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For about half a century, the radio pulsar population was observed to spin in the ∼0.002–12 s range, with different pulsar classes having a spin-period evolution that differs substantially depending on their magnetic fields or past accretion history. The recent detection of several slowly rotating pulsars has reopened the long-standing question of the exact physics, and observational biases, driving the upper bound of the period range of the pulsar population. In this work, we perform a parameter study of the spin-period evolution of pulsars interacting with supernova fallback matter and specifically look at the fallback accretion disk scenario. Depending on the initial conditions at formation, this evolution can differ substantially from the typical dipolar spin-down, resulting in pulsars that show spin periods longer than their coeval peers. By using general assumptions for the pulsar spin period and magnetic field at birth, initial fallback accretion rates, and including magnetic field decay, we find that very long spin periods (≳100 s) can be reached in the presence of strong, magnetar-like magnetic fields (≳1014 G) and moderate initial fallback accretion rates (∼1022−1027 g s−1). In addition, we study the cases of two recently discovered periodic radio sources, the pulsar PSR J0901–4046 (P = 75.9 s) and the radio transient GLEAM-X J162759.5–523504.3 (P = 1091 s), in light of our model. We conclude that the supernova fallback scenario could represent a viable channel to produce a population of long-period isolated pulsars that only recent observation campaigns are starting to unveil.

Glioblastoma is the most malignant and frequently occurring type of brain tumors in adults. Its treatment has been greatly hampered by the difficulty to achieve effective therapeutic concentration in the tumor sites due to its location and the blood–brain barrier. Intranasal administration has emerged as an alternative for drug delivery into the brain though mucopenetration, and rapid mucociliary clearance still remains an issue to be solved before its implementation. To address these issues, based on the intriguing properties of proteins secreted by mussels, polyphenol and catechol functionalization has already been used to promote mucopenetration, intranasal delivery and transport across the blood–brain barrier. Thus, herein we report the synthesis and study of complex 1, a Pt(IV) prodrug functionalized with catecholic moieties. This complex considerably augmented solubility in contrast to cisplatin and showed a comparable cytotoxic effect on cisplatin in HeLa, 1Br3G and GL261 cells. Furthermore, preclinical in vivo therapy using the intranasal administration route suggested that it can reach the brain and inhibit the growth of orthotopic GL261 glioblastoma. These results open new opportunities for catechol-bearing anticancer prodrugs in the treatment for brain tumors via intranasal administration.

The shuttling of soluble lithium polysulfides (LiPS) and the sluggish Li-S conversion kinetics are two main barriers toward the practical application of lithium-sulfur batteries (LSBs). Herein, we propose the addition of copper selenide nanoparticles at the cathode to trap LiPS and accelerate the Li-S reaction kinetics. Using both computational and experimental results, we demonstrate the crystal phase and concentration of copper vacancies to control the electronic structure of the copper selenide, its affinity toward LiPS chemisorption, and its electrical conductivity. The adjustment of the defect density also allows for tuning the electrochemically active sites for the catalytic conversion of polysulfide. The optimized S/Cu1.8Se cathode efficiently promotes and stabilizes the sulfur electrochemistry, thus improving significantly the LSB performance, including an outstanding cyclability over 1000 cycles at 3 C with a capacity fading rate of just 0.029% per cycle, a superb rate capability up to 5 C, and a high areal capacity of 6.07 mAh cm-2 under high sulfur loading. Overall, the present work proposes a crystal phase and defect engineering strategy toward fast and durable sulfur electrochemistry, demonstrating great potential in developing practical LSBs.

MXene/polyoxometalate (POM) hybrids are useful target materials for a variety of applications. Yet, the goal of preparing simple binary hybrids by intercalation of POMs into MXene has not been achieved. We propose and demonstrate here a method to intercalate POMs (phosphotungstate, PW12) into TiCT MXene through the interaction between POM anions and pre-intercalated surfactant cations. A variety of quaternary ammonium cations have been used to expand TiCT interlayer spacing. Cetyltrimethylammonium cations (CTA) lead to an expansion of 2 nm while allowing intercalation of a considerable load (10 wt%) thanks to their tadpole-like shape and size. CTAPW12 has a layered structure compatible with TiCT. The CTA-delaminated TiCT keeps the large interlayer spacing after being coupled with PW12. The PW12 clusters are dispersed and kept isolated thanks to CTA surfactant and the confinement into TiCT layers. The redox reactions in CTA-delaminated TiCT/PW12 are diffusion-controlled, which proves the well-dispersed PW12 clusters are not adsorbed on the surface of TiCT particles but within TiCT layers. The CTA- delaminated TiCT/PW12 shows superior electrochemical stability (remaining redox active after 5000 cycles) over the other MXene/POM hybrids prepared in this work (inactive after 500 cycles). We associate this improved stability to the effective intercalation of PW12 within TiCT layers helped by the CTA cations, as opposed to the external aggregation of PW12 clusters into micro or nanocrystals taking place for the other cations. The results provide a solid guide to help develop high-performance MXene/POM hybrid materials for a variety of applications.

Nanoparticles (NPs) show promising applications in biomedicine, catalysis, and energy harvesting. This applicability relies on controlling the material’s features at the nanometer scale. Surfactants, a unique class of surface-active molecules, have a remarkable ability to tune NPs activity; provide specific functions, avoid their aggregation, and create stable colloidal solutions. Surfactants also control nanoparticles’ nucleation and growth processes by modifying nuclei solubility and surface energy. While nucleation seems independent from the surfactant, NP’s growth depends on it. NP`s size is influenced by the type of functional group (C, O, S or N), length of its C chain and NP to surfactant ratio. In this paper, gold nanoparticles (Au NPs) are taken as model systems to study how nucleation and growth processes are affected by the choice of surfactants by Dissipative Particle Dynamics (DPD) simulations. DPD has been mainly used for studying biochemical structures, like lipid bilayer models. However, the study of solid NPs, and their conjugates, needs the introduction of a new metallic component. To represent the collective phenomena of these large systems, their degrees of freedom are reduced by Coarse-Grained (CG) models. DPD behaved as a powerful tool for studying complex systems and shedding some light on some experimental observations, otherwise difficult to explain.

