Acylated flavonol glycosides from the forage legume, Onobrychis viciifolia (sainfoin)

Ten acylated flavonol glycosides were isolated from aqueous acetone extracts of the aerial parts of the forage legume, Onobrychis viciifolia, and their structures determined using spectroscopic methods. Among these were eight previously unreported examples which comprised either feruloylated or sinapoylated derivatives of 3-O-di- and 3-O-triglycosides of kaempferol (3,5,7,4'-tetrahydroxyflavone) or quercetin (3,5,7,3',4'-pentahydroxyflavone). The diglycosides were acylated at the primary Glc residue of O-α-Rhap(1→6)-β-Glcp (rutinose), whereas the triglycosides were acylated at the terminal Rha residues of the branched trisaccharides, O-α-Rhap(1→2)[α-Rhap(1→6)]-β-Galp or O-α-Rhap(1→2)[α-Rhap(1→6)]-β-Glcp. Identification of the primary 3-O-linked hexose residues as either Gal or Glc was carried out by negative ion electrospray and serial MS, and cryoprobe NMR spectroscopy. Analysis of UV and MS spectra of the acylated flavonol glycosides provided additional diagnostic features relevant to direct characterisation of these compounds in hyphenated analyses. Quantitative analysis of the acylated flavonol glycosides present in different aerial parts of sainfoin revealed that the highest concentrations were in mature leaflets.     

Flavonol tetraglycosides and other constituents from leaves of Styphnolobium japonicum (Leguminosae) and related taxa

Two flavonol tetraglycosides comprising a trisaccharide at C-3 and a monosaccharide at C-7 were isolated from the leaves of Styphnolobium japonicum (L.) Schott and characterised as the 3-O-alpha-rhamnopyranosyl(1-->2)[alpha-rhamnopyranosyl(1-->6)]-beta-glucopyranoside-7-O-alpha-rhamnopyranosides of quercetin and kaempferol. The 3-O-alpha-rhamnopyranosyl(1-->2)[alpha-rhamnopyranosyl(1-->6)]-beta-galactopyranoside-7-O-alpha-rhamnopyranoside of kaempferol, the 3-O-alpha-rhamnopyranosyl(1-->2)[alpha-rhamnopyranosyl(1-->6)]-beta-glucopyranosides of kaempferol and quercetin and the 3-O-alpha-rhamnopyranosyl(1-->2)[alpha-rhamnopyranosyl(1-->6)]-beta-galactopyranoside of kaempferol were also obtained from this species for the first time. Some or all of these flavonol tetra- and triglycosides were detected in 17 of 18 specimens of S. japonicum examined from living and herbarium material, although the most abundant flavonoid in the leaves was generally quercetin 3-O-alpha-rhamnopyranosyl(1-->6)-beta-glucopyranoside (rutin). The triglycosides, but not the tetraglycosides, were detected in herbarium specimens of Styphnolobium burseroides M. Sousa, Rudd & Medrano and Styphnolobium monteviridis M. Sousa & Rudd, but specimens of Styphnolobium affine (Torrey & A. Gray) Walp. contained a different profile of flavonol glycosides. The flavonol tetra- and triglycosides of S. japonicum were also present in leaves of Cladrastis kentukea (Dum. Cours.) Rudd, a representative of a genus placed close to Styphnolobium in current molecular phylogenies. An additional constituent obtained from leaves of Styphnolobium japonicum was identified as the maltol derivative, 3-hydroxy-2-methyl-4H-pyran-4-one 3-O-(4'-O-p-coumaroyl-6'-O-(3-hydroxy-3-methylglutaroyl))-beta-glucopyranoside.     

New trans- and cis-p-coumaroyl flavonol tetraglycosides from the leaves of Mitragyna rotundifolia

Two new flavonol tetraglycosides, quercetin 3-O-(4-O-trans-p-coumaroyl)-α-l-rhamnopyranosyl (1→2) [α-l-rhamnopyranosyl (1→6)]-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside (krathummuoside A) and quercetin 3-O-(4-O-cis-p-coumaroyl)-α-l-rhamnopyranosyl (1→2) [α-l-rhamnopyranosyl (1→6)]-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside (krathummuoside B) were isolated from the leaves of Mitragyna rotundifolia in addition to eight known compounds, quercetin 3-O-α-l-rhamnopuranosyl (1→2) [α-l-rhamnopyranosyl (1→6)]-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside, rutin, (−)-epi-catechin, 3,4,5-trimethoxyphenyl β-d-glucopyranoside, (6S, 9R)-roseoside, 3-O-β-d-glucopyranosyl quinovic acid 28-O-β-d-glucopyranosyl ester, (+)-lyoniresinol 3α-O-β-d-glucopyranoside, and (+)-syringaresinol-4-O-β-d-glucopyranoside. The structure elucidation of these compounds was based on analyses of spectroscopic data including 1D- and 2D-NMR.     

