Brain size predicts bees' tolerance to urban environments.

The rapid conversion of natural habitats to anthropogenic landscapes is threatening insect pollinators worldwide, raising concern regarding the negative consequences on their fundamental role as plant pollinators. However, not all pollinators are negatively affected by habitat conversion, as certain species find appropriate resources in anthropogenic landscapes to persist and proliferate. The reason why some species tolerate anthropogenic environments while most find them inhospitable remains poorly understood. The cognitive buffer hypothesis, widely supported in vertebrates but untested in insects, offers a potential explanation. This theory suggests that species with larger brains have enhanced behavioural plasticity, enabling them to confront and adapt to novel challenges. To investigate this hypothesis in insects, we measured brain size for 89 bee species, and evaluated their association with the degree of habitat occupancy. Our analyses revealed that bee species mainly found in urban habitats had larger brains relative to their body size than those that tend to occur in forested or agricultural habitats. Additionally, urban bees exhibited larger body sizes and, consequently, larger absolute brain sizes. Our results provide the first empirical support for the cognitive buffer hypothesis in invertebrates, suggesting that a large brain in bees could confer behavioural advantages to tolerate urban environments.

Non-random interactions within and across guilds shape the potential to coexist in multi-trophic ecological communities.

Theory posits that the persistence of species in ecological communities is shaped by their interactions within and across trophic guilds. However, we lack empirical evaluations of how the structure, strength and sign of biotic interactions drive the potential to coexist in diverse multi-trophic communities. Here, we model community feasibility domains, a theoretically informed measure of multi-species coexistence probability, from grassland communities comprising more than 45 species on average from three trophic guilds (plants, pollinators and herbivores). Contrary to our hypothesis, increasing community complexity, measured either as the number of guilds or community richness, did not decrease community feasibility. Rather, we observed that high degrees of species self-regulation and niche partitioning allow for maintaining larger levels of community feasibility and higher species persistence in more diverse communities. Our results show that biotic interactions within and across guilds are not random in nature and both structures significantly contribute to maintaining multi-trophic diversity.

The non-random assembly of network motifs in plant-pollinator networks.

Ecological processes leave distinct structural imprints on the species interactions that shape the topology of animal-plant mutualistic networks. Detecting how direct and indirect interactions between animals and plants are organised is not trivial since they go beyond pairwise interactions, but may get blurred when considering global network descriptors. Recent work has shown that the meso-scale, the intermediate level of network complexity between the species and the global network, can capture this important information. The meso-scale describes network subgraphs representing patterns of direct and indirect interactions between a small number of species, and when these network subgraphs differ statistically from a benchmark, they are often referred to as 'network motifs'. Although motifs can capture relevant ecological information of species interactions, they remain overlooked in natural plant-pollinator networks. By exploring 60 empirical plant-pollinator networks from 18 different studies with wide geographical coverage, we show that some network subgraphs are consistently under- or over-represented, suggesting the presence of worldwide network motifs in plant-pollinator networks. In addition, we found a higher proportion of densely connected network subgraphs that, based on previous findings, could reflect that species relative abundances are the main driver shaping the structure of the meso-scale on plant-pollinator communities. Moreover, we found that distinct subgraph positions describing species ecological roles (e.g. generalisation and number of indirect interactions) are occupied by different groups of animal and plant species representing their main life-history strategies (i.e. functional groups). For instance, we found that the functional group of 'bees' was over-represented in subgraph positions with a lower number of indirect interactions in contrast to the rest of floral visitors groups. Finally, we show that the observed functional group combinations within a subgraph cannot be retrieved from their expected probabilities (i.e. joint probability distributions), indicating that plant and floral visitor associations within subgraphs are not random either. Our results highlight the presence of common network motifs in plant-pollinator communities that are formed by a non-random association of plants and floral visitors functional groups.

Can aluminum, a non-redox metal, alter the thermodynamics of key biological redox processes? The DPPH-QH2 radical scavenging reaction as a test case.

The increased bioavailability of aluminum has led to a concern about its toxicity on living systems. Among the most important toxic effects, it has been proven that aluminum increases oxidative stress in biological systems, a controversial fact, however, due to its non-redox nature. In the present work, we characterize in detail how aluminum can alter redox equilibriums by analyzing its effects on the thermodynamics of the redox scavenging reaction between DPPH., a radical compound often used as a reactive oxygen species model, and hydroquinones, a potent natural antioxidant. For the first time, theoretical and experimental redox potentials within aluminum biochemistry are directly compared. Our results fully agree with experimental reduction and oxidation potentials, unequivocally revealing how aluminum alters the spontaneity of the reaction by stabilizing the reduction of DPPH⋅ to DPPH- and promoting a proton transfer to the diazine moiety, leading to the production of a DPPH-H species. The capability of aluminum to modify redox potentials shown here confirms previous experimental findings on the role of aluminum to interfere with free radical scavenging reactions, affecting the natural redox processes of living organisms.

New Insights on the Interaction of Phenanthroline Based Ligands and Metal Complexes and Polyoxometalates with Duplex DNA and G-Quadruplexes.

This work provides new insights from our team regarding advances in targeting canonical and non-canonical nucleic acid structures. This modality of medical treatment is used as a form of molecular medicine specifically against the growth of cancer cells. Nevertheless, because of increasing concerns about bacterial antibiotic resistance, this medical strategy is also being explored in this field. Up to three strategies for the use of DNA as target have been studied in our research lines during the last few years: (1) the intercalation of phenanthroline derivatives with duplex DNA; (2) the interaction of metal complexes containing phenanthroline with G-quadruplexes; and (3) the activity of Mo polyoxometalates and other Mo-oxo species as artificial phosphoesterases to catalyze the hydrolysis of phosphoester bonds in DNA. We demonstrate some promising computational results concerning the favorable interaction of these small molecules with DNA that could correspond to cytotoxic effects against tumoral cells and microorganisms. Therefore, our results open the door for the pharmaceutical and medical applications of the compounds we propose.

