Two New Oleanane Saponins from Anemone flaccida

Two new oleanane saponins, named flaccidoside II and III, were isolated from the rhizome of ANEMONE FLACCIDA Fr. Schmidt. On the basis of spectroscopic analysis and chemical transformation their structures were elucidated as 3- O-[alpha- L-rhamnopyranosyl-(1-->2)-beta- D-xylopyranosyl]-oleanolic acid 28- O-[alpha- L-rhamnopyranosyl-(1-->4)-beta- D-glucopyranosyl-(1-->6)-beta- D-glucopyranoside] and 3- O-[beta- D-glucopyranosyl-(1-->2)-beta- D-xylopyranosyl]-oleanolic acid 28- O-[alpha- L-rhamnopyranosyl-(1-->4)-beta- D-glucopyranosyl-(1-->6)-beta- D-glucopyranoside].     

Triterpenoid Saponins from Anemone flaccida

From the rhizome of ANEMONE FLACCIDA Fr. Schmidt, used in Chinese folk medicine, four saponins of oleanolic acid-A,B,C,D were isolated. By means of spectroscopy and chemical transformation, saponins A, B, and D were identified as 3- O-[alpha- L-rhamnopyranosyl-(1-->2)-alpha- L-arabinopyrasyl]-oleanolic acid, 3- O-[alpha- L-rhamnopyranosyl-(1-->2)-beta- D-xylopyranosyl]-oleanolic acid, and 3- O-[alpha- L-rhamnopyranosyl-(1-->2)-beta- D-glucopyranosyl]-oleanolic acid. These three saponins are known compounds but isolated from ANEMONE plants for the first time. Saponin C was elucidated as 3- O-[beta- D-glucopyranosyl-(1-->2)-beta- D-xylopyranosy1]-oleanolic acid, which has not been reported in the literature before, and is named as flaccidoside I.     

Triterpenoid saponins from Androsace umbellata and their anti-proliferative activities in human hepatoma cells

Two new triterpenoid saponins, along with five known ones, were isolated from the EtOH extract of the whole plants of Androsace umbellata. The structures of the new triterpenoid saponins were identified as 3- O-[ beta- D-xylopyranosyl-(1-->2)- beta- D-glucopyranosyl-(1-->4)-[ beta- D-glucopyranosyl-(1-->2)]- alpha- L-arabinopyranosyl]-3 beta-hydroxy-13 beta,28-epoxy-16-oxo-oleanan-30-al ( 1) and 3- O- beta- D-xylopyranosyl-(1-->2)- beta- D-glucopyranosyl-(1-->4)- alpha- L-arabinopyranosyl-3 beta-hydroxy-13 beta,28-epoxy-16-oxo-oleanan-30-al ( 2) on the basis of their spectral and chemical properties. All these compounds showed significant cytotoxic activities in human hepatoma cells.     

Two New Saponins from Phytolacca americana

Two new monodesmosidic saponins (Phytolaccosides F and D (2)) have been isolated from the roots of PHYTOLACCA AMERICANA and identified as 3- O-[alpha- L-rhamnopyranosyl(1-->2)-beta- D-glucopyranosyl (1-->2)-beta- D-xylopyranosyl]phytolaccagenic acid and 3- O-[beta- D-glucopyranosyl(1-->2)-beta- D-xylopyranosyl]phytolaccagenic acid, respectively.     

Triterpenoid saponins with anti-inflammatory activity from Codonopsis lanceolata

Six triterpenoid saponins, including a new compound named codonolaside III, were isolated from the roots of Codonopsis lanceolata. The spectral and chemical data revealed the structure of codonolaside III to be 3- O-[ beta- D-xylopyranosyl -(1-->3)- beta- D-glucuronopyranosyl]-3 beta,16 alpha-dihydroxyolean-12-ene-28-oic acid 28- O-[ beta- D-xylopyranosyl-(1-->4)- alpha- L-rhamnpyranosyl-(1-->2)][ beta- D-glucopyranosyl -(1-->4)]- alpha- L-arabinopyranosyl ester. The xylene-induced mouse ear edema inhibitory effect assay disclosed codonolaside and codonolasides I - III as the major anti-inflammatory constituents in this crude drug.     

