Síntesis y caracterización de zeolitas micro-mesoporosas obtenidas a partir de surfactantes bifuncionales

[ES] Se han obtenido materiales zeolíticos mediante nuevas estrategias de síntesis que incluyen el uso de surfactantes como agentes directores de estructura. Los materiales han sido caracterizado tanto Física como químicamente.[EN] Zeolitic materials are obtained through new synt11esis strategies include the use of surfactants as structure directing agents. The materials have been characterized physically and chemically.Margarit Benavent, VJ. (2012). Síntesis y caracterización de zeolitas micro-mesoporosas obtenidas a partir de surfactantes bifuncionales. http://hdl.handle.net/10251/30013Archivo delegad

Propuesta de metodología para la estimación de la resistencia del hormigón en un punto de una estructura a través de ensayos de información, en éste y/u otros puntos

The destructive character of the extraction of test specimens, which at present is the only test that provides trustworthy data with regard to strength, makes it necessary to assign a strength to areas in the structure that are at a greater or lesser distance from the extraction points. &#13; The variables of the problem are the number of extractions and their emplacement. At one end we would have the case in which samples are taken from all the structural parts at the risk of weakening the structure, above all during the sampling process itself, as well as the negative financial and time factors, that this procedure would imply. At the other far end we would place the case of evaluating the strength in a great structural area on the basis of the results from breaking a small quantity of test pieces, by way of an extrapolation without the required guarantees.&#13; Naturally, the number of test and their emplacement situates the problem in between the two above mentioned extremes. The necessary extrapolation of some results that by nature are not exhaustive, is then carried out with greater or lesser guarantee with regard to advance knowledge of the execution of the work: the greater this knowledge is, the easier it is to establish the strength relation between the specimens and the pieces, which without being represented directly by samples, can adapt themselves to their characteristics, either by proximity or known execution rhythm. &#13; The most important problem arises when there is not enough knowledge on how the work was carried out, so that it is impossible to relate the strength of the test specimens with the actual strength of the rest of the structure under investigation. &#13; In this case it does not seem possible to establish the relation between two points in the structure other than on the basis of the actual physical distances and the results obtained through the test specimens. This report dealts with the application of the Information theory to quantify these relations and to group the points at which the concrete strength is estimated.<br><br>El carácter destructivo de la extracción de probetas testigo, actualmente el único ensayo de información que facilita datos de partida fidedignos desde el punto de vista resistente, obliga a asignar una resistencia a zonas de la estructura más o menos lejanas de los puntos de extracción. &#13; Las variables del problema son el número de extracciones y su localización. En un extremo tendríamos el caso de la obtención de testigos en todas las piezas estructurales, con el consiguiente riesgo de debilitación de la estructura, sobre todo durante las operaciones necesarias para ello, y el gravoso factor económico y de tiempo que este planteamiento lleva aparejado. En el otro extremo se situaría el caso de la evaluación de la resistencia de una gran zona de estructura en base a los resultados de la rotura de un mínimo número de probetas, a través de una extrapolación sin las necesarias garantías. &#13; Naturalmente, el número de ensayos de Información y su localización sitúa el problema en una región intermedia entre los dos extremos expuestos. La necesaria extrapolación de unos resultados, forzosamente no exhaustivos, se realiza, entonces, con una mayor o menor garantía en función del conocimiento previo de la ejecución de la obra: cuanto mayor es este conocimiento más fácilmente se podrá establecer la relación de resistencias entre los testigos y las piezas que, sin tener probetas que los representen directamente, puedan, por proximidad o ritmo de ejecución conocido, asimilarse a las características de dichos testigos. &#13; El problema más grave se plantea cuando el desconocimiento de la ejecución de la obra no permite establecer nexos de conocimiento entre los resultados obtenidos en determinados testigos y el resto de la zona de estructura cuya capacidad resistente se trata de evaluar. &#13; En este caso no parece posible el establecimiento de relaciones entre dos puntos de la estructura más que basándose en las distancias físicas y los resultados obtenidos en los testigos ensayados. Este trabajo trata de la aplicación de la teoría de la información para cuantificar estas relaciones y agrupar los puntos en los cuales el hormigón es objeto de estimación resistente

Propuesta de metodología para la estimación de la resistencia del hormigón en un punto de una estructura a través de ensayos de información, en éste y/u otros puntos

