薤白中两种新呋甾皂甙的结构

自中药薤白(Allium macrostemon Bunge)鳞茎中分得三种甾体皂甙。经过化学降解和光谱(UV、IR,MS,¹H-NMR,¹³C-NMR和FAB-MS)分析,鉴定其结构分别为(25R)-26-O-β-D-吡喃葡萄糖-5α-呋甾-20(22)-烯-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)[β-D-吡喃葡萄糖基(1→3)]-β-D-吡喃葡萄精基(1→4)-β-D-吡喃半乳糖甙(Ⅰ),(25R)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-3β,26-二醇-3-P-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅱ)和异菝契皂甙元-3-O-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅵ)。Ⅰ和Ⅱ为新的呋甾皂甙,分别命名为薤白甙戊和莲白甙己,初步药理实验测试二青均有较强的抑制ADP诱导的人血小板聚集作用。     

薤白甙J,K和L的结构

进一步用HPLC自小根蒜(Allium macrostemon Bunge)鳞茎中分得两种新的呋甾皂甙,薤白甙J(1)和薤白甙L(III),以及I的甲基化人工产物薤白甙K(II)。经过化学降解和光谱(¹H-NMR,¹³C-NMR和FAB-MS等)分析,确定其结构分别为:(25R)-26-O-β-D-吡喃葡萄糖基-22-羟基-5β-呋甾-2β,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(I);(25R)-26-O-β-D-吡喃葡萄糖基-22-甲氧基-5β-呋甾-2β,3β,26-.三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(II)和(25R)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-26β,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(III)。     

薤白中两种新甾体皂甙成分

从中药薤白(Allium macrostemon Bunge)鳞茎中分得两种流的甾体皂甙,薤白甙甲(macrostemonoside A,1)和薤白甙丁(macrostemonoside D,2),通过光谱(IR,MS,~1HNMR,~(12)CNMR,~1H-~1H COSY和NOESY等)分析和衍生化研究,分别确定为:tigogenin-3-O-β-D-glucopyranosyl(1→2)[β-D-glucopyranosyl(1→3)]-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside(1)和tigotenin-3-O-β-D-glucopyranosyl(1→2)[β-D-glucopyranosyl(1→3)(6-O-acetyl-β-D-glucopyranosyl)](1→4)-β-D-galactopyranoside(2)。     

中药升麻的化学成分

从中药兴安升麻[Cimicifuga dahurica(Turcz.)Maxim.]的干燥根茎中分得五个化合物,其中四个为三萜木糖甙:升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(Ⅰ),25-O-乙酰升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(Ⅱ),12-羟基升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(Ⅲ),升麻醇-3-O-β-D-吡喃木糖基(3→1)-β-D-吡喃木糖甙(23R,24S)(Ⅳ),另一个为异阿魏酸(Ⅴ)。Ⅲ和Ⅳ为新化合物,通过光谱(IR,MS,¹H及¹³C NMR)解析确定了它们的结构,分别命名为升麻甙A(cimiside A)和升麻甙B(cimiside B)。     

太白木忽木根皮中三萜皂甙成分研究

从太白木忽木(Aralia taibaiensis Z.Z.WangetH.C.Zheng)根皮中首次分离到四个三萜皂甙,根据理化性质和光谱数据,分别鉴定为齐墩果酸-3-O-[β-D-吡喃木糖(1→2)][β-D-吡喃葡萄糖(1→3)]-β-D-吡喃葡萄糖醛酸甙(1),tarasaponinV(2),3-O-｛β-D-吡喃木糖(1→2)[β-D-吡喃葡萄糖(1→3)]-β-D-吡喃葡萄糖醛酸乙酯｝-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(3)和3-O-｛β-D-吡喃木糖(1→2)[β-D-吡喃葡萄糖(1→3)]-β-D-吡喃葡萄糖醛酸丁酯｝-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(4)。1为新天然产物,3和4为新化合物,分别命名为太白木忽木皂甙VI(taibaienosideVI)、太白木忽木皂甙VII(taibaienoside VII)和太白木忽木皂甙VII(taibaienoside VII)。     

