Phylogenetic signal in amphibian sensitivity to copper sulfate relative to experimental temperature

The release of large quantities of chemicals into the environment represents a major source of environmental disturbance. In recent years, the focus of ecotoxicology has shifted from describing the effects of chemical contaminants on individual species to developing more integrated approaches for predicting and evaluating long term effects of chemicals across species and ecosystems. Traditional ecotoxicology is typically based on data of sensitivity of a few surrogate species to a contaminant and often considers little variability in chemical sensitivity within and among taxonomic groups. This approach assumes that evolutionary history and phylogenetic relatedness among species have little or no impact on species’ sensitivity to chemical compounds. Few studies have tested this assumption. Using phylogenetic comparative methods and published data for amphibians, we show that sensitivity to copper sulfate, a commonly used pesticide, exhibits a strong phylogenetic signal when controlling for experimental temperature. Our results indicate that evolutionary history needs to be accounted for to make accurate predictions of amphibian sensitivity to this contaminant under different temperature scenarios. Since physiological and metabolic traits showing high phylogenetic signal likely underlie variation in species sensitivity to chemical stressors, future studies should evaluate and predict species vulnerability to pollutants using evolutionarily informed approaches

Adaptation of Cu(In, Ga)Se2 photovoltaics for full unbiased photocharge of integrated solar vanadium redox flow batteries

The integration of photovoltaics and vanadium redox flow batteries (VRFB) is a promising alternative for the direct conversion and storage of solar energy in a single device, considering their inherent higher energy density versus other redox pairs. However, this integration is not seamless unless the photovoltaic system is customized to the voltage needs of the battery, which unlike artificial photosynthesis, continuously increase with the state-of-charge. We have developed integrated solar VRFB with adapted low-cost Cu(In, Ga)Se2 modules of 3 and 4 series-connected cells (solar efficiency of mini-solar module 8.1%), and considering the voltage requirements (1.3-1.6V), we have evaluated the influence of the photovoltaic operation region on the final efficiency of the solar VRFB. Full unbiased photocharge under 1 Sun illumination has been achieved reaching high energy (77%), solar-to-charge (7.5%) and overall round trip energy conversion efficiencies (5.0%) excelling the values reported in literature for other solar VRFB, thus demonstrating the feasibility and intrinsic potential of adapting low-cost commercial photovoltaics to such energy storage systems.Peer ReviewedPostprint (author's final draft

Insight into the Degradation Mechanisms of Atomic Layer Deposited TiO2 as Photoanode Protective Layer

Around 100 nm thick TiO layers deposited by atomic layer deposition (ALD) have been investigated as anticorrosion protective films for silicon-based photoanodes decorated with 5 nm NiFe catalyst in highly alkaline electrolyte. Completely amorphous layers presented high resistivity; meanwhile, the ones synthesized at 300 °C, having a fully anatase crystalline TiO structure, introduced insignificant resistance, showing direct correlation between crystallization degree and electrical conductivity. The conductivity through crystalline TiO layers has been found not to be homogeneous, presenting preferential conduction paths attributed to grain boundaries and defects within the crystalline structure. A correlation between the conductivity atomic force microscopy measurements and grain interstitials can be seen, supported by high-resolution transmission electron microscopy cross-sectional images presenting defective regions in crystalline TiO grains. It was found that the conduction mechanism goes through the injection of electrons coming from water oxidation from the electrocatalyst into the TiO conduction band. Then, electrons are transported to the Si/SiO/TiO interface where electrons recombine with holes given by the pn-Si junction. No evidences of intra-band-gap states in TiO responsible of conductivity have been detected. Stability measurements of fully crystalline samples over 480 h in anodic polarization show a continuous current decay. Electrochemical impedance spectroscopy allows to identify that the main cause of deactivation is associated with the loss of TiO electrical conductivity, corresponding to a self-passivation mechanism. This is proposed to reflect the effect of OH ions diffusing in the TiO structure in anodic conditions by the electric field. This fact proves that a modification takes place in the defective zone of the layer, blocking the ability to transfer electrical charge through the layer. According to this mechanism, a regeneration of the degradation process is demonstrated possible based on ultraviolet illumination, which contributes to change the occupancy of TiO electronic states and to recover the defective zone's conductivity. These findings confirm the connection between the structural properties of the ALD-deposited polycrystalline layer and the degradation mechanisms and thus highlight main concerns toward fabricating long-lasting metal-oxide protective layers for frontal illuminated photoelectrodes

Adaptation of Cu(In, Ga)Se2 photovoltaics for full unbiased photocharge of integrated solar vanadium redox flow batteries

The integration of photovoltaics and vanadium redox flow batteries (VRFBs) is a promising alternative for the direct conversion and storage of solar energy in a single device, considering their inherent higher energy density versus other redox pairs. However, this integration is not seamless unless the photovoltaic system is customized to the voltage needs of the battery, which unlike artificial photosynthesis, continuously increase with the state-of-charge. We have developed an integrated solar VRFB with adapted low-cost Cu(In, Ga)Se2 modules of 3 and 4 series-connected cells (solar efficiency of mini-solar module 8.1%), and considering the voltage requirements (1.3-1.6 V), we have evaluated the influence of the photovoltaic operation region on the final efficiency of the solar VRFB. Full unbiased photocharge under 1 Sun illumination has been achieved resulting in high energy (77%), solar-to-charge (7.5%) and overall round trip energy conversion efficiencies (5.0%) exceeding the values reported in the literature for other solar VRFBs, thus demonstrating the feasibility and intrinsic potential of adapting low-cost commercial photovoltaics to such energy storage systems

