The systematic implications of the complexity of leaf flavonoids in the bromeliaceae

In a leaf survey of 61 species of the Bromeliaceae, an unexpectedly wide spectrum of flavonoid constituents was encountered. The family is unique amongst the monocotyledons in the frequency and variety of flavonoids with extra hydroxylation or methoxylation at the 6-position. More common flavonols (in 43% of species) and flavones (in 13%) are distributed throughout the family whereas the rarer flavonoid classes are restricted to one or two of the three subfamilies. Thus 6-hydroxyflavones were found in both the Pitcairnioideae (in 50%) and the Tillandsioideae (in 14%) but patuletin (in 19%), gossypetin (in 1 species) and methylated 6-hydroxymyricetin derivatives (in 24%) were detected only in the Tillandsioideae. A new flavonol, 6,3′,5′-trimethoxy-3,5,7-4′-tetrahydroxyflavone, was identified as the 3-glucoside in Tillandsia usneoides and a new glycoside, patuletin 3-rhamnoside, in Vriesea regina. Myricetin glycosides were found only in the Bromelioideae and their presence here and the concomitant absence of 6-hydroxyflavonoids could indicate the primitive condition of this subfamily. The flavonoid results, in toto, confirm the view based on morphology, that the Bromeliaceae occupies an isolated position in relation to other monocot families.     

Leaf flavonoid patterns in the winteraceae

In a leaf flavonoid survey of 59 specimens of the Winteraceae and related families, representing nine genera, luteolin 7,3′-dimethyl ether (in 77%) and flavonols (in 81%) were found to be major constituents. Indeed the high incidence of luteolin 7,3′-dimethyl ether chemically isolates the family from all other angiosperm groups, including families and genera that have been taxonomically associated with the Winteraceae in the past. Simple flavones (in 16%), on the other hand, were found only in some Drimys s. str., Tasmannia and Pseudowintera species. Similarly, the distribution of flavone C-glycosides was restricted to specimens of T. piperita and one specimen of D. winteri. The frequent occurrence of procyanidin (in 60%) and dihydroquercetin (in 44%) reflects the primitive and woody nature of the family. The combined flavonoid data clearly support previous cytological, morphological and phylogenetic studies in the division of the Winteraceae into three groups of genera: (1) Bubbia, Belliolum, Exospermum and Zygogynum; (2) Drimys s. str. and Pseudowintera and (3) Tasmannia. Some generic variations were found within the Bubbia, Belliolum, Expospermum and Zygogynum group but apart from minor geographic variations within Belliolum the flavonoid results do not appear to provide suitable evidence for subgeneric taxonomy.     

Two new C-methylated flavonoids from Myrica gale

From the leaves of Myrica gale 2′,4′-dihydroxy-6′-methoxy-3′,5′-dimethylchalcone has been isolated. The fruits yielded 2′-hydroxy-4′,6′-dimethoxy-3′-methyldihydrochalcone. The constitutions were deduced from spectroscopic data and confirmed by synthesis.     

The leaf flavonoids of the Zingiberales

A survey of flavonoids in the leaves of 81 species of the Zingiberales showed that, while most of the major classes of flavonoid are represented in the order, only two families, the Zingiberaceae and Marantaceae are rich in these constituents. In the Musaceae (in 9 species), Strelitziaceae (in 8 species) and Cannaceae (1 of 2 species) flavonol glycosides were detected in small amount and in the Lowiaceae no flavonoids were fully identified. In the Zingiberaceae kaempferol (in 22%), quercetin (72%) and proanthocyanidins (71%) are distributed throughout the family. The two subfamilies of the Zingiberaceae may be distinguished by the presence of myricetin (in 26%), isorhamnetin (10%) and syringetin (3%) in the Zingiberoideae and of flavone $\text{C-}\text{glycosides}$ (in 86% of taxa) in the Costoideae. A number of genera have distinctive flavonol profiles: e.g. Hedychium species have myricetin and quercetin. Roscoea species isorhamnetin and quercetin and Alpinia species kaempferol and quercetin glycosides. A new glycoside, syringetin 3-rhamnoside was identified in Hedychium stenopetalum. In the Zingiberoideae flavonols were found in glycosidic combination with glucuronic acid, rhamnose and glucose but glucuronides were not detected in the Costoideae or elsewhere in the Zingiberales. The Marantaceae is chemically the most diverse group and may be distinguished from other members of the Zingiberales by the occurrence of both flavone $\text{O-}$ and $\text{C-}\text{glycosides}$ and the absence of kaempferol and isorhamnetin glycosides. The distribution of flavonoid constituents within the Marantaceae does not closely follow the existing tribai or generic limits. Flavonols (in 50% of species). flavones (20%) and flavone $\text{C-}\text{glycosides}$ (40%) are found with similar frequency in the two tribes and in the genera Calathea and Maranta both flavone and flavonol glycosides occur. Apigenin- and luteolin-7-sulphates and luteolin-7,3′-disulphate were identified in Maranta bicolor and M. leuconeura var. kerchoveana and several flavone $\text{C-}\text{glycosides}$ sulphates in Stromanthe sanguinea. Anthocyanins were identified in those species with pigmented leaves or stems and a common pattern based on cyanidin-and delphinidin-3-rutinosides was observed throughout the group. Finally the possible relationship of the Zingiberales to the Commelinales, Liliales, Bromeliales and Fluviales is discussed.     