薤中抗凝和抗癌活性成分的结构鉴定

从百合科葱属植物薤(Alium chinense)鳞茎的抗凝和抗癌活性部位中,分离得到了6个化合物。经过化学方法和光谱分析(IR,EI-MS,¹HNMR,¹³HNMR,¹H-¹HCOSY,HMBC,HMQC和NOESY谱),鉴定它们的结构分别为(25R,S)-5α-spirostane-3β-ol 3-O-｛β-D-glucopyranosyl-(1→2)-[β-D-glucopyra-nosyl-(1→3)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside｝(1),(25R,S)-5α-spirostane-3β-ol 3-O-｛β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)](6-acetyl-β-D-glucopyranosyl)-(1→4)-β-D-galac-topyranoside｝(2),(25R,S)-5α-spirostane-2α,3β-diol3-O-｛β-D-glucopyranosyl-(1→2)-O-β-D-glucopyra-nosyl-(1→4)-β-D-galactopyranoside｝(3),(25S)-24-O-β-D-glucopyranosyl 3β,24β-dihydroxy-5α-spirost-3-O-α-arabinopyranosyl-(1→6)-β-D-glucopyranoside(4),chinenosideI(5)及2,3,4,9-tetrahydro-1-methyl-1H-pyrido[3,4-b]indole-3-carboxylicacid(6)。化合物4为一新的甾体皂甙,命名为chinenosideVI。化合物1～3为3对甾体皂甙差向异构体。其中,化合物2的25S型异构体为首次报道;25R型异构体和化合物6为首次从本种植物中分得。此外,通过NOESY谱还首次确定了化合物6的相对构型,并对其C和H信号进行了确切归属。     

朝藿甙甲和朝藿甙乙的结构鉴定

自朝鲜淫羊藿(Epimedium koreanum Nakai)地上部分中分离得到二个黄酮类化合物I和II,根据理化数据及光谱分析,其结构分别鉴定为:脱水淫羊藿素3-O-β-D-(6-乙酰基)吡喃葡萄糖(1→3)-α-L-(4-乙酰基)吡喃鼠李糖甙(I)和脱水淫羊藿素3-O-β-D-(2,6-二乙酰基)吡喃葡萄糖(1→3)-α-L-(4-乙酰基)吡喃鼠李糖-7-O-β-D-吡喃葡萄糖甙(II)。I和I为新化合物,分别命名为朝藿甙甲(korepimedoside A)和朝藿甙乙(korepimedoside B)。     

黑种草子化学成分研究

从民族药黑种草子(Semen nigellae)中分离得到七个化合物,其中两个为新化合物,分别命名为黑种草甙(nigeglanoside)和黑种草糖(nigelancae)。经理化常数测定和光谱解析确定其结构分别为山萘酚-3-O-β-D-吡喃半乳糖基(1→3)-β-D-吡喃葡萄糖基(1→3)-β-D-吡喃葡萄糖甙和2-O-α-D-吡喃半乳糖基(1→4)-β-D-吡喃葡萄糖基-β-D-呋喃果糖甙。另外五个已知化合物分别为附子碱的氯化物(fuzitinechloride)、常春藤皂甙、蔗糖(sucrose)、β-谷甾醇(β-sitosterol)和环劳顿醇(cyclolandenol)。     

知母中呋甾皂甙的研究

自知母 Anemarrhena asphodeloides Bge.根茎的乙醇提取物中,经硅胶柱层析和制备型HPLC分得四种呋甾皂甙。用化学反应和波谱(IR,FAB-MS,EI-MS,¹HNMR,¹³CNMR,DEPT,一维多重接力CoSY,二维接力HOHAHA,¹H-¹H COSY,¹H-¹³C COSY和NOE差谱)解析,确定其结构为知母皂贰B(anemarsaponinB,I),(25S)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃哺葡萄糖甙(Ⅱ),(25S)-26-O-β-D-吡喃葡萄糖基-22-羟基-5β-呋甾-3β,26-二醉-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅲ),(25S)-26-O-β-D-吡喃葡萄糖基-22-甲氧基-5β-呋甾-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅳ)。Ⅱ为一新的呋甾皂甙,命名为知母皂甙C;化合物Ⅳ为首次从知母中分离得到,命名为知母皂甙E。初步的药理实验显示,化合物1～Ⅳ均有一定的清除羟自由基的作用。     

