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.     

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).     

A New Triterpenoid and its Glycoside from Phytolacca esculenta

A new triterpenoid and its glycoside, designated as esculentagenic acid and esculentoside J, have been isolated and characterized from the roots of PHYTOLACCA ESCULENTA. The new compounds have been identified as 2beta,3beta,23,30-tetrahydroxyolean-12-en-28-oic acid and 3- O-[beta- D-glucopyranosyl(1-->4)-beta- D-xylopyranosyl] - 28- O-beta- D-glucopyranosyl- 2beta,3beta,23,30-tetrahydroxyolean-12-en-28-oic acid.     

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.     

A New Bidesmosidic Triterpenoidal Saponin from the Roots of Symphytum officinale

A new triterpenoidal saponin having hederagenin as the aglycone was isolated from the roots of SYMPHYTUM OFFICINALE L. The structure of this saponin was elucidated by FAB-MS, (1)H-, (13)C-NMR, 2D-NMR analyses and chemical studies as 3- O-[beta- D-glucopyranosyl-(1-->4)-alpha- L-arabinopyranosyl]-hederagenin 28- O-[beta- D-glucopyranosyl-(1-->6)-beta- D-glucopyranosyl] ester.     

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.     

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].     

Antiviral, haemolytic and molluscicidal activities of triterpenoid saponins from Maesa lanceolata: establishment of structure-activity relationships

Ten saponins isolated from the leaves of Maesa lanceolata were tested for their antiviral, haemolytic and molluscicidal activities. The influence of the substitution pattern of these acylated triterpenoid saponins on their biological activities was investigated and structure-activity relationships were established. Maesasaponin VI(2) (3 beta-O-[[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-galactopyranosyl-(1 --> 3)]-[beta-D-galactopyranosyl-(1 --> 2)]-beta-D-glucopyranuronyl]-21 beta,22 alpha-diangeloyloxy-13 beta,28-epoxyolean-16 alpha,28 alpha-diol), the most potent molluscicidal compound (LC(50) 0.5 ppm), also showed virucidal and haemolytic activity. In general, 21,22-diacylation appeared to be associated with a virucidal (reduction factor of the viral titer > or = 10(3) at 50 microg/ml) and haemolytic activity (HC(50) < or = 1 microg/ml).     

Sesquiterpene lactone glycosides,eudesmanolides, and other constituents from Carpesium macrocephalum

Two new sesquiterpene lactone glycosides and two new eudesmanolides, along with twelve known compounds were isolated from seeds of Carpesium macrocephalum. The structures of these new compounds were elucidated as 2alpha- O-beta- D-glucopyranosyl-5alpha, 11alpha H-eudesma-4(15)-en-12,8beta-olide ( 1), 2alpha- O-beta- D-glucopyranosyl-5alpha H-eudesma-4(15),11(13)-dien-12,8beta-olide ( 2), 2alpha-acetoxy-5alpha-hydroxy-11alpha H-eudesma-4(15)-en-12,8beta-olide ( 3) and 2alpha,5alpha-dihydroxy-11alphaH-eudesma-4(15)-en-12,8beta-olide ( 4) by spectroscopic methods including 2D NMR techniques ( (1)H- (1)H COSY, (1)H- (1)H NOESY, HMQC, HMBC) and chemical transformations. Compounds 1, 6, 8, 9 and 10 exhibited moderate antibacterial activity, while compound 4 showed appreciable cytotoxic activity against cultured SMMC-7721 (human hepatoma cell).     

