Unusual oleanane-type saponins from Arenaria montana

Three oleanane-type saponins, 3-O-β-d-glucopyranosylechinocystic acid 28-O-β-d-xylopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→2)]-α-l-rhamnopyranosyl ester (1), 3-O-β-d-glucopyranosylechinocystic acid 28-O-α-l-arabinopyranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→2)]-α-l-rhamnopyranosyl ester (2), 3-O-β-d-glucopyranosylcaulophyllogenin 28-O-β-d-apiofuranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-[β-d-apiofuranosyl-(1→3)]-α-l-rhamnopyranosyl-(1→2)-α-l-rhamnopyranosyl ester (3) were isolated from the whole plant of Arenaria montana. Their unusual structures for the Caryophyllaceae family were established mainly by 2D NMR techniques and mass spectrometry.     

Four new steroidal glycosides from Solanum torvum and their cytotoxic activities

Two novel C-22 steroidal lactone saponins, namely solanolactosides A, B (1, 2) and two new spirostanol glycosides, namely torvosides M, N (3, 4) were isolated from ethanol extract of aerial parts of Solanum torvum. Their structures were characterized as solanolide 6-O-[α-l-rhamnopyranosyl-(1 → 3)-O-β-d-quinovopyranoside] (1), solanolide 6-O-[β-d-xylopyranosyl-(1 → 3)-O-β-d-quinovopyranoside] (2), yamogenin 3-O-[β-d-glucopyranosyl-(1 → 6)-O-β-d-glucopyranoside] (3) and neochlorogenin 3-O-[β-d-glucopyranosyl-(1 → 6)-O-β-d-glucopyranoside] (4) on the basis of spectroscopic analysis. The cytotoxicities of the saponins (1-4) were evaluated in vitro against a panel of human cancer cell lines. Compounds 3 and 4 showed significant cytotoxic activity with the cell lines.     

Acylated flavonol tetraglycosides from Delphinium gracile

An ethanol extract of the aerial parts of Delphinium gracile DC. yielded five flavonol glycosides quercetin-3-O-{[β-d-xylopyranosyl (1 → 3)-4-O-(E-p-caffeoyl)-α-l-rhamnopyranosyl (1 → 6)][β-d-glucopyranosyl (1 → 2)]}-β-d-glucopyranoside (1), quercetin-3-O-{[β-d-xylopyranosyl (1 → 3)-4-O-(E-p-coumaroyl)-α-l-rhamnopyranosyl (1 → 6)][β-d-glucopyranosyl (1 → 2)]}-β-d-glucopyranoside (2), quercetin-3-O-{[β-d-xylopyranosyl (1 → 3)-4-O-(Z-p-coumaroyl)-α-l-rhamnopyranosyl (1 → 6)][β-d-glucopyranosyl (1 → 2)]}-β-d-glucopyranoside (3), kaempferol-3-O-{[β-d-glucopyranosyl (1 → 3)-4-O-(E-p-coumaroyl)-α-l-rhamnopyranosyl (1 → 6)][β-d-glucopyranoside-7-O-(4-O-acetyl)-α-l-rhamnopyranoside (4) kaempferol-3-O-{[β-d-glucopyranosyl (1 → 3)-4-O-(E-p-coumaroyl)-α-l-rhamnopyranosyl (1 → 6)][β-d-glucopyranoside-7-O-(4-O-acetyl)-α-l-rhamnopyranoside (5) in addition to 4-(β-d-glucopyranosyloxy)-6-methyl-2H-pyran-2-one (6) and rutin. Structures were elucidated by spectroscopic methods.     

