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The bottom-up synthesis of carbon-based nanomaterials directly on semiconductor surfaces allows for the decoupling of their electronic and magnetic properties from the substrates. However, the typically reduced reactivity of such nonmetallic surfaces adversely affects the course of these reactions. Here, we achieve a high polymerization yield of halogenated polyphenyl molecular building blocks on the semiconducting TiO2(110) surface via concomitant surface decoration with cobalt atoms, which catalyze the Ullmann coupling reaction. Specifically, cobalt atoms trigger the debromination of 4,4″-dibromo-p-terphenyl molecules on TiO2(110) and mediate the formation of an intermediate organometallic phase already at room temperature (RT). As the debromination temperature is drastically reduced, homocoupling and polymerization readily proceed, preventing presursor desorption from the substrate and entailing a drastic increase of the poly-para-phenylene polymerization yield. The general efficacy of this mechanism is shown with an iodinated terphenyl derivative, which exhibits similar dehalogenation and reaction yield.

Ferromagnetism is the collective alignment of atomic spins that retain a net magnetic moment below the Curie temperature, even in the absence of external magnetic fields. Reducing this fundamental property into strictly two-dimensions was proposed in metal-organic coordination networks, but thus far has eluded experimental realization. In this work, we demonstrate that extended, cooperative ferromagnetism is feasible in an atomically thin two-dimensional metal-organic coordination network, despite only ≈ 5% of the monolayer being composed of Fe atoms. The resulting ferromagnetic state exhibits an out-of-plane easy-axis square-like hysteresis loop with large coercive fields over 2 Tesla, significant magnetic anisotropy, and persists up to TC ≈ 35 K. These properties are driven by exchange interactions mainly mediated by the molecular linkers. Our findings resolve a two decade search for ferromagnetism in two-dimensional metal-organic coordination networks.

Atxurra Cave (Berriatua, Northern Spain) contains an important Magdalenian archaeological assemblage comprising evidence of ephemeral occupation in the lower cave level and a unique assemblage of rock art. With the aim of understanding the palaeoenvironmental conditions and the nature of the human occupation, detailed micromorphological, mineralogical, palynological and anthracological analyses were undertaken near the entrance of the cave. The lower part of the excavated sequence comprises almost unfossiliferous silty units deposited over a thick speleothem deposit, which alternates with a sandy-silt matrix-supported microfacies dated about 33.4 kyr B.P. Palynological assemblage in this unit suggest regional vegetation was formed by montane pines, junipers and broadleaved elements like birch and hazel. Overlying units of brown clayey material, dated to ca. 19.7–18.4 kyr B.P., contain evidence of a Gravettian occupation with Noailles burins, and a palynoflora indicative of localized conifers with a dense herbaceous steppe understory, in an arid and cold climate. At ca. 15.5–14.5 kyr B.P. there is a return to meso-thermophilous tree and shrub taxa within a warmer and humid climate background, which may have favored the regional development of the Magdalenian culture. The uppermost unit, dated ca. 7.7–7 kyr B.P., reveals postglacial expansion of a mixed Atlantic forest with no signals of anthropization before the start of the Neolithic.

[Context] Global change is leading to more frequent and intense tree damage and mortality events. Drought-induced tree mortality is occurring worldwide leading to broad-scale events, but the spatial patterns of tree damage and mortality, their underlying drivers and their variation over time is largely unknown., [Objectives] We investigated the spatial patterns of tree damage and mortality across Mediterranean forests of the Iberian Peninsula, the underlying effects of stand structure and climate, and how the spatial patterns and relationships with underlying drivers changed over time., [Methods] We used the Spanish Forest Inventory to analyse the autocorrelation in tree damage and mortality across forest types, hurdle-gamma models to quantify the effect of stand structure and climate on tree damage and mortality, and cross-correlograms to assess their spatial dependence and its change over time., [Results] We observed a greater magnitude and a stronger autocorrelation in tree damage than mortality, with positive aggregation up to 20 kms. There was a spatial dependence between tree damage and mortality with their drivers, with spatial aggregation increasing with water availability, drought intensity and stand structure. The spatial dependence of tree damage and mortality with the underlying drivers increased over time, particularly for drought intensity., [Conclusions] Our results suggest that the combined effect of intense competition and drought could favour more extensive die-off and tree mortality events, providing key information for identifying vulnerable areas and the planning of adaptation measures.

This work explores the biological evaluation of novel cyanomethyl vinyl ether derivatives as antiproliferative agents. Tubulin, crucial to microtubule structure and function, is a target for cancer therapies. In vitro cytotoxicity assessments revealed significant activity in SKOV3 ovarian carcinoma cells and A549 lung carcinoma cells. Structure-Activity Relationship (SAR) analysis indicated that the E isomer and specific substitutions influenced the biological activity. Computational assays predicted favorable ADME properties, highlighting potential as anticancerous agents. Molecular docking studies demonstrated that compound 12E, with the E geometry of the double bond and fused polyaromatic rings such as phenanthrene, has robust interaction with tubulin, suggesting enhanced stability due to diverse amino acid interactions. Comparative spatial distributions with colchicine further indicated potential mechanistic similarities.

Superconductivity in the new polymerized C60 fullerite clathrate doped with simple metals is investigated through density functional theory methods. The phonon dispersion curves are systematically computed for the clathrate structures containing the guest dopants (Li, Na, K, Be, Mg, Ca, Al, Ga, Ge) in one of the two distinct cages, fullerene-like C60 and sodalite-like C24, exhibited by this structure. Only four of these structures, Li@C24, Na@C24, Ga@C24, and Be@C60, are dynamically stable in the harmonic approximation. They all show superconducting behavior, although their critical temperatures are predicted to be below 2 K.

The development of self-assembled dyes able to display J-aggregation-induced emission has gained a renewed interest as an appealing and distinctive approach for the design of smart photoactive materials. F-BODIPY dyes have been exploited to this aim since J-type supramolecular organization has been effectively photoinduced under specific surrounding conditions (hydrophilic or constrained media) although, up to date, it has never been observed in pure organic media. Herein, we report the first systematic study of the self-assembly properties of F-BODIPYs in pure organic solvents and analyze in depth the control exerted by the substitution pattern of its carbon skeleton into the formation of emissive J-aggregates. Spontaneous J-aggregation in F-BODIPYs is evidenced by their lasing properties and supported by the analysis of their solid-state photophysics and X-ray crystalline packing as well as by molecular dynamics in solvent cages. These studies point out the key role of the stereoelectronic properties of the substituents orthogonally grafted at the dipyrrin core (meso and C-2 and C-6 positions) as the main driving force to control the molecular stacking arrangement of F-BODIPYs in common organic solvents. The understanding of the interplay between the molecular structure and the properties of the resulting aggregates sheds light on the workability of BODIPY-based self-assembly as a tool for advanced luminescent materials.

