ITQ-39 zeolite, an efficient catalyst for the conversion of low value naphtha fractions into diesel fuel: The role of pore size on molecular diffusion and reactivity

[EN] ITQ-39, a multipore zeolite with interconnected 12- and 10-ring channel systems, effectively catalyzes the alkylation of two low value naphtha fractions for the production of diesel range alkylaromatics. A catalytic and molecular dynamics study allows us to conclude that its higher selectivity to the desired diesel fraction and, especially, its longer catalyst life as compared to beta or MCM-22, conventionally used as heterogeneous alkylation catalysts, are due to the combined contribution of its small nano-sized crystallites, moderate Bronsted acidity and unique framework topology. The small diffusion coefficients obtained for alkylaromatics on ITQ-39 as compared to those corresponding to the large pore beta zeolite evidence the significant diffusional problems of most of the reactants and products through the channels of the ITQ-39 structure. Thus, alkylation reactions on this zeolite seem to occur mainly on the most external acid sites (external surface, pore mouths), whereas the zeolite structure contributes positively by preventing undesired reactions to occur, which would result in lower selectivity to the monoalkylated products and in a faster catalyst deactivation.Financial support by the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), Consolider Ingenio 2010-Multicat, MAT2012-37160 and MAT2012-31657, by the European Union through ERC-AdG-2014-671093 - SynCatMatch and by the Generalitat Valenciana through the Prometeo program (PROME-TEOII/2013/011) is acknowledged. Repsol is thanked for financial support and permission to publish these results. G.S. thanks ASIC-UPV for computing time. The Electron Microscopy Service of the UPV is acknowledged for their help in samples characterization.Martínez Armero, ME.; Moliner Marin, M.; Sastre Navarro, GI.; Rey Garcia, F.; Martínez, C.; Corma Canós, A. (2016). ITQ-39 zeolite, an efficient catalyst for the conversion of low value naphtha fractions into diesel fuel: The role of pore size on molecular diffusion and reactivity. Journal of Catalysis. 333:127-138. https://doi.org/10.1016/j.jcat.2015.10.024S12713833

Supra-molecular assembly of aromatic proton sponges to direct the crystallization of extra-large-pore zeotypes

The combination of different experimental techniques, such as solid C-13 and H-1 magic-angle spinning NMR spectroscopy, fluorescence spectroscopy and powder X-ray diffraction, together with theoretical calculations allows the determination of the unique structure directing the role of the bulky aromatic proton sponge 1,8-bis(dimethylamino)naphthalene (DMAN) towards the extra-large-pore ITQ-51 zeolite through supra-molecular assemblies of those organic molecules.This work has been supported by the Spanish Government through Consolider Ingenio 2010-Multicat, the 'Severo Ochoa Programme' (SEV 2012-0267), MAT2012-37160; UPV through PAID-06-11 (no. 1952); the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA).Martínez Franco, R.; Sun, J.; Sastre Navarro, GI.; Yun, Y.; Zou, X.; Moliner Marin, M.; Corma Canós, A. (2014). Supra-molecular assembly of aromatic proton sponges to direct the crystallization of extra-large-pore zeotypes. Proceedings of the Royal Society of London. Series A, Mathematical and physical sciences. 470:1-13. https://doi.org/10.1098/rspa.2014.0107S113470Moliner, M., Rey, F., & Corma, A. (2013). Towards the Rational Design of Efficient Organic Structure-Directing Agents for Zeolite Synthesis. Angewandte Chemie International Edition, 52(52), 13880-13889. doi:10.1002/anie.201304713Freyhardt, C. C., Tsapatsis, M., Lobo, R. F., Balkus, K. J., & Davis, M. E. (1996). A high-silica zeolite with a 14-tetrahedral-atom pore opening. Nature, 381(6580), 295-298. doi:10.1038/381295a0Wagner, P., Yoshikawa, M., Tsuji, K., Davis, M. E., Wagner, P., Lovallo, M., & Taspatsis, M. (1997). CIT-5: a high-silica zeolite with 14-ring pores. Chemical Communications, (22), 2179-2180. doi:10.1039/a704774fBurton, A., Elomari, S., Chen, C.-Y., Medrud, R. C., Chan, I. Y., Bull, L. M., … Vittoratos, E. S. (2003). SSZ-53 and SSZ-59: Two Novel Extra-Large Pore Zeolites. Chemistry - A European Journal, 9(23), 5737-5748. doi:10.1002/chem.200305238Corma, A., Díaz-Cabañas, M. J., Rey, F., Nicolopoulus, S., & Boulahya, K. (2004). ITQ-15: The first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications. Chem. Commun., (12), 1356-1357. doi:10.1039/b406572gSun, J., Bonneau, C., Cantín, Á., Corma, A., Díaz-Cabañas, M. J., Moliner, M., … Zou, X. (2009). The ITQ-37 mesoporous chiral zeolite. Nature, 458(7242), 1154-1157. doi:10.1038/nature07957Jiang, J., Jorda, J. L., Yu, J., Baumes, L. A., Mugnaioli, E., Diaz-Cabanas, M. J., … Corma, A. (2011). Synthesis and Structure Determination of the Hierarchical Meso-Microporous Zeolite ITQ-43. Science, 333(6046), 1131-1134. doi:10.1126/science.1208652Kubota, Y., Helmkamp, M. M., Zones, S. I., & Davis, M. E. (1996). Properties of organic cations that lead to the structure-direction of high-silica molecular sieves. 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Aproximació química al tractament de residus

En aquesta comunicació es resumeixen alguns dels treballs realitzats en la caracterització, tractament i estudi de propietats fisicoquímiques de diferent tipus de residus industrials: orgànics, metàl·lics i radioactius

Análisis de la tasa de abandono de primer año del Grado en Estadística Aplicada. Evolución