1,3 Dipolar Cycloaddition of Münchnones: Factors behind the Regioselectivity.

The 1,3 dipolar cycloaddition reactions of münchnones and alkenes provide an expedite synthetic way to substituted pyrroles, an exceedingly important structural motif in the pharmaceutical and material science fields of research. The factors governing their regioselectivity rationalization are not well understood. Using several approaches, we investigate a set of 14 reactions (featuring two münchnones, 12 different alkenes, and two alkynes). The Natural Bond Theory and the Non-Covalent Interaction Index analyses of the noncovalent interaction energies fail to predict the experimental major regioisomer. Employing global cDFT descriptors or local ones such as the Fukui function and dual descriptor yields similarly inaccurate predictions. Only the local softness pairing, within Pearson's Hard and Soft Acids and Bases principle, constitutes a reliable predictor for the major reaction product. By taking into account an estimator for the steric effects, the correct regioisomer is predicted. Steric effects play a major role in driving the regioselectivity, as was corroborated by energy decomposition analysis of the transition states.

Disturbance and the (surprising?) role of ecosystem engineering in explaining spatial patterns of non-native plant establishment.

Different conceptions of disturbance differ in the degree to which they appeal to mechanisms that are general and equivalent, or species-, functional group-, or interaction-specific. Some concepts of disturbance, for example, predict that soil disturbances and herbivory have identical impacts on species richness via identical mechanisms (reduction in biomass and in competition). An alternative hypothesis is that the specific traits of disturbance agents (small mammals) and plants differentially affect the richness or abundance of different plant groups. We tested these hypotheses on a degu (Octodon degus) colony in central Chile. We ask whether native and non-native forbs respond differently to degu bioturbation on runways versus herbivory on grazing lawns. We ask whether this can explain the increase in non-native plants on degu colonies. We found that biopedturbation did not explain the locations of non-native plants. We did not find direct evidence of grazing increasing non-native herbs either, but a grazing effect appears to be mediated by grass, which is the dominant cover. Further, we provide supplementary evidence to support our interpretation that a key mechanism of non-native spread is the formation of dry soil conditions on grazing lawns. Thus, ecosystem engineering (alteration of soil qualities) may be an outcome of disturbances, in which each interacts with specific plant traits, to create the observed pattern of non-native spread in the colony. Based on these results, we propose to extend Jentsch and White (Ecology, 100, 2019, e02734) concept of combined pulse/ disturbance events to the long-term process duality of ecosystem engineering/ disturbance.

Crossing a critical threshold: Accelerated and widespread land use changes drive recent carbon and nitrogen dynamics in Vichuquén Lake (35°S) in central Chile.

Global afforestation/deforestation processes (e.g., Amazon deforestation and Europe afforestation) create new anthropogenic controls on carbon cycling and nutrient supply that have not been fully assessed. Here, we use a watershed-lake dynamics approach to investigate how human-induced land cover changes have altered nutrient transference during the last 700 years in a mediterranean coastal area (Vichuquén Lake). We compare our multiproxy reconstruction with historical documentation and use satellite images to reconstruct land use/cover changes for the last 45 years. Historical landscape changes, including those during the indigenous settlements, Spanish conquest, and the Chilean Republic up to mid-20th century did not significantly alter sediment and nutrient fluxes to the lake. In contrast, the largest changes in the lake-watershed system occurred in the mid-20th century and particularly after the 1980s-90s and were characterized by a large increase in total nitrogen and organic carbon fluxes as well as negative shifts in sediment δ15N and δ13C values. This shift was coeval with the largest land cover transformation in the Vichuquén watershed, as native forests nearly disappeared while anthropogenic tree plantations expanded up to 60% of the surface area.

COSORE: A community database for continuous soil respiration and other soil-atmosphere greenhouse gas flux data.

