Four new hypocretenolides (guaian-12,5-olides) from Leontodon rosani (Asteraceae,Cichorieae)

Subaerial parts of Leontodon rosani (Ten.) DC. collected in the South Italian Basilicata region yielded four new hypocretenolides, 11β,13-dihydro-15-hydroxyhypocretenolide (2), 15-hydroxyhypocretenolide (3), 11β,13-dihydro-15-hydroxyhypocretenolide-β-glucopyranoside (4), and 15-hydroxyhypocretenolide-β-glucopyranoside (5). Structure elucidations were based on MS experiments and extensive one- and two-dimensional NMR experiments. None of the isolated compounds showed any activity in an in vitro acetylcholinesterase inhibition assay. The chemosystematic impact of the occurrence of hypocretenolides in L. rosani is discussed with regards to the supposed allotetraploid origin of the title species. Moreover, HPLC retention times and online mass signals for all currently known hypocretenolide derivatives are described to ease future studies screening for this rare group of natural products.     

Natural products from Tolpis barbata (L.) Gaertn. (Asteraceae,Cichorieae)

One sesquiterpene lactone – 9α-hydroxy-3-deoxyzaluzanin C, three benzopyrans: desmethoxyencecalin (6-acetyl-2,2-dimethylchromene), desacetylripariochromen B and 6-(1-hydroxyethyl)-2,2-dimethylchromene, one coumarin – scopoletin and two eugenol derivatives were isolated from the roots of Tolpis barbata (L.) Gaertn, hitherto unexamined species. In the extract from aerial parts of the plant, five known phenolic compounds, namely: esculin, esculetin, chlorogenic acid (5-CQA), luteolin 7-O-glucoside and 3,5-dicaffeoylquinic acid (3,5-DCQA) were identified as major constituents. Except for the two coumarins – scopoletin and esculetin, which were previously obtained from Tolpis webbii Sch.Bip. and T. proustii Pit., the isolated and identified compounds have not been previously reported as constituents of Tolpis spp. Though benzopyrans were found in numerous species of the Asteraceae, their occurrence in the tribe Cichorieae has not been demonstrated before.     

Phytotoxic Potential of Onopordum acanthium L. (Asteraceae)

Onopordum acanthium L. (Asteraceae) is a plant native to southern Europe and southwestern Asia, but it is invasive in disturbed areas and agricultural fields around the world, causing many agronomic problems by interfering with crops or preventing animals from grazing on pastures. Allelopathy could be one of the reasons that this plant has spread over different continents. The aim of the present study was to bioprospect O. acanthium leaf extracts through the isolation and purification of allelopathic secondary metabolites with phytotoxicity to explain their invasive behavior. Phytotoxic activity was tested using etiolated wheat coleoptiles. The most active extract was selected to perform a bioassay‐guided isolation of two flavonoids, pectolarigenin ( 1 ) and scutellarein 4′‐methyl ether ( 2 ), and two sesquiterpene lactones, elemanolide 11(13)‐dehydromelitensin β‐hydroxyisobutyrate ( 3 ) and acanthiolide ( 4 ). All compounds were isolated for the first time from O. acanthium, and acanthiolide ( 4 ) is described for the first time. Compound 3 strongly inhibited the growth of wheat coleoptiles and 1 showed an intermediate effect. The results indicate that these compounds could contribute to the invasion of O. acanthium in ecological systems and agricultural fields.     

