Publications

A new, direct, and diastereoselective synthesis of activated 2,3,4,6-tetrasubstituted tetrahydro-2H-pyrans is described. In this reaction, iron(III) catalyzed an SN2′–Prins cyclization tandem process leading to the creation of three new stereocenters in one single step. These activated tetrahydro-2H-pyran units are easily derivatizable through CuAAC conjugations in order to generate multifunctionalized complex molecules. DFT calculations support the in situ SN2′ reaction as a preliminary step in the Prins cyclization.

Seed dispersal and seedling recruitment are crucial phases in the life cycle of all spermatophyte plants. The net contribution of seed dispersers to plant establishment is known as seed dispersal effectiveness (SDE) and is defined as the product of a quantitative (number of seeds dispersed) and a qualitative (probability of recruitment) component. In Galápagos, we studied the direct contribution to SDE (number of seeds dispersed and effect on seedling emergence) provided by the five island groups of frugivores (giant tortoises, lizards, medium-sized passerine birds, small non-finch passerine birds, and finches) in the two main habitats in this archipelago: the lowland and the highland zones, and found 16 vertebrate species dispersing 58 plant species. Data on frequency of occurrence of seeds in droppings and number of seeds dispersed per unit area produced contrasting patterns of seed dispersal. Based on the former, giant tortoises and medium-sized passerines were the most important seed dispersers. However, based on the latter, small non-finch passerines were the most important dispersers, followed by finches and medium-sized passerines. The effect of disperser gut passage on seedling emergence varied greatly depending on both the disperser and the plant species. Although the contribution to SDE provided by different disperser guilds changed across plant species, medium-sized passerines (e.g., mockingbirds) provided a higher contribution to SDE than lava lizards in 10 out of 16 plant species analysed, whereas lava lizards provided a higher contribution to SDE than birds in five plant species. While both the quantitative and qualitative components addressed are important, our data suggests that the former is a better predictor of SDE in the Galápagos archipelago.

An all‐pericyclic manifold is developed for the construction of topologically diverse, structurally complex and natural product‐like polycyclic chemotypes. The manifold uses readily accessible tertiary propargyl vinyl ethers as substrates and imidazole as a catalyst to form up to two new rings, three new C−C bonds, six stereogenic centers and one transannular oxo‐bridge. The manifold is efficient, scalable and instrumentally simple to perform and entails a propargyl Claisen rearrangement–[1,3]H shift, an oxa‐6π‐electrocyclization, and an intramolecular Diels–Alder reaction.

A phytochemical study of the aerial parts of Persea indica has permitted the isolation of two diterpenes with novel skeletons derived from isoryanodane, which have named perseaindicol and secoperseanol. A third compound, also with a new carbon framework, proved to be identical with cinncassiol E, whose structure has been now corrected.

We report a new and efficient synthetic strategy that allows access to flexible and functionalized benzocyclotrimers under mild conditions and in few steps. The Negishi cross-coupling reaction was used for the C-C bond formation, whereas intramolecular O-alkylations provided the oxepane rings.

[Aim] How non-dispersive taxa colonize islands is generalized as being by wind, or rafting, with the implicit assumption that such events involve one (wind) or a few (rafting) individuals. However, because of the evolutionary time-scale for colonization events, the fit of individual species to a conceptual model of wind or rafting is difficult to assess. Here, we describe an alternative testable geological model for inter-island colonization that can result in larger effective founding population sizes than traditionally accepted colonization mechanisms. We then test for the fit of genetic data to this model using weevils from the Laparocerus tessellatus species complex. [Location] Canary Islands. Methods: Using a combination of geological data for the Canary Islands, and mtDNA data from a weevil radiation within the Canary Islands, we test three species-level predictions for mega-landslides as drivers of oceanic rafting between islands and subsequent speciation: (1) colonization should involve multiple female lineages, (2) founding lineages should have a common geographical origin, consistent with a mega-landslide event, and (3) colonization direction should be consistent with ocean currents. [Results] Both individual-level and population-level analyses support a mega-landslide event as the driver of colonization from the island of Tenerife to La Palma. At least four female lineages colonized La Palma from Tenerife, with the geographical range of ancestral sequences to these four lineages describing the limits of the La Orotava mega-landslide in Tenerife. [Main conclusions] In the context of island biogeographical theory, mega-landslides may be an important driver of colonization, and subsequent lineage diversification. They provide a framework for hypothesis testing using genetic data from species, or closely related species, with ranges that encompass landslides and potential areas of colonization.

