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    Driving the Crystallization of Zeolites

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    [EN] The synthesis of zeolites with new structures and/or improved properties heavily relies on trial and error efforts that are not entirely blind, as the large empirical background accumulated for the last 7 decades can be, to some extent, rationalized and purposefully used to make new materials. The so-called structure-directing factors may be combined to promote (or frustrate) the crystallization of a particular structure. This personal account opens with the concept of geoinspiration, as suggested by Prof. Ruiz-Hitzky, and its application to zeolite synthesis. We then provide a concise overview of structure-direction in the synthesis of zeolites and detail examples, both new and from the literature, on how they can be combined to drive the crystallization towards (or away from) structures displaying particular features.Financial support by the Spanish Ministry of Economy and Competitiveness (MAT2015-71117-R and AGL2015-70235-C2-R) is acknowledged. P. 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    Cancer Survival in Adults in Spain: A Population-Based Study of the Spanish Network of Cancer Registries (REDECAN)

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    © 2022.This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/ This document is the published version of a published work that appeared in final form in CancersThe assessment of cancer survival at the population level is essential for monitoring progress in cancer control. We aimed to assess cancer survival and its trends in adults in Spain. Individual records of 601,250 adults with primary cancer diagnosed during 2002-2013 and followed up to 2015 were included from 13 population-based cancer registries. We estimated net survival up to five years after diagnosis and analyzed absolute changes between 2002-2007 and 2008-2013. Estimates were age-standardized. Analyses were performed for 29 cancer groups, by age and sex. Overall, age-standardized five-year net survival was higher in women (61.7%, 95% CI 61.4-62.1%) than in men (55.3%, 95% CI 55.0-55.6%), and ranged by cancer from 7.2% (pancreas) to 89.6% (prostate) in men, and from 10.0% (pancreas) to 93.1% (thyroid) in women in the last period. Survival declined with age, showing different patterns by cancer. Between both periods, age-standardized five-year net survival increased overall by 3.3% (95% CI 3.0-3.7%) in men and 2.5% (95% CI 2.0-3.0%) in women, and for most cancer groups. Improvements were greater in patients younger than 75 years than in older patients. Chronic myeloid leukemia and myeloma showed the largest increases. Among the most common malignancies, the greatest absolute increases in survival were observed for colon (5.0%, 95% CI 4.0-6.0%) and rectal cancers (4.5%, 95% CI 3.2-5.9%). Survival improved even for some cancers with poor prognosis (pancreas, esophagus, lung, liver, and brain cancer). Further investigation of possible sociodemographic inequalities is warranted. This study contributes to the evaluation of cancer control and health services' effectiveness

    Synthesis of the Ti-Silicate Form of BEC Polymorph of B-Zeolite Assisted by Molecular Modeling

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    This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/jp805400u Published Work, see http://pubs.acs.org/page/policy/articlesonrequest/index.html[EN] The K(+) free pure silica form of polymorph C (BEC) of beta-zeolite has been synthesized with a cationic organic structure directing agent (SDA) that was predicted best, out of a series of nine potentials, by means of modeling techniques. On the bases of this synthesis method, the Ti-BEC zeolite has been obtained which owing to the pore topology and dimensions shows a higher epoxidation activity than the Ti-beta-polymorph either with H(2)O(2) or organic peroxides as oxidants.The authors thank the CICYT for financial support (Project MAT 2006-14274-CO2-01). G.S. thanks "Centro de Calculo de la Universidad Politecnica de Valencia" for the use of their computational facilities. M.M. and P.S. thank ITQ for a scholarship. We also thank intramural project CRENATUM.Moliner Marin, M.; Serna Merino, PM.; Cantin Sanz, A.; Sastre Navarro, GI.; Díaz Cabañas, MJ.; Corma Canós, A. (2008). Synthesis of the Ti-Silicate Form of BEC Polymorph of B-Zeolite Assisted by Molecular Modeling. The Journal of Physical Chemistry C. 112(49):19547-19554. https://doi.org/10.1021/jp805400uS19547195541124

    Compromised Hippocampal Neuroplasticity in the Interferon-α and Toll-like Receptor-3 Activation-Induced Mouse Depression Model.

