Acylated anthocyanins from red radish (Raphanus sativus L.)

Twelve acylated anthocyanins were isolated from the red radish (Raphanus sativus L.) and their structures were determined by spectroscopic analyses. Six of these were identified as pelargonidin 3-O-[6-O-(E)-feruloyl-2-O-beta-D-glucopyranosyl]-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-caffeoyl-2-O-(6-(E)-feruloyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-p-coumaroyl-2-O-(6-(E)-caffeoyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-feruloyl-2-O-(6-(E)-caffeoyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-p-coumaroyl-2-O-(6-(E)-feruloyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), and pelargonidin 3-O-[6-O-(E)-feruloyl-2-O-(2-(E)-feruloyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside).     

Bioactive flavonoids and saponins from Climacoptera obtusifolia

Two bidesmosidic saponins were isolated from Climacoptera obtusifolia (Chenopodiaceae) and their structures were determined as gypsogenin 3-O-[beta-D-xylopyranosyl-(1-->3)-beta-D-glucopyranoside]-28-O-{beta-D-glucopyranosyl} ester (1) and hederagenin 3-O-[beta-D-xylopyranosyl-(1-->3)-beta-D-glucopyranoside]-28-O-[beta-D-glucopyranosyl} ester (2), by spectroscopic methods. Two known compounds, isorhamnetin 3-O-beta-D-glucopyranoside (3), and isorhamnetin 3-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (4) were also isolated for the first time from this plant. Compounds 1-4 were tested in various immunomodulatory assays. Compound 2 suppressed (92%) the reactive oxygen species (ROS) production on mononuclear cells in luminol-based chemiluminescence (CL) assay at a higher concentration (50 microg/mL). Compounds 3 and 4 demonstrated a strong inhibition on ROS production in the oxidative burst activity of whole blood, neutrophils, and mononuclear cells. Additionally compounds 3 and 4 also suppressed PHA T-cell proliferation with no cytotoxic effects.     

Flavonoid and phenolic glycosides from Salvia officinalis

Two novel phenolic glycosides cis-p-coumaric acid 4-O-(2'-O-beta-D-apiofuranosyl)-beta-D-glucopyranoside and trans-p-coumaric acid 4-O-(2'-O-beta-D-apiofuranosyl)-beta-D-glucopyranoside were isolated and identified from Salvia officinalis together with 4-hydroxyacetophenone 4-O-(6'-O-beta-D-apiofuranosyl)-beta-D-glucopyranoside, luteolin 7-O-beta-D-glucoside, 7- and 3'-O-beta-D-glucuronide, 6-hydroxyluteolin 7-O-beta-D-glucoside and 7-O-glucuronide, and 6,8-di-C-beta-D-glucosylapigenin (vicenin-2). The luteolin glucuronides and vicenin-2 were identified as new sage constituents.     

Phenolic glycosides from Kaempferia parviflora

Three phenolic glycosides were isolated together with two known flavonol glycosides from the H2O-soluble fraction of rhizomes of Kaempferia parviflora. Their structures were determined to be rel-(5aS,10bS)-5a,10b-dihydro-1,3,5a,9-tetrahydroxy-8-methoxy-6H-benz[b]indeno[1,2-d]furan-6-one 5a-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-d-glucopyranoside] (1), its rel-5aS,10bR isomer (2), and (2R,3S,4S)-3-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-d-glucopyranosyl]-3'-O-methyl-ent-epicatechin-(2alpha-->O-->3,4alpha-->4)-(5aS,10bS)-5a,10b-dihydro-1,3,5a,9-tetrahydroxy-8-methoxy-6H-benz[b]indeno[1,2-d]furan-6-one 5a-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside] (3). The structures were elucidated on the basis of analyses of chemical and spectroscopic evidence.     