A new ursane-type triterpenoid glycoside from Centella asiatica leaves modulates the production of nitric oxide and secretion of TNF-α in activated RAW 264.7 cells

One new ursane-type triterpenoid glycoside, asiaticoside G (1), five triterpenoids, asiaticoside (2), asiaticoside F (3), asiatic acid (4), quadranoside IV (5), and 2α,3β,6β-trihydroxyolean-12-en-28-oic acid 28-O-[α-l-rhamnopyranosyl-(1→4)-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl] ester (6), and four flavonoids, kaempferol (7), quercetin (8), astragalin (9), and isoquercetin (10) were isolated from the leaves of Centella asiatica. Their chemical structures were elucidated by mass, 1D- and 2D-nuclear magnetic resonance (NMR) spectroscopy. The structure of new compound 1 was determined to be 2α,3β,23,30-tetrahydroxyurs-12-en-28-oic acid 28-O-[α-l-rhamnopyranosyl-(1→4)-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl] ester. The anti-inflammatory activities of the isolated compounds were investigated on lipopolysaccharide (LPS)-stimulated RAW 264.7 cells. Asiaticoside G (1) potently inhibited the production of nitric oxide and tumor necrosis factor-α with inhibition rates of 77.3% and 69.0%, respectively, at the concentration of 100 μM.     

Cycloartane glycosides from Astragalus campylosema Boiss. ssp. campylosema

Four cycloartane glycosides, 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-3β,6α,16β,23α,25-pentahydroxy-20(R),24(S)-epoxycycloartane (1), 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-16-O-hydroxyacetoxy-23-O-acetoxy-3β,6α,25-trihydroxy-20(R),24(S)-epoxycycloartane (2), 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-3β,6α,23α,25-tetrahydroxy-20(R),24(R)-16β,24;20,24-diepoxycycloartane (3), 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-25-O-β-d-glucopyranosyl-3β,6α,16β,25-tetrahydroxy-20(R),24(S)-epoxycycloartane (4), along with three known cycloartane glycosides were isolated from the MeOH extract of the roots of Astragalus campylosema ssp. campylosema. Their structures were established by the extensive use of 1D- and 2D-NMR experiments along with ESIMS and HRMS analysis. The occurrence of the hydroxyl function at position 23 (1-2) and of the ketalic function at C-24 (3) are very unusual findings in the cycloartane class.     

Phenolic compounds and rare polyhydroxylated triterpenoid saponins from Eryngium yuccifolium

Phytochemical investigation on the whole plant of Eryngium yuccifolium resulted in the isolation and identification of three phenolic compounds (1-3) and 12 polyhydroxylated triterpenoid saponins, named eryngiosides A-L (4-15), together with four known compounds kaempferol-3-O-(2,6-di-O-trans-p-coumaroyl)-β-d-glucopyranoside (16), caffeic acid (17), 21β-angeloyloxy-3β-[β-d-glucopyranosyl-(1→2)]-[β-d-xylopyranosyl-(1→3)]-β-d-glucuronopyranosyloxyolean-12-ene-15α,16α,22α,28-tetrol (18), and saniculasaponin III (19). This study reports the isolation of these compounds and their structural elucidation by extensive spectroscopic analyses and chemical degradation.     

Triterpenoid saponins from a cytotoxic root extract of Sideroxylonfoetidissimum subsp. gaumeri

Evaluation of the cytotoxicity of an ethanolic root extract of Sideroxylonfoetidissimum subsp. gaumeri (Sapotaceae) revealed activity against the murine macrophage-like cell line RAW 264.7. Systematic bioassay-guided fractionation of this extract gave an active saponin-containing fraction from which four saponins were isolated. Use of 1D (¹H, ¹³C, DEPT135) and 2D (COSY, TOCSY, HSQC, and HMBC) NMR, mass spectrometry and sugar analysis gave their structures as 3-O-(β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl)-28-O-(α-l-rhamnopyranosyl-(1 → 3)[β-d-xylopyranosyl-(1 → 4)]-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl)-16α-hydroxyprotobassic acid, 3-O-β-d-glucopyranosyl-28-O-(α-l-rhamnopyranosyl-(1 → 3)[β-d-xylopyranosyl-(1 → 4)]-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl)-16α-hydroxyprotobassic acid, 3-O-(β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl)-28-O-(α-l-rhamnopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)[β-d-apiofuranosyl-(1 → 3)]-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl)-16α-hydroxyprotobassic acid, and the known compound, 3-O-β-d-glucopyranosyl-28-O-(α-l-rhamnopyranosyl-(1 → 3)[β-d-xylopyranosyl-(1 → 4)]-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl)-protobassic acid. Two further saponins were obtained from the same fraction, but as a 5:4 mixture comprising 3-O-(β-d-glucopyranosyl)-28-O-(α-l-rhamnopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)[β-d-apiofuranosyl-(1 → 3)]-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl)-16α-hydroxyprotobassic acid and 3-O-(β-d-apiofuranosyl-(1 → 3)-β-d-glucopyranosyl)-28-O-(α-l-rhamnopyranosyl-(1 → 3)[β-d-xylopyranosyl-(1 → 4)]-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl)-16α-hydroxyprotobassic acid, respectively. This showed greater cytotoxicity (IC₅₀ = 11.9 ± 1.5 μg/ml) towards RAW 264.7 cells than the original extract (IC₅₀ = 39.5 ± 4.1 μg/ml), and the saponin-containing fraction derived from it (IC₅₀ = 33.7 ± 6.2 μg/ml).     