Globally, soils store two to three times as much carbon as currently resides in the atmosphere, and it is critical to understand how soil greenhouse gas (GHG) emissions and uptake will respond to ongoing climate change. In particular, the soil-to-atmosphere CO2 flux, commonly though imprecisely termed soil respiration (RS ), is one of the largest carbon fluxes in the Earth system. An increasing number of high-frequency RS measurements (typically, from an automated system with hourly sampling) have been made over the last two decades; an increasing number of methane measurements are being made with such systems as well. Such high frequency data are an invaluable resource for understanding GHG fluxes, but lack a central database or repository. Here we describe the lightweight, open-source COSORE (COntinuous SOil REspiration) database and software, that focuses on automated, continuous and long-term GHG flux datasets, and is intended to serve as a community resource for earth sciences, climate change syntheses and model evaluation. Contributed datasets are mapped to a single, consistent standard, with metadata on contributors, geographic location, measurement conditions and ancillary data. The design emphasizes the importance of reproducibility, scientific transparency and open access to data. While being oriented towards continuously measured RS , the database design accommodates other soil-atmosphere measurements (e.g. ecosystem respiration, chamber-measured net ecosystem exchange, methane fluxes) as well as experimental treatments (heterotrophic only, etc.). We give brief examples of the types of analyses possible using this new community resource and describe its accompanying R software package.

Freezing and water availability structure the evolutionary diversity of trees across the Americas.

The historical course of evolutionary diversification shapes the current distribution of biodiversity, but the main forces constraining diversification are still a subject of debate. We unveil the evolutionary structure of tree species assemblages across the Americas to assess whether an inability to move or an inability to evolve is the predominant constraint in plant diversification and biogeography. We find a fundamental divide in tree lineage composition between tropical and extratropical environments, defined by the absence versus presence of freezing temperatures. Within the Neotropics, we uncover a further evolutionary split between moist and dry forests. Our results demonstrate that American tree lineages tend to retain their ancestral environmental relationships and that phylogenetic niche conservatism is the primary force structuring the distribution of tree biodiversity. Our study establishes the pervasive importance of niche conservatism to community assembly even at intercontinental scales.

Soil invertebrate diversity loss and functional changes in temperate forest soils replaced by exotic pine plantations.

The global expansion of tree plantations is often claimed to have positive effects for mitigating global warming, preventing soil erosion, and reducing biodiversity loss. However, questions remain unanswered about the impacts of plantations on belowground diversity and soil properties. Here, we examine how forestry plantations of exotic trees affect critical soil functions and the composition of invertebrate assemblages, by comparing invertebrate diversity and soil physico-chemical properties between non-native Pinus radiata plantations, and nearby native forests in a region of extensive plantation activity in south-central Chile. We quantified differences in diversity, abundance, and community composition of soil invertebrates, as well as fundamental soil properties such as soil water content, water infiltration, nutrient status, and pH. We show that in this landscape mosaic of native forest and plantations, both soil invertebrate communities and physical soil properties differed significantly between systems, despite similar soil origins and topographies. We found a significant loss of soil carbon and a major reduction in taxonomic and functional diversity of soil invertebrates in pine plantation sites. Soil biotic and abiotic characteristics of plantations differed significantly from native forests in plantation-dominated south-central Chile, with profound consequences for ecosystem processes and resilience to future climate change.

Coupling of microbial nitrogen transformations and climate in sclerophyll forest soils from the Mediterranean Region of central Chile.

The Mediterranean region of central Chile is experiencing extensive "mega-droughts" with detrimental effects for the environment and economy of the region. In the northern hemisphere, nitrogen (N) limitation of Mediterranean ecosystems has been explained by the decoupling between N inputs and plant uptake during the dormant season. In central Chile, soils have often been considered N-rich in comparison to other Mediterranean ecosystems of the world, yet the impacts of expected intensification of seasonal drought remain unknown. In this work, we seek to disentangle patterns of microbial N transformations and their seasonal coupling with climate in the Chilean sclerophyll forest-type. We aim to assess how water limitation affects microbial N transformations, thus addressing the impact of ongoing regional climate trends on soil N status. We studied four stands of the sclerophyll forest-type in Chile. Field measurements in surface soils showed a 67% decline of free-living diazotrophic activity (DA) and 59% decrease of net N mineralization rates during the summer rainless and dormant season, accompanied by a stimulation of in-situ denitrification rates to values 70% higher than in wetter winter. Higher rates of both free-living DA and net N mineralization found during spring, provided evidence for strong coupling of these two processes during the growing season. Overall, the experimental addition of water in the field to litter samples almost doubled DA but had no effect on denitrification rates. We conclude that coupling of microbial mediated soil N transformations during the wetter growing season explains the N enrichment of sclerophyll forest soils. Expected increases in the length and intensity of the dry period, according to climate change models, reflected in the current mega-droughts may drastically reduce biological N fixation and net N mineralization, increasing at the same time denitrification rates, thereby potentially reducing long-term soil N capital.