Antihyperglycemic effect of constituents from Hintonia standleyana in streptozotocin-induced diabetic rats

An extract (100 mg/kg) of the stem bark of Hintonia standleyana caused a significant decrease in blood glucose levels in both normal and streptozotocin (STZ)-diabetic rats when compared with vehicle-treated groups (p < 0.05). From the active extract, 3- O- beta- D-glucopyranosyl-23,24-dihydrocucurbitacin F ( 1), 5- O-beta- D-glucopyranosyl-7-methoxy-3',4'-dihydroxy-4-phenylcoumarin ( 2) and 5- O-[ beta- D-apiofuranosyl-(1-->6)- beta- D-glucopyranosyl]-7-methoxy-3',4'-dihydroxy-4-phenylcoumarin ( 3) were isolated. Coumarin 3 is a new natural product and was identified by spectroscopic methods. Compounds 1 and 3 did not decrease blood glucose levels in normal rats. However, in two different long-term subacute experiments, using animals with a developing diabetes condition and with STZ-induced diabetes, both compounds at daily doses of 10 mg/kg (developing diabetes condition) or 30 mg/kg (STZ-induced diabetes condition) provoked a significant antihyperglycemic activity (p < 0.05). Furthermore, compound 3 restored normal blood glucose levels in STZ-induced diabetic rats. In all cases, the groups treated with the active principles and the extract showed less body weight lost than the glibenclamide-treated and diabetic control groups (p < 0.05). These results showed that the antihyperglycemic active principles of H. standleyana are both 4-phenylcoumarins and cucurbitacin glycosides.     

Four new glycosides from Pleurospermum franchetianum

Four new glycosides, pleurofranosides I-IV, together with eight known compounds were isolated from the whole plants of Pleurospermum franchetianum Hemsl. Based on the spectral data and chemical evidence, the structures of pleurofranosides 1, II, III and IV were elucidated to be 16beta, 21beta, 23, 28-tetrahydroxyolean-12-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucopyranoside, 13beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-beta-D-fucopyranoside, 13beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-fucopyranosyl-(1 --> 2)]-beta-D-glucopyranoside and 12beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 3)-[beta-D-glucopyranosyl-(1 --> 2)]-beta-D-glucopyranoside. The known compounds identified were octadecyl caprate, beta-sitosterol, (22E, 20S, 24R)-5alpha, 8alpha-epidioxy-ergosta-6, 22-dien-3-beta-ol, daucosterol, alpha-spinasterol-3-O-beta-D-glucopyranoside, quercetin-3, 7-di-O-beta-D-glucopyranoside, kaempferol-3, 7-di-O-alpha-L-rhamnopyranoside and kaempferol-3-O-beta-D-glucopyranosyl-7-O-alpha-L-rhamnopyranoside, respectively.     

Two new triterpenoid saponins from Ardisia crenata

Two new triterpenoid saponins, ardisicrenoside K (1) and ardisicrenoside L (2), have been isolated from the roots of Ardisia crenata Sims. Their structures have been determined as 3beta-O-[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-alpha-L-arabinopyranosyl]-13beta,28-epoxy-16-oxo-30,30-dimethoxyoleanane and 3beta-O-[beta-D-xylopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-alpha-L-arabinopyranosyl]-13beta,28-epoxy-16alpha,20-dihydroxyoleanane by means of chemical evidences and spectral analysis. Their weak anti-fungal activity against the plant pathogenic fungus Pyricularia oryzae was evaluated in vitro.     

Two New Glycosides from the Roots of Cynanchum versicolor

Two new glycosides named cynanversicoside-A and -B, together with glaucogenin-C as the aglycone, were isolated from the Chinese crude drug "Pai-Wei", CYNANCHUM VERSICOLOR Bunge (Asclepiadaceae). Their structures were determined on the basis of spectral and chemical evidence as glaucogenin-C 3- O-beta- D-cymaropyranosyl-(1-->4)-alpha- L-diginopyranosyl-(1-->4)-beta- D-thevetopyranoside and glaucogenin-C 3- O-beta- D-glucopyranosyl-(1-->4)-beta- D-cymaropyranosyl-(1-->4)-alpha- L-diginopyranosyl-(1-->4)-beta- D-thevetopyranoside.     

