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    Aryne‐Based Synthesis of Cyclobutadiene‐Containing Oligoacenes and Related Extended Biphenylene Derivatives

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    A previously undescribed aryne derived from a π-extended biphenylene, 2,3-didehydrobenzo[b]biphenylene, has been developed. The participation of this new aryne building block in [4+2] and palladium-catalyzed [2+2+2] cycloaddition reactions has been applied to the synthesis of a variety of polycyclic conjugated hydrocarbons (PCHs) with appealing structures which combine (aromatic) benzene and (antiaromatic) cyclobutadiene (CBD) rings. Among them, a family of unsubstituted (or barely substituted) CBD-oligoacenes has been accessed by iterative Diels-Alder reactions of the new aryne with furans and/or isobenzofurans, followed by deoxygenative aromatization of the resulting epoxy-derivatives. The experimental and computational studies of the newly synthesized PCHs suggest an important degree of electron delocalization along the polycyclic skeleton, more pronounced in the linearly fused derivatives. The computed ACID plots reveal clockwise current density vectors at the peripheral bonds, originating from the σ contributions of the antiaromatic cyclobutadiene rings.Financial support from grants PID2019-110037GB-I00, PID2022-140845OB-C62 and PID2022-139933NB-I00, funded by MCIN/AEI/10.13039/501100011033, the European Union’s Horizon 2020 (FET-Open project SPRING, Grant No. 863098), and ERC Synergy Grant MOLDAM (951519), the Xunta de Galicia (ED431C 2020/22, ED431H 2020/21 and Centro singular de investigación de Galicia accreditation 2019–2022, ED431G 2019/03) and the European Union (European Regional Development Fund-ERDF) is gratefully acknowledged. The authors thank the Centro de Supercomputación de Galicia (CESGA) for generous allocation of computer time. BA and JJ thank the Agencia Estatal de Investigación for the award of pre-doctoral fellowships (BES-2017-079748 and PRE2020- 092897, respectively)S

    Inquiry-based activities with woodlice in Early Childhood Education

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    This study aims to describe the implementation of a teaching sequence where preschool-age children participate in activities related with woodlice. Although there is extensive literature on inquiry-based activities, most studies have been conducted in higher educational stages. Data were collected though audio and video recordings of the sessions, which have then been transcribed. The children participated in research activities in which they had no difficulty in posing hypotheses and making predictions. In relation to the experimental design, we observed difficulties in understanding the purpose of the experiment and how to reach conclusions from the experimental results. From the results of this study, we can conclude that children from an early age can engage in inquiry activities where they are given opportunities to make predictions, formulate hypotheses, and, with the help of the teacher, plan simple experiments to test their ideasThis research was developed within RODA (Ref. ED431C2021/05) research group and was funded by the Spanish Ministry of Science, Innovation and Universities, partly funded by the European Regional Development Fund (ERDF). Grant code PID2022-138166NB-C21S

    Alginate aerogels by spray gelation for enhanced pulmonary delivery and solubilization of beclomethasone dipropionate

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    Aerogel technology is an emerging platform that offers alternative and cost-effective dry carriers with advanced performances for the pharmaceutical industry. The innovative combination of compressed air-assisted spray gelation and “green” supercritical fluid (SCF) technology was used in this study to produce alginate aerogel microparticles with adequate properties for pulmonary drug delivery. Beclomethasone dipropionate (BDP), a poorly water-soluble anti-inflammatory drug for asthma treatment, was loaded into alginate aerogel particles by SCF-assisted impregnation ensuring high loading, as well as the amorphization of the drug. The production of aerogels was optimized through the fine-tuning of parameters in compressed air-assisted spray gelation, specifically adjusting the air flow rate and the pump speed. Alginate aerogels were aimed to be produced with an appropriate aerodynamic diameter from 1 to 5 µm, measured by in vitro deposition tests with Next Generation impactor and potential for deep lung penetration. Nuclear magnetic resonance (NMR) relaxometry was used to assess aerogel hydration and unveiled structure–property relationships leading to the sudden release of the drug. Finally, in vitro cytotoxicity tests in fibroblasts and ex vivo permeability tests were conducted. These biological tests confirmed the excellent biocompatibility of the aerogel formulations and demonstrated the efficient deposition of BDP in porcine bronchial tissues assisted by the porous alginate aerogel carrierWork supported by MICINN [PID2020-120010RB-I00/AEI/10.13039/501100011033], Xunta de Galicia [ED431C 2020/17], Agencia Estatal de Investigación [AEI] and FEDER funds. This publication is based on work from AERoGELS COST Action (ref. CA18125) supported by COST (European Cooperation in Science and Technology). Th. D. acknowledges the support of Diputación Provincial de A Coruña for research in health science 2022-2023 (BINV-CS/2022) and of AERoGELS COST Action (ref. CA18125) for a Short Term Scientific Missions (STSM) grant, enabling for the collaboration with HUN-REN-DE Mechanisms of Complex Homogeneous and Heterogeneous Chemical Reactions Research Group, Department of Inorganic and Analytical Chemistry, University of Debrecen (Hungary). The authors would like to thank Ezequiel Vázquez Fernández (University of Santiago de Compostela, Spain), Laura Juhász and Krisztián Moldován (University of Debrecen, Hungary) for their valuable support and technical help with Raman spectroscopy, X-ray diffraction, IR-ATR and SEM analysesS

