Flavonol glycosides from whole cottonseed by-product

Cottonseeds are fed to high-producing dairy cows as a source of fat and highly-digestible fibre. Seven flavonol glycosides have been identified from whole cottonseed by-product. Their structures were established as quercetin 3-O-{β-d-apiofuranosyl-(1 → 2)-[α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside} (1), kaempferol 3-O-{β-d-apiofuranosyl-(1 → 2)-[α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside} (2), quercetin 3-O-[β-d-apiofuranosyl-(1 → 2)-β-d-glucopyranoside] (3), quercetin 3-O-β-d-glucopyranoside (4), kaempferol 3-O-[α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside] (5), quercetin 3-O-[α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside] (6), and kaempferol 3-O-α-l-rhamnopyranoside (7). Gallic acid (8) and 3,4-dihydroxybenzoic acid (9) were also found. All structures were elucidated by ESI-MS and NMR spectroscopic methods. Total polyphenols were assayed by the Folin–Ciocalteu method.     

Chemical characterisation of anthocyanins in tamarillo (Solanum betaceum Cav.) and Andes berry (Rubus glaucus Benth.) fruits

The anthocyanin composition of tamarillo (Solanum betaceum Cav., red variety) and Andes berry (Rubus glaucus Benth.) was determined by HPLC–PDA and HPLC–ESIMS. From the anthocyanin-rich extracts (AREs), pure compounds (1–7) were obtained by MLCCC (multilayer countercurrent chromatography) and further preparative HPLC, and their unequivocal structures were obtained by 1D and 2D NMR analyses. The new anthocyanin delphinidin 3-O-α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside-3′-O-β-d-glucopyranoside, as well as the known cyanidin-3-O-rutinoside, pelargonidin-3-O-rutinoside, and delphinidin-3-O-rutinoside were identified as constituents of tamarillo fruit. Although the anthocyanin composition of Andes berry had been reported before in the literature, the unequivocal structure elucidation of the major compound, cyanidin-3-O-α-l-rhamnopyranosyl-(1 → 6)-O-β-d-xylopyranosyl-(1 → 2)-β-d-glucopyranoside, was achieved for the first time.     

Identification,quantification and antioxidant activity of acylated flavonol glycosides from sea buckthorn (Hippophae rhamnoides ssp. sinensis)

A novel acylated flavonol glycoside: isorhamnetin (3-O-[(6-O-E-sinapoyl)-β-d-glucopyranosyl-(1 → 2)]-β-d-glucopyranosyl-7-O-α-l-rhamnopyranoside) (1), together with two known acylated flavonol glycosides: quercetin (3-O-[(6-O-E-sinapoyl)-β-d-glucopyranosyl-(1 → 2)]-β-d-glucopyranosyl-7-O-α-l-rhamnopyranoside) (2) and kaempferol (3-O-[(6-O-E-sinapoyl)-β-d-glucopyranosyl-(1 → 2)]-β-d-glucopyranosyl-7-O-α-l-rhamnopyranoside) (3) were isolated from the n-butanol fraction of sea buckthorn (Hippophae rhamnoides ssp. sinensis) berries for the first time by chromatographic methods, and their structures were elucidated using UV, MS, ¹H and ¹³C NMR, and 2D NMR. Compounds 1–3 showed good scavenging activities, with respective IC₅₀ values of 8.91, 4.26 and 30.90 μM toward the 2,2′-diphenyl-1-picrylhydrazyl (DPPH) radical; respective Trolox equivalent antioxidant capacities of 2.89, 4.04 and 2.44 μM μM⁻¹ toward 2,2′-azino-bis-3-ethyl-benzothiazoline-6-sulphonate (ABTS) radical. The quantitative analysis of the isolated acylated flavonol glycosides was performed by HPLC–DAD method. The contents of compounds 1–3 were in the range of 12.2–31.4, 4.0–25.3, 7.5–59.7 mg/100 g dried berries and 9.1–34.5, 75.1–182.1, 29.2–113.4 mg/100 g dried leaves, respectively.     

