872 research outputs found

    Lifetime predictions of non-ionic and ionic biopolymers: kinetic studies by non-isothermal thermogravimetric analysis

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    In this paper, films based on sustainable polymers with variable charge have been investigated by non-isothermal thermogravimetry in order to predict their lifetime, which is a key parameter for their potential use in numerous technological and biomedical applications. Specifically, chitosan has been selected as positively charged biopolymer, while alginate has been chosen as negatively charged biopolymer. Among non-ionic polymers, methylcellulose has been investigated. Thermogravimetric measurements at variable heating rates (5, 10, 15 and 20 °C min−1) have been performed for all the polymers to study their degradation kinetics by using isoconversional procedures combined with ‘Master plot’ analyses. Both integral (KAS and Starink methods) and differential (Friedman method) isoconversional procedures have shown that chitosan possesses the highest energetic barrier to decomposition. Based on the Master plot analysis, the decomposition of ionic polymers can be described by the R2 kinetic model (contracted cylindrical geometry), while the degradation of methylcellulose reflects the D2 mechanism (two-dimensional diffusion). The determination of both the decomposition mechanism and the kinetic parameters (activation energy and pre-exponential factor) has been used to determine the decay time functions of the several biopolymers. The obtained insights can be helpful for the development of durable films based on sustainable polymers with variable electrostatic characteristics. Graphical abstract: [Figure not available: see fulltext.

    Size-Controlled Water-Soluble Ag Nanoparticles

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    Ag nanoparticles of two different sizes (1 and 4 nm) were prepared within an apoferritin cavity by using an Ag+-loaded apoferritin as a nanoconfined environment for their construction. The initial amount of Ag' ions injected in the apoferritin cavity dictates the size of the final Ag particles. The protein shell prevents bulk aggregation of the metal particles, which renders them water soluble and extremely stable

    You’re the emotional one: the role of perspective for emotion processing in reading comprehension

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    Two experiments were conducted to explore whether perspective influences the way readers engage with and process emotional information while reading. Texts presenting characters in an emotional situation from either a personal or an onlooker perspective were presented and reading times were measured for each sentence. Participants also provided emotional self-ratings after reading. In the first experiment, positive texts were processed with greater ease, especially when readers experienced the texts from a personal perspective. In Experiment 2, an emotional match/mismatch was inserted so that a final explicit emotion word either matched or mismatched the emotional valence of the text. Mismatch effects were stronger and more consistent for the personal perspective. The two experiments provide evidence that the perspective of the reader can influence emotion processing. Processing of emotional information was easier for the personal perspective, and readers were more sensitive to inconsistent emotional information from that perspective

    Regioselective Generation of Single-Site Iridium Atoms and Their Evolution into Stabilized Subnanometric Iridium Clusters in MWW Zeolite