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    Disrupted neuronal plasticity due to subtle inflammation is considered to play a fundamental role in the pathogenesis of major depressive disorder. Interferon-α (IFN-α) potentiates immune responses against viral pathogens that induce toll-like receptor-3 (TLR3) activation but evokes severe major depressive disorder in humans by mechanisms that remain insufficiently described. By using a previously established mouse model of depression induced by combined delivery of IFN-α and polyinosinic:polycytidylic acid (poly(I:C)), a TLR3 agonist, we provide evidence that IFN-α and poly(I:C) reduce apical dendritic spine density in the hippocampal CA1 area ex vivo via mechanisms involving decreased TrkB signaling. In vitro, IFN-α and poly(I:C) treatments required neuronal activity to reduce dendritic spine density and TrkB signaling. The levels of presynaptic protein vesicular glutamate transporter (VGLUT)-1 and postsynaptic protein postsynaptic density-95 (PSD95) were specifically decreased, whereas the expression of both synaptic and extrasynaptic α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor 1 (AMPAR1) was increased by IFN-α and poly(I:C) delivery. Patch clamp recordings in primary hippocampal neurons revealed that morphological changes at the synapse induced by IFN-α and poly(I:C) costimulation were accompanied by an increased action potential threshold and action potential frequency, indicative of impaired neuronal excitability. Taken together, IFN-α and poly(I:C) delivery leads to structural and functional alterations at the synapse indicating that compromised neuroplasticity may play an integral role in the pathogenesis of immune response-induced depression

    A new microporous zeolitic silicoborate (ITQ-52) with interconnected small and medium pores

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    A new zeolite (named as ITQ-52) having large cavities and small and medium channels has been synthesized. This was achieved by using a new family of amino-phosphonium cations as organic structure directing agents (OSDA). These cations contain P&#8722;C and P&#8722;N bonds, and therefore they lie between previously reported P-containing OSDA, such as tetraalkylphosphonium and phosphazenes. In this study, it has been found that 1,4- butanediylbis[tris(dimethylamino)]phosphonium dication is a very efficient OSDA for crystallization of several zeolites, and in some particular conditions, the new zeolite ITQ-52 was synthesized as a pure phase. The structure of ITQ-52 has been solved using high-resolution synchrotron X-ray powder diffraction data of the calcined solid. This new zeolite crystallizes in the space group I2/m, with cell parameters a = 17.511 Å, b = 17.907 Å, c = 12.367 Å, and &#946; = 90.22°. The topology of ITQ-52 can be described as a replication of a composite building unit with ring notation [435461] that gives rise to the formation of an interconnected 8R and 10R channel system.We thank financial support by the Spanish Government (MAT2012-38567-C02-01, MAT2012-38567-C02-02, Consolider Ingenio 2010-Multicat CSD-2009-00050 and Severo Ochoa SEV-2012-0267). R.S. acknowledges to UPV for a FPI predoctoral fellowship. Authors thank ALBA Light Source for beam allocation at beamline MSPD. We thank G. Sastre and J. A. Vidal for computational calculations and MAS NMR experiments, respectively.Simancas Coloma, R.; Jorda Moret, JL.; Rey Garcia, F.; Corma Canós, A.; Cantin Sanz, A.; Peral, I.; Popescu, C. (2014). A new microporous zeolitic silicoborate (ITQ-52) with interconnected small and medium pores. Journal of the American Chemical Society. 136(9):3342-3345. doi:10.1021/ja411915cS33423345136

    Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D

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    [EN] Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 degrees C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation-reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.This work was funded by the Spanish Government (Consolider Ingenio 2010-MULTICAT (CSD2009-00050) and MAT2014-52085-C2-1-P) and by the Generalitat Valenciana (Prometeo). The Severo Ochoa Program (SEV-2012-0267) is gratefully acknowledged. L.L. thanks ITQ for a contract. The authors also thank the Microscopy Service of UPV for the TEM and STEM measurements. The HAADF-HRSTEM works were conducted in the Laboratorio de Microscopias Avanzadas (LMA) at the Instituto de Nanociencia de Aragon (INA)-Universidad de Zaragoza (Spain), a Spanish ICTS National Facility. Some of the research leading to these results has received funding from the European Union Seventh Framework Program under Grant Agreement 312483-ESTEEM2 (Integrated Infrastructure Initiative-I3). R.A. also acknowledges funding from the Spanish Ministerio de Economia y Competitividad (FIS2013-46159-C3-3-P) and the European Union Horizon 2020 research and innovation programme under the Marie Sldodowska-Curie grant agreement No. 642742.Liu, L.; DĂ­az Morales, UM.; Arenal, R.; Agostini, G.; ConcepciĂłn Heydorn, P.; Corma CanĂłs, A. (2017). Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials. 16(1):132-138. https://doi.org/10.1038/NMAT4757S132138161Boronat, M., Leyva-Perez, A. & Corma, A. Theoretical and experimental insights into the origin of the catalytic activity of subnanometric gold clusters: attempts to predict reactivity with clusters and nanoparticles of gold. Acc. Chem. Res. 47, 834–844 (2014).Flytzani-Stephanopoulos, M. & Gates, B. C. Atomically dispersed supported metal catalysts. Ann. Rev. Chem. Bio. Eng. 3, 545–574 (2012).Gates, B. C. Supported metal clusters: synthesis, structure, and catalysis. 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Ed. 50, 3947–3949 (2011).Kim, J., Kim, W., Seo, Y., Kim, J.-C. & Ryoo, R. n-Heptane hydroisomerization over Pt/MFI zeolite nanosheets: effects of zeolite crystal thickness and platinum location. J. Catalys. 301, 187–197 (2013).Goel, S., Wu, Z., Zones, S. I. & Iglesia, E. Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites. J. Am. Chem. Soc. 134, 17688–17695 (2012).Choi, M., Wu, Z. & Iglesia, E. Mercaptosilane-assisted synthesis of metal clusters within zeolites and catalytic consequences of encapsulation. J. Am. Chem. Soc. 132, 9129–9137 (2010).Choi, M., Yook, S. & Kim, H. Hydrogen spillover in encapsulated metal catalysts: new opportunities for designing advanced hydroprocessing catalysts. ChemCatChem 7, 1048–1057 (2015).Kulkarni, A., Lobo-Lapidus, R. J. & Gates, B. C. Metal clusters on supports: synthesis, structure, reactivity, and catalytic properties. Chem. Commun. 46, 5997–6015 (2010).Guzman, J. & Gates, B. C. Supported molecular catalysts: metal complexes and clusters on oxides and zeolites. Dalton Trans. 1, 3303–3318 (2003).Leonowicz, M. E., Lawton, J. A., Lawton, S. L. & Rubin, M. K. MCM-22: a molecular sieve with two independent multidimensional channel systems. Science 264, 1910–1913 (1994).Camblor, M. A. et al. A new microporous polymorph of silica isomorphous to zeolite MCM-22. Chem. Mater. 8, 2415–2417 (1996).Hyotanishi, M., Isomura, Y., Yamamoto, H., Kawasaki, H. & Obora, Y. Surfactant-free synthesis of palladium nanoclusters for their use in catalytic cross-coupling reactions. Chem. Commun. 47, 5750–5752 (2011).Duchesne, P. N. & Zhang, P. Local structure of fluorescent platinum nanoclusters. Nanoscale 4, 4199–4205 (2012).Lu, J., Aydin, C., Browning, N. D. & Gates, B. C. Imaging isolated gold atom catalytic sites in zeolite NaY. Angew. Chem. Int. Ed. 51, 5842–5846 (2012).YacamĂĄn, M. J., Santiago, U. & MejĂ­a-Rosales, S. in Advanced Transmission Electron Microscopy: Applications to Nanomaterials (eds Francis, L., Mayoral, A. & Arenal, R.) 1–29 (Springer, 2015).Jena, P., Khanna, S. N. & Rao, B. K. Physics and Chemistry of Finite Systems: From Clusters to Crystals (Springer, 1992).Yamasaki, J. et al. Ultramicroscopy 151, 224–231 (2015).Sohlberg, K., Pennycook, T. J., Zhoud, W. & Pennycook, S. J. Insights into the physical chemistry of materials from advances in HAADF-STEM. Phys. Chem. Chem. Phys. 17, 3982–4006 (2015).Aydin, C., Lu, J., Browning, N. D. & Gates, B. C. A ‘smart’ catalyst: sinter-resistant supported iridium clusters visualized with electron microscopy. Angew. Chem. Int. Ed. 51, 5929–5934 (2012).Wei, H. et al. FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat. Commun. 5, 5634 (2014).Addou, R. et al. Influence of hydroxyls on Pd atom mobility and clustering on rutile TiO2(011)-2 × 1. ACS Nano 8, 6321–6333 (2014).Jung, U. et al. Comparative in operando studies in heterogeneous catalysis: atomic and electronic structural features in the hydrogenation of ethylene over supported Pd and Pt catalysts. ACS Catal. 5, 1539–1551 (2015).Agostini, G. et al. Effect of different face centered cubic nanoparticle distributions on particle size and surface area determination: a theoretical study. J. Phys. Chem. C 118, 4085–4094 (2014).Alexeev, O. & Gates, B. C. EXAFS characterization of supported metal-complex and metal-cluster catalysts made from organometallic precursors. Top. Catal. 10, 273–293 (2000).Chakraborty, I., Bhuin, R. G., Bhat, S. & Pradeep, T. Blue emitting undecaplatinum clusters. Nanoscale 6, 8561–8564 (2014).Zheng, J., Nicovich, P. R. & Dickson, R. M. Highly fluorescent noble-metal quantum dots. Ann. Rev. Phys. Chem. 58, 409–431 (2007).Okrut, A. et al. 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    Predicting non-invasive ventilation failure in children from the SpO₂/FiO₂ (SF) ratio