Assessing the influence of life form and life cycle on the response of desert plants to past climate change: Genetic diversity patterns of an herbaceous lineage of Nolana along western South America.

PREMISE OF THE STUDY: Plant responses to past climate change could have been shaped by life-history traits. Here we explore the influence of life form on the response of xerophytic plants to Quaternary climate fluctuations, through a comparison of genetic patterns of codistributed herbaceous and shrubby lineages of the genus Nolana. METHODS: We reconstructed the phylogeographic history of a herbaceous lineage of three species of Nolana distributed from a northern arid zone (30°S) to a southern wet-temperate (42°S) zone, by sequencing two cpDNA regions. Results were compared with similar data published earlier for a congeneric, codistributed shrubby lineage. KEY RESULTS: We detected significant genetic differentiation among populations. Divergence of all haplotypes occurred during the Pleistocene, between 245 and 62 kyr ago. For both the shrubby and herbaceous lineages, the greatest haplotype diversity was found in their northern range. However, herbs also retained some diversity at higher latitude. Herbaceous populations were less genetically structured and less differentiated than shrubby ones. CONCLUSION: Genetic evidence revealed that both lineages of Nolana survived climate change through the Quaternary, experiencing population collapses and recoveries. Phylogeographic histories present similarities between the two lineages, but also marked differences that can be explained by their differences in life form and life cycle. While the shrubby lineage followed the classical pattern of postglacial expansion toward higher latitudes, species in the herbaceous lineage showed evidence of long-lasting persistence at the southern edge of their current range, suggesting for the first time multiple glacial refugia for a xerophytic plant in southern South America.

Relationship between soil nutrients and mycorrhizal associations of two Bipinnula species (Orchidaceae) from central Chile.

BACKGROUND AND AIMS: Mycorrhizal associations are influenced by abiotic and biotic factors, including climate, soil conditions and the identity of host plants. However, the effect of environmental conditions on orchid mycorrhizal associations remains poorly understood. The present study examined how differences in soil nutrient availability are related to the diversity and composition of mycorrhizal fungi associated with two terrestrial orchid species from central Chile. METHODS: For 12 populations of Bipinnula fimbriata and B. plumosa, OTU (operational taxonomic unit) richness, phylogenetic diversity and community composition of mycorrhizal fungi in root samples were estimated using internal transcribed spacer (ITS) sequences. Then, these mycorrhizal diversity variables were related to soil nutrients and host species using generalized linear models and non-metric multidimensional scaling. KEY RESULTS: Variation in OTU composition of mycorrhizal fungi among sites was explained mainly by orchid host species. Fungi in Tulasnellaceae and Ceratobasidiaceae were isolated from both orchid species, but the former were more frequent in B. fimbriata and the latter in B. plumosa. Soil nutrients and orchid host species had significant effects on OTU richness and phylogenetic diversity. Mycorrhizal diversity decreased in habitats with higher N in both species and increased with P availability only in B. fimbriata CONCLUSIONS: The results suggest that soil nutrient availability modulates orchid mycorrhizal associations and provide support for the hypothesis that specialization is favoured by higher soil nutrient availability. Inter-specific differences in mycorrhizal composition can arise due to a geographical pattern of distribution of orchid mycorrhizal fungi, host preferences for fungal partners or differential performance of mycorrhizal fungi under different nutrient availabilities. Further experiments are needed to evaluate these hypotheses.

Functional traits variation explains the distribution of Aextoxicon punctatum (Aextoxicaceae) in pronounced moisture gradients within fog-dependent forest fragments.

