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The progressive increase in nitrate's (NO3-) presence in surface and groundwater enhances environmental and human health risks. The aim of this work is the fabrication and characterization of sensitive, real-time, low-cost, and portable amperometric sensors for low NO3- concentration detection in water. Copper (Cu) micro-flowers were electrodeposited on top of carbon screen-printed electrodes (SPCEs) via cyclic voltammetry (with voltage ranging from -1.0 V to 0.0 V at a scan rate of 0.1 V s-1). The obtained sensors exhibited a high catalytic activity toward the electro-reduction in NO3-, with a sensitivity of 44.71 µA/mM. They had a limit of detection of 0.87 µM and a good dynamic linear concentration range from 0.05 to 3 mM. The results were compared to spectrophotometric analysis. In addition, the devices exhibited good stability and a maximum standard deviation (RSD) of 5% after ten measurements; reproducibility, with a maximum RSD of 4%; and repeatability after 10 measurements with the RSD at only 5.63%.
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Innovation is essential around the themes of climate change and sustainability. Commercial photovoltaics (PV) have noticeably contributed to getting to 22.1% share of the gross final energy consumption in Europe from renewable sources in 2020 but a steep further increase is urgent in the near future. Over the last few years, great success has been achieved by perovskites applied to PV, with mixed anions and cations in shared lattices that reached record efficiency values close to those of Si in laboratory-scale solar cells (â¼26%). Their use has recently shed light on a medium/long-term compositional instability that arises from the partial miscibility of the species with similar role in the atomic lattice. The chemical route to prepare the materials for Perovskite Solar Cells (PSCs) also needs to be critically reviewed. Material waste and reuse are other concerns to be faced. This perspective paper indeed tackles some aspects for innovation and sustainability on the PSC field for production purposes. Some hints for technologically affordable processes based on in-vacuum deposition of Perovskites are provided in light of their sustainability and for the need to reduce production/maintenance costs. It is also discussed how to make in-vacuum production further competitive by boosting the material quality. Innovation is also projected into the theme of making sustainable choices for device architectures and materials. Carbon-based PSCs are highly focused since they allow avoiding the use of complex, unstable and costly HTLs. From the material side, pros and cons of using fully inorganic CsPbI3 are commented, framed by the current revival of single-cation perovskites. CsPbI3, in particolar, enables recycling and reuse initiatives thanks to the overall mass preservation under degradation. Some closing remarks are provided on the safe use of Pb as its effective sequestration before release from the PSC into the environment is properly engineered. We lastly trust that initiatives bringing together academic and industrial know-how in complementary fields able to take up responsible innovation will contribute to accelerating the ecological transition and will enable the societal transformation to fulfil the 2050 EU agenda for a sustainable future.
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We provide a semi-empirical model based on in situ degradation measurements to predict the durability of hybrid perovskite materials under simulated thermal operation conditions. In the model, the degradation path of MAPbI3 layers is proved to follow an Arrhenius-type law. The predictive role is played by the activation energy combined with its pre-exponential factor. Our comparative study under moisture conditions with respect to vacuum and nitrogen treatments has assessed the occurrence of an intrinsic dynamic exchange of protons between the organic cations and the inorganic cage with a direct impact on the lattice stability, for which the presence of water molecules is not mandatory. This mutual interaction produces defects inside the material and volatile species, such as HI, CH3NH2 or MAI, with an associated experimental activation energy of 1.54 eV measured under vacuum conditions in dark. This value is comparable to that calculated by the density functional theory for defect generation in MAPbI3. In air, the action of water molecules reduces the activation energy for proton exchanges in dark to 0.96 eV. As an alternative solution to increase the material stability, we demonstrate that the substitution of methylammonium (MA(+)) with the formamidinium (FA(+)) cations inside the inorganic cage gives greater robustness to the overall lattice and extends the material durability due to a different interaction between the organic molecules and the inorganic cage. This definitely supports the use of FAPbI3 in applications, provided its structure can be stabilized in the dark phase at room temperature.
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We investigate the degradation path of MAPbI3 (MA=methylammonium) films over flat TiO2 substrates at room temperature by means of X-ray diffraction, spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI2 . We describe how this degradation product is structurally coupled with the original MAPbI3 lattice through the orientation of its constituent PbI6 octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH3 NH2 or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.