The destructive character of the extraction of test specimens, which at present is the only test that provides trustworthy data with regard to strength, makes it necessary to assign a strength to areas in the structure that are at a greater or lesser distance from the extraction points. The variables of the problem are the number of extractions and their emplacement. At one end we would have the case in which samples are taken from all the structural parts at the risk of weakening the structure, above all during the sampling process itself, as well as the negative financial and time factors, that this procedure would imply. At the other far end we would place the case of evaluating the strength in a great structural area on the basis of the results from breaking a small quantity of test pieces, by way of an extrapolation without the required guarantees. Naturally, the number of test and their emplacement situates the problem in between the two above mentioned extremes. The necessary extrapolation of some results that by nature are not exhaustive, is then carried out with greater or lesser guarantee with regard to advance knowledge of the execution of the work: the greater this knowledge is, the easier it is to establish the strength relation between the specimens and the pieces, which without being represented directly by samples, can adapt themselves to their characteristics, either by proximity or known execution rhythm. The most important problem arises when there is not enough knowledge on how the work was carried out, so that it is impossible to relate the strength of the test specimens with the actual strength of the rest of the structure under investigation. In this case it does not seem possible to establish the relation between two points in the structure other than on the basis of the actual physical distances and the results obtained through the test specimens. This report dealts with the application of the Information theory to quantify these relations and to group the points at which the concrete strength is estimated.El carácter destructivo de la extracción de probetas testigo, actualmente el único ensayo de información que facilita datos de partida fidedignos desde el punto de vista resistente, obliga a asignar una resistencia a zonas de la estructura más o menos lejanas de los puntos de extracción. Las variables del problema son el número de extracciones y su localización. En un extremo tendríamos el caso de la obtención de testigos en todas las piezas estructurales, con el consiguiente riesgo de debilitación de la estructura, sobre todo durante las operaciones necesarias para ello, y el gravoso factor económico y de tiempo que este planteamiento lleva aparejado. En el otro extremo se situaría el caso de la evaluación de la resistencia de una gran zona de estructura en base a los resultados de la rotura de un mínimo número de probetas, a través de una extrapolación sin las necesarias garantías. Naturalmente, el número de ensayos de Información y su localización sitúa el problema en una región intermedia entre los dos extremos expuestos. La necesaria extrapolación de unos resultados, forzosamente no exhaustivos, se realiza, entonces, con una mayor o menor garantía en función del conocimiento previo de la ejecución de la obra: cuanto mayor es este conocimiento más fácilmente se podrá establecer la relación de resistencias entre los testigos y las piezas que, sin tener probetas que los representen directamente, puedan, por proximidad o ritmo de ejecución conocido, asimilarse a las características de dichos testigos. El problema más grave se plantea cuando el desconocimiento de la ejecución de la obra no permite establecer nexos de conocimiento entre los resultados obtenidos en determinados testigos y el resto de la zona de estructura cuya capacidad resistente se trata de evaluar. En este caso no parece posible el establecimiento de relaciones entre dos puntos de la estructura más que basándose en las distancias físicas y los resultados obtenidos en los testigos ensayados. Este trabajo trata de la aplicación de la teoría de la información para cuantificar estas relaciones y agrupar los puntos en los cuales el hormigón es objeto de estimación resistente

Epigenetic and sex differences in opioid use disorder in chronic pain: A real-world study linked with OPRM1 DNA methylation

Opioid use disorder (OUD) is a multifaceted condition influenced by sex, genetic and environmental factors that could be linked with epigenetic changes. Understanding how these factors interact is crucial to understand and address the development and progression of this disorder. Our aim was to elucidate different potential epigenetic and genetic mechanisms between women and men that correlate with OUD under real-world pain unit conditions. Associations between analgesic response and the DNA methylation level of the opioid mu receptor (OPRM1) gene (CpG sites 1–5 selected in the promoter region) were evaluated in 345 long opioid-treated chronic non cancer pain: cases with OUD (n = 67) and controls (without OUD, n = 278). Cases showed younger ages, low employment status and quality of life, but higher morphine equivalent daily dose and psychotropic use, compared to the controls. The patients with OUD showed a significant decrease in OPRM1 DNA methylation, which correlated with clinical outcomes like pain relief, depression and different adverse events. Significant differences were found at the five CpG sites studied for men, and exclusively in women for CpG site 3, in relation to OUD diagnosis. These findings support the importance of epigenetics and sex as biological variables to be considered toward efficient OUD understanding and therapy developmen

On the usage of GRECOSAR: an orbital polarimetric SAR simulator of complex targets for vessel classification studies