Rapid identification of acylated flavonol tetraglycosides in oolong teas using HPLC-MSn

A method was developed to separate and identify acylated flavonol tetraglycosides (AFTGs) by combining isocratic HPLC with electrospray ionisation tandem mass spectrometry. Better separation was obtained for oolong tea infusion using a manually packed Sephadex LH-20 mini-column than with an ACCUBOND ODS solid-phase column. Seven unknown and one known AFTGs were found in oolong teas prepared by various semi-fermentation processes and their structures were identified by mass spectrometry. According to the analyses of diverse oolong teas including Dongding Oolong, Tieguanyin, Wuyi Oolong, Fenghuang Oolong, Gaoshan Shibi, Laocong Shuixian and Baihao Oolong, AFTGs seemed to be universally present, and each oolong tea could be classified into one of three groups (Dongding Oolong, Tieguanyin and Wuyi Oolong) on the basis of its AFTGs profile. The results suggest that the developed method is rapid and sensitive for identifying natural compounds.     

Flavonol tetraglycosides from fruits of Styphnolobium japonicum (Leguminosae) and the authentication of Fructus Sophorae and Flos Sophorae

The dried fruits and seeds of Styphnolobium japonicum (L.) Schott (syn. Sophora japonica L.) are used in traditional Chinese medicine and known as Fructus Sophorae or Huai Jiao. The major flavonoids in these fruits and seeds were studied by LC-MS and other spectroscopic techniques to aid the chemical authentication of Fructus Sophorae. Among the flavonoids were two previously unreported kaempferol glycosides: kaempferol 3-O-β-glucopyranosyl(1 → 2)-β-galactopyranoside-7-O-α-rhamnopyranoside and kaempferol 3-O-β-xylopyranosyl(1 → 3)-α-rhamnopyranosyl(1 → 6)[β-glucopyranosyl(1 → 2)]-β-glucopyranoside, the structures of which were determined by NMR. Two further tetraglycosides were identified for the first time in S. japonicum as kaempferol 3-O-β-glucopyranosyl(1 → 2)[α-rhamnopyranosyl(1 → 6)]-β-glucopyranoside-7-O-α-rhamnopyranoside and kaempferol 3-O-β-glucopyranosyl(1 → 2)[α-rhamnopyranosyl(1 → 6)]-β-galactopyranoside-7-O-α-rhamnopyranoside; the latter was the main flavonoid in mature seeds. The chromatographic profiles of 27 recorded flavonoids were relatively consistent among fruits of similar ages collected from five trees of S. japonicum, and those of maturing unripe and ripe fruits were similar to a market sample of Fructus Sophorae, and thus provide useful markers for authentication of this herbal ingredient. The flower buds (Huai Mi) and flowers (Huai Hua) of S. japonicum (collectively Flos Sophorae) contained rutin as the main flavonoid and lacked the flavone glycosides that were present in flower buds and flowers of Sophora flavescens Ait., reported to be occasional substitutes for Flos Sophorae. The single major flavonoid in fruits of S. flavescens was determined as 3′-hydroxydaidzein.     

Chemical diversification trends in Astragalus caprinus (Leguminosae), based on the flavonoid pathway

Flavonoid glycosides of Astragalus caprinus (Leguminosae) were investigated; more than 30 glycosides were found in leaf material, based on the aglycones kaempferol, quercetin and their methylated derivatives. Among them 14 compounds were found in significant amounts and showed a contrasting distribution. They could be ordered into three groups: polyglycosides, acylated polyglycosides and methylated polyglycosides. The distribution of these compounds was studied within a large collection of individual plants harvested in Tunisia; the results showed a relationship between metabolic trends and ecological diversification.     

Regeneration of Cladrastis lutea (Fabaceae) via somatic embryogenesis

Summary Immature embryos from 5 Cladrastis lutea (Michx.) K. Koch (yellowwood) trees were initially cultured on modified Schenk and Hildebrandt medium (SH) containing either 4.5, 9.0, 13.5 or 23 M 2,4-D. One-third of the explants were transferred to SH medium supplemented with 25.0 M NAA after 2 and 3 weeks respectively. The remaining explants were incubated on the initial 2,4-D containing media for 6 weeks. Groups of somatic embryos formed directly only at the proximal end of cotyledons; only a few formed as single embryos. The greatest numbers were formed from zygotic embryos explanted from 6–8 weeks post-anthesis and initially cultured on medium containing 9 or 13 M 2,4-D. However, all treatments supported somatic embryogenesis. In the second year, explants were initially cultured on SH medium containing either 9.0, 13.5, or 23 M 2,4-D and then transferred to SH medium containing 4.0 M ABA after 2 or 3 weeks. ABA did not affect the development of somatic embryos. Six of 21 somatic embryos germinated on half-strength SH medium without growth regulators. Three entire plantlets were formed, but only one was established in soil.Abbreviations 2,4-D 2,4-dichlorophenoxyacetic acid - NAA 1-naphthaleneacetic acid - ABA abscisic acid - CRAF III chromium trioxide-acetic acidformalin     

Calliandra (Leguminosae) in continental Africa

The mainly neotropical genus Calliandra Benth. (Leguminosae–Mimosoideae–Ingeae) is reported for the first time as native in continental Africa. There are two species known, C. gilbertii Thulin & Hunde sp. nov. in E Kenya and Somalia and C. redacta (J. H. Ross) Thulin & Hunde comb. nov. in South Africa near the Namibia border. On pollen morphological grounds they are supposed to be most related to certain neotropical species but the pollen does not agree entirely with any previously known group of the genus. The distribution of C gilbertii and C. redacta stresses the phytogeographical link between the arid zones of northern and southern Africa.     