朝藿甙A的结构

从朝鲜淫羊藿(Epimedium koreanum Nakai)地上部分分离得到一个新黄酮醇甙类成分:朝藿甙A(ChaohuosideA,I),经光谱分析证明,其结构为7-O-β-D-吡喃葡萄糖-脱水淫羊藿素-3-O-β-D-(3,6-O-二乙酰基)-吡喃葡萄糖-(1→3)-α-L-(4-O-乙酰基)-吡喃鼠李糖甙。     

Saponins from Fagonia glutinosa

Twelve triterpenoid saponins, including six new, were isolated and identified from the aerial parts of Fagonia glutinosa. The new saponins were characterised as 3-O-[beta-D-glucopyranosyl(1-->2)][beta-D-glucopyranosyl(1-->3)]-alpha-L - arabinopyranosyl-27-hydroxy oleanolic acid 28-O-beta-D-glucopyranosyl ester, 3-O-[beta-D-glucopyranosyl(1-->3)]-alpha-L-arabinopyranosyl ursolic acid, 3-O-alpha-L-arabinopyranosyl ursolic acid 28-O-beta-D-glucopyranosyl ester, 3-O-[beta-D-xylopyranosyl(1-->2)][beta- D-glucopyranosyl(1-->3)]-alpha-L-arabinopyranosyl ursolic acid, 3-O-[beta-D-glucopyranosyl(1-->2)][beta-D- glucopyranosyl(1-->3)]-alpha-L-arabinopyranosyl ursolic acid 28-O-beta-D-glucopyranosyl ester and 3-O-[beta-D-glucopyranosyl(1-->2)][beta-D-glucopyranosyl(1-->3)]-alpha-L - arabinopyranosyl-27-hydroxy ursolic acid 28-O-beta-D-glucopyranosyl ester. The structures of the saponins were established by spectral and chemical evidences. The assignments of the NMR signals were performed by means of HOHAHA, 1H-1H COSY, ROE, HMQC and HMBC experiments.     

川续断中皂甙Ⅸ和Ⅹ的结构研究

从川续断(Dipsacus asper Wall.)根的乙醇提取物中得到二个新三萜皂甙(Ⅸ和Ⅹ),根据光谱分析和化学反应,其结构分别确定为3-O-[β-D-吡喃木糖(1→4)-β-D-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-常春藤皂甙元(Ⅸ)及其28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙(Ⅹ)。     

Anticomplement activities of oleanolic acid monodesmosides and bisdesmosides isolated fromTiarella polyphylla

Seven known oleanolic acid glycosides (1-7) were isolated from the MeOH extract of Tiarella polyphylla. The structures were identified to be 3-O-(beta-D-glucopyranosyl) oleanolic acid (1), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl] oleanolic acid (2), 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl] oleanolic acid (3), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (4), 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (5), 3-O-[a-L-rhamnopyranosyl-(1-->3)-beta-D-glucuronopyranosyl] oleanolic acid (6), and 3-O-[alpha-L-rhamnopyranosyl-(1-->3)-beta-D-glucuronopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (7) on the basis of physicochemical and spectral data. These triterpene glycosides were tested for the anticomplement activity and hemolytic activity. Bisdesmosidic saponins, 4, 5, and 7, showed anticomplement activity; in contrast, monodesmosidic saponins, 1-3, and 6, showed direct hemolytic activity. Methyl esterified monodesmosidic saponins showed anticomplement activity at a low concentration and hemolytic activity at a high concentration.     