This paper presents a synthetic aperture radar (SAR) simulator that is able to generate polarimetric SAR (POLSAR) and polarimetric inverse SAR data of complex targets. It solves the electromagnetic problem via high-frequency approximations, such as physical optics and the physical theory of diffraction, with notable computational efficiency. In principle, any orbital monostatic sensor working at any band, resolution, and operating mode can be modeled. To make simulations more realistic, the target’s bearing and speed are considered, and for the particular case of vessels, even the translational and rotational movements induced by the sea state. All these capabilities make the simulator a powerful tool for supplying large amounts of data with precise scenario information and for testing future sensor configurations. In this paper, the usefulness of the simulator on vessel classification studies is assessed. Several simulated polarimetric images are presented to analyze the potentialities of coherent target decompositions for classifying complex geometries, thus basing an operational algorithm. The limitations highlighted by the results suggest that other approaches, like POLSAR interferometry, should be explored.Peer Reviewe

Malaltia de Kikuchi-Fujimoto: presentació d'un cas pediàtric

Introducció. La malaltia de Kikuchi-Fujimoto, o limfadenitis necrosant histiocítica, és una patologia benigna poc freqüent que es caracteritza per clínica de febre i limfadenopatia cervical. Predomina en noies joves i habitualment s'autolimita entre els 2 i els 4 mesos sense complicacions. Cas clínic. Es presenta el cas d'una pacient de 14 anys que presenta febre de tres dies d'evolució i adenopaties cervicals dretes. Les setmanes prèvies va presentar un quadre febril que es va autolimitar sense poder filiar-ne l'etiologia. S'amplia l'estudi amb proves complementàries, i es descarten amb l'analítica sanguínia i les proves d'imatge les causes infeccioses o tumorals. Es fa exèresi quirúrgica d'una adenopatia cervical amb intenció diagnosticoterapèutica. L'estudi immunohistoquímic presenta característiques típiques de la limfadenitis necrosant histiocítica. La pacient presenta remissió de la simptomatologia i desaparició de les adenopaties. Comentaris. La limfadenitis necrosant histiocítica és una malaltia poc freqüent, però és important tenir-la en compte en pacients joves amb quadre febril i adenopaties de llarga evolució. La biòpsia del gangli per al diagnòstic definitiu és important per evitar altres proves o tractaments més agressius i innecessaris

Control of the Reaction Mechanism of Alkylaromatics Transalkylation by Means of Molecular Confinement Effects Associated to Zeolite Channel Architecture

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.9b00763"[EN] Transalkylation of alkylaromatics catalyzed by acid zeolites is a process widely employed in the petrochemical industry for upgrading aromatic fractions. The reaction mechanism is complex as it can proceed either by intermolecular alkyl-transfer involving dealkylation-alkylation steps with surface alkoxy species as reaction intermediates or through the formation of bulkier diaryl intermediates. We have investigated how the possible formation of such bulky intermediates in the microporous channel system of different zeolite structures, together with their stabilization by confinement effects, can determine the preferential mechanism and, therefore, the selectivity of ethylbenzene disproportionation into benzene and diethylbenzene. For testing the concept, four zeolites, MCM-22 (3D MWW) with 1OR pores, 12R cavities and external 12R hemicavities or "cups", DS-ITQ2, (2D MWW) with the same 1OR channels as MCM-22, no 12R cavities and much larger proportion of external "cups", a 10R ZSM-5 (MFI) and a 12R mordenite (MOR) have been used. The higher activity of DS-ITQ2 and MCM-22 as compared to ZSM-5 at low temperature (573 K) and the high selectivity to diethylbenzene of the bidimensional material under all reaction conditions considered have been explained by means of DFT calculations. Contrary to what could be expected according to the available space at the external "cups" and at the lOR channels of the MWW structure, the bulkier diaryl intermediates are better stabilized within the lOR channel system than at the "cups" open at the external surface of the MWW materials. We show from this perspective how the channel structure and molecular confinement stabilization also explain the operating reaction mechanism in ZSM-5 and mordenite.This work was supported by the Spanish Government through "Severo Ochoa Program" (SEV 2012-0267; SEV-2016-0683), RTI2018-101033-B-I00 and MAT2017-82288-C2-1-P, by the Fundacion Ramon Areces through a research contract of the "Life and Materials Science" program, and by the European Union through ERC-AdG-2014-671093 (SynCatMatch). Red Espanola de Supercomputacion (RES) and Centre de Calcul de la Universitat de Valencia are gratefully acknowledged for computational resources and technical support. We thank the Electron Microscopy Service of the UPV for their help in sample characterization.Margarit Benavent, VJ.; Osman, M.; Al-Khattaf, S.; Martínez, C.; Boronat Zaragoza, M.; Corma Canós, A. (2019). Control of the Reaction Mechanism of Alkylaromatics Transalkylation by Means of Molecular Confinement Effects Associated to Zeolite Channel Architecture. ACS Catalysis. 9(7):5935-5946. https://doi.org/10.1021/acscatal.9b00763S593559469

