Diterpenoids from the Chinese liverwort Frullania hamatiloba and their Nrf2 inducing activities.

Six previously undescribed labdane diterpenoids, frullanians A-F, along with five known diterpenoids, were isolated from the Chinese liverwort Frullania hamatiloba Stephani. Their structures were determined using NMR data, electronic circular dichroism (ECD) calculations as well as the single crystal X-ray diffraction measurement. NAD(P)H: QR (quinone reductase) assay demonstrated that frullanian D and four known compounds displayed antioxidant effect mediated via Nrf2 (Nuclear factor-erythroid 2-related factor 2) induction. Further investigation of the most bioactive frullanian D in MOVAS cells revealed that it ameliorated H2O2-induced oxidative insults without toxicity by increasing cell viability, attenuating morphological changes, and reducing intracellular ROS production. In addition, frullanian D promoted the nuclear translocation of Nrf2 and upregulated the expressions of antioxidant proteins NQO1 (NAD(P)H quinone oxidoreductase 1) and γ-GCS (γ-glutamyl cysteine synthetase). Docking analysis using MOE software further supported the activation of the Nrf2 pathway by frullanian D.

Species delimitation and biogeography of a southern hemisphere liverwort clade, Frullania subgenus Microfrullania (Frullaniaceae, Marchantiophyta).

Frullania subgenus Microfrullania is a clade of ca. 15 liverwort species occurring in Australasia, Malesia, and southern South America. We used combined nuclear and chloroplast sequence data from 265 ingroup accessions to test species circumscriptions and estimate the biogeographic history of the subgenus. With dense infra-specific sampling, we document an important role of long-distance dispersal in establishing phylogeographic patterns of extant species. At deeper time scales, a combination of phylogenetic analyses, divergence time estimation and ancestral range estimation were used to reject vicariance and to document the role of long-distance dispersal in explaining the evolution and biogeography of the clade across the southern Hemisphere. A backbone phylogeny for the subgenus is proposed, providing insight into evolution of morphological patterns and establishing the basis for an improved sectional classification of species within Microfrullania. Several species complexes are identified, the presence of two undescribed but genetically and morphologically distinct species is noted, and previously neglected names are discussed.

Cyanobacterial gardens: the liverwort Frullania asagrayana acts as a reservoir of lichen photobionts.

Cyanobacteria are important mediators of unrelated lichen species, which form epiphytic communities that share the same cyanobiont. No study to date, however, has considered the role of cyanobacteria as mediator between lichens and bryophytes. In the present study, DNA barcoding (16S rDNA, rbcLX) was used to identify filamentous cyanobacteria living in close association with members of an epiphytic liverwort-lichen community on balsam fir in Newfoundland. This study is the first to confirm the presence of Rhizonema strains in boreal forests where they are associated with the liverwort Frullania asagrayana and several lichen species. The majority of cyanobacterial haplotypes can associate with the liverwort, however, some lichen species appear to be more selective for single or closely related haplotypes. Some Rhizonema strains were found exclusively in association with boreal lichens, while others seem to be globally distributed and involved in different lichen symbioses of unrelated fungal lineages and of varying ecological traits. Complex biological interactions in a cyanobacteria-mediated guild are proposed here, which explains composition and dynamics in bryophyte and lichen-dominated epiphytic communities.

Volatile Constituents of New Caledonian Frullania Species.

Volatile components of seven Frullania species (Frullaniaceae) from New Caledonia, including five endemic species (F. bella, F. scalaris, F. mamnmillosa, F. cornita and F. falsicornuta), were analyzed by GC-MS in order to index these plants to known chemotypes. Constituents detected in these Frullania species were mainly sesquiterpenes, as well as the bibenzyl dihydrognetin, and the flavonoid naringinin-5,7,4'-trimethyl ether. These compositions allowed an indexation of Frullania species from New Caledonia to cyclocolorenone, sesquiterpene lactone and bibenzyl chemotypes. In addition, qualitative intraspecies variations of chemical composition were very important and made indexation to known chemotypes very tricky. Moreover, two of the endemic liverworts did not possess any biomarker that linked to a known chemotype.

Two new cadinane-type sesquiterpenes from the Chinese liverwort Frullania serrata.

Two new cadinane-type sesquiterpenes, frullanic acid (1) and frullanic acid methyl ester (2), together with four known bibenzyls, brittonin B (3), 3,3'-dimethoxy-4,5-methylenedioxybibenzyl (4), 3,4,5,3',4'-penlamethoxybibenzyl (5) and (±)-3-(4'-methoxybenzyl)-5,6-dimethoxyphtbalide (6), were isolated from the Chinese liverwort Frullania serrata. The structures of the new metabolites were elucidated by analysing the spectroscopic data (1D NMR, 2D NMR, HR-ESI-MS and IR). The absolute configurations of compounds 1 and 2 were determined by comparing the experimental and calculated electronic circular dichroism spectra predicted by using time-dependent density functional theory as well as the CD exciton chirality method.

