Flavonoid glycoside accumulation trends of Achillea nobilis L. and related species

More than 50 collections of five species forming the Achillea nobilis group were analysed for their leaf flavonoid complement. Major accumulation trends were found to be C-glycosylflavones and flavonol 3-O-glycosides. The most common pattern consisted of the C-8-glycosylfiavones (vitexin and orientin), the C-6-glycosylflavone (isoörientin) together with minor amounts of di-C-glycosylapigenins and quercetin 3-O-glycosides. Additionally, C-6-glycosylflavones (isovitexin) and their 7-methyl ethers swertisin and swertiajaponin were sporadically accumulated, characterizing particularly two subspecies of A. nobilis. Whereas C-glycosylflavone dominated profiles were typical of most species, two taxa exhibited a flavonol dominated profile (A. ligustica; A. virescens p.p.). Regarding the infraspecific and interpopulational variations of flavonoid accumulation trends, their systematic and ecological significance is briefly discussed.     

Distribution of charged flavones and caffeylshikimic acid in Palmae

Identification of the phenolic constituents in flowers of nine palm species has revealed that charged C-glycosylflavones and caffeylshikimic acid are characteristically present. Flavonol glycosides are also common; the 3-glucosides, 3-rutinosides and 3,4′-diglucosides of quercetin and isorhamnetin and the 7-glucoside and 3,7-diglucoside of quercetin are all variously present. Tricin 7-glucoside, luteolin 7-rutinoside and several unchanged C-glycosylflavones were also detected. Male flowers of Phoenix canariensis differ from female flowers in having flavonol glycosides. As expected, in most species studied, flavonoid patterns in the flowers vary considerably from those found in the leaves.     

Flavonoid pattern and systematics of the genus Leucocyclus

The flavonoid pattern of the monotypic Turkish genus Leucocyclus consists of C-glycosylflavones (isovitexin; isoorientin and derivatives; several di-C-glycosylapigenins; schaftoside, isoschaftoside and vicenin-3; lucenin-2), of flavonol 3-O-glycosides (quercetin and kaempferol 3-O-rhamnoglucoside) and trace amounts of luteolin 7-O-rhamnoglucoside. The systematic significance of the flavonoid diversification within Leucocyclus as well as possible relationships to other genera of the Anthemideae are discussed.     

Flavonoids variation in seven tetraploid populations of Dactylis glomerata

133 individual plants representing seven tetraploid populations of Dactytis glomerata were examined for their flavonoid pattern by using HPLC. The chemical results expressed quantitatively as peak heights were submitted to multivariate analysis. This data treatment suggested an obvious discrimination between Eurasian and Mediterranean types, lending support to the taxonomic status of the species. This segregation is based on the distribution of C-glycosylluteolins and methylated derivatives. Moreover among the Mediterranean collections, a Coraica population was conspicuously separated from the other three in regard to the distributionof di-C-glycosylflavones. This chemical approach was compared with an electrophoretic assay concerning seven enzyme systems; their respective conclusions were in good agreement.     

The flavonoids of phragmites australis flowers

The major flavonoid constituents of Phragmites australis flowers are the C-glycosylflavones swertiajaponin, isoswertiajaponin and two new O-glycosides, the 3′-O-gentiobioside and the 3′-O-glucoside of swertiajaponin. Two unusual flavonol glycosides, rhamnetin 3-O-rutinoside and rhamnetin 3-O-glucoside, were also characterized from the same tissue.     

Flavonoids of gaura triangulata

Ten flavonoids were obtained from Gaura triangulata including luteolin and luteolin 7-glycoside derivatives which are atypical for the family Onagraceae. Apigenin-based C-glycosylflavones, previously reported from the Onagraceae in the monogeneric tribe Circaeeae, have also been identified. The flavonoid profile of G. triangulata is distinctive for the family since previous studies of the Onagraceae reported primarily flavonols.     