Triterpenoidal saponins of Pulsatilla koreana roots

Sixteen (1-16) triterpenoidal saponins were isolated from the roots of Pulsatilla koreana, of which four were determined as the previously unknown 23-hydroxy-3β-[(O-α-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid 28-O-β-D-glucopyranosyl ester (1), 23-hydroxy-3β-[(O-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid 28-O-β-D-glucopyranosyl ester (2), 3β-[(O-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid 28-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranosyl ester (3), and 3β-[(O-α-L-rhamnopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 4)]-α-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid 28-O-α-L-rhamnopyranosyl-(1 → 4)-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranosyl ester (4), respectively, based on spectroscopic analysis. The inhibition of the lipopolysaccharide-induced nitric oxide production of sixteen isolated compounds was evaluated in RAW 264.7 cells at concentrations ranging from 1 μM to 100 μM.     

Antibacterial phenolic components from Eriocaulon buergerianum

Five phenolic components, 1,3,6-trihydroxy-2,5,7-trimethoxyxanthone (1), 7,3′-dihydroxy-5,4′,5′-trimethoxyisoflavone (2), toralactone-9-O-β-d-glucopyranoside (3), patuletin-3-O-[2-O-E-feruloyl-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranoside] (4), patuletin-3-O-[β-d-glucopyranosyl-(1 → 3)-2-O-E-caffeoyl-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranoside] (5), along with 19 known compounds were isolated from Eriocaulon buergerianum (Eriocaulaceae). Their structures were determined by spectroscopic and chemical methods. All 24 isolated compounds were tested against the pathogenic bacteria Staphylococcus aureus (ATCC 25923); as a result, 10 compounds were found to exhibit antibacterial activity with MICs ranging from 32 to 256 μg/ml.     

A new naturally acetylated triterpene saponin from Nigella sativa

A new glycosylated triterpene 1 was identified as 3-O-[β-d-xylopyranosyl-(1→3)-α-l-rhamnopyranosyl-(1→4)-β-d-glucopyranosyl]-11-methoxy-16-hydroxy-17-acetoxy hederagenin from an ethanolic extract of seeds of Nigella sativa Linn. Identification of the naturally acetylated saponin was based on chemical and spectroscopic analyses including FABMS, ¹H, ¹³C, and 2D NMR and DEPT. The saponin was a penta hydroxy pentacyclic triterpene, in which one hydroxyl group was acetylated and other one was methylated naturally.     

Synthesis of oleanolic acid saponins mimicking components of Chinese folk medicine Di Wu