Cisplatin has been described as a potent anticancer agent for decades. However, in the case of glioblastomas, it is only considered a rescue treatment applied after the failure of second-line treatments. Herein, based on the versatility offered by coordination chemistry, we engineered nanoparticles by reaction of a platinum (IV) prodrug and iron metal ions showing in vitro dual pH-and redox-sensitivity, controlled release and comparable cytotoxicity to cisplatin against HeLa and GL261 cells. In vivo intranasal administration in orthotopic preclinical GL261 glioblastoma tumor-bearing mice demonstrated increased accumulation of platinum in tumors, leading in some cases to complete cure and prolonged survival of the tested cohort. This was corroborated by a magnetic resonance imaging follow-up, thus opening new opportunities for intranasal glioblastoma therapies while minimizing side effects. The findings derived from this research showed the potentiality of this approach as a novel therapy for glioblastoma treatment.

Several composites based on an L-rich poly(lactic acid) (PLA) and mesoporous Santa Barbara Amorphous-15 (SBA-15) are prepared by their addition through two methods: solution-mixed (solvent casting) or melt-mixed (extrusion). Subsequently, films of all the materials are processed by compression molding. The nucleating capacity of silica on PLA crystallization is found to be strongly dependent on protocol used for SBA-15 incorporation. Thus, mesoporous particles induce some PLA ordering in composites when extrusion is used but nucleating ability is much more remarkable when PLA-SBA composites are prepared by SBA-15 addition through casting, PLA crystallization being observed on cooling even at 40 °C min. Crystallinity, crystallization temperature, and polymorphs developed are also dependent on preparation method and cooling rate. Mechanical properties are tested on the just compressed-molded films. At a given SBA-15 content, the melt-mixed composite is less stiff than the solution-mixed material despite both are completely amorphous. Accordingly, microhardness shows a smaller value in the former. For the solution-mixed approach, a partial coating (either external or internal) of the silica particles by PLA chains is suggested to occur during the first preparation stage, enabling a better transfer of reinforcement exerted by SBA-15 silica into the PLA matrix.

Recycling of plastics is absolutely essential in a circular economy, especially in the case of commodity polymers from fossil resources, like isotactic polypropylene (iPP). Therefore, evaluation of the factors that are decisive for an optimum performance of the recycled based materials becomes mandatory for the obtainment of new products with optimal properties. One of the most important aspects is the protection of the plastics materials not only against the external degradation agents, but also from the radicals generated during their previous service life. Accordingly, several materials have been prepared by extrusion based on virgin iPP with different amounts of the same polypropylene severely degraded, which has been used as model component to be recycled. Previous to the extrusion, a mixture of antioxidants was added to all the samples, and special attention has been paid to consumption of those additives during the extrusion. The results show an increasing reduction of antioxidants with rising content of the degraded material. But, importantly, a rather analogous mechanical response has been found for all the recycled materials in relation to the virgin iPP, pointing out a satisfactory dilution effect of the existing degradation points within the virgin polymeric chains, and indicating the very relevant action of the antioxidants used.

This manuscript proves the reproducibility and robustness of cerium oxide nanoparticles, nanoceria, employed as a chemical reagent with oxidizing capacity (as an electron sink) at acidic pH. Unlike nanoceria multi-enzyme-mimetic capabilities at neutral or high pH, nanoceria can behave as a stoichiometric reagent at low pH where insoluble Ce4+ ions transform into soluble Ce3+ in the nanocrystal that finally dissolves. This behaviour can be interpreted as enzyme-like when nanoceria is in excess with respect to the substrate. Under these conditions, the Ce3+/Ce4+ ratio in the NPs can easily be estimated by titration with ferrocyanide. This procedure could become a rapid assessment tool for evaluating nanoceria capacity in liquid environments.

Risk estimators for COVID-19 propagation based on the incidence rate of new cases can be misleading as they usually fail to account for the fraction of population immunized by infection or vaccination.This misconception yields different incidence rates, as we illustrate using the daily number of COVID-19 reported cases in Spain during the pre-vaccine period, between 15/01/2020 and 11/07/2021. An increase in the incidence rate of about 7% is found when properly accounting for the population at risk. Our results demonstrate that accounting for dynamic changes to the immunized fraction of the population is necessary for accurate risk estimation. We hope that our findings can lead to more effective strategies for pandemic response.

Biomarkers are nucleic acids, peptides, proteins, lipids metabolites, or other small molecules in human tissues or biological fluids whose accurate detection contributes to the prediction and determination of diseases and their status. In recent years, platforms that allow the detection of important biomarkers at the point-of-care (PoC) are moving the field of diagnostics towards personalized medicine. In order to comply with the REASSURED criteria stated by the WHO, the most efficient solution is to integrate PoC devices with smartphones. Without a doubt the smartphone camera is a “smart detector,” and almost all the optical-based methods have been integrated, including absorbance, fluorescence, microscopic bio-imaging, surface plasmon resonance, chemiluminescence, bioluminescence, and photoluminescence. In this chapter, we explain how smartphones can be used as smart detectors in diagnostic devices and we will provide an overview of recent developments of smartphone-based optical PoC devices.

Correction to: Scientific Reports https://doi.org/10.1038/srep31803, published online 18 August 2016.

This manuscript aims at raising the attention of the scientific community to the need for better characterised bioreceptors for fast development of point-of-care diagnostic devices able to support mass frequency testing. Particularly, we present the difficulties encountered in finding suitable antibodies for the development of a lateral flow assay for detecting the nucleoprotein of SARS-CoV-2.