First asymmetric total syntheses and determination of absolute configurations of (+)-eudesmadiene-12,6-olide and (+)-frullanolide.

The first asymmetric total syntheses of sesquiterpene lactones (+)-eudesmadiene-12,6-olide (1) and (+)-frullanolide (2) have been accomplished from 4-bromo-2-methoxyphenol (5) in 12 and 13 synthetic steps, respectively, and the absolute configurations of these two natural products were determined.

Labdane diterpenoids and highly methoxylated bibenzyls from the liverwort Frullania inouei.

Four undescribed labdane diterpenoids, 1,2-dehydro-3,7-dioxo-manoyl oxide (1), 1,2-dehydro-7 beta-hydroxy-3-oxo-manoyl oxide (2), 3,7-dioxo-manoyl oxide (3), and 3beta-hydroxy-7-oxo-manoyl oxide (4) together with three known diterpenoids (5-7) and four highly methoxylated bibenzyls (8-11) were isolated from the liverwort Frullania inouei. The absolute structures of 1-4 were established by combined analysis of NMR data, CD data coupled with TDDFT CD calculations, and single-crystal X-ray diffraction measurement. Cytotoxicity tests to human tumor KB, KB/VCR, K562 or K562/A02 cells showed bibenzyls 8-11 inhibited cell proliferation with ID(50) values ranging from 11.3 to 49.6 microM and overcame the multidrug resistance (MDR) with the reversal fold (RF) values ranging from 3.19 to 10.91 (5 microM) for vincristine-resistant KB/VCR and RF values from 4.40 to 8.26 (5 microM) for adriamycin-resistant K562/A02 cells, respectively. However, none of the diterpenoids were found to be active (ID(50)>50 microM).

Bazzanane sesquiterpenoids from the New Zealand liverwort Frullania falciloba.

Two new bazzanane-type sesquiterpenoids have been isolated from the New Zealand liverwort Frullania falciloba. Their structures were confirmed by NMR and CD spectroscopy and chemical reactivity.

Novas ocorrências de hepáticas (Marchantiophyta) para o estado do Pará, Brasil / New occurrences of liverworts for the Pará state, Brazil

Durante o inventário das hepáticas da Serra dos Carajás, foram identificadas quatro novas ocorrências para o estado do Pará: Frullania beyrichiana (Lehm. & Lindenb.) Lehm. & Lindenb, Frullania kunzei (Lehm. & Lindenb.) Lehm. & Lindenb, Symphyogyna aspera Steph. e Lophocolea leptantha (Hook. & Tayl.) Tayl. Esta última espécie, antes somente relacionada para as regiões Sudeste e Sul do Brasil, é nova ocorrência para o eixo Norte-Nordeste brasileiro. Cada espécie é acompanhada de comentários morfológicos, taxonômicos e ecológicos.

Routine patch testing with frullanolide mix: an European Environmental and Contact Dermatitis Research Group multicentre study.

Contact sensitivity to plants containing 1 or more sesquiterpene lactones (SLs) is difficult to diagnose. The mixture of SLs (SL mix) has been shown to detect only about 60% of sensitized individuals. In order to improve the diagnosis of sensitization to plants containing SLs, we have tested a mixture of frullanolides contained in Frullania dilatata and Frullania tamarisci at 3 different concentrations (0.01%, 0.033% and 0.1% in petrolatum). 8605 consecutive eczema patients in 1 North American and 15 European dermatology departments were tested with this mix, and 0.35% of positive cases to the different concentrations were found. Routine use of this mix permitted detection of only a small percentage of extra cases and did not improve the SL mix score. The frullanolide mix should therefore be restricted to investigations in particular geographical zones and/or in particular occupations.

Volatile components of selected species of the liverwort genera Frullania and Schusterella (Frullaniaceae) from New Zealand, Australia and South America: a chemosystematic approach.

The volatile components of 25 taxa of the liverwort family Frullaniaceae from New Zealand, Australia and South America have been analyzed by GC-MS. The present Frullania species are chemically divided into five major types: (1) sesquiterpene lactones, (2) sesquiterpene lactones-bibenzyls, (3) bibenzyls, (4) 2-alkanone and (5) triterpene types; the latter two chemo-types are newly proposed for the genus. Schusterella chevalierii, belonging to the Frullaniaceae, is closely related chemically to the sesquiterpene lactone type of the Frullania species since it elaborates two eudesmanolides, beta-cyclocostunolide and dihydro-beta-cyclocostunolide as major components.

A cytotoxic diterpenoid and antifungal phenolic compounds from Frullania muscicola Steph.

A novel ent-labdane type diterpenoid, muscicolone (1), as well as two bibenzyls (2, 3) and four flavonoids (4-7) were isolated from the liverwort Frullania muscicola Steph. Their structures were established by analysis of the spectral data of IR, UV, ID-, 2D-NMR, and ORD. The stereostructure of 1 was confirmed by X-ray crystallographic analysis. Bioassay experiments showed that compound 3 and 4 have potent inhibitory effects against some fungi while 1 showed cytotoxic effects to some human tumor cells.