3,28-Di-O-rhamnosylated oleanolic acid saponins, mimicking components of Chinese folk medicine Di Wu, have been designed and synthesized. One-pot glycosylation and ‘inverse procedure’ technologies have been applied thus significantly simplifying the preparation of desired saponins. The cytotoxic activity of compounds 3-O-[α-l-rhamnopyranosyl-(1→2)-β-d-xylopyranosyl]oleanolic acid 28-O-[α-l-rhamnopyranosyl-(1→4)-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl] ester (3), 3-O-[α-l-rhamnopyranosyl]oleanolic acid 28-O-[α-l-rhamnopyranosyl- (1→4)-β-d-glucopyranosyl-(1→6)-β-d-glucopyranosyl] ester (4), 3-O-[α-l-rhamnopyranosyl]oleanolic acid 28-O-[α-l-rhamnopyranosyl] ester (5), and 3-O-[α-l-rhamnopyranosyl]oleanolic acid 28-O-[6-O-(α-l-rhamnopyranosyl)hexyl] ester (6) was preliminarily evaluated against HL-60 human promyelocytic leukemia cells. The natural saponin 3 and designed saponin 4 exhibited comparable moderate cytotoxic activity under our testing conditions.     

Acylated triterpene saponins from the roots of Securidaca longepedunculata

Four triterpene saponins, 3-O-β-d-glucopyranosylpresenegenin 28-O-β-d-apiofuranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-[β-d-apiofuranosyl-(1 → 3)]-α-l-rhamnopyranosyl-(1 → 2)-{4-O-[(E)-3,4,5-trimethoxycinnamoyl]}-β-d-fucopyranosyl ester, 3-O-β-d-glucopyranosylpresenegenin 28-O-β-d-apiofuranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-[β-d-apiofuranosyl-(1 → 3)]-α-l-rhamnopyranosyl-(1 → 2)-[(6-O-acetyl)-β-d-glucopyranosyl-(1 → 3)]-{4-O-[(E)-3,4,5-trimethoxycinnamoyl]}-β-d-fucopyranosyl ester, 3-O-β-d-glucopyranosylpresenegenin 28-O-β-d-apiofuranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-[β-d-apiofuranosyl-(1 → 3)]-α-l-rhamnopyranosyl-(1 → 2)-[β-d-galactopyranosyl-(1 → 3)]-{4-O-[(E)-3,4,5-trimethoxycinnamoyl]}-β-d-fucopyranosyl ester, and 3-O-β-d-glucopyranosylpresenegenin 28-O-β-d-apiofuranosyl-(1 → 3)-[α-l-arabinopyranosyl-(1 → 4)]-β-d-xylopyranosyl-(1 → 4)-[β-d-apiofuranosyl-(1 → 3)]-α-l-rhamnopyranosyl-(1 → 2)-{4-O-[(E)-3,4,5-trimethoxycinnamoyl]}-β-d-fucopyranosyl ester, were isolated from the roots of Securidaca longepedunculata, together with three known compounds. Their structures were established mainly by 2D NMR techniques and mass spectrometry.     

Phytoconstituents from the root of Streptocaulon tomentosum and their chemotaxonomical relevance for separation from S. juventas

A new cardenolide, 17β-H-periplogenin-3-O-β-d-digitoxoside (1), and a new pregnane glycoside, Δ⁵-pregnene-3β,16α-diol-d-O-[2,4-O-diacetyl-β-digitalopyranosyl-(1 → 4)-β-d-cymaropyranoside]-16-O-[β-d-glucopyranoside] (2) were isolated from the roots of Streptocaulon tomentosum (Asclepiadaceae) together with a series of known compounds. Their chemotaxonomic significance for the separation of S. tomentosum from Streptocaulon juventas is discussed, suggesting a rather clear distinction of these species.     

Synthetic studies on the carbohydrate moiety of the antigen from the parasite Echinococcusmultilocularis

Stereocontrolled syntheses of branched tri-, tetra-, and pentasaccharides displaying a Galβ1→3GalNAc core in the glycan portion of the glycoprotein antigen from the parasite Echinococcusmultilocularis have been accomplished. Trisaccharide Galβ1→3(GlcNAcβ1→6)GalNAcα1-OR (A), tetrasaccharide Galβ1→3(Galβ1→4GlcNAcβ1→6)GalNAcα1-OR (D), and pentasaccharides Galβ1→3(Galβ1→4Galβ1→4GlcNAcβ1→6)GalNAcα1-OR (E) and Gal β1→3(Galα1→4Galβ1→4GlcNAcβ1→6)GalNAcα1-OR (F) (R = 2-(trimethylsilyl)ethyl) were synthesized by block synthesis. The disaccharide 2-(trimethylsilyl)ethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl-(1→3)-2-azido-4-O-benzyl-2-deoxy-α-d-galactopyranoside served as a common glycosyl acceptor in the synthesis of the branched oligosaccharides. Moreover, linear trisaccharide Galβ1→4Galβ1→3GalNAcα1-OR (B) and branched tetrasaccharide Galβ1→4Galβ1→3(GlcNAcβ1→6)GalNAcα1-OR (C) were synthesized by stepwise condensation.     