[ES] The intensification of agriculture is impacting farmland and is recognised as a main driver for biodiversity loss in these environments. Many farmland bird populations have been declining in recent decades because of agricultural intensification. This is the case of the Red-legged Partridge Alectoris rufa, a game bird that inhabits farming landscapes and has recently suffered drastic population declines in Spain. To fully understand the effects that agricultural intensification has on these birds, it is crucial to deepen the knowledge regarding their feeding habits and how these may vary seasonally. The aim of this study was to provide a detailed and reliable description of wild partridges’ plant diet composition. For this purpose, we collected faecal samples from 35 partridge flocks during autumn, winter and spring, and used DNA metabarcoding to identify plants consumed by this species. We used nuclear and chloroplastic barcodes for the amplification of ITS2 and rbcL gene regions, respectively. Our results showed that the diet of partridges was highly diverse, mainly consisting of cereals, weeds and legumes. The most frequently consumed genus was Hordeum, followed by Lolium, Papaver, Medicago and Avena. We further showed that diet composition varied significantly amongst seasons, with a higher proportion of cultivated plants (> 25%) being consumed during autumn and winter. During the cereal sowing period, cropped plants might be consumed as sown seeds, which are often coated with pesticides and could represent an important risk. In spring, before breeding, the diet was mostly composed of weeds. Plants of the Papaver genus could be consumed for anti-parasitic purposes, and as a source of antioxidants and carotenoids to increase ornamental coloration, especially during pairing and laying. Our results highlight the importance of maintaining heterogenous farming landscapes with fallow lands and field margins as sources of weeds to help the conservation of this spe, [DE] Die Intensivierung der Landwirtschaft hat Auswirkungen auf die landwirtschaftlich genutzten Flächen und gilt als Hauptursache für den Rückgang der biologischen Vielfalt in diesen Lebensräumen. Viele Vogelpopulationen in ländlichen Gegenden sind in den letzten Jahrzehnten aufgrund der Intensivierung der Landwirtschaft geschrumpft. Das trifft für das Rothuhn Alectoris rufa, zu, einem Wildvogel, der in Agrarlandschaften lebt und in letzter Zeit in Spanien einen drastischen Bestandsrückgang erlebt hat. Um die Auswirkungen der Intensivierung der Landwirtschaft auf diese Vögel vollständig zu verstehen, ist es entscheidend wichtig, mehr über ihre Ernährungsgewohnheiten und ihre jahreszeitlichen Schwankungen herauszufinden. Ziel dieser Studie war die Erstellung einer detaillierten und belastbaren Beschreibung der pflanzlichen Nahrungszusammensetzung von Rothühnern. Hierfür sammelten wir im Herbst, Winter und Frühjahr Kotproben von 35 Rothuhngruppen und identifizierten mit Hilfe von DNA-Metabarcoding die von ihnen gefressenen Pflanzen. Für die Amplifizierung der ITS2- bzw. rbcL-Genregionen setzten wir Barcodes von Zellkernen und Chloroplasten ein. Unsere Ergebnisse zeigen, dass die Ernährung der Rothühner sehr vielfältig ist und hauptsächlich aus Getreide, Unkräutern und Hülsenfrüchten besteht. Die am häufigsten gefressene Gattung war Hordeum, gefolgt von Lolium, Papaver, Medicago und Avena. Wir konnten außerdem zeigen, dass die Zusammensetzung der Nahrung je nach Jahreszeit erheblich variiert, wobei im Herbst und Winter ein höherer Anteil an Kulturpflanzen (> 25%) verzehrt wird. Während der Getreideaussaat wurden die geernteten Pflanzen vermutlich als Saatgut verzehrt, das wegen seiner häufigen Pestizid-Belastung ein erhebliches Risiko darstellen könnte. Im Frühjahr, vor der Paarung, bestand die Nahrung hauptsächlich aus Kräutern. Pflanzen der Gattung Papaver werden möglicherweise zur Bekämpfung von Parasiten und als Quelle von Antioxidantien und Carotinoiden für die S

Despite the increasing availability of genomic data and enhanced data analysis procedures, predicting the severity of associated diseases remains elusive in the absence of clinical descriptors. To address this challenge, we have focused on the KV7.2 voltage-gated potassium channel gene (KCNQ2), known for its link to developmental delays and various epilepsies, including self-limited benign familial neonatal epilepsy and epileptic encephalopathy. Genome-wide tools often exhibit a tendency to overestimate deleterious mutations, frequently overlooking tolerated variants, and lack the capacity to discriminate variant severity. This study introduces a novel approach by evaluating multiple machine learning (ML) protocols and descriptors. The combination of genomic information with a novel Variant Frequency Index (VFI) builds a robust foundation for constructing reliable gene-specific ML models. The ensemble model, MLe-KCNQ2, formed through logistic regression, support vector machine, random forest and gradient boosting algorithms, achieves specificity and sensitivity values surpassing 0.95 (AUC-ROC > 0.98). The ensemble MLe-KCNQ2 model also categorizes pathogenic mutations as benign or severe, with an area under the receiver operating characteristic curve (AUC-ROC) above 0.67. This study not only presents a transferable methodology for accurately classifying KCNQ2 missense variants, but also provides valuable insights for clinical counseling and aids in the determination of variant severity. The research context emphasizes the necessity of precise variant classification, especially for genes like KCNQ2, contributing to the broader understanding of gene-specific challenges in the field of genomic research. The MLe-KCNQ2 model stands as a promising tool for enhancing clinical decision making and prognosis in the realm of KCNQ2-related pathologies.

Marine sediments impacted by urban and industrial pollutants are typically exposed to reducing conditions and represent major reservoirs of toxic mercury species. Mercury methylation mediated by anaerobic microorganisms is favored under such conditions, yet little is known about potential microbial mechanisms for mercury detoxification. We used culture-independent (metagenomics, metabarcoding) and culture-dependent approaches in anoxic marine sediments to identify microbial indicators of mercury pollution and analyze the distribution of genes involved in mercury reduction (merA) and demethylation (merB). While none of the isolates featured merB genes, 52 isolates, predominantly affiliated with Gammaproteobacteria, were merA positive. In contrast, merA genes detected in metagenomes were assigned to different phyla, including Desulfobacterota, Actinomycetota, Gemmatimonadota, Nitrospirota, and Pseudomonadota. This indicates a widespread capacity for mercury reduction in anoxic sediment microbiomes. Notably, merA genes were predominately identified in Desulfobacterota, a phylum previously associated only with mercury methylation. Marker genes involved in the latter process (hgcAB) were also mainly assigned to Desulfobacterota, implying a potential central and multifaceted role of this phylum in the mercury cycle. Network analysis revealed that Desulfobacterota were associated with anaerobic fermenters, methanogens and sulfur-oxidizers, indicating potential interactions between key players of the carbon, sulfur and mercury cycling in anoxic marine sediments

This study describes both experimentally and theoretically an important hitherto undiscovered feature of the scattering of micron-sized spherical objects when illuminated with highly focused circularly polarized light. This is a regime of high experimental relevance which has not been described in full detail. The experiments are complemented with the analytical formulas explaining the field scattered directed toward the backward hemispace. In particular, it is proven that this field shows a very regular oscillatory dependency with the optical size. This phenomenon is typically hidden in the total scattered field, as the field is scattered much less toward the backward hemisphere than toward the forward one. These regular oscillations are measured experimentally. It is proven that, by analyzing them, it is possible to determine the index of refraction of isolated micron-sized particles, opening new paths for applications in sensing and metrology.