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In this paper, the structural and electrical modifications induced, in the nanoscale, by a rapid thermal oxidation process on AlGaN/GaN heterostructures, are investigated. A local rapid oxidation (900 ° C in O2, 10 min) localized under the anode region of an AlGaN/GaN diode enabled a reduction of the leakage current with respect to a standard Schottky contact. The insulating properties of the near-surface oxidized layer were probed by a nanoscale electrical characterization using scanning probe microscopy techniques. The structural characterization indicated the formation of a thin uniform oxide layer on the surface, with preferential oxidation paths along V-shaped defects penetrating through the AlGaN/GaN interface. The oxidation process resulted in an expansion of the lattice parameters due to the incorporation of oxygen atoms, accompanied by an increase of the crystal mosaicity. As a consequence, a decrease of the sheet carrier density of the two-dimensional electron gas and a positive shift of the threshold voltage are observed. The results provide useful insights for a possible future integration of rapid oxidation processes during GaN device fabrication.
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BACKGROUND: We aimed to investigate the effect of cell-cell dipole interactions in the equilibrium distributions in dielectrophoretic devices. METHODS: We used a three dimensional coupled Monte Carlo-Poisson method to theoretically study the final distribution of a system of uncharged polarizable particles suspended in a static liquid medium under the action of an oscillating non-uniform electric field generated by polynomial electrodes. The simulated distributions have been compared with experimental ones observed in the case of MDA-MB-231 cells in the same operating conditions. RESULTS: The real and simulated distributions are consistent. In both cases the cells distribution near the electrodes is dominated by cell-cell dipole interactions which generate long chains. CONCLUSIONS: The agreement between real and simulated cells' distributions demonstrate the method's reliability. The distribution are dominated by cell-cell dipole interactions even at low density regimes (105 cell/ml). An improved estimate for the density threshold governing the interaction free regime is suggested.
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Comunicación Celular , Electroforesis/instrumentación , Algoritmos , Línea Celular Tumoral , Impedancia Eléctrica , Electrodos , Humanos , Método de Montecarlo , Distribución de PoissonRESUMEN
An improvement of water supply and sanitation and better management of water resources, especially in terms of water reuse, is one of the priorities of the European Green Deal. In this context, it is crucial to find new strategies to recycle wastewater efficiently in a low-cost and eco-friendly manner. The immobilization of inorganic nanomaterials on polymeric matrices has been drawing a lot of attention in recent years due to the extraordinary properties characterizing the as-obtained nanocomposites. The hybrid materials, indeed, combine the properties of the polymers, such as flexibility, low cost, mechanical stability, high durability, and ease of availability, with the properties of the inorganic counterpart. In particular, if the inorganic fillers are nanostructured photocatalysts, the materials will be able to utilize the energy delivered by light to catalyze chemical reactions for efficient wastewater treatment. Additionally, with the anchoring of the nanomaterials to the polymers, the dispersion of the nanomaterials in the environment is prevented, thus overcoming one of the main limits that impede the application of nanostructured photocatalysts on a large scale. In this work, we will present nanocomposites made of polymers, i.e., polymethyl methacrylate (PMMA), and photocatalytic semiconductors, i.e., TiO2 nanoparticles (Evonik). MoS2 nanoflakes were also added as co-catalysts to improve the photocatalytic performance of the TiO2. The hybrid materials were prepared using the sonication and solution casting method. The nanocomposites were deeply characterized, and their remarkable photocatalytic abilities were evaluated by the degradation of two common water pollutants: methyl orange and diclofenac. The relevance of the obtained results will be discussed, opening the route for the application of these materials in photocatalysis and especially for novel wastewater remediation.
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Fostered by the top power conversion efficiencies (PCEs) of lab-scale devices, industrialization of perovskite solar cells is underway. Nevertheless, the intrinsically poor stability of these materials still represents a major concern. Herein, inspired by Nature, the use of ß-carotene in perovskite solar cells is proposed to mimic its role as a protective pigment, as occurs in natural photosynthesis. Laser-mediated photostability (LMPS) assessment, Fourier-transform infrared spectra analysis acquired in attenuate total reflectance (ATR-FTIR), spectroscopy ellipsometry (SE), and time-resolved photoluminescence (TRPL) measurements under stress conditions prove that the inclusion of a thin ß-carotene interlayer promotes a high improvement in the photostability of the perovskite films against photooxidation. Importantly, this is accompanied by an improvement of the solar cell PCE that approaches 20% efficiency with no hysteresis, which is among the highest values reported for a mixed halide (I-Br) perovskite with a band gap of 1.74 eV, relevant for coupling with silicon in tandem cells.