Antifungal steroid saponins from Dioscorea cayenensis

From the rhizomes of Dioscorea cayenensis Lam.-Holl (Dioscoreaceae), the new 26- O- beta- D-glucopyranosyl-22-methoxy-3 beta,26-dihydroxy-25( R)-furost-5-en-3- O- alpha- L-rhamnopyranosyl-(1-->4)- alpha- L-rhamnopyranosyl-(1-->4)-[ alpha- L-rhamnopyranosyl-(1-->2)]- beta- D-glucopyranoside ( 1) was isolated together with the known dioscin ( 2) and diosgenin 3- O- alpha- L-rhamnopyranosyl-(1-->4)- alpha- L-rhamnopyranosyl-(1-->4)-[ alpha- L-rhamnopyranosyl-(1-->2)]- beta- D-glucopyranoside ( 3). Their structures were established on the basis of spectral data. Compound 2 exhibited antifungal activity against the human pathogenic yeasts Candida albicans, C. glabrata and C. tropicalis (MICs of 12.5, 12.5 and 25 micro g/mL, respectively) whereas 3 showed weak activity and 1 was inactive.     

Microbial metabolism of pseudoprotodioscin

Microbial transformation of the furostanol saponin pseudoprotodioscin ( 1) using Aspergillus fumigatus resulted in the isolation of two new steroidal metabolites, 3- O-[bis- alpha- L-rhamnopyranosyl-(1-->2 and 1-->4)- beta- D-glucopyranosyl]-22 R,25 R-spirost-5-ene-3 beta,20 alpha-diol ( 2) and 3- O-[bis- alpha- L-rhamnopyranosyl-(1-->2 and 1-->4)- beta- D-glucopyranosyl]-25 R-furost-5-ene-3 beta,22 alpha,26-triol ( 3), in addition to the previously reported steroidal saponins: dioscin ( 4) and progenin II ( 5). The structure elucidation of these metabolites was based primarily on 1D and 2D NMR analyses. Metabolites 2 - 5 showed significant cytotoxicity against cancer cell lines A375, L929, and HeLa with IC (50) values ranging from 1.18 microM to 17.88 microM.     

Cussonosides A and B, two Triterpene-saponins from Cussonia barteri.

Two major saponins have been isolated from the stem bark of CUSSONIA BARTERI Seem (Araliaceae). Structural elucidation employing mainly (1)H- and (13)C-NMR, FAB-MS and GC-MS spectroscopic methods revealed a new hederagenin 28- O-[alpha- L-rhamnopyranosyl (1 --> 4)-beta- D-glucopyranosyl (1 --> 6)]-beta- D-glucopyranosyl ester (Cussonoside A), and the corresponding oleanolic acid analogue (Cussonoside B). Cussonoside A exhibits a pronounced sedative effect.     

Steroidal saponins from Myriopteron extensum and their cytotoxic activity

Two new steroidal saponins, extensumsides A ( 1) and B ( 2), were isolated from the whole plants of Myriopteron extensum (Wight) K. Schum. Their structures were elucidated as 17 beta-uzarigenin-3- O- beta-glucopyranosyl-(1-->6)- beta-glucopyranosyl-(1-->4)- beta-thevetopyranosyl-(1-->4)- beta-cymaropyranoside ( 1) and 12-(3-methylbut-2-enoyloxy)pregn-5-en-20-one 3- O-[beta-cymaropyranosyl-(1-->4)-beta-cymaropyranosyl-(1-->4)-beta-thevetopyranosyl-(1-->4)-(6- O-sulfo-beta-glucopyranoside)] ( 2) on the basis of chemical and spectral evidence. Extensumside A exhibited significant cytotoxicity against eight cancer cell lines with a mean GI (50) value of 0.346 microg/mL.     

Guaiacin A and B from the Leaves of Guaiacum officinale

Guaiacin A and B, two new saponins, have been isolated from the leaves of G. OFFICINALE and were characterised on the basis of (13)C-NMR and FAD mass spectroscopy as 3- O-(beta- D-glucopyranosyl (1-->3)-alpha- L-arabinopyranosyl]-30-nor-olean-12,20(29)-dien-28- O-beta- D-glucopyranosyl ester ( 1) and 3- O-[ D-glucopyranosyl-(1-->3)-alpha- L-arabinopyranosyl] oleanolic acid-28- O-beta- D-glucopyranosyl ester ( 2).     