Direct Synthesis of Nano-Ferrierite along the 10-Ring-Channel Direction Boosts Their Catalytic Behavior

[EN] Ferrierite zeolites with nanosized crystals and external surface areas higher than 250m(2)g(-1) have been prepared at relatively low synthesis temperature (120 degrees C) by means of the collaborative effect of two organic structure directing agents (OSDA). In this way, hierarchical porosity is achieved without the use of post-synthesis treatments that usually involve leaching of Tatoms and solid loss. Adjusting the synthesis conditions it is possible to decrease the crystallite size in the directions of the 8- and 10-ring channels, [010] and [001] respectively, reducing their average pore length to 10-30nm and increasing the number of pores accessible. The small crystal size of the nano-ferrierites results in an improved accessibility of reactants to the catalytic active centers and enhanced product diffusion, leading to higher conversion and selectivity with lower deactivation rates for the oligomerization of 1-pentene into longer-chain olefins.This work has been supported by the European Union through the European Research Council (ERC-AdG-2014-671093, SynCatMatch) the Spanish government through the "Severo Ochoa Program" (SEV-2016-0683) and CTQ2015-70126-R, and by the Fundacion Ramon Areces through a research project within the "Life and Materials Sciences" program. M.R.D.-R. acknowledges "La Caixa-Severo Ochoa" International PhD Fellowships (call 2015). The Electron Microscopy Service of the Universitat Politecnica de Valencia is acknowledged for its help in sample characterization. We thank Dr. Manuel Moliner for helpful discussions.Margarit Benavent, VJ.; Díaz-Rey, MDR.; Navarro Villalba, MT.; Martínez, C.; Corma Canós, A. (2018). Direct Synthesis of Nano-Ferrierite along the 10-Ring-Channel Direction Boosts Their Catalytic Behavior. Angewandte Chemie International Edition. 57(13):3459-3463. https://doi.org/10.1002/anie.201711418S34593463571

Production of aromatics from biomass by computer-aided selection of the zeolite catalyst