Geographic variation of life-history traits in the sand lizard, Lacerta agilis: testing Darwin's facundity-advantage hypothesis

The fecundity-advantage-hypothesis (FAH) explains larger female size relative to male size as a correlated response to fecundity selection. We explored FAH by investigating geographic variation in female reproductive output and its relation to sexual size dimorphism (SSD) in Lacerta agilis, an oviparous lizard occupying a major part of temperate Eurasia. We analysed how sex-specific body size and SSD are associated with two putative indicators of fecundity selection intensity (clutch size and the slope of the clutch size-female size relationship), and with two climatic variables throughout the species range and across two widespread evolutionary lineages. Variation within the lineages provides no support for FAH. In contrast, the divergence between the lineages is in line with FAH: the lineage with consistently female-biased SSD (L. a. agilis) exhibits higher clutch size and steeper fecundity slope than the lineage with an inconsistent and variable SSD (L. a. exigua). L. a. agilis shows lower offspring size (egg mass, hatchling mass) and higher clutch mass relative to female mass than L. a. exigua, i.e. both possible ways to enhance offspring number are exerted. As the SSD difference is due to male size (smaller males in L. a. agilis), fecundity selection favouring larger females, together with viability selection for smaller size in both sexes, would explain the female-biased SSD and reproductive characteristics of L. a. agilis. The pattern of intraspecific life-history divergence in L.agilis is strikingly similar to that between oviparous and viviparous populations of a related species Zootoca vivipara. Evolutionary implications of this parallelism are discussed

Environmental factors influence cross-talk between a heat shock protein and an oxidative stress protein modification in the lizard Gallotia galloti

Better understanding how organisms respond to their abiotic environment, especially at the biochemical level, is critical in predicting population trajectories under climate change. In this study, we measured constitutive stress biomarkers and protein post-translational modifications associated with oxidative stress in Gallotia galloti, an insular lizard species inhabiting highly heterogeneous environments on Tenerife. Tenerife is a small volcanic island in a relatively isolated archipelago off the West coast of Africa. We found that expression of GRP94, a molecular chaperone protein, and levels of protein carbonylation, a marker of cellular stress, change across different environments, depending on solar radiation-related variables and topology. Here, we report in a wild animal population, cross-talk between the baseline levels of the heat shock protein-like GRP94 and oxidative damage (protein carbonylation), which are influenced by a range of available temperatures, quantified through modelled operative temperature. This suggests a dynamic trade-off between cellular homeostasis and oxidative damage in lizards adapted to this thermally and topologically heterogeneous environment

Controlling the electrochemical hydrogen generation and storage in graphene oxide by in-situ Raman spectroscopy

Hydrogen, generated from water splitting, is postulated as one of the most promising alternatives to fossil fuels. In this context, direct hydrogen generation by electrolysis and fixation to graphene oxide in an aqueous suspension could overcome storage and distribution problems of gaseous hydrogen. This study presents time-resolved determination of the electrochemical hydrogenation of GO by in-situ Raman spectroscopy, simultaneous to original functional groups elimination. Hydrogenation is found favoured by dynamic modulation of the electrochemical environment compared to fixed applied potentials, with a 160% increase of C-H bond formation. Epoxide groups suppression and generated hydroxide groups point at these epoxide groups being one of the key sites where hydrogenation was possible. FTIR revealed characteristic symmetric and asymmetric stretching vibrations of C-H bonds in CH and CH groups. This shows that hydrogenation is significantly also occurring in defective sites and edges of the graphene basal plane, rather than H-Csp groups as graphane. We also determined a −0.05 V reduction starting potential in alkaline electrolytes and a 150 mV cathodic delay in acid electrolytes. The identified key parameters role, together with observed diverse C-H groups formation, points at future research directions for large-scale hydrogen storage in graphene

RAD21 Cooperates with Pluripotency Transcription Factors in the Maintenance of Embryonic Stem Cell Identity

For self-renewal, embryonic stem cells (ESCs) require the expression of specific transcription factors accompanied by a particular chromosome organization to maintain a balance between pluripotency and the capacity for rapid differentiation. However, how transcriptional regulation is linked to chromosome organization in ESCs is not well understood. Here we show that the cohesin component RAD21 exhibits a functional role in maintaining ESC identity through association with the pluripotency transcriptional network. ChIP-seq analyses of RAD21 reveal an ESC specific cohesin binding pattern that is characterized by CTCF independent co-localization of cohesin with pluripotency related transcription factors Oct4, Nanog, Sox2, Esrrb and Klf4. Upon ESC differentiation, most of these binding sites disappear and instead new CTCF independent RAD21 binding sites emerge, which are enriched for binding sites of transcription factors implicated in early differentiation. Furthermore, knock-down of RAD21 causes expression changes that are similar to expression changes after Nanog depletion, demonstrating the functional relevance of the RAD21 - pluripotency transcriptional network association. Finally, we show that Nanog physically interacts with the cohesin or cohesin interacting proteins STAG1 and WAPL further substantiating this association. Based on these findings we propose that a dynamic placement of cohesin by pluripotency transcription factors contributes to a chromosome organization supporting the ESC expression program

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries