Xanthones from fungi, lichens, and bacteria : the natural products and their synthesis

Many fungi, lichens, and bacteria produce xanthones (derivatives of 9H-xanthen-9-one, “xanthone” from the Greek “xanthos”, for “yellow”) as secondary metabolites. Xanthones are typically polysubstituted and occur as either fully aromatized, dihydro-, tetrahydro-, or, more rarely, hexahydro-derivatives. This family of compounds appeals to medicinal chemists because of their pronounced biological activity within a notably broad spectrum of disease states, a result of their interaction with a correspondingly diverse range of target biomolecules. This has led to the description of xanthones as “privileged structures”.(1) Historically, the total synthesis of the natural products has mostly been limited to fully aromatized targets. Syntheses of the more challenging partially saturated xanthones have less frequently been reported, although the development in recent times of novel and reliable methods for the construction of the (polysubstituted) unsaturated xanthone core holds promise for future endeavors. In particular, the fascinating structural and biological properties of xanthone dimers and heterodimers may excite the synthetic or natural product chemist.

Species of Lissothrips and Williamsiella from mosses and lichens in Australia and New Zealand (Thysanoptera, Phlaeothripinae)

Species of Lissothrips and Williamsiella live in association with mosses and lichens. Their gut contents are commonly blue-green, suggesting that they possibly feed on blue-green algae. Three species of Lissothrips are known from New Zealand, of which two are here recorded from Australia together with six new species. Williamsiella is recorded from Australia for the first time, with one new species.

Phylogenetic studies of cyanobacterial lichens

Phylogenetic studies of cyanobacterial lichens Lichens are symbiotic assemblages between fungi (mycobiont) and green algae (phycobiont) or/and cyanobacteria (cyanobiont). Fossil records show that lichen-like symbioses occurred already 600 million years ago. Lichen symbiosis has since then become an important life strategy for the Fungi, particularly for species in the phylum Ascomycota as approximately 98% of the lichenized fungal species are ascomycetes. The taxonomy of lichen associations is based on the mycobiont. We reconstructed, using DNA sequence data, hypotheses of phylogenetic relationships of lichen-forming fungi that include species associated with cyanobacteria. These hypotheses of phylogeny should form the basis for the taxonomy. They also allowed studies of the origin and the evolution of specific symbioses. Genetic diversity and phylogenetic relationships of symbiotic cyanobionts were also studied in order to examine selectivity of cyanobionts and mycobionts as well as possible co-evolution between partners involved in lichen associations. The suggested circumscription of the family Stereocaulaceae to include Stereocaulon and Lepraria is supported. The recently described crustose Stereocaulon species seem to be correctly placed in the genus, although Stereocaulon traditionally included only fruticose species. The monospecific crustose genus Muhria is also shown to be best placed in Stereocaulon. Family Lobariaceae as currently delimited is monophyletic. Within Lobariaceae genus Sticta including Dendriscocaulon dendroides form a monophyletic group while the genera Lobaria and Pseudocyphellaria are non-monophyletic. A new classification of Lobariaceae is obviously needed. Further studies are however required before a final proposal for a new classification can be made. Our results show that the cyanobacterial symbiotic state has been gained repeatedly in the Ascomycota while losses of symbiotic cyanobacteria appear to be rare. The symbiosis with green algae is confirmed to have been gained repeatedly in Ascomycota but also repeatedly lost. Cyanobacterial symbioses therefore seem to be more stable than green algal associations. Cyanobacteria are perhaps more beneficial for the lichen fungi and therefore maintained. The results indicate a dynamic association of the lichen symbiosis. This evolutionary instability will perhaps be important for the lichen fungi as the utilization of options will perhaps enable lichens to colonize new substrates and survive environmental changes. Some cyanobacterial lichen genera seem to be highly selective towards the cyanobiont while others form symbioses with a broad spectrum of cyanobacteria. No evidence of co-evolution between fungi and cyanobacteria in cyanolichens could be demonstrated.