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In this study, we explore the potential of a blended material comprising CsPbI3:EuCl3 perovskite and Gig-Lox TiO2, a unique transparent spongy material known for its multi-branched porous structure, for application in solar cells. The inclusion of EuCl3 in CsPbI3 serves to stabilize the photoactive γ-phase with a bandgap of 1.75 eV, making it suitable for solar energy conversion in tandem solar cells. Our study applies X-ray-based techniques to investigate the structural properties and interfacial behavior within this blended material, in comparison with a reference perovskite layer deposited on glass. In addition, Spectroscopic ellipsometry is complemented with density functional theory calculations and photoluminescence measurements to elucidate the absorption and radiative emission properties of the blend. Notably, our findings reveal a significant quenching of photoluminescence within the blended material, underscoring the pivotal role of the distributed interfaces in facilitating efficient carrier injection from the CsPbI3:EuCl3 perovskite into the Gig-Lox TiO2 sponge. These findings pave the way for the application of the blend as an Electron Transport Layer (ETL) in semi-transparent perovskite solar cells for tandem and building integrated photovoltaics.
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The importance of lead analysis in environmental matrices becomes increasingly relevant due to the anthropogenic spread of toxic species in nature. Alongside the existing analytical methods to detect lead in a liquid environment, we propose a new dry approach for lead detection and measurement based on its capture from a liquid solution by a solid sponge and subsequent quantification based on X-ray analyses. The detection method exploits the relationship between the electronic density of the solid sponge, which depends on the captured lead, and the critical angle for total reflection of the X-rays. For this purpose, gig-lox TiO2 layers, grown by modified sputtering physical deposition, were implemented for their branched multi-porosity spongy structure that is ideal for capturing lead atoms or other metallic ionic species in a liquid environment. The gig-lox TiO2 layers grown on glass substrates were soaked into aqueous solutions containing different concentrations of Pb, dried after soaking, and finally probed through X-ray reflectivity analyses. It has been found that lead atoms are chemisorbed onto the many available surfaces within the gig-lox TiO2 sponge by establishing stable oxygen bonding. The infiltration of lead into the structure causes an increase in the overall electronic density of the layer and, thus, an increment of its critical angle. Based on the established linear relationship between the amount of lead adsorbed and the augmented critical angle, a standardized quantitative procedure to detect Pb is proposed. The method can be, in principle, applied to other capturing spongy oxides and toxic species.
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Replication Protein A (RPA) is a heterotrimeric single stranded DNA-binding protein with essential roles in DNA replication, recombination and repair. Little is known about the structure of RPA in Archaea, the third domain of life. By using an integrative structural, biochemical and biophysical approach, we extensively characterize RPA from Pyrococcus abyssi in the presence and absence of DNA. The obtained X-ray and cryo-EM structures reveal that the trimerization core and interactions promoting RPA clustering on ssDNA are shared between archaea and eukaryotes. However, we also identified a helical domain named AROD (Acidic Rpa1 OB-binding Domain), and showed that, in Archaea, RPA forms an unanticipated tetrameric supercomplex in the absence of DNA. The four RPA molecules clustered within the tetramer could efficiently coat and protect stretches of ssDNA created by the advancing replisome. Finally, our results provide insights into the evolution of this primordial replication factor in eukaryotes.
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Replicación del ADN , Proteína de Replicación A , Proteína de Replicación A/metabolismo , ADN/metabolismo , ADN de Cadena Simple/genética , Reparación del ADN , Unión ProteicaRESUMEN
Mesothelin (MSLN) is an attractive immuno-oncology target, but the development of MSLN-targeting therapies has been impeded by tumor shedding of soluble MSLN (sMSLN), on-target off-tumor activity, and an immunosuppressive tumor microenvironment. We sought to engineer an antibody-based, MSLN-targeted T-cell engager (αMSLN/αCD3) with enhanced ability to discriminate high MSLN-expressing tumors from normal tissue, and activity in the presence of sMSLN. We also studied the in vivo antitumor efficacy of this molecule (NM28-2746) alone and in combination with the multifunctional checkpoint inhibitor/T-cell co-activator NM21-1480 (αPD-L1/α4-1BB). Cytotoxicity and T-cell activation induced by NM28-2746 were studied in co-cultures of peripheral blood mononuclear cells and cell lines exhibiting different levels of MSLN expression, including in the presence of soluble MSLN. Xenotransplant models of human pancreatic cancer were used to study the inhibition of tumor growth and stimulation of T-cell infiltration into tumors induced by NM28-2746 alone and in combination with NM21-1480. The bivalent αMSLN T-cell engager NM28-2746 potently induced T-cell activation and T-cell mediated cytotoxicity of high MSLN-expressing cells but had much lower potency against low MSLN-expressing cells. A monovalent counterpart of NM28-2746 had much lower ability to discriminate high MSLN-expressing from low MSLN-expressing cells. The bivalent molecule retained this discriminant ability in the presence of high concentrations of sMSLN. In xenograft models, NM28-2746 exhibited significant tumor suppressing activity, which was significantly enhanced by combination therapy with NM21-1480. NM28-2746, alone or in combination with NM21-1480, may overcome shortcomings of previous MSLN-targeted immuno-oncology drugs, exhibiting enhanced discrimination of high MSLN-expressing cell activity in the presence of sMSLN.