Anthocyanin pigments and leaf flavonoids in the family araceae

Anthocyanins, variously identified in inflorescence, fruit, leaf or petiole of 59 representative species of the Araccae, are of a simple type. The most common pigment is cyanidin 3-rutinoside, while pelargonidin 3-rutinoside and cyanidin 3-glucoside are regularly present. Two rare pigments are: cyanidin 3-gentiobioside in Anchomanes and Rhektophyllum, both in the subfamily Lasioideae; and delphinidin 3-rutinoside in Schismatoglottis concinna. In a leaf survey of 144 species from 58 genera, flavone C-glycosides (in 82%) and proanthocyanidins (in 35–45%) were found as the major flavonoids. In the subfamily Calloideae, subtribe Symplocarpeae, flavonols replace glycoflavones as the major leaf components but otherwise flavonols are uncommon in the family (in 27% of the sample) and more usually co-occur with flavone C-glycosides. Two new flavonol glycosides were characterized from Lysichiton camtschatcense: kaempferol 3-(6-arabinosylgalactoside)and kaempferol 3-xylosylgalactoside. Simple flavones, luteolin and chrysoeriol (in 6%) were found only in the subtribes Arinae and Cryptocoryninae, subfamily Aroideae. Flavonoid sulphates were identified in only four taxa: glycoflavone sulphates in two Culcasia species and Philodendron ornatum and a mixture of flavone and flavonol sulphates in Scindapsus pictus. Caffeic ester sulphates were more common and their presence in Anthurium hookeri was confirmed. These results show that the Araceae are unusual amongst the monocots in their simple and relatively uniform flavonoid profile; no one subfamily is clearly distinguished, although at tribal level some significant taxonomic patterns are observed. The best defined groups are the subfamilies Lasioideae and Monsteroideae, and the tribes Symplocarpeae and Arophyteae, and the subtribe Arinae. The greatest chemical diversity occurs in Anthurium and Philodendron, but this may only reflect the fact that these are the two largest genera in the family. The origin and relationship of the Araccae to other monocot groups are discussed in the light of the flavonoid evidence.     

Evolution of yellow flavonols in flowers of anthemideae

Yellow flavonols have been identified in flowers of Coleostephus myconis, Glossopappus macrotus, Lepidophorum repandum and Leucanthemopsis flaveola. In addition to quercetagetin, gossypetin, patuletin and quercetagetin 3′-methyl ether previously reported in other species of the tribe Anthemideae of the Compositae, spinacetin, the 6,3′-dimethyl ether of quercetagetin, has been found for the first time as a flower pigment. It occurs as the 7-glucoside in flowers of Lepidophorum repandum, the leaves of which contain patuletin 3-rhamnoside. The presence of spinacetin and the 3′-methyl ether of quercetagetin in Lepidophorum fits in with the results of recent taxonomic studies which place this genus closer to Chrysanthemum than to Anthemis. Similarly, the occurrence of quercetagetin and gossypetin in Leucanthemopsis confirms its recently proposed separation from Tanacetum. The chemical data indicate that there is an evolutionary trend in yellow flower pigmentation, with Leucanthemopsis and Chrysanthemum segetum as the two least specialized species and Lepidophorum as the most advanced.     

