Synthesis of mechanically strong waterborne poly(urethane-urea)s capable of self-healing at elevated temperatures

Although various chemistries have been introduced into polyurethanes in order to obtain self-healing abilities, implementing these materials in applications requiring high strength is challenging as strong materials imply a limited molecular motion, but without movement of polymer chains self-healing is not possible. Here, waterborne poly(urethane-urea)s (PU(U)s) based on aromatic disulfide compounds are developed which balance these contradictory requirements by presenting good mechanical properties at room temperature, while showing the mobility necessary for healing when moderately heated. The influence of hard monomers on the stability and mobility of the materials is investigated by scratch closure, cut healing and rheological measurements, so that the limits of the readily available aromatic disulfide compounds, bis(4-aminophenyl)- and bis(4-hydroxyphenyl)disulfide, can be determined. Subsequently, a modified aromatic disulfide compound, bis[4-(3'-hydroxypropoxy)phenyl]disulfide, with increased reactivity, solubility and flexibility is synthesized and incorporated into the PU backbone, so that materials with more attractive mechanical properties, reaching ultimate tensile strengths up to 23 MPa, and self-healing abilities at elevated temperatures could be obtained.The European Union’s Horizon 2020 research and innovation programme is accredited for the financial support through Project TRACKWAY-ITN 642514 under the Marie Sklodowska-Curie grant agreement. N.B. acknowledges the financial support obtained through the Post-Doctoral fellowship Juan de la Cierva - Incorporación (IJCI-2016-28442), from the Ministry of Economy and Competitiveness of Spai

Optimization of Ultrasound Assisted Extraction of Bioactive Compounds from Apple Pomace

In the present work, the optimization of the extraction of antioxidant compounds from apple pomace using ultrasound technology as an environmentally friendly and intensification process was developed. Different sonication powers, extraction temperatures and extraction times were studied and their influence on extraction yield and characteristics of the extracted samples (total phenolic compounds, flavonoid content and antioxidant capacity) are presented. The elaborated experimental design and the analysis of Pareto and response surface diagrams allowed us to determine the optimal extraction conditions. The conditions that allow the maximum extraction of phenolic compounds were found at 20 min, 90 °C and 50% ultrasound amplitude. Nevertheless, at these conditions, the antioxidant capacity measured by DPPH decreased in the extracted samples.This research was funded by Diputación Foral de Gipuzcoa, Departamento de Promoción económica, Turismo y Medio Rural, Proyecto Fortalecimiento-96, grant number LEHIAKORTASUNA INDARTZEA-97/18

Bicolour fluorescent molecular sensor for cations: design and experimental validation

Molecular entities whose fluorescence spectra are different when they bind metal cations are termed bicolour fluorescent molecular sensors. The basic design criteria of this kind of compound are presented and the different fluorescent responses are discussed in terms of their chemical behaviour and electronic features. These latter elements include intramolecular charge transfer (ICT), formation of intramolecular and intermolecular excimer/exciplex complexes and Fo ̈rster resonance energy transfer (FRET). Changes in the electronic properties of the fluorophore based on the decoupling between its constitutive units upon metal binding are also discussed. The possibility of generating fluorescent bicolour indicators that can capture metal cations in the gas phase and at solid–gas interfaces is also discussedThis work was supported by the Basque Government (Grants IT-1346-19 and IT1180-19), by the Spanish Ministry of Science and Innovation (MICINN-FEDER, Grants PID2019-104772GB-I00, PID2019-111281GB-I00, RED2018-102387-T, and RED2018-102471-T), and by the European Research Council (ERC) under the European's Union Horizon 2020 research and innovation programme (Grant agreement ERC-2020-SyG 951281)

Upgrading Polyurethanes into Functional Ureas through the Asymmetric Chemical Deconstruction of Carbamates

The importance of systematic and efficient recycling of all forms of plastic is no longer a matter for debate. Constituting the sixth most produced polymer family worldwide, polyurethanes, which are used in a broad variety of applications (buildings, electronics, adhesives, sealants, etc.), are particularly important to recycle. In this study, polyurethanes are selectively recycled to obtain high value-added molecules. It is demonstrated that depolymerization reactions performed with secondary amines selectively cleave the C–O bond of the urethane group, while primary amines unselectively break C–O and C–N bonds. The selective cleavage of C–O bonds, catalyzed by an acid:base mixture, led to the initial polyol and a functional diurea in several hours to a few minutes for both model polyurethanes and commercial polyurethane foams. Different secondary amines were employed as nucleophiles to synthesize a small library of diureas obtained in good to excellent yields. This study not only targets the recovery of the initial polyol but also aims to form new diureas which are useful building blocks for the polymerization of innovative materials.C.J. acknowledges the financial support from el Ministerio de ciencia e innovación from the Juan de la Cierva Program (FJC2020045872-I). The funding from the European Union’s Horizon 2020 framework programme under the Marie Skłodowska Curie agreement No. 101028975 and Ministerio de ciencia e innovación under PDC2021-121461-I00 project are acknowledged

Tecnologías digitales en estudiantes de actividad física y deportes ¿Percepción de competencia o competencia real?