Fluctuations in environmental conditions greatly influence life on earth. Plants, as sessile organisms, have developed molecular mechanisms to adapt their development to changes in daylength, or photoperiod. One of the first plant features that comes to mind as affected by the duration of the day is flowering time; we all bring up a clear image of spring blossom. However, for many plants flowering happens at other times of the year, and many other developmental aspects are also affected by changes in daylength, which range from hypocotyl elongation in Arabidopsis thaliana to tuberization in potato or autumn growth cessation in trees. Strikingly, many of the processes affected by photoperiod employ similar gene networks to respond to changes in the length of light/dark cycles. In this review, we have focused on developmental processes affected by photoperiod that share similar genes and gene regulatory networks.

We estimate the magnitude of the direct rebound effect (DRE) of households’ electricity consumption in Spain, through an econometric estimation method of panel data. The results indicate a DRE between 26 and 35% in the short run and around 36% in the long run. Moreover, we find a significant influence of other energy sources that appear to be complementary to electricity consumption according to our estimation. Hence, our results suggest that an improvement in the energy efficiency of an energy service may affect its own energy consumption as well as the energy consumption of other energy services. This would entail a new source of DRE.

Regulating the coordination environment via heteroatoms to break the symmetrical electronic structure of M-N active sites provides a promising route to engineer metal-nitrogen-carbon catalysts for electrochemical CO reduction reaction. However, it remains challenging to realize a site-specific introduction of heteroatoms at atomic level due to their energetically unstable nature. Here, this paper reports a facile route via using an oxygen- and nitrogen-rich metal–organic framework (MOF) (IRMOF-3) as the precursor to construct the Fe-O and Fe-N chelation, simultaneously, resulting in an atomically dispersed axial O-coordinated FeN active site. Compared to the FeN active sites without O coordination, the formed FeN-O sites exhibit much better catalytic performance toward CO, reaching a maximum FE of 95% at −0.50 V versus reversible hydrogen electrode. To the best of the authors’ knowledge, such performance exceeds that of the existing Fe-N-C-based catalysts derived from sole N-rich MOFs. Density functional theory calculations indicate that the axial O-coordination regulates the binding energy of intermediates in the reaction pathways, resulting in a smoother desorption of CO and increased energy for the competitive hydrogen production.

Neutron star models with maxim mass close to 2 M reach high central densities, which may activate nucleonic and hyperon direct Urca neutrino emission. To alleviate the tension between fast theoretical cooling rates and theal luminosity observations of moderately magnetized, isolated theally emitting stars (with L1031 erg s-1 at t 105.3 yr), some internal heating source is required. The power supplied by the internal heater is estimated for both a phenomenological source in the inner crust and Joule heating due to magnetic field decay, assuming different superfluidity models and compositions of the outer stellar envelope. It is found that a theal power of W(t) ≈ 1034 erg s-1 allows neutron star models to match observations of moderately magnetized, isolated stars with ages t 105.3 yr. The requisite W(t) can be supplied by Joule heating due to crust-confined initial magnetic configurations with (i) mixed poloidal-toroidal fields, with surface strength Bdip = 1013 G at the pole of the dipolar poloidal component and 90 per cent of the magnetic energy stored in the toroidal component; and (ii) poloidal-only configurations with Bdip = 1014 G.

To analyze which ethically relevant biases have been identified by academic literature in artificial intelligence (AI) algorithms developed either for patient risk prediction and triage, or for contact tracing to deal with the COVID-19 pandemic. Additionally, to specifically investigate whether the role of social determinants of health (SDOH) have been considered in these AI developments or not. We conducted a scoping review of the literature, which covered publications from March 2020 to April 2021. ​Studies mentioning biases on AI algorithms developed for contact tracing and medical triage or risk prediction regarding COVID-19 were included. From 1054 identified articles, 20 studies were finally included. We propose a typology of biases identified in the literature based on bias, limitations and other ethical issues in both areas of analysis. Results on health disparities and SDOH were classified into five categories: racial disparities, biased data, socio-economic disparities, unequal accessibility and workforce, and information communication. SDOH needs to be considered in the clinical context, where they still seem underestimated. Epidemiological conditions depend on geographic location, so the use of local data in studies to develop international solutions may increase some biases. Gender bias was not specifically addressed in the articles included. The main biases are related to data collection and management. Ethical problems related to privacy, consent, and lack of regulation have been identified in contact tracing while some bias-related health inequalities have been highlighted. There is a need for further research focusing on SDOH and these specific AI apps.

Surfactants are commonly used as disinfection agents in personal care products against bacteria and viruses, including SARS-CoV-2. However, there is a lack of understanding of the molecular mechanisms of the inactivation of viruses by surfactants. Here, we employ coarse grain (CG) and all-atom (AA) molecular dynamics simulations to investigate the interaction between general families of surfactants and the SARS-CoV-2 virus. To this end, we considered a CG model of a full virion. Overall, we found that surfactants have only a small impact over the virus envelope, being inserted into the envelope without dissolving it or generating pores, at the conditions considered here. However, we found that surfactants may induce a deep impact on the spike protein of the virus (responsible for its infectivity), easily covering it and inducing its collapse over the envelope surface of the virus. AA simulations confirmed that both negatively and positively charged surfactants are able to extensively adsorb over the spike protein and get inserted into the virus envelope. Our results suggest that the best strategy for the design of surfactants as virucidal agents will be to focus on those strongly interacting with the spike protein.