[EN] Taking into account that the transformation of biomass-derived 2,5-dimethylfuran (DMF) top-xylene involves Diels-Alder (DA) cycloaddition as the limiting step, the use of an ITQ-2 zeolite obtained by direct synthesis (DS-ITQ-2) as a catalyst for this reaction is proposed based on the fact that the organic molecule employed for its synthesis mimics the size and shape of the DA oxanorbornene cycloadduct intermediate. Periodic Density Functional Theory (DFT) calculations reveal a better stabilization of the oxanorbornene intermediate within the external hemicavities or "cups" of the DS-ITQ-2 zeolite (MWW-framework) than in other zeolites employed for this reaction, such as FAU and Beta. Interestingly, experimental results also show improved catalytic conversion values for the DS-ITQ-2 zeolite compared to FAU and Beta, in good agreement with the stabilization energies calculated by DFT. The "ab initio" catalyst design presented here to enhance the catalytic performance for the transformation of biomass-derived products is a valuable example that could be employed for the rationalization of other chemical processes catalyzed by zeolites.This work has been supported by the European Union through ERC-AdG-2014-671093 (SynCatMatch) and by Spanish Government through "Severo Ochoa" (SEV-2016-0683, MINECO), MAT2017-82288-C2-1-P (AEI/FEDER, UE) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE). E. M. G. acknowledges "La Caixa - Severo Ochoa" International PhD Fellowships (call 2015). Elisa Garcia is acknowledged for her technical assistance in this work. The Electron Microscopy Service of the UPV is also acknowledged for their help in sample characterization. We appreciate the support of ExxonMobil Research and Engineering for their help with our efforts in fundamental catalytic research.Margarit Benavent, VJ.; Gallego, EM.; Paris, C.; Boronat Zaragoza, M.; Moliner Marin, M.; Corma Canós, A. (2020). Production of aromatics from biomass by computer-aided selection of the zeolite catalyst. Green Chemistry. 22(15):5123-5131. https://doi.org/10.1039/d0gc01031fS512351312215Owusu, P. A., & Asumadu-Sarkodie, S. (2016). A review of renewable energy sources, sustainability issues and climate change mitigation. Cogent Engineering, 3(1), 1167990. doi:10.1080/23311916.2016.1167990Corma, A., Iborra, S., & Velty, A. (2007). Chemical Routes for the Transformation of Biomass into Chemicals. Chemical Reviews, 107(6), 2411-2502. doi:10.1021/cr050989dSettle, A. E., Berstis, L., Rorrer, N. A., Roman-Leshkóv, Y., Beckham, G. T., Richards, R. M., & Vardon, D. R. (2017). Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds. 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Renewablep-Xylene from 2,5-Dimethylfuran and Ethylene Using Phosphorus-Containing Zeolite Catalysts. ChemCatChem, 9(3), 398-402. doi:10.1002/cctc.201601294Zhao, R., Zhao, Z., Li, S., Parvulescu, A.-N., Müller, U., & Zhang, W. (2018). Excellent Performances of Dealuminated H-Beta Zeolites from Organotemplate-Free Synthesis in Conversion of Biomass-derived 2,5-Dimethylfuran to Renewable p -Xylene. ChemSusChem, 11(21), 3803-3811. doi:10.1002/cssc.201801504Chang, C.-C., Green, S. K., Williams, C. L., Dauenhauer, P. J., & Fan, W. (2014). Ultra-selective cycloaddition of dimethylfuran for renewable p-xylene with H-BEA. Green Chem., 16(2), 585-588. doi:10.1039/c3gc40740cLi, Y.-P., Head-Gordon, M., & Bell, A. T. (2014). Computational Study of p-Xylene Synthesis from Ethylene and 2,5-Dimethylfuran Catalyzed by H-BEA. The Journal of Physical Chemistry C, 118(38), 22090-22095. doi:10.1021/jp506664cNikbin, N., Feng, S., Caratzoulas, S., & Vlachos, D. G. (2014). p-Xylene Formation by Dehydrative Aromatization of a Diels–Alder Product in Lewis and Brønsted Acidic Zeolites. The Journal of Physical Chemistry C, 118(42), 24415-24424. doi:10.1021/jp506027fRohling, R. Y., Hensen, E. J. M., & Pidko, E. A. (2017). Multi-site Cooperativity in Alkali-Metal-Exchanged Faujasites for the Production of Biomass-Derived Aromatics. ChemPhysChem, 19(4), 446-458. doi:10.1002/cphc.201701058DEROUANE, E. (1988). Surface curvature effects in physisorption and catalysis by microporous solids and molecular sieves. Journal of Catalysis, 110(1), 58-73. doi:10.1016/0021-9517(88)90297-7Corma, A. (2004). Attempts to Fill the Gap Between Enzymatic, Homogeneous, and Heterogeneous Catalysis. Catalysis Reviews, 46(3-4), 369-417. doi:10.1081/cr-200036732Gounder, R., & Iglesia, E. (2013). The catalytic diversity of zeolites: confinement and solvation effects within voids of molecular dimensions. 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Sex Differences in Opioid Response Linked to OPRM1 and COMT genes DNA Methylation/Genotypes Changes in Patients with Chronic Pain

Analgesic-response variability in chronic noncancer pain (CNCP) has been reported due to several biological and environmental factors. This study was undertaken to explore sex differences linked to OPRM1 and COMT DNA methylation changes and genetic variants in analgesic response. A retrospective study with 250 real-world CNCP outpatients was performed in which data from demographic, clinical, and pharmacological variables were collected. DNA methylation levels (CpG island) were evaluated by pyrosequencing, and their interaction with the OPRM1 (A118G) and COMT (G472A) gene polymorphisms was studied. A priori-planned statistical analyses were conducted to compare responses between females and males. Sex-differential OPRM1 DNA methylation was observed to be linked to lower opioid use disorder (OUD) cases for females (p = 0.006). Patients with lower OPRM1 DNA methylation and the presence of the mutant G-allele reduced opioid dose requirements (p = 0.001), equal for both sexes. Moreover, COMT DNA methylation levels were negatively related to pain relief (p = 0.020), quality of life (p = 0.046), and some adverse events (probability > 90%) such as constipation, insomnia, or nervousness. Females were, significantly, 5 years older with high anxiety levels and a different side-effects distribution than males. The analyses demonstrated significant differences between females and males related to OPRM1 signalling efficiency and OUD, with a genetic–epigenetic interaction in opioid requirements. These findings support the importance of sex as a biological variable to be factored into chronic pain-management studies