Anti-inflammatory and antinociceptive activity of flavonoids isolated from Viscum album ssp. album

Viscum album L. has been used in the indigenous systems of medicine for treatment of headache and some inflammatory diseases. In order to evaluate this information, antinociceptive and anti-inflammatory activities of the five flavonoids (5,7-dimethoxy naringenin or 4',6'-dimethoxy chalcononaringenin) derivatives, isolated from the ethyl acetate fraction of the extract from V. album ssp. album, were investigated, namely 5,7-dimethoxy-flavanone-4'-O-beta-D-glucopyranoside (1), 2'-hydroxy-4',6'-dimethoxy-chalcone-4-O-beta-D-glucopyranoside (2), 5,7-dimethoxy-flavanone-4'-O-[2"-O-(5"'-O-trans-cinnamoyl)-beta-D-apiofuranosyl]-beta-D-glucopyranoside (3), 2'-hydroxy-4',6'-dimethoxy-chalcone-4-O-[2"-O-(5"'-O-trans-cinnamoyl)-beta-Dapiofuranosyl]-beta-D-glucopyranoside (4), 5,7-dimethoxy-flavanone-4'-O-[beta-D-apiofuranosyl-(1 --> 2)]-beta-D-glucopyranoside (5). For the antinociceptive activity assessment the p-benzoquinone-induced writhing test and for the anti-inflammatory activity the carrageenan-induced hind paw edema model in mice were used. The ethyl acetate fraction in a dose of 250 mg/kg as well as compounds 2 and 5 in a 30 mg/kg dose were shown to possess remarkable antinociceptive and anti-inflammatory activities per os without inducing any apparent acute toxicity as well as gastric damage.     

Acylated flavonol glycosides as probing stimulants of a bean aphid,Megoura crassicauda,from Vicia angustifolia

A bean aphid, Megoura crassicauda, which feeds selectively on the plant genus Vicia (Fabaceae), was found to be stimulated to probe an extract solution of the host plant, narrowleaf vetch, Vicia angustifolia L., depositing characteristic stylet sheaths on a parafilm membrane. Two acylated flavonol glycosides were isolated as the specific probing stimulants from the extracts and characterized as quercetin 3-O-alpha-L-arabinopyranosyl-(1-->6)-[2"-O-(E)-p-coumaroyl]-beta-D-glucopyranoside and quercetin 3-O-alpha-L-arabinopyranosyl-(1-->6)-[2"-O-(E)-p-coumaroyl]-beta-D-galactopyranoside. A mixture of these compounds in the same equivalency strongly induced the probing response from M. crassicauda, suggesting their kairomonal roles during host recognition.     

Steroidal saponins from the fruits of Asparagus racemosus

Three steroidal saponins, racemosides A (1), B (2) and C (3), were isolated from the methanolic extract of the fruits of Asparagus racemosus, and characterized as (25S)-5beta-spirostan-3beta-ol-3-O-{beta-D- glucopyranosyl (1-->6)-[alpha-L-rhamnopyranosyl (1-->6)-beta-D-glucopyranosyl (1-->4)]-beta-D-glucopyranoside}, (25S)-5beta-spirostan-3beta-ol-3-O-alpha-L-rhamnopyranosyl (1-->6)-beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranoside and (25S)-5beta-spirostan-3beta-ol-3-O-{alpha-L-rhamnopyranosyl-(1-->6)-[alpha-L-rhamnopyranosyl (1-->4)]-beta-D-glucopyranoside}, respectively, by spectrometric analysis and some chemical strategies.     

Biologically active phenols from Saussurea medusa

Sixteen phenolic compounds were isolated from the polar fraction of Saussurea medusa and were structurally elucidated by chemical evidences and spectral methods. These compounds include two new lignan glucosides, namely medusasides A (1) and B (2), and fourteen known phenolic compounds (3-16). One major compound, apigenin 7-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside] (6) showed remarkable activity to attenuate the scopolamine induced memory deficit of mice. Compound 6 and another major one, quercetin (8) also exhibited moderate cell protecting activities against hydrogen peroxide (H(2)O(2)) induced PC12 cell damage.     

