秦艽中的环烯醚萜甙成分

秦艽为著名传统中药。中青海西宁产秦艽的甲醇提取物的水溶性部分分离到１个新裂环烯醚萜甙,命名为秦艽甙Ａ,２个已知的环烯醚萜甙即龙胆苦甙和哈马甙以及２个甾醇甙,胡萝卜甙和β－谷甾醇－３－Ｏ－龙胆糖甙。这些化合物的结构通过红外光谱、紫外光谱、核磁共振波谱（包括－维氢醇－３－Ｏ－龙胆糖甙。这些化合牧的结构通过红外光谱、紫外光谱、核磁共振波谱（包括一维氢谱、碳谱、氢－氢相关谱、碳－氢相关谱、远程碳－氢相关谱     

坚龙胆中的一个新裂环烯醚萜甙

从坚龙胆（Gentiana rigescens）的根中分离得到1个新的裂环烯醚萜甙,命名为坚龙胆甙A（1）,以及8个已知化合物：龙胆苦甙（2）,6＇-O-β-D-吡喃葡萄糖基-龙胆苦甙（3）,马钱子酸（4）,6＇-O-β-D-吡喃葡萄糖基．马钱子酸（5）,獐牙菜甙（6）,2＇-（邻,间-二羟基苯甲酰基）．獐牙菜甙（7）,獐牙菜苦甙（8）,四乙酰开联番木鳖甙（9）。它们的化学结构通过现代波谱解析得以鉴定。化合物3,5和9为首次从坚龙胆中分离得到。     

翅萼龙胆中的两个寡聚裂环烯醚萜甙

从翅萼龙胆的全株中分离得到两个新的寡聚裂环烯醚萜甙：翅萼龙胆甙Ｉａ和Ｉｂ,其结构通过光谱分析推定。     

坚龙胆环烯醚萜甙的HPLC分析

应用HPLC分析方法,建立了坚龙胆中5个主要环烯醚萜甙的含量测定方法。在ZORBAXSB—C18色谱柱,乙腈-0．2％磷酸水溶液为流动相,梯度洗脱,流速1．0mL/min,柱温为40℃,检测波长254nm的色谱条件下,化合物得到良好的分离,并具线性相关。本方法操作简便,重现性好,灵敏度高。对不同产地的样品进行比较分析的结果表明,产地对坚龙胆中环烯醚萜甙的组成和含量有显著的影响。     

鞭打绣球中的苯丙素甙和环烯醚萜甙

从鞭打绣球（ＨｅｍｉｐｈｒａｇｍａｈｅｔｅｒｏｐｈｙｌｌｕｍＷａｌｌ．）（玄参科）的全草中分离到２个新的苯丙素甙,命名为鞭打绣球甙Ａ和Ｂ（ｈｅｍｉｐｈｒｏｓｉｄｅＡａｎｄＢ）,２个已知的苯丙素甙,ｐｌａｎｔａｍａｊｏｓｉｄｅ和ｐｌａｎｔａｉｎｏｓｉｄｅＤ,以及３个已知的环烯醚萜甙,ｇｌｏｂｕｌａｒｉｃｉｓｉｎ,ｇｌｏｂｕｌａｒｉｎ和ｉｓｏ－ｓｃｒｏｐｈｕｌａｒｉｏｓｉｄｅ．通过化学和光谱分析,鞭打绣球甙Ａ和Ｂ的结构分别鉴定为２－（３－羟基－４－甲氧基苯基）乙基０－β－Ｄ－葡萄吡喃糖基（１→３）－４－Ｏ－反式阿魏醚基－β－Ｄ－葡萄吡喃糖试和２－（３,４－二羟基苯基）乙基Ｏ－［６－Ｏ－乙醚基－β－Ｄ－葡萄吡喃糖基（１→３）］－４－Ｏ－反式咖啡醚基－β－Ｄ－葡萄吡喃糖甙．     