Three new triterpenoid saponins from Ixeris sonchifolia and their cytotoxic activity

Bioassay-guided fractionation of an active n-BuOH extract of the whole plant of Ixeris sonchifolia, using a cytotoxicity assay, resulted in the isolation of three new triterpenoid saponins, ixeris saponins A (1), B (2), and C (3). On the basis of chemical evidence and extensive spectral studies, their structures were established as echinocystic acid 3-O-beta-D-glucopyranosyl(1-->3)-beta-D-glucopyranosyl(1-->3)-alpha- L-arabinopyranoside (1), 3-O-[bis[beta-D-glucopyranosyl(1-->2 and 1-->3)-alpha-L-arabinopyranosyl]]echinocystic acid 28-O-beta-D-glucopyranosyl ester (2), and 3- O-[beta-D-glucopyranosyl(1-->3)-beta- D-glucopyranosyl(1-->3)-alpha-L-arabinopyranosyl]-16alpha, 23-dihydroxyolean-12-ene 28-O-beta-D-glucopyranosyl ester (3). Compounds 2 and 3 showed significant cytotoxicity against cancer cell lines A375, L929, and HeLa with IC50 values ranging from 8.83 microM to 15.83 microM, while compound 1 was inactive against these three cell lines.     

朝鲜白头翁的三萜皂苷成分研究

目的　研究朝鲜白头翁［Pulsatilla cernua(Thunb.) Bercht. et Opiz.］ 根茎的化学成分。 方法　朝鲜白头翁根茎的乙醇提取物经大孔树脂、硅胶、ODS柱以及HPLC分离得到6个化合物, 通过波谱(1H,¹³CNMR,FAB-MS等)分析和化学方法进行结构鉴定。结果　6个化合物分别被鉴定为pulsatilla saponin A(1), 常春藤皂苷元3-O-β-D-吡喃葡糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖苷(2), pulsatilla saponin D(3), dipsacoside B(4), 3-O-α-L-吡喃鼠李糖(1→2)［β-D-吡喃葡糖(1→4)］-α-L-吡喃阿拉伯糖常春藤皂苷元28-O-β-D-吡喃葡糖酯苷(5)和胡萝卜苷(6)。 结论　5为新化合物, 命名为朝鲜白头翁丙苷(cernuoside C)。 2,4和6为首次从朝鲜白头翁中分离获得。     

New steroidal saponins from Agave lophantha Schiede and their pharmacological evaluation

The structures of one new monodesmosidic spirostanoside and one new bisdesmosidic furanostanol glycoside isolated from leaves of Agave lophantha Schiede have been determined by means of spectroscopic and chemical methods as (25R)-5 beta-spirostan-3 beta-ol-3-O-(beta-D-apiofuranosyl(1-->4)beta-D -glucopyranosyl(1-->3)[beta-D-glucopyranosyl(1-->2)]beta-D -galactopyranoside) and 26-O-beta-D-glucopyranosyl(25R)-5 beta-furost-20(22)-ene-3 beta, 26-diol-3-O-(beta-D-xylopyranosyl(1-->3)-[beta-D-glucopyranosyl(1--2)] beta-D-galactopyranoside), respectively. The 1H and 13C NMR resonances of the two compounds were assigned by NMR (1H, 13C, HOHAHA, 1H-1H COSY, HMQC, HMBC, NOE difference) studies. The pharmacological activities of the saponin containing fraction are discussed.     

New lupane glycosides from Pulsatilla chinensis

Two new lupane glycosides along with five known triterpenoids were isolated from the roots of Pulsatilla chinensis (Ranunculaceae). The structures of the new glycosides were determined to be 3-O-beta-D-glucopyranosyl(1-->3)-alpha-L-arabinopyranosyl-23-hydroxybetulinic acid 28-O-alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl(1-->6)-beta-D-glucopyranosyl ester (pulsatilloside D, 6) and 3-O-[beta-D-glucopyranosyl(1-->4)][alpha-L-rhamnopyranosyl(1-->2)]-alpha-L-arabinopyranosyl-23-hydroxybetulinic acid 28-O-alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl(1-->6)-beta-D-glucopyranosyl ester (pulsatilloside E, 7) by spectroscopic analysis and chemical methods. The compounds were evaluated for cytotoxic activities against K-562 human leukemia and HeLa cells.     