Flavonoids as taxonomic markers in old world Lupinus species

In a leaf survey of 54 specimens of 11 Old World Lupinus species three classes of flavonoids were detected: flavones (in 82%), flavonols (in 36%) and flavone C-glycosides (in 55%). The rough-seeded species were clearly distinguished from the smooth-seeded taxa by the presence of a novel 2′-hydroxyflavone, luteolin and flavone C-glycosides as major leaf constituents and by the absence of flavonols. Within the smooth-seeded species, there are three flavonoid patterns: (a) flavonols only, L. albus; (b) flavones and flavonols, L. luteus, L. hispanicus and L. angustifolius; and (c) flavones only, L. micranthus. L. angustifolius further differed in uniquely producing diosmetin as a major leaf constituent. These divisions coincide exactly with previous groupings based on alkaloidal and morphological data. Amongst the 12 samples of L. angustifolius three chemical races were distinguished and a number of diosmetin glucoside malate esters detected. The flower flavonoid aglycone patterns of the nine Old World species surveyed differed markedly from the corresponding leaf profiles by the presence of flavones: luteolin and apigenin in eight and chrysoeriol in seven species as major constituents, while flavone C-glycosides were found only in trace amount in three species. In a leaf flavonoid survey of 13 representative New World Lupinus taxa, glycoflavones were major leaf components, a variety of methylated flavones were identified and flavonols were absent. The presence of the novel 2′-hydroxyflavone in five New World species may indicate some evolutionary link with the rough seeded taxa of the Old World.     

Flavonoids and xanthones from the leaves of Amorphophallus titanum (Araceae)

The flavonoids and xanthones in the leaves of Amorphophallus titanum, which has the largest inflorescence among all Araceous species, were surveyed. Eight C-glycosylflavones, five flavonols, one flavone O-glycoside and two xanthones were isolated and characterized as vitexin, isovitexin, orientin, isoorientin, schaftoside, isoschaftoside, vicenin-2 and lucenin-2 (C-glycosylflavones), kaempferol 3-O-robinobioside, 3-O-rutinoside and 3-O-rhamnosylarabinoside, and quercetin 3-O-robinobioside and 3-O-rutinoside (flavonols), luteolin 7-O-glucoside (flavone), and mangiferin and isomangiferin (xanthones). Although the inflorescence of this species has been surveyed for flavonoids, those of the leaves were reported for the first time.     

Leaf flavonoids from Croton urucurana and C. floribundus (Euphorbiaceae)

Flavonoids were isolated by PVPP column chromatography of leaf extracts of Croton floribundus Spreng and C. urucurana Baill. and identified by NMR and co-chromatography with standards. The two species revealed highly distinct flavonoid profiles. C. urucurana, belonging to the phylogenetically basal section Cyclostigma, yielded the flavone C-glycosides vitexin and orientin, quercetin and the O-glycosides quercetin 7-O-rhamnoside, rhamnitrin and rutin, in addition to tiliroside. Instead, C. floribundus, from the more derived section Lasiogyne, yielded no C-glycosides, but a high diversity of classes of flavonols, including kaempferol, three flavonol O-methyl ethers, isoquercitrin, three tri-O-galactosides, in addition to tiliroside and an isorhamnetin-coumaroyl-O-glycoside. The present work is the first report for Croton of two rhamnosides (isolated from C. urucurana). It is also the first report for Euphorbiaceae of two tri-O-glycosides obtained from C. floribundus. The distribution of flavonoids in the two species as determined by HPLC-DAD of extracts of small leaf samples of herbarium specimens is highly similar with the profiles resulting from isolation of compounds from bulky leaf samples. Differences among specimens of the same species were restricted to relative proportions of individual constituents. The results indicate that flavonoid profiles are effective to characterize and distinguish the two species. The present results, combined with literature data, supports the condition of tiliroside as a marker of Croton and the hypothesis of an evolutionary trend in the genus toward the loss of C-glycosides and a progressive complexity of flavonoid profiles.     