In diverse fields, machine learning (ML) has sparked transformative changes, primarily driven by the wealth of big data. However, an alternative approach seeks to mine insights from “precious data”, offering the possibility to reveal missed knowledge and escape potential knowledge traps. In this context, Bayesian optimization (BO) protocols have emerged as crucial tools for optimizing the synthesis and discovery of a broad spectrum of compounds including nanoparticles. In our work, we aimed to go beyond the commonly explored experimental conditions and showcase a workflow capable of unearthing fresh insights, even in well-studied research domains. The growth of AuNRs is a nonequilibrium process that remains poorly understood despite the presence of well-established seeded growth protocols. Traditional research aimed at understanding the mechanism of AuNR growth has primarily relied on altering one reaction condition at a time. While these studies are undeniably valuable, they often fail to capture the synergies between different reaction conditions, thus constraining the depth of insights they can offer. In the present study, we exploit BO, to identify diverse experimental conditions yielding AuNRs with similar spectroscopic characteristics. Notably, we identify viable and accelerated synthesis conditions involving elevated temperatures (36–40 °C) as well as high ascorbic acid concentrations. More importantly, we note that ascorbic acid and temperature can modulate each other’s undesirable influences on the growth of AuNRs. Finally, by harnessing the power of interpretable ML algorithms, complemented by our deep chemical understanding, we revisited the established hierarchical relationships among reaction conditions that impact the El-Sayed-based growth of AuNRs.

Coastal circulation influences the distribution of European anchovy (Engraulis encrasicolus) at early life stages (ELS) in the Bay of Biscay (BoB). However, how this happens is not yet fully understood. In this work, further insight is provided by performing Lagrangian diagnostics based on observations of ELS anchovies' initial distributions and currents. Surface diagnostics were obtained by using high-frequency radar (HFR) currents and were applied to analyse multiyear variability and detect the coastal processes that affect the distribution. Since ELS anchovies are also located at subsurface levels, subsurface diagnostics were obtained by using currents reconstructed from HFR and ADCP observations with a reduced order optimal interpolation (ROOI) method. The analyses included transport computations as well as the analysis of flow properties by Lagrangian Coherent Structures and chlorophyll-a satellite images. Results suggest that ELS anchovies are mostly retained over the shelf and slope, and that transport patterns highly vary across different periods. Mesoscale structures such as eddies, fronts and along-slope currents within the slope and the Capbreton canyon area, as well as strong and persistent winds, could significantly impact the distribution of ELS anchovies. In some periods, the resulting distribution might be due to a combination of these processes. Circulation can also play a key role in ELS anchovy aggregation within short time scales (20 days). This work showcases the potential of observation-based approaches and emphasizes the relevance of coastal observatories for integrated studies.

Gluten consumption causes several immunological and non-immunological intolerances in susceptible individuals. In this study, the dextran-producing Weissella cibaria BAL3C-5 and its derivative, the riboflavin-overproducing strain BAL3C-5 C120T, together with a commercial bakery yeast, were used to ferment gluten-free (GF)-doughs obtained from corn and rice flours at two different concentrations and supplemented with either quinoa, buckwheat, or chickpea to obtain laboratory-scale GF bread. The levels of dextran, riboflavin, and total flavins were determined in the fermented and breads. Both strains grew in fermented doughs and contributed dextran, especially to those made with corn plus quinoa (~1 g/100 g). The highest riboflavin (350–150 µg/100 g) and total flavin (2.3–1.75 mg/100 g) levels were observed with BAL3C-5 C120T, though some differences were detected between the various doughs or breads, suggesting an impact of the type of flour used. The safety assessment confirmed the lack of pathogenic factors in the bacterial strains, such as hemolysin and gelatinase activity, as well as the genetic determinants for biogenic amine production. Some intrinsic resistance to antibiotics, including vancomycin and kanamycin, was found. These results indicated the microbiological safety of both W. cibaria strains and indicated their potential application in baking to produce GF bread.

Nonenveloped virus-like particles (VLPs) are self-assembled oligomeric structures composed of one or more proteins that originate from diverse viruses. Because these VLPs have similar antigenicity to the parental virus, they are successfully used as vaccines against cognate virus infection. Furthermore, after foreign antigenic sequences are inserted in their protein components (chimVLPs), some VLPs are also amenable to producing vaccines against pathogens other than the virus it originates from (these VLPs are named platform or epitope carrier). Designing chimVLP vaccines is challenging because the immunogenic response must be oriented against a given antigen without altering stimulant properties inherent to the VLP. An important step in this process is choosing the location of the sequence modifications because this must be performed without compromising the assembly and stability of the original VLP. Currently, many immunogenic data and computational tools can help guide the design of chimVLPs, thus reducing experimental costs and work. In this study, we analyze the structure of a novel VLP that originate from an insect virus and describe the putative regions of its three structural proteins amenable to insertion. For this purpose, we employed molecular dynamics (MD) simulations to assess chimVLP stability by comparing mutated and wild-type (WT) VLP protein trajectories. We applied this procedure to design a chimVLP that can serve as a prophylactic vaccine against the SARS-CoV-2 virus. The methodology described in this work is generally applicable for VLP-based vaccine development.

Metal–air batteries are an emerging technology with great potential to satisfy the demand for energy in high-consumption applications. However, this technology is still in an early stage, facing significant challenges such as a low cycle life that currently limits its practical use. Poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer has already demonstrated its efficiency as catalyst for oxygen reduction reaction (ORR) discharge as an alternative to traditional expensive and nonsustainable metal catalysts. Apart from that, in most electrochemical processes, three phenomena are needed: redox activity and electronic and ionic conduction. Material morphology is important to maximize the contact area and optimize the 3 mechanisms to obtain high-performance devices. In this work, porous scaffolds of PEDOT–organic ionic plastic crystal (OIPC) are prepared through vapor phase polymerization to be used as porous self-standing cathodes. The scaffolds, based on abundant elements, showed good thermal stability (200 °C), with potential ORR reversible electrocatalytic activity: 60% of Coulombic efficiency in aqueous medium after 200 cycles.

Over the last two decades, a significant body of research has been developed trying to understand the association and properties of mixtures formed by oppositely charged polyelectrolytes and surfactants. Particular emphasis has been given to their interfacial properties and the intriguing formation of nonequilibrium states. The synergy between these components at interfaces has attracted considerable attention due to its relevance in various industrial and biological applications. The combination of oppositely charged entities leads to complex interactions that influence the stability and behavior of interfaces. This review critically examines recent advances toward understanding the interfacial behavior when polyelectrolytes and surfactants coexist. Emphasis is placed on the existence of nonequilibrium states, shedding light on transient phenomena and kinetic aspects that play a crucial role in the overall system behavior. This will provide insights into the mechanisms governing the interfacial phenomena in these mixed systems. In summary, this review will contribute to the fundamental understanding of colloidal and interfacial science, offering a valuable perspective on designing and optimizing materials with tailored properties.

The report of near-ambient superconductivity in nitrogen-doped lutetium hydrides (Lu-N-H) has generated a great interest. However, conflicting results raised doubts regarding superconductivity. Here, we combine high-throughput crystal structure predictions with a fast predictor of superconducting critical temperature (Tc) based on electron localization function to shed light on the properties of Lu-N-H at 1 GPa. None of the predicted structures supports high-temperature superconductivity and the inclusion of nitrogen in the crystal structure predictions leads to more insulating structures than metallic ones in quantity. Despite the lack of near-ambient superconductivity, we consider alternative metastable templates and study their Tc and dynamical stability including quantum anharmonic effects. Lu4H11N exhibits a Tc of 100 K at only 20 GPa, a large increase compared to 30 K of its parent LuH3. Interestingly, it has a similar X-ray pattern to the experimental one. The LaH10-like LuH10 and CaH6-like LuH6 become high-temperature superconductors at 175 GPa and 100 GPa, with Tc of 286 K and 246 K, respectively. Our findings suggest that high-temperature superconductivity is not possible in stable phases at near-ambient pressure. However, at a slightly enhanced pressure of 20 GPa, high-Tc superconductivity emerges in Lu-H-N, and metastable room-temperature superconducting templates persist at high pressures.