Isolation of saponins with the inhibitory effect on nitric oxide, prostaglandin E2 and tumor necrosis factor-alpha production from Pleurospermum kamtschaticum

As an attempt to search for bioactive natural products exerting antiinflammatory activity, we have isolated two saponins were isolated from the aerial portion of Pleurospermum kamtschaticum (Umbelliferae) by nitrite assay activity-directed chromatographic fractionation. They were identified as saikogenin F 3-O-{beta-D-glucopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->3)]-beta-D-fucopyranoside} (buddlejasaponin IV, 1) and 3beta,16beta,23,28-tetrahydroxy-11alpha-methoxyolean-12-ene 3-O-{beta-D-glucopyranosyl(1-->2)-[beta-D-glucopyranosyl(1-->3)]-beta-D-fucopyranoside} (buddlejasaponin IVa, 2). Compound 1 significantly inhibited nitric oxide (NO) production, and it also significantly decreased prostaglandin E2 (PGE2) and tumor necrosis factor-alpha (TNF-alpha) release in the lipopolysaccharide (LPS)-activated macrophage Raw 264.7 cells whereas compound 2 was much less active. Saikogenin A (3) and -H (4) were obtained by hydrolyzing 1 and 2. Although these sapogenin showed strong NO inhibition, these effects were caused by the cytotoxic effect on Raw 264.7 cells. These results supported the notion that buddlejasaponin IV is a major inhibitors of NO, PGE2 and TNF-alpha production in P. kamtschaticum.     

CNS active principles from Alangium plantanifolium

A 70% EtOH extract of root bark of Alangium plantanifolium showed binding activities to nine receptors in the central nervous system (CNS). In an attempt to search for CNS active ingredients, the extract was isolated and five compounds were identified as beta-sitosterol, stigmasterol, sitosterol 3- O-beta- D-gluco-pyranoside, beta- D-fructofuranosyl(1-->4)-alpha- D-fructopyranoside and 5beta,6beta-dihydroxycyclohex-2-en-1-ol 1-beta-glucoside, a possibly new compound, by El-mass, (1)H-NMR, and (13)C-NMR spectra. Stigmasterol and 5beta,6beta-dihydroxycyclohexa-2-en-1-ol 1-beta-glucoside were able to bind to muscarinic receptors with IC (50) values of 8.52 microM and 6.74 microM, respectively. In addition, beta-sitosterol, sitosterol 3- O-beta- D-glucopyranoside and 5beta,6beta-dihydroxy-cyclohex-2-en-1-ol 1-beta-glucoside were found to affect the binding of other compounds to the receptors.     

Lugrandoside: a new phenylpropanoid glycoside from various digitalis species

A novel phenylpropanoid glycoside, lugrandoside, has been isolated from the caulinary leaves of DIGITALIS LUTEA L. and DIGITALIS GRANDIFLORA Miller. The structure of this compound has been elucidated on the basis of its chemical properties and spectral data as 3,4-dihydroxy-beta-phenylethoxy- O-beta- D-glucopyranosyl-(1-->6)-4- O-TRANS-caffeoyl-beta- D-glucopyranoside ( 1).     

Antifungal saponins from Paris polyphylla Smith

Three steroidal saponins, including one new and two known compounds, were isolated from the rhizomes of Paris polyphylla Smith. One- and two-dimensional NMR, LC-MS, and interpretation of hydrolytic cleavage experiments led to the identification of the structure of the new saponin as ( 25R)-spirost-5-ene-3 beta,17 alpha-diol (pennogenin) 3- O-{ O- alpha- L-rhamnopyranosyl-(1-->2)- O-[ O- beta-xylopyranosyl-(1-->5)- alpha- L-arabinofuranosyl-(1-->4)]- beta- D-glucopyranoside}. The isolated saponins were evaluated for their antifungal activity against Cladosporium cladosporioides and Candida species and showed comparable activity to chemicals used in some commercial products.     

