Publicaciones

Baylis–Hillman reaction in ionic liquid ([BMIM][PF]) solution under stirring conditions and in the presence of a base (DABCO) can also be performed efficiently in non-stirred gel phase upon gelation of the ionic liquid using a LMW gelator (i.e., (S)-N-(1-oxo-3-phenyl-1-(tridecylamino)propan-2-yl)benzamide). In this preliminary study, the authors have compared both reaction media and the results showed similar behaviors. Interestingly, the ionogel is found to be slightly more effective affording the desired products with moderately higher yields within a reaction period of 24 h.

[Aim] To assess whether the reduced nutritional resources available for pollinators due to plant community simplification along an elevational plant-diversity gradient changes pollinator niche breadth and richness. Additionally, we evaluated how body size and proboscis length of pollinators shifted along the gradient, and whether these changes were related to pollinator niche breadth, [Location] An elevational gradient (2,350–3,520 m a.s.l.) on the oceanic high-mountain strato-volcano of El Teide (Tenerife, Canary Islands), [Taxon] Flowering plant and pollinator species, [Methods] We compared quantitative plant–pollinator networks along the plant-diversity gradient. We calculated a set of niche-based topological metrics that capture the degree of specialization, niche breadth and niche overlap. Furthermore, we obtained β-diversity measures and the proportion of replacement and richness components, [Results] There was an overall decline in species richness of pollinators with increasing elevation. This decline was mainly driven by the loss of species along the elevational gradient, which conformed a nested subset pattern. The whole network showed less specialization, greater connectance and lower modularity towards the summit. At high elevations, pollinators were more generalized and less selective in their flower choice, showing a greater trophic niche breadth compared to pollinators at lower elevations. Mean body size of pollinators increased with elevation, and species body size and proboscis length were positively associated with the number of plant species visited, [Main conclusions] Overall, results indicated that the elevational gradient filters pollinator species, probably according to their thermal tolerance and ability to exploit a wide range of trophic resources. The finding that pollinators become more generalized and opportunistic at higher elevations is a novel result, which may have implications for new research into how ecological networks vary over environmental gradients. From an applied perspective, our results highlight the importance of considering the spatial variation of species assemblages when aiming to construct functionally reliable interaction networks along environmental gradients.

A systematic study to include J couplings into DP4 formalism (J-DP4) led to the development of three alternative strategies. The dJ-DP4 (direct) approach involves a new DP4-like equation including an additional probability term given by J. The iJ-DP4 (indirect) approach explores the original DP4 method with a restricted conformational search. Despite both strategies performing better than DP4, their combined use (iJ/dJ-DP4) provided the best results, with a 2.5-fold performance improvement at similar or lower computational cost.

A systematic study to include J couplings into DP4 formalism (J-DP4) led to the development of three alternative strategies. The dJ-DP4 (direct) approach involves a new DP4-like equation including an additional probability term given by J. The iJ-DP4 (indirect) approach explores the original DP4 method with a restricted conformational search. Despite both strategies performing better than DP4, their combined use (iJ/dJ-DP4) provided the best results, with a 2.5-fold performance improvement at similar or lower computational cost.

An efficient conversion of hydroxyproline >customizable> units into new amino acids with a variety of N-alkyl substituents is described. The process is versatile and can afford valuable N-methyl amino acids and N,O-acetals. In addition, it allows the introduction of N-homoallylic substituents and N-chains with terminal ester, ketone, or cyano groups. These chains could be used for peptide extension or conjugation to other molecules (e.g., by olefin metathesis, peptide ligation, etc.). The transformation is carried out in just two (for R = CHOAc) or three steps (scission of the pyrrolidine ring, manipulation of the α-chain, and the N-substituent) under mild, metal-free conditions, affording products with high optical purity.

[Background] The diversity and evolutionary success of beetles (Coleoptera) are proposed to be related to the diversity of plants on which they feed. Indeed, the largest beetle suborder, Polyphaga, mostly includes plant eaters among its approximately 315,000 species. In particular, plants defend themselves with a diversity of specialized toxic chemicals. These may impose selective pressures that drive genomic diversification and speciation in phytophagous beetles. However, evidence of changes in beetle gene repertoires driven by such interactions remains largely anecdotal and without explicit hypothesis testing.
[Results] We explore the genomic consequences of beetle-plant trophic interactions by performing comparative gene family analyses across 18 species representative of the two most species-rich beetle suborders. We contrast the gene contents of species from the mostly plant-eating suborder Polyphaga with those of the mainly predatory Adephaga. We find gene repertoire evolution to be more dynamic, with significantly more adaptive lineage-specific expansions, in the more speciose Polyphaga. Testing the specific hypothesis of adaptation to plant feeding, we identify families of enzymes putatively involved in beetle-plant interactions that underwent adaptive expansions in Polyphaga. There is notable support for the selection hypothesis on large gene families for glutathione S-transferase and carboxylesterase detoxification enzymes. [Conclusions] Our explicit modeling of the evolution of gene repertoires across 18 species identifies putative adaptive lineage-specific gene family expansions that accompany the dietary shift towards plants in beetles. These genomic signatures support the popular hypothesis of a key role for interactions with plant chemical defenses, and for plant feeding in general, in driving beetle diversification.

