化合物Z是第一次从自然界生物体中分离得到。这一研究结果为小刺猴头菌化学成分的研究增添了新的内容。
甾醇类化合物结构特殊，具有重要的生理功能，在医药、食品、化妆品、饲料等行业中都得到广泛应用。
Hericium spp. are valuable edible and medical fungi. The medicines made from the concentrated ferment liquid of Hericium caput-medusae(Bu\l.:Fr.) Pers show obvious effects on gastricism, gastic ulcer and other digestive system diseases in clinical applications. In addition, many researches in medicine and pharmacology have proved that the fungi in Hericium spp. have certain therapeutical effects on improving immunity, restraining cancer, reducing blood pressure and blood sugar, and so on. Therefore, in recent years studies on chemical compositions in Hericium spp. are gaining more and more recognition.
Studies on chemical compositions of Hericium spp. were mainly restricted in polysaccharide, fat acids and their derivatives, as well as some nutritional compositions such as proteins, amino acids and trace elements both in China and aboard, while studies on organic small molecular compositions were fairly scarce. H. caput-medusae is a main species in genus Hericium, whose compositions were studied much less than other species in this genus. It is significant to make its chemical compositions clear and to make further studies on its medical effects.
Solvent extracting method was employed to thoroughly extract chemical compositions from the fruiting body of H.caput-medusae. Powder the dried fruiting body of H. caput-medusae, soak and extract the powder with 95% ethanol at room temperature for many times. The ethanol extract was combined and distilled at 40℃ at a reduced pressure to obtain ethanol concentrated extract liquid. Laid at room temperature, the ethanol concentrated extract liquid divided into four obvious layers. After filtration, the extraction was gained by continuing concentration. The preliminary tests revealed that the test phenomena of sterols were comparatively obvious and positive.
Systematic solvent separation, two phases solvent extraction, chromatography, crystallization and re-crystallization methods and diverse separation technology routes were applied to separate and purify the ethanol extraction of the fruiting body of
国内外对猴头菌属的研究范围主要局限于多糖、脂肪酸及其衍生物和一些营养成分如蛋白质、氨基酸及微量元素等方面，对小分子有机化学成分的研究很少。小刺猴头菌[Hericium caput-medusae(Bull.:Fr.)Pers.]作为猴头菌属的一个主要种，其化学成分的研究很少，弄清其化学成分组成，进而研究其药用价值，具有重要意义。
本论文采用有机溶剂浸提法提取小刺猴头菌子实体中化学成分。将小刺猴头菌子实体干品粉碎成粉末，室温下用95％医用乙醇多次进行浸泡提取，合并提取液，在40℃条件下减压浓缩，得到乙醇提取液浓缩液。浓缩液在室温下自然放置分为四层，过滤后继续浓缩至浸膏。预试验结果显示：甾醇类化合物定性实验现象比较明显，呈阳性。
采用系统溶剂分离法、萃取法、层析法、结晶及重结晶等多种方法和不同的分离工艺路线，对小刺猴头菌子实体乙醇提取浓缩液浸膏进行逐级分离纯化，得到结晶型化合物X、Y和Z。通过物理常数、化学方法和波谱分析[核磁共振(NMR)和质谱(MS)]等方法对化合物X、Y和Z进行了结构鉴定。分析结果表明化合物X为豆甾醇，化合物Z为甾醇类化合物，分子式为C_(29)H_(48)O_2，分子量为428，其母核与豆甾醇相同，为首次发现，并命名为28ξ-羟基-豆甾-4-烯-3-醇。
本研究从小刺猴头菌子实体中首次提取分离得到的甾醇类化合物，且化合物Z是第一次从自然界生物体中分离得到。这一研究结果为小刺猴头菌化学成分的研究增添了新的内容。
甾醇类化合物结构特殊，具有重要的生理功能，在医药、食品、化妆品、饲料等行业中都得到广泛应用。
Hericium spp. are valuable edible and medical fungi. The medicines made from the concentrated ferment liquid of Hericium caput-medusae(Bu\l.:Fr.) Pers show obvious effects on gastricism, gastic ulcer and other digestive system diseases in clinical applications. In addition, many researches in medicine and pharmacology have proved that the fungi in Hericium spp. have certain therapeutical effects on improving immunity, restraining cancer, reducing blood pressure and blood sugar, and so on. Therefore, in recent years studies on chemical compositions in Hericium spp. are gaining more and more recognition.
Studies on chemical compositions of Hericium spp. were mainly restricted in polysaccharide, fat acids and their derivatives, as well as some nutritional compositions such as proteins, amino acids and trace elements both in China and aboard, while studies on organic small molecular compositions were fairly scarce. H. caput-medusae is a main species in genus Hericium, whose compositions were studied much less than other species in this genus. It is significant to make its chemical compositions clear and to make further studies on its medical effects.
Solvent extracting method was employed to thoroughly extract chemical compositions from the fruiting body of H.caput-medusae. Powder the dried fruiting body of H. caput-medusae, soak and extract the powder with 95% ethanol at room temperature for many times. The ethanol extract was combined and distilled at 40℃ at a reduced pressure to obtain ethanol concentrated extract liquid. Laid at room temperature, the ethanol concentrated extract liquid divided into four obvious layers. After filtration, the extraction was gained by continuing concentration. The preliminary tests revealed that the test phenomena of sterols were comparatively obvious and positive.
Systematic solvent separation, two phases solvent extraction, chromatography, crystallization and re-crystallization methods and diverse separation technology routes were applied to separate and purify the ethanol extraction of the fruiting body of
引文
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[2]翟凤艳．小刺猴头菌化学成分研究[D]．吉林农业大学植物病理专业硕士学位论文．2004,06．
[3]Masao Hirotani,Seiko Hirotani,Takafumi Yoshikawa.Blazeispirol X and Y, two novel carbon skeletal sterols from the cultured mycelia of the fungus Agaricus blazei[J].Tetrahedron Letters. 2000,41:5107～5110.
[4]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．
[5]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．
[6]YANG,ShengPing XU,Jun YUE,JianMin Sterols from the Fungus Catathelasma imperiale [J].Chin Jour Chem.2003,21,1390～1394.
[7]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．
[8]万辉．褐圆孔牛肝菌化学成分的研究[J]．中草药．2000,31(5)：328～330．
[9]王赛贞，林树钱，林志彬．灵芝子实体胆甾醇的分离与鉴定[J]．食用菌学报．2005，12(1)：5～8．
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