Flavonoids from seeds of Camellia semiserrata Chi. and their estrogenic activity

Two new flavonol glycosides and three known flavonoids were isolated from seeds of Camellia semiserrata Chi. The structures of these new flavonol glycosides were established as kaempferol 3-O-[(2',3',4'-triacetyl)-alpha-L-rhamnopyranosyl(1-->3)(2',4'-diacetyl)-alpha-L-rhamnopyranosyl (1-->6)-beta-D-glucopyranoside] and kaempferol 3-O-[(3',4'-diacetyl)-alpha-L-rhamnopyranosyl(1-->3)(2',4'-diacetyl)-alpha-L-rhamnopyranosyl(1-->6)-beta-D-glucopyranoside] by spectroscopic methods. The estrogenic activity of these compounds was investigated by a recombinant yeast screening assay.     

Isoflavonoid glycosides from Dalbergia sissoo.

Two isoflavone glycosides, biochanin A 7-O-[beta-D-apiofuranosyl-(1-->5)-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside] and tectorigenin 7-O-[beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside], were isolated from Dalbergia sissoo. Their structures were elucidated on the basis of spectral and chemical evidence.     

In vivo anti-inflammatory and antinociceptive activity evaluation of phenolic compounds from Sideritis stricta

An acetone extract obtained from aerial parts of S. stricta Boiss. & Heldr. apud Bentham, its fractions and phenolic compounds were investigated for their in vivo anti-inflammatory and antinociceptive activities. For the anti-inflammatory activity and for the antinociceptive activity assessment, carrageenan-induced hind paw edema and p-benzoquinone-induced abdominal constriction tests were used, respectively. The acetone extract of the plant and its phenolic fraction exhibited potent inhibitory activity against both bioassay models in mice. From the active phenolic fraction a well-known phenylethanoid glycoside, verbascoside (acteoside) (1), and two flavonoid glycosides, isoscutellarein 7-O-[6"'-O-acetyl-beta-D-allopyranosyl-(1-->2)]-beta-D-glucopyranoside (2) and isoscutellarein 7-O-[6"'-O-acetyl-beta-D-allopyranosyl-(1-->2)]-6"-O-acetyl-beta-D-glucopyranoside (3), were isolated. During phytochemical studies we also isolated a methoxyflavone, xanthomicrol (4), from the non-polar fraction. The structures of the isolated compounds were established by spectroscopic evidence (UV, IR, 1D- and 2D-NMR, MS). Although antinociceptive and anti-inflammatory activities of the phenolic components were found not significant in the statistical analysis, compounds 1 to 3 showed a notable activity without inducing any apparent acute toxicity as well as gastric damage. Furthermore, a mixture of flavonoid glycosides (2 + 3) exhibited a significant inhibitory effect in both models at a higher dose.     

Acylated anthocyanins from the violet-blue flowers of Orychophragonus violaceus

Three acylated cyanidin 3-sambubioside-5-glucosides (1-3) were isolated from the violet-blue flowers of Orychophragonus violaceus, and their structures were determined by chemical and spectroscopic methods. Two of those acylated anthocyanins (1 and 3) were cyanidin 3-O-[2-O-(2-O-(4-O-(6-O-(4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-xylopyranosyl)-6-O-(4-O-(beta-D-glucopyranosyl)-trans-acyl)-beta-D-glucopyranoside]-5-O-(6-O-malonyl-beta-D-glucopyranoside)s, in which the acyl groups were p-coumaric acid for 1, and sinapic acid for 3, respectively. The last anthocyanin 2 was cyanidin 3-O-[2-O-(2-O-(4-O-(6-O-(4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-xylopyranosyl)-6-O-(4-O-(beta-D-glucopyranosyl)-trans-feruloyl)-beta-D-glucopyranoside]-5-O-beta-D-glucopyranoside. In these flowers, the anthocyanins 2 and 3 were present as dominant pigments, and 1 was obtained in rather small amounts.     