Spirostane and cholestane glycosides from the bulbs of Allium nigrum L

A phytochemical investigation of the fresh bulbs of Allium nigrum L. led to the isolation of new spirostane-type glycosides as two inseparable isomer mixtures, nigrosides A1/A2 (1a/1b) and nigrosides B1/B2 (2a/2b), two new cholestane-type glycosides, nigrosides C and D (3 and 4), together with the known compounds, 25(R,S)-5α-spirostan-2α,3β,6β-trio1-3-O-β-d-glucopyranosyl-(1 → 2)-O-[β-d-xylopyranosyl-(1 → 3)]-O-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranoside (5a/5b) and 25(R,S)-5α-spirostan-2α,3β,6β-trio1 3-O-β-d-glucopyranosyl-(1 → 2)-O-[4-O-(3S)-3-hydroxy-3-methylglutaryl-β-d-xylopyranosyl-(1 → 3)]-O-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranoside (6a/6b), isolated from this plant for the first time. All structures were elucidated mainly by spectroscopic analysis (1D and 2D NMR experiments, FABMS, HRESIMS) and by comparison with literature data. Cytotoxicity of the isolated compounds was assessed against human colon carcinoma (HT-29 and HCT 116) cell lines. Compounds 5a/5b and 6a/6b were found to be the most active with IC₅₀ values 1.09 and 2.82 μM against HT-29 and 1.59 and 3.45 μM against HCT 116, respectively.     

Identification of phenolic compounds isolated from pigmented rices and their aldose reductase inhibitory activities

Two anthocyanins (cyanidin-3-O-β-glucoside and peonidin-3-O-β-glucoside) and other phenolic (ferulic acid) were, respectively isolated from black and pigmented brown rices (Oryza sativa L. japonica) and their complete structures were determined by spectroscopic analyses (H NMR, C NMR and MALDI MASS). The HPLC profile of anthocyanins extracted from black rice showed cyanidin-3-O-β-glucoside as the first peak (85%) and peonidin 3-O-β-d-glucoside as the second (15%), while that of pigmented brown rice showed ferulic acid as the first peak (85.7%) and tocols as the second (14.3%). Several tocols were isolated and identified from the unsaponifiable fractions of both rices having some difference on their structures and amounts. The aldose reductase inhibitory activity of isolated compounds was in the following decreasing order: cyanidin-3-glucoside > quercetin > ferulic acid > peonidin-3-glucoside > tocopherol.     

Chemical properties of the cultivated Sideritis raeseri Boiss. & Heldr. subsp. raeseri

Phytochemical analyses of the cultivated Sideritis raeseri subsp. raeseri in four different stages of flower development were performed. Traditionally used infusion and decoction were also prepared from aerial parts in full flowering stage, and analyses of active compounds and radical scavenging capacity were performed. The highest yield of the essential oil, obtained by hydrodistillation, was noticed in the full flowering phase (0.11%), with sesquiterpene bicyclogermacrene as the main constituent (42.5%). All examined extracts contained phenolic compounds and their amounts varied from 15.3 to 34.1 mg GAE/g DW. The amounts of total phenolics in infusion and decoction were similar (46.5 and 43.9 mg GAE/100 ml, respectively). LC–ESI-MS analyses of all samples allowed the characterisation of 22 phenolic compounds. Two dominant flavone glycosides, 4′-O-methylhypolaetin-7-O-[6?-O-acetyl-β-d-allopyranosyl (1 → 2)-β-d-glucopyranoside (17) and 4′-O-methylisoscutellarein-7-O-[6?-O-acetyl-β-d-allopyranosyl-(1 → 2)]-β-d-glucopyranoside (19) were quantified using HPLC. Moreover, the mineral content and the percent of transportation were investigated.     

