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[EU] Proteinak polimero lineal gisa sintetizatzen dira eta beren jatorrizko egitura tridimentsionalean tolestu behar dira zelulan hainbat funtzio betetzeko. Proteinen tolespena ulertzea funtsezkoa da, tolespen okerrak hainbat gaixotasun neuro-degeneratiboren jatorria direlako. Proteinen tolespena modu koitzultzailean has daiteke, hau da, sortzen ari den peptidoa erribosomari lotuta dagoenean oraindik. Izan ere, zelularen proteinen heren bat baino gehiago erribosomaren tunelaren espazio mugatuan tolesten direla frogatu da, hau da, erribosomaren gainazalarekiko interakzioek modulatuta eta erribosoma-tunelaren beraren mugen pean. Gero eta ebidentzia gehiagok iradokitzen dute erribosomak funtsezko zeregina duela proteinen tolespenean. Erribosomak proteina trinkotzea erraztu dezake, soluzioan ikusten ez diren bitartekoak sortzea eragin dezake edo tolestearen hasiera atzeratu dezake. Hala ere, proteinen koitzulpenezko tolesdura aztertzeak zailtasun handiak ditu, batik bat, egungo teknikek dituzten mugengatik. Hori dela eta, proteinen tolesteari buruzko ikerketa gehienak soluzioan dauden proteinetan oinarritzen dira, proteina tolestuz eta destolestuz egiten direnak, prozesu horretan erribosomak duen rola kontuan hartu gabe. Artikulu honetan, azken urteotan proteinen koitzulpenezko tolestura ikertzeko garatu diren tekniken laburpena egin da., [EN] Proteins are synthesised as linear polymers and must fold into their native three-dimensional structure to perform various functions in the cell. Understanding protein folding is crucial because protein misfolding is at the origin of several neurodegenerative diseases. Protein folding can start co-translationally, i.e. when the emerging peptide is still associated with the ribosome. Indeed, it has been shown that more than one third of the cell’s proteins fold in the limited space of the ribosome tunnel. Increasing evidence suggests that the ribosome plays a critical role in protein folding. The ribosome can facilitate protein compaction, cause the creation of non-visible media in solution or delay the onset of folding. However, the study of co-translational folding presents serious difficulties, mainly due to the limitations of the different current techniques. Hence, most studies on protein folding are based on proteins in solution, which are carried out by unfolding and refolding the protein, without taking into account the role of the ribosome in this process. In this article, we summarised the techniques developed in recent years for the study of co-translational protein folding.

Dental morphology is a major aspect of ecological and evolutionary studies of both extant and fossil mammalian species. Mammalian dentitions are diverse feeding systems that can be defined through continuous numerical descriptors of the enamel pattern. We developed a comprehensive toolkit to quantify complex occlusal enamel patterns from two-dimensional images of herbivore mammals, widespread in the scientific literature, in form of three novel enamel complexity descriptors: two-dimensional orientation patch count (2D OPC), enamel folding (EF), and enamel thickness (ET). Previously proposed parameters such as occlusal enamel index or indentation index are implemented as well. The current method is devised for extracting continuous variables of enamel complexity from macro and microherbivore mammalian species with conspicuous wear facets. A general case study is proposed using two clades within the Family Rhinocerotidae containing species regarded as hypsodonts. The results show that antagonist dental adaptations were achieved through disparate evolutionary strategies in both groups. To test the robustness of this tool under different practical scenarios, other mammalian groups have been evaluated as well. Additional sensitivity analyses include the impact of image size, rotation, or differences in dental wear. Our approach differs from previous 2D techniques in its affordability, versatility, and control over individual regions within each tooth while delivering continuous numerical data. Additionally, the 2D reference images required as input are widespread in the literature and easier to process in comparison to 3D data alternatives.

In macroautophagy, the autophagosome (AP) engulfs portions of cytoplasm to allow their lysosomal degradation. AP formation in humans requires the concerted action of the ATG12 and LC3/GABARAP conjugation systems. The ATG12-ATG5-ATG16L1 or E3-like complex (E3 for short) acts as a ubiquitin-like E3 enzyme, promoting LC3/GABARAP proteins anchoring to the AP membrane. Their role in the AP expansion process is still unclear, in part because there are no studies comparing six LC3/GABARAP family member roles under the same conditions, and also because the full human E3 was only recently available. In the present study, the lipidation of six members of the LC3/GABARAP family has been reconstituted in the presence and absence of E3, and the mechanisms by which E3 and LC3/GABARAP proteins participate in vesicle tethering and fusion have been investigated. In the absence of E3, GABARAP and GABARAPL1 showed the highest activities. Differences found within LC3/GABARAP proteins suggest the existence of a lipidation threshold, lower for the GABARAP subfamily, as a requisite for tethering and inter-vesicular lipid mixing. E3 increases and speeds up lipidation and LC3/GABARAP-promoted tethering. However, E3 hampers LC3/GABARAP capacity to induce inter-vesicular lipid mixing or subsequent fusion, presumably through the formation of a rigid scaffold on the vesicle surface. Our results suggest a model of AP expansion in which the growing regions would be areas where the LC3/GABARAP proteins involved should be susceptible to lipidation in the absence of E3, or else a regulatory mechanism would allow vesicle incorporation and phagophore growth when E3 is present.

Cardiolipin (CL) is a key lipid for damaged mitochondrial recognition by the LC3/GABARAP human autophagy proteins. The role of ceramide (Cer) in this process is unclear, but CL and Cer have been proposed to coexist in mitochondria under certain conditions. Varela et al. showed that in model membranes composed of egg sphingomyelin (eSM), dioleoyl phosphatidylethanolamine (DOPE), and CL, the addition of Cer enhanced the binding of LC3/GABARAP proteins to bilayers. Cer gave rise to lateral phase separation of Cer-rich rigid domains but protein binding took place mainly in the fluid continuous phase. In the present study, a biophysical analysis of bilayers composed of eSM, DOPE, CL, and/or Cer was attempted to understand the relevance of this lipid coexistence. Bilayers were studied by differential scanning calorimetry, confocal fluorescence microscopy, and atomic force microscopy. Upon the addition of CL and Cer, one continuous phase and two segregated ones were formed. In bilayers with egg phosphatidylcholine instead of eSM, in which the binding of LC3/GABARAP proteins hardly increased with Cer in the former study, a single segregated phase was formed. Assuming that phase separation at the nanoscale is ruled by the same principles acting at the micrometer scale, it is proposed that Cer-enriched rigid nanodomains, stabilized by eSM:Cer interactions formed within the DOPE- and CL-enriched fluid phase, result in structural defects at the rigid/fluid nanointerfaces, thus hypothetically facilitatingLC3/GABARAP protein interaction.

In this paper, we address the optomechanical effects in surface-enhanced resonant Raman scattering (SERRS) from a single molecule in a nanoparticle on mirror (NPoM) nanocavity by developing a quantum master-equation theory, which combines macroscopic quantum electrodynamics and electron-vibration interaction within the framework of open quantum system theory. We supplement the theory with electromagnetic simulations and time-dependent density functional theory calculations in order to study the SERRS of a methylene blue molecule in a realistic NPoM nanocavity. The simulations allow us not only to identify the conditions to achieve conventional optomechanical effects, such as vibrational pumping, nonlinear scaling of Stokes and anti-Stokes scattering, but also to discovery distinct behaviors, such as the saturation of exciton population, the emergence of Mollow triplet side bands, and higher-order Raman scattering. All in all, our study might guide further investigations of optomechanical effects in resonant Raman scattering.