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    This is the peer reviewed version of the following article: L. Liu, M. Lopez-Haro, D. M. Meira, P. Concepcion, J. J. Calvino, A. Corma, Angew. Chem. Int. Ed. 2020, 59, 15695, which has been published in final form at https://doi.org/10.1002/anie.202005621. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Preparation of supported metal catalysts with uniform particle size and coordination environment is a challenging and important topic in materials chemistry and catalysis. In this work, we report the regioselective generation of single-site Ir atoms and their evolution into stabilized subnanometric Ir clusters in MWW zeolite, which are located at the 10MR window connecting the two neighboring 12MR supercages. The size of the subnanometric Ir clusters can be controlled by the post-synthesis treatments and maintain below 1 nm even after being reduced at 650 degrees C, which cannot be readily achieved with samples prepared by conventional impregnation methods. The high structure sensitivity, size-dependence, of catalytic performance in the alkane hydrogenolysis reaction of Ir clusters in the subnanometric regime is evidenced.This work has been supported by the European Union through the European Research Council (grant ERC-AdG-2014-671093, SynCatMatch) and the Spanish government through the "Severo Ochoa Program" (SEV-2016-0683). The authors also thank Microscopy Service of UPV for the TEM and STEM measurements. High-resolution STEM measurements were performed at the DME-UCA node of the ELECMI National Singular Infrastruture, in Cadiz University, with financial support from FEDER/MINECO (MAT2017-87579-R and MAT2016-81118-P). This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No.DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. The financial support from ExxonMobil on this project is also greatly acknowledged.Liu, L.; Lopez-Haro, M.; Meira, DM.; Concepción Heydorn, P.; Calvino, JJ.; Corma Canós, A. (2020). Regioselective Generation of Single-Site Iridium Atoms and Their Evolution into Stabilized Subnanometric Iridium Clusters in MWW Zeolite. Angewandte Chemie International Edition. 59(36):15695-15702. https://doi.org/10.1002/anie.202005621S15695157025936Liu, L., & Corma, A. (2018). Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles. Chemical Reviews, 118(10), 4981-5079. doi:10.1021/acs.chemrev.7b00776Thomas, J. M., Raja, R., & Lewis, D. W. (2005). Single-Site Heterogeneous Catalysts. Angewandte Chemie International Edition, 44(40), 6456-6482. doi:10.1002/anie.200462473Thomas, J. M., Raja, R., & Lewis, D. W. (2005). Heterogene Single-Site-Katalysatoren. Angewandte Chemie, 117(40), 6614-6641. doi:10.1002/ange.200462473Wang, A., Li, J., & Zhang, T. (2018). Heterogeneous single-atom catalysis. Nature Reviews Chemistry, 2(6), 65-81. doi:10.1038/s41570-018-0010-1Pelletier, J. D. A., & Basset, J.-M. (2016). Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts. Accounts of Chemical Research, 49(4), 664-677. doi:10.1021/acs.accounts.5b00518Pan, Y., Zhang, C., Liu, Z., Chen, C., & Li, Y. (2020). Structural Regulation with Atomic-Level Precision: From Single-Atomic Site to Diatomic and Atomic Interface Catalysis. Matter, 2(1), 78-110. doi:10.1016/j.matt.2019.11.014Gates, B. C., Flytzani-Stephanopoulos, M., Dixon, D. A., & Katz, A. (2017). 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Molecular Metal Catalysts on Supports: Organometallic Chemistry Meets Surface Science. Accounts of Chemical Research, 47(8), 2612-2620. doi:10.1021/ar500170kLu, J., Aydin, C., Browning, N. D., & Gates, B. C. (2012). Imaging Isolated Gold Atom Catalytic Sites in Zeolite NaY. Angewandte Chemie International Edition, 51(24), 5842-5846. doi:10.1002/anie.201107391Lu, J., Aydin, C., Browning, N. D., & Gates, B. C. (2012). Imaging Isolated Gold Atom Catalytic Sites in Zeolite NaY. Angewandte Chemie, 124(24), 5944-5948. doi:10.1002/ange.201107391Liu, L., & Corma, A. (2020). Evolution of Isolated Atoms and Clusters in Catalysis. Trends in Chemistry, 2(4), 383-400. doi:10.1016/j.trechm.2020.02.003Pan, C., Pelzer, K., Philippot, K., Chaudret, B., Dassenoy, F., Lecante, P., & Casanove, M.-J. (2001). Ligand-Stabilized Ruthenium Nanoparticles:  Synthesis, Organization, and Dynamics. Journal of the American Chemical Society, 123(31), 7584-7593. doi:10.1021/ja003961mMartínez-Prieto, L. M., & Chaudret, B. (2018). Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination. Accounts of Chemical Research, 51(2), 376-384. doi:10.1021/acs.accounts.7b00378Liu, L., Díaz, U., Arenal, R., Agostini, G., Concepción, P., & Corma, A. (2016). Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials, 16(1), 132-138. doi:10.1038/nmat4757Sun, Q., Wang, N., Zhang, T., Bai, R., Mayoral, A., Zhang, P., … Yu, J. (2019). Zeolite‐Encaged Single‐Atom Rhodium Catalysts: Highly‐Efficient Hydrogen Generation and Shape‐Selective Tandem Hydrogenation of Nitroarenes. Angewandte Chemie International Edition, 58(51), 18570-18576. doi:10.1002/anie.201912367Sun, Q., Wang, N., Zhang, T., Bai, R., Mayoral, A., Zhang, P., … Yu, J. (2019). Zeolite‐Encaged Single‐Atom Rhodium Catalysts: Highly‐Efficient Hydrogen Generation and Shape‐Selective Tandem Hydrogenation of Nitroarenes. Angewandte Chemie, 131(51), 18743-18749. doi:10.1002/ange.201912367Liu, Y., Li, Z., Yu, Q., Chen, Y., Chai, Z., Zhao, G., … Li, Y. (2019). A General Strategy for Fabricating Isolated Single Metal Atomic Site Catalysts in Y Zeolite. Journal of the American Chemical Society, 141(23), 9305-9311. doi:10.1021/jacs.9b02936Wu, S., Yang, X., & Janiak, C. (2019). Confinement Effects in Zeolite‐Confined Noble Metals. Angewandte Chemie International Edition, 58(36), 12340-12354. doi:10.1002/anie.201900013Wu, S., Yang, X., & Janiak, C. (2019). Confinement Effects in Zeolite‐Confined Noble Metals. Angewandte Chemie, 131(36), 12468-12482. doi:10.1002/ange.201900013Liu, L., Lopez-Haro, M., Lopes, C. W., Li, C., Concepcion, P., Simonelli, L., … Corma, A. (2019). Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis. Nature Materials, 18(8), 866-873. doi:10.1038/s41563-019-0412-6Camblor, M. 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E., Carr, R. T., Guzman, J., Casty, G. L., … Corma, A. (2016). Reversible Transformation of Pt Nanoparticles into Single Atoms inside High-Silica Chabazite Zeolite. Journal of the American Chemical Society, 138(48), 15743-15750. doi:10.1021/jacs.6b10169Liu, L., Zakharov, D. N., Arenal, R., Concepcion, P., Stach, E. A., & Corma, A. (2018). Evolution and stabilization of subnanometric metal species in confined space by in situ TEM. Nature Communications, 9(1). doi:10.1038/s41467-018-03012-6Yan, W., Xi, S., Du, Y., Schreyer, M. K., Tan, S. X., Liu, Y., & Borgna, A. (2018). Heteroatomic Zn-MWW Zeolite Developed for Catalytic Dehydrogenation Reactions: A Combined Experimental and DFT Study. ChemCatChem, 10(14), 3078-3085. doi:10.1002/cctc.201800199De Graaf, J., van Dillen, A. ., de Jong, K. ., & Koningsberger, D. . (2001). Preparation of Highly Dispersed Pt Particles in Zeolite Y with a Narrow Particle Size Distribution: Characterization by Hydrogen Chemisorption, TEM, EXAFS Spectroscopy, and Particle Modeling. Journal of Catalysis, 203(2), 307-321. doi:10.1006/jcat.2001.3337Jentys, A. (1999). Estimation of mean size and shape of small metal particles by EXAFS. Physical Chemistry Chemical Physics, 1(17), 4059-4063. doi:10.1039/a904654bLu, J., Serna, P., Aydin, C., Browning, N. D., & Gates, B. C. (2011). Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands. Journal of the American Chemical Society, 133(40), 16186-16195. doi:10.1021/ja206486jZhao, A., & Gates, B. C. (1996). Hexairidium Clusters Supported on γ-Al2O3:  Synthesis, Structure, and Catalytic Activity for Toluene Hydrogenation. Journal of the American Chemical Society, 118(10), 2458-2469. doi:10.1021/ja952996xNoei, H., Franz, D., Creutzburg, M., Müller, P., Krausert, K., Grånäs, E., … Stierle, A. (2018). Monitoring the Interaction of CO with Graphene Supported Ir Clusters by Vibrational Spectroscopy and Density Functional Theory Calculations. The Journal of Physical Chemistry C, 122(8), 4281-4289. doi:10.1021/acs.jpcc.7b10845Fielicke, A., Gruene, P., Meijer, G., & Rayner, D. M. (2009). The adsorption of CO on transition metal clusters: A case study of cluster surface chemistry. Surface Science, 603(10-12), 1427-1433. doi:10.1016/j.susc.2008.09.064Henninen, T. R., Bon, M., Wang, F., Passerone, D., & Erni, R. (2020). The Structure of Sub‐nm Platinum Clusters at Elevated Temperatures. Angewandte Chemie International Edition, 59(2), 839-845. doi:10.1002/anie.201911068Henninen, T. R., Bon, M., Wang, F., Passerone, D., & Erni, R. (2019). The Structure of Sub‐nm Platinum Clusters at Elevated Temperatures. Angewandte Chemie, 132(2), 849-855. doi:10.1002/ange.201911068Okumura, M., Irie, Y., Kitagawa, Y., Fujitani, T., Maeda, Y., Kasai, T., & Yamaguchi, K. (2006). 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    Origin of the solid-state luminescence of MIL-53(Al) and its connection to the local crystalline structure