Climate changes are top biodiversity shapers, both during the past and future. Mapping the most climatic stable and unstable zones on Earth could improve our understanding of biodiversity distribution and evolution. Here, we present a set of maps based on a global scale, high resolution (ca. 5¿km) new Climate Stability Index (CSI). The CSI considers bioclimatic variables for two different time ranges: (1) from Pliocene (3.3¿Ma) to the present (CSI-past map set), using 12 time periods of PaleoClim representing warm and cold cycles; and (2) from present to the year 2100 (CSI-future), using nine general circulation models of climate change of four periods available from WorldClim. We calculated standard deviation of the variables and selected an uncorrelated set for summing, normalizing and obtaining the CSI maps. Our approach is useful for fields such as biogeography, earth sciences, agriculture, or sociology. However, CSI is an index that can be re-calculated according to particular criteria and objectives (e.g. temperature variables); maps are, therefore, customizable to every user.

ct The Convention on Biological Diversity is defining the goals that will frame future global biodiversity policy in a context of rapid biodiversity decline and under pressure to make transformative change. Drawing on the work of Indigenous and non-Indigenous scholars, we argue that transformative change requires the foregrounding of Indigenous peoples’ and local communities’ rights and agency in biodiversity policy. We support this argument with four key points. First, Indigenous peoples and local communities hold knowledge essential for setting realistic and effective biodiversity targets that simultaneously improve local livelihoods. Second, Indigenous peoples’ conceptualizations of nature sustain and manifest CBD’s 2050 vision of ‘‘Living in harmony with nature.’’ Third, Indigenous peoples’ and local communities’ participation in biodiversity policy contributes to the recognition of human and Indigenous peoples’ rights. And fourth, engagement in biodiversity policy is essential for Indigenous peoples and local communities to be able to exercise their recognized rights to territories and resources.

Most studies on climate change’s impacts on agriculture focus on modeling techniques based on large-scale meteorological data, while few have investigated how farmer’s perception of climate change’s impacts can affect crop diversity and crop management practices, especially in industrialized contexts. To fill this gap, we conducted 24 semi-structured interviews in a study site located in the Catalan Pyrenees. Our results show for the first time in an industrialized context that farmers perceive multiple interrelated climate change impacts on local agroecosystems. For instance, snowfall and freeze events have decreased, which respondents associated with the increase of pests and diseases affecting both wild flora and cultivated plants. Similarly, changes in precipitation patterns lead to a perceived decrease in useful rain for agriculture. Farmers are also reporting changes in their management practices, such as increased irrigation or use of pesticides, which respond to these climatic factors but also to changes in the crops that are cultivated. Crop diversity is in decline in the area both at the species and landrace levels, especially in rainfed fields. This is mainly driven by socioeconomic factors such as agricultural abandonment or access to commercial seeds, although climate change factors such as increased pests or decreased rainfall can have an impact. Despite the crop diversity losses found, many landraces have been maintained, mainly due to their cultural value, and also new crop species have been introduced, which are now viable due to the increase in temperature. Although we focused on a specific case study, we found several trends that are also present in other contexts. Therefore, the results of this research are relevant at a global scale since they show that climate change is affecting mountain agroecosystems in industrialized contexts and may affect more drastically both agrobiodiversity and crop management practices in agroecosystems worldwide.

This paper addresses the impact of political regimes on carbon emissions (CO2) from a historical perspective, covering the period of 1970–2015. Our sample consists of 153 countries that we follow for 20 years before the transition (1970–1990) and 26 years after it (1990–2015). During transition, post-Communist states experienced a decline in CO2, when controlling for economic variables. Transition had a positive impact on the environment only in cases when it was associated with democratization. When transition has led to consolidation of autocratic regimes, CO2 has increased.

La idea de racionalidad en Michel Foucault no se refiere a un criterio de razón universal a modo de conocimiento puro y neutral, sino conjugada en plural como «racionalidades». Funciona como un régimen de verdad que no solo produce nuevos conceptos y una organización histórica de la observación, sino también dominios de regulación e intervenciones políticas y técnicas. Aplicadas a la economía punitiva, y por extensión a la del poder, las racionalidades punitivas han permitido aflorar un análisis crítico inusual de los sistemas del castigo mediante diferentes conceptos en apariencia usuales que alcanzan una radicalidad inusitada en la objetivación de las redes de poder/saber, y que desbordan tanto el campo de la política penal como el de las rígidas explicaciones materialistas. En última instancia, han permitido construir un orden punitivo macrosocial y unas macroformas de dominación a partir de la diversidad de micropoderes., Michel Foucault’s idea of rationality does not refer to a universal criterion of reason as pure and neutral knowledge, but rather is understood in the plural, as «rationalities». His perspective functions as a regime of truth that not only produces new concepts and a historical organisation of observation, but also areas of regulation and political and technical intervention. Applied to the punitive economy, and by extension to the economy of power, punitive rationalities have enabled an unusual critical analysis of punishment systems to flourish. This analysis is produced through different concepts, apparently usual, that reach an unusual radicality in the objectification of the networks of power/knowledge that spread beyond both the field of penal policy and that of rigid materialist explanations. And ultimately it has allowed a macro-social punitive order and macro-forms of domination to be constructed out of the diversity of micropower., Depto. de Sociología: Metodología y Teoría, Fac. de Ciencias Políticas y Sociología, TRUE, pub

Aunque la cuestión más controvertida del Ente Público canario ha sido, sin duda, la externalización de la producción, la programación de TvCanaria ha logrado consolidarse como una opción que se sitúa a la altura del resto de televisiones que compiten actualmente dentro del panorama audiovisual estatal y autonómico. Desde su primera emisión en 1999, contenidos canarios, de entretenimiento, eventos deportivos y espacios de servicio público configuran una parrilla que es muy bien recibida por los miles de espectadores que siguen día a día su programación, llegando a todos los hogares de las Islas y, a través de TelevisiónCanariaNet, al mundo.