Structural determination of C-glycosylflavones by mass spectrometry of their permethyl ethers: O-glycosyl-6-C-glycosylflavones

Permethylated O-glycosyl-C-glycosylflavones give well defined MS including an important molecular peak. Permethyl 6-C-glycosylflavones O-glycosylated on a phenolic hydroxyl group are easily distinguished from the isomeric permethyl 6-C-diholosylflavones. In both types, the position of the O-glycosidic bond can be deduced from the MS, eventually after acid hydrolysis. 2″-O-glycosyl-6-C-glycosylflavones can be differentiated from their 8-C isomers.     

Intra- and interspecific variations in vacuolar flavonoids among Ficus species from the Budongo Forest,Uganda

Leaves of 14 species of Ficus growing in the Budongo Forest, Uganda, were analysed for vacuolar flavonoids. Three to six accessions were studied for each species to see whether there was intraspecific chemical variation. Thirty-nine phenolic compounds were identified or characterised, including 14 flavonol O-glycosides, six flavone O-glycosides and 15 flavone C-glycosides. In some species the flavonoid glycosides were acylated. Ficus thonningii contained in addition four stilbenes including glycosides. Most of the species could be distinguished from each other on the basis of their flavonoid profiles, apart from Ficus sansibarica and Ficus saussureana, which showed a very strong intraspecific variation. However, on the whole flavonoid profiles were sufficiently distinct to help in future identifications.     

The flavonoids of Trichophorum cespitosum

Fifteen flavonoids were isolated from Trichophorum cespitosum, including two new di-C-glycosylflavones, 6-C -arabinosyl-8-C-glucosylchr     

Structural determination of C-glycosylflavones by mass spectrometry of their permethyl ethers

Permethylated C-glycosylflavones give well defined MS, including in all cases an important molecular peak. The observed fragmentations are characteristic for the nature and position of the sugar. The 6-C and 8-C glycosylated derivatives are clearly differentiated. In dissymmetrical 6,8-di-C-glycosylflavones, the natures of the sugar in both the 6- and 8- positions can be determined. The structures of several natural compounds are discussed.     

Flavonoid diversification in Achillea ptarmica and allied taxa

More than 50 collections of 12 species forming the A. ptarmica group have been analysed for their leaf flavonoids. C-Glycosylflavones (iso-orientin and derivatives, vicenins and lucenins) were found to be the main components, whereas flavonol 3-O-glycosides (based on quercetin and kaempferol) and flavone 7-O-glycosides (based on luteolin and diosmetin) were of restricted distribution. Infraspecific variability regarding C-glycosylflavones was observed in most of the taxa investigated. By contrast, flavonol 3-O-glycosides appeared to be stable characters and were sometimes accumulated instead of C-glycosylflavones. In addition to the flavonoids, the geographical distribution patterns and the possible origin of the A. sibirica in Eastern Asia are briefly discussed.     

The distribution of flavonoids in chloroplasts of twenty five species of vascular plants

A survey was made of the major flavonoids in whole leaf extracts and in chloroplast preparations from twenty five species of vascular plants including Anthophyta (20), Coniferophyta (1), Ginkophyta (1), Pterophyta (2), and Arthrophyta (1). The chloroplasts variously contained derivatives of flavones, C-glycosylflavones, flavonols, flavanones, isoflavones, 3-deoxyanthocyanidins, and anthocyanins. Twenty three species contain one or more flavonoids in isolated chloroplast, usually in a pattern quite similar to that found in whole-leaf extracts but occasionally showing enrichment of one or more flavonoids in the chloroplasts. Flavonoids are apparently absent from chloroplasts of Phaseolus aureus and Morus alba although whole-leaf extracts of these species are rich in quercetin derivatives.     

Paleobiochemistry of North American fossil Liriodendron sp.

