Search

Rapid environmental changes across Europe include warmer and increasingly variable temperatures, changes in soil nutrient availability, and pollinator decline. These abiotic and biotic changes can affect natural plant populations and force them to optimize resource use against competitors. To date, the evolution of competitive ability in the context of changes in nutrient availability remains understudied. In this study, we investigated whether the common calcareous grassland herb Leontodon hispidus recently evolved its competitive ability and response to nutrient availability. We compared ancestors sampled in 1995 and descendants sampled in 2018 and applied a competition treatment in combination with weekly nutrient treatments (no fertilizer, nitrogen, phosphorus, and both). We found evidence for evolution of increased competitive ability, with descendants producing more vegetative biomass than ancestors when grown under competition. Furthermore, supplementing nutrients (especially N) reduced differences in competitive ability between ancestors and descendants, suggesting that nutrients are a limiting factor in interspecific competition, which could be linked to the decreasing nitrogen emissions into the atmosphere since the 1990s. Our study demonstrates rapid contemporary evolution of competitive ability, but also the complexity of the underlying processes of contemporary evolution, and sheds light on the importance of understudied potential selection agents such as nutrient availability., Competing Interests: Declarations. Conflict of interest: The authors declare that they have no conflict of interests. Ethic approval: Not applicable. Consent to participate: Not applicable. Consent for publication: Not applicable., (© 2024. The Author(s).)

Deforestation and forest degradation are key drivers of biodiversity loss and global environmental change. Ecosystem restoration is recognized as a global priority to counter these processes. Forest restoration efforts have commonly adopted a predominantly ecological approach, without including broader socioeconomic variables and the characteristics of the rural context. In this study, we developed a spatially-explicit modelling method to identify priority areas for forest restoration at a landscape scale, integrating both ecological and socioeconomic variables. This framework was applied to a case study in the Chilean temperate forests. We used a multicriteria analysis to assess the ecological suitability and socioeconomic feasibility of forest restoration. The approach and methodology were structured into four main steps: (i) defining potential areas for restoration in deforested lands and degraded forest; (ii) assessing and mapping the ecological suitability for restoration, including both potential biodiversity values and provision of ecosystem services; (iii) assessing and mapping the socioeconomic feasibility of restoration; and (iv) combining suitability and feasibility maps to identify priority areas. Restoration priorities were identified as areas consistently showing the highest values under scenarios representing differing restoration priorities. While the case study presented is context-specific, the approach and methodology used can be readily adapted to various contexts and objectives., Competing Interests: Compliance with Ethical Standards. Conflict of Interest: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

This work investigates the sustainable reuse of expanded polystyrene (EPS) waste through a multi-cycle physical recycling process involving dissolution in acetone and subsequent manufacturing via Direct Ink Write (DIW) 3D printing and casting. Morphology and mechanical properties were evaluated as a function of the manufacturing technique and number of dissolution cycles. Morphological analysis revealed that casted specimens better replicated the target geometry, while voids in 3D-printed specimens aligned with the printing direction due to rapid solvent evaporation. These voids contributed to slightly reduced stiffness in 3D-printed specimens compared to casted ones, particularly for transverse printing orientation. The defoaming process during dissolution significantly increased the density of the material, as well as removed low molecular weight additives like plasticizers, leading to a notable enhancement in stiffness. Successive dissolution cycles led to increased removal of plasticizers, enhancing stiffness up to 52 times (cast), 42 times (longitudinally printed), and 35 times (transversely printed) relative to as-received EPS waste. The glass transition temperature remained unchanged, confirming the preservation of polymer integrity. This work highlights the potential of EPS inks for sustainable, multi-cycle recycling, combining enhanced mechanical performance with the flexibility of 3D printing for complex, cost-effective designs, aligning with circular economy principles.

This review explores the advancements in additive manufacturing (AM) of biodegradable iron (Fe) and zinc (Zn) alloys, focusing on their potential for medical implants, particularly in vascular and bone applications. Fe alloys are noted for their superior mechanical properties and biocompatibility but exhibit a slow corrosion rate, limiting their biodegradability. Strategies such as alloying with manganese (Mn) and optimizing microstructure via laser powder bed fusion (LPBF) have been employed to increase Fe's corrosion rate and mechanical performance. Zn alloys, characterized by moderate biodegradation rates and biocompatible corrosion products, address the limitations of Fe, though their mechanical properties require improvement through alloying and microstructural refinement. LPBF has enabled the fabrication of dense and porous structures for both materials, with energy density optimization playing a critical role in achieving defect-free parts. Fe alloys exhibit higher strength and hardness, while Zn alloys offer better corrosion control and biocompatibility. In vitro and in vivo studies demonstrate promising outcomes for both materials, with Fe alloys excelling in load-bearing applications and Zn alloys in controlled degradation and vascular applications. Despite these advancements, challenges such as localized corrosion, cytotoxicity, and long-term performance require further investigation to fully harness the potential of AM-fabricated Fe and Zn biodegradable implants.