Biosystematics of the monocotyledoneae—flavonoid patterns in leaves of the liliaceae

In a leaf survey of 168 species of the Liliaceae, most of the major flavonoid classes were found to be represented in the family. Flavonols occurred most frequently: quercetin and kaempferol were detected in 40% and 42% of the sample respectively, while the flavones luteolin and apigenin were present in only 24% and 20% of the sample. Methylated derivatives, i.e. isorhamnetin, diosmetin and tricin were rare. Procyanidins were present in 17 species, flavonoid sulphates in only one species and flavone C-glycosides in only three species. Anthraquinone pigments were identified in species of Aloe Asphodeline and Asphodelus. Three new flavonoid glycosides were characterised during the course of the survey: diosmetin 7-diglucoside in Colchicum byzanthinum and tricin 7-fructosylglucoside and tricin 7-rutinoside-4′-glucoside in Hyacinthus orientalis cv. ‘Quean of the Pinks’. On the basis of the flavonoid survey, the subfamilies of the Liliaceae may be grouped into those containing flavonols only, those with flavones only or those having both flavonols and flavones. Members of the related families: Amaryllidaceae (17 species), Agavaceae (1 species) and Xanthorrhoeaceae (1 species) contained only flavonols. The subfamilies Scilloideae, Asphodeloideae and Melanthioideae show the most chemical variation whilst the Wurmbaeoideae and Lilioideae are the most homogeneous groups. The tribe Scilleae is unusual in that both flavone- and flavonol-containing genera occur and a wide variety of flavonoid types are represented. A comparison of the leaf flavonoids of the Liliaceae with those found in families related to the grasses showed that all except two classes of flavonoid compound (5-methylated flavones and 5-deoxyflavonoids) found in the Juncaceae. Cyperaceae, Palmae and Gramineae are present in the Liliaceae thus supporting the view that all four families could have arisen from Liliaceae-like ancestors.     

Flavonoids in leaves and inflorescences of australian Cyperus species

A survey of the flavonoids of some 92 species of Australian Cyperus, mainly of subtropical or tropical origin, has confirmed a correlation previously reported in this family between flavonoid pattern and plant geography. The pattern found was similar to that of African and South American Cyperaceae, particularly in the occurrence of the rare marker substance, luteolin 5-methyl ether. Tricin and luteolin are relatively common, in glycosidic form, in the leaves while the flavonol quercetin is infrequent. When present, quercetin occurs either in glycosidic form or free as a methyl ether. The 3-monomethyl and 3, 7-dimethyl ethers of kaempferol and quercetin and the 3, 7, ?-trimethyl ether of quercetin are reported for the first time from the Cyperaceae. The flavonoid pattern of inflorescences is distinct from that of the leaves in that tricin is not detectable and that luteolin 5-methyl ether appears to be replaced by 7, 3′, 4′-trihydroxyflavone. In addition, the aurone aureusidin is more commonly present than in the leaves and is occasionally accompanied by two further aurones. The glycoxanthones mangiferin and isomangiferin occur rarely in all three species examined in the section Haspani, i.e. in C. haspan, C. prolifer and C. tenuispica. In general, however, the flavonoid data do not offer any markers which separate off different sections within the genus; there are, however, some significant correlations between the frequency of the flavonoid classes and subgeneric groupings.     

Variations in flavonoid patterns within the genus Chondropetalum (restionaceae)

HPLC and chemical analyses of the flavonoids in culms of 11 Chondropetalum species divide the genus into two groups: seven, with glycosides of myricetin larycitin and syringetin; and four, with glycosides of kaempferol, quercetin, gossypetin, gossypetin 7-methyl ether and herbacetin 4′-methyl ether. This chemical dichotomy is correlated with anatomical differences and confirms the view that the genus requires taxonomic revision. HPLC measurements on those species with myricetin derivatives show that taxa with a qualitatively similar pattern of glycosides can be readily separated on quantitative grounds. Syringetin 3-arabinoside and a glycoside of herbacetin 4′-methyl ether are reported for the first time from the genus.     