Las tecnologías digitales (TD) pueden ofrecer flexibilidad y avances en los procesos de enseñanza-aprendizaje. Una incógnita acerca de su implementación en Educación Física (EF) es la diferencia entre competencia percibida y real. Para poder acotar hipótesis contrastables debemos conocer disponibilidad de equipos, formación y percepción de competencia en alumnos y profesores. El objetivo del estudio fue analizar percepción de competencia digital y uso real de TD en alumnos de cursos de entrenador de fútbol (ENF), Técnicos en Actividad Física y Deportes (TAFAD) y Ciencias de la Actividad Física y el Deporte (CCAFD)

Effect of carbon nanostructures and fatty acid treatment on the mechanical and thermal performances of flax/polypropylene composites

Four different strategies for mitigating the highly hydrophilic nature of flax fibers were investigated with a view to increase their compatibility with apolar polypropylene. The effects of two carbon nanostructures (graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs)), of a chemical modification with a fatty acid (stearic acid), and of maleated polypropylene on interfacial adhesion, mechanical properties (tensile and flexural), and thermal stability (TGA) were compared. The best performance was achieved by a synergistic combination of GNPs and maleated polypropylene, which resulted in an increase in tensile strength and modulus of 42.46% and 54.96%, respectively, compared to baseline composites. Stearation proved to be an effective strategy for increasing the compatibility with apolar matrices when performed in an ethanol solution with a 0.4 M concentration. The results demonstrate that an adequate selection of surface modification strategies leads to considerable enhancements in targeted properties

The role of experience, perceived match importance, and anxiety on cortisol response in an official esports competition

The aim of the present study was to analyse the neuroendocrine stress response, psychological anxiety response, and perceived match importance (PMI) between expert and non-expert control gamers in an official competitive context. We analyzed, in 25 expert esports players and 20 control participants, modifications in their somatic anxiety, cognitive anxiety, self-confidence, PMI, and cortisol in a League of Legends competition. We found how expert esports players presented higher cortisol concentrations (Z = 155.5; p = 0.03; Cohen’s d = −0.66), cognitive anxiety (Z = 99.5; p = 0.001), and PMI (Z = 50.5; p < 0.001) before the competition than non-experts participants. We found a greater statistical weight in the cognitive variables than in the physiological ones. The results obtained suggest that real competitive context and player’s expertise were factors associated with an anticipatory stress response. The PMI proved to be a differentiating variable between both groups, highlighting the necessity to include subjective variables that contrast objective measurements

Determining optimal flight paths for cellular network connectivity for the transmission of real-time physiological data in support of big data analytics during airborne critical care transport

This thesis presents a methodology for determining the optimal flight paths between two geographical points based on distance and cellular reception over the path. This methodology consists of two main concepts: coverage map generation, and path planning. Coverage map generation creates a grid map of the total planning space that contains coverage information for each grid point. Coverage is calculated based on geographical and technical information regarding each cell tower in the planning area. The planning step utilises the coverage map to plan a route based on minimum distance and maximum coverage, which is then smoothed into a feasible route for an aircraft to follow. This methodology is demonstrated in an airborne critical care transport within the Province of Ontario in Canada context. Leveraging available cellular information, this methodology is used to determine optimal paths between various care centres or their closest airport. Evaluation reveals that optimal routes can be found through this methodology

Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids

Organocatalysis is becoming an important tool in polymer science because of its versatility and specificity. To date a limited number of organic catalysts have demonstrated the ability to promote stereocontrolled polymerizations. In this work we report one of the first examples of chirality transfer from a catalyst to a polymer in the organocatalyzed ring-opening polymerization (ROP) of rac-lactide (rac-LA). We have polymerized rac-LA using the diastereomeric densely substituted amino acids (2S,3R,4S,5S)-1-methyl-4-nitro-3,5-diphenylpyrrolidine- 2-carboxylic acid (endo-6) and (2S,3S,4R,5S)-1-methyl-4- nitro-3,5-diphenylpyrrolidine-2-carboxylic acid (exo-6), combined with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a cocatalyst. Both diastereoisomers not only showed the ability to synthesize enriched isotactic polylactide with a Pm higher than 0.90 at room temperature but also were able to preferentially promote the polymerization of one of the isomers (L or D) with respect to the other. Thus, exo-6 preferentially polymerized Llactide, whereas endo-6 preferred D-lactide as the substrate. Density functional theory calculations were conducted to investigate the origins of this unique stereocontrol in the polymerization, providing mechanistic insight and explaining why the chirality of the catalyst is able to define the stereochemistry of the monomer insertion.Financial support of this research by the MINECO (CTQ2016-80375-P, Consolider CTQ2016-81797-REDC, SUSPOL, and FDI 16507), the Gobierno Vasco/Eusko Jaurlaritza (Grants IT673-13 and IT618-13), the University of the Basque Country UPV/EHU (UFI 11/22 QOSYC), and the European Commission (SUPSOL-EJD 642671) is gratefully acknowledged. A.S.-S. is thankful for the Postdoctoral Funding for Doctoral Research Staff Improvement Grant from the Basque Government

Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(II) and copper(II) complex

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(II) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N-metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [pi4s + pi2s] mechanisms leading to the exclusive formation of racemic endo-cycloadducts.MINECO: Grants CTQ2013-45415-P, CTQ2016-80375-P MAT2013-46006-R, CTQ2016-81797-REDC and PCIN-2015-240 Gobierno Vasco / Eusko Jaurlaritza: Grants IT673-13 and PI-2013 57 European Commission: Grants ERC Starting-Grant St 209842 (MATRIX) and ERC PoC 713641 (ESSENS