Chern insulators are two-dimensional magnetic topological materials that conduct electricity along their edges via the one-dimensional chiral modes. The number of these modes is a topological invariant called the first Chern number C that defines the quantized Hall conductance as Sxy = Ce2/h. Increasing C is pivotal for the realization of low-power-consumption topological electronics, but there has been no clear-cut solution to this problem so far, with the majority of existing Chern insulators showing C = 1. Here, by using state-of-the-art theoretical methods, we propose an efficient approach for the realization of the high-C state in MnBi2Te4/hBN van der Waals multilayer heterostructures. We show that a stack of n MnBi2Te4 films with C = 1 intercalated by hBN monolayers gives rise to a high Chern number state with C = n, characterized by n chiral edge modes. This state can be achieved both under the external magnetic field and without it, both cases leading to the quantized Hall conductance Sxy = Ce2/h. Our results, therefore, pave the way to practical high-C quantized Hall systems.

[EN] Flint was the most widely used lithic raw material in Europe in Prehistory and, more specifically, was a fundamental resource in the economic and social networks of hunter-gatherer groups in the Cantabrian Spain during the Upper Palaeolithic. The undeniable preference for it compared with other resources was due to a series of factors, such as its easy availability because of its abundance and wide distribution of outcrops, and its excellent qualities for knapping. This summary of the available information about flint and other raw materials used by hunter-gatherers is framed in the context of Upper Palaeolithic occupations in Cantabrian Spain. First, it presents the studies focusing on the provenance of the different types of flint that are found in those occupations; their quantitative representation at each of the sites; their preference, if that is the case, over other raw materials; and the model of their diffusion across the territory. Then other resources are considered, such as quartzite, ochre and different metamorphic, sedimentary and igneous rocks, as well as some materials of biological origin, such as amber, jet/lignite and fossils of animal origin. However, the information available about the use of the latter raw materials in Cantabrian Spain during the Upper Palaeolithic is quite limited and studies of their characterisation are very recent., [FR] Le silex est la principale matière première lithique utilisée dans la Préhistoire du continent européen et c’est une ressource fondamentale dans les circuits économiques et sociaux des groupes de chasseurs-cueilleurs pendant le Paléolithique supérieur de la région cantabrique (nord de l’Espagne). Sa préférence incontestable par rapport aux autres ressources repose sur une série de qualités telles qu’une disponibilité facile du fait de sa grande abondance, de la grande dispersion des affleurements, ainsi que les excellentes qualités pour sa taille. Dans cet article, nous présentons une synthèse des informations disponibles à partir des études sur le silex et d’autres matières premières utilisées par les groupes de chasseurs-cueilleurs. Cette révision a été abordée dans le cadre des occupations archéologiques de la région cantabrique datées du Paléolithique supérieur. D’une part, il s’agit des études relatives à la provenance des différents types de silex trouvés, leur représentation quantitative dans chacun des gisements révisées, préférence, si c’est le cas, par rapport aux autres matières premières documentées, ainsi que leur modèle de diffusion sur le territoire. D’autre part, d’autres ressources sont traitées, comme le quartzite, l’ocre et différentes roches métamorphiques, sédimentaires et ignées, ainsi que quelques matériaux d’origine biologique, comme l’ambre, le jais/lignite et les fossiles d’origine animale. Les informations disponibles concernant l’utilisation de ces matières premières dans le contexte du Paléolithique supérieur cantabrique sont assez rares et leurs études de caractérisation sont récentes.

In recent years, much effort has been invested into developing multifunctional drug delivery systems to overcome the drawbacks of conventional carriers. Magnetic nanoparticles are not generally used as carriers but can be functionalised with several different biomolecules and their size can be tailored to present a hyperthermia response, allowing for the design of multifunctional systems which can be active in therapies. In this work, we have designed a drug carrier nanosystem based on Fe3O4 nanoparticles with large heating power and 4-amino-2-pentylselenoquinazoline as an attached drug that exhibits oxidative properties and high selectivity against a variety of cancer malignant cells. For this propose, two samples composed of homogeneous Fe3O4 nanoparticles (NPs) with different sizes, shapes, and magnetic properties have been synthesised and characterised. The surface modification of the prepared Fe3O4 nanoparticles has been developed using copolymers composed of poly(ethylene-alt-maleic anhydride), dodecylamine, polyethylene glycol and the drug 4-amino-2-pentylselenoquinazoline. The obtained nanosystems were properly characterised. Their in vitro efficacy in colon cancer cells and as magnetic hyperthermia inductors was analysed, thereby leaving the door open for their potential application as multimodal agents.

Biodegradation of polyesters driven by enzymes is considered as one of the most effective way of degradation of these materials, as a way to control plastics accumulation in the environment. In this study, we present two different strategies to tune the enzymatic degradation of PBS films triggered by a lipase from Pseudomonas cepacia. Firstly, the kinetics of enzymatic degradation of PBS films was regulated by applying multilayer coats of polysaccharide alginate and chitosan (Alg/Chi) films. Secondly, self-degradable PBS films were prepared by embedding lipase-filled alginate particles. For comparison purposes, a detailed enzymatic degradation study of neat PBS films exposed to a lipase from P. cepacia in solution was made to determine the main experimental parameters influencing their degradation in solution. The results showed that an increase in enzyme concentration increased the degradation extent and rate of neat PBS films. At a fixed enzyme concentration, stirring of the solution containing the enzyme and the PBS also increased the biodegradation rate. In the case of the PBS films coated with a different number of Alg/Chi layers by spray-assisted LbL and subjected to enzymatic degradation experiments in solution, the extent of degradation was found to be dependent on the number of protective coating layers. Therefore, the Alg/Chi biobased coating constitutes an effective barrier to the diffusion of the lipase, thus proving its effectiveness in modulating the enzymatic activity as a function of coating thickness. In the case of self-degradable PBS containing lipase-embedded alginate beads (employed to protect the enzyme during high-temperature processing), only limited biodegradation was observed as the amount of encapsulated enzyme employed was too small. Nonetheless, these results are promising, as the enzymatic activity –indicative of the degradation capacity of the enzyme– determined for all these samples was about 2 orders of magnitude lower than that of p

132 p, I. Abstracts. Idatzizko komunikazioak / Comunicaciones escritas: 1. Biozientziak / Biociencias. 2. Fisika eta Ingenieritza Elektronika / Física e Ingeniería Electrónica. 3. Matematika / Matemáticas. 4. Geología / Geología. 5. Kimika / Química. 6. Ingenieritza Kimikoa / Ingeniería Química. 7. SGIker. II. Abstracts. Ahozko komunikazioak / Comunicaciones orales: 1. Biozientziak / Biociencias. 2. Fisika eta Ingenieritza Elektronika / Física e Ingeniería Electrónica. 3. Matematika / Matemáticas. 4. Geología / Geología. 5. Kimika / Química. 6. Ingenieritza Kimikoa / Ingeniería Química.

Stem cell-based therapies have shown promising results for the regeneration of the nervous system. However, the survival and integration of the stem cells in the neural circuitry is suboptimal and might compromise the therapeutic outcomes of this approach. The development of functional scaffolds capable of actively interacting with stem cells may overcome the current limitations of stem cell-based therapies. In this study, three-dimensional hydrogels based on graphene derivatives and cerium oxide (CeO2) nanoparticles are presented as prospective supports allowing neural stem cell adhesion, migration and differentiation. The morphological, mechanical and electrical properties of the resulting hydrogels can be finely tuned by controlling several parameters of the self-assembly of graphene oxide sheets, namely the amount of incorporated reducing agent (ascorbic acid) and CeO2 nanoparticles. The intrinsic properties of the hydrogels, as well as the presence of CeO2 nanoparticles, clearly influence the cell fate. Thus, stiffer adhesion substrates promote differentiation to glial cell lineages, while softer substrates enhance mature neuronal differentiation. Remarkably, CeO2 nanoparticle-containing hydrogels support the differentiation of neural stem cells to neuronal, astroglial and oligodendroglial lineage cells, promoting the in vitro generation of nerve tissue grafts that might be employed in neuroregenerative cell therapies.