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    Metal-organic frameworks (MOFs) are extensively studied due to their unique surface properties, enabling many intriguing applications. Breathing MOFs, a subclass of MOFs, have gained recent interest for their ability to undergo structural changes based on factors like temperature, pressure, adsorbed molecules. Certain MOFs also exhibit remarkable optical properties useful for applications such as sensors, light-emitting diodes, and scintillators. The most promising MOFs possess high porosity, breathing properties, and photoluminescence activities, allowing for improved device responsiveness and selectivity. Understanding the relationship between crystal structures and photoluminescence properties is crucial in these cases. As studies on this topic are still very limited, we report for the first time an exhaustive study on the solid-state luminescence of the breathing MOF MIL-53(Al), that can stabilize in three different crystalline structures: open-pore, hydrated narrow-pore and closed-pore. We unveil a fascinating solid-state luminescence spectrum, comprising three partially overlapping bands, and elucidate the intricate electronic transitions within each band as well as their intimate correlation with the local crystalline structures. Our characterizations of spectroscopic properties and decay times provide a deeper understanding of the luminescent behaviour of MIL-53(Al) and demonstrate that is possible to identify present crystalline structures by optical measurements or to modify the optical properties inducing structural transitions for this type of materials. These insights could help to design next-generation, selective sensors or smart light emitting devices

    Perfil epidemiológico das internações por condições sensíveis à atenção primária de saúde no estado de Roraima

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    Introduction: The Primary Care Sensitive Conditions (CSAP) comprise the health problems that are treated in the first level of health care; if this care is neglected, an evolution of the illness may happen, requiring hospitalization. Objective: Understand the characteristics of hospitalizations due to primary care sensitive conditions that occurred in the Hospitals of Roraima during the period from 2011 to 2015. Methods: This is a population-based ecological study using DATASUS secondary data. Results: During the period under study, 155,063 hospitalizations were detected in HGR, of which 22.79% (35,344) were consequences from Primary Care Sensitive Conditions and 82.19% of the hospitalizations were from patients living in Boa Vista; the bacterial pneumonia was the main cause of hospitalization, followed by skin and subcutaneous tissue infections. Conclusions: : In this study, it was possible to quantify the number of hospitalizations that occurred in the state of Roraima from 2011 to 2015 and to outline a profile of the hospitalizations by CSAP, identifying the main causes that require interventions through programs in primary care.Introdução: As Condições Sensíveis à Atenção Primária (CSAP) compreendem os agravos em saúde que são atendidos no primeiro nível de atenção à saúde, caso esse atendimento seja negligenciado pode haver evolução deste agravo sendo necessária internação hospitalar. Objetivo: Conhecer as características das internações por condições sensíveis à atenção primária que ocorreram nas Instituições Hospitalares do estado de Roraima no período de 2011 à 2015. Métodos: Trata-se de um estudo ecológico de base populacional que utiliza dados secundários do DATASUS. Resultados: No período estudado, evidenciou-se a ocorrência de 155.063 internações no HGR, sendo que 22,79% (35.344) destas foram internações por Condições Sensíveis a Atenção Primária e 82,19% referentes a e pacientes residentes em Boa Vista, visto que as pneumonias bacterianas foram as principais causas de internação, seguido por infecção da pele e tecido subcutâneo. Conclusões: Neste estudo foi possível quantificar as internações ocorridas no estado de Roraima de 2011 à 2015 e traçar um perfil das internações pelas CSAP, identificando as principais causas de internação que necessitam de intervenção por meio de programas dirigidos na atenção primária

