6-Methoxyflavonoids from Brickellia californica

Two new and eleven known 6-methoxyflavonoids were identified in leaf tissue of Brickellia californica. The new flavonols are eupatin 3-SO₃ Ca_1/2 and patuletin 3-SO₃K. The known compounds include the flavones hispidulin and eupafolin and their respective 7- and 4′-monomethyl ethers and the flavonols; spinacetin, eupatin, patuletin 3-glucoside and 3-galactoside, and eupatolitin 3-galactoside.     

Flavonoids of the Muhlenbergia montana complex

Specimens from natural populations of Muhlenbergia montana (Nutt.) Hitch. and related species were analysed for their flavonoid content. Twenty-four flavonoids from 14 species were separated and 22 of the compounds identified. Most were glycosylated derivatives of luteolin, apigenin and tricin. Two flavonols, quercetin 3-O-rutinoside and quercetin 3-O-glycoside, and two flavanones were also identified. Flavonoid patterns were distinct for all perennial species and identical for the two annual species examined. Phenetic analysis of the flavonoid characters does not support the inclusion of the annual species M. crispiseta and M. peruviana as part of the M. montana complex.     

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.     

6-Methoxyflavonols from disjunct populations of Brickellia cylindracea (compositae)

Eight identical 6-methylated flavonols including aglycones and glycosides were isolated from two geographically disjunction population of Brickellia cylindracea from Mount Livermore and Austin, Texas, suggesting that they are best treated as a single taxon. Among the flavonol aglycones identified were patuletin, centaureidin, quercetagetin 3,6,3′,4′-tetramethyl ether and artemetin. The flavonol glycosides were patuletin and its 3-galactoside, 3-galactogalactoside, 3-rhamnogalactoside and a 3-rhamnogalactoside derivative.     

6-methoxyflavonoids from Brickellia laciniata (compositae)

One new and fourteen known flavonoids, including thirteen containing 6-methoxy groups, were isolated from Brickellia laciniata. The new flavonol is quercetagetin 6,4′-dimethyl ether. Among the known compounds identified were the 4′-methyl and 7,4′-dimethyl ethers of eupafolin and luteolin 4′-methyl ether, and the flavonols: patuletin, spinacetin, eupatolitin, eupatin, centaureidin, casticin, patuletin 3-glucoside and 3-galactoside, eupatolitin 3-galactoside, patuletin 3-SO₃K and eupatin 3-SO₃Ca_1/2.     

The metabolism of [3-H]oleanolic acid and its monoglycosides in cytoplasm and vacuole of protoplasts isolated from Calendula officinalis leaves

Isolated protoplasts from C. officinalis leaves were supplied with [3-³H]oleanolic acid, its 3-O-monoglucoside and 3-O-monoglucuronide. Transformations of these compounds into two series of oleanolic acid glycosides, i.e. glucosides (derivatives of 3-O-monoglucoside) and glucuronides (derivatives of 3-O-monoglucuronide) in the extravacuolar space and the vacuole were investigated. In the cytoplasm free oleanolic acid is glycosylated to both monoglycosides and to higher glycosides. Monoglycosides are partly hydrolysed to free oleanolic acid and partly glycosylated to higher derivatives. The vacuole contains the same radioactive compounds as the extravacuolar space. However, it seems most likely that these compounds are transported there from the sites of their synthesis in the cytoplasm.     

Pentacyclic triterpenes from Myrianthus liberecus

From the methylated trunk wood extracts of Myrianthus liberecus, six pentacyclic triterpenes have been isolated as their methyl esters. These included the known methyl benthamate, methyl euscaphate, methyl tormentate, methyl arjunolate, methyl 3-isoarjunolate and methyl 3β-O-(4″-O-methyl-E-coumaroyl)-arjunolate, a new triterpene derivative.     

Flavonoids of Pallenis spinosa (Asteraceae)

Pallenis spinosa was investigated for its flavonoid content. Two mono- and diglycosides of patuletin, a quercetin monoglycoside, two tricin monoglycosides, and four methoxylated flavonols were reported.     

Use of Mucor miehei lipase in the preparation of long chain 3-O-acylcatechins

Long chain 3-O-acylcatechins were prepared in high yield by alcoholysis with n-butanol of the corresponding pentaacylderivatives in the presence of lipase from Mucor miehei (immobilised, Lipozyme® IM). In an alternative procedure, the mixed ester, tetraacetyl-3-O-acylcatechin, was synthesised and used as substrate for the same alcoholysis process that proceeds with higher reaction rate. The obtained 3-O-acyl derivatives are more lipophilic than the parent catechin and thus suitable for a possible application of their antioxidative properties in hydrophobic matrices.     

Flavonoids of the Hydrangeaceae Dumortier

Fourteen species representing nine genera of the Hydrangeaceae Dumortier were surveyed for their flavonoid pigments. All taxa exhibited profiles based upon common flavonols. Myricetin was seen in two genera: Jamesia and Decumaria. Jamesia was further distinguished by the absence of kaempferol or its glycosides. A complex array of 3-O-mono-, 3-O-di- and 3-O-triglycosides was observed, although not all species had all levels of glycosylation. Decumaria barbara was unique within the species studied in its possession of 3,7-di- and 3,7-triglycosides. The overall pattern of flavonol glycosides observed for the Hydrangeaceae closely resembles that found in herbaceous genera of Saxifragaceae. The comparatively low frequency of myricetin contrasts with its high occurrence in herbaceous genera.     

荷花花粉的类黄酮组成

利用超高效液相色谱质谱联用(I-Class UPLC/Xevo TQ MS)技术, 对50个品种荷花干燥花粉中的类黄酮代谢产物进行了分离及结构鉴定。结果表明, 在荷花(Nelumbo nucifera)花粉中检测到了13种黄酮醇和2种黄酮, 这15种类黄酮化合物均为首次从荷花花粉中检出, 其中槲皮素3-O-葡萄糖醛酸苷(quercetin 3-O-glucuronide)、槲皮素3-O-新橙皮糖苷(quercetin 3-O-rhamnopyranosyl-(1→2)-glucopyranoside)以及槲皮素3-O-阿拉伯糖-(1→2)-半乳糖苷(quercetin 3-O-arabinopy- ranosyl-(1→2)- galactopyranoside)含量较高, 且在所有品种中均有检出。不同品种花粉中检测到的类黄酮总含量(TF)差异较大, 绯云千叶类黄酮总含量最高, 为281.08 mg∙100 g^-1; 仙女散花最低, 仅为82.64 mg∙100 g^-1。通过聚类分析, 将50个品种聚为4组, B组类黄酮化合物种类最多, 而且该组总类黄酮含量最高, 其中绯云千叶、伯里小姐和蜀红莲的干燥花粉中总类黄酮含量均超过200 mg∙100 g^-1, 可推荐为采集荷花花粉用的优良品种。     

6-Methoxyflavonols from Brickellia veronicaefolia (compositae)

Three new and eight known flavonols, all containing 6-methoxyl groups, were isolated from Brickellia veronicaefolia. The new compounds were eupatolitin 3-sulfate, 6-methoxyquercetin 7,3′-dimethyl ether (veronicafolin) 3-digalactoside and veronicafolin 3-sulfate. The known flavonoids were eupatolitin, quer-cetagetin 3,6,7-trimethyl ether, eupatin, casticin, artemetin, eupatolitin 3-galactoside, patuletin 3-sulfate and eupatin 3-sulfate.     