Weaning is a critical period in the life of pigs with repercussions on their health and welfare and on the economy of the swine industry. This study aimed to assess the efect of the commercial early weaning on gut microbiota, intestinal gene expression and serum metabolomic response via an integratedomic approach combining 16S rRNA gene sequencing, the OpenArray gene expression technology and 1 H-NMR spectroscopy. Fourteen piglets from diferent litters were sampled for blood, jejunum tissue and caecal content two days before (− 2d), and three days after (+3d) weaning. A clearly diferential ordination of caecal microbiota was observed. Higher abundances of Roseburia, Ruminococcus, Coprococcus, Dorea and Lachnospira genera in weaned piglets compared to prior to weaning showed the quick microbial changes of the piglets’ gut microbiota. Downregulation of OCLN, CLDN4, MUC2, MUC13, SLC15A1 and SLC13A1 genes, also evidenced the negative impact of weaning on gut barrier and digestive functions. Metabolomic approach pinpointed signifcant decreases in choline, LDL, triglycerides, fatty acids, alanine and isoleucine and increases in 3-hydroxybutyrate after weaning. Moreover, the correlation between microbiota and metabolome datasets revealed the existence of metabolic clusters interrelated to diferent bacterial clusters. Our results demonstrate the impact of weaning stress on the piglet and give insights regarding the associations between gut microbiota and the animal gene activity and metabolic response.

Atomically dispersed metals maximize the number of catalytic sites and enhance their activity. However, their challenging synthesis and characterization strongly complicates their optimization. Here, the aim is to demonstrate that tuning the electronic environment of atomically dispersed metal catalysts through the modification of their edge coordination is an effective strategy to maximize their performance. This article focuses on optimizing nickel-based electrocatalysts toward alcohol electrooxidation in alkaline solution. A new organic framework with atomically dispersed nickel is first developed. The coordination environment of nickel within this framework is modified through the addition of carbonyl (CO) groups. The authors then demonstrate that such nickel-based organic frameworks, combined with carbon nanotubes, exhibit outstanding catalytic activity and durability toward the oxidation of methanol (CHOH), ethanol (CHCHOH), and benzyl alcohol (CHCHOH); the smaller molecule exhibits higher catalytic performance. These outstanding electrocatalytic activities for alcohol electrooxidation are attributed to the presence of the carbonyl group in the ligand chemical environment, which enhances the adsorption for alcohol, as revealed by density functional theory calculations. The work not only introduces a new atomically dispersed Ni-based catalyst, but also demonstrates a new strategy for designing and engineering high-performance catalysts through the tuning of their chemical environment.

The photodehydrogenation of ethanol is a sustainable and potentially cost-effective strategy to produce hydrogen and acetaldehyde from renewable resources. The optimization of this process requires the use of highly active, stable and selective photocatalytic materials based on abundant elements and the proper adjustment of the reaction conditions, including temperature. In this work, CuO-TiO type-II heterojunctions with different CuO amounts are obtained by a one-pot hydrothermal method. The structural and chemical properties of the produced materials and their activity toward ethanol photodehydrogenation under UV and visible light illumination are evaluated. The CuO-TiO photocatalysts exhibit a high selectivity toward acetaldehyde production and up to tenfold higher hydrogen evolution rates compared to bare TiO . We further discern here the influence of temperature and visible light absorption on the photocatalytic performance. Our results point toward the combination of energy sources in thermo-photocatalytic reactors as an efficient strategy for solar energy conversion.

Although the Faraday efficiencies (FEs) obtained on most of the Ni based single-atom catalysts (Ni-N-C) are satisfactory (generally >90%) for the electrochemical transfer CO2 to CO, their practical application is still limited by their high overpotentials (>600 mV vs. RHE), which implies a higher energy consumption to drive the CO2 RR. In this work, we have prepared a quasi-double star catalyst composed of nearby Ni and Fe active sites via a simple pyrolysis of Ni and Fe co-doped Zn-based MOFs in order to achieve a high selectivity at a low overpotential during the CO2 RR. Specifically, the optimized Ni/Fe-N-C catalyst shows an exclusive selectivity (a maximum FE(CO) of 98%) at a low overpotential of 390 mV vs. RHE, which is superior to both the single metal counterparts (Ni-N-C and Fe-N-C catalysts) and other state-of-the-art M-N-C catalysts. The DFT results further reveal that regulating the catalytic CO2 RR performance via nearby Ni and Fe active sites can potentially break the activity benchmark of the single metal counterparts because the neighboring Ni and Fe active sites not only function in synergy to decrease the reaction barrier for the formation of COOH∗ and desorption of CO∗ in comparison to their single metal counterparts, but also prevent the undesired hydrogen evolution reaction (HER). This work presents a quasi-double-star catalyst composed of two metal sites for high-efficiency CO2 reduction, which paves the way for the rational design of bimetallic catalysts with separated active sites for other reactions.

Point-of-care (PoC) tests are practical and effective diagnostic solutions for major clinical problems, ranging from the monitoring of a pandemic to recurrent or simple measurements. Although, in recent years, a great improvement in the analytical performance of such sensors has been observed, there is still a major issue that has not been properly solved: The ability to perform adequate sample treatments. The main reason is that normally sample treatments require complicated or long procedures not adequate for deployment at the PoC. In response, a sensing platform, called paperbased electrophoretic bioassay (PEB), that combines the key characteristics of a lateral flow assay (LFA) with the sample treatment capabilities of electrophoresis is developed. In particular, the ability of PEB to separate different types of particles and to detect human antibodies in untreated spiked whole blood is demonstrated. Finally, to make the platform suitable for PoC, PEB is coupled with a smartphone that controls the electrophoresis and reads the optical signal generated. It is believed that the PEB platform represents a much-needed solution for the detection of low target concentrations in complex media, solving one of the major limitations of LFA and opening opportunities for point-of-care sensors.

Recent research has demonstrated the importance of rural settlement in the Iberian culture, although there are still few rural sites explored in depth. `Rural settlement¿ is the term we use to designate the small habitation sites or agricultural structures that became common from the Middle Iberian Period (450¿200 bc) onward; such sites constituted the basis of a hierarchical settlement system characteristic of societies developing towards archaic states. These settlements consist of one or two buildings together with silos and/or artisanal features. The main difficulty in studying such sites is their poor preservation. They are usually located on flat areas suit- able for cultivation, and research has traditionally prioritised the study of larger sites. In this study, we revise the data from previous investigations in the territory of ancient Iberian Cessetania and present the results of recent research, paying particular attention to the Rabassats site. We compare these rural settlements to those in other nearby territories in the Iberian area as well as in the wider Mediterranean context. Detailed analy- ses of the remains of rural sites show a greater complexity than is often assumed and suggest that a variety of small settlements, from an economic and probably also from a social point of view, should be included under the generic heading of `fourth order¿.