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Antineoplásicos , Mesotelina , Humanos , Proteínas Ligadas a GPI/genética , Linfocitos T , Leucocitos Mononucleares/metabolismo , Antineoplásicos/farmacologíaRESUMEN
Hybrid photovoltaics (H-PV), initiated as dye-sensitized solar cells (DSC) by prof [...].
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Copper oxide thin films have been successfully synthesized through a metal-organic chemical vapor deposition (MOCVD) approach starting from the copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), Cu(tmhd)2, complex. Operative conditions of fabrication strongly affect both the composition and morphologies of the copper oxide thin films. The deposition temperature has been accurately monitored in order to stabilize and to produce, selectively and reproducibly, the two phases of cuprite Cu2O and/or tenorite CuO. The present approach has the advantages of being industrially appealing, reliable, and fast for the production of thin films over large areas with fine control of both composition and surface uniformity. Moreover, the methylammonium lead iodide (MAPI) active layer has been successfully deposited on the ITO/Cu2O substrate by the Low Vacuum Proximity Space Effusion (LV-PSE) technique. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM) analyses have been used to characterize the deposited films. The optical band gap (Eg), ranging from 1.99 to 2.41 eV, has been determined through UV-vis analysis, while the electrical measurements allowed to establish the p-type conductivity behavior of the deposited Cu2O thin films with resistivities from 31 to 83 Ω cm and carrier concentration in the order of 1.5-2.8 × 1016 cm-3. These results pave the way for potential applications of the present system as a hole transporting layer combined with a perovskite active layer in emergent solar cell technologies.
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The realization of stable inorganic perovskites is crucial to enable low-cost solution-processed photovoltaics. However, the main candidate material, CsPbI3, suffers from a spontaneous phase transition at room temperature towards a photo-inactive orthorhombic δ-phase (yellow phase). Here we used theoretical and experimental methods to study the structural and electronic features that determine the stability of the CsPbI3 perovskite. We argued that the two physical characteristics that favor the black perovskite phase at low temperatures are the strong spatial confinement in nanocrystalline structures and the level of electron doping in the material. Within this context, we discussed practical procedures for the realization of long-lasting inorganic lead halide perovskites.
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We present a method for the simulation of the kinetic evolution in the sub µs timescale for composite materials containing regions occupied by alloys, compounds, and mixtures belonging to the Ni-Si-C ternary system. Pulsed laser irradiation (pulses of the order of 100 ns) promotes this evolution. The simulation approach is formulated in the framework of the phase-field theory and it consists of a system of coupled non-linear partial differential equations (PDEs), which considers as variables the following fields: the laser electro-magnetic field, the temperature, the phase-field and the material (Ni, Si, C, C clusters and Ni-silicides) densities. The model integrates a large set of materials and reaction parameters which could also self-consistently depend on the model variables. A parameter calibration is also proposed, specifically suited for the wavelength of a widely used class of excimer lasers (λ = 308 nm). The model is implemented on a proprietary laser annealing technology computer-aided design (TCAD) tool based on the finite element method (FEM). This integration allows, in principle, numerical solutions in systems of any dimension. Here we discuss the complex simulation trend in the one-dimensional case, considering as a starting state, thin films on 4H-SiC substrates, i.e., a configuration reproducing a technologically relevant case study. Simulations as a function of the laser energy density show an articulated scenario, also induced by the variables' dependency of the materials' parameters, for the non-melting, partial-melting and full-melting process conditions. The simulation results are validated by post-process experimental analyses of the microstructure and composition of the irradiated samples.