藏药黑边假龙胆的化学研究

龙胆科植物黑边假龙胆（Ｇｅｎｔｉａｎｅｌｌａａｚｕｒｅａ（Ｂｕｎｇｅ）Ｈｏｌｕｂ）是治疗肝胆湿热的１种藏药,从西藏日喀则产的全草中分离得到９个化合物,其中１个Ｃ一甙黄酮,异荭草素（ｉｓｏｏｒｉｅｎｔｉｎ）;１个山酮甙,獐牙菜酚甙（ｓｗｅｒｔｉａｎｏｌｉｎ）;１个木质体甙,橄榄脂素４一Ｏ一β－Ｄ－葡萄糖甙（ｏｌｉｖｉｌ４一Ｏ一β一ｇｌｕｃｏｓｉｄｅ）;３个环烯醚萜甙,龙胆苦甙（ｇｅｎｔｉｏｐｉｃｒｏｓｉｄｅ）,獐牙菜甙（ｓｗｅｒｔｉａｍａｒｉｎ）和马钱子酸（ｌｏｇａｎｉｃａｃｉｄ）;１个三萜,齐敦果酸（ｌｏｅａｎｏｌｉｃａｃｉｄ）１个甾醇,β谷甾醇葡萄糖甙（ｄａｕｃｏｓｔｅｒｏｌ）以及１个长链脂肪醇,三十烷醇（ｎ一１一ｔｒｉａｃｏｎｔａｎｏｌ）。它们的结构通过光谱和化学的方法得到了鉴定。上述结果,从次生代谢产物的角度为假龙胆属在系统分类上与龙胆属和獐牙菜属有着密切的联系提供了旁证。     

不同生长季节下藏药麻花秦艽活性成分含量研究

采用高效液相色谱法测定了野生与栽培藏药麻花秦艽（Gentiana straminea）根中龙胆苦苷、落干酸、獐牙菜苦苷和獐牙菜苷四种环烯醚萜苷类化学成分的含量及其在不同生长季节的变化趋势。结果表明,4种环烯醚萜苷类成分的含量随植物的生长季节而波动,其活性成分含量在野生种与栽培种之间发生了一定的差异。但是,栽培根中的龙胆苦甙已达到药典的标准,可供药用。     

黑蒴中的单萜甙类化合物

自黑蒴(Melasma arvense[Benth.]H.-M.)根中分离鉴定了羟基-β-紫罗兰酮葡萄醣甙(hydroxy-β-ionone glucosid 1)和一新的环烯醚萜甙—桃叶珊瑚甙元-1-O-β-龙胆双醣甙(aucubigenin-1-O-β-gentiobioside 2)。     

环烯醚萜甙的快速原子轰击质谱和场解吸质谱研究

环烯醚萜甙是植物界分布较广泛的一类配糖体成分,极性较大,用通常的电子轰击质谱测试不能得到分子离子信息,且离子碎片零碎,难以进行结构解析。本文对２５个不同类型的环烯醚萜甙进行正,负离子快速原子轰击质谱和场解吸质谱分析,并讨论这两种质谱新技术在环烯醚萜甙类化合物结构解析中的应用。     

仙茅根茎中的配糖体

从仙茅（ Ｃｕｒｃｕｌｉｇｏ ｏｒｃｈｉｏｉｄｅｓＧａｅｒｔｎ） 根茎中分离到７ 个化合物, 经光谱分析推定其化学结构分别为： ２, ６ － 二甲氧基苯甲酸（Ａ） ; 苔黑酚葡萄糖甙（Ｂ） ; 仙茅素Ａ （Ｃ） ; 仙茅甙（Ｄ） ; ２４ｓ, ３β, １１α, １６β, ２４ － 四羟基环阿尔廷醇－ ３ － Ｏ－ α－ Ｌ－ 鼠李吡喃糖基（１ →２） － β－Ｄ－ 葡萄吡喃糖甙（Ｅ） ; ２４ｓ, ３β, １１α, １６β, ２４ － 四羟基环阿尔廷醇－ ３－ Ｏ－ β－ Ｄ－ 葡萄吡喃糖基（１ →２） － β－ Ｄ－ 葡萄吡喃糖甙（Ｆ） 和胡萝卜甙（Ｇ） 。Ｆ为一新甙。     