Furostanol saponins in Allium caepa L. Var. tropeana seeds

An analysis of the polar extracts from seeds of Allium caepa L. var. tropeana led to the isolation of eight furostanol saponins, one of which was previously reported in the literature. On the basis of 1D, 2D NMR and mass spectrometry data, the structures of the compounds were elucidated as 1-O-β-D-glucopyranosyl-(25R)-furost-5(6)-en-1β,3β,22α,26-tetraol-26-O-α-L-rhamnopyranosyl-(1‴ → 2″)-O-α-L-arabinopyranoside (1a), its epimer at position 22, 1-O-β-D-glucopyranosyl-(25R)-furost-5(6)-en-1β,3β,22β,26-tetraol-26-O-α-L-rhamnopyranosyl-(1‴ → 2″)-O-α-L-arabinopyranoside (1b), 1-O-β-D-glucopyranosyl-22-O-methyl-(25R)-furost-5(6)-en-1β,3β,22ξ,26-tetraol-26-O-α-L-rhamnopyranosyl-(1‴ → 2″)-O-α-L-arabinopyranoside (probably artefact) (2), 1-O-β-D-glucopyranosyl-(25R)-furost-5(6)-en-1β,3β,22β,26-tetraol-26-O-α-L-rhamnopyranosyl-(1‴ → 6″)-O-β-D-galactopyranoside (3), 1-O-β-D-glucopyranosyl-22-O-methyl-(25R)-furost-5(6)-en-1β,3β,22ξ,26-tetraol-26-O-α-L-rhamnopyranosyl-(1‴ → 6″)-O-β-D-galactopyranoside (probably artefact) (4), 26-O-β-D-glucopyranosyl-(25R)-furost-5(6)-en-3β,22α,26-triol-3-O-α-L-rhamnopyranosyl-(1″ → 2′)-O-[β-D-glucopyranosyl-(1‴ → 6′)-O]-β-D-glucopyranoside (5a) and its epimer at position 22,26-O-β-D-glucopyranosyl-(25R)-furost-5(6)-en-3β,22β,26-triol-3-O-α-L-rhamnopyranosyl-(1″ → 2′)-O-[β-D-glucopyranosyl-(1‴ → 6′)-O]-β-D-glucopyranoside (5b) and the known compound 26-O-β-D-glucopyranosyl-22-O-methyl-(25R)-furost-5(6)-en-3β,22ξ,26-triol-3-O-α-L-rhamnopyranosyl-(1″ → 2′)-O-[β-D-glucopyranosyl-(1‴ → 6′)-O]-β-D-glucopyranoside (6) [Mimaki, Y., Satou, T., Kuroda, M., Sashida, Y., & Hatakeyama, Y. (1999). Steroidal saponins from the bulbs of Lilium candidum. Phytochemistry, 51, 567–573]. This is the first report on furostanol saponins in the seeds of Allium caepa L. var. tropeana.     

Saponins in Ipomoeabatatas tubers: Isolation,characterization, quantification and antioxidant properties

Triterpene saponins are a class of plant natural products with a wide range of bioactivities, which makes them an interesting research subject. This work reports, for the first time, the isolation and characterization of saponins in Ipomoeabatatas tuber flour, their quantification and antioxidant properties. Their structures were characterized on the basis of UV, FAB–MS, ESI–MS, GC–MS, polarimetry and NMR data, as: oleanolic acid-3-O-[β-d-glucopyranosyl-(1→2)-β-d-galactopyranosyl-(1→2)-β-d-glucuronopyranosyl]-28-O-β-d-glucopyranoside (sandrosaponin IX) (1) and oleanolic acid-3-O-[β-d-galactopyranosyl-(1→3)-β-d-glucuronopyranosyl]-28-O-β-d-glucopyranoside (2). A new quantitative HPLC–DAD method for saponin content determination in this tuber was developed and validated. Their total content was 200.01 mg/100 g dry weight (RSD = 7.2%; p < 0.001). The single saponin contents were: 161.20 mg/100 g dry weight (RSD = 0.58%; p < 0.001) for saponin 1 and 14.67 mg/100 g dry weight (RSD = 0.41%; p < 0.001) for saponin 2. The antioxidant activities, tested by DPPH and FRAP assay, of total phytochemical fraction and of single saponins were moderate in relation to commercial standards.     

Separation and structure analysis of trisaccharide isomers produced from lactose by Lactobacillus bulgaricus L3 β-galactosidase

Using lactose as the substrate, galacto-oligosaccharides containing β-d-galactose residues were synthesised with β-galactosidase from Lactobacillus bulgaricus L3. The reaction mixture was fermented by yeast cells to consume the monosaccharides and disaccharides, and then it was fully acetylated in the presence of acetic anhydride under I₂ catalysis. Column chromatography of the resulting products, using ethyl acetate: petroleum ether as the eluent, generated two isomers of trisaccharide derivatives (I and II) in gram scale for the first time. Their structure characteristics were investigated by ESI-MS and NMR spectra. They were identified as (2,3,4,6-tetra-O-acetyl-d-galactopyranosyl)-β-(1 → 6)-(2,3,4-tri-O-acetyl-d-galactopyranosyl)-β-(1 → 4)-1,2,3,6-tetra-O-acetyl-α-d-glucopyranose (I) and (2,3,4,6-tetra-O-acetyl-d-galactopyranosyl)-β-(1 → 3)-(2,4,6-tri-O-acetyl-d-galactopyranosyl)-β-(1 → 4)-1,2,3,6-tetra-O-acetyl-α-d-glucopyranose (II), respectively. ESI-MS analysis of both deacetylated products of the two trisaccharide derivatives I and II revealed molecular ion peaks of free trisaccharides, which were structurally identified as Gal-β-(1 → 6)-Gal-β-(1 → 4)-Glc and Gal-β-(1 → 3)-Gal-β-(1 → 4)-Glc, respectively.     