Deformable colloids and macromolecules adsorb at interfaces as they decrease the interfacial energy between the two media. The deformability, or softness, of these particles plays a pivotal role in the properties of the interface. In this study, we employ a comprehensive in situ approach, combining neutron reflectometry with molecular dynamics simulations, to thoroughly examine the profound influence of softness on the structure of microgel Langmuir monolayers under compression. Lateral compression of both hard and soft microgel particle monolayers induces substantial structural alterations, leading to an amplified protrusion of the microgels into the aqueous phase. However, a critical distinction emerges: hard microgels are pushed away from the interface, in stark contrast to the soft ones, which remain firmly anchored to it. Concurrently, on the air-exposed side of the monolayer, lateral compression induces a flattening of the surface of the hard monolayer. This phenomenon is not observed for the soft particles as the monolayer is already extremely flat even in the absence of compression. These findings significantly advance our understanding of the key role of softness on both the equilibrium phase behavior of the monolayer and its effect when soft colloids are used as stabilizers of responsive interfaces and emulsions.

We present a theory of weak localization (WL) in the presence of generic spin-dependent fields, including any type of spin-orbit coupling, Zeeman fields, and nonhomogeneous magnetic textures. We go beyond the usual diffusive approximation, considering systems with short-range disorder of arbitrary strength and obtain a compact expression for the weak localization (WL) correction to the conductivity in terms of the singlet-triplet polarization operator in momentum space. The latter can be directly related to the solution of the quasiclassical Eilenberger equation for superconducting systems. This formulation presents an intuitive framework to explore how the interplay of various spin-dependent fields drives weak (anti) localization. We apply our results to study in-plane magnetoconductivity in systems with spin-orbit coupling and in newly discovered altermagnets. Our results enable straightforward calculation of the WL conductivity at arbitrary disorder strength, which can be particularly useful for interpreting experiments on high-mobility samples.

Unraveling the nuanced interplay between the morphology and the optical properties of plasmonic nanoparticles is crucial for targeted applications. Managing the relationship becomes significantly complex when dealing with anisotropic nanoparticles that defy a simple description using parameters like length, width, or aspect ratio. This complexity requires computationally intensive numerical modeling and advanced imaging techniques. To address these challenges, we propose a detailed structural parameter determination of gold nanoparticles using their two-dimensional projections (e.g., micrographs). Employing gold bipyramids (AuBPs) as a model morphology, we can determine their three-dimensional geometry and extract optical features computationally for comparison with the experimental data. To validate our inversion model’s effectiveness, we apply it to derive the structural parameters of AuBPs undergoing shape modification through oxidative etching. In summary, our findings allow for the precise characterization of structural parameters for plasmonic nanoparticles during shape transitions, potentially enhancing the comprehension of nanocrystal growth and optimizing plasmonic material design for various applications.

A direct current through a metal-insulator-metal tunneling junction emits light when surface-plasmon polaritons (SPPs) are excited. Two distinct processes are believed to coexist in this light emission mediated by surface plasmons: inelastic tunneling, where electrons excite SPPs in the insulator gap, and hot-electron radiative decay, which occurs in the electrodes after elastic tunneling. Previous theoretical approaches to study light emission by inelastic tunneling have relied on Bardeen’s approximation where the electronic wave functions are considered only in the barrier of the junction. In this work, we introduce an extension to models of inelastic tunneling by incorporating the full quantum device solution of the Schrödinger equation, which can also account for processes in the metallic electrodes. The extension unveils the existence of long-range correlations of the current density across the barrier and enables us to establish the equivalence between two models widely used in the past: (i) a calculation of the inelastic transition rate between two states across the barrier based on Fermi’s golden rule and (ii) a calculation of the power transferred to plasmons by current fluctuations. Importantly, the new model accounts for processes that take place in the metallic electrodes and that could not be described within Bardeen’s approximation. Hence, it is no longer necessary to invoke a hot-electron mechanism to obtain a dependence on the geometry of metallic electrodes. The new framework enables to discuss the role of surface plasmons localized in different metal-insulator interfaces and to include possible nonlocal effects at the interfaces.

Understanding and mastering quantum electrodynamics phenomena is essential to the development of quantum nanophotonics applications. While tailoring of the local vacuum field has been widely used to tune the luminescence rate and directionality of a quantum emitter, its impact on their transition energies is barely investigated and exploited. Fluorescent defects in nanosized diamonds constitute an attractive nanophotonic platform to investigate the Lamb shift of an emitter embedded in a dielectric nanostructure with high refractive index. Using spectral and time-resolved optical spectroscopy of single SiV defects, we unveil blue shifts (up to 80 meV) of their emission lines, which are interpreted from model calculations as giant Lamb shifts. Moreover, evidence for a positive correlation between their fluorescence decay rates and emission line widths is observed, as a signature of modifications not only of the photonic local density of states but also of the phononic one, as the nanodiamond size is decreased. Correlative light–electron microscopy of single SiVs and their host nanodiamonds further supports these findings. These results make nanodiamond-SiVs promising as optically driven spin qubits and quantum light sources tunable through nanoscale tailoring of vacuum-field fluctuations.

We investigate the chemical interaction of carbon monoxide (CO) and oxygen (O2) with kink atoms on steps of platinum crystal surfaces using a specially designed Pt curved sample. We aim at describing the fundamental stages of the CO oxidation reaction, i.e., CO-covered/poisoned stage and O-covered/active stage, at the poorly known kinked Pt facets by probing CO uptake/saturation and O2 saturation, respectively. Based on the systematic analysis that the curved surface allows, and using high-resolution X-ray photoemission, a diversity of terrace and step/kink species are straightforwardly identified and accurately quantified, defining a smooth structural and chemical variation across different crystal planes. In the CO-saturated case, we observe a preferential adsorption at step edges, where the CO coverage reaches a CO molecule per step Pt atom, significantly higher than their close-packed analogous steps with straight terrace termination. For the O-saturated surface, a significantly higher O coverage is observed in kinked planes compared to the Pt(111) surface. While the strong adsorption of CO at the kinked edges points toward a higher ignition temperature of the CO oxidation at kinks as compared to terraces, the large O coverage at steps may lead to an increased reactivity of kinked surfaces during the active stage of the CO oxidation.

The search for superconducting systems exhibiting nonreciprocal transport and, specifically, the diode effect, has proliferated in recent years. This trend has encompassed a wide variety of systems, including planar hybrid structures, asymmetric SQUIDs, and certain noncentrosymmetric superconductors. A common feature of such systems is a gyrotropic symmetry, realized on different scales and characterized by a polar vector. Alongside time-reversal symmetry breaking, the presence of a polar axis allows for magnetoelectric effects, which, when combined with proximity-induced superconductivity, results in spontaneous non-dissipative currents that underpin the superconducting diode effect. With this symmetry established, we present a comprehensive theoretical study of transport in a lateral Josephson junction composed of a normal metal supporting the spin Hall effect, and attached to a ferromagnetic insulator. Due to the presence of the latter, magnetoelectric effects arise without requiring external magnetic fields. We determine the dependence of the anomalous currents on the spin relaxation length and the transport parameters commonly used in spintronics to characterize the interface between the metal and the ferromagnetic insulator. Therefore, our theory naturally unifies nonreciprocal transport in superconducting systems with classical spintronic effects, such as the spin Hall effect, spin galvanic effect, and spin Hall magnetoresistance. We propose an experiment involving measurements of magnetoresistance in the normal state and nonreciprocal transport in the superconducting state. Such experiment would, on the one hand, allow for determining the parameters of the model and thus verifying with a greater precision the theories of magnetoelectric effects in normal systems. On the other hand, it would contribute to a deeper understanding of the underlying microscopic origins that determine these parameters.