Antileishmanial activity and ultrastructural changes of sesquiterpene lactones isolated from Calea pinnatifida (Asteraceae)

Bioactivity-guided fractionation of antileishmanial active CH₂Cl₂ phase of MeOH extract from leaves of Calea pinnatifida led to isolation of two sesquiterpene lactones calein C (1) and calealactone C (2), which structures were stablished on the basis of spectroscopic analysis. Compounds 1 and 2 displayed potent activity against Leishmania amazonensis promastigotes with EC₅₀ of 1.7 and 4.6 µg mL⁻¹, respectively. Compound 2 presented low cytotoxicity for J774 macrophages and displayed activity against amastigote forms of L. amazonensis similar to miltefosine with CC₅₀ values of 31.73 and 27.18 µg mL⁻¹, respectively. Additionally, compounds 1 and 2 caused ultrastructural changes in promastigotes leading to a loss of their classical structural morphology, as evidenced by electron microscopy. Also compound 2 decreased the mitochondria membrane potential. To the best of our knowledge, this is the first occurrence of 1 and 2 in C. pinnatifida. The results obtained highlighted the importance of studying sesquiterpene lactones isolated from Calea pinnatifida in terms of antileishmanial activity, in order to understand the mechanism of action of the isolated compounds in promastigotes forms of L. amazonensis.     

Flavonoids as chemosystematic markers in the tribe Cichorieae of the Asteraceae

This review summarizes reports on flavonoids from the Cichorieae (Lactuceae) tribe of the Asteraceae family. A total of 135 different compounds have been reported from 354 taxa belonging to 299 species, including many cultivars of common vegetables like chicory and lettuce. The reported compounds encompass flavanones (11 compounds), flavanonols (2 compounds), flavones (72 compounds), flavonols (35 compounds), anthocyanidins (9 compounds), isoflavonoids (2 compounds), chalcones (3 compounds), and an aurone. So far only 43 of the approximately 100 currently recognized genera of the tribe Cichorieae have been investigated for the occurrence of flavonoids. The distribution of the various classes of flavonoids is analyzed with regards to data from the current molecular-based reassessment of the systematics of the tribe.     

Characterization and evolution of secondary metabolites in Brazilian Vernonieae (Asteraceae) assessed by LC‐MS fingerprinting

Tribe Vernonieae are well represented in Brazil, mainly by subtribe Lychnophorinae comprising mostly perennial plants that inhabit arid lands, where species have developed a number of adaptations with recognized ecological protective functions, including secondary metabolite diversification. Recent phylogenetic studies indicate that the subtribe is monophyletic, but questions regarding lineage relationships have yet to be resolved. Phytochemical investigations have also been conducted recently and provide information on the secondary metabolite chemistry of Lychnophorinae. Chemotaxonomic studies have also been carried out. However, these phytochemical investigations are fragmentary and non‐standardized. Therefore, in this study, 15 species representing the major lineages of the subtribe were selected for phytochemical investigation and reconstruction of the ancestral states of their secondary metabolites. The main secondary metabolites of these species were detected by UHPLC‐UV‐MS in different types of extract, showing the presence of trans‐cinnamic acid derivatives, flavonoids, polyacetylenes and sesquiterpene lactones. The ancestral states of these secondary metabolites were reconstructed by parsimony and indicate the occurrence of 12 putative chemical synapomorphies. In this study, we present for the first time phytochemical and evolutionary studies based on the reconstruction of the ancestral chemical character states on a phylogenetic tree of Lychnophorinae.     

Sesquiterpene lactones from glandular trichomes of Viguiera radula (Heliantheae; Asteraceae)

In addition to known compounds, the floral parts of Viguiera radula afforded two new sesquiterpene lactones. All compounds were detected in glandular trichomes, which were micromechanically collected from the anther appendages and analyzed by HPLC. Structure identification was performed by NMR and MS techniques.     

Molecular phylogenetics reveals Leontodon (Asteraceae, Lactuceae) to be diphyletic

The plastid matK gene, trnL/F spacer, and nuclear rDNA ITS were sequenced for 36 species of Leontodon and 29 taxa of related genera of tribe Lactuceae. Phylogenetic relationships inferred from the independent and combined data are largely congruent and reveal that Leontodon sensu lato (s.l.) as presently defined is diphyletic: L. subgenus Leontodon forms a clade with Helminthotheca, Picris and Hypochaeris as sister genera, whereas L. subgenus Oporinia appears as a separate clade with strong bootstrap support and is thus better treated as a separate genus. Previous sectional classifications of Leontodon s.l. are considered in the light of DNA and additional morphological and karyological data. Support is presented for a core group of Hypochaeridinae sensu stricto (s.s.) with the two clades of Leontodon s.l., Helminthotheca, Picris, and Hypochaeris, whereas Urospermum, Hyoseris, Aposeris, and Rhagadiolus appear to be positioned more distantly.     

