Polymorphism for novel tetraglycosylated flavonols in an Eco-model crucifer, Barbarea vulgaris.

Nineteen apparent flavonoids were determined by HPLC-DAD in foliage of a chemotype (G-type) of Barbarea vulgaris , and four were isolated. Two were novel tetraglycosylated flavonols with identical glycosylation patterns, kaempferol 3-O-(2,6-di-O-ß-d-glucopyranosyl)-ß-d-glucopyranoside-7-O-α-l-rhamnopyranoside (1) and quercetin 3-O-(2,6-di-O-ß-d-glucopyranosyl)-ß-d-glucopyranoside-7-O-α-l-rhamnopyranoside (2). The identification of d/l configuration was tentatively based on susceptibility to α-l-rhamnosidase and ß-d-glucosidases. A characteristic feature of 1 and 2 was appreciable water solubility, an expected consequence of the extensive glycosylation. A less complex pair of flavonols comprised 3-O-ß-d-glucopyranoside-7-O-α-l-rhamnopyranosides of kaempferol and quercetin. Two natural chemotypes of B. vulgaris differed in levels of 1 and 2, with the P-type deficient in 1 and 2 and the insect-resistant G-type rich in 1 (ca. 3-4 µmol/g dry wt) and with moderate levels of 2 (ca. 0.3-0.8 µmol/g dry wt). However, there was only modest seasonal variation in flavonols 1 and 2, in contrast to a strong seasonal variation in insect resistance.

Synergistic antioxidative effects of alkamides, caffeic acid derivatives, and polysaccharide fractions from Echinacea purpurea on in vitro oxidation of human low-density lipoproteins.

Preparations of Echinacea are widely used as alternative remedies to prevent the common cold and infections in the upper respiratory tract. After extraction, fractionation, and isolation, the antioxidant activity of three extracts, one alkamide fraction, four polysaccharide-containing fractions, and three caffeic acid derivatives from Echinacea purpurea root was evaluated by measuring their inhibition of in vitro Cu(II)-catalyzed oxidation of human low-density lipoprotein (LDL). The antioxidant activities of the isolated caffeic acid derivatives were compared to those of echinacoside, caffeic acid, and rosmarinic acid for reference. The order of antioxidant activity of the tested substances was cichoric acid > echinacoside > or = derivative II > or = caffeic acid > or = rosmarinic acid > derivative I. Among the extracts the 80% aqueous ethanolic extract exhibited a 10 times longer lag phase prolongation (LPP) than the 50% ethanolic extract, which in turn exhibited a longer LPP than the water extract. Following ion-exchange chromatography of the water extract, the majority of its antioxidant activity was found in the latest eluted fraction (H2O-acidic 3). The antioxidant activity of the tested Echinacea extracts, fractions, and isolated compounds was dose dependent. Synergistic antioxidant effects of Echinacea constituents were found when cichoric acid (major caffeic acid derivative in E. purpurea) or echinacoside (major caffeic acid derivative in Echinacea pallida and Echinacea angustifolia) were combined with a natural mixture of alkamides and/or a water extract containing the high molecular weight compounds. This contributes to the hypothesis that the physiologically beneficial effects of Echinacea are exerted by the multitude of constituents present in the preparations.