Hydrogen molecules dissociate on clean W(110) surfaces. This reaction is progressively inhibited as the tungsten surface is precovered with oxygen. We use density functional theory and ab initio molecular dynamics to rationalize, at the atomic scale, the influence of the adsorbed O atoms on the H2 dissociation process. The reaction probability is calculated for kinetic energies below 300 meV and different O nominal coverages. We show that the adsorbed O atoms act as repulsive centers that modulate the dynamics of the impinging H2 molecules by closing dissociation pathways. In agreement with existing experimental information, H2 dissociation is absent for an O coverage of half a monolayer. The results show that the influence of O adsorbates on the dissociation dynamics on W(110) goes much beyond the blocking of possible H adsorption sites. Adsorbed O atoms create a sort of chemical shield at the surface that prevents further approach and dissociation of the H2 molecules.

Using relativistic spin-polarized density functional theory calculations we investigate magnetism, electronic structure and topology of the ternary thallium gadolinium dichalcogenides TlGdZ2 (Z= Se and Te) as well as superlattices on their basis. We find TlGdZ2 to have an antiferromagnetic exchange coupling both within and between the Gd layers, which leads to frustration and a complex magnetic structure. The electronic structure calculations reveal both TlGdSe2 and TlGdTe2 to be topologically trivial semiconductors. However, as we show further, a three-dimensional (3D) magnetic topological insulator (TI) state can potentially be achieved by constructing superlattices of the TlGdZ2/(TlBiZ2)n type, in which structural units of TlGdZ2 are alternated with those of the isomorphic TlBiZ2 compounds, known to be non-magnetic 3D TIs. Our results suggest a new approach for achieving 3D magnetic TI phases in such superlattices which is applicable to a large family of thallium rare-earth dichalcogenides and is expected to yield a fertile and tunable playground for exotic topological physics.

The design of high-temperature ferrimagnetic materials is highly demanded for next-generation functional spintronic devices. Here, we propose that the combination of nonmetallic structural units and magnetic atoms is an effective way to achieve high-temperature magnetism in two-dimensional (2D) materials. The predicted FeP4 monolayer, consisting of quasisquare P4 units, shows intrinsic half-metal ferrimagnetism above room temperature. Each Fe atom is coordinated with four P atoms associated with the surrounding four quasisquare P4 units. First-principles calculations suggest that the FeP4 monolayer presents a Curie temperature of 460 K. More interestingly, the itinerant electrons and the unique quasisquare P4 units act as intermediaries and play an important role in promoting the Ruderman-Kittel-Kasuya-Yosida and superexchange interactions, respectively, which induces a robust ferrimagnetism. Our findings not only shed light on the promising future of 2D magnetic materials, but also are of interest for high-temperature spintronic applications.

Polycarboxylic ethers or polycarboxylate (PCEs) are one of the most employed superplasticizers in construction. However, the understanding of their microstructure–property relationship is still incomplete. Recently, a theoretical model was proposed that relates the microstructure–conformation of the PCE to its effect on the adsorption onto cement particles and cement hydration time. In this work, the effects of a wide range of PCEs with different side chain lengths (P = 5, Group 1; P = 20, Group 2; and P = 45 and 113, Group 3) having flexible backbone worm conformation except one which has stretch backbone worm conformation (P = 113) were experimentally investigated for their effect on adsorption and cement hydration. It is found that PCEs from Group 1 show electrostatic repulsion as dispersing mechanism, unlike PCEs from Groups 2 and 3. Furthermore, the prediction of the theoretical model is also assessed for all the studied PCEs. Only Group 1 PCEs (shortest side chains) showed deviation from the theoretical predictions, and it was attributed to their different behaviors from the standard PCEs for which the theoretical model was developed.

This study investigates the possibility of using municipal solid waste incineration fly ash as a supplementary cementitious material to replace part of the clinker in cement. Life cycle assessment has shown that the partial replacement of clinker with blast furnace slag (CEM III) reduces cement’s global warming potential by ~30%, while replacing clinker with fly ash reduces it by up to 55%. When using CEM III as the control binder in cement in which 55 wt% of the clinker was replaced with hydrothermally treated fly ash, the flexural strength decreased by ~60% and the compressive strength by ~65%. When the fly ash was mixed with calcined and vitrified demolition materials, flexural strength decreased by ~30% and compressive strength by ~50%. The hardening of the hydraulic binders fixed the heavy metals in the municipal solid waste incineration fly ash.

Oxyfluoride glass-ceramics (OxGCs) with the molar composition 80SiO2-20(1.5Eu3+: NaGdF4) were prepared with sol-gel following the “pre-crystallised nanoparticles route” with promising optical results. The preparation of 1.5 mol % Eu3+-doped NaGdF4 nanoparticles, named 1.5Eu3+: NaGdF4, was optimised and characterised using XRD, FTIR and HRTEM. The structural characterisation of 80SiO2-20(1.5Eu3+: NaGdF4) OxGCs prepared from these nanoparticles’ suspension was performed by XRD and FTIR revealing the presence of hexagonal and orthorhombic NaGdF4 crystalline phases. The optical properties of both nanoparticles’ phases and the related OxGCs were studied by measuring the emission and excitation spectra together with the lifetimes of the 5D0 state. The emission spectra obtained by exciting the Eu3+-O2− charge transfer band showed similar features in both cases corresponding the higher emission intensity to the 5D0→7F2 transition that indicates a non-centrosymmetric site for Eu3+ ions. Moreover, time-resolved fluorescence line-narrowed emission spectra were performed at a low temperature in OxGCs to obtain information about the site symmetry of Eu3+ in this matrix. The results show that this processing method is promising for preparing transparent OxGCs coatings for photonic applications.

Fermentative processes by lactic acid bacteria can produce metabolites of interest to the health and food industries. Two examples are the production of B-group vitamins, and of prebiotic and immunomodulatory dextran-type exopolysaccharides. In this study, three riboflavin- and dextran-producing Weissella cibaria strains (BAL3C-5, BAL3C-7 and BAL3C-22) were used to develop a new method for selection and isolation of spontaneous riboflavin-overproducing W. cibaria mutants. This method was based on the selection of strains resistant to roseoflavin. The DNA sequencing of the FMN riboswitch of bacterial cell populations treated with various roseoflavin concentrations, revealed the existence of at least 10 spontaneous and random point mutations at this location. Folding and analysis of the mutated FMN riboswitches with the RNA fold program predicted that these mutations could result in a deregulation of the rib operon expression. When the roseoflavin-treated cultures were plated on medium supporting dextran synthesis, the most promising mutants were identified by the yellow color of their mucous colonies, exhibiting a ropy phenotype. After their isolation and recovery in liquid medium, the evaluation of their riboflavin production revealed that the mutant strains synthesized a wide range of riboflavin levels (from 0.80 to 6.50 mg/L) above the wild-type level (0.15 mg/L). Thus, this was a reliable method to select spontaneous riboflavin-overproducing and dextran-producing strains of W. cibaria. This species has not yet been used as a starter or adjunct culture, but this study reinforces the potential that it has for the food and health industry for the production of functional foods or as a probiotic. Furthermore, analysis of the influence of FMN present in the growth medium, on rib mRNA and riboflavin levels, revealed which mutant strains produce riboflavin without flavin regulation. Moreover, the BAL3C-5 C120T mutant was identified as the highest riboflavin-overproducer

We present a code modularization approach to design efficient and massively parallel cubic and linear-scaling solvers for electronic structure calculations using atomic orbitals. The modular implementation of the orbital minimization method, in which linear algebra and parallelization issues are handled via external libraries, is demonstrated in the SIESTA code. The DBCSR and ScaLAPACK libraries are used for algebraic operations with sparse and dense matrices, respectively. The MatrixSwitch and libOMM libraries, recently developed within the Electronic Structure Library, facilitate switching between different matrix formats and implement the energy minimization. We show results comparing the performance of several cubic-scaling algorithms, and also demonstrate the parallel performance of the linear-scaling solvers, and their supremacy over the cubic-scaling solvers for insulating systems with sizes of several hundreds of atoms.