Comparative phytochemistry and systematics of Anacyclus

Leaf flavonoids of 13 Anacyclus taxa have been identified and compared. The most common compounds are 3-, 7- or 5-glycosylated flavonols which, together with the accumulation of 2 diosmetin 7-glycosides, help to delimitate species groups according to recent morphological and cytological findings. In addition to quercetagetin, quercetagetin 3'-methyl ether, patuletin and spinacetin have been isolated as 7-glucosides from the yellow disc and ray flowers of Anacyclus radiatus. The distribution patterns of polyacetylenes and particularly related amides, characterize different Anacyclus species and apparently contribute to a more natural interpretation of relationships with other genera, which may also be underlined by the distribution of cyanogenic glycosides.     

THE FLAVONOIDS OF LASTHENIA (COMPOSITAE)

Lasthenia (Compositae: Helenieae), a western North American-Chilean genus of 16 species, produces 22 flavonoid glycosides. Flavonoids are the chalcones butein and okanin, the aurones maritimetin and sulfuretin, the flavone luteolin, and the flavonols kaempferol, quercetin, and patuletin. The presence or absence of various of these classes of compounds in general follows sectional alignments in the genus, confirms affinities based on morphological and cytological evidence, and suggests relationships of problematical species. Intraspecific variation in flavonoid constituents occurs in several species, and in one taxon intrapopulation variation seems to exist as well. Evolution within Lasthenia has been associated with a loss of the ability to produce or accumulate luteolin, chalcones, and aurones; an increase in diversity of quercetin glycosides; acquisition of the ability to produce patuletin; and an elaboration of glycosylation patterns of patuletin.     

Synthesis of 2,3-O-(propane-1,2-diyl)- and 2,3-O-(3-hydroxypropane-1,2-diyl)-cyclomaltoheptaose

2¹,3¹-O-(Propane-1,2-diyl)cyclomaltoheptaose has been prepared from 2-O-allylcyclomaltoheptaose by mercuration in trifluoroacetic acid, followed by reduction with sodium borohydride. 2-O-(2,3-Epoxypropyl)cyclomaltoheptaose, prepared from 2-O-allylcyclomaltoheptaose by oxidation with dimethyldioxirane, was converted into 2¹,3¹-O-(3-hydroxypropane-1,2-diyl)cyclomaltoheptaose by treatment with trifluoroacetic acid. Both derivatives containing fused 1,4-dioxane rings are mixtures of stereoisomers, in which the methyl and hydroxymethyl group, respectively, that is linked to this ring, occupies an axial or an equatorial position.     

Uptake and metabolism of epicatechin and its access to the brain after oral ingestion

Epicatechin is a flavan-3-ol that is commonly present in green teas, red wine, cocoa products, and many fruits, such as apples. There is considerable interest in the bioavailability of epicatechin after oral ingestion. In vivo studies have shown that low levels of epicatechin are absorbed and found in the circulation as glucuronides, methylated and sulfated forms. Recent research has demonstrated protective effects of epicatechin and one of its in vivo metabolites, 3′-O-methyl epicatechin, against neuronal cell death induced by oxidative stress. Thus, we are interested in the ability of ingested epicatechin to cross the blood brain barrier and target the brain. Rats were administered 100 mg/kg body weight/d epicatechin orally for 1, 5, and 10 d. Plasma and brain extracts were analyzed by HPLC with photodiode array detection and LC-MS/MS. This study reports the presence of the epicatechin glucuronide and 3′-O-methyl epicatechin glucuronide formed after oral ingestion in the rat brain tissue.     

Quercetin and patuletin 33′-disulphates from flaveria chloraefolia

Quercetin 3,4′-disulphate and an equimolar mixture of two novel flavonol sulphates, quercetin 3,3′-disulphate and patuletin 3,3′-disulphate, were isolated from the butanolic extract of the leaves of Flaveria chloraefolia. Purification of these components was carried out by gel filtration, and their structures elucidated by UV, IR, ¹H and ¹³C NMR spectroscopy, as well as FAB-MS. The effect of 3′- and 4′-sulphation on the ¹³C NMR spectra of flavonols is discussed.     

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.