The quest for nanomaterial-based imaging probes that can provide positive contrast in MRI is fueled by the necessity of developing novel diagnostic applications with potential for clinical translation that current gold standard probes cannot provide. Although interest in nanomaterials for positive contrast has increased in recent years, their study is less developed than that of traditional negative contrast probes in MRI. In our search for new magnetic materials with enhanced features as positive contrast probes for MRI, we decided to explore the chemical space to comprehensively analyze the effects of different metals on the performance of iron oxide nanomaterials already able to provide positive contrast in MRI. To this end, we synthesized 30 different iron oxide-based nanomaterials. Thorough characterization was performed, including multivariate analysis, to study the effect of different variables on their relaxometric properties. Based on these results, we identified the best combination of metals for in vivo imaging and tested them in different experiments. First, we tested its performance on magnetic resonance angiography using a concentration ten times lower than that clinically approved for Gd. Finally, we studied the capability of these nanomaterials to cross the affected blood–brain barrier in a glioblastoma model. The results showed that the selected nanomaterials provided excellent positive contrast at large magnetic field and were able to accumulate at the tumor site, highlighting the affected tissue.

Crimean-Congo haemorrhagic fever (CCHF) virus (CCHFV) is a tick-borne zoonotic pathogen that can cause a lethal haemorrhagic disease in humans. Although the virus appears to be endemically established in the Iberian Peninsula, CCHF is an emerging disease in Spain. Clinical signs of CCHFV infection are mainly manifested in humans, but the virus replicates in several animal species. Understanding the determinants of CCHFV exposure risk from animal models is essential to predicting high-risk exposure hotspots for public health action. With this objective in mind, we designed a cross-sectional study of Eurasian wild boar (Sus scrofa) in Spain and Portugal. The study analysed 5,291 sera collected between 2006 and 2022 from 90 wild boar populations with a specific double-antigen ELISA to estimate CCHFV serum prevalence and identify the main determinants of exposure probability. To do so, we statistically modelled exposure risk with host- and environment-related predictors and spatially projected it at a 10 × 10 km square resolution at the scale of the Iberian Peninsula to map foci of infection risk. Fifty-seven (63.3 %) of the 90 populations had at least one seropositive animal, with seroprevalence ranging from 0.0 to 88.2 %. Anti-CCHFV antibodies were found in 1,026 of 5,291 wild boar (19.4 %; 95 % confidence interval: 18.3–20.5 %), with highest exposure rates in southwestern Iberia. The most relevant predictors of virus exposure risk were wild boar abundance, local rainfall regime, shrub cover, winter air temperature and soil temperature variation. The spatial projection of the best-fit model identified high-risk foci as occurring in most of western and southwestern Iberia and identified recently confirmed risk foci in eastern Spain. The results of the study demonstrate that serological surveys of CCHFV vector hosts are a powerful, robust and highly informative tool for public health authorities to take action to prevent human cases of CCHF in enzootic and emergency set

Aberrant cholesterol metabolism causes neurological disease and neurodegeneration, and mitochondria have been linked to perturbed cholesterol homeostasis via the study of pathological mutations in the ATAD3 gene cluster. However, whether the cholesterol changes were compensatory or contributory to the disorder was unclear, and the effects on cell membranes and the wider cell were also unknown. Using patient-derived cells, we show that cholesterol perturbation is a conserved feature of pathological ATAD3 variants that is accompanied by an expanded lysosome population containing membrane whorls characteristic of lysosomal storage diseases. Lysosomes are also more numerous in Drosophila neural progenitor cells expressing mutant Atad3, which exhibit abundant membrane-bound cholesterol aggregates, many of which co-localize with lysosomes. By subjecting the Drosophila Atad3 mutant to nutrient restriction and cholesterol supplementation, we show that the mutant displays heightened cholesterol dependence. Collectively, these findings suggest that elevated cholesterol enhances tolerance to pathological ATAD3 variants; however, this comes at the cost of inducing cholesterol aggregation in membranes, which lysosomal clearance only partly mitigates.

Liquid-phase transmission electron microscopy is a burgeoning experimental technique for monitoring nanoscale dynamics in a liquid environment, increasingly employing microfluidic reactors to control the composition of the sample solution. Current challenges comprise fast mass transport dynamics inside the central nanochannel of the liquid cell, typically flow cells, and reliable fixation of the specimen in the limited imaging area. In this work, we present a liquid cell concept – the diffusion cell – that satisfies these seemingly contradictory requirements by providing additional on-chip bypasses to allow high convective transport around the nanochannel in which diffusive transport predominates. Diffusion cell prototypes are developed using numerical mass transport models and fabricated on the basis of existing two-chip setups. Important hydrodynamic parameters, i.e., the total flow resistance, the flow velocity in the imaging area, and the time constants of mixing, are improved by 2-3 orders of magnitude compared to existing setups. The solution replacement dynamics achieved within seconds already match the mixing timescales of many ex-situ scenarios, and further improvements are possible. Diffusion cells can be easily integrated into existing liquid-phase transmission electron microscopy workflows, provide correlation of results with ex-situ experiments, and can create additional research directions addressing fast nanoscale processes.

Division of intracellular organelles often correlates with additional membrane wrapping, e.g., by the endoplasmic reticulum or the outer mitochondrial membrane. Such wrapping plays a vital role in proteome and lipidome organization. However, how an extra membrane impacts the mechanics of the division has not been investigated. Here we combine fluorescence and cryo-electron microscopy experiments with self-consistent field theory to explore the stress-induced instabilities imposed by membrane wrapping in a simple double-membrane tubular system. We find that, at physiologically relevant conditions, the outer membrane facilitates an alternative pathway for the inner-tube fission through the formation of a transient contact (hemi-fusion) between both membranes. A detailed molecular theory of the fission pathways in the double membrane system reveals the topological complexity of the process, resulting both in leaky and leakless intermediates, with energies and topologies predicting physiological events.

Opuntia ficus-indica fruits have been widely used due to their nutritional composition and beneficial effects on health, particularly against chronic diseases such as diabetes, obesity, cardiovascular diseases and cancer, among others. In recent years, prickly pear peel and pulp extracts have been characterised, and a high number of bioactive compounds have been identified. This study aimed to analyse the triglyceride-lowering effect of prickly pear peel and pulp extracts obtained from fruits of three varieties (Pelota, Sanguinos, and Colorada) in 3T3-L1 maturing and mature adipocytes. At a concentration of 50 µg/mL, peel extracts from Colorada reduced triglyceride accumulation in pre-adipocytes and mature adipocytes. Additionally, at 25 µg/mL, Pelota peel extract decreased triglyceride content in mature adipocytes. Moreover, maturing pre-adipocytes treated with 50 and 25 µg/mL of Sanguinos pulp extract showed a reduction of triglyceride accumulation. In addition, the lipid-lowering effect of the main individual betalain and phenolic compounds standards were assayed. Piscidic acid and isorhamnetin glycoside (IG2), found in Colorada peel extract, were identified as the bioactive compounds that could contribute more notably to the triglyceride-lowering effect of the extract. Thus, the betalain and phenolic-rich extracts from Opuntia ficus indica fruits may serve as an effective tool in obesity management.