[EN] This volume presents part of the results obtained during the international cooperation project PIRAGUA (EFA210/16), co-financed by the Interreg EFA Program (Spain-France-Andorra). Between 2018 and 2021, the PIRAGUA project addressed, through cross-border cooperation, the evaluation of the hydrological cycle and water resources in the Pyrenees, in the present and in the future, in the context of climate change. To do this, the project partners unified and homogenized the existing hydrological information, proposed hydrological indicators, analyzed the trends observed in said indicators, developed simulation models to know in detail the different components of the water balance, and carried out numerical simulations based on projections under different scenarios of greenhouse gas emissions to assess the consequences of climate change on the hydrological cycle and the water resources of the Pyrenees. The objective of this volume is to carry out a characterization of the surface and underground water resources of the Pyrenees, as well as the management and use of said resources (Chapter 1); analyze flow records, aquifer levels, and floods to determine spatial patterns and determine temporal trends observed in recent decades (Chapter 2); apply simulation tools to expand knowledge about the different components of the water balance of the Pyrenees (Chapter 3); and carry out a series of numerical simulation experiments to determine possible changes in the water balance and water resources of the Pyrenees throughout the 21st century, in a context of climate change (Chapter 4)., [ES] Este trabajo presenta una parte de los resultados obtenidos durante el proyecto de cooperación internacional PIRAGUA (EFA210/16), co-financiado por el Programa Interreg EFA (España-Francia-Andorra). Entre 2018 y 2021, el proyecto PIRAGUA abordó, mediante la cooperación transfronteriza, la evaluación del ciclo hidrológico y los recursos hídricos en los Pirineos, en el presente y en futuro, en el contexto del cambio climático. Para ello, los socios del proyecto unificaron y homogeneizaron la información hidrológica existente, propusieron indicadores hidrológicos, analizaron las tendencias observadas en dichos indicadores, desarrollaron modelos de simulación para conocer en detalle los distintos componentes del balance hídrico, y realizaron simulaciones numéricas a partir de proyecciones climáticas bajo distintos escenarios de emisiones de gases de efecto invernadero para evaluar las consecuencias del cambio climático sobre el ciclo hidrológico y los recursos hídricos de los Pirineos. El objetivo de este volumen es realizar una caracterización de los recursos hídricos superficiales y subterráneos de los Pirineos, así como de la gestión y uso de dichos recursos (Capítulo 1); analizar los registros de caudal, niveles de acuíferos e inundaciones para determinar patrones espaciales y determinar las tendencias temporales observadas en las últimas décadas (Capítulo 2); aplicar herramientas de simulación para ampliar el conocimiento sobre los distintos componentes del balance hídrico de los Pirineos (Capítulo 3); y realizar una serie de experimentos de simulación numérica para determinar los posibles cambios del balance hídrico y los recursos hídricos de los Pirineos a lo largo del siglo XXI, en un contexto de cambio climático (Capítulo 4)., [FR] Ce travail présente une partie des résultats d'un projet de coopération internationale du Programme Interreg EFA (Espagne-France-Andorre). Entre 2018 et 2021, le projet PIRAGUA (EFA210/16) a abordé, par le biais de la coopération transfrontalière, l'évaluation du cycle hydrologique et des ressources hydriques dans les Pyrénées, pour le présent et l'avenir, dans le contexte du changement climatique. Pour cela, les partenaires du projet ont unifié et homogénéisé les informations hydrologiques existantes, proposé des indicateurs hydrologiques, analysé les tendances observées pour ces indicateurs, développé des modèles de simulation pour connaître les détails du bilan hydrique et réalisé des expériences de simulation numérique, afin d'évaluer les conséquences de scénarios de changement climatique sur le cycle hydrologique et les ressources hydriques des Pyrénées. L'objectif de ce volume est de réaliser une caractérisation des ressources hydriques de surface et souterraines des Pyrénées, de la gestion et de l'emploi des ressources (Chapitre 1) ; analyser les registres de débit, le niveau des aquifères et les inondations afin de déterminer des schémas spatiaux ainsi que les tendances temporelles observées ces dernières décennies (Chapitre 2) ; appliquer des outils de simulation pour réaliser un diagnostic des différents éléments du bilan hydrique des Pyrénées (Chapitre 3); réaliser une série d'expériences de simulation pour déterminer les éventuels changements du bilan hydrique et des ressources hydriques des Pyrénées tout au long du XXIᵉ siècle, dans un contexte de changement climatique (Chapitre 4).

[EN] Recent climate change is one of the main threats to the sustainability of human societies. The reports of the IPCC, the Paris Agreement or the United Nations Conferences on climate change attest to the global political interest in urgently taking action to mitigate climate change. Mitigation efforts, however, are not enough to minimize the negative consequences of climate change. It is necessary, in parallel to the mitigation measures, to develop adaptation strategies that make it possible to minimize the risks that climate change poses to societies. With a necessarily local focus, the development of adaptation strategies must be based on an assessment of the vulnerability of society as a whole or of sectors of it to the expected consequences of climate change. This volume explores options for adaptation to climate change in relation to the management of water resources in an important transboundary region such as the Pyrenees mountain range. After a general assessment of the region's water resources and their governance, seven local and regional case studies are presented where, in collaboration with the relevant stakeholders, different adaptation options are explored., [ES] El cambio climático reciente es una de las principales amenazas para la sostenibilidad de las sociedades humanas. Los informes del IPCC, el Acuerdo de París o las Conferencias de las Naciones Unidas sobre cambio climático atestiguan el interés político global por emprender con urgencia acciones para la mitigación del cambio climático. Los esfuerzos en mitigación, sin embargo, no son suficientes para minimizar las consecuencias negativas del cambio climático. Es necesario, en paralelo a las medidas de mitigación, desarrollar estrategias de adaptación que permitan minimizar los riesgos que supone el cambio climático para las sociedades. Con un enfoque necesariamente local, el desarrollo de estrategias de adaptación debe partir de una evaluación de la vulnerabilidad del conjunto de la sociedad o de sectores de ésta a las consecuencias esperables del cambio climático. En este volumen se exploran opciones de adaptación al cambio climático en relación con la gestión de los recursos hídricos de una importante región transfronteriza como es la cordillera de los Pirineos. Tras una evaluación general sobre los recursos hídricos de la región y su gobernanza, se presentan siete casos de estudio locales y regionales donde, en colaboración con los actores locales, se exploran diferentes opciones de adaptación., [FR] Le changement climatique récent est l'une des principales menaces à la durabilité des sociétés humaines. Les rapports du GIEC, l'Accord de Paris ou les Conférences des Nations Unies sur le changement climatique attestent de l'intérêt politique mondial à agir de toute urgence pour atténuer le changement climatique. Cependant, les efforts d'atténuation ne suffisent pas à minimiser les conséquences négatives du changement climatique. Il est nécessaire, parallèlement aux mesures d'atténuation, de développer des stratégies d'adaptation qui permettent de minimiser les risques que le changement climatique fait peser sur les sociétés. Dans une optique nécessairement locale, l'élaboration de stratégies d'adaptation doit reposer sur une évaluation de la vulnérabilité de la société dans son ensemble ou de secteurs de celle-ci aux conséquences attendues du changement climatique. Ce volume explore les options d'adaptation au changement climatique en relation avec la gestion des ressources en eau dans une région transfrontalière importante telle que la chaîne de montagnes des Pyrénées. Après une évaluation générale des ressources en eau de la région et de leur gouvernance, sept études de cas locales et régionales sont présentées où, en collaboration avec les acteurs locaux, différentes options d'adaptation sont explorées.

[EN] The reconstruction of behavioural patterns performed by non-avian dinosaurs is an important task of palaeontology in order to globally understand how these animals interacted with their environment. Their relation with aquatic lifestyles has always been an intriguing question that has been extensively studied during the last decades, especially focused on some specific groups. The present work describes a new tracksite with 27 swimming tracks located in a fluvial setting from the Lower Cretaceous Urbion Group of La Rioja (Spain). They are preserved as natural casts with sizes between 8.5 and 29.2 cm and a predominant orientation. The tracks have been classified into 6 different morphotypes according to their morphology, and grouped into 5 different categories depending on the different pes-substrate interactions, following the proposal of Romilio et al. (2013). Some tracks were produced while the animal was moving in partial or complete buoyancy, and displacement was conducted by water and sediment impulsion, not just a mere paddling. Other tracks could be impressed in a bottom-walked, when the trackmaker touched the digit tips on the ground vertically or sub-vertically. This new tracksite confirms the capabilities of some groups of non-avian dinosaurs to interact with shallow water environments where they could print their pedes as they moved, either in complete buoyancy or during a displacement with some vertical component in the water column. It also contributes to the better understanding of swimming track morphologies as especially dependent on pes-sediment interaction and environment more than differences in pes configuration itself, causing the high variability of swimming footprints even when they belong to the same trackway. The classification of swimming tracks and footprints into categories dependent on the pes-substrate interaction could be a good guiding principle to avoid problematics about ichnotaxonomical definition.

Time-dependent density functional theory (TDDFT) has established itself as a computationally efficient and effective alternative to the many-body perturbation theory for calculating the optical properties of solids. Within the framework of linear response formalism, TDDFT exhibits good agreement between optical absorption spectra and experimental data, as well as the possibility of directly determining exciton binding energies. However, the family of exchange-correlation kernels, known as long-range-corrected kernels, which accurately capture excitonic features, face challenges in simultaneously generating visually appealing spectra and precise exciton binding energies. Recently, progress has been made in addressing this discrepancy through a hybrid-TDDFT approach. Our study reveals that the key lies in the numerical treatment of the long-range Coulomb singular term. We conduct a meticulous investigation of the impact of the term in both pure-TDDFT and hybrid approaches using a Wigner-Seitz truncated kernel. Notably, we show that computing this term presents formidable technical difficulties in both approaches, pointing to the need for an improved description of the electron-hole interaction.

Electrolytic hydrogen appears as one of the most promising options to store renewable energy. In this water splitting process, the sluggish kinetics of the 4-electron oxygen evolution reaction (OER) with its high overpotentials have been widely regarded as the bottleneck to facilitate a fast, energy-efficient process. In alkaline media, numerous earth-abundant metal oxides are efficient OER catalysts, stabilized by the high concentration of hydroxide anions in the electrolyte. However, under acidic conditions, where the hydrogen evolution reaction (HER) is technologically preferred, only noble metal-based oxides (RuO2 and IrO2) are suitable OER catalysts, putting into question the scalability to wide-spread applications due to their scarcity and high cost. Most earth abundant metal oxides dissolve at high proton concentrations. A promising strategy to avoid this drawback consists of incorporating these catalysts into partially hydrophobic composite electrodes. Following this strategy, we have been able to conduct an extensive survey of the activity and stability of mono-, bi- and trimetallic earth-abundant transition metal oxides during the electrocatalytic OER under strongly acidic conditions. Our results confirm the general validity of the strategy by using a hydrophobic electrode to confer high stability to common metal oxides under these harsh conditions. Among all OER catalysts investigated, we found that simple manganese oxides appeared as the most active also exhibiting high, long-term stability. In particular, the stability of Mn2O3 oxide in the OER in acidic media was well confirmed by post-electrolysis characterization data.

Artificial intelligence (AI) has emerged as a cutting-edge tool, simultaneously accelerating, securing, and enhancing the diagnosis and treatment of patients. An exemplification of this capability is evident in the analysis of peripheral blood smears (PBS). In university medical centers, hematologists routinely examine hundreds of PBS slides daily to validate or correct outcomes produced by advanced hematology analyzers assessing samples from potentially problematic patients. This process may logically lead to erroneous PBC readings, posing risks to patient health. AI functions as a transformative tool, significantly improving the accuracy and precision of readings and diagnoses. This study reshapes the parameters of blood cell classification, harnessing the capabilities of AI and broadening the scope from 5 to 11 specific blood cell categories with the challenging 11-class PBC dataset. This transformation facilitates a more profound exploration of blood cell diversity, surpassing prior constraints in medical image analysis. Our approach combines state-of-the-art deep learning techniques, including pre-trained ConvNets, ViTb16 models, and custom CNN architectures. We employ transfer learning, fine-tuning, and ensemble strategies, such as CBAM and Averaging ensembles, to achieve unprecedented accuracy and interpretability. Our fully fine-tuned EfficientNetV2 B0 model sets a new standard, with a macro-average precision, recall, and F1-score of 91%, 90%, and 90%, respectively, and an average accuracy of 93%. This breakthrough underscores the transformative potential of 11-class blood cell classification for more precise medical diagnoses. Moreover, our groundbreaking “Naturalize” augmentation technique produces remarkable results. The 2K-PBC dataset generated with “Naturalize” boasts a macro-average precision, recall, and F1-score of 97%, along with an average accuracy of 96% when leveraging the fully fine-tuned EfficientNetV2 B0 model. This innovation not only elevate

The Aneto glacier, although it may be considered a very small glacier (<0.5 km2), is the largest glacier in the Pyrenees. Its surface and thickness loss have been continuous in recent decades, and there have been signs of accelerated melting in recent years. In this study, thickness and surface losses of the Aneto glacier from 1981 to 2022 are investigated using historical aerial imagery, airborne lidar point clouds and unoccupied aerial vehicle (UAV) imagery. A ground-penetrating radar (GPR) survey conducted in 2020, combined with data from photogrammetric analyses, allowed us to reconstruct the current ice thickness and also the existing ice distribution in 1981 and 2011. Over the last 41 years, the total glacierised area has decreased by 64.7 %, and the ice thickness has decreased, on average, by 30.5 m. The mean remaining ice thickness in autumn 2022 was 11.9 m, as against the mean thickness of 32.9, 19.2 and 15.0 m reconstructed for 1981 and 2011 and observed in 2020, respectively. The results demonstrate the critical situation of the glacier, with an imminent segmentation into two smaller ice bodies and no evidence of an accumulation zone. We also found that the occurrence of an extremely hot and dry year, as observed in the 2021–2022 season, leads to a drastic degradation of the glacier, posing a high risk to the persistence of the Aneto glacier, a situation that could extend to the rest of the Pyrenean glaciers in a relatively short time.

[Purpose of Review] Familial hypercholesterolemia (FH) is a hereditary condition characterized by elevated levels of low-density lipoprotein cholesterol (LDL-C), which increases the risk of cardiovascular disease if left untreated. This review aims to discuss the role of bioinformatics tools in evaluating the pathogenicity of missense variants associated with FH. Specifically, it highlights the use of predictive models based on protein sequence, structure, evolutionary conservation, and other relevant features in identifying genetic variants within LDLR, APOB, and PCSK9 genes that contribute to FH., [Recent Findings] In recent years, various bioinformatics tools have emerged as valuable resources for analyzing missense variants in FH-related genes. Tools such as REVEL, Varity, and CADD use diverse computational approaches to predict the impact of genetic variants on protein function. These tools consider factors such as sequence conservation, structural alterations, and receptor binding to aid in interpreting the pathogenicity of identified missense variants. While these predictive models offer valuable insights, the accuracy of predictions can vary, especially for proteins with unique characteristics that might not be well represented in the databases used for training., [Summary] This review emphasizes the significance of utilizing bioinformatics tools for assessing the pathogenicity of FH-associated missense variants. Despite their contributions, a definitive diagnosis of a genetic variant necessitates functional validation through in vitro characterization or cascade screening. This step ensures the precise identification of FH-related variants, leading to more accurate diagnoses. Integrating genetic data with reliable bioinformatics predictions and functional validation can enhance our understanding of the genetic basis of FH, enabling improved diagnosis, risk stratification, and personalized treatment for affected individuals. The comprehensive approach outlined in this review promises to advance the management of this inherited disorder, potentially leading to better health outcomes for those affected by FH.

Deep learning (DL) has made significant advances in computer vision with the advent of vision transformers (ViTs). Unlike convolutional neural networks (CNNs), ViTs use self-attention to extract both local and global features from image data, and then apply residual connections to feed these features directly into a fully networked multilayer perceptron head. In hospitals, hematologists prepare peripheral blood smears (PBSs) and read them under a medical microscope to detect abnormalities in blood counts such as leukemia. However, this task is time-consuming and prone to human error. This study investigated the transfer learning process of the Google ViT and ImageNet CNNs to automate the reading of PBSs. The study used two online PBS datasets, PBC and BCCD, and transferred them into balanced datasets to investigate the influence of data amount and noise immunity on both neural networks. The PBC results showed that the Google ViT is an excellent DL neural solution for data scarcity. The BCCD results showed that the Google ViT is superior to ImageNet CNNs in dealing with unclean, noisy image data because it is able to extract both global and local features and use residual connections, despite the additional time and computational overhead.

We study the similarities and differences in the shift photocurrent contribution to the bulk photovoltaic effect between transition-metal dichalcogenide monolayers and nanotubes. Our analysis is based on density functional theory in combination with the Wannier interpolation technique for the calculation of the shift photoconductivity tensor. Our results show that for nanotube radii of practical interest, r>60 Å, the shift photoconductivity of a single-wall nanotube is well described by that of the monolayer. Additionally, we quantify the shift photocurrent generated under realistic experimental conditions like device geometry and absorption capabilities. We show that a typical nanotube can generate a photocurrent of around 10 nA, while the monolayer only attains a maximum of 1 nA. This enhancement is mainly due to the larger conducting cross section of a nanotube in comparison to a monolayer. Finally, we discuss our results in the context of recent experimental measurements on WS2 monolayer and nanotubes [Zhang et al., Nature (London) 570, 349 (2019)].

Using many-body perturbation theory and density functional perturbation theory, we study the vibrational spectra of the internal stretch (IS) mode of CO on Pd(111) for the bridge and hollow adsorption structures that are experimentally identified at 0.5 ML coverage. Our theoretical treatment allows us to determine the temperature dependence of the IS vibrational spectra under thermal conditions as well as the time evolution of the nonequilibrium transient spectra induced by femtosecond laser pulses. Under thermal conditions (i.e., for equal electronic Te and phononic Tl temperatures), the calculated lifetimes at 10–150 K are mostly due to nonadiabatic couplings (NCs), i.e., first-order electronic excitations. As temperature increases, also the contribution of the second-order electron-mediated phonon-phonon couplings (EMPPCs) progressively increases from 25% at low temperatures to 50% at 300 K. Our calculations for the laser-induced nonequilibrium conditions comprise experimental absorbed fluences of 6–130J/m2. For fluences for which Te>2000K, the transient vibrational spectra are characterized by two different regimes that follow the distinct time evolution of Te and Tl and are respectively dominated by NC and EMPPC processes. At lower fluences, the initial fast regime becomes progressively negligible as Te decreases and only the steady second regime remains visible. Qualitatively, all these spectral properties are common to both of the adsorption structures studied here.

Phytostabilization of metal-contaminated soils is effective to reduce their solubility and availability in soils and reduce their toxicity to plants. However, the evaluation of appropriate treatments and efficient plant species needs to consider the effects not only of soil characteristics, but also of microbial population. In this work, the effects of seven different plants, including crops and locally adapted species, in two metal-contaminated soils based on a field phytoremediation experiment were evaluated. The two soils (agricultural and mining) contained 6.1, 2322 and 1422, and 13.5, 2071 and 13,971 ​mg ​kg−1 Cd, Pb and Zn concentrations, respectively. In the agricultural soil, combination of crop species Cynara cardunculus and Brassica juncea Czern. was the most effective in reducing metal extractability and in stimulating microbial activity. In the mining soil, compost-assisted phytostabilization decreased CaCl2-extractable Cd and Zn (12–50% for Cd and 71–76% for Zn). The reduced metal toxicity enhanced microbial biomass activity and diversity, particularly under B. juncea. Thus, phytostabilization using selected species was effective in reducing metal toxicity in contaminated soils

The shift current is part of the second-order optical response of materials with a close connection to topology. Here we report a sign inversion in the band-edge shift photoconductivity of the Haldane model when the system undergoes a topological phase transition. This result is obtained following two complementary schemes. On one hand, we derive an analytical expression for the band-edge shift current in a two-band tight-binding model showing that the sign reversal is driven by the mass term. On the other hand, we perform a numerical evaluation on a continuum version of the Haldane model. This approach allows us to include off-diagonal matrix elements of the position operator, which are discarded in tight-binding models but can contribute significantly to the shift current. Explicit evaluation of the shift current shows that while the model predictions remain accurate in the deep tight-binding regime, significant deviations arise for shallow potential landscapes. Notably, the sign reversal across the topological phase transition is observed in all regimes, implying it is a robust effect that could be observable in a wide range of topological insulators.

Optical anapoles are intriguing charge-current distributions characterized by a strong suppression of electromagnetic radiation. They originate from the destructive interference of the radiation produced by electric and toroidal multipoles. Although anapoles in dielectric structures have been probed and mapped with a combination of near- and far-field optical techniques, their excitation using fast electron beams has not been explored so far. Here, we theoretically and experimentally analyze the excitation of optical anapoles in tungsten disulfide (WS2) nanodisks using Electron Energy Loss Spectroscopy (EELS) in Scanning Transmission Electron Microscopy (STEM). We observe prominent dips in the electron energy loss spectra and associate them with the excitation of optical anapoles and anapole-exciton hybrids. We are able to map the anapoles excited in the WS2 nanodisks with subnanometer resolution and find that their excitation can be controlled by placing the electron beam at different positions on the nanodisk. Considering current research on the anapole phenomenon, we envision EELS in STEM to become a useful tool for accessing optical anapoles appearing in a variety of dielectric nanoresonators.