Climate change and fragmentation are major threats to world forests. Understanding how functional traits related to drought tolerance change across small-scale, pronounced moisture gradients in fragmented forests is important to predict species' responses to these threats. In the case of Aextoxicon punctatum, a dominant canopy tree in fog-dependent rain forest patches in semiarid Chile, we explored how the magnitude, variability and correlation patterns of leaf and xylem vessel traits and hydraulic conductivity varied across soil moisture (SM) gradients established within and among forest patches of different size, which are associated with differences in tree establishment and mortality patterns. Leaf traits varied across soil-moisture gradients produced by fog interception. Trees growing at drier leeward edges showed higher leaf mass per area, trichome and stomatal density than trees from the wetter core and windward zones. In contrast, xylem vessel traits (vessels diameter and density) did not vary producing loss of hydraulic conductivity at drier leeward edges. We also detected higher levels of phenotypic integration and variability at leeward edges. The ability of A. punctatum to modify leaf traits in response to differences in SM availability established over short distances (<500 m) facilitates its persistence in contrasting microhabitats within forest patches. However, xylem anatomy showed limited plasticity, which increases cavitation risk at leeward edges. Greater patch fragmentation, together with fluctuations in irradiance and SM in small patches, could result in higher risk of drought-related tree mortality, with profound impacts on hydrological balances at the ecosystem scale.

Understanding litter decomposition in semiarid ecosystems: linking leaf traits, UV exposure and rainfall variability.

Differences in litter quality, microbial activity or abiotic conditions cannot fully account for the variability in decomposition rates observed in semiarid ecosystems. Here we tested the role of variation in litter quality, water supply, and UV radiation as drivers of litter decomposition in arid lands. And show that carry-over effects of litter photodegradation during dry periods can regulate decomposition during subsequent wet periods. We present data from a two-phase experiment, where we first exposed litter from a drought-deciduous and an evergreen shrub to natural UV levels during five, rainless summer months and, subsequently, in the laboratory, we assessed the carry-over effects of photodegradation on biomass loss under different irrigation treatments representing the observed range of local rainfall variation among years (15-240 mm). Photodegradation of litter in the field produced average carbon losses of 12%, but deciduous Proustia pungens lost >25%, while evergreen Porlieria chilensis less than 5%. Natural exposure to UV significantly reduced carbon-to-nitrogen and lignin:N ratios in Proustia litter but not in Porlieria. During the subsequent wet phase, remaining litter biomass was lower in Proustia than in Porlieria. Indeed UV exposure increased litter decomposition of Proustia under low and medium rainfall treatments, whereas no carry-over effects were detected under high rainfall treatment. Consequently, for deciduous Proustia carry-over effects of UV exposure were negligible under high irrigation. Litter decomposition of the evergreen Porlieria depended solely on levels of rainfall that promote microbial decomposers. Our two-phase experiment revealed that both the carry-over effects of photodegradation and litter quality, modulated by inter-annual variability in rainfall, can explain the marked differences in decomposition rates and the frequent decoupling between rainfall and litter decomposition observed in semiarid ecosystems.

Ecosystem properties self-organize in response to a directional fog-vegetation interaction.

Feedbacks between vegetation and resource inputs can lead to the local, self-organization of ecosystem properties. In particular, feedbacks in response to directional resources (e.g., coastal fog, slope runoff) can create complex spatial patterns, such as vegetation banding. Although similar feedbacks are thought to be involved in the development of ecosystems, clear empirical examples are rare. We created a simple model of a fog-influenced, temperate rainforest in central Chile, which allows the comparison of natural banding patterns to simulations of various putative mechanisms. We show that only feedbacks between plants and fog were able to replicate the characteristic distributions of vegetation, soil water, and soil nutrients observed in field transects. Other processes, such as rainfall, were unable to match these diagnostic distributions. Furthermore, fog interception by windward trees leads to increased downwind mortality, leading to progressive extinction of the leeward edge. This pattern of ecosystem development and decay through self-organized processes illustrates, on a relatively small spatial and temporal scale, the patterns predicted for ecosystem evolution.

Decadal trends in the pollinator assemblage of Eucryphia cordifolia in Chilean rainforests.