The possibility of contamination of human skin by infectious virions plays an important role in indirect transmission of respiratory viruses but little is known about the fundamental physico-chemical aspects of the virus-skin interactions. In the case of coronaviruses, the interaction with surfaces (including the skin surface) is mediated by their large glycoprotein spikes that protrude from (and cover) the viral envelope. Here, we perform all atomic simulations between the SARS-CoV-2 spike glycoprotein and human skin models. We consider an "oily" skin covered by sebum and a "clean" skin exposing the stratum corneum. The simulations show that the spike tries to maximize the contacts with stratum corneum lipids, particularly ceramides, with substantial hydrogen bonding. In the case of "oily" skin, the spike is able to retain its structure, orientation and hydration over sebum with little interaction with sebum components. Comparison of these results with our previous simulations of the interaction of SARS-CoV-2 spike with hydrophilic and hydrophobic solid surfaces, suggests that the"soft" or "hard" nature of the surface plays an essential role in the interaction of the spike protein with materials.

The eastern Mediterranean basin hosts a remarkably high plant diversity. Historical connections between currently isolated areas across the Aegean region and long-distance dispersal events have been invoked to explain current distribution patterns of species. According to most recent treatments, at least two Cymbalaria species occur in this area, Cymbalaria microcalyx and C. longipes. The former comprises several intraspecific taxa, treated at different ranks by different authors based on morphological data, evidencing the need of a taxonomic revision. Additionally, some populations of C. microcalyx show exclusive morphological characters that do not match any described taxon. Here, we aim to shed light on the systematics of eastern Mediterranean Cymbalaria and to propose a classification informed by various sources of evidence. We performed molecular phylogenetic analyses using ITS, 3¿ETS, ndhF and rpl32-trnL sequences and estimated the ploidy level of some taxa performing relative genome size measures. Molecular data combined with morphology support the division of traditionally delimited C. microcalyx into C. acutiloba, C. microcalyx and C. minor, corresponding to well-delimited nrDNA lineages. Furthermore, we propose to combine C. microcalyx subsp. paradoxa at the species level. A group of specimens previously thought to belong to Cymbalaria microcalyx constitute a well-defined phylogenetic and morphological entity and are described here as a new species, Cymbalaria spetae. Cymbalaria longipes is non-monophyletic, but characterized by being glabrous and diploid, unlike other eastern species. The nrDNA data suggest at least two dispersals from the mainland to the Aegean Islands, potentially facilitated by marine regressions.

Advice processes are omnipresent in our professional and private lives. We use a laboratory experiment to study how gender and gender matching affect advice giving and how gender matching affects advice following about entry into a real-effort tournament. For advice giving we find that women are less likely than men to recommend tournament entry to advisees than are intermediate performers. Furthermore, women maximize less often the expected earnings of advisees than intermediate performers. For advice following we find that men enter the tournament significantly more often than women in the intermediate-performance group do. Gender matching does not seem to affect advice giving or following. Overall, when it is less clear what the better advice or decision is, gender differences emerge. These results are consistent with findings in other areas that document that gender differences emerge in situations that are more ambiguous.

Public procurement has recently taken into account social and sustainable factors, increasing academic literature in this field. The aim of this paper is to map the intellectual structure of social and sustainable public procurement research by means of delimiting the scientific domain’s research traditions, its disciplinary composition, and influential research topics. Given that there is a literature gap in bibliometric studies applied to this field, we conducted a co-citation analysis to identify the intellectual structure of this area of knowledge. Co-citation analyses identify networks of interconnections and, consequently, detect the most (and the least) active research areas, being a good complement to traditional literature reviews. This article contributes to science development because it is the first paper to carry out a bibliometric analysis in the field of social and sustainable public procurement, as well as the first one to conduct a co-citation analysis among public procurement research. Consequently, it is also the first article to detect which papers have become burst in this research field. The results show twelve different clusters of publications that were cited by researchers who wrote papers on social and sustainable public procurement. In other words, the sources of knowledge that scholars used as references are analysed, identifying papers that can be considered turning points, as well as those that became specially cited over a discrete period of time. Six different research trends were identified over the last decade in regard to social and sustainable public procurement research. The conclusions highlight the relevance of the findings, especially because they provide guidance to researchers when conducting literature reviews, given that the most significant journals and papers are identified.

Anthropogenic pollution coming from industrial processes, agricultural practices and consumer products, results in the release of toxic substances into rural and urban environments. Once released, these chemicals migrate through the atmosphere and water, and find their way into matrices such as sediments and groundwaters, thus making large areas potentially uninhabitable. Common pollutants, including heavy metal(loid)s, radionuclides, aliphatic hydrocarbons and halogenated organics, are known to adversely affect physiological systems in animal species. Pollution can be cleaned up using techniques such as coagulation, reverse osmosis, oxidation and biological methods, among others. The use of nanoparticles (NPs) extends the range of available technologies and offers particular benefits, not only by degrading, transforming and immobilizing contaminants, but also by reaching inaccessible areas and promoting biotic degradation. The development of NPs is understandably heralded as an environmentally beneficial technology; however, it is only now that the ecological risks associated with their use are being evaluated. This review presents recent developments in the use of engineered NPs for the in situ remediation of two paramount environmental matrices: soils and groundwaters. Emphasis will be placed on (i) the successful applications of nano-objects for environmental cleanup, (ii) the potential safety implications caused by the challenging requirements of [high reactivity toward pollutants] vs. [none reactivity toward biota], with a thorough view on their transport and evolution in the matrix, and (iii) the perspectives on scientific and regulatory challenges. To this end, the most promising nanomaterials will be considered, including nanoscale zerovalent iron, nano-oxides and carbonaceous materials. The purpose of the present review is to give an overview of the development of nanoremediators since they appeared in the 2000s, from their chemical modifications, mechanis