Constituents from the bark of Tabebuia impetiginosa

The bark of Tabebuia impetiginosa afforded nineteen glycosides, consisting of four iridoid glycosides, two lignan glycosides, two isocoumarin glycosides, three phenylethanoid glycosides and eight phenolic glycosides. Their structures were determined using both spectroscopic and chemical methods. Iridoid glycosides, phenylethanoid glycosides and lignan glycosides had ajugol, osmanthuside H and secoisolariciresinol 4-O-beta-D-glucopyranoside as their structural elements, respectively, whereas the aglycone moieties of the isocoumarin glycosides were considered to be (-)-6-hydroxymellein. Phenolic glycosides had 4-methoxyphenol, 2,4-dimethoxyphenol, 3,4-dimethoxyphenol, 3,4,5-trimethoxyphenol and vanillyl 4-hydroxybenzoate as each aglycone moiety. Additionally, the sugar chains of these isocoumarin glycosides and phenolic glycosides were concluded to be beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside as well as those of osmanthuside H and above phenylethanoid glycosides.     

4-Trifluoromethylumbelliferyl glycosides as new substrates for revealing diseases connected with hereditary deficiency of lysosome glycosidases.

The following glycosides of 4-trifluoromethylumbelliferone: alpha-D-mannopyranoside, alpha-L-fucopyranoside, alpha-D-glucopyranoside, beta-D-glucopyranoside, alpha-D-galactopyranoside, beta-D-galactopyranoside, alpha-L-iduronide and beta-D-glucuronide were studied. 4-Trifluoromethylumbelliferyl glycosides were shown to be substrates for glycosidases. Some of them were cleaved even better than the corresponding methylumbelliferyl glycosides. 4-Trifluoromethylumbelliferyl glycosides were applied for revealing the corresponding enzyme deficiencies upon diagnosis of Gaucher and Hurler diseases as well as GM1 gangliosidosis and alpha-mannosidosis. 4-Trifluoromethylumbelliferone released after enzymatic hydrolysis of 4-trifluoromethylumbelliferyl glycosides exhibits more contrast yellow fluorescence in UV-light than the blue one of methylumbelliferone upon exposure of enzyme activity on solid supports. Therefore 4-trifluoromethylumbelliferyl glycosides are convenient substrates for revealing glycosidase activity directly in tissue samples, e.g. in placenta, and thus for fast prenatal diagnosis of lysosomal diseases.     

4'-deoxy iridoid glycosides from Centranthus longiflorus

The new iridoid glycosides, 4'-deoxykanokoside A and 4'-deoxykanokoside C, were isolated from the methanolic root extract of Centranthus longiflorus ssp. longiflorus. They were accompanied by the three known iridoid glycosides, kanokoside A, kanokoside C and valerosidatum, and two known phenylpropanoid glycosides, coniferin and isoconiferinoside. The structures were elucidated mainly by spectroscopic methods. The presence of 4-deoxy glucose as a part of plant glycosides is rather unusual. Cytotoxic effects of the isolated compounds were also investigated.     

甜叶菊糖苷对果蝇生长和繁殖的影响

以黑腹果蝇Drosophila melanogaster Meigen作试验材料,探讨甜叶菊糖苷(steviol glycosides)对果蝇生殖、寿命等的影响。方法:在果蝇培养基中添加甜叶菊糖苷,质量分数分别为0,1%,2%,5%,10%;培养温度为(25±1)℃;取1对未交配的雌雄果蝇放入培养基中,待出现子代成蝇时,统计成蝇数量,记录成蝇羽化的数目,连续培养4代,观察甜叶菊糖苷对果蝇生育能力的影响;随机选取100只雌雄成蝇放入培养基中,统计其寿命,结果:过高浓度的甜叶菊糖苷对果蝇有一定程度的伤害,致使果蝇寿命和生育能力下降。     