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    PURPOSE: Our objective was to assess whether SpO₂/FiO₂ (SF) ratio could be a useful NIV outcome predictor in children with acute respiratory failure (ARF) and tried to develop a predictive model of NIV failure. METHODS: Prospective, observational, multicenter study. Episodes of ARF-fulfilling inclusion criteria from 15 January 2010 to 14 January 2011 were treated with NIV according to a pre-established protocol. Clinical variables were collected at baseline and at 1, 2, 6, 12 and 24 h. Failure criterion was the need for endotracheal intubation. Failures were considered as "early" if occurring ≀6 h after NIV initiation, "intermediate" if occurring between 6 and 24 h, and "late" if occurring after 24 h. Variables with a p < 0.1 in univariate analysis corrected by age were included in multivariate analysis. Models were calculated based on multivariate analysis. RESULTS: During the study period, 390 episodes were included. NIV success rate was 81.3 %. Among ARF causes, failure occurred most frequently in ARDS episodes. The failure predictive model for the whole sample included SF ratio at 1 h, age and PRISM III-24 (area under the curve AUC of 0.755). For early NIV failures, SF ratio at 1 h was the only variable within model (AUC 0.748). The analysis of intermediate NIV failures identified 3 variables independently linked to NIV outcome: PRISM III-24, RR decrease at 6 h, and SF ratio at 6 h (AUC 0.895). No model was identified for late NIV failure. CONCLUSIONS: SF ratio is a reliable predictor of early NIV failure in children
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