A full-scale passive treatment plant using barium carbonate (BaCO 3 ), the mineral witherite, as a Dispersed Alkaline Substrate (DAS) for strongly contaminated acid mine drainage was implemented for the first time globally at Mina Concepción, located in the Iberian Pyrite Belt (SW Spain). The plant was monitored over a 105-day period, covering the wettest months of the hydrological year and with a mean flow around 4 L s -1 . The AMD treated in the plant exhibits a high strength, with an average sulfate concentration around 1500 mg L -1 and net acidity close to 1000 mg L -1 as CaCO₃ equivalent. According to the above, the loading rate for SO 4 and Fe was around 400 and 80 kg day -1 , respectively. The treatment process produced an alkaline effluent with low metal content. Nearly complete removal of most metal(loid)s was achieved, with significant sulfate decrease to below 500 mg L -1 in the alkaline outflow of the barium carbonate tank. Barium carbonate demonstrated superior performance compared to magnesia, particularly in enhancing alkalinity and lowering net acidity and concentrations of sulfate and manganese. The high efficiency attained by the plant after the barium carbonate treatment is evidenced by compliance with environmental water quality standards for most contaminants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Blowouts are wind-formed depressions that help maintain the sediment budget and enhance biodiversity in coastal dunes. However, the drivers controlling their evolution and the temporal scales associated to their genesis, development and decay phases remain unclear. To address this, the morphometric characteristics of a series of blowouts on the Ancão Peninsula (South Portugal) were digitized using imagery from 1972 to 2021, and used to analyse changes in the number of blowouts, total area, morphometric characteristics (width, length, orientation), and elongation rate over time. These data were compared with metocean time series and human activities, allowing the identification of blowout phases, drivers, and associated temporal scales. This work revealed that the blowout genesis phase primarily arised from the impact of physical external factors (e.g., non-storm low-to-moderate winds blowing out sand from dune scarp irregularities formerly created by extreme wave events), creating incisions across the foredune crest, and lasted 1 or 2 years. The blowout development phase, still ongoing, was characterized mainly by blowout expansion and rotation of large blowouts from North-northeast (NNE) to the East-northeast (ENE) controlled by external physical forces at specific times (e.g., low-to-moderate winds) and blowout internal factors (e.g., size and orientation). Complete blowout decay phases were not observed, except the complete artificial sealing of some blowouts due to fencing, which lasted 4 years. These findings suggest that a complete and natural blowout genesis-development-decay cycle could likely take more than five decades, with complex and spatiotemporally variable ecogeomorphic feedbacks driving their evolution. The only phase reversal documented was the reactivation of the artificially sealed blowouts, due to storm impacts. Allowing the dune and blowouts to evolve naturally appears to be the current best approach for the dune management at the studied area., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Considering the complexity in terms of design that characterizes the different tissues of the human body, it is necessary to study and develop more precise therapies. In this sense, this article presents the possibility of fabricating photocurable thermosensitive hydrogels with free geometry and based on N-Vinyl Caprolactam (VCL) with the aim of modulating the adhesion of non-planar cell cultures. The fabrication process is based on the use as a mold of two-layer thick water-soluble polyvinyl alcohol (PVA) previously printed by Extrusion Material (MatEx). From this technology it has been possible to obtain hydrogels with different 3D geometries and different crosslinking percentages (2, 4 and 6 mol%). Studies have shown that networks reduce their thermosensitivity not only when the percentage of crosslinking in the formulation increases, but also when the thickness of the hydrogel obtained increases. Based on this reduction in thermosensitivity, the less crosslinked (2 mol%) hydrogels have been evaluated to carry out a novel direct application in which hydrogels with curved geometry have allowed cell adhesion and proliferation at 37 °C with the endothelial cell line C166-GFP; likewise, non-aggressive cell detachment was observed when the hydrogel temperature was reduced to values of 20 °C. Therefore, the present manuscript shows a novel application for the synthesis of free-form thermosensitive hydrogels that allows modulation of non-planar cell cultures.

Fast detection of viral infections is a key factor in the strategy for the prevention of epidemics expansion and follow-up. Hepatitis C is paradigmatic within viral infectious diseases and major challenges to elimination still remain. Near infrared spectroscopy (NIRS) is an inexpensive, clean, safe method for quickly detecting viral infection in transmission vectors, aiding epidemic prevention. Our objective is to evaluate the combined potential of machine learning and NIRS global molecular fingerprint (GMF) from biobank sera as an efficient method for HCV activity discrimination in serum. GMF of 151 serum biobank microsamples from hepatitis C patients were obtained with a FT-NIR spectrophotometer in reflectance mode. Multiple scatter correction, smoothing and Saviztsky-Golay second derivative were applied. Spectral analysis included Principal Component Analysis (PCA), Bootstrap and L1-penalized classification. Microsamples of 70 µl were sufficient for GMF acquisition. Bootstrap evidenced significant difference between HCV PCR positive and negative sera. PCA renders a neat discrimination between HCV PCR-positive and negative samples. PCA loadings together with L1-penalized classification allow the identification of discriminative bands. Active virus positive sera are associated to free molecular water, whereas water in solvation shells is associated to HCV negative samples. Divergences in the water matrix structure and the lipidome between HCV negative and positive sera, as well as the relevance of prooxidants and glucose metabolism are reported as potential biomarkers of viral activity. Our proof of concept demonstrates that NIRS GMF of hepatitis C patients' sera aided by machine learning allows for efficient discrimination of viral presence and simultaneous potential biomarker identification., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Oscar Barquero reports financial support was provided by Spanish Ministry of Education and Science. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Metal halide perovskites are mixed ionic-electronic semiconductors that involve an important and particular phenomenology that negatively affects the performance and stability of next-generation photovoltaic devices based on such material. The ionic nature of perovskites is shown to undergo not only a simple redistribution of charges but also influences the electronic processes and ultimately the steady-state device operation. Nevertheless, a comprehensive understanding of the internal contributions of ionic and electronic conductivities to the evolution of current during device performance experiments and to degradation losses in ageing tests is currently missing. Here the ionic- and electronic-based currents are separately shown in photovoltaic perovskites by means of transient experiments, beyond the external measured response. From an advanced mathematical model, the experimental observations attributing the partial transient features to physical effects in perovskites are rationalized. It is revealed that ion-driven surface recombination effects are a dominant factor in the slowdown of efficiency measurements and in the long-term degradation of perovskites under operational conditions. This work contributes to tracing a more accurate physical picture of the complex energy landscape of the perovskite-based solar cells, which will be key to taking steps toward industrialization., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