Plant-animal interactions are pivotal for ecosystem functioning, and usually form complex networks involving multiple species of mutualists as well as antagonists. The costs and benefits of these interactions show a strong context-dependency directly related to individual variation in partner identity and differential strength. Yet understanding the context-dependency and functional consequences of mutualistic and antagonistic interactions on individuals remains a lasting challenge. We use a network approach to characterize the individual, plant-based pollination interaction networks of the Canarian Isoplexis canariensis (Plantaginaceae) with a mixed assemblage of vertebrate mutualists (birds and lizards) and invertebrate antagonists (florivores, nectar larcenists, and predispersal seed predators). We identify and quantify interaction typologies based on the sign (mutualistic vs. antagonistic) and strength (weak vs. strong) of animal-mediated pollination and test the relationship with individual female reproductive success (FRS). In addition, we document pollinator movement patterns among individual plants to infer events of pollen transfer/receipt that define the plant mating networks and test the relationship with FRS. We identify six interaction typologies along a mutualism-antagonism gradient, with two typologies being over-represented involving both mutualists and antagonists and influencing FRS. Plants showing strong mutualistic interactions, but also (weak or strong) interactions with antagonists are relatively better connected in the mating network (i.e., with higher potential to transfer or receive pollen). Thus, mixed flower visitor assemblages with mutualists and antagonists give plants increased their importance in the mating networks, promote outcrossing and increasing both female and male fitness. Our approach helps characterize plant-animal interaction typologies, the context-specificity of diversified mutualisms, and a better forecasting of their functional consequences.

In this study, we investigated the effects of synthetic 3′,4′-dibenzyloxyflavonol on viabilities of eight human tumor cells. It was cytotoxic against leukemia cells (HL-60, U-937, MOLT-3, K-562, NALM-6, Raji), with significant effects against P-glycoprotein-overexpressing K-562/ADR and Bcl-2-overexpressing U-937/Bcl-2 cells, but had no significant cytotoxic effects against quiescent or proliferating human peripheral blood mononuclear cells. The IC50 value for the leukemia HL-60 cells was 0.8 ± 0.1 μM. This indicates a 60–fold greater toxicity than the naturally occurring flavonol quercetin. Synthetic 3′,4′-dibenzyloxyflavonol induced S phase cell cycle arrest and was a potent apoptotic inducer in human leukemia cells. Cell death was (i) mediated by the activation and the cleavage of initiator and executioner caspases; (ii) prevented by the pan-caspase inhibitor z-VAD-fmk; (iii) associated with the release of cytochrome c and with the phosphorylation of members of the mitogen activated protein kinases including p38MAPK, JNK/SAPK and ERK, and (iv) independent of the generation of reactive oxygen species. The synthetic 3′,4′-dibenzyloxyflavonol is a potent cytotoxic compound against several human leukemia cells and might be useful in the development of new strategies in the fight against cancer.

The objective of this study was the characterization of nematicidal activity and valorization of hydrolate obtained as a byproduct of the semi industrial vapor-pressure essential oil extraction of a domesticated Artemisia absinthium population (Teruel, Spain), in comparison with a population (Sierra Nevada, Spain) undergoing the domestication process. Hydrolates from three crops of these two populations showed strong in vitro nematicidal effects against the root knot nematode Meloidogyne javanica and similar chemical profiles. The hydrolate of the A. absinthium population from Teruel strongly suppressed nematode egg hatching (>95%) after 5 days of incubation. In vivo tests on tomato seedlings showed a significant reduction in the of root penetration rate of M. javanica J2 treated with a hydrolate sublethal concentration (33%). In pot experiments, the hydrolate of A. absinthium tested on tomato plants significantly affected the nematode population, the infection frequency and the reproduction rate. The extraction of the organic fraction of the hydrolate gave a nematicidal extract and an inactive aqueous residue. The chemical profile of the active organic extract showed the presence of (5Z)-2,6-dimethylocta-5,7-diene-2,3-diol, previously described in the hydrodistilled essential oil of this A. absinthium population, among other compounds. This study demonstrates that the organic fraction of the A. absinthium hydrolate is a potential root-nematode control agent. Therefore, the hydrolate byproduct of the semi industrial vapor-pressure essential oil extraction could be a source of new nematicidal products.

Aims: The 50th anniversary of the publication of the seminal book, The Theory of Island Biogeography, by Robert H. MacArthur and Edward O. Wilson, is a timely moment to review and identify key research foci that could advance island biology. Here, we take a collaborative horizon-scanning approach to identify 50 fundamental questions for the continued development of the field. Location: Worldwide. Methods: We adapted a well-established methodology of horizon scanning to identify priority research questions in island biology, and initiated it during the Island Biology 2016 conference held in the Azores. A multidisciplinary working group prepared an initial pool of 187 questions. A series of online surveys was then used to refine a list of the 50 top priority questions. The final shortlist was restricted to questions with a broad conceptual scope, and which should be answerable through achievable research approaches. Results: Questions were structured around four broad and partially overlapping island topics, including: (Macro)Ecology and Biogeography, (Macro)Evolution, Community Ecology, and Conservation and Management. These topics were then subdivided according to the following subject areas: global diversity patterns (five questions in total); island ontogeny and past climate change (4); island rules and syndromes (3); island biogeography theory (4); immigration–speciation–extinction dynamics (5); speciation and diversification (4); dispersal and colonization (3); community assembly (6); biotic interactions (2); global change (5); conservation and management policies (5); and invasive alien species (4). Main conclusions: Collectively, this cross-disciplinary set of topics covering the 50 fundamental questions has the potential to stimulate and guide future research in island biology. By covering fields ranging from biogeography, community ecology and evolution to global change, this horizon scan may help to foster the formation of interdisciplinary research networks, enhancing joint efforts to better understand the past, present and future of island biotas.