The tandem isomerization-hydrosilylation reaction is a highly valuable process able to transform mixtures of internal olefins into linear silanes. Unsaturated and cationic hydrido-silyl-Rh(iii) complexes have proven to be effective catalysts for this reaction. Herein, three silicon-based bidentate ligands, 8-(dimethylsilyl)quinoline (L1), 8-(dimethylsilyl)-2-methylquinoline (L2) and 4-(dimethylsilyl)-9-phenylacridine (L3), have been used to synthesize three neutral [RhCl(H)(L)PPh] (1-L1, 1-L2 and 1-L3) and three cationic [Rh(H)(L)(PPh)][BAr] (2-L1, 2-L2 and 2-L3) Rh(iii) complexes. Among the neutral compounds, 1-L2 could be characterized in the solid state by X-ray diffraction showing a distorted trigonal bipyramidal structure. Neutral complexes (1-L1, 1-L2 and 1-L3) failed to catalyze the hydrosilylation of olefins. On the other hand, the cationic compound 2-L2 was also characterized by X-ray diffraction showing a square pyramidal structure. The unsaturated and cationic Rh(iii) complexes 2-L1, 2-L2 and 2-L3 showed significant catalytic activity in the hydrosilylation of remote alkenes, with the most sterically hindered (2-L2) being the most active one.

Superionic and electride behaviors in materials, which induce a variety of exotic physical properties of ions and electrons, are of great importance both in fundamental research and for practical applications. However, their coexistence in hot alkali-metal borides has not been observed. In this work, we apply first-principles structure search calculations to identify eight Na–B compounds with host–guest structures, which exhibit a wide range of building blocks and interesting properties linked to the Na/B composition. Among the known borides, Na-rich Na9B stands out as the composition with the highest alkali-metal content, featuring vertex- and face-sharing BNa16 polyhedra. Notably, it exhibits electride characteristics and transforms into a superionic electride at 200 GPa and 2000 K, displaying unusual Na atomic diffusion behavior attributed to the modulation of the interstitial anion electrons. It demonstrates semiconductor behavior in the solid state, and metallic properties associated with Na 3p/3s states in the superionic and liquid regions. On the other hand, B-rich NaB7, consisting of a unique covalent B framework, is predicted to exhibit low-frequency phonon-mediated superconductivity with a Tc of 16.8 K at 55 GPa. Our work advances the understanding of the structures and properties of alkali-metal borides.

Motivated by recent discoveries of superconductivity in lightly doped multilayer graphene systems, we present a low-energy model to study superconductivity in two-dimensional materials whose Fermi surface consists of two valleys at ±K points. We assume a triplet odd-valley superconducting order with a pair potential that is isotropic in each valley but has a different sign in the two different valleys. Our theory predicts the emergence of an almost flat band of edge states centered at zero energy for certain edge orientations. As a result, a prominent experimental signature of this type of superconductivity is the presence of a large zero-energy peak in the local density of states near specific edges. The results of the effective low-energy theory are confirmed by numerically analyzing a specific microscopic tight-binding realization of odd-valley superconductivity: f-wave superconductivity on a honeycomb lattice in a ribbon geometry. Our work provides a test for odd-valley superconductivity through edge spectroscopy.

Located at crystal voids, interstitial anion electrons (IAEs) have diverse topologies, which may be tuned to achieve different properties. Elucidating the role of IAEs in electron-phonon coupling (EPC), and using it to design electride superconductors, leads to the current prediction of superconducting Li8Au at high pressure. We suggest that the occurence of high-temperature superconductivity in electrides requires high-symmetry structures with hydrogenlike cages, an electron acceptor element to balance charges, and isolated IAEs coupled with medium-frequency vibrations. The uniquely designed Li8Au electride has a NaCl-type (B1) lattice, with atomic Au and cubic Li8 cages as bases. Isolated IAEs are formed at the cage centers, with extra charges taken up by Au. These octahedrally coordinated IAEs have a p-orbital-like attribute and are strongly coupled with atomic vibrations in the Li8 cages. The strong EPC in Li8Au results in a calculated Tc of 73.1 K at 250 GPa, which is the highest Tc reported to date for all the electrides. A slight substitutional Pt doping can enhance the Tc of Li8Au to exceed liquid nitrogen temperature.

The role played by electronic and phononic excitations in the femtosecond laser induced desorption and oxidation of CO coadsorbed with O on Ru(0001) is investigated using ab initio molecular dynamics with electronic friction. To this aim, simulations that account for both kind of excitations and that only consider electronic excitations are performed. Results for three different surface coverages are obtained. We unequivocally demonstrate that CO desorption is governed by phononic excitations. In the case of oxidation the low statistics does not allow to give a categorical answer. However, the analysis of the adsorbates kinetic energy gain and displacements strongly suggest that phononic excitations and surface distortion also play an important role in the oxidation process.

Molecular doping provides a route toward designing new organic compounds with improved performance for optoelectronics. Here, we investigate the p-type doping of crystalline diindenoperylene (DIP) with two recently proposed electron-accepting molecular dopants using many-body perturbation theory. For the pristine DIP crystal, the quasiparticle band structure and the optical absorption spectra are found in agreement with the experimental data. Using the same methodology, we then characterize the optical and electronic properties of the two doped DIP crystals. The bandgap of both doped crystals is narrowed considerably due to the formation of hybridized states at the valence band edge. Moreover, a hybrid unoccupied mid-gap band is created with a host–dopant charge-transfer characteristic, giving rise to broader absorption spectra and a much lower absorption onset as compared to pristine DIP. Our results highlight that the interaction and hybridization with the host environment, including many-body effects, must be carefully considered in order to identify appropriate molecular dopants for a given organic crystal.

Interferometry is a powerful technique used to extract valuable information about the wave function of a system. In this work, we study the response of spin carriers to the effective field textures developed in curved one-dimensional interferometric circuits subject to the joint action of Rashba and Dresselhaus spin-orbit interactions. By using a quantum network technique, we establish that the interplay between these two non-Abelian fields and the circuit’s geometry modify the geometrical characteristics of the spinors, particularly on square circuits, leading to the localisation of the electronic wave function and the suppression of the quantum conductance. We propose a topological interpretation by classifying the corresponding spin textures in terms of winding numbers.

Tantalum (Ta) is an interesting transition metal that exhibits superconductivity in its elemental states. Additionally, several Ta chalcogenides (S and Se) have also demonstrated superconducting properties. In this work, we propose the existence of five high-pressure metallic Ta–O compounds (e.g., TaO3, TaO2, TaO, Ta2O, and Ta3O), composed of polyhedra centered on Ta/O atoms. These compounds exhibit distinct characteristics compared to the well-known semiconducting Ta2O5. One particularly interesting finding is that TaO3 shows an estimated superconducting transition temperature (Tc) of 3.87 K at 200 GPa. This superconductivity is primarily driven by the coupling between the low-frequency phonons derived from Ta and the O 2p and Ta 5d electrons. Remarkably, its dynamically stabilized pressure can be as low as 50 GPa, resulting in an enhanced electron–phonon coupling and a higher Tc of up to 9.02 K. When compared to the superconductivity of isomorphic TaX3 (X = O, S, and Se) compounds, the highest Tc in TaO3 is associated with the highest NEF and phonon vibrational frequency. These characteristics arise from the strong electronegativity and small atomic mass of the O atom. Consequently, our findings offer valuable insights into the intrinsic physical mechanisms of high-pressure behaviors in Ta–O compounds.