Acylated delphinidin 3-rutinoside-5-glucosides in the flowers of Petunia reitzii

Two acylated anthocyanins were isolated from selected individuals of Petunia reitzii, and identified to be delphinidin 3-O-[6-O-(4-O-(4-O-(6-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-tr ans-p-coumaroyl)-alpha-L-rhamnopyranosyl)-beta-D-glucopyranoside]- 5-O-[beta-D-glucopyranoside] and delphinidin 3-O-[6-O-(4-O-(4-O-(beta-D-glucopyranosyl)-trans-p-coumaroyl)-alph a-L-rhamnopyranosyl)-beta-D-glucopyranoside]-5-O-[beta-D-glucopyranoside ]. Nine known anthocyanins were also identified.     

Acylated peonidin glycosides from duskish mutant flowers of Ipomoea nil

Five acylated peonidin glycosides were isolated from the pale gray-purple flowers of a duskish mutant in the Japanese morning glory (Ipomoea nil or Pharbitis nil) as major pigments, along with a known anthocyanin, Heavenly Blue Anthocyanin (HBA). Three of these were based on peonidin 3-sophoroside and two on peonidin 3-sophoroside-5-glucoside as their deacylanthocyanins; both deacylanthocyanins were acylated with caffeic acid and/or glucosylcaffeic acids. By spectroscopic and chemical methods, the structures of the former three pigments were determined to be 3-O-[2-O-(6-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-beta-D-glucopyranoside], 3-O-[2-O-(6-O-(3-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-6-O-(4-O-(6-O-(3-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-glucopyranoside], and 3-O-[2-O-(6-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-6-O-(4-O-(6-O-(3-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranoside] of peonidin. The structures of the latter two pigments were also confirmed as 3-O-[2-O-(6-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-beta-D-glucopyranoside]-5-O-beta-D-glucopyranoside, and 3-O-[2-O-(6-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-6-O-(4-O-(6-O-(3-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranoside]-5-O-beta-D-glucopyranoside of peonidin. The mutation affecting glycosylation and acylation in anthocyanin biosynthesis of Japanese morning glory was discussed.     

Spirostanol saponins of Allium porrum L.

An investigation of the extracts from bulbs of Allium porrum L. has led to the isolation of four spirostanol saponins. Two of them are new compounds and have been identified as: (25R)-5 alpha-spirostan-3 beta, 6 beta-diol 3-O-{O-beta-D-glucopyranosyl-(1-->2)-O-[beta-D-xylopyranosyl-(1-->3)]-O- beta -D-glucopyranosyl-(1-->4)-beta-D-galactopyranoside} (3) and (25R)-5 alpha-spirostan-3 beta,6 beta-diol 3-O-{O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->2)-O- [beta-D-xylopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D- galactopyranoside} (4). The isolated compounds were evaluated for their antifungal activity.     

The flavonoids of leek, Allium porrum

A phytochemical investigation of the extracts obtained from bulbs of leek. Allium porrum L. has led to the isolation of five flavonoid glycosides based on the kaempferol aglycone. Two of them are new compounds and have been identified as kaempferol 3-O-[2-O-(trans-3-methoxy-4-hydroxycinnamoyl)-beta-D-galactopyranosyl]-(1-->4)-O-beta-D-glucopyranoside, and kaempferol 3-O-[2-O-(trans-3-methoxy-4-hydroxycinnamoyl)-beta-D-glucopyranosyl]-(1-->6)-O-beta-D-glucopyranoside, on the basis of spectroscopic methods, including 2D NMR. The isolated compounds have been evaluated for their human platelet anti-aggregation activity.     

Modulation of sodium pumps by steroidal saponins

Costus spicatus, used in Brazilian traditional medicine to expel kidney stones, contains steroidal saponins with different chemical characteristics. In spite of its popular utilization as potent diuretic, no scientific reports correlate this activity with the chemical constituents of the extract. Therefore, two steroidal saponins (3 beta,22 alpha,25R)-26-(beta-D-glucopyranosyloxy)-2-methoxyfurost-5-en-3-yl O-D-apio-beta-D-furanosyl-(1-->2)-O-[6-deoxy-alpha-L-mannopyranosyl-(1-->4)]-beta-D-glucopyranoside (1) and (3 beta,22 alpha,25R)-spirostan-3-yl O-D-apio-beta-D-furanosyl-(1-->2)-O-[6-deoxy-alpha-L-mannopyranosyl-(1-->4)]-beta-D-glucopyranoside (1a), were isolated from the rhizomes of this plant and their effects on the Na+-ATPase and (Na+ + K+)-ATPase activities of the proximal tubule from pig kidney were evaluated. It was observed that 1 and 1a inhibit specifically the Na+-ATPase activity.     