Long-term studies of plant-pollinator interactions are almost nonexistent in the scientific literature. The objective of the present study was to determine changes and trends in the pollinator assemblage of ulmo (Eucryphia cordifolia; Cunoniaceae), a canopy-emergent tree found in Chilean temperate rainforests. We assessed the temporal variability of the pollinator assemblage and identified possible modulators of the observed temporal shifts. We sampled insect visitors to the flowers of 16 individual trees of E. cordifolia during 10 consecutive flowering seasons (2000-2009), recording a total of 137 pollinator species with a mean number of species per year of 44. Only three pollinator species (2.2%) were recorded every year. Two bee species accounted for 50% of all insect visits to flowers. One bee species, Bombus dahlbomii (native), was dominant in one season, whereas Apis mellifera (exotic) dominated during the next season. These interannual shifts in population abundances presented first-order dynamics that were characterized by oscillations with a period of 2 years. Changes in the abundances of the dominant pollinators, as well as differences in temperature and precipitation during insect emergence and flowering, led to a nested temporal structure of pollinator composition. Furthermore, the abundances of less common pollinators were sensitive to the abundance of the dominant bee species and to monthly maximum temperatures and the average precipitation during spring and summer. Based on our results and those from other studies, we predict a decline in the numbers of Bombus dahlbomii and nondominant native pollinators in response to new exotic arrivals.

Increased drought impacts on temperate rainforests from southern South America: results of a process-based, dynamic forest model.

Increased droughts due to regional shifts in temperature and rainfall regimes are likely to affect forests in temperate regions in the coming decades. To assess their consequences for forest dynamics, we need predictive tools that couple hydrologic processes, soil moisture dynamics and plant productivity. Here, we developed and tested a dynamic forest model that predicts the hydrologic balance of North Patagonian rainforests on Chiloé Island, in temperate South America (42°S). The model incorporates the dynamic linkages between changing rainfall regimes, soil moisture and individual tree growth. Declining rainfall, as predicted for the study area, should mean up to 50% less summer rain by year 2100. We analysed forest responses to increased drought using the model proposed focusing on changes in evapotranspiration, soil moisture and forest structure (above-ground biomass and basal area). We compared the responses of a young stand (YS, ca. 60 years-old) and an old-growth forest (OG, >500 years-old) in the same area. Based on detailed field measurements of water fluxes, the model provides a reliable account of the hydrologic balance of these evergreen, broad-leaved rainforests. We found higher evapotranspiration in OG than YS under current climate. Increasing drought predicted for this century can reduce evapotranspiration by 15% in the OG compared to current values. Drier climate will alter forest structure, leading to decreases in above ground biomass by 27% of the current value in OG. The model presented here can be used to assess the potential impacts of climate change on forest hydrology and other threats of global change on future forests such as fragmentation, introduction of exotic tree species, and changes in fire regimes. Our study expands the applicability of forest dynamics models in remote and hitherto overlooked regions of the world, such as southern temperate rainforests.

Avian ecosystem functions are influenced by small mammal ecosystem engineering.

BACKGROUND: Birds are important mobile link species that contribute to landscape-scale patterns by means of pollination, seed dispersal, and predation. Birds are often associated with habitats modified by small mammal ecosystem engineers. We investigated whether birds prefer to forage on degu (Octodon degus) runways by comparing their foraging effort across sites with a range of runway densities, including sites without runways. We measured granivory by granivorous and omnivorous birds at Rinconada de Maipú, central Chile. As a measure of potential bird foraging on insects, we sampled invertebrate prey richness and abundance across the same sites. We then quantified an index of plot-scale functional diversity due to avian foraging at the patch scale. RESULTS: We recorded that birds found food sources sooner and ate more at sites with higher densities of degu runways, cururo mounds, trees, and fewer shrubs. These sites also had higher invertebrate prey richness but lower invertebrate prey abundance. This implies that omnivorous birds, and possibly insectivorous birds, forage for invertebrates in the same plots with high degu runway densities where granivory takes place. In an exploratory analysis we also found that plot-scale functional diversity for four avian ecosystem functions were moderately to weakly correllated to expected ecosystem function outcomes at the plot scale. CONCLUSIONS: Degu ecosystem engineering affects the behavior of avian mobile link species and is thus correlated with ecosystem functioning at relatively small spatial scales.

Diverging drought-tolerance strategies explain tree species distribution along a fog-dependent moisture gradient in a temperate rain forest.