Taxonomy and phylogeny of the manna lichens and allied species (Megasporaceae)

This dissertation is focused on the taxonomy, phylogeny, and ecology of the vagrant, erratic and allied terricolous and saxicolous species of the genera Aspicilia A. Massal. and Circinaria Link (Megasporaceae), particularly those traditionally referred to as manna lichens . The group has previously been defined on the basis of few morphological characters. The phylogeny of the family Megasporaceae is inferred from the combined dataset of nuLSU and mtSSU sequences. Five genera Aspicilia, Circinaria, Lobothallia, Megaspora, and Sagedia are recognized. Lobothallia is sister of the four other genera, while Aspicilia and Sagedia form the next clade. All these genera have small asci with eight spores. Circinaria is a sister genus of Megaspora, and these two have in common asci with (1 4) 6 8 large spores. Circinaria forms a monophyletic group and sphaerothallioid species form a monophyletic group within Circinaria. The presence of certain morphological characters such as pseudocyphellae, thickness of cortex and medulla layers, as well as ecological differences in sphaerothallioid species distinguish it from some other crustose species, especially those containing aspicilin and characterised by thin cortex and medulla layers, conidium length c. 6 12 µm and absence of pseudocyphellae. If sphaerothallioid species are accepted as a distinct genus, the rest of the Circinaria species would remain as a paraphyletic assemblage. Currently, the genus Circinaria includes all the sphaerothallioid species and its generic position is confirmed and accepted. Thus, it is proposed as a correct generic name also for the manna lichens described originally in other genera. Phylogeny at the species level was studied using nrITS sequence data. Traditionally, morphological characters have been used for the recognition of species. They were re-evaluated in the light of molecular data. Since characters such as vagrant, erratic and crustose growth forms proved to be misleading for the recognition of some species, a combination of several characters (including molecular data) is recommended. Vagrant growth form seems to have evolved several times among the distantly related lineages and even within a single population. The reasons behind the high plasticity in the external morphology of the sphaerothallioid Circinaria remain, however, unknown. Six new species are recognized: Aspicilia tibetica, Circinaria arida, C. digitata nom provis., C. gyrosa nom. provis., C. rogeri nom. provis., and C. rostamii nom. provis. Based on an analysis of nrITS dataset, three new erratic, vagrant and crustose species were also recognized, but these require additional study. The results also reveal that C. elmorei and C. hispida are not monophyletic as currently understood. In addition, 13 new combinations in the genus Circinaria are proposed.

Biomonitoring of air pollutants by using lichens (Evernia prunastri) in areas between Kenitra and Mohammedia cities in Morocco.

In this study, Evernia prunastri, a lichen growing in its natural habitat in Morocco was analysed for the concentration of five heavy metals (Fe, Pb, Zn, Cu and Cr) from eleven sites between Kenitra and Mohammedia cities. The control site was Dar Essalam, an isolated area with low traffic density and dense vegetation. In the investigated areas, the concentration of heavy metals was correlated with vehicular traffic, industrial activity and urbanization. The total metal concentration was highest in Sidi Yahya, followed by Mohammedia and Bouznika. The coefficient of variation was higher for Pb and lower for Cu, Zn and Fe. The concentrations of most heavy metals in the thalli differed significantly between sites (p<0.01). Principal component analysis (PCA) revealed a significant correlation between heavy metal accumulation and atmospheric purity index. This study demonstrated also that the factors most strongly affecting the lichen flora were traffic density, the petroleum industry and paper factories in these areas. Overall, these results suggest that the index of atmospheric purity and assessment of heavy metals in lichen thalli are good indicators of the air quality at the studied sites.

Validations and descriptions of European syntaxa of vegetation dominated by lichens, bryophytes and algae