New furostanol saponins from the bulbs of Allium macrostemon Bunge and their cytotoxic activity

Four new furostanol saponins, named as macrostemonoside O, macrostemonoside P, macrostemonoside Q and macrostemonoside R, along with five known compounds, were isolated from the dried bulbs of Allium macrostemon Bunge. The structures of these new compounds were established by the spectral data elucidation (IR, ESIMS, 1D and 2D NMR) as 26-O-beta-D-glucopyranosyl-22-hydroxyl-5beta-furost-25 (27)-ene-3beta, 26-diol-3-O-beta-D-glucopyranosyl (1-->2)-beta-D-galactopyranoside (macrostemonoside O), (25R)-26-O-beta-D-glucopyranosyl-22-hydroxyl-5beta-furost-1beta, 3beta, 26-triol-3- O-beta-D-glucopyranosyl (1-->2)-beta-D-galactopyranoside (macrostemonoside P), (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5beta-furost-1alpha, 2beta, 3beta, 26-tetraol-3-O-beta-D-glucopyranosyl (1-->2)-beta-D-galactopyranoside (macrostemonoside Q) and (25R)-26-O-beta-D-glucopyranosyl-22-hydroxyl-5beta-furost-2alpha, 3beta, 26-triol-3-O-beta-D-glucopyranosyl (1-->2) [beta-D-glucopyranosyl (1-->3)]-beta-D-glucopyranosyl (1-->4)-beta-D-galactopyranoside (macrostemonoside R), respectively. Their cytotoxic activities on several cancer cell lines including solid tumor (HepG2, MCF-7, NCI-H460 and SF-268) and drug resistant tumor (R-HepG2) were investigated and five compounds showed diverse cytotoxity to these cancer cell lines which suggest that they might be used as potential leading compounds to cure cancer diseases.     

In vitro and in vivo antifungal activities of the eight steroid saponins from Tribulus terrestris L. with potent activity against fluconazole-resistant fungal pathogens

Antifungal activity of natural products is being studied widely. Saponins are known to be antifungal and antibacterial. We have isolated eight steroid saponins from Tribulus terrestris L., namely TTS-8, TTS-9, TTS-10, TTS-11, TTS-12, TTS-13, TTS-14 and TTS-15. TTS-12 and TTS-15 were identified as tigogenin-3-O-beta-D-xylopyranosyl(1-->2)-[beta-D-xylopyranosyl(1-->3)]-beta-D-glucopyranosyl(1-->4)-[alpha-L-rhamnopyranosyl(1-->2)]-beta-D-galactopyranoside and tigogenin-3-O-beta-D-glucopyranosyl(1-->2)-[beta-D-xylopyranosyl(1-->3)]-beta-D-glucopyranosyl(1-->4)-beta-D-galactopyranoside, respectively. The in vitro antifungal activities of the eight saponins against six fluconazole-resistant yeasts, Candida albicans, Candida glabrata, Candida parapsilosis, Candida tropicalis, Candida krusei, and Cryptococcus neoformans were studied using microbroth dilution assay. The results showed that TTS-12 and TTS-15 were very effective against several pathogenic candidal species and C. neoformans in vitro. It is noteworthy that TTS-12 and TTS-15 were very active against fluconazole-resistant C. albicans (MIC(80)=4.4, 9.4 microg/ml), C. neoformans (MIC(80)=10.7, 18.7 microg/ml) and inherently resistant C. krusei (MIC(80)=8.8, 18.4 microg/ml). So in vivo activity of TTS-12 in a vaginal infection model with fluconazole-resistant C. albicans was studied in particular. Our studies revealed TTS-12 also showed in vivo activities against fluconazole-resistant yeasts. In conclusion, steroid saponins TTS-12 and TTS-15 from Tribulus terrestris L. have significant in vitro antifungal activity against fluconazole-resistant fungi, especially TTS-12 also showed in vivo activity against fluconazole-resistant C. albicans.     

风轮菜中三萜皂甙的研究

从风轮菜[Clinopodium chinense(Benth)O.Kuntze]全草中分离得一个新三萜皂甙,根据化学方法和光谱分析确定其化学结构为3-O-β-D-吡喃葡萄糖(1→6)-[β-D-吡喃葡萄糖(1→4)-β-D-吡喃葡萄糖-11,13(18)-二烯-3β,16β,23,28-四羟基齐墩果烷,命名为风轮菜皂甙A(clinodiside A)。