Graphene active sensors have demonstrated promising capabilities for the detection of electrophysiological signals in the brain. Their functional properties, together with their flexibility as well as their expected stability and biocompatibility have raised them as a promising building block for large-scale sensing neural interfaces. However, in order to provide reliable tools for neuroscience and biomedical engineering applications, the maturity of this technology must be thoroughly studied. Here, we evaluate the performance of 64-channel graphene sensor arrays in terms of homogeneity, sensitivity and stability using a wireless, quasi-commercial headstage and demonstrate the biocompatibility of epicortical graphene chronic implants. Furthermore, to illustrate the potential of the technology to detect cortical signals from infra-slow to high-gamma frequency bands, we perform proof-of-concept long-term wireless recording in a freely behaving rodent. Our work demonstrates the maturity of the graphene-based technology, which represents a promising candidate for chronic, wide frequency band neural sensing interfaces.

Halide perovskite solar cells (PSCs) have already demonstrated power conversion efficiencies above 25%, which makes them one of the most attractive photovoltaic technologies. However, one of the main bottlenecks towards their commercialization is their long-term stability, which should exceed the 20-year mark. Additive engineering is an effective pathway for the enhancement of device lifetime. Additives applied as organic or inorganic compounds, improve crystal grain growth enhancing power conversion efficiency. The interaction of their functional groups with the halide perovskite (HP) absorber, as well as with the transport layers, results in defect passivation and ion immobilization improving device performance and stability. In this review, we briefly summarize the different types of additives recently applied in PSC to enhance not only efficiency but also long-term stability. We discuss the different mechanism behind additive engineering and the role of the functional groups of these additives for defect passivation. Special emphasis is given to their effect on the stability of PSCs under environmental conditions such as humidity, atmosphere, light irradiation (UV, visible) or heat, taking into account the recently reported ISOS protocols. We also discuss the relation between deep-defect passivation, non-radiative recombination and device efficiency, as well as the possible relation between shallow-defect passivation, ion immobilization and device operational stability. Finally, insights into the challenge and criteria for additive selection are provided for the further stability enhancement of PSCs.

Utilization of the renewable energy sources is one of the main challenges in the state-of-the-art technologies for CO recycling. Here we have taken advantage of the solar light harvesting in the thermocatalytic approach to carbon dioxide methanation. The large-surface-area Ni/CeO catalyst produced by a scalable low-cost method was characterized and tested in the dark and under solar light irradiation conditions. Light-assisted CO conversion experiments as well as in-situ DRIFT spectrometry, performed at different illumination intensities, have revealed a dual effect of the incident photons on the catalytic properties of the two-component Ni/CeO catalyst. On the one hand, absorbed photons induce a localized surface plasmon resonance in the Ni nanoparticles followed by dissipation of the heat to the oxide matrix. On the other hand, the illumination activates the photocatalytic properties of the CeO support, which leads to an increase in the concentration of the intermediates being precursor for methane production. Analysis of the methane production at different temperatures and illumination conditions has shown that the methanation reaction in our case is controlled by a photothermally-activated process. The used approach has allowed us to increase the reaction rate up to 2.4 times and consequently to decrease the power consumption by 20 % under solar illumination, thus replacing the conventional thermal activation of the reaction with a green energy source.

With the rise of two-dimensional (2D) transition-metal dichalcogenide (TMD) semiconductors and their prospective use in commercial (opto)electronic applications, it has become key to develop scalable and reliable TMD synthesis methods with well-monitored and controlled levels of impurities. While metal-organic chemical vapor deposition (MOCVD) has emerged as the method of choice for large-scale TMD fabrication, carbon (C) incorporation arising during MOCVD growth of TMDs has been a persistent concern-especially in instances where organic chalcogen precursors are desired as a less hazardous alternative to more toxic chalcogen hydrides. However, the underlying mechanisms of such unintentional C incorporation and the effects on film growth and properties are still elusive. Here, we report on the role of C-containing side products of organosulfur precursor pyrolysis in MoS2 thin films grown from molybdenum hexacarbonyl Mo(CO)6 and diethyl sulfide (CH3CH2)2S (DES). By combining in situ gas-phase monitoring with ex situ microscopy and spectroscopy analyses, we systematically investigate the effect of temperature and Mo(CO)6/DES/H2 gas mixture ratios on film morphology, chemical composition, and stoichiometry. Aiming at high-quality TMD growth that typically requires elevated growth temperatures and high DES/Mo(CO)6 precursor ratios, we observed that temperatures above DES pyrolysis onset (â 600 °C) and excessive DES flow result in the formation of nanographitic carbon, competing with MoS2 growth. We found that by introducing H2 gas to the process, DES pyrolysis is significantly hindered, which reduces carbon incorporation. The C content in the MoS2 films is shown to quench the MoS2 photoluminescence and influence the trion-To-exciton ratio via charge transfer. This finding is fundamental for understanding process-induced C impurity doping in MOCVD-grown 2D semiconductors and might have important implications for the functionality and performance of (opto)electronic device

MELiSSA (Micro Ecological Life Support System Alternative) is developing bioregenerative Life Support technologies for long-term Space missions. The MELiSSA concept is conceived as a loop with several compartments, each one performing a specific function, providing all together edible material production, atmosphere regeneration and water recovery with a concomitant use of wastes, i.e., CO and organic wastes. Each one of the compartments is colonized with specific bacteria or higher plants depending on its specific function. The MELiSSA Pilot Plant is a facility designed for the terrestrial demonstration of this concept, hosting laboratory rats as a crew mock-up mimicking the respiration of humans. Currently, the MELiSSA Pilot Plant focus on the integration of three compartments: Compartment 3 (nitrifying packed-bed bioreactor based on the co-culture of immobilized Nitrosomonas europaea and Nitrobacter winogradsky), compartment 4a (an air-lift photobioreactor for the culture of the edible cyanobacteria Limnospira indica with concomitant oxygen production) and Compartment 5 (an animal isolator with rats as mock-up crew). The output from these tests shows a high robustness and reliability and the performance of oxygen producing and oxygen consuming compartments is successfully demonstrated under transitory and steady-state conditions. This contribution reports on the current state of development of the MELiSSA Pilot Plant Facility and the most recent results of the integration work.