Flavonoid glycosides from Pouteria obovata (R. Br.) fruit flour

Three unknown dihydroflavanol glycosides: 2R,3R-4′O-methyl dihydrokaempferol 7-O-[3″-O-acetyl]-β-d-glucopyranoside (1), 2R,3R-4′-O-methyl dihydrokaempferol 7-O-β-d-β-l-xylopyranosyl-(1″′ → 6″)-[3″-O-acetyl]-β-d-glucopyranoside (2), 2R,3R-4′-O-methyl dihydrokaempferol 3-O-β-d-β-l-xylopyranosyl-(1″′ → 6″)-[3″-O-acetyl]-β-d-glucopyranoside (3), together with gallic acid (4) were isolated from the n-butanol fraction of Pouteria obovata fruit flour by chromatographic methods and their structures were elucidated on the basis of CD, UV, MS, monodimensional NMR (¹H and ¹³C) and bidimensional NMR (COSY, HSQC and HMBC). The quantitative analysis of flavonoids and phenols were also reported. Total phenolic amount (51.1 ± 14.1 mg GAE/1000 g; p < 0.0006) and flavonoid content (153.2 ± 3.5 mg CE/100 g; p < 0.004) were detected spectrophotometrically.     

Enzymatic synthesis of primeverosides using transfer reaction by Trichoderma longibrachiatum xylanase

Enzymatic synthesis of two phenyl xylopyranosyl glucopyranosides, through transfer reaction by Trichoderma longibrachiatum endoxylanase, was achieved in the presence of n-hexane used as solvent, phenyl glucoside (10 mM) as acceptor and xylan (2 g/l) as donor. Kinetic study showed that only one compound, identified by ¹H and ¹³C NMR and heteronuclear 2D (¹H–¹³C) chemical shift correlation as phenyl primeveroside (phenyl 6-O-β-xylopyranosyl-1-β-d-glucopyranoside), was synthesized when the reaction time was beyond 1 h. Benzyl and hexyl primeverosides were obtained under the same conditions. When several phenyl glucoside concentrations, from 5 to 50 mM, were used with 2 g/l of xylan, a phenyl primeveroside isomer, identified as phenyl 4-O-β-xylopyranosyl-β-d-glucopyranoside, accumulated in the medium whereas the production of phenyl primeveroside decreased. Only phenyl primeveroside was produced when several xylan concentrations from 2 to 10 g/l were used with 10 mM of phenyl glucoside and its concentration in the reaction mixture increased with the increase of xylan concentration.     

α-Glucosidase inhibitors from Devil tree (Alstonia scholaris)

α-Glucosidase inhibitors are used in the treatment of non-insulin-dependent diabetes mellitus. We attempt to isolate α-glucosidase inhibitors from 24 traditional Thai medicinal plant samples. Potent α-glucosidase inhibitory activity was found in aqueous methanol extract of dried Devil tree (Alstonia scholaris) leaves. Active principles against α-glucosidase, prepared from rat small intestine acetone powder, were isolated and identified. The structures of these isolated compounds were found to be quercetin 3-O-β-d-xylopyranosyl (1? → 2″)-β-d-galactopyranoside and (−)-lyoniresinol 3-O-β-d-glucopyranoside on the basis of chemical and spectral evidence. The latter exhibited an inhibitory activity against both sucrase and maltase with IC₅₀ values of 1.95 and 1.43 mM, respectively, whereas the former inhibited only maltase with IC₅₀ values of 1.96 mM. This preliminary observation will provide the basis for further examination of the suitability of Alstonia scholaris as a medicinal supplement that contributes toward the treatment and prevention of diabetes.     

Antithrombotic activity of fractions and components obtained from raspberry leaves (Rubus chingii)

The 70% ethanol fraction from an aqueous extract of raspberry leaves was shown to be the most antithrombotic fraction in in vitro and in vivo tests. The total flavonoids and phenolics in this fraction were 0.286 g/g and 0.518 g/g by colorimetry. Six compounds, including salicylic acid, kaempferol, quercetin, tiliroside, quercetin 3-O-β-d-glucopyranoside and kaempferol 3-O-β-d-glucopyranoside, were isolated from the active fraction. Among them, kaempferol, quercetin and tiliroside obviously delayed plasma recalcification time (PRT) in blood.     

Identification of phenolic antioxidants from Sword Brake fern (Pteris ensiformis Burm.)