Two chromone-secoiridoid glycosides and three indole alkaloid glycosides from Neonauclea sessilifolia

From the dried roots of Neonauclea sessilifolia, two new chromone-secoiridoid glycosides, sessilifoside and 7"-O-beta-D-glucopyranosylsessilifoside, and three novel indole alkaloid glycosides, neonaucleosides A, B, and C, were isolated along with the main known glycosides, 5-hydroxy-2-methylchromone-7-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside, sweroside, loganin, grandifloroside, and quinovic acid 3 beta-O-beta-D-quinovopyranoside-28-O-beta-D-glucopyranoside. The structures of these new glycosides were determined by spectroscopic and chemical means. Neonaucleoside A and its C-3 epimer were prepared from secologanin and tryptamine.     

Identification of tyrosinase inhibitors from Marrubium velutinum and Marrubium cylleneum

Tyrosinase is a key enzyme in the production of melanins in plants and animals. Forty-five secondary metabolites isolated from Marrubium velutinum and Marrubium cylleneum belonging to the classes of flavonoids, phenylethanoid glycosides, phenolic acids and lignan glycosides were screened for their inhibitory activity against mushroom tyrosinase. Flavonoids and phenylethanoid glycosides showed moderate inhibitory activity, while phenolic acids were less active than phenylethanoid glycosides, suggesting that both phenolic groups are important for the activity.     

Chalcone and flavonol glycosides from Asarum canadense (Aristolochiaceae)

Two chalcone glycosides were isolated, together with seven known flavonol glycosides, from the leaves of Asarum canadense. The structures of the chalcone glycosides were established as chalcononaringenin 2',4'-di-O-glucoside and chalcononaringenin 2'-O-glucoside-4'-O-gentiobioside by chemical, UV, FAB MS, 1H and 13C NMR evidence.     

Permeation of hesperidin glycosides across Caco-2 cell monolayers via the paracellular pathway

The intestinal permeability to hesperidin glycosides was investigated by using a cultured monolayer of Caco-2 as a model for the small intestinal epithelium. Hesperidin glycosides were added to the apical side of the monolayer, and the substances that permeated to the basolateral side were determined by HPLC. Whereas hesperidin did not permeate across the Caco-2 monolayer, probably owing to its low solubility, the hesperidin glycosides did permeate. The transepithelial transport of hesperidin glycosides occurred in time- and dose-dependent manners. The transport was observed to be energy-independent, and was inversely correlated with the transepithelial electrical resistance (TEER) of the monolayer. These results suggest that hesperidin glycosides permeate across the Caco-2 cell monolayer via the paracellular pathway.     

Neolignan and flavonoid glycosides in Juniperus communis var. depressa

Two neolignan glycosides (junipercomnosides A and B) were isolated from aerial parts of Juniperus communis var. depressa along with two known neolignan glycosides and seven flavonoid glycosides. The structures of the isolated compounds were determined by spectral analysis, in particular by 2D-NMR analysis. The significance of distribution of flavonoids in the chemotaxonomy of genus Juniperus was also discussed.     

Efficient synthesis of alpha- and beta-chacotriosyl glycosides using appropriate donors, and their cytotoxic activity

Natural steroidal glycosides containing alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranose (chacotriose) at the oligosaccharide moiety exhibit anti-cancer and anti-herpes activities. To investigate the structure-activity relationships of the aglycone parts of chacotriosides, we developed a synthesis method for chacotriosyl glycosides having various aglycones. In the process, it was revealed that alpha-chacotriosyl glycosides could be obtained mainly by using a trichloroacetimidate donor, while beta-chacotriosyl glycosides were afforded by using phosphite and phosphate donors. In cytotoxicity tests using the A549 and HepG2 cell lines, naturally occurring beta-chacotriosyl diosgenin and cholestanol exhibited higher activities than the corresponding alpha-chacotriosyl glycosides.