Stipule arrangement in the genus Caesalpinia (Leguminosae)

Stipular development in Caesalpinia displays two patterns. More commonly, stipules, throughout the development of the leaf, assume a subordinate position never keeping pace with the petiole-blade portion. In two out of eight species the stipules showed strong proleptic development exceeding in size their own leaf within a plastochron of initiation and soon thereafter covering that leaf. Information on stipule development, as well as other features of the embryonic leaf may be of use to the taxonomist and such data can now be obtained relatively easily using SEM.     

Systematic studies in Tylosema (Leguminosae)

A contribution to the knowledge of Tylosema (Schweinf.) Torre & Hillc. is presented. The main objectives of this revision were: (1) to elucidate the taxonomic position of the specimens collected in south Angola, (2) to provide a review of species boundaries in the genus, especially between T. fassoglense (Schweinf.) Torre & Hillc. and T. esculentum (Burch.) A.Schreib. and (3) to evaluate the contribution of pollen morphology for delimitation of the species in this genus. Numerical analyses were performed based on morphometric data taken from herbarium specimens. Principal component analysis and cluster analysis divided specimens of Tylosema into four major groups, corresponding to three recognized species and a new taxon. A new micromorphometric character (swollen base of hairs) was found that further contributes to the distinction of T. humifusum (Pic.Serm. & Roti Mich.) Brenan from other species. A new species, T. angolense P. Silveira & S. Castro sp. nov. , is described and illustrated. A taxonomic key and distribution map of studied taxa is also provided. The analyses of pollen morphology allowed for the distinction of the taxonomic groups.  © 2005 The Linnean Society of London, Botanical Journal of the Linnean Society , 2005, 147 , 99–115.     

Pollen-ovule patterns in tribeTrifolieae (Leguminosae)

Relative pollen and ovule production in the genera of the legume tribeTrifolieae is explored particularly as to howMedicago with its explosive pollination mechanism compares with its allies.Medicago produces much larger, although much fewer pollen per ovule than the other five genera in the tribe; this is interpreted as a consequence of its highly specialized, irreversible pollination mechanism, which allows only one effective exchange of pollen with pollinators.Melilotus andTrifolium produce a comparatively large quantity of pollen; this can be related to their floral characteristics requiring abundant pollen to achieve fertilization. InMedicago andTrigonella, annuals convert a higher proportion of pollen grains and ovules into seeds than perennials.     

Eight flavonol glycosides in Pyrola (pyrolaceae)

As part of a general survey of the flavonoids of Pyrolaceae, the flavonoids of Pyrola virens and P. chlorantha were investigated. Eight flavonol glycosides based upon kaempferol, quercetin and rhamnetin were identified from each of the two species. Two of the glycosides, rhamnetin 3,3′,4′-tri-O-glucoside and rhamnetin 3-O-arabinoside-3′,4′-di-O-glucoside are previously unreported and further, represent an unusual pattern of glycosylation. The similarity of flavonoids and the presence of the unusual substitution pattern supports a conspecific status for the two taxa.     

中国岩黄芪属(豆科)植物资料增补

根据对标本的研究及文献资料的整理,证实了西伯利亚岩黄芪在中国的分布;山竹岩黄芪在新疆的分布新记录。另外,还报道了地中海岩黄芪在陕西的栽培记录。     

Pollination-related characteristics in the mimosoid legumeAcacia terminalis (Leguminosae)

Intraspecific variation has been found for several pollination-related characteristics in two isolated populations of the self-incompatible treeAcacia terminalis: floral characteristics including colour and flowering time; style length; size and colour of extrafloral nectaries on the leaf petioles; chemical components of the extrafloral nectar; different taxa of bee pollinators; and frequency differences in bird pollinators. These differences possibly reflect the evolution of two different pollination syndromes within this species.     

Leontidine-type quinolizidine alkaloids in Orphanodendron (Leguminosae)

Herbarium leaf fragments of the two known species of Orphanodendron (Leguminosae), O. bernalii and O. grandiflorum, were found to contain the quinolizidine alkaloids camoensine (1), camoensidine (2) and guianodendrine (3), supporting the recent phylogenetic placement of the genus in the genistoid clade of subfamily Papilionoideae rather than its traditional placement in subfamily Caesalpinioideae.