The exponential number of food alerts about concerning levels of some plant-alkaloids, such as pyrrolizidine, tropane and opium alkaloids, have stressed the need to monitor their occurrence in foods to avoid toxic health effects derived from their intake. Therefore, analytical strategies to simultaneously monitor the occurrence of these alkaloids should be developed to ensure food safety an comply with regulations. Accordingly, this work proposes an efficient multicomponent analytical strategy for the simultaneous extraction of these alkaloids from commercial bakery products. The analytical method was validated and applied to the analysis of 15 samples, revealing that 100% of them contained at least one of the target alkaloids, in some cases exceeding the maximum limits legislated. Moreover, in two samples the 3 different alkaloid families were detected. These results confirm the importance of simultaneously monitoring these alkaloids in food and highlight also considering some opium alkaloids in current legislation., Competing Interests: Declaration of competing interest I, Isabel Sierra Alonso, hereby declare that I have read and understood the policies of the Food Research International regarding competing interests. I wish to inform the editorial team and readers about any potential conflicts of interest associated with the submitted manuscript entitled " Improving the food safety of bakery products by simultaneously monitoring the occurrence of pyrrolizidine, tropane and opium alkaloids"., (Copyright © 2024. Published by Elsevier Ltd.)

Aldol condensation of biomass-derived compounds offers a sustainable route to jet fuel precursors. This study explores catalysts based on nanocrystalline ZSM-5 zeolite (n-ZSM-5) modified with various metals (Ca, Mg, Sn, Ti, Zr) for the aldol condensation of furfural (FFL) and cyclopentanone (CPO). While both reactants can enter the ZSM-5 micropores, the resulting C10 (FC) and C15 (F 2 C) adducts are too large to be formed within or to exit the microporosity, being instead produced over the external acid sites. Metal modification significantly impacts catalytic activity: Ca and Mg reduce conversion, Sn is neutral, whereas Zr and Ti leads to enhanced performance. The TiO 2 /n-ZSM-5 catalyst shows by far the best behavior, doubling FFL conversion and sharply increasing the FC + F 2 C yield, which is attributed to a synergistic effect arising from the generation of accessible weak Lewis acid sites by highly dispersed TiO 2 that complement the external Brønsted acidity of ZSM-5., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Carbon fiber, with its strong mechanical properties and electrical conductivity, is ideal as a fiber electrode in wearable or structural energy storage devices. However, its energy storage capacity is limited, and coatings like transition metal oxides (TMOs) enhance its electrochemical performance. Metal-organic frameworks (MOFs) are commonly used to grow TMOs on carbon fibers, increasing the surface area for better energy storage. Despite this, TMOs have limited electrical conductivity, so ion exchange is often used to dope them with additional cations, improving both conductivity and energy storage capacity. This study compares different ion-exchange cations in ZIF-L-derived TMO coatings on carbon fiber. Testing both supercapacitor and Li-ion battery applications, Ni-doped samples showed superior results, attributed to their higher exchange ratio with cobalt. As a supercapacitor electrode, the Ni-doped material achieved 13.3 F/g at 50 mA/g-66% higher than undoped samples. For Li-ion battery anodes, it reached a specific capacity of 410.5 mAh/g at 25 mA/g, outperforming undoped samples by 21.4%.

The introduction of Diels-Alder (D-A) bonds into epoxy resins is a promising pathway to convert these unrecyclable materials into sustainable materials. However, D-A bonds make epoxy resins extremely brittle materials and hinder their practical usability. Nonetheless, the reversibility of D-A bonds allows the transition of the material to a de-crosslinked network formed by separated oligomers that can melt above 90-100 °C. This means that D-A epoxy resins can be reprocessed after being cured like thermoplastics. In the present work, a thermoset blend is made by adding spent epoxy particles to a D-A epoxy resin to increase its thermal and mechanical properties and to evaluate a possible reuse of conventional thermoset wastes. The application of hot-pressing to a mixture of epoxy particles and powder of cured D-A epoxy creates a material in which the interaction of the particles with the D-A resin increases the thermal resistance of the material and prevents the D-A epoxy from melting at high temperatures. In addition, the flexural strength is increased by 80% and the chemical resistance against organic solvents is also improved.

Macroscopic systems present particle-type solutions. Spontaneous symmetry-breaking can cause these solutions to travel in different directions, and the inclusion of random fluctuations can induce them to run and tumble. We investigate the running and tumbling of localized structures observed on a prototype model of one-dimensional pattern formation with noise. Statistically, the dynamics of localized structures are examined, particularly the mean square displacement as a function of time. It initially shows a diffusive behavior, replaced by a ballistic one, and finally manifests itself as diffusive again. We derive a minimal model for the position and velocity of localized structures, which reveals the origin of the observed dynamics.

The problem of estimating the constant parameters of the Kuramoto-Sivashinsky (KS) equation from observed data has received attention from researchers in physics, applied mathematics, and statistics. This is motivated by the various physical applications of the equation and also because it often serves as a test model for the study of space-time pattern formation. Remarkably, most existing inference techniques rely on statistical tools, which are computationally very costly yet do not exploit the dynamical features of the system. In this paper, we introduce a simple, online parameter estimation method that relies on the synchronization properties of the KS equation. In particular, we describe a master-slave setup where the slave model is driven by observations from the master system. The slave dynamics are data-driven and designed to continuously adapt the model parameters until identical synchronization with the master system is achieved. We provide a simple analysis that supports the proposed approach and also present and discuss the results of an extensive set of computer simulations. Our numerical study shows that the proposed method is computationally fast and also robust to initialization errors, observational noise, and variations in the spatial resolution of the numerical scheme used to integrate the KS equation.

Invasive species are a major threat to global diversity and can interact synergistically or antagonistically with various components of climate change. Using species distribution models (SDMs) at different spatial scales and resolutions, we determined the main variables affecting the distribution of six invasive macroalgae present on European coasts. We also studied occupation of the thermal realized niche and predicted areas potentially at risk of invasion. The climatic variables related to warming had a greater influence on distribution at large scales, while non-climatic variables related to river influence and maritime transport at regional scale. Invaders often seemed to occupy colder areas than in their native area. The combination of SDMs with thermal niche of species is a useful way of clarifying the invasion process. This approach will help in the development of preventive strategies whereby the responsible authorities can implement early detection systems and respond swiftly to the appearance of biopollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Understanding trait-trait coordination is essential for successful plant breeding and crop modeling. Notably, plant size drives variation in morphological, physiological, and performance-related traits, as described by allometric laws in ecology. Yet, as allometric relationships have been limitedly studied in crops, how they influence and possibly limit crop performance remains unknown. Here, we review how an allometry perspective on crops gains insights into the phenotypic evolution during crop domestication, the breeding of varieties adapted to novel conditions, and the prediction of crop yields. As allometry is an active field of research, modeling and manipulating crop allometric relationships can help to develop more resilient and productive agricultural systems to face future challenges., (© 2024 The Author(s). New Phytologist © 2024 New Phytologist Foundation.)

The diffusion-bonding technique has been utilized to join various Al alloys (AA1060, AA2024, AA3003) to Cu for bimetallic anode application. This process aims to achieve robust metallic continuity to facilitate electron transfer, while carefully managing the growth of the intermetallic layer at the bonding interface. This control preserves the active volume of aluminum and prevents excessive brittleness of the anode. Optimization efforts have focused on different pressures, surface treatments of parent materials, and bonding parameters (temperature 450-500 °C and time 5-60 min). The optimal conditions identified include low bonding pressures (8 MPa), surface treatment involving polishing followed by chemical cleaning of the surfaces to be bonded, and energetic bonding conditions tailored to each specific aluminum alloy. Preliminary electrochemical characterization via cyclic voltammetry (CV) tests has demonstrated high reversibility intercalation/deintercalation reactions for up to seven cycles. The presence of the different alloying elements appears to contribute significantly to maintaining the high intercalation/deintercalation reaction reversibility without considerable modification of the reaction potentials. This effect may be attributed to alloying elements effectively reducing the overall alloy volume expansion, potentially forming highly reversible ternary/quaternary active phases, and creating a porous reaction layer on the exposed aluminum surface. These factors along with the influence of the Cu parent material collectively reduce the stress during volume expansion, which is the responsible phenomenon of the anode degradation in common Al anodes.

On global scale, eutrophication is one of the most prevalent environmental threats to water quality, primarily caused by elevated concentration of nutrients in wastewater. This study utilizes aluminum dross (AD), an industrial waste, to create a value-added material by improving its operational feasibility and application for removing phosphate and ammonium from water. The operational challenges of AD such as its powdered nature and effective operation under only extreme pH conditions were addressed by immobilizing in calcium alginate to form calcium alginate aluminium dross (Ca-Alg-Al dross) beads. These Ca-Alg-Al dross beads were further tested for phosphate and ammonium removal from natural wastewater in two different aqueous environment systems: (i) vertical flow constructed wetlands (VF-CWs) followed by Ca-Alg-Al dross beads fixed bed system and (ii) Ca-Alg-Al dross beads mounted floating constructed wetlands (FCW) for remediating polluted lentic ecosystems. Our results show maximum phosphate and ammonium removal of 85 ± 0.41 % and 93.44 %, respectively, in VF-CWs followed by Ca-Alg-Al dross beads fixed bed system. The Ca-Alg-Al dross beads mounted FCW system achieved maximum phosphate removal of 79.18 ± 8.56 % and ammonium removal of 65.45 ± 21.04 %. Furthermore, the treated water from the FCW system was assessed for its potential to inhibit algal growth by artificially inoculating treated water with natural algae to simulate eutrophic conditions. Interestingly, treated water from the FCW system was found capable of arresting the algal growth. Besides, scanning electron microscopy with energy dispersive X-ray (SEM-EDX) and Fourier transform infrared (FTIR) spectroscopy confirmed the functional groups and surface properties and probable participation of multiple mechanisms including ion exchange, electrostatic attraction, and ligand complexation for phosphate and ammonium removal. Overall, these results offer a promising way to utilize AD for high-end applications in wastewater treatment., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: This work reports financial support was provided by Council of Scientific and Industrial Research Institute of Minerals and Materials Technology. AKY reports a relationship with Council of Scientific and Industrial Research Institute of Minerals and Materials Technology Department of Hydro & ElectroMetallurgy that includes: funding grants. AKY has patent pending to none. Asheesh Kumar Yadav reports financial support, administrative support, equipment, drugs, or supplies, statistical analysis, travel, and writing assistance were provided by Council of Scientific and Industrial Research Institute of Minerals and Materials Technology. Asheesh K Yadav reports financial support was provided by Council for Scientific and Industrial Research. Asheesh K Yadav reports financial support was provided by DST India. Yamini Mittal reports financial support was provided by Council for Scientific and Industrial Research. Asheesh K Yadav and Others has patent pending to CSIR. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

A new method for radionuclide labeling by the use of graphene thin films was previously presented. In this work, a comparison among low energy radioactive sources supported on carbonaceous thin films on polyvinyl chloride-polyvinyl acetate copolymer (VYNS), based on the use of aqueous solutions is investigated as a feasible alternative to the traditional metallized films avoiding the downside of the loss of many broken films. Graphene-based materials were prepared by both oxidation-exfoliation-reduction and direct graphite exfoliation routes. In addition, multiwalled carbon nanotubes (MWCNTs) thin films were also evaluated. The stability of both carbonaceous materials aqueous dispersions were studied by using ionic and non-ionic surfactants. Solid carbon-based materials were characterized by X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) whereas the colloidal nature of the aqueous dispersions was verified by the measurement of Tyndall effect and the morphology of thin films was evaluated by Scanning Electron Microscopy (SEM). 55 Fe solutions were used to prepare the radioactive sources on the thin films by quantitative drop deposition. The quality of spectra was measured in a pressurized proportional counter. Results showed a resolution higher than 0.9 keV for all the tested sources. However, MWCNT-based along with non-surfactant sources presented non-adequate escape peaks and low energy tails. On the contrary, all the graphene-based sources prepared using surfactants to stabilize aqueous solutions presented an energy resolution comparable to that of the metallized source while offering notable advantages in terms of cost efficiency and reliability of the as-prepared supports., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. None., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The catalytic activity and stability of sulfonic-based UiO-66(Zr) materials were tested in the Friedel-Crafts acylation of anisole with acetic anhydride. The materials were prepared using microwave-assisted synthesis, producing microporous materials with remarkable crystallinity and physicochemical features as acid catalysts. Different ratios between both organic ligands, terephthalic acid (H 2 BDC) and monosodium 2-sulfoterephthalic acid (H 2 BDC-SO 3 Na), were used for the synthesis to modulate the sulfonic content. The sulfonic-based UiO-66(Zr) material synthesized with a H 2 BDC/H 2 BDC-SO 3 Na molar ratio of 40/60 exhibited the best catalytic performance in the acidic-catalyzed Friedel-Crafts acylation reaction. This ratio balanced the number of sulfonic acid sites and their accessibility within the UiO-66 microporous structure. The catalytic performance of this material increased remarkably at 200 °C, outperforming reference acids and commercial heterogeneous catalysts such as Nafion-SAC-13 and Amberlyst-70. Additionally, the best sulfonic-based UiO-66(Zr) material proved to be stable in four successive reaction cycles, maintaining both its catalytic activity and its structural integrity.

Bacterial diseases caused by superbugs are expected to be the main cause of death worldwide within a decade as a consequence of the resistance they are acquiring to the antibiotics currently in use, therefore, the field of new antibacterial treatments is currently being thoroughly studied. The present work focuses on the synthesis, functionalization, characterization and antibacterial behaviour of different systems based on three different silica-based nanostructured materials (MSN, mesoporous silica nanoparticles, SBA-15 Santa Barbara amorphous-15 and FSP fibrous slica nanoparticles) which serve as scaffolds for the support of different platforms to target and treat bacterial diseases and biofilm formation. Thus, (3-carboxypropyl)triphenylphosphonium bromide (PPh 3 + ) and a cytotoxic organotin(IV) fragment (Sn) have been incorporated in the silica-based materials to study their potential activity in different antibacterial applications. After a complete characterization of the synthesized systems, which confirmed the incorporation of both the targeting and the therapeutic fragments within the nanostructured materials, the antibacterial study of the materials demonstrated bactericidal capacity against Escherichia coli and perturbation of the bacteria metabolism via oxidative stress through an enhanced ROS (reactive oxygen species) production. In addition, biofilm inhibition and eradication tests of bacterial strains were carried out, showing that the activity of the materials in both biofilm inhibition and eradication is dependent on the concentration of the material. Furthemore, the material MSN-AP(1:1)-PPh 3 + -Sn containing the targeting triphenylphosphonium and a "SnPh 3 " fragment is capable of inhibiting and eradicating up to 50% of the formation of biofilms, which is outstanding for metallodrug-functionalized silica-based systems compared with other materials based on metal nanoparticles supported on silica. Finally, a hemolysis study was carried out with the nanostructured systems proving to be non-toxic, making them adequate for their subsequent use in preclinical trials through in vivo models.

Dendritic ZSM-5 zeolites were investigated in the isomerization of monoterpene epoxides, including limonene-1,2-epoxide (LE), α-pinene epoxide, and β-pinene epoxide, which yields high-value compounds used in fragrances, cosmetics, and pharmaceuticals. The fresh catalysts were thoroughly characterized using XRD, Ar physisorption, pyridine-FTIR, TEM, FTIR/DTBPyr, and 27 Al MAS NMR. In comparison with conventional and hierarchical ZSM-5 materials, the dendritic zeolite with a crystallization time of 4 days (d-ZSM-5/4d) was the most active material, with a turnover frequency value of 4.4 min -1 for LE isomerization. Likewise, remarkable yields of dihydrocarvone (DHC, 63%, 70 °C, 2 h), campholenic aldehyde (72.4%, 70 °C, 5 min), and myrtanal (47.7%, 50 °C, 5 min) were obtained with this material that exhibited the largest mesopore/external surface area (360 m 2 g -1 ), showing also the narrowest mesopore size distribution. A direct relationship was observed between the TOF values and the concentration of external Brønsted acid sites, showing the presence of strong steric/diffusional limitations that are greatly overcome with the dendritic zeolites. The lower reactivity of trans -LE compared to cis -LE was attributed to the larger steric hindrance of the oxygen atom. Exploration of the solvent influence revealed that the reaction rate of LE was favored by non-polar solvents, while highly selective DHC formation occurred in the solvents of medium polarity. The d-ZSM-5/4d sample was shown to be robust because catalytic activity could be completely recovered by air calcination., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This study examines the potential of fungal chitosan derived from Aspergillus niger as a sustainable alternative to traditional petrochemical-based ingredients in cosmetic products. Specifically, the research examines the solubility of fungal chitosan in aqueous solutions of varying ionic strength and its adsorption onto negatively charged surfaces that mimic human hair keratin. The adsorption behavior, water content, and frictional properties of chitosan films were evaluated using a quartz crystal microbalance with dissipation monitoring and a surface force apparatus (SFA). The findings indicated that fungal chitosan exhibits good solubility at a pH of 4.5. Conversely, the adsorption of chitosan is subject to the influence of both polymer concentration and ionic strength. At the lowest ionic strengths, a screening-enhanced adsorption process occurs as a consequence of the reduction in chitosan solubility in the presence of salt. This results in the depletion of polymer chains from the solution and their subsequent deposition. An increase in ionic strength above 15-20 mM results in a worsening of the chitosan-surface interaction, due to the simultaneous screening of both the chitosan and the surface charges. This results in a hindrance to the adsorption process. The deposited films are highly hydrated, and this hydration increases with both polymer concentration and ionic strength. Furthermore, the films exhibit a predominantly elastic behavior, and the response of the films under shear deformations shows a strong dependence on the polymer concentration. These findings contribute to the development of environmentally friendly cosmetic formulations that meet consumer demands for sustainability.

Undiagnosed and untreated human immunodeficiency virus (HIV) infection increases morbidity in the HIV-positive person and allows onward transmission of the virus. Minimizing missed opportunities for HIV diagnosis when a patient visits a healthcare facility is essential in restraining the epidemic and working toward its eventual elimination. Most state-of-the-art proposals employ machine learning (ML) methods and structured data to enhance HIV diagnoses, however, there is a dearth of recent proposals utilizing unstructured textual data from Electronic Health Records (EHRs). In this work, we propose to use only the unstructured text of the clinical notes as evidence for the classification of patients as suspected or not suspected. For this purpose, we first compile a dataset of real clinical notes from a hospital with patients classified as suspects and non-suspects of having HIV. Then, we evaluate the effectiveness of two types of classification models to identify patients suspected of being infected with the virus: classical ML algorithms and two Large Language Models (LLMs) from the biomedical domain in Spanish. The results show that both LLMs outperform classical ML algorithms in the two settings we explore: one dataset version is balanced, containing an equal number of suspicious and non-suspicious patients, while the other reflects the real distribution of patients in the hospital, being unbalanced. We obtain F 1 score figures of 94.7 with both LLMs in the unbalanced setting, while in the balance one, RoBERTa Bio model outperforms the other one with a F 1 score of 95.7. The findings indicate that leveraging unstructured text with LLMs in the biomedical domain yields promising outcomes in diminishing missed opportunities for HIV diagnosis. A tool based on our system could assist a doctor in deciding whether a patient in consultation should undergo a serological test., Competing Interests: Declaration of competing interest None declared., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Quantum dots (QDs) semiconducting nanomaterials, have garnered attention due to their distinctive properties, including small size, high luminescence, and biocompatibility. In the context of triple-negative breast cancer (TNBC), notorious for its resistance to conventional treatments, QDs exhibit promising potential for enhancing diagnostic imaging and providing targeted therapies. This review underscores recent advancements in the utilization of QDs in imaging techniques, such as fluorescence tomography and magnetic resonance imaging, aiming at the early and precise detection of tumors. Emphasis is placed on the significance of QD design, synthesis and functionalization processes as well as their use in innovative strategies for targeted drug delivery, capitalizing on their ability to selectively deliver therapeutic agents to cancer cells. As the research in this field advances rapidly, this review covers a classification of QDs according to their composition, the characterization techniques than can be used to determine their properties and, subsequently, emphasizes recent findings in the field of TNBC-targeting, highlighting the imperative need to address challenges, like potential toxicity or methodologies standardization. Collectively, the findings explored thus far suggest that QDs could pave the way for early diagnosis and effective therapy of TNBC, representing a significant stride toward precise and personalized strategies in treating TNBC., (© 2024 The Authors. ChemMedChem published by Wiley-VCH GmbH.)

New clinical strategies for treating severe bone and cartilage injuries are required, especially for use in combination with implant procedures. For this purpose, p(VCL-co-HEMA) thermosensitive hydrogels have been activated with icariin-loaded nanoparticles to be used as bone-cell-harvesting platforms. Supercritical CO 2 -SAS technology has been applied to encapsulate icariin, a small molecule that is involved in osteoblastic differentiation. Thus, physical-chemical analysis, including swelling and transmittance, showed the impact of HEMA groups in hydrogel composition. Moreover, icariin (ICA) release from p(VCL-co-HEMA) platforms, including pVCL@ICA nanoparticles, has been studied to evaluate their efficacy in relevant conditions. Finally, the thermosensitive hydrogels' cell compatibility, transplant efficiency, and bone differentiation capacity were tested. This study identifies the optimal formulations for icariin-activated hydrogels for both control and HEMA formulations. Using this technique, osteoblastic sheets that were rich in collagen type I were successfully transplanted and recultivated, maintaining an optimal extracellular matrix (ECM) composition. These findings suggest a new cell-sheet-based therapy for bone regeneration purposes using customized and NP-activated pVCL-based cell platforms.

As major terrestrial carbon sinks, forests play an important role in mitigating climate change. The relationship between the seasonal uptake of carbon and its allocation to woody biomass remains poorly understood, leaving a significant gap in our capacity to predict carbon sequestration by forests. Here, we compare the intra-annual dynamics of carbon fluxes and wood formation across the Northern hemisphere, from carbon assimilation and the formation of non-structural carbon compounds to their incorporation in woody tissues. We show temporally coupled seasonal peaks of carbon assimilation (GPP) and wood cell differentiation, while the two processes are substantially decoupled during off-peak periods. Peaks of cambial activity occur substantially earlier compared to GPP, suggesting the buffer role of non-structural carbohydrates between the processes of carbon assimilation and allocation to wood. Our findings suggest that high-resolution seasonal data of ecosystem carbon fluxes, wood formation and the associated physiological processes may reduce uncertainties in carbon source-sink relationships at different spatial scales, from stand to ecosystem levels., (© 2024. The Author(s).)

Nowadays, owing to the new technological and industrial requirements for equipment, such as flexibility or multifunctionally, the development of all-solid-state supercapacitors and Li-ion batteries has become a goal for researchers. For these purposes, the composite material approach has been widely proposed due to the promising features of woven carbon fiber as a substrate material for this type of material. Carbon fiber displays excellent mechanical properties, flexibility, and high electrical conductivity, allowing it to act as a substrate and a collector at the same time. However, carbon fiber's energy-storage capability is limited. Several coatings have been proposed for this, with nanostructured transition metal oxides being one of the most popular due to their high theoretical capacity and surface area. In this overview, the main techniques used to achieve these coatings-such as solvothermal synthesis, MOF-derived obtention, and electrochemical deposition-are summarized, as well as the main strategies for alleviating the low electrical conductivity of transition metal oxides, which is the main drawback of these materials.

The Newton-Raphson method is a fundamental root-finding technique with numerous applications in physics. In this study, we propose a parameterized variant of the Newton-Raphson method, inspired by principles from physics. Through analytical and empirical validation, we demonstrate that this approach offers increased robustness and faster convergence during root-finding iterations. Furthermore, we establish connections to the Adomian series method and provide a natural interpretation within a series framework. Remarkably, the introduced parameter, akin to a temperature variable, enables an annealing approach. This advancement sets the stage for a fresh exploration of numerical iterative root-finding methodologies.

The prolonged impact over the Tinto River estuary by both the significant pollution by acid mine drainage (AMD) affecting this river and the polluted releases from phosphogypsum (PG) piles has led to the severe environmental degradation of this ecosystem. The aim of this work was to assess the current environmental quality of the Tinto River estuary through the study of the spatial distribution of metal(loid)s and natural radionuclides in the surface sediments from the channel edge. The sediments contain mean concentrations 5-20 times higher than the background values for pollutants such as Zn, As, Cu, Pb, or U, and up to two orders of magnitude higher for P. The studied sediments are heavily polluted by toxic heavy metals and metalloids (Pb, Zn, Cu, and As) according to the US EPA guidelines. Most of the analyzed sediment samples are also strongly polluted by long-lived natural radionuclides, mainly U-isotopes and 210 Pb with concentrations up to one order of magnitude higher than unpolluted sediments, mostly due to the contribution by the PG leachates. The enrichment factors (EF) were extremely high (EF > 50) for As and very severe enrichment (25 ≤ EF < 50) for P, Cd, Zn, Cu, and Pb., (© 2024. The Author(s).)

Combining ionic liquids (ILs) and metal-organic frameworks (MOFs) can be an intriguing opportunity to develop advanced materials with different adsorption capabilities for environmental applications. This study reports the preparation and characterization of a 3D pillared-layered compound, namely, [Zn 2 (tz) 2 (bdc)] (CIM91), formed by 1,2,4-triazole (Htz) and 1,4-benzenedicarboxylic acid (H 2 bdc) ligands. Then, various loadings of the water-stable and hydrophobic IL, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF 6 ]), and the water-soluble 1-n-butyl-3-methylimidazolium chloride ([BMIM][Cl]) were incorporated into CIM91. Detailed characterization by X-ray powder diffraction (XRD), FT-IR spectra, scanning electron microscopy (SEM), Energy dispersive X-ray (EDX) analysis, N 2 adsorption measurements, and thermogravimetric analysis confirmed the formation of [BMIM][X]/CIM91 composites and the structural stability of the MOF after the incorporation of the ionic liquids. CO 2 adsorption-desorption analysis was experimentally carried out for all the materials at 298 K and 318 K, demonstrating a great enhancement in the CO 2 adsorption properties of the sole MOF CIM91, particularly by including [BMIM][PF 6 ] species in its structure with a double isosteric heat of CO 2 adsorption. The composites were also tested for the adsorption of methylene blue (MB) dye. The results indicate that the incorporation of [BMIM][X] into CIM91 can substantially modify the adsorption properties of the MOF. The influence of the nature of the [BMIM][X] anions on these properties has also been analyzed.

Elementary cellular automata are the simplest form of cellular automata, studied extensively by Wolfram in the 1980s. He discovered complex behavior in some of these automata and developed a classification for all cellular automata based on their phenomenology. In this paper, we present an algorithm to classify them more effectively by measuring difference patterns using the Hamming distance. Our classification aligns with Wolfram's and further categorizes them into additional subclasses. Finally, we have found a heuristic reasoning providing and explanation about why some rules evolve into fractal patterns., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Diglycidylether of vanillyl alcohol (DGEVA), in combination with mechanically recycled carbon fibers (RCFs), was used to make, via Radical-Induced Cationic Frontal Photopolymerization (RICFP), fully sustainable and bio-based conductive composites with good electrical conductivity and consequent Joule effect proprieties. Three different fiber lengths, using three different sieve sizes during the mechanical recycling process (0.2, 0.5, and 2.0 mm), were used in five different amounts (ranging from 1 to 25 phr). The samples were first characterized by dynamic mechanical thermal analysis (DMTA), followed byelectrical conductivity and Joule heating tests. More specifically, the mechanical properties of the composites increased when increasing fiber content. Furthermore, the composites obtained with the longest fibers showed the highest electrical conductivity, reaching a maximum of 11 S/m, due to their higher aspect ratio. In this context, the temperature reached by Joule effect was directly related to the electrical conductivity, and was able to reach an average and maximum temperatures of 80 °C and 120 °C, respectively, just by applying 6 V.

The variability arising from the LPBF process, the multitude of manufacturing parameters available, and the intrinsic anisotropy of the process, which causes different mechanical properties in distinct building directions, result in a wide range of variables that must be considered when designing industrial parts. To understand the effect of these variables on the LPBF manufacturing process, the performance of the AlSi10Mg alloy produced through this technique has been tested through several mechanical tests, including hardness, tensile, shear, and fracture toughness. The results have been correlated with the microstructure, together with manufacturing parameters, building directions, border scanning strategy, and layer height. Significant differences were observed for each mechanical behavior depending on the configuration tested. As a result, an anisotropic material model has been developed from tested samples, which allows to numerically model the alloy and is unique in the current literature., Competing Interests: The authors declare no conflict of interest.

Phycoerythrin (PE) extraction from Porphyridium sp. was studied employing ultrasound-assisted extraction combined with aqueous mixtures of two imidazolium-based ionic liquids (ILs) simultaneously, marking a significant novelty. A face-centred central composite design and response surface optimised PE yield (E PE ), considering the effects of ionic liquid concentration (IL), [Emim][EtSO 4 ]/[Bmim][EtSO 4 ] mass ratio (E/B), biomass concentration (BM), and time (t). Improvements in E PE by 300 % and 115 % were achieved compared to a phosphate buffer solution and the freeze-thaw method, respectively. Temperature and pH effects were examined independently, leading to the determination of optimal operating conditions: BM = 10 mg mL -1 , IL = 18.6 wt%, E/B = 0.78/0.22, t = 10 min, T = 35 °C, and pH = 7.5. Results indicated the potential for reusing the ILs for at least five consecutive extraction cycles, maintaining an E PE of 94.2 % compared to fresh ones. This underscores the success and innovation of the developed technology in enhancing PE extraction from Porphyridium sp., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)