Studies on the cytotoxicity of miscellaneous compounds from Eupatorium betonicaeforme (D.C.) Baker (Asteraceae)

A detailed study on the cytotoxic effects of five known constituents isolated from the flowers and roots of Eupatorium betonicaeforme is reported, including 2,2-dimethyl-6-vinylchroman-4-one (1), 2-senecioyl-4-vinylphenol (2), 6-acetyl-2,2-dimethylchroman-4-one (3), (4E)-8beta-angeloyloxy-9beta,10beta-dihydroxy-1-oxogermacra-4,11(13)-dien-12,6alpha-olide (4), and 3beta-hydroxyicosan-1,5beta-olide (5). The sesquiterpene lactone 4 exhibited the highest cytotoxicity, with IC50 values ranging from 3.9 to 9.9 microM, showing some degree of cell selectivity. The antiproliferative activity of 4 was examined towards HL-60 cells, and found to diminish cell viability in a dose-dependent manner. Moreover, at all concentrations tested, there was a decrease in the number of cells capable of incorporating 5-bromo-2'-deoxyuridine (BrdU), indicating disruption of DNA synthesis. The morphological changes induced by 4 were compatible with apoptotic cell death. This work, thus, corroborates the anticancer potential of Eupatorium secondary metabolites.     

Molecular and phytochemical systematics of the subtribe Hypochaeridinae (Asteraceae,Cichorieae)

The systematics of the Hypochaeridinae subtribe was re-evaluated based on a combination of published and new molecular data. Newly found clades were additionally characterized using published and new phytochemical data. In addition to flavonoids and sesquiterpene lactones, which had been reviewed recently as chemosystematic markers in the Cichorieae, we analysed the reported occurrences of caffeic acid derivatives and their potential as chemosystematic markers. Our molecular results required further changes in the systematics of the genus Leontodon. Based on previous molecular data, Leontodon s.l.—i.e. including sections Asterothrix, Leontodon, Thrincia, Kalbfussia, and Oporinia (Widder 1975)—had been split into the genera Leontodon s.str. (sections Asterothrix, Leontodon, and Thrincia) and Scorzoneroides (sections Kalbfussia and Oporinia). Instead of splitting Leontodon into even a higher number of segregate genera we propose to include Hedypnois into Leontodon s.str. and here into section Leontodon. Moreover, sections Asterothrix and Leontodon should be merged into a single section Leontodon. The newly defined genus Leontodon is characterised by the unique occurrence of hydroxyhypocretenolides. The monophyly of the genus Hypochaeris is neither supported nor contradicted and potentially comprises two separate molecular clades. The clade Hypochaeris I comprises the majority of the European and Mediterranean as well as all South American taxa of Hypochaeris s.l. while the clade Hypochaeris II encompasses only H. achyrophorus L., H. glabra L., H. laevigata Benth. & Hook.f., and H. radicata L.     

A new species and two new combinations of Leontodon (Asteraceae, Hypochoeridinae)

Leontodon palisiae sp. nov. occurring in the Iberian Peninsula, Morocco and the Canary Islands is described and illustrated. Cytological data as well as some preliminary results of self-incompatibility tests in L. palisiae are presented. A comparative carpological study of L. muelleri, L. palisiae and L. salzmannii using the SEM is made, and an identification key of these three species is provided. Two new combinations, L. muelleri ssp. trivialis comb. nov., from Morocco, and L. kralikii comb. nov., from Libya and Tunisia, are proposed. All taxa belong to the series Annui of sect. Kalbfussia in subgenus Oporinia. The basic chromosome number x=5 is here reported for the first time within the genus.     