OBJECTIVE: Obesity is associated with a proinflammatory and prothrombotic state that supports atherosclerosis progression. The goal of this study was to gain insights into the phosphorylation events related to platelet reactivity in obesity and identify platelet biomarkers and altered activation pathways in this clinical condition. APPROACH AND RESULTS: We performed a comparative phosphoproteomic analysis of resting platelets from obese patients and their age- A nd gender-matched lean controls. The phosphoproteomic data were validated by mechanistic, functional, and biochemical assays. We identified 220 differentially regulated phosphopeptides, from at least 175 proteins; interestingly, all were up-regulated in obesity. Most of the altered phosphoproteins are involved in SFKs (Src-family kinases)-related signaling pathways, cytoskeleton reorganization, and vesicle transport, some of them validated by targeted mass spectrometry. To confirm platelet dysfunction, flow cytometry assays were performed in whole blood indicating higher surface levels of GP (glycoprotein) VI and CLEC (C-type lectin-like receptor) 2 in platelets from obese patients correlating positively with body mass index. Receiver operator characteristics curves analysis suggested a much higher sensitivity for GPVI to discriminate between obese and lean individuals. Indeed, we also found that obese platelets displayed more adhesion to collagen-coated plates. In line with the above data, soluble GPVI levels-indicative of higher GPVI signaling activation-were almost double in plasma from obese patients. CONCLUSIONS: Our results provide novel information on platelet phosphorylation changes related to obesity, revealing the impact of this chronic pathology on platelet reactivity and pointing towards the main signaling pathways dysregulated

Aging and cancer are two interrelated processes, with aging being a major risk factor for the development of cancer. Parallel epigenetic alterations have been described for both, although differences, especially within the DNA hypomethylation scenario, have also been recently reported. Although many of these observations arise from the use of mouse models, there is a lack of systematic comparisons of human and mouse epigenetic patterns in the context of disease. However, such comparisons are significant as they allow to establish the extent to which some of the observed similarities or differences arise from pre-existing species-specific epigenetic traits. Here, we have used reduced representation bisulfite sequencing to profile the brain methylomes of young and old, tumoral and nontumoral brain samples from human and mouse. We first characterized the baseline epigenomic patterns of the species and subsequently focused on the DNA methylation alterations associated with cancer and aging. Next, we described the functional genomic and epigenomic context associated with the alterations, and finally, we integrated our data to study interspecies DNA methylation levels at orthologous CpG sites. Globally, we found considerable differences between the characteristics of DNA methylation alterations in cancer and aging in both species. Moreover, we describe robust evidence for the conservation of the specific cancer and aging epigenomic signatures in human and mouse. Our observations point toward the preservation of the functional consequences of these alterations at multiple levels of genomic regulation. Finally, our analyses reveal a role for the genomic context in explaining disease- and species-specific epigenetic traits.

Glioblastoma (GBM) is a highly aggressive brain tumor and almost all patients die because of relapses. GBM-derived cells undergo cell death without nuclear fragmentation upon treatment with different apoptotic agents. Nuclear dismantling determines the point-of-no-return in the apoptotic process. DFF40/CAD is the main endonuclease implicated in apoptotic nuclear disassembly. To be properly activated, DFF40/CAD should reside in the cytosol. However, the endonuclease is poorly expressed in the cytosol and remains cumulated in the nucleus of GBM cells. Here, by employing commercial and non-commercial patient-derived GBM cells, we demonstrate that the natural terpenoid aldehyde gossypol prompts DFF40/CAD-dependent nuclear fragmentation. A comparative analysis between gossypol- and staurosporine-treated cells evidenced that levels of neither caspase activation nor DNA damage were correlated with the ability of each compound to induce nuclear fragmentation. Deconvoluted confocal images revealed that DFF40/CAD was almost completely excluded from the nucleus early after the staurosporine challenge. However, gossypol-treated cells maintained DFF40/CAD in the nucleus for longer times, shaping a ribbon-like structure piercing the nuclear fragments and building a network of bridged masses of compacted chromatin. Therefore, GBM cells can fragment their nuclei if treated with the adequate insult, making the cell death process irreversible.

Capacitive response at long time scales seems to remain an elusive feature in the analysis of the electrical properties of perovskite-based solar cells. It belongs to one of the critical anomalous effects that arises from the characteristic phenomenology of this type of emerging photovoltaic devices. Thereby, accurately deducing key capacitance feature of new light harvesting perovskites from electrical measurements represents a significant challenge regarding the interpretation of physical processes and the control of undesired mechanisms, such as slow dynamic effects and/or current density–voltage (J–V) hysteresis. Herein, it is shown that long timescale mechanisms that give rise to hysteresis in stable and high-efficiency quadruple-cation perovskites are not due to a classical capacitive behavior in the sense of ideal charge accumulation processes. Instead, it is a phenomenological consequence of slow memory-based capacitive currents and the underlying cooperative relaxations. A fractional dynamics approach, based on the idea of capacitance distribution in perovskite devices, reliably models the slow transient phenomena and the consequent scan-rate- and bias-dependent hysteresis. Observable for a wide variety of photovoltaic halide perovskites, distributed capacitive effects are rather universal anomalous phenomena, which can be related to the long-time electrical response and hysteresis.

The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni1−xFexSe2 nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, Ni0.75Fe0.25Se2, this diselenide is able to produce 0.47 mmol cm−2 h−1 of formate at 50 mA cm−2 with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm−2 and 2.2 A mg−1 in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals.