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    Coupling glycerol oxidation reaction using Ni-Co foam anodes to CO2 electroreduction in gas-phase for continuous co-valorization

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    Electrocatalytic reduction of CO2 is a promising alternative for storing energy and producing valuable products, such as formic acid/formate. Continuous gas-phase CO2 electroreduction has shown great potential in producing high concentrations of formic acid or formate at the cathode while allowing the oxygen evolution or the hydrogen oxidation reactions to occur at the anode. It is advantageous to use a more relevant oxidation reaction, such as glycerol which is a plentiful by-product of current biodiesel production process. This work successfully manages to couple the glycerol oxidation reaction with continuous gas-phase CO2 electroreduction to formate with the implementation of Ni-Co foam-based anodes. The MEA-electrolyzer developed can achieve significantly high formate concentrations of up to 359 g L-1 with high Faradaic efficiencies of up to 95%, while also producing dihydroxyacetone at a rate of 0.434 mmol m−2 s−1. In comparison with existing literature, this represents an excellent trade-off between relevant figures of merit and can remarkably contribute to a future implementation of this coupled electrochemical system approach at larger scales.The authors gratefully acknowledge financial support through projects PID2019-108136RB-C31, PID2019-108136RB-C32 and PID2019-108136RB-C33, PID2020-112845RB-I00, TED2021–129810B-C21 and PLEC2022-009398 (MCIN/AEI/10.13039/501100011033 and Unión Europea Next GenerationEU/PRTR). This project has received funding from the European Union’s Horizon Europe research and innovation programme under grant agreement No 101118265​

    An ontology-based secure design framework for graph-based databases

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    Graph-based databases are concerned with performance and flexibility. Most of the existing approaches used to design secure NoSQL databases are limited to the final implementation stage, and do not involve the design of security and access control issues at higher abstraction levels. Ensuring security and access control for Graph-based databases is difficult, as each approach differs significantly depending on the technology employed. In this paper, we propose the first technology-ascetic framework with which to design secure Graph-based databases. Our proposal raises the abstraction level by using ontologies to simultaneously model database and security requirements together. This is supported by the TITAN framework, which facilitates the way in which both aspects are dealt with. The great advantages of our approach are, therefore, that it: allows database designers to focus on the simultaneous protection of security and data while ignoring the implementation details; facilitates the secure design and rapid migration of security rules by deriving specific security measures for each underlying technology, and enables database designers to employ ontology reasoning in order to verify whether the security rules are consistent. We show the applicability of our proposal by applying it to a case study based on a hospital data access control.This work has been developed within the AETHER-UA (PID2020-112540RB-C43), AETHER-UMA (PID2020-112540RB-C41) and AETHER-UCLM (PID2020-112540RB-C42), ALBA (TED2021-130355B-C31, TED2021-130355B-C33), PRESECREL (PID2021-124502OB-C42) projects funded by the “Ministerio de Ciencia e Innovación, Spain”, Andalusian PAIDI program with grant (P18-RT-2799) and the BALLADER Project (PROMETEO/2021/088) funded by the “Consellería de Innovación, Universidades, Ciencia Sociedad Digital”, Generalitat Valenciana, Spain . Funding for open access charge: Universidad de Málaga / CBUA

    Fibroblast-derived extracellular vesicles as trackable efficient transporters of an experimental nanodrug with fibrotic heart and lung targeting

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    The discovery of extracellular vesicles (EVs) as efficient exogenous biotransporters of therapeutic agents into cells across biological membranes is an exciting emerging field. Especially the potential of EVs as targeted delivery systems for diseases with selective treatments, such as fibrosis, whose treatment causes side effects in other organs not involved in the disease. Methods: In this study, we collected embryonic fibroblast-derived EVs from two different centrifugation fractions, 10 K g and 100 K g fractions from a NIH-3T3 cell line loaded with an experimental drug. Mice with fibrotic hearts and lungs were obtained by administration of angiotensin II. We generated fluorescent EVs and bioluminescent drug to observe their accumulation by colocalization of their signals in fibrotic heart and lung. The biodistribution of the drug in various organs was obtained by detecting the Au present in the drug nanostructure. Results: The drug-loaded EVs successfully reduced fibrosis in pathological fibroblasts in vitro, and modified the biodistribution of the experimental drug, enabling it to reach the target organs in vivo. We described the pre-analytical characteristics of EVs related to physical variables, culture and harvesting conditions, crucial for their in vivo application as nanotransporters using a previously validated protein-based antifibrotic drug. The results showed the colocalization of EVs and the experimental drug in vivo and ex vivo and the efficient reduction of fibrosis in vitro. This work demonstrates that 10K-EVs and 100K-EVs derived from fibroblasts can act as effective biotransporters for targeted drug delivery to profibrotic fibroblasts, lungs, or heart.The discovery of extracellular vesicles (EVs) as efficient exogenous biotransporters of therapeutic agents into cells across biological membranes is an exciting emerging field. Especially the potential of EVs as targeted delivery systems for diseases with selective treatments, such as fibrosis, whose treatment causes side effects in other organs not involved in the disease. Methods: In this study, we collected embryonic fibroblast-derived EVs from two different centrifugation fractions, 10 K g and 100 K g fractions from a NIH-3T3 cell line loaded with an experimental drug. Mice with fibrotic hearts and lungs were obtained by administration of angiotensin II. We generated fluorescent EVs and bioluminescent drug to observe their accumulation by colocalization of their signals in fibrotic heart and lung. The biodistribution of the drug in various organs was obtained by detecting the Au present in the drug nanostructure. Results: The drug-loaded EVs successfully reduced fibrosis in pathological fibroblasts in vitro, and modified the biodistribution of the experimental drug, enabling it to reach the target organs in vivo. We described the pre- analytical characteristics of EVs related to physical variables, culture and harvesting conditions, crucial for their in vivo application as nanotransporters using a previously validated protein-based antifibrotic drug. The results showed the colocalization of EVs and the experimental drug in vivo and ex vivo and the efficient reduction of fibrosis in vitro. This work demonstrates that 10K-EVs and 100K-EVs derived from fibroblasts can act as effective biotransporters for targeted drug delivery to profibrotic fibroblasts, lungs, or heart. Conclusion: We observed that fibroblast-derived 10K-EVs and 100K-EVs are useful biotransporters encapsulating a new generation drug leading to a reduction of fibrosis in profibrotic fibroblasts in vitro. In addition, drug containing EVs were shown to reach fibrotic heart and lungs in vivo, enhancing free drug biodistribution.Acknowledgements. This work was partially supported by Agencia Estatal de Investigación, Spain PID2021-125702OBI00; RTI2018-095214-B-I00). A.L.C. acknowledges support by the European Research Council grant ERC-CoG-648071-ProNANO; the Agencia Estatal de Investigación Grant PDC2021-120957-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by the “European Union NextGenerationEU/PRTR” and Grant PID2019-111649RB-I00-ProTools funded by MCIN/AEI/ 10.13039/501100011033; and the Basque Government (RIS3-2019222005). G.G. thanks the financial support of “la Caixa” Foundation (ID100010434, fellowship: LCF/BQ/DI20/11780020). This work was performed under the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency – Grant No. MDM-2017-0720 (CIC biomaGUNE). We thank Dr. L Martin-Jaular, and the Institut Curie EV platform, for helpful discussion. We thank Dr. S Mobini and Dr. M.U. González for their collaboration with the tracking analysis studies. We express our gratitude to Dr. V Gabarra for her valuable advice and assistance in finalizing the text

    Photodegradation kinetics and halogens release of the emerging concern pollutants dexamethasone and S-metolachlor on TiO2/rGO composites

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    This work studies the photocatalytic degradation of solutions containing 0.11 mM of a glucocorticoid (dexamethasone, DEX) and 0.11 mM of an herbicide (S-metolachlor, MTLC), organohalogenated compounds containing fluorine and chlorine atoms in their molecules, respectively. To treat 1 L volume, a mass of 0.5 g of TiO2/rGO composite in suspension has been used as photocatalyst, irradiated with UV-A LEDs with 200 W m−2 of irradiance. MTLC is partially adsorbed on the surface of the catalyst, while DEX is not adsorbed, showing different degradation kinetics. The halogen ions released into the solution from the breakage of the parent molecules, F− and Cl− respectively, were analysed. In the case of MTLC, the released Cl− followed two different kinetic trends, being faster, and with a rate that matched the rate of MTLC disappearance, the part corresponding to non-adsorbed MTLC. In the experiments with DEX solutions a different behaviour was observed; the released F− in the photocatalytic degradation was partially adsorbed on the catalyst surface, but the adsorption capacity decreased with the use of the photocatalyst in consecutive cycles until the solubilised F− matched the degraded concentration of DEX. Furthermore, the mass balance between the degraded contaminant and the solubilised halogen anion, for both contaminants, allowed to conclude the absence of halogenated intermediates under the final operating conditions, that is a remarkable outcome in water remediation processes.These results are part of the R&D projects PID2021-122563OB-I00 funded by MCIN/AEI/10.13039/501100011033 and “ERDF A way of making Europe” and PDC2022-133563-I00, funded by MCIN/AEI/10.13039/501100011033 and “UE Next Generation EU/PRTR”. Carmen Barquín is also grateful for the FPI contract PRE2019-089096

    Computation of parabolic cylinder functions having complex argument

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    Numerical methods for the computation of the parabolic cylinder function U(a,z) for real a and complex z are presented. The main tools are recent asymptotic expansions involving exponential and Airy functions, with slowly varying analytic coefficient functions involving simple coefficients, and stable integral representations; these two main methods can be complemented with Maclaurin series and a Poincaré asymptotic expansion. We provide numerical evidence showing that the combination of these methods is enough for computing the function with 5 × 10-13 relative accuracy in double precision floating point arithmetic.The authors acknowledge financial support from Ministerio de Ciencia e Innovación, projects PGC2018-098279-B-I00 (MCIN/AEI/10.13039/ 501100011033/FEDER “Una manera de hacer Europa”) and PID2021-127252NB-I00 (MCIN/AEI/10.13039/ 501100011033/FEDER, UE)

    Impacto clínico del diagnóstico genético en la hipoacusia del adulto

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    Tesis doctoral en período de exposición públicaMedicina y Ciencias de la Salu

    Solubility of difluoromethane (R-32) and pentafluoroethane (R-125) in 1-alkyl-3-methylimidazolium tricyanomethanide ionic liquids

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    The recovery of refrigerant blends and the subsequent separation of value-added hydrofluorocarbons (HFCs) for reuse would help to meet the phase-down in the production of virgin HFCs established by the Kigali Amendment to the Montreal Protocol. The use of ionic liquids (ILs) in extractive distillation processes has become particularly relevant. In this process, the selection of the IL is the core element for a technically and economically feasible design. For this purpose, the absorption of the HFCs difluoromethane (R-32) and pentafluoroethane (R-125), components of the equimassic mixture R-410A, in 1-alkyl-3-methylimidazolium tricyanomethanide ILs was studied. The isochoric saturation method was applied to report vapor-liquid equilibrium data over a temperature range of 283.15–323.15 K and up to 0.9 MPa. These data were fitted accurately to the NRTL activity coefficient model and the Henry's law constants, the activity coefficients at infinite dilution, the enthalpies and entropies of solvation and the thermodynamic mixing properties were calculated. Finally, [C2C1im][tcm] ranked as one of the most selective ILs to date, exhibiting a good R-32 absorption capacity that could make it a valuable solvent for the separation of R-410A by extractive distillation.The authors acknowledge the financial support of MCIN/AEI/10.13039/501100011033 and the European Union NextGenerationEU/PRTR to projects PID2019–105827RB-I00 and TED2021–129844B-I00. F. Pardo thanks the postdoctoral fellowship IJC2020–043134-I “Juan de la Cierva Incorporación”. M. Viar acknowledges the Concepción Arenal UC-22–23 pre-doctoral fellowship, funded by the University of Cantabria and the Government of Cantabria

    Unlocking energy potential: decarbonizing water reclamation plants with salinity gradient energy recovery

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    Climate change, together with the ecological droughts suffered by a large part of the European Union's territory, calls for joint environmental solutions. In this regard, water reclamation is a promising way to alleviate the pressure on existing water resources. However, reuse strategies are penalized by the extra energy consumed in urban wastewater treatment plants (UWWTPs), facilities mainly powered by fossil fuels. The opportunity to integrate renewable sources of energy into the energy-intensive UWWTPs holds great promise towards decarbonization of the sector. In this context, the energy harvested from a Salinity Gradient (SGE) has attracted great interest in the last decade. This work aims at the analysis of opportunity of implementing integrated processes for water reclamation and SGE recovery in the coastal EU UWWTPs. According to the selection criteria, a total of 281 potential sites located across eighteen coastal countries of the EU have been inventoried attending to the current state of the art. The water reclamation potential has been estimated at 3.7 million m3/day. As a consequence, the environmental burdens of the reclamation process could result in the reduction of 1.5·105 t CO2/year. The Mediterranean region, highly affected by hydrological drought, has proved to be a hot spot for water reclamation, with the highest number of plants inventoried in the study and a predicted potential for SGE harvesting of 60 Wh/m3 of reclaimed water. These results highlight a niche of opportunities to encourage water reclamation, avoid water bodies' degradability due to effluent discharge and the further decarbonization of reclamation processes.This research work is supported by the European LIFE Programme (LIFE19 ENV/ES/000143), and the projects RTI2018-093310-B-I00, PID2020-115409RB-I00, PDC2021-120786-I00 and PLEC2021-007718 funded by the Spanish Ministry of Science and Innovation

    Polarization-independent hollow nanocuboid metasurfaces with robust quasi-bound states in the continuum

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    All-dielectric metasurfaces supporting resonant quasi-bound states in the continuum (qBIC) offer an ideal platform for various applications relying on intense light-matter interaction in highly localized and enhanced fields. Here, we propose a dielectric metasurface composed of hollow GaP nanocuboid quadrumers periodically arranged on a silica substrate. The metasurface supports a qBIC resonant mode with an antiferroelectric field configuration, which is very robust to large perturbations of the cuboid structure thanks to its perpendicular electric dipole field profile. The perturbed quadrumer arrangement retains C 4v symmetry, thus allowing for polarization-independent optical response for normally incident planewaves. In addition, the resonant mode dispersion is investigated, revealing interesting features, such as low birefringence along the contour of the Brillouin zone and very low dispersion for the TM polarization along the direction. The metasurface is designed to resonate close to , which is highly relevant for Raman spectroscopy, leveraging the strong field enhancement at the interface with the overlayer material. Moreover, its performance as a bulk refractometric sensor is discussed. The proposed dielectric metasurface is promising for emerging photonic phenomena where strong light-matter interaction plays a key role.This work was supported by the CNR-FAPESP biennial (2022–2023) bilateral project StReAM “Strongly Resonant All-dielectric Metasurfaces based on quasi-dark and toroidal modes” and by the projects PID2019-107270RB-C21, PDC2021-121172-C21 and TED2021-1303 78B-C21 funded by MCIN/AEI/10.13039/501100011033, FEDER and EU NextGenerationEU. J.F.A. received funding from Ministerio de Ciencia, Innovación Universidades of Spain under Juan de la Cierva-Incorporación grant. V.D. thanks the Brazilian Agency National Council of Technological and Scientific Development (CNPq) for financial support. D.C.Z. and F.D’O. acknowledge the support of the project PRIN-2022 ALPHA “ALl-dielectric resonant metasurfaces enhancing PHoton emission phenomenA” (CUP:D53D23001060006) funded by the Italian Ministry of University and Research. H.E.H.F. acknowledges the financial support of the São Paulo Research Foundation (FAPESP), projects 2015/24517-8 (Thematic), 2021/11380-5 (CCD/CPTEn), and 2021/06506-0 (CNR Italy); and the Brazilian Council for Scientific and Technological Development (CNPq), projects 312714/2019-0 (HEHF) and 433175/2018-4 (Universal). F. D.’O acknowledges the support of the European Union under the Italian National Recovery and Resilience Plan (NRRP) of NextGenerationEU , partnership on “Telecommunications of the Future” (PE00000001 - program “RESTART”)

    Electrochemical degradation of key drugs to treat COVID-19: experimental analysis of the toxic by-products formation (PCDD/Fs)

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    Drug consumption has grown exponentially in recent decades, particularly during the COVID-19 pandemic, leading to their presence in various water sources. In this way, degradation technologies for pollutants, such as electrochemical oxidation (ELOX), have become crucial to safeguard the quality of natural resources. This study has as its starting point a previous research, which demonstrated the efficacy of ELOX in the removal of COVID-19 related-drugs, such as dexamethasone (DEX), paracetamol (PAR), amoxicillin (AMX), and sertraline (STR), using the electrolytes NaCl and Na2SO4. The present research aims to study the potential risks associated with the generation of toxic by-products, during the ELOX of cited drugs, specifically focusing on the highly chlorinated persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Dioxins and furans can be formed potentially in electrochemical systems from precursor molecules or non-precursor molecules in chloride medium. First, the degradation of the parent compounds was found to be complete. At this point, a comprehensive investigation was conducted to identify and analyse the by-products formed during the degradation process; precursors of PCDD/Fs, such as chlorophenols or hydroquinones were identified. Additionally, in continuation of the previous study, PCDD/Fs congeners were investigated, revealing elevated concentrations; the highest concentration obtained was for the congener 1,2,3,4,6,7,8-HpCDF (234.6 pg L-1 in NaCl) during degradation of the AMX. Finally, an assessment of the toxicity based on TEQ values was conducted, with DEX exhibiting the highest concentration among all compounds: 30.1 pg L-1 for NaCl medium. Therefore, the formation of minor by-products should not be underestimated, as they can significantly enhance the toxicity of the final sample, so the selection of the appropriate remediation technology, as well as the optimization of experimental operating variables, is determining in the treatment of pharmaceutical-contaminated waters.This research was developed in the framework of the project PID2020-115409RB-I00 (MCIN/AEI) financed by the Spanish Ministry of Science and Innovation. Sophie Schröder is also grateful for the FPI predoctoral contract, PRE2018-083526

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