    Education, World Development and Quality of Life, 2001-2023

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    Chapter 1 of book EE12 presents several studies: 1) economic studies of the period 2014-2017 on the impact of Manufacturing on development of 132 countries; 2) economic studies of year 2020 on World Food, Poverty and CO2 Emissions; 3) econometric models of years 2021 to 2023, relating indicators of quality of life and development in 164 countries; 4) other international comparisons of quality of lif

    Polyelectrolyte complexes based on a novel and sustainable hemicellulose-rich lignosulphonate for drug delivery applications

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    Polyelectrolyte complexes (PECs) are polymeric structures formed by the self-assembly of oppositely charged polymers. Novel biomaterials based on PECs are currently under investigation as drug delivery systems, among other applications. This strategy leverages the ability of PECs to entrap drugs under mild conditions and control their release. In this study, we combined a novel and sustainably produced hemicellulose-rich lignosulphonate polymer (EH, negatively charged) with polyethyleneimine (PEI) or chitosan (CH, positively charged) and agar for the development of drug-releasing PECs. A preliminary screening demonstrated the effect of several parameters (polyelectrolyte ratio, temperature, and type of polycation) on PECs formation. From this, selected formulations were further characterized in terms of thermal properties, surface morphology at the microscale, stability, and ability to load and release methylene blue (MB) as a model drug. EH/PEI complexes had a more pronounced gel-like behaviour compared to the EH/CH complexes. Differential scanning calorimetry (DSC) results supported the establishment of polymeric interactions during complexation. Overall, PECs’ stability was positively affected by low pH, ratios close to 1:1, and the addition of agar. PECs with higher EH content showed a higher MB loading, likely promoted by stronger electrostatic interactions. The EH/CH formulation enriched with agar showed the best sustained release profile of MB during the first 30 h in a pH-dependent environment simulating the gastrointestinal tract. Overall, we defined the conditions to formulate novel PECs based on a sustainable hemicellulose-rich lignosulphonate for potential applications in drug delivery, which promotes the valuable synergy between sustainability and the biomedical fieldThe authors would like to thank Dr. P. Oinonen and Ecohelix AB for providing samples of the Ecohelix polymer and scientific advice on its use. The research leading to these results was financially supported by Nordforsk, within the Nordic Green Growth Research and Innovation Program (project name: “High-Value Products from Lignin”). A.A. acknowledges funding from ‘la Caixa’ Foundation (ID 100010434) with a fellowship code LCF/BQ/ PR22/11920003. Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. The research leading to these results was financially supported by Nordforsk, within the Nordic Green Growth Research and Innovation Program (project name: “High-Value Products from Lignin”). A.A. acknowledges funding from ‘la Caixa’ Foundation (ID 100010434) with a fellowship code LCF/BQ/ PR22/11920003S

    La temática jacobea y compostelana en la literatura contemporánea: evolución desde 2010 a 2014 e impacto en la práctica turística de los visitantes españoles. Un estudio a través de técnicas estadísticas y textométricas

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    Se analizarán los discursos sobre Santiago de Compostela y el Camino de Santiago presentes en la literatura española actual de 2010 y 2014 y la práctica turística de los visitantes españoles. Para ello se empleará un corpus literario de novelas y diarios de viaje y un corpus de entrevistas cuantitativas. Una vez establecidas las principales líneas discursivas de cada corpus utilizando técnicas de estadísticas y textométricas comprobaremos su grado de prevalencia en el otro para identificar y describir los procesos de interacción que se dan entre estos los ámbitos, literario y turístico

    Econometric Models of OECD Countries and Regions, 2001-2023

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    Pharmacological intestinal obstruction because of calcium polystyrene sulfonate administration

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    Cation exchange resins are commonly used as treatment for hyperkalaemia in patients with chronic renal disease. There is a relation between cation exchange resins and the development of gastrointestinal adverse effects. A case of an intestinal obstruction at the terminal ileum is presented that underwent an ileocolic resection because of a critical stenosis of the intestine. The pathologist revealed abundant inflammatory cells together with deposits of calcium polystyrene crystals responsible of the intestinal obstruction. A rare cause of intestinal obstruction to bear in mind in chronically medicated patients with cation exchange resins.S

    Capacity of Aqueous Solutions of the Ionic Liquid 1-Ethyl-3-methylimidazolium Acetate to Partially Depolymerize Lignin at Ambient Temperature and Pressure

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    Lignin is a very attractive and abundant biopolymer with the potential to be a biorenewable source of a large number of value-added organic chemicals. The current state-of-the-art methods fail to provide efficient valorization of lignin in this regard without the involvement of harsh conditions and auxiliary substances that compromise the overall sustainability of the proposed processes. Making an original approach from the set of mildest temperature and pressure conditions, this work identifies and explores the capacity of an aqueous solution of the nonvolatile ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) to partially depolymerize technical lignin (Indulin AT) by means of a treatment consisting in the simple contact at ambient temperature and pressure. Among a considerable number of valuable phenolic molecules that were identified in the resulting fluid, vanillin (yield of about 3 g/kg) and guaiacol (yield of about 1 g/kg) were the monophenolic compounds obtained in a higher concentration. The properties of the post-treatment solids recovered remain similar to those of the original lignin, although with a relatively lower abundance of guaiacyl units (in agreement with the generation of guaiacyl-derived phenolic molecules, such as vanillin and guaiacol). The assistance of the treatment with UV irradiation in the presence of nanoparticle catalysts does not lead to an improvement in the yields of phenolic compounds.This work was supported by Xunta de Galicia (project ED431B 2020/21, cofunded by the European Regional Development Fund). The use of RIAIDT-USC analytical facilities is also acknowledged.S

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