Fourty-two high-rank syntaxa and seven associations of the thallophyte system of syntaxa are either described as new or validated in this paper. Among those, there are the following nine classes: Aspicilietea candidae, Caulerpetea racemosae, Desmococcetea olivacei, Entophysalidetea deustae, Gloeocapsetea sanguineae, Mesotaenietea berggrenii, Naviculetea gregariae, Porpidietea zeoroidis, Roccelletea phycopsis. Eleven orders and ten alliances as well as three associations are described or validated: the Aspicilietalia verruculosae (incl. Aspicilion mashiginensis and Teloschistion contortuplicati), the Caulerpetalia racemosae (incl. Caulerpion racemosae), the Desmococcetalia olivacei (incl. Desmococcion olivacei), the Dirinetalia massiliensis, the Fucetalia vesiculosi (incl. Ascophyllion nodosi), the Gloeocapsetalia sanguineae, the Lecideetalia confluescentis (incl. Lecideion confluescentis), the Mesotaenietalia berggrenii (incl. Mesotaenion berggrenii, Mesotaenietum berggrenii and Chloromonadetum nivalis), the Naviculetalia gregariae (incl. Oscillatorion limosae and Oscillatorietum limosae), the Porpidietalia zeoroidis (incl. Porpidion zeoroidis), and the Roccelletalia fuciformis (incl. Paralecanographion grumulosae). Further, five orders, seven alliances and four associations, classified in known classes, were described as well. These include: the Bacidinetalia phacodis, the Agonimion octosporae and the Dendrographetalia decolorantis (all in the Arthonio radiatae-Lecidelletea elaeochromae), the Staurothelion solventis (in the Aspicilietea lacustris), the Pediastro duplicis-Scenedesmion quadricaudae and the Pediastro duplicis-Scenedesmetum quadricaudae (both in the Asterionelletea formosae), the Peccanion coralloidis and the Peltuletalia euplocae (both in the Collematetea cristati), the Laminarion hyperboreae, the Saccorhizo polyschidi-Laminarietum and the Alario esculenti-Himanthalietum elongatae (all in the Cystoseiretea crinitae), the Delesserietalia sanguinei, the Delesserion sanguinei and the Delesserietum sanguineae (all in the Lithophylletea soluti), as well as the the Rinodino confragosae-Rusavskietalia elegantis and the Rhizocarpo geographici-Rusavskion elegantis (both in the Rhizocarpetea geographici).

Microfaunal communities associated with epiphytic lichens in Belfast

The composition and richness of the microfauna on lime trees was surveyed in relation to the distribution and cover of lichens in Belfast. Parameters used to help interpret the results included distance from the city centre and available data on air quality. The percentage epiphyte cover on the trunks of lime trees was significantly correlated with distance from the city centre whereas that on tree bases as not. In contrast, the number of microfaunal species revealed strong positive correlations with distance for both the bases and the trunks of trees. Most of this increase in microfaunal species richness towards rural areas was due to protistans which are thus proposed as useful bioindicators of air pollution. The total species richness of fauna showed slight negative correlation with smoke but not SO2 levels.

The use of lichens as indicators of ambient air quality in Southern Ontario

The inverse relationship between arboreal lichen species richness and sulphur dioxide in ambient air has been thoroughly documented in the literature. Previous work in southern Ontario has shown that lichen bioindication can identify areas of potential concern regarding air quality. The EMAN suite of l i chens was applied in the City of Samia by surveying 458 Sugar Maple trees, in order to test the applicability of lichen bioindication under conditions of high mean S02 levels and high species richness values. The results of the survey were explored using Geographic Information Systems. A spatial relationship between lichen community variables, the Bluewater Bridge and the highway was identified. Lichen species richness, lichen percent cover and Index of Atmospheric Purity values were higher along the bridge and highway. No strong gradients were found between other known pollution sources and no lichen deserts were identified. The most common community grouping consisted of Physcia millegrana Degel, Candelaria concolor (Dicks) B. Stein, Physcia aipolia (Ehrh ex Humb.) Furnrohr; all of which are known nitrophytes. The relationship between substrate pH and lichen species richness was examined. Sites with a known source of anthropogenic chemical contamination were found to have a correlation of l=0.8 between lichen species richness and pH. The inverse was found for sites with no known source of contamination with a correlation of r 2 =-0.72. The findings suggest that species richness may be influenced by altering substrate pH which promotes the growth of nitrophytic species capable of tolerating high S02 levels.

Lichens used as monitors of atmospheric pollution around Agadir (Southwestern Morocco) - a case study predating lead-free gasoline

More than 30 epiphytic lichens, collected in Agadir (Morroco) and along a 150-km transect from the Atlantic Ocean eastward, were analyzed for their metal content and lead isotopic composition. This dataset was used to evaluate atmospheric metal contamination and the impact of the city on the surrounding area. The concentrations of Cu, Pb, and Zn (average ± 1 SD) were 20.9 ± 15.2 μg g−1, 13.8 ± 9.0 μg g−1, and 56.6 ± 26.6 μg g−1, respectively, with the highest values observed in lichens collected within the urban area. The 206Pb/207Pb and 208Pb/207Pb ratios in the lichens varied from 1.146 to 1.186 and from 2.423 to 2.460, respectively. Alkyllead-gasoline sold in Morocco by the major petrol companies gave isotopic ratios of 206Pb/207Pb = 1.076–1.081 and 208Pb/207Pb = 2.348–2.360. These new, homogeneous values for gasoline-derived lead improve and update the scarce isotopic database of potential lead sources in Morocco, and may be of great value to future environmental surveys on the presence of lead in natural reservoirs, where it persists over time (e.g., soils and sediments). The interest of normalizing metal concentrations in lichens to concentrations of a lithogenic element is demonstrated by the consistency of the results thus obtained with lead isotopic ratios. Leaded gasoline contributed less than 50% of the total amount of lead accumulated in lichens, even in areas subject to high vehicular traffic. This strongly suggests that the recent banishment of leaded gasoline in Morocco will not trigger a drastic improvement in air quality, at least in Agadir.