Mechanistic Insights into Promoted Hydrolysis of Phosphoester Bonds by MoO2Cl2(DMF)2.

A phosphoester bond is a crucial structural block in biological systems, whose occurrence is regulated by phosphatases. Molybdenum compounds have been reported to be active in phosphate ester hydrolysis of model phosphates. Specifically, MoO2Cl2(DMF)2 is active in the hydrolysis of para-nitrophenyl phosphate (pNPP), leading to heteropolyoxometalate structures. We use density functional theory (DFT) to clarify the mechanism by which these species promote the hydrolysis of the phosphoester bond. The present calculations give insight into several key aspects of this reaction: (i) the speciation of this complex prior to interaction with the phosphate (DMF release, Mo-Cl hydrolysis, and pH influence on the speciation), (ii) the competition between phosphate addition and the molybdate nucleation process, (iii) and the mechanisms by which some plausible active species promote this hydrolysis in different conditions. We described thoroughly two different pathways depending on the nucleation possibilities of the molybdenum complex: one mononuclear mechanism, which is preferred in conditions in which very low complex concentrations are used, and another dinuclear mechanism, which is preferred at higher concentrations.

Probing the Catalytically Active Species in POM-Catalysed DNA-Model Hydrolysis*.

Phosphoester hydrolysis is an important chemical step in DNA repair. One archetypal molecular model of phosphoesters is para-nitrophenylphosphate (pNPP). It has been shown previously that the presence of molecular metal oxide [Mo7 O24 ]6- may catalyse the hydrolysis of pNPP through the partial decomposition of polyoxomolybdate framework resulting in a [(PO4 )2 Mo5 O15 ]6- product. Real-time monitoring of the catalytic system using electrospray ionisation mass spectrometry (ESI-MS) provided a glance into the species present in the reaction mixture and identification of potential catalytic candidates. Following up on the obtained spectrometric data, Density Functional Theory (DFT) calculations were carried out to characterise the hypothetical intermediate [Mo5 O15 (pNPP)2 (H2 O)6 ]6- that would be required to form under the hypothesised transformation. Surprisingly, our results point to the dimeric [Mo2 O8 ]4- anion resulting from the decomposition of [Mo7 O24 ]6- as the active catalytic species involved in the hydrolysis of pNPP rather than the originally assumed {Mo5 O15 } species. A similar study was carried out involving the same species but substituting Mo by W. The mechanism involving W species showed a higher barrier and less stable products in agreement with the non-catalytic effect found in experimental results.

Opposing effects of floral visitors and soil conditions on the determinants of competitive outcomes maintain species diversity in heterogeneous landscapes.

Theory argues that both soil conditions and aboveground trophic interactions have equivalent potential to limit or promote plant diversity. However, it remains unexplored how they jointly modify the niche differences stabilising species coexistence and the average fitness differences driving competitive dominance. We conducted a field study in Mediterranean annual grasslands to parameterise population models of six competing plant species. Spatially explicit floral visitor assemblages and soil salinity variation were characterised for each species. Both floral visitors and soil salinity modified species population dynamics via direct changes in seed production and indirect changes in competitive responses. Although the magnitude and sign of these changes were species-specific, floral visitors promoted coexistence at neighbourhood scales, while soil salinity did so over larger scales by changing the superior competitors' identity. Our results show how below and aboveground interactions maintain diversity in heterogeneous landscapes through their opposing effects on the determinants of competitive outcomes.

Mesoscopic length scale controls the rheology of dense suspensions.

From the flow properties of dense granular suspensions on an inclined plane, we identify a mesoscopic length scale strongly increasing with volume fraction. When the flowing layer height is larger than this length scale, a diverging Newtonian viscosity is determined. However, when the flowing layer height drops below this scale, we evidence a nonlocal effective viscosity, decreasing as a power law of the flow height. We establish a scaling relation between this mesoscopic length scale and the suspension viscosity. These results support recent theoretical and numerical results implying collective and clustered granular motion when the jamming point is approached from below.

Spreading of a granular droplet.

The influence of controlled vibrations on the granular rheology is investigated in a specifically designed experiment in which a granular film spreads under the action of horizontal vibrations. A nonlinear diffusion equation is derived theoretically that describes the evolution of the deposit shape. A self-similar parabolic shape (the "granular droplet") and a spreading dynamics are predicted that both agree quantitatively with the experimental results. The theoretical analysis is used to extract effective friction coefficients between the base and the granular layer under sustained and controlled vibrations. A shear thickening regime characteristic of dense granular flows is evidenced at low vibration energy, both for glass beads and natural sand. Conversely, shear thinning is observed at high agitation.

Reorganization of a dense granular assembly: the unjamming response function.

We investigate the mechanical properties of a static dense granular assembly in response to a local forcing. To this end, a small cyclic displacement is applied on a grain in the bulk of a two-dimensional disordered packing under gravity and the displacement fields are monitored. We evidence a dominant long range radial response in the upper half part above the solicitation and after a large number of cycles the response is "quasireversible" with a remanent dissipation field exhibiting long range streams and vortexlike symmetry.

Erosion patterns in a sediment layer.

We report here on a laboratory-scale experiment which reproduces a rich variety of natural patterns with few control parameters. In particular, we focus on intriguing rhomboid structures often found on sandy shores and flats. We show that the standard views based on water surface waves do not explain the phenomenon, and we evidence a different mechanism based on mud avalanche instability.