New guaiane, megastigmane and eudesmane-type sesquiterpenoids and anti-inflammatory constituents from Youngia japonica

Eleven sesquiterpenoids have been isolated from the whole plants of Youngia japonica (Asteraceae). Among these sesquiterpenoids, five were identified as new compounds on the basis of spectroscopic methods and chemical analysis. Their structures were 3-oxo-8alpha-(4-hydoxyphenyl)acetoxy-10(14),11(13)-guaiadien-12,6-olide ( 1), 3beta-[3-(4-hydroxyphenyl)acetyl-beta- D-glucopyranosyloxy]-8alpha-hydroxy-4(15),10(14),11(13)-guaiatrien-12,6-olide ( 2), 3beta-[3-(4-hydroxyphenyl)acetyl-beta- D-glucopyranosyloxy]-4(15),10(14),11(13)-guaiatrien-12,6-olide ( 3), 3alpha,5beta,6alpha-trihydroxy-4alpha-(beta- D-glucopyranosyloxy)-7-megastigmen-9-one ( 4), and 3alpha-(beta- D-glucopyranosyloxy)-4(15),11(13)-eudesmadien-12-oic acid ( 5). The three known components 3beta-(beta- D-glucopyranosyloxy)-8alpha-(4-hydroxyphenyl)acetoxy-4(15),10(14),11(13)-guaiatrien-12,6-olide ( 8), 3beta-(beta- D-glucopyranosyloxy)-4(15),10(14),11 (13)-guaiatrien-12,6-olide ( 9), and 3alpha-hydroxy-4alpha-(beta- D-glucopyranosyloxy)-5,7-megastigmadien-9-one ( 11) showed inhibitory activity against the proliferation of T and B lymphocytes of mice in vitro at concentrations of 1 x 10 ( - 7), 1 x 10 ( - 6), and/or 1 x 10 ( - 5) M without obvious cytotoxicity. Compound 9, the major component of the plant extract, exhibited weak anti-inflammatory activity at a dosage of 50 mg/kg ( p. o.) in in vivo anti-inflammatory experiments of mice.     

Two new antifungal saponins from the Tibetan herbal medicine Clematis tangutica

Bioassay-guided fractionation of the ethanol extract of the aerial parts of Clematis tangutica led to the isolation of two new antifungal triterpene saponins. Their structures were determined to be 3- O-alpha- L-arabinopyranosyl hederagenin 28- O-alpha- L-rhamnopyranosyl ester ( 1) and 3- O-beta- D-glucopyranosyl-(1--> 4)-alpha- L-arabinopyranosyl hederagenin 28- O-alpha- L-rhamnopyranosyl ester ( 2) on the basis of spectral data and chemical evidence. Inhibitory activities of the two saponins against seven fungal strains were evaluated. Compounds 1 and 2 showed evident antifungal activity (MIA approximately 2.5 micrograms/disc) against Saccharomyces cerevisiae, similar to the positive control amphotericin B and ordinary activities (MIA approximately 10 micrograms/disc) against Penicillium avellaneum UC-4376, Candida glabrata, Trichosporon beigelii and Pyricularia oryzae. Compound 2 is a better antifungal agent than compound 1 against most of the fungal strains that were tested.     

Triterpenoid Glycosides from the Roots of Patrinia scabiosaefolia

Four saponins were isolated from the roots of PATRINIA SCABIOSAEFOLIA (Valerianaceae) and identified as 3- O-alpha- L-arabinopyranosylhederagenin 28- O-beta- D-glucopyranosyl(1-->6)-beta- D-glucopyranoside ( 2) and its 2'-acetate ( 1) and 3- O-beta- D-glucopyranosyl(1-->3)-alpha- L-rhamnopyranosyl(1-->2)-alpha- L-arabinopyranosyloleanolic acid ( 3) and its 28- O-beta D-glucopyranosyl(1-->6)-beta- D-glucopyranoside ( 4).