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Halide perovskites containing a mixture of formamidinium (FA+), methylammonium (MA+) and cesium (Cs+) cations are the actual standard for obtaining record-efficiency perovskite solar cells. Although the compositional tuning that brings to optimal performance of the devices has been largely established, little is understood on the role of even small quantities of MA+ or Cs+ in stabilizing the black phase of FAPbI3 while boosting its photovoltaic yield. In this paper, we use Car-Parrinello molecular dynamics in large supercells containing different ratios of FA+ and either MA+ or Cs+, in order to study the structural and kinetic features of mixed perovskites at room temperature. Our analysis shows that cation mixing relaxes the rotational disorder of FA+ molecules by preferentially aligning their axis toward ⟨100⟩ cubic directions. The phenomenon stems from the introduction of additional local minima in the energetic landscape, which are absent in pure FAPbI3 crystals. As a result, a higher structural order is achieved, characterized by a pronounced octahedral tilting and a lower vibrational activity for the inorganic framework. We show that both MA+ and Cs+ are qualified for this enhancement, with Cs+ being particularly effective when diluted within the FAPbI3 perovskite.
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Single crystals represent a benchmark for understanding the bulk properties of halide perovskites. We have indeed studied the dielectric function of lead bromide perovskite single crystals (MAPbBr3, CsPbBr3 and for the first time FAPbBr3) by spectroscopic ellipsometry in the range of 1-5 eV while varying the temperature from 183 to 440 K. An extremely low absorption coefficient in the sub-band gap region was found, indicating the high optical quality of all three crystals. We extracted the band gap values through critical point analysis showing that Tauc-based values are systematically underestimated. The two structural phase transitions, i.e., orthorhombic-tetragonal and tetragonal-cubic, show distinct optical behaviors, with the former having a discontinuous character. The cross-correlation of optical data with DFT calculations evidences the role of octahedral tilting in tailoring the value of the band gap at a given temperature, whereas differences in the thermal expansion affect the slope of the band gap trend as a function of temperature.
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Carbon-based top electrodes for hole-transporting-layer-free perovskite solar cells (PSCs) were made by hot press (HP) transfer of a free-standing carbon-aluminum foil at 100°C and at a pressure of 0.1 MPa on a methylammonium lead iodide (MAPbI3) layer. Under these conditions, the perovskite surface was preserved from interaction with the solvent. Over a timescale of 90 days, HP-PSCs were systematically compared to reference cells with carbon-based top electrodes deposited by doctor blading (DB). We found that all the photovoltaic parameters recorded in HP-PSCs during time under ambient conditions settled on values systematically higher than those measured in the reference DB-PSCs, with efficiency stabilized at around 6% within the first few measurements. On the other hand, in DB-PSCs, a long-lasting (~14 days) degrading transient of the performances was observed, with a loss of efficiency from an initial ~8% to ~3%. Moreover, in HP-PSCs, a systematic day-by-day recovery of the efficiency after operation was observed (Δ~2%) by leaving the cell under open circuit, a nitrogen environment, and dark conditions. Noteworthily, a full recovery of all the parameters was observed at the end of the experiment, while DB-PSCs showed only a partial recovery under the same conditions. Hence, the complete release of solvent from the carbon contact, before an interface is established with the perovskite layer, offers a definite advantage through the long period of operation in preventing irreversible degradation. Our findings indeed highlight the crucial role of the interfaces and their feasible preservation under nitrogen atmosphere.
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Gold nanostructures absorb visible light and show localized surface plasmon resonance bands in the visible region. Semiconducting ZnO nanostructures are excellent for ultraviolet detection, thanks to their wide band gap, large free exciton binding energy, and high electron mobility. Therefore, the coupling of gold and ZnO nanostructures represents the best-suited way to boost photodetection. With the above perspective, we report on the high photocatalytic activity of some Au_ZnO core-shell nanoparticles (NPs) recently prepared by a one-pot synthesis in which a [zinc citrate]- complex acted as the ZnO precursor, a reducing agent for Au3+, and a capping anion for the obtained Au NPs. The overall nanostructures proved to be Au(111) NPs surrounded by a thin layer of [zinc citrate]- that evolved to Au_ZnO core-shell nanostructures. Worthy of note, with this photocatalyst, sun light efficiently decomposes a standard methylene blue solution according to ISO 10678:2010. We rationalized photodetection, reaction rate, and quantum efficiency.