Sword Brake fern (Pteris ensiformis Burm.) is one of the most common ingredients of traditional herbal drinks in Taiwan. In an effort to identify antioxidants from the aqueous extract of Sword Brake fern (SBF), the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity-guided isolation was employed. Three new compounds, kaempferol 3-O-α-l-rhamnopyranoside-7-O-[α-d-apiofuranosyl-(1-2)-β-d-glucopyranoside] (1), 7-O-caffeoylhydroxymaltol 3-O-β-d-glucopyranoside (3) and hispidin 4-O-β-d-glucopyranoside (4), together with five known compounds, kaempferol 3-O-α-l-rhamnopyranosid-7-O-β-d-glucopyranoside (2), caffeic acid (5), 5-O-caffeoylquinic acid (6), 3,5-di-O-caffeoylquinic acid (7) and 4,5-di-O-caffeoylquinic acid (8) were isolated and determined on the basis of spectroscopic analyses. HPLC with UV detector was further employed to analyze the content of each compound in SBF based on the retention time by comparison with isolated pure compounds. It was found that the most abundant phenolic compound was compound 3, followed by compounds 7 and 4. The di-O-caffeoylquinic acids (7 and 8) have the strongest DPPH scavenging potential with IC₅₀ around 10 μM and the highest Trolox equivalent antioxidant capacity (TEAC) about 2 mM. This data indicates that SBF is rich in phenolic antioxidants.     

Identification of antioxidants from rhizome of Davallia solida

Davallia solida rhizome has long been used as an herb tonic to treat osteoporosis, arthralgia, and arthritis. The aqueous extract of D. solida rhizome contains a high content of phenolic compounds [210.8 ± 4.6 mg catechin equivalents (CE)/g dry weight] and shows a strong 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging activity (IC₅₀ = 15.93 ± 1.21 μg dry weight/ml). Further solvent partition of the aqueous extract yielded chloroform, n-butanol, and water layers. Among them, n-butanol layer has the highest phenol content (806.3 ± 12.3 mg CE/g dry weight) and DPPH scavenging potential (IC₅₀ = 3.93 ± 0.31 μg dry weight/ml). Isolation and purification from the n-butanol layer identified 12 compounds. They included four new compounds: 3′-O-p-hydroxybenzoylmangiferin (1), 4′-O-p-hydroxybenzoylmangiferin (2), 6′-O-p-hydroxybenzoylmangiferin (3), and 3-O-p-hydroxybenzoylmangiferin (4); as well as eight known compounds: mangiferin (5), 2-C-β-d-xylopyranosyl-1,3,6,7-tetrahydroxyxanthone (6), 4β-carboxymethyl-(−)-epicatechin (7), 4β-carboxymethyl-(−)-epicatechin methyl ester (8), eriodictyol (9), eriodictyol-8-C-β-d-glucopyranoside (10), icariside E₅ (11), and icariside E₃ (12). DPPH scavenging and Trolox equivalent antioxidant capacity (TEAC) analyses revealed that the most potent antioxidants are 1, 2, and 3, which exerted more than triple activity as compared with the positive controls, α-tocopherol and Trolox.     

Novel acetylated flavonoid glycosides from the leaves of Allium ursinum

Seven flavonoid glycosides, kaempferol 3-O-α-L-rhamnopyranosyl (1→2)-[3-O-acetyl]-β-D-glucopyranoside (1), kaempferol 3-O-α-L-rhamnopyronosyl (1→2)-[6-O-acetyl]-β-D-glucopyranoside (2), kaempferol 3-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside (3), kaempferol 3-O-β-D-glucopyranoside (4), kaempferol 3,7-di-O-β-D-glucopyranoside (5), 7-O-β-D-glucopyranosyl kaempferol 3-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside (6), kaempferol 3-O-α-L-rhamnopyranosyl (1→2)-β-D-glucopyranoside-7-O-[2-O-(trans-p-coumaroyl)]-β-D-glucopyranoside (7) were isolated from the n-butanol fraction of Allium ursinum L. and the structures of these compounds were elucidated on the basis of mass spectrometry, ¹H NMR, ¹³C NMR, HMQC and HMBC data. Among them, 1 and 2 are novel compounds and compounds 4 and 5 were isolated from this plant species for the first time.     