Steroidal saponins from Tribulus terrestris

Three new steroidal saponins were isolated from the fruits of Tribulus terrestris, and their structures were elucidated as (25R,S)-5 alpha-spirostane-12-one-3 beta-ol-3-O-beta-xylopyranosyl(1-->2)- [beta-xylopyranosyl(1-->3)]-beta-glucopyranosyl(1-->4)-[alpha-rhamno- pyranosyl(1-->2)]-beta-galactopyranoside; 26-O-beta-glucopyranosyl-(25S)-5 alpha-furostane-12-one-3 beta,22 alpha,26-triol-3-O-beta-glucopyranosyl(1-->2)-beta-galactopyranoside; 26-O-beta-glucopyranosyl-(25S)-5 alpha-furostane-12-one-3 beta,22 alpha,26-triol-3-O-beta-glucopyranosyl(1-->4)-[alpha- rhamnopyranosyl(1-->2)]-beta-galactopyranoside, respectively, by spectroscopic analysis and color reaction.     

Bioactive sesquiterpene lactones from Centaurea species and their cytotoxic/cytostatic activity against human cell lines in vitro

Sesquiterpene lactones isolated from the aerial parts of various species of the genus Centaurea were examined for their in vitro cytotoxic/cytostatic activity against five human cell lines (i. e., DLD1, SF268, MCF7, H460 and OVCAR3). Compounds 1 - 4 were isolated from C. zuccariniana, 5 and 6 from C. achaia, 7 from C. thessala ssp. drakiensis and compounds 8 and 9 from C. deusta. Compound 1, 8alpha- O-(3,4-dihydroxy-2-methylenebutanoyloxy)dehydromelitensine was found to be the most active, exhibited a considerable growth inhibiting activity against three of the cell lines tested, while compound 5 8alpha- O-(3-hydroxy-2-methylenepropanoyl)dehydromelitensin exhibited a growth inhibiting effect against most of the tested cell lines. A new eudesmanolide (8alpha-hydroxysonchucarpolide, 4) was isolated from C. zuccariniana and its structure was elucidated by spectroscopic methods.     

Anticomplement and antioxidant activities of new acetylated flavonoid glycosides from Centaurium spicatum

In addition to the three acetylated flavonol glycosides, quercetin 3- O-[(2,3,4-triacetyl-alpha-rhamnopyranosyl)-(1-->6)]-beta-galactopyranoside, quercetin 3- O-[(2,3,4-triacetyl-alpha-rhamnopyranosyl)-(1-->6)]-3-acetyl-beta-galactopyranoside, and quercetin 3- O-[(2,3,4- triacetyl-alpha-rhamnopyranosyl)-(1-->6)]-4-acetyl-beta-galactopyranoside, which have recently been isolated from Centaurium spicatum (L.) Fritsch (Gentianaceae), a new pentaacetylated flavonoid glycoside was isolated from the same plant. Structure elucidation, especially the localization of the acetyl groups, and complete (1)H- and (13)C-NMR assignments, was carried out using one- and two-dimensional NMR methods, including (1)H- and (13)C-NMR, DEPT-135 and DEPT-90, and gradient-assisted experiments such as DQF-COSY, TOCSY, HSQC and HMBC. The structure of the new flavonoid glycoside was established as quercetin 3- O-[(2,3,4-triacetyl-alpha-rhamnopyranosyl)-(1-->6)]-3,4-diacetyl-beta-galactopyranoside. The anticomplement and antioxidant activities of these compounds were evaluated. The triacetylated flavonoid glycoside showed the highest activity in the two assays.     

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 saponins from Tribulus terrestris

Three new steroidal saponins 1-3, together with five known steroidal saponins, L-mannitol and an inorganic salt were isolated from Tribulus terrestris L. (Zygophyllaceae). The structures of the new steroidal saponins were elucidated as hecogenin 3-O-beta-xylopyranosyl(1-->3)-beta-glucopyranosyl(1-->4)-beta-galactopyr anoside (1), hecogenin 3-O-beta-glucopyranosyl(1-->2)-beta-glucopyranosyl(1-->4)- beta-galactopyranoside (2) and 3-O-[beta-xylopyranosyl(1-->2)-[beta-xylopyranosyl(1-->3)]-beta- glucopyranosyl(1-->4)-[alpha-rhamnopyranosyl(1-->2)]-beta-galactopyranos yl]- 26-O-beta-glucopyranosyl-22-methoxy-(3 beta,5 alpha,25R)-furostan-3,26-diol (3). Structure elucidation was accomplished by 1D and 2D NMR spectra (13C-1H COSY, HMQC, HMBC, 1H-1H COSY, TOCSY, and NOESY), mass spectrometry (FABMS, ESIMS) and chemical methods.     