The study of functional traits and physiological mechanisms determining species' drought tolerance is important for the prediction of their responses to climatic change. Fog-dependent forest patches in semiarid regions are a good study system with which to gain an understanding of species' responses to increasing aridity and patch fragmentation. Here we measured leaf and hydraulic traits for three dominant species with contrasting distributions within patches in relict, fog-dependent forests in semiarid Chile. In addition, we assessed pressure-volume curve parameters in trees growing at a dry leeward edge and wet patch core. We predicted species would display contrasting suites of traits according to local water availability: from one end favoring water conservation and reducing cavitation risk, and from the opposite end favoring photosynthetic and hydraulic efficiency. Consistent with our hypothesis, we identified a continuum of water use strategies explaining species distribution along a small-scale moisture gradient. Drimys winteri, a tree restricted to the humid core, showed traits allowing efficient water transport and high carbon gain; in contrast, Myrceugenia correifolia, a tree that occurs in the drier patch edges, exhibited traits promoting water conservation and lower gas exchange rates, as well low water potential at turgor loss point. The most widespread species, Aextoxicon punctatum, showed intermediate trait values. Osmotic compensatory mechanism was detected in M. correifolia, but not in A. punctatum. We show that partitioning of the pronounced soil moisture gradients from patch cores to leeward edges among tree species is driven by differential drought tolerance. Such differences indicate that trees have contrasting abilities to cope with future reductions in soil moisture.

Selection and implementation of a flagship fleet in a locally undervalued region of high endemicity.

Flagships are one conservation education tool. We present a proposed flagship species fleet for environmental education in central Chile. Our methods followed recent flagship guidelines. We present our selection process and a detailed justification for the fleet of flagship species that we selected. Our results are a list of eight flagship species forming a flagship fleet, including two small- and medium-sized mammals, the degu (Octodon degus) and the culpeo fox (Lycalopex culpeaus), two birds, the turca (Pteroptochos megapoidius) and the burrowing owl (Athene cunicularia), the Chilean iguana (Calopistes palluma), the tarantula (Grammostola mollicoma), and two trees, the litre (Lithrea caustica) and the espino (Acacia caven). We then describe how these flagships can be deployed most effectively, describing their audience, effective narrative frames, and modes of presentation. We conclude that general selection rules paired with social science background data allow for an efficient selection process.

NK-1 receptor antagonists as antitumor drugs: a survey of the literature from 2000 to 2011.

INTRODUCTION: After binding to the neurokinin (NK-1) receptor, substance P (SP) induces tumor cell proliferation, the migration of tumor cells (invasion and metastasis) and angiogenesis. By contrast, NK-1 receptor antagonists inhibit tumor cell proliferation (tumor cells die by apoptosis), block the migratory activity of tumor cells and exert antiangiogenic properties. AREAS COVERED: This review offers a 12-year overview of the underlying mechanism of the action of the SP/NK-1 receptor system and NK-1 receptor antagonists in cancer, providing a new approach to the treatment of tumors. EXPERT OPINION: Chemically diverse NK-1 receptor antagonists have been identified. The antitumor action of these compounds is independent of their chemical structures and such action is associated with their affinity for the NK-1 receptor and with the dose of the antagonist administered. The NK-1 receptor can be considered as a target in cancer treatment and NK-1 receptor antagonists could be considered as new antitumor drugs. The NK-1 receptor antagonist aprepitant is used in clinical practice and exerts an antitumor action against tumor cells in vitro. In the future, such antitumor action should be tested in human clinical trials.

Extreme climatic events change the dynamics and invasibility of semi-arid annual plant communities.

Extreme climatic events represent disturbances that change the availability of resources. We studied their effects on annual plant assemblages in a semi-arid ecosystem in north-central Chile. We analysed 130 years of precipitation data using generalised extreme-value distribution to determine extreme events, and multivariate techniques to analyse 20 years of plant cover data of 34 native and 11 exotic species. Extreme drought resets the dynamics of the system and renders it susceptible to invasion. On the other hand, by favouring native annuals, moderately wet events change species composition and allow the community to be resilient to extreme drought. The probability of extreme drought has doubled over the last 50 years. Therefore, investigations on the interaction of climate change and biological invasions are relevant to determine the potential for future effects on the dynamics of semi-arid annual plant communities.