Organic geochemical analyses are presented for a fossil Liriodendron sp. from the Miocene, Clarkia Flora of Northern Idaho. Flavonoid profiles determined for the fossil and two extent species of Liriodendron (L. chinense and L. tulipifera) confirm the generic status of the fossil material, but owing to a generic uniformity in flavonoid composition, fail to resolve taxonomic affinities at the species level. Steroid and other cycloalkane-alkene profiles indicate that the fossil taxon has a greater chemical similarity with L. chinense than L. tulipifera, despite the general leaf outline similarity between the fossil species and extent L. tulipifera. The morphologic and chemical data are interpreted as evidence for mosaic evolution within the genus, and the non-canalization of character states in some Miocene species.     

Flavonoid diversification in the polemoniaceae

Analysis of species representing most sections of all the genera in the family Polemoniaceae showed a range of variation in flavonoids comparable to variation already documented for gross morphological features, karyotypes and pollen grains. Three main groups of flavonoids predominate: (A) common flavonols (kaempferol, quercetin, myricetin); (B) 6-methoxyflavonols (patuletin, eupalitin, eupatolitin); and (C) C-glycosylflavones (apigenin and luteolin based). Cobaea, Loeselia], Polemonium, Allophyllum, Collomia and Gymnosteris have predominantly Group A flavonoids; Bonplandia, Ipomopsis and Eriastrum have predominantly Group B flavonoids; Phlox, Microsteris and Leptodactylon have predominantly Group C flavonoids; while the remaining genera (Cantua, Huthia, Gilia, Langloisia, Navarretia and Linanthus) either have flavonoids of all three groups, or some species within a genus have flavonoids of one group, while other species have flavonoids of another group. Linanthus, Gilia and Navarretia (3 of the larger genera in the family) show great flavonoid diversity, while Langloisia (4 species) has 2 species with Group A flavonoids and the other two species have Group B pigments. Two rare hydroxycoumarins, one being daphnetin, were detected in five genera but they proved to be only of limited systematic interest.     

Structural determination of 6-C-diglycosyl-8-C-glycosyl-flavones and 6-C-glycosyl-8-C-diglycosylflavones by mass spectrometry of their permethyl ethers

Permethylated 6-C-diglycosyl-8-C-glycosylflavones and 6-C-glycosyl-8-C-diglycosylflavones gave well defined EIMS including the molecular peak and a fragmentation pattern characteristic of the 6-C-glycosyl residue. X″′-O-glycosides (8-C-disaccharides) are thus easily distinguished from X″-O-glycosides (6-C-disaccharides) and, in the latter, the position of the O-glycosidic bond should be deduced from the MS, after acid hydrolysis. Three new C-glycosylflavones have been characterized in this way from Spergularia rubra and Stellaria holostea.     

Flavone di-C-glycosides from Scutellaria baicalensis

From the roots of Scutellaria baicalensis two new di-C-glycosylflavones have been isolated. Their structures have been established on the basis of mass, ¹H and ¹³C NMR spectroscopy as chrysin 6-C-glucoside-8-C-arabinoside and chrysin 6-C-arabinoside-8-C-glucoside.     

Flavonoids in the leaves of twenty-eight polygonaceous plants

Flavonoids in the leaves of twenty-eight species belonging to the Polygonaceae were studied. Thirty-three kinds of flavonoids were isolated, and eighteen kinds were obtained as crystals. Quercetin glycosides were commonly found in the family. In the quercetin glycosides, 3-O-rhamnoside was most frequently found: 3-O-glucuronide is also distributed widely. Myricetin glycosides were rare. Methylated flavonols were found in some species of the sectionsEchinocaulon andPersicaria. Eleven kinds ofC-glycosylflavones were found in the present survey, andC-glycosylflavones were distributed in all species of the genusRheum and in almost all species of the section Tiniaria.Rumex Acetosella andPolygonum suffultum are exceptional, the former contains flavone glycoside and the latterC-glycosylflavones only, as main components.