Intermediate reactive oxygen and nitrogen from macrophages induced by Brazilian lichens

The activity of ten compounds isolated from Brazilian lichen over the release of hydrogen peroxide and nitric oxide was evaluated in the culture of peritoneal macrophage cells from mice. Salazinic, secalonic A and fumarprotocetraric acids were the compounds that induced the greatest release of H2O2, whereas 12R-usnic and diffractaic acids induced the release of NO. These results indicate that lichen products have potential immunological modulating activities. (C) 2004 Elsevier B.V. All rights reserved.

Immunostimulatory effects of the phenolic compounds from lichens on nitric oxide and hydrogen peroxide production

The effects of isolated compounds from Brazilian lichens and their derivatives on H 2O 2 and NO production were studied using murine macrophages as a part of an attempt to understand their possible immunomodulatory properties. The compound cytotoxicity was studied using MTT assay. Macrophage stimulation was evaluated by the determination of NO (Griess assay) and H 2O 2 (horseradish peroxidase/phenol red) in supernatants of peritoneal macrophage cultures of Swiss mice. This research demonstrated stimulatory activities of some phenolic compounds isolated from lichens and their derivatives on H 2O 2 and NO production. Structure-activity relationships suggest several synthetic directions for further improvement of immunological activity.

Elemental composition evaluation in lichens collected in the industrial city of So Mateus Sul, Parana, Brazil

In this study, Canoparmelia texana lichenized fungi species was used as a passive biomonitor of the atmospheric pollution from the industrial city of So Mateus do Sul, PR, Brazil. Lichen samples collected from tree barks were cleaned, freeze-dried and analyzed by neutron activation analysis. Comparisons were made between the element concentrations obtained in lichens from this city and that from a clean area of Atlantic Forest in Intervales Park, SP. The high concentrations of elements As, Ca, Co, Cr, Fe, Hf, Sb, and Th found in lichens could be attributed to the emissions from a ceramic and an oil shale plants.

Process-based modelling of lichens and bryophytes and their role in global biogeochemical cycles

This thesis presents a process-based modelling approach to quantify carbon uptake by lichens and bryophytes at the global scale. Based on the modelled carbon uptake, potential global rates of nitrogen fixation, phosphorus uptake and chemical weathering by the organisms are estimated. In this way, the significance of lichens and bryophytes for global biogeochemical cycles can be assessed. The model uses gridded climate data and key properties of the habitat (e.g. disturbance intervals) to predict processes which control net carbon uptake, namely photosynthesis, respiration, water uptake and evaporation. It relies on equations used in many dynamical vegetation models, which are combined with concepts specific to lichens and bryophytes, such as poikilohydry or the effect of water content on CO2 diffusivity. To incorporate the great functional variation of lichens and bryophytes at the global scale, the model parameters are characterised by broad ranges of possible values instead of a single, globally uniform value. The predicted terrestrial net uptake of 0.34 to 3.3 Gt / yr of carbon and global patterns of productivity are in accordance with empirically-derived estimates. Based on the simulated estimates of net carbon uptake, further impacts of lichens and bryophytes on biogeochemical cycles are quantified at the global scale. Thereby the focus is on three processes, namely nitrogen fixation, phosphorus uptake and chemical weathering. The presented estimates have the form of potential rates, which means that the amount of nitrogen and phosphorus is quantified which is needed by the organisms to build up biomass, also accounting for resorption and leaching of nutrients. Subsequently, the potential phosphorus uptake on bare ground is used to estimate chemical weathering by the organisms, assuming that they release weathering agents to obtain phosphorus. The predicted requirement for nitrogen ranges from 3.5 to 34 Tg / yr and for phosphorus it ranges from 0.46 to 4.6 Tg / yr. Estimates of chemical weathering are between 0.058 and 1.1 km³ / yr of rock. These values seem to have a realistic order of magnitude and they support the notion that lichens and bryophytes have the potential to play an important role for global biogeochemical cycles.