Synthesis of potentially-bioactive lactosyl-oligofructosides by a novel bi-enzymatic system using bacterial fructansucrases

Efficient enzymatic synthesis of lactosyl-oligofructosides (LFOS) with a degree of polymerization from 4 to 8 was achieved in the presence of sucrose:lactosucrose and sucrose:lactose mixtures by transfructosylation reaction. The main synthesized LFOS which consist of β-2,1-linked fructose to lactosucrose: β-d-galactopyranosyl-(1 → 4)-α-d-glucopyranosyl-[(1 → 2)-β-d-fructofuranosyl]n-(1 → 2)-β-d-fructofuranoside (where n refers to the number of transferred fructose moieties) was structurally characterized by nuclear magnetic resonance (NMR). The maximum formation of LFOS was 81% (in weight with respect to the initial amount of lactosucrose) and was obtained after 24 h of transfructosylation reaction based on sucrose:lactosucrose (250 g L^− 1 each) catalyzed by an inulosucrase from Lactobacillus gasseri DSM 20604 (IS). The production of LFOS in the presence of sucrose:lactose mixtures required a previous high-yield lactosucrose synthesis step catalyzed by using a levansucrase from Bacillus subtilis CECT 39 (LS) before the inulosucrase-catalyzed reaction. This novel one-pot bi-enzymatic system led to the synthesis of about 22% LFOS in weight, with respect to the initial amount of lactose (250 g L^− 1). The results revealed a high specificity for the substrate involved in the inulosucrase-catalyzed reaction given that, although lactosucrose (O-β-d-galactopyranosyl-(1 → 4)-O-α-d-glucopyranosyl-(1 → 2)-β-d-fructofuranoside) acted as a strong acceptor of β-2,1-linked fructose, lactose (β-d-galactopyranosyl-(1 → 4)-α-d-glucose) was found to be an extremely weak acceptor.     

Structural investigation of a novel fucoglucogalactan isolated from the fruiting bodies of the fungus Hericium erinaceus

A new heteropolysaccharide with a molecular weight of 1.94 × 10⁴ Da, HEPF1, was isolated from the fruiting bodies of Hericium erinaceus. It is composed of fucose, galactose and glucose in the ratio of 1:4:1, as well as a minor proportion of 3-O-methyl rhamnose. Sugar analyses, methylation analysis, together with ¹H and ¹³C NMR spectroscopy established that HEPF1 has a (1 → 6)-linked α-d-galactopyranosyl backbone with branches that are composed of fucose attached to O-2; it also contains 6-O-substituted-β-d-oligoglucosyl units and a minor terminal 3-O-methyl rhamnose residue.     

Spirostane,furostane and cholestane saponins from Persian leek with antifungal activity

A phytochemical investigation of the seeds of Persian leek afforded the isolation of two new spirostane glycosides, persicosides A (1) and B (2), four new furostane glycosides, isolated as a couple of inseparable mixture, persicosides C1/C2 (3a/3b) and D1/D2 (4a/4b), one cholestane glycoside, persicoside E (5), together with the furostane glycosides ceposides A1/A2 and C1/C2 (6a/6b and 7a/7b), tropeosides A1/A2 and B1/B2 (8a/8b and 9a/9b), and ascalonicoside A1/A2 (10a/10b), already described in white onion, red Tropea onion, and shallot, respectively. Structure elucidation of the compounds was carried out by comprehensive spectroscopic analyses, including 2D NMR spectroscopy and MS spectrometry, and by chemical evidences. The chemical structure of new compounds were identified as (25S)-spirostan-2α,3β,6β-triol 3-O-[β-d-glucopyranosyl-(1 → 3)] [β-d-xylopyranosyl-(1 → 2)]-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranoside (1), (25S)-spirostan-2α,3β,6β-triol 3-O-[β-d-xylopyranosyl-(1 → 3)] [α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranosyl-(1 → 4)-O-β-d-galactopyranoside (2), furosta-1β,3β,22ξ,26-tetraol 5-en 1-O-β-d-glucopyranosyl (1 → 3)-β-d-glucopyranosyl (1 → 2)-β-d-galactopyranosyl 26-O-α-l-rhamnopyranosyl (1 → 2)-β-d-galactopyranoside (3a,3b), furosta-2α,3β,22ξ,26-tetraol 3-O-β-d-glucopyranosyl (1 → 3)-β-d-glucopyranosyl (1 → 2)-β-d-galactopyranosyl 26-O-β-d-glucopyranoside (4a,4b), (22S)-cholesta-1β,3β,16β,22β-tetraol 5-en 1-O-α-l-rhamnopyranosyl 16-O-α-l-rhamnopyranosyl (1 → 2)-β-d-galactopyranoside (5).