Acylated pelargonidin glycosides in the red-purple flowers of Pharbitis nil.

Four acylated pelargonidin glycosides and pelargonidin 3-sophoroside-5-glucoside were isolated from 23 red-purple cultivars of Pharbitis nil. The acylated anthocyanins were all based on pelargonidin 3-sophoroside-5-glucoside and were identified as the 3-O-[2-O-(beta-D-glucopyranosyl)-6-O-(trans-caffeyl)-beta-D- glucopyranoside]-5-O-(beta-D-glucopyranoside), the 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta- D-glucopyranosyl)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), the 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta- D-glucopyranosyl)-6-O-(trans-caffeyl)-beta-D-glucopyranoside]-5-O-(beta- D-glucopyranoside); and the 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta-D- glucopyranosyl)-6-O-(trans-4-O-(6-O-(trans-3-O-(beta-D- glucopyranosyl)caffeyl)- beta-D-glucopyranosyl)caffeyl)-beta-D-glucopyranoside]-5-O-(beta-D- glucopyranoside). By the analysis of these anthocyanin constituents variously in 23 cultivars, it was found that the red flower colour gradually changed into more bluish colour with increasing numbers of caffeic acid residues in the acylated pelargonidin glycosides. The stabilities of these anthocyanins increased in the order of increasing caffeyl substitution.     

Triterpenoid saponins from the stem bark of Elattostachys apetala

Six new triterpenoid saponins have been isolated from the stem bark of Elattostachys apetala together with four known triterpenoid saponins. Three of these new compounds are glycosides of a newly described genin, 29-hydroxyhederagenin (1). On the basis of spectral evidence, the structures of the new saponins were concluded to be alpha-hederin 28-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl] ester (2), sapindoside B 28-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl] ester (3), 3-O-beta-D-xylopyranosyl astrantiasaponin VII (4), 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]-28-O-[beta-D-glucopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranosyl]-29-hydroxyhederagenin (5), 3-O-[alpha-L-arabinopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]-28-O-[beta-D-glucopyranosyl(1-->2)-[beta-D-glucopyranosyl(1-->6)]-beta-D-glucopyranosyl]-29-hydroxyhederagenin (6), and 3-O-[beta-D-xylopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]-28-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-gluco pyranosyl-(1-->6)]-beta-D-glucopyranosyl]-29-hydroxyhederagenin (7).     

Newbouldiosides A-C, phenylethanoid glycosides from the stem bark of Newbouldia laevis

From the stem bark of Newbouldia laevis three phenylethanoid glycosides, designated as newbouldioside A-C, were isolated together with a sodium salt of analogue B and the known compounds, verbascoside, 5-hydroxydehydro-iso-alpha-lapachone, 3,8-dihydroxydehydro-iso-alpha-lapachone, apigenin and luteolin. The structures of the phenylethanoid glycosides were elucidated by spectroscopic methods as beta-(3,4-dihydroxyphenyl)ethyl 5-O-syringoyl-beta-D-apiofuranosyloxy-(1-->2)-O-[alpha-L-rhamnopyranosyl-(1-->3)]-beta-D-glucopyranoside, ss-(3,4-dihydroxyphenyl)ethyl 5-O-syringoyl-beta-D-apiofuranosyloxy-(1-->2)-O-[alpha-L-rhamnopyranosyl-(1-->3)]-6-O-E-feruloyl-beta-D-glucopyranoside, and beta-(3,4-dihydroxyphenyl)ethyl 3-O-E-feruloyl-beta-D-apiofuranosyloxy-(1-->2)-O-alpha-L-rhamnopyranosyl-(1-->2)-6-O-E-sinapoyl-beta-D-glucopyranoside, respectively.