Flavonoids of the citrus cultivar calamondin and synthetic 2′β-dihydroxychalcones

Eight methoxyflavones were isolated and identified from the peel of calamondin. Citromitin and 5-O-desmethylcitromitin are actually nobiletin and 5-O-desmethylnobiletin, respectively. 5,6,7,8,3′,4′-Hexamethoxyflavanone and 5-hydroxy-6,7,8,3′,4′-pentamethoxyflavanone are not constituents of calamondin, although previously reported.     

Flavonoids from the exudate of Acacia neovernicosa

2′,4′-Dihydroxychalcone, 4′-hydroxy-2′-methoxychalcone and 2′,4′-dihydroxy-3′-methoxychalcone were isolated and characterized from the resinous exudate produced by Acacia neovernicosa. Smaller amounts of isoliquiritigenin, pinocembrin and chrysin were also found and identified by their chromatographic properties and UV spectra. The material of one collection contained galangin, 3-methylkaempferol and 3,3′ -dimethylquercetin.     

Three highly oxygenated flavone glucuronides in leaves of Spinacia oleracea

Droplet counter-current chromatographic separation and subsequent TLC demonstrated the existence of at least 14 phenolics in the leaves of Spinacia oleracea. Three have now been isolated and identified, respectively, as the 4′-glucuronides of 5,7,4'-trihydroxy-3,6,3′-trimethoxyflavone (jaceidin), 5,3′,4′-trihydroxy-3-methoxy-6:7-methylene-dioxyflavone and 5,4′-dihydroxy-3,3′-dimethoxy-6:7-methylenedioxyflavone.     

Allometric analysis of the induced flavonols on the leaf surface of wild tobacco (Nicotiana attenuata)

Trichomes excrete secondary metabolites that may alter the chemical composition of the leaf surface, reducing damage caused by herbivores, pathogens and abiotic stresses. We examined the surface exudates produced by Nicotiana attenuata Torr. Ex Wats., a plant known to contain and secrete a number of secondary metabolites that are toxic or a deterrent to herbivorous insects. Extractions specific to the leaf surface, the trichomes, and the laminar components demonstrated the localization of particular compounds. Diterpene glycosides occurred exclusively in leaf mesophyll, whereas nicotine was found in both the trichomes and mesophyll. Neither rutin nor nicotine was found on the leaf surface. Quercetin and 7 methylated derivatives were found in the glandular trichomes and appeared to be excreted onto the leaf surface. We examined the elicitation of these flavonols on the leaf surface with a surface-area allometric analysis, which measures changes in metabolites independent of the effects of leaf expansion. The flavonols responded differently to wounding, methyl jasmonate (MeJA), herbivore attack and UV-C radiation, and the response patterns corresponded to their compound-specific allometries. Finding greater amounts of quercetin on younger leaves and reduced amounts after herbivore feeding and MeJA treatment, we hypothesized that quercetin may function as an attractant, helping the insects locate a preferred feeding site. Consistent with this hypothesis, mirids (Tupiocoris notatus) were found more often on mature leaves sprayed with quercetin at a concentration typical of young leaves than on unsupplemented mature leaves. The composition of metabolites on the leaf surface of N. attenuata changes throughout leaf development and in response to herbivore attack or environmental stress, and these changes are mediated in part by responses of the glandular trichomes.     

Flavonoids from the external leaf resins of four hemizonia species (asteraceae)

The external leaf resins of four Hemizonia species afforded nine methylated flavonoids, including flavanones, flavones and flavonols. Besides the rare compounds 7-methyleriodictyol and 3,6,8-trimethoxy-5,7,3′,4′-tetrahydroxyflavone the new 6-methoxy-5,7,8,3′,4′-pentahydroxyflavone was isolated and identified by spectroscopic means.     

The flavonoids of Megalodonta beckii and isolation of 2′-3-Dihydroxy-4-methoxy-4′-glucosyl chalcone

A new naturally occurring chalcone glycoside, $\text{2′,-}\text{dihydroxy}\text{-4-}\text{methoxy}\text{-4′-O-β-}\text{d}\text{-}\text{glucosyl}$ chalcone, and other chalcones, aurones, flavonols, and anthocyanins are reported from Megalodonta (Bidens) beckii. The plan is an amphibious aquatic with heterophyllous leaves, but the presence of certain flavonoids is correlated with vegetative versus floral tissues rather than vegetative leaf form. The implications of flavonoid chemistry with respect to the relationship of M. beckii to several sections of Bidens are discussed.