Steroids from the leaves of Chinese Melia azedarach and their cytotoxic effects on human cancer cell lines

Three new (1-3) and several known (4-6) steroids were isolated from the leaves of Chinese Melia azedarach. The structures of the new compounds were elucidated by means of spectroscopic methods including 2D NMR techniques and mass spectrometry to be (20S)-5,24(28)-ergostadiene-3β,7α,16β,20-tetrol (1), (20S)-5-ergostene-3β,7α,16β,20-tetrol (2), and 2α,3β-dihydro-5-pregnen-16-one (3). The cytotoxicities of the isolated compounds against three human cancer cell lines (A549, H460, U251) were evaluated; only compounds 1, 2, and (20S)-5-stigmastene-3β,7α,20-triol (4) were found to show significant cyctotoxic effects with IC₅₀s from 12.0 to 30.1 μg/mL.     

Methylated anthocyanidin glycosides from flowers of Canna indica

Methylated anthocyanin glycosides were isolated from red Canna indica flower and identified as malvidin 3-O-(6-O-acetyl-β-d-glucopyranoside)-5-O-β-d-glucopyranoside (1), malvidin 3,5-O-β-d-diglucopyranoside (2), cyanidin-3-O-(6″-O-α-rhamnopyranosyl-β-glucopyranoside (3), cyanidin-3-O-(6″-O-α-rhamnopyranosyl)-β-galactopyranoside (4), cyanidin-3-O-β-glucopyranoside (5) and cyanidin-O-β-galactopyranoside (6) by HPLC-PDA. Their structures were subsequently determined on the basis of spectroscopic analyses, that is, ¹H NMR, ¹³C NMR, HMQC, HMBC, ESI-MS, and UV-vis. Compounds (1-4) were found to be in major quantity while compounds (5-6) were in minor quantity.     

Antiproliferative and apoptotic sesquiterpene lactones from Carpesium faberi

Four new (1-4) and 13 known (5-17) sesquiterpene lactones along with two known diterpenes (18, 19) were isolated from the whole plant of Carpesium faberi. The new structures were elucidated by means of spectroscopic techniques and some chemical transformations to be pseudoguaian-1α(H)-8α,12-olide-4β-O-β-d-glucopyranoside (1), 4β,10α-dihydroxy-5α(H)-1,11(13)-guaidien-8α,12-olide (2), 4β,10β-dihydroxy-5α(H)-1, 11(13)-guaidien-8β,12-olide (3), and (4S)-acetyloxyl-11(13)-carabren-8β,12-olide (4). All isolates were tested against MCF-7 human breast cancer cells using the MTT assay. Among them, the sesquiterpene lactones (except tomentosin 17) possessing an α-methylene-γ-lactone moiety were found to have in vitro antiproliferative activities, with IC₅₀ values of 3.0-38.8 μg/mL. The effects of four selected sesquiterpene lactones (guaianolide 2, carabranolide 4, pseudoguaianolide 9, eudesmanolide 13) on the cell cycle were examined using flow cytometry (FCM).     

Steroidal glycosides from the marine sponge Pandaros acanthifolium

The chemical composition of the Caribbean sponge Pandaros acanthifolium was investigated and led to the isolation of seven new steroidal glycosides namely pandarosides A-D (1, 3, 4 and 6) along with the three methyl esters of pandarosides A, C, and D (2, 5 and 7). Their structures were characterized as 3β-[β-glucopyranosyl-(1→2)-β-glucopyranosyloxyuronic acid]-16-hydroxy-5α,14β-poriferast-16-ene-15,23-dione (1) and its methyl ester (2), 3β-[β-glucopyranosyloxyuronic acid]-16-hydroxy-5α,14β-poriferast-16-ene-15,23-dione (3), 3β-[β-glucopyranosyl-(1→2)-β-glucopyranosyloxyuronic acid]-16-hydroxy-5α,14β-cholest-16-ene-15,23-dione (4) and its methyl ester (5), 3β-(β-glucopyranosyloxyuronic acid)-16-hydroxy-5α,14β-cholest-16-ene-15,23-dione (6) and its methyl ester (7) on the basis of detailed spectroscopic analyses, including 2D NMR and HRESIMS studies. Pandarosides A-D and their methyl esters (1-7) are all characterized by a rare 2-hydroxycyclopentenone D-ring with a 14β configuration. The absolute configuration of the aglycon part of pandaroside A (1) was assigned by comparison between experimental and TDDFT calculated circular dichroism spectra on the more stable conformer.     

Steroidal saponins from the leaves of Beaucarnea recurvata

Thirteen steroidal saponins were isolated from the leaves of Beaucarnea recurvata Lem. Their structures were established using one- and two-dimensional NMR spectroscopy and mass spectrometry. Six of them were identified as: 26-O-β-d-glucopyranosyl (25S)-furosta-5,20(22)-diene 1β,3β,26-triol 1-O-α-l-rhamnopyranosyl-(1 → 2) β-d-fucopyranoside, 26-O-β-d-glucopyranosyl (25S)-furosta-5,20(22)-diene 1β,3β,26-triol 1-O-α-l-rhamnopyranosyl-(1 → 2)-4-O-acetyl-β-d-fucopyranoside, 26-O-β-d-glucopyranosyl (25R)-furosta-5,20(22)-diene-23-one-1β,3β,26-triol 1-O-α-l-rhamnopyranosyl-(1 → 2) β-d-fucopyranoside, 26-O-β-d-glucopyranosyl (25S)-furosta-5-ene-1β,3β,22α,26-tetrol 1-O-α-l-rhamnopyranosyl-(1 → 4)-6-O-acetyl-β-d-glucopyranoside, 26-O-β-d-glucopyranosyl (25S)-furosta-5-ene-1β,3β,22α,26-tetrol 1-O-α-l-rhamnopyranosyl-(1 → 2) β-d-fucopyranoside, and 24-O-β-d-glucopyranosyl (25R)-spirost-5-ene-1β,3β,24-triol 1-O-α-l-rhamnopyranosyl-(1 → 2)-4-O-acetyl-β-d-fucopyranoside. The chemotaxonomic classification of B. recurvata in the family Ruscaceae was discussed.     

A sensitive liquid chromatography–electrospray tandem mass spectrometric method for lancemaside A and its metabolites in plasma and a pharmacokinetic study in mice

A high-performance liquid chromatography tandem mass spectrometry (HPLC–MS/MS) method employing electrospray ionization (ESI) has been developed for simultaneous determination of lancemaside A (3-O-β-d-glucuronopyranosyl-3β, 16α-dihydroxyolean-12-en-28-oic acid 28-O-β-d-xylopyranosyl(1→3)-β-d-xylopyranosyl-(1→4)-α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranosyl ester) and its metabolites in mouse plasma. When lancemaside A (60 mg/kg) was orally administered to mice, echinocystic acid was detected in the blood. T_max and C_max of the echinocystic acid were 6.5 ± 1.9 h and 56.7 ± 29.1 ppb. Orally administered lancemaside A was metabolized to lancemaside X (3β, 16α-dihydroxyolean-12-en-28-oic acid 28-O-β-d-xylopyranosyl(1→3)-β-d-xylopyranosyl-(1→4)-α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranosyl ester) by intestinal microflora in mice, which was metabolized to echinocystic acid by intestinal microflora and/or intestinal tissues. Human intestinal microflora also metabolized lancemaside A to echinocystic acid via lancemaside X. These results suggest that the metabolism by intestinal microflora may play an important role in pharmacological effects of orally administered lancemaside A.