Interstitial anionic electrons (IAEs) at lattice cavities of electrides, which have diverse morphologies and concentrations, can induce interesting physical and chemical properties. Understanding the correlation between IAEs and electron-phonon coupling is crucial for the development of new electride superconductors. We have applied first-principles structural search calculations to predict new high-pressure Li-As electrides, such as P6/mmm LixAs (x=5 and 8), Li6As with Cmc21 and C2/c symmetries, and C2/mLi10X (X=As and Sb), which together with the already known C2/mLi10Te compound present favorable characteristics (i.e., variable donor content, structural symmetries, and acceptor species) to explore IAE-related superconductivity. According to our results, the predicted superconducting temperatures of these electrides are positively correlated with the number and connectivity of IAEs.

Copper-based hydrogen evolution electrocatalysts are promising materials to scale-up hydrogen production due to their reported high current densities; however, electrode durability remains a challenge. Here, we report a facile, cost-effective, and scalable synthetic route to produce Cu2-xS electrocatalysts, exhibiting hydrogen evolution rates that increase for ∼1 month of operation. Our Cu2-xS electrodes reach a state-of-the-art performance of ∼400 mA cm-2 at -1 V vs RHE under mild conditions (pH 8.6), with almost 100% Faradaic efficiency for hydrogen evolution. The rise in current density was found to scale with the electrode electrochemically active surface area. The increased performance of our Cu2-xS electrodes correlates with a decrease in the Tafel slope, while analyses by X-ray photoemission spectroscopy, operando X-ray diffraction, and in situ spectroelectrochemistry cooperatively revealed the Cu-centered nature of the catalytically active species. These results allowed us to increase fundamental understanding of heterogeneous electrocatalyst transformation and consequent structure-activity relationship. This facile synthesis of highly durable and efficient Cu2-xS electrocatalysts enables the development of competitive electrodes for hydrogen evolution under mild pH conditions.

Helium, the second most abundant element in the universe, exhibits an extremely large electronic band gap of about 20 eV at ambient pressures. While the metallization pressure of helium has been accurately determined, thus far little attention has been paid to the specific mechanisms driving the band-gap closure and electronic properties of this quantum crystal in the terapascal regime (1 TPa = 10 Mbar). Here, we employ density functional theory and many-body perturbation calculations to fill up this knowledge gap. It is found that prior to reaching metallicity helium becomes an excitonic insulator (EI), an exotic state of matter in which electrostatically bound electron-hole pairs may form spontaneously. Furthermore, we predict metallic helium to be a superconductor with a critical temperature of ≈ 20 K just above its metallization pressure and of ≈ 70 K at 100 TPa. These unforeseen phenomena may be critical for improving our fundamental understanding and modeling of celestial bodies.

Femtosecond laser-induced dynamics of molecules on metal surfaces can be seamlessly simulated with all nuclear degrees of freedom using ab initio molecular dynamics with electronic friction (AIMDEF) and stochastic forces, which are a function of a time-dependent electronic temperature. This has recently been demonstrated for hot-electron-mediated desorption of hydrogen molecules from a Ru(0001) surface covered with H and D atoms [Juaristi, J. I. Phys. Rev. B 2017, 95, 125439]. Unfortunately, AIMDEF simulations come with a very large computational expense that severely limits statistics and propagation times. To keep ab initio accuracy and allow for better statistical sampling, we have developed a neural network interatomic potential of hydrogen on the Ru(0001) surface based on data from ab initio molecular dynamics simulations of recombinative desorption. Using this potential, we simulated femtosecond laser-induced recombinative desorption using varying unit cells, coverages, laser fluences, and isotope ratios with reliable statistics. As a result, we can systematically study a wide range of these parameters and follow dynamics over longer times than hitherto possible, demonstrating that our methodology is a promising way to realistically simulate femtosecond laser-induced dynamics of molecules on metals. Moreover, we show that previously used cell sizes and propagation times were too small to obtain converged results.

Ever since hydrogen-based superconductors have been actively considered as candidates for room-temperature superconductors, binary hydrides have been almost completely explored theoretically. Now researchers are turning their interest to ternary hydrides. However, the enormous compositional and structural possibilities in the ternary hydride space limit the search efficiency. Here, using an advanced crystal structure search method combined with first-principles calculations, a series of ternary hydrides AXH6 (MgPH6, MgAsH6, CaSbH6, CaSnH6, NaSbH6 and ScSiH6) with the A15-type structure are predicted to be stable at around one million atmospheres. Among them, CaSnH6 presents the lowest thermodynamically stable pressure of 110 GPa. CaSbH6, CaSnH6 and ScSiH6 may be dynamically stable down to 41 (70), 71 (90) and 86 (70) GPa, respectively, without (with) anharmonic effects and temperature effects. Hydrogen atoms in these A15-type structures are found to form weak covalent bonds to X atoms. More interestingly, we find that ternary hydrides with the AXH6 stoichiometry may assume the A15-type structure under pressure when the sum of the chemical valences of the two non-hydrogen atoms is six or seven. Based on electron-phonon coupling (EPC) calculations, all these ternary hydrides are estimated to be superconductors. CaSbH6, CaSnH6 and ScSiH6 have superconducting transition temperatures (Tcs) of 65, 53 and 116 K at 45, 75 and 90 GPa, respectively, while MgPH6 has the highest Tc of 148 K at 135 GPa. Our study will provide guidance for designing high Tc ternary hydrides near ambient pressures.

We study theoretically electron interference in a Mach–Zehnder-like geometry formed by four zigzag graphene nanoribbons arranged in parallel pairs, one on top of the other, such that they form intersection angles of 60∘. Depending on the interribbon separation, each intersection can be tuned to act either as an electron beam splitter or as a mirror, enabling tuneable circuitry with interfering pathways. Based on the mean-field Hubbard model and Green's function techniques, we evaluate the electron transport properties of such eight-terminal devices and identify pairs of terminals that are subject to self-interference. We further show that the scattering matrix formalism in the approximation of independent scattering at the four individual junctions provides accurate results as compared with the Green's function description, allowing for a simple interpretation of the interference process between two dominant pathways. This enables us to characterize the device sensitivity to phase shifts from an external magnetic flux according to the Aharonov–Bohm effect as well as from small geometric variations in the two path lengths. The proposed devices could find applications as magnetic field sensors and as detectors of phase shifts induced by local scatterers on the different segments, such as adsorbates, impurities or defects. The setup could also be used to create and study quantum entanglement.

We extend the Mattis-Bardeen theory for the dynamical response of superconductors to include different types of Hall responses. This is possible thanks to a recent modification of the quasiclassical Usadel equation, which allows for analyzing Hall effects in disordered superconductors and including the precise frequency dependence of such effects. Our results form a basis for analyzing dynamical experiments especially on novel thin-film superconductors, where ordinary Hall and spin Hall effects can both show up.

The search for intrinsic half-metallic ferromagnetic (FM) monolayers with a high Curie temperature (TC), considerable magnetic anisotropy energy (MAE), and multiferroic coupling is key for the development of ultra-compact spintronics. Here, we have identified a new stable FM Janus monolayer, the tetrahedral CrSSe, through first-principles structural search calculations, which not only exhibits very interesting magnetoelectric properties with a high TC of 790 K, a large MAE of 0.622 meV per Cr, and robust half-metallicity, but also shows obvious ferroelasticity with a modest energy barrier of 0.31 eV per atom. Additionally, there appears to be interesting multiferroic coupling between in-plane magnetization and ferroelasticity. Furthermore, by replacing the Se/S atoms in the CrSSe monolayer with S/Se atoms, we obtained two new half-metallic FM CrS2 and CrSe2 monolayers, which also exhibit excellent magnetoelectric properties. Therefore, our findings provide a pathway to design novel multiferroic materials and enrich the understanding of 2D transition metal chalcogenides.