HIV-1 antibodies targeting the carboxy-terminal area of the membrane-proximal external region (ctMPER) are close to exerting viral pan-neutralization. Here, we reconstituted the ctMPER epitope as the N-terminal extremity of the Env glycoprotein transmembrane domain helix and immobilized it onto biosensor-supported lipid bilayers. We assessed the binding mechanism of anti-MPER antibody 10E8 through Surface Plasmon Resonance, and found, through equilibrium and kinetic binding analyses as a function of bilayer thickness, peptide length, and paratope mutations, that 10E8 engages first with the epitope peptide (encounter), limited by ctMPER helix accessibility at the membrane surface, and then inserts into the lipid bilayer assisted by favorable Fab-membrane interactions (docking). This mechanistic information may help in devising new strategies to develop more efficient MPER-targeting vaccines.

Familial hypercholesterolemia (FH) is an inherited metabolic disease affecting cholesterol metabolism, with 90% of cases caused by mutations in the LDL receptor gene (LDLR), primarily missense mutations. This study aims to integrate six commonly used predictive software to create a new model for predicting LDLR mutation pathogenicity and mapping hot spot residues. Six predictive-software are selected: Polyphen-2, SIFT, MutationTaster, REVEL, VARITY, and MLb-LDLr. Software accuracy is tested with the characterized variants annotated in ClinVar and, by bioinformatic and machine learning techniques all models are integrated into a more accurate one. The resulting optimized model presents a specificity of 96.71% and a sensitivity of 98.36%. Hot spot residues with high potential of pathogenicity appear across all domains except for the signal peptide and the O-linked domain. In addition, translating this information into 3D structure of the LDLr highlights potentially pathogenic clusters within the different domains, which may be related to specific biological function. The results of this work provide a powerful tool to classify LDLR pathogenic variants. Moreover, an open-access guide user interface (OptiMo-LDLr) is provided to the scientific community. This study shows that combination of several predictive software results in a more accurate prediction to help clinicians in FH diagnosis.

Nearly 57 Mt of food waste are generated annually in the EU for many reasons, for instance, because of microbial food spoilage. So, actions to reduce food loss and waste are needed and active packaging could offer a new approach towards this aim. In this study, antimicrobial gelatin films were prepared via the solution casting technique and their physicochemical, optical, mechanical, structural, barrier and antimicrobial properties were analysed. First, gelatin films were photo-crosslinked with riboflavin and the photo-curation time (0–4 h) was optimized. The optimal crosslinking time was 2 h since the solubility dropped down from 100% to 30% after 2 or 4 h of UV exposure. Then, 2 types of chitin nanowhiskers (CNWs) obtained via acid hydrolysis (AH) and TEMPO-mediated oxidation processes were added in 2 concentrations (2 and 4 wt %) into the film-forming solution (FFS) as reinforcements before film photo-crosslinking. The AH-CNW at 4 wt % was chosen as an optimal CNW type and concentration because they further decreased the solubility (∼24%) of films and improved mechanical properties up to values similar to those of commercially available synthetic packaging films. Finally, various concentrations (0, 7.5, 15 and 30 wt %) of the antimicrobial compound (Nisin A®) were added to the optimized formulation which showed good antimicrobial properties on both spoilage and pathogen strains, as well as over the native microbiota of chilled sea bream fillets, sliced cold-smoked salmon and chicken breast fillets. The developed films displayed promising properties as antimicrobial packaging for myosistem foods.

Pockmarks are concave depressions on the sea bottom produced by fluid escape from subaqueous sediments which can be found worldwide in muddy and silt/clay sediments. Due to their morphological and geochemical characteristics, certain pockmarks play an important role in structuring benthic communities, and consequently, they have been proposed to be protected. The present research provides a characterisation of the benthic macrofauna composition in pockmark fields in the southeaster Bay of Biscay. A total of 11 samples were acquired in and close to pockmarks covering a range of depths of 414–992 m. The survey strategy considered the acquisition of one sample inside of each of the selected pockmarks and another sample near, but out of them. Collected macrofaunal organisms were identified at lowest taxonomical level (species) when possible, structural parameters were calculated and a hierarchical cluster analysis carried out with species data. Species density, biomass, richness, diversity and evenness were found to be higher in samples collected inside pockmarks in comparison to samples obtained outside but not statistically significant. This could be explained by the inactivity of the studied pockmarks, which do not offer/generate a particular environment with unusual characteristics that limit or enhance the development of specific species/groups with special traits.

The mechanism of the enantioselective (4+3) cycloaddition between furan derivatives and oxyallylcations, which are generated from the corresponding oxiranes through in situ oxidation of allenamides, has been studied using DFT methods. The research has revealed that, under acid-catalysis by a chiral non-racemic phosphoramide, the epoxide ring-opening proceeds without any energy barrier, while the rate-limiting step is the electrophilic attack of the intermediate enaminium ion on the furan ring. The reaction exhibits low energy barriers when dealing with furan derivatives unsubstituted at C2 and C5. Calculations predict the formation of an achiral regioisomer for 2-substituted furans, a prediction that has been experimentally confirmed. Additionally, the calculations accurately predict the reaction with substituted allenamides.

Background: The ongoing issues with post-COVID conditions (PCC), where symptoms persist long after the initial infection, highlight the need for research into blood lipid changes in these patients. While most studies focus on the acute phase of COVID-19, there's a significant lack of information on the lipidomic changes that occur in the later stages of the disease. Addressing this knowledge gap is critical for understanding the long-term effects of COVID-19 and could be key to developing personalized treatments for those suffering from PCC. Methods: We employed untargeted lipidomics to analyze plasma samples from 147 PCC patients, assessing nearly 400 polar lipids. Data mining (DM) and machine learning (ML) tools were utilized to decode the results and ascertain significant lipidomic patterns. Results: The study uncovered substantial changes in various lipid subclasses, presenting a detailed profile of the polar lipid fraction in PCC patients. These alterations correlated with ongoing inflammation and immune response. Notably, there were elevated levels of lysophosphatidylglycerols (LPGs) and phosphatidylethanolamines (PEs), and reduced levels of lysophosphatidylcholines (LPCs), suggesting these as potential lipid biomarkers for PCC. The lipidomic signatures indicated specific anionic lipid changes, implicating antimicrobial peptides (AMPs) in inflammation. Associations between particular medications and symptoms were also suggested. Classification models, such as multinomial regression (MR) and random forest (RF), successfully differentiated between symptomatic and asymptomatic PCC groups using lipidomic profiles. Conclusions: The study's groundbreaking discovery of specific lipidomic disruptions in PCC patients marks a significant stride in the quest to comprehend and combat this condition. The identified lipid biomarkers not only pave the way for novel diagnostic tools but also hold the promise to tailor individualized therapeutic strategies, potentially revolut

Salmonella enterica subsp. enterica serovar Typhimurium variant 4,[5],12:i:- (so called S. 4,[5],12:i:-) has rapidly become one of the most prevalent serovars in humans in Europe, with clinical cases associated with foodborne from pork products. The mechanisms, genetic basis and biofilms relevance by which S. 4,[5],12:i:- maintains and spreads its presence in pigs remain unclear. In this study, we examined the genetic basis of biofilm production in 78 strains of S. 4,[5],12:i:- (n = 57) and S. typhimurium (n = 21), from human gastroenteritis, food products and asymptomatic pigs. The former showed a lower Specific Biofilm Formation index (SBF) and distant phylogenetic clades, suggesting that the ability to form biofilms is not a crucial adaptation for the S. 4,[5],12:i:- emerging success in pigs. However, using a pan-Genome-Wide Association Study (pan-GWAS) we identified genetic determinants of biofilm formation, revealing 167 common orthologous groups and genes associated with the SBF. The analysis of annotated sequences highlighted specific genetic deletions in three chromosomal regions of S. 4,[5],12:i:- correlating with SBF values: i) the complete fimbrial operon stbABCDE widely recognized as the most critical factor involved in Salmonella adherence; ii) the hxlA, hlxB, and pgiA genes, which expression in S. typhimurium is induced in the tonsils during swine infection, and iii) the entire iroA locus related to the characteristic deletion of the second-phase flagellar genomic region in S. 4,[5],12:i:-. Consequently, we further investigated the role of the iro-genes on biofilm by constructing S. typhimurium deletion mutants in iroBCDE and iroN. While iroBCDE showed no significant impact, iroN clearly contributed to S. typhimurium biofilm formation. In conclusion, the pan-GWAS approach allowed us to uncover complex interactions between genetic and phenotypic factors influencing biofilm formation in S. 4,[5],12:i:- and S. typhimurium.

1. Trait-based approaches have received increasing interest among freshwater scientists given their capacity to predict community structure and biodiversity effects on ecosystem functioning. However, the inconsistent development and use of trait concepts and terms across freshwater scientific disciplines may have limited realisation of the potential of traits., 2. Here, we reviewed trait definitions and terms use to provide recommendations for their consistent application in freshwater science. To do so, we first reviewed literature to identify established trait definitions, historical and current use of trait terms and challenges restricting the application of trait-based approaches in freshwater science. Next, we surveyed 414 freshwater researchers from 54 countries to assess variability in the current use of trait terminology in relation to respondent characteristics (i.e., professional experience, geographical region, research discipline, and focal freshwater ecosystem, biotic group, and ecosystem function)., 3. Our literature review identified two well-established trait definitions, which emphasise individual phenotypic characteristics that influence either eco-evolutionary aspects (i.e., organism performance and fitness) or ecosystem dynamics and processes (i.e., responses to the environment and/or effects on ecosystem functioning). Publications used a range of trait-related terms and their frequency of use varied among scientific fields. The term functional trait dominated fields such as biodiversity conservation, environmental sciences and ecology, plant sciences and microbiology. In contrast, the terms biological trait, functional trait, and species trait were used with similar frequencies in fields such as entomology, fisheries, marine and freshwater biology, and zoology. We also found that well-established trait definitions are difficult to apply to freshwater unicellular organisms, colonial multicellular organisms, genomic information, and cultural traits., 4. Our survey revealed highly inconsistent use of trait terms among freshwater researchers. Terms including biological trait, functional trait, structural measure, and ecosystem function were commonly used to describe the same traits or functions. Variability in the use of terms was generally explained by research discipline, geographical region, and focal biotic group and ecosystem functions., 5. We propose making the trait concept flexible enough to be applicable to all freshwater biota and their characteristics, while keeping and integrating links to eco-evolutionary and ecosystem aspects. Specifically, our new definition expands the established functional trait definition by considering also supra-individual scales of trait measurement (colonial- or community-mean traits), genotypic traits (e.g., functional gene markers of enzymes) and cultural traits (e.g., feeding behaviours, communication skills). To reduce terminological ambiguity, we also recommend that researchers define trait terms, prioritising the use of functional trait as an overarching term over alternative terms (e.g., biological trait), and restricting specific terms (e.g., morphological trait) to situations in which such precision is desirable. The findings of our integrative study could help to improve terminological consistency across freshwater disciplines and to better recognise the potential of traits to elucidate the mechanisms behind ecological patterns.

Autophagy is a catabolic process in which a double-membrane organelle, the autophagosome (AP), engulfs cellular components that will be degraded in the lysosomes. ATG8 protein family members participate at various stages of AP formation. The present study compares the capacity to induce lipid-vesicle tethering and fusion of two ATG8 family members, LC3B and LC3C, with model membranes. LC3B is the most thoroughly studied ATG8 protein. It is generally considered as an autophagosomal marker and a canonical representative of the LC3 subfamily. LC3C is less studied, but recent data have reported its implication in various processes, crucial to cellular homeostasis. The results in this paper show that LC3C induces higher levels of tethering and of intervesicular lipid mixing than LC3B. As the N-terminus of LC3C is different from that of the other family members, various mutants of the N-terminal region of both LC3B and LC3C were designed, and their activities compared. It was concluded that the N-terminal region of LC3C was responsible for the enhanced vesicle tethering, membrane perturbation and vesicle-vesicle fusion activities of LC3C as compared to LC3B. The results suggest a specialized function of LC3C in the AP expansion process.

Three naphthorosarins, antiaromatic expanded porphyrins bearing different meso substituents (NRos 1–3), designed to self-assemble into columnar liquid crystalline (LC) structures, were synthesized and characterized using polarized optical microscopy (POM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), as well as supporting computational calculations. The substituents were found to play a crucial role in modulating the LC behaviour.

Smart materials with controlled stimuli-responsive functions are at the forefront of technological development. In this work, we present a generic strategy that combines simple components, physicochemical responses, and easy fabrication methods to achieve a dual stimuli-responsive system capable of location-specific antimicrobial cargo delivery. The encapsulated system is fabricated by combining a biocompatible inert polymeric matrix of poly(dimethylsiloxane) (PDMS) and a bioactive cargo of saturated fatty acids. We demonstrate the effectiveness of our approach to deliver antimicrobial activity for the model bacteria Escherichia coli. The system responds to two control variables, temperature and pH, delivering two levels of antimicrobial response under distinct combinations of stimuli: one response toward the planktonic media and another response directly at the surface for sessile bacteria. Spatially resolved Raman spectroscopy alongside thermal and structural material analysis reveals that the system not only exhibits ON/OFF states but can also control relocation and targeting of the active cargo toward either the surface or the liquid media, leading to different ON/OFF states for the planktonic and sessile bacteria. The approach proposed herein is technologically simple and scalable, facing low regulatory barriers within the food and healthcare sectors by using approved components and relying on fundamental chemical processes. Our results also provide a proof-of-concept platform for the design and easy fabrication of delivery systems capable of operating as Boolean logic gates, delivering different responses under different environmental conditions.

Ocean warming and acidification, decreases in dissolved oxygen concentrations, and changes in primary production are causing an unprecedented global redistribution of marine life. The identification of underlying ecological processes underpinning marine species turnover, particularly the prevalence of increases of warm-water species or declines of cold-water species, has been recently debated in the context of ocean warming. Here, we track changes in the mean thermal affinity of marine communities across European seas by calculating the Community Temperature Index for 65 biodiversity time series collected over four decades and containing 1,817 species from different communities (zooplankton, coastal benthos, pelagic and demersal invertebrates and fish). We show that most communities and sites have clearly responded to ongoing ocean warming via abundance increases of warm-water species (tropicalization, 54%) and decreases of cold-water species (deborealization, 18%). Tropicalization dominated Atlantic sites compared to semi-enclosed basins such as the Mediterranean and Baltic Seas, probably due to physical barrier constraints to connectivity and species colonization. Semi-enclosed basins appeared to be particularly vulnerable to ocean warming, experiencing the fastest rates of warming and biodiversity loss through deborealization

NEXT-100 is currently being constructed at the Laboratorio Subterráneo de Canfranc in the Spanish Pyrenees and will search for neutrinoless double beta decay using a high-pressure gaseous time projection chamber (TPC) with 100 kg of xenon. Charge amplification is carried out via electroluminescence (EL) which is the process of accelerating electrons in a high electric field region causing secondary scintillation of the medium proportional to the initial charge. The NEXT-100 EL and cathode regions are made from tensioned hexagonal meshes of 1 m diameter. This paper describes the design, characterization, and installation of these parts for NEXT-100. Simulations of the electric field are performed to model the drift and amplification of ionization electrons produced in the detector under various EL region alignments and rotations. Measurements of the electrostatic breakdown voltage in air characterize performance under high voltage conditions and identify breakdown points. The electrostatic deflection of the mesh is quantified and fit to a first-principles mechanical model. Measurements were performed with both a standalone test EL region and with the NEXT-100 EL region before its installation in the detector. Finally, we describe the parts as installed in NEXT-100, following their deployment in Summer 2023.

Temperature-modulated colloidal phase of plasmonic nanoparticles is a convenient playground for resettable soft-actuators or colorimetric sensors. To render reversible clustering under temperature change, bulky ligands are required, especially if anisotropic morphologies are of interest. This study showcases thermoresponsive gold nanorods by employing small surface ligands, bis (p-sulfonatophenyl) phenyl-phosphine dihydrate dipotassium salt (BSPP) and native cationic surfactant. Temperature-dependent analysis in real-time allowed to describe the structural features (interparticle distance and cluster size) as well as thermal parameters, melting and freezing temperatures. These findings suggest that neither covalent Au-S bonds nor bulky ligands are required to obtain a robust thermoresponsive system based on anisotropic gold nanoparticles, paving the way to stimuli-responsive nanoparticles with a wide range of sizes and geometries.

The discovery of novel structural units in compounds is of great interest in condensed matter and materials science. This not only leads to interesting properties, especially in superconductivity, as seen in materials like MgB2, H3S, and LaH10, but also enhances the understanding of elemental attributes. While various phosphorous (P) structural units have been reported, planar ones remain relatively rare. In this study, based on first-principles calculations, we propose two pressurized compounds: Ce2P3 and CeP2. These compounds exhibit unprecedented planar arrangements, with Ce2P3 featuring a dense 3-4-5-polygon arrangement and CeP2 showcasing a honeycomb structure. This achievement was realized by strategically adjusting the distribution of non-bonding electrons of P atoms. In Ce2P3, the P layer consists of two interleaved linear arrays composed of edge-shared irregular triangles, quadrilaterals, and pentagons. More interestingly, CeP2 retains dynamic stability at ambient pressure, with a superconducting transition temperature (Tc) of 30.77 K. This superconductivity is attributed to the strong interaction between Ce 4f electrons and the phonons of P–P and coupled Ce–P vibrations, and its dynamic stability at ambient pressure is mainly associated with the strong Ce–P interaction. Our work represents a significant step forward in stabilizing metal phosphides with planar P layers.

We investigated the Kondo effect of cobalt(II)-5-15-bis(4′-bromophenyl)-10,20-bis(4′-iodophenyl)porphyrin (CoTPPBr2I2) molecules on Au(111) with low-temperature scanning tunneling microscopy under ultrahigh vacuum conditions. The molecules exhibit four adsorption configurations at the top and bridge sites of the surface with different molecular orientations. The Kondo resonance shows extraordinary sensitivity to the adsorption configuration. By switching the molecule between different configurations, the Kondo temperature is varied over a wide range from ≈8 up to ≈250 K. Density functional theory calculations reveal that changes of the adsorption configuration lead to distinct variations of the hybridization between the molecule and the surface. Furthermore, we show that surface reconstruction plays a significant role for the molecular Kondo effect.

[Hypothesis]: Graphene oxide-based nanotechnology has aroused a great interest due to its applications in the biomedical and optoelectronic fields. The wide use of these materials makes it necessary to study its potential toxicity associated with the inhalation of Graphene Oxide (GO) nanoparticles and its interaction with the lung surfactant. Langmuir monolayers have proven to be an excellent tool for studying the properties of the lung surfactant and the effect of intercalation of nanoparticles on its structure and properties. Therefore, to know the origin of the phospholipids/GO interaction and the structure of the lipid layer with GO, in this work we study the effect of the insertion of GO sheets on a Langmuir film of 1,2-Dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC)., [Experiments]: Surface pressure-area isotherms, Neutron (NR) and X-ray Reflectivity (XRR) and Grazing Incidence X-ray Diffraction (GIXD) measurements of hydrogenated and deuterated DPPC monolayers with and without GO have been carried out., [Findings]: The results outline a strong interaction between the GO and the zwitterionic form of DPPC and prove that GO is in three regions of the DPPC monolayer, the aliphatic chains of DPPC, the head groups and water in the subphase. Comparison between results obtained with hydrogenated and deuterated DPPC allows concluding that both, electrostatic attractions, and dispersion forces are responsible of the interaction GO/DPPC. Results also demonstrated that the insertion of GO into the DPPC aliphatic chains does not induce significant changes on unit cell of DPPC.

The functions of electrochemical energy conversion and storage devices rely on the dynamic junction between a solid and a fluid: the electrochemical interface (EI). Many experimental techniques have been developed to probe the EI, but they provide only a partial picture. Building a full mechanistic understanding requires combining multiple probes, either successively or simultaneously. However, such combinations lead to important technical and theoretical challenges. In this Review, we focus on complementary optoelectronic probes and modelling to address the EI across different timescales and spatial scales — including mapping surface reconstruction, reactants and reaction modulators during operation. We discuss how combining these probes can facilitate a predictive design of the EI when closely integrated with theory.

The exploration of new pathways to achieve superconductivity in materials has always been a central focus of research in condensed matter physics. Skutterudites have garnered attention due to their intriguing physical properties and broad range of applications. In this study, we propose that rotating the planar P4 units within skutterudites is a viable method to induce superconductivity. The predicted compound, referred to as skutterudite-like CeP3, exhibits phonon-mediated superconductivity at ambient pressure. This phenomenon arises from the interaction between Ce/P-derived phonons and the Ce 4f and P3p electrons. The energy barrier for transitioning from the skutterudite-like CeP3 to the conventional skutterudite-type CeP3 is as high as 1.53 eV/atom, indicating a substantial irreversibility. Additional calculations reveal that skutterudite-like CeP3 becomes thermodynamically stable at 25 GPa in the binary Ce-P phase diagram. Consequently, the skutterudite-like CeP3 can be synthesized by initially compressing the most stable bulk binary CeP and P at 25 GPa, followed by decompression. This work represents a significant step forward in the design of superconducting skutterudite-like compounds.