Reticulitermes flavipes, one of the most harmful subterranean termite pests, is reported for the first time from Tenerife (Canary Islands, Spain). Cytochrome oxidase II was sequenced from five specimens in order to confirm the identification. To date, this invasive species has been detected in a limited area in the northeast of the island, affecting buildings, crops and native plant species. Another colony with the identical haplotype found in the southwest, 60 km away from the main population, indicates that this invasive insect may be more widespread over the island.

Subtropical islands are often viewed as refuges where Quaternary climatic shifts driving global episodes of extinction were buffered. Island biodiversity, however, may have been impacted by climatic fluctuations at local scales, particularly in spatially heterogeneous island systems. In this study, we generated a conceptual framework for predicting the potential impact of Pleistocene extinctions on the biogeographical pattern of the Canarian spermatophyte flora, with a focus on the easternmost Canarian islands (ECI). Then, we performed an exhaustive bibliographic revision (270 studies) to examine whether taxonomic, phylogenetic and phylogeographical data support our predictions. Although molecular information is limited for many lineages, the available data suggest that the majority of extant ECI plant taxa may be the result of relatively recent (<1 Ma) dispersal from surrounding insular and mainland areas. Different lines of evidence are compatible with the idea of a Pleistocene period of frequent lineage extirpation on ECI. Extinction may thus have provided new ecological opportunities for recent (re)colonization, with some cases of recent establishment mediated by facilitation. Considering background extinction on ECI, we describe five general patterns of colonization for Canarian plant lineages. In addition to factors related to island ontogeny and long-distance dispersal, we suggest that Pleistocene extinctions may have significantly contributed to extant biogeographical patterns in the Canarian archipelago, such as the biased distribution ranges of island plants and the low endemic richness on ECI. This new scenario provides testable hypotheses for future studies dealing with the phylogeography, taxonomy and conservation of terrestrial biodiversity on the Canarian islands, and possibly, on other near-shore islands.

Nature is intrinsically able to control kinetics, conversion, and selectivity of biochemical processes by means of confined reaction environments such as enzyme pockets, bilayer membranes, micelles, vesicles, cells, or bioorganic frameworks. The main reason for this fact is the optimal molecular alignment and restricted motion of reactant molecules compared to those found in bulk solution. Under this inspiration, a number of synthetic photo-nanoreactors based on supramolecular self-assembled systems have been developed during the last decades, including mesoporous inorganic materials, microemulsions, micelles, vesicles, lipid bilayer foams, polyelectrolyte nanoparticles, etc. In a broader sense, nanoreactor technology constitutes nowadays a promising tool to enhance organic synthesis under sustainable reaction conditions. In general, nanoreactors change the essential properties of the molecules within them, thus affecting their chemical reactivity

[Premise of the Study] The characteristic scarcity of insects on remote oceanic islands has driven nonflower-specialized vertebrates to broaden their trophic niches and explore floral resources. From our previous studies in the Galápagos, we know that native insectivorous and frugivorous birds visit a wide range of entomophilous flowers and can also act as effective pollinators. Here, we tested whether opportunistic Galápagos birds show any preference for specific floral traits, and if so, this preference differs from that of insects, [Methods] Sixteen floral morphology and nectar traits of 26 native species were studied, as well as the frequency with which they are visited by birds and insects. Nonmetric multidimensional scaling (NMDS) was used to evaluate the distribution of flower traits values along two main dimensions and measure the similarity between the plants visited mostly by birds versus those by insects, [Key Results] NMDS of floral traits resulted in two species groups: (1) bell-shaped, white flowers with wider corollas at nectary level and higher nectar volume, associated with high bird visitation rates; and (2) bowl and tubular-shaped flowers with narrower corollas at nectary level and lower nectar volume, associated with high insect visitation rates, [Conclusions] Despite the divergence in floral trait preferences between opportunistic Galápagos birds and insects, bird-visited flowers display mixed traits not fitting the classical ornithophilous syndrome. This finding is compatible with the existence of a transitional or bet-hedging phenotype between insect and bird visitors and underscores the importance of coevolution and floral diversification in nonspecialized plant–visitor interactions.