The infraspecific taxa of Pleiotaxis huillensis (Mutisieae, Asteraceae)

The species from Angola Pleiotaxis huillensis (Mutisieae, Asteraceae) is subdivided into three subspecies and one variety. Specifically, P. huillensis subsp axillaris and P. huillensis subsp. huillensis var. macrocephala are described as new taxa, and a new nomenclatural combination is proposed ( P. huillensis subsp. argentea ).     

微生物异源合成咖啡酸及其酯类衍生物研究进展

咖啡酸及其酯类衍生物如绿原酸、迷迭香酸和咖啡酸苯乙酯等具有天然抗氧化、抗肿瘤、抗病毒和抗炎等重要的药理活性,具有广阔的药用开发前景。从天然药物中提取或者化学合成咖啡酸及其酯类衍生物,存在含量低、提取效率不高、催化成本高昂以及环境污染等问题。随着咖啡酸及其酯类衍生物合成途径解析和合成生物学的快速发展,微生物异源合成咖啡酸及其酯类衍生物的研究已逐渐展开。对微生物异源合成咖啡酸及其酯类衍生物合成途径的最新进展以及代谢工程策略进行了综述,并讨论了目前存在的问题和未来的发展趋势。     

Metabolomic Profile of the Genus Inula

Plants have a long history as therapeutics in the treatment of human diseases and have been used as source of medicines for ages. Searching for new biologically active natural products, many plants and herbs are screened for natural products with pharmacological activities. In this field, the genus Inula, which comprises more than 100 species, several of them being used in traditional medicine, is very important, especially due to the finding that several of the isolated pure secondary metabolites proved to possess important biological activities. Inula species have been reported as rich sources of sesquiterpene lactones, including eudesmanes, germacranes, guaianes, and dimeric structures, and since 2006 ca. 400 secondary metabolites, including more than 100 new natural products, some of them with relevant pharmacological activities, have been identified. Herein, we critically compile and update the information regarding the types of secondary metabolites found in the genus Inula and the progress in their isolation.     

Chemotaxonomic value of flavonoids in Chromolaena congesta (Asteraceae)

The phytochemical investigation on the aerial parts of Chromolaena congesta led to the isolation of nine flavonoids, known in the literature as genkwanin (1) kumatakenin (2) acacetin (3), kaempferol 3-methyl ether (4), apigenin (5), apigenin 5,7-dimethyl ether (6), apigenin 5-methyl ether (7), luteolin (8) and kaempferol (9). The chemical structures were established on the basis of spectral evidence. All the compounds were isolated from this species for the first time. The results from the present study provide further information about the flavonoids as taxonomic marker of the genus Chromolaena, and the chemotaxonomic significance of these compounds were also summarized.     

Systematic significance of achene morphology in Soroseris,Syncalathium and Parasyncalathium (Asteraceae: Cichorieae)

The systematic significance of the morphological structure of achenes in the Himalayan–Tibetan Plateau endemic genera Soroseris, Syncalathium and Parasyncalathium is described and discussed. The achene surface sculpturing of 15 samples representing 13 species of the three genera was investigated using scanning electronic microscopy (SEM) to evaluate inter‐ and intrageneric relationships of the three genera. Characters such as cell arrangement, shape of the epidermis, type of ornamentation of the outer cell wall and degree of wax development are described. The results show that characters such as the shape of the epidermis and the type of ornamentation of the outer cell wall are distinct between the three genera and useful for species‐level classification. Parasyncalathium souliei differs from Syncalathium, in which it has traditionally been placed, in the short, stout beak of the achene and especially in the obscure outline of the epidermal cells and their long acuminate, steeple‐like, end walls. Combined with karyological and molecular data, the differences in achene morphology and sculpturing further support our recognition of Parasyncalathium as distinct from Syncalathium. The achene characters are not only useful for assessing relationships, but are also useful for delimiting species. © 2013 The Linnean Society of London, Botanical Journal of the Linnean Society, 2013, 173 , 476–486.