    Inhibition of αvβ5 Integrin Attenuates Vascular Permeability and Protects against Renal Ischemia-Reperfusion Injury

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    Ischemia-reperfusion injury (IRI) is a leading cause of AKI. This common clinical complication lacks effective therapies and can lead to the development of CKD. The αvβ5 integrin may have an important role in acute injury, including septic shock and acute lung injury. To examine its function in AKI, we utilized a specific function-blocking antibody to inhibit αvβ5 in a rat model of renal IRI. Pretreatment with this anti-αvβ5 antibody significantly reduced serum creatinine levels, diminished renal damage detected by histopathologic evaluation, and decreased levels of injury biomarkers. Notably, therapeutic treatment with the αvβ5 antibody 8 hours after IRI also provided protection from injury. Global gene expression profiling of post-ischemic kidneys showed that αvβ5 inhibition affected established injury markers and induced pathway alterations previously shown to be protective. Intravital imaging of post-ischemic kidneys revealed reduced vascular leak with αvβ5 antibody treatment. Immunostaining for αvβ5 in the kidney detected evident expression in perivascular cells, with negligible expression in the endothelium. Studies in a three-dimensional microfluidics system identified a pericyte-dependent role for αvβ5 in modulating vascular leak. Additional studies showed αvβ5 functions in the adhesion and migration of kidney pericytes in vitro Initial studies monitoring renal blood flow after IRI did not find significant effects with αvβ5 inhibition; however, future studies should explore the contribution of vasomotor effects. These studies identify a role for αvβ5 in modulating injury-induced renal vascular leak, possibly through effects on pericyte adhesion and migration, and reveal αvβ5 inhibition as a promising therapeutic strategy for AKI

    From micro to macro: Physical-chemical characterization of wheat starch-based films modified with PEG200, sodium citrate, or citric acid

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    Needing to extend the shelf-life of packaged food and the evolving consumer demands led researchers to seek innovative, eco-friendly, and biocompatible packaging solutions. Starch is among the most promising natural and renewable alternatives to non-degradable plastics. Here, we deeply study the structural features of starch films modified by adding citric acid (CA) or sodium citrate (SC) as a cross-linker and polyethylene glycol 200 (PEG200) as a plasticizer and obtained through solvent casting. The substances' influence on starch films was evaluated through Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) and Solid-state Nuclear Magnetic Resonance (ss-NMR) spectroscopies. Films' macroscopic properties, such as swelling index, solubility, thermo-mechanical features, and moisture absorption, were also assessed to foresee potential applications. Proper amounts of CA, CS, and PEG200 improve film properties and inhibit starch chains' retrogradation and recrystallization. Besides, the chemical neighbourhood of nuclei observed through ss-NMR significantly changed alongside the polymer chains' mobility. The latter result indicates a different polymer chain structural organization that could justify the film's higher resistance to thermal degradation and elongation at the break. This methodological approach is effective in predicting the macroscopic behaviour of a polymeric material and could be helpful for the application of such products in food preservation

    Present Status and Future Programs of the n_TOF Experiment

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    This is an Open Access article distributed under the terms of the Creative Commons Attribution-Noncommercial License 3.0, which permits unrestricted use, distribution, and reproduction in any noncommercial medium, provided the original work is properly citedThe neutron time-of-flight facility n_TOF at CERN, Switzerland, operational since 2001, delivers neutrons using the Proton Synchrotron (PS) 20 GeV/c proton beam impinging on a lead spallation target. The facility combines a very high instantaneous neutron flux, an excellent time of flight resolution due to the distance between the experimental area and the production target (185 meters), a low intrinsic background and a wide range of neutron energies, from thermal to GeV neutrons. These characteristics provide a unique possibility to perform neutron-induced capture and fission cross-section measurements for applications in nuclear astrophysics and in nuclear reactor technology.The most relevant measurements performed up to now and foreseen for the future will be presented in this contribution. The overall efficiency of the experimental program and the range of possible measurements achievable with the construction of a second experimental area (EAR-2), vertically located 20 m on top of the n_TOF spallation target, might offer a substantial improvement in measurement sensitivities. A feasibility study of the possible realisation of the installation extension will be also presented
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