Structural features of a pectic polysaccharide from mulberry leaves

A pectic polysaccharide SDA was obtained from the boiling water extract of mulberry leaves. It consisted of rhamnose, arabinose, xylose, glucose, galactose, and galacturonic acid units in the molar ratio of 5:4:1:2:6:38. Its molecular weight was determined to be 1.5 x 10(4) by high-performance gel filtration chromatography. A combination of linkage analysis, partial acid hydrolysis, ESIMS, (1)H-NMR, and (13)C-NMR spectral analyses revealed its structural features. It was found that SDA possessed an alpha-(1 --> 4)-galacturonan backbone with some insertions of (1 --> 2) Rha residues, with the side chains attached to the O-3 or O-2 position of GalA residues, or the O-4 position of 1,2-linked Rha residues. The side chains contained branched (1 --> 5) linked arabinan, branched (1 --> 3) linked rhamman, linear (1 --> 4) linked xylan, linear (1 --> 4) linked glucan, and linear (1 --> 2) linked galactan. SDA was a new acidic polysaccharide isolated from mulberry leaves for the first time.     

Oligofurostanosides from Asparagus cochinchinensis

The aqueous extract of ASPARAGUS COCHINCHINENSIS yielded a new oligofurostanoside 3- O-[alpha- L-rhamnopyranosyl-(1-->4)-beta- D-glucopyranosyl]-26- O-(beta- D-glucopyranosyl)-(25 R)-furosta-5,20-diene,-3beta,26-diol as well as two known furostanosides, methylprotodioscin and pseudoprotodioscin.     

蒺藜化学成分的研究

目的:研究蒺藜( Tribulusterrestris L.) 中生物活性物质。方法:用硅胶柱色谱、HPLC进行分离,根据光谱数据鉴定其结构。结果:分离纯化得到两种呋甾皂苷,确定其结构为26-O-β-D 吡喃葡糖基-(25 R,S)-5α- 呋甾-12-羰基-20(22)-烯基-3β,26-二醇-3-O-β-D-吡喃葡糖基(1 →4)-β-D-吡喃半乳糖苷(I) ;26 O-β-D-吡喃葡糖基-(25 R)-5α-呋甾-12-羰基 3β,22α,26 三醇-3-O-β-D-吡喃葡糖基(1→2)-β-D-吡喃半乳糖苷(II)。结论:I,II均为新化合物。     

Triterpenoidal saponins from Cornulaca monacantha

From the aerial parts of Cornulaca monacantha, three new triterpenoidal saponins have been isolated and their genuine structures were identified as 3-O-[beta-xylopyranosyl-(1-->3)-beta- glucuronopyranosyl]-30-methylphytolaccagenate (2), 3-O-[beta-xylopyranosyl- (1-->3)-beta-glucuronopyranosyl]-30-methylphytolaccagenate 28-O-beta-gluco-pyranoside (3) and 3-O-[beta-xylopyranosyl-(1-->3)-beta- glucurono-pyranosyl]-30-methylserjanate 28-O-beta glucopyranoside (4) together with nine known saponins of oleanolic acid (5-9), hederagenin (1, 10, 11) and 30-methyl phytolaccagenate (12).     

Two new furostanol saponins from Tribulus terrestris L

Two new furostanol saponins, tribufurosides B (1) and C (2), were isolated from the fruits of Tribulus terrestris L. With the help of chemical and spectral analyses (IR, MS, 1D NMR and 2D NMR), the structures of two new furostanol saponins were established as 26-O-beta-d-glucopyranosyl-(25S)-5alpha-furost-20(22)-en-2alpha,3beta,26-triol-3-O-beta-d-galactopyranosyl(1 --> 2)-beta-d-glucopyranosyl(1 --> 2)-beta-d-galactopyranoside (1) and (25S)-5alpha-furost-20(22)-en-12-one-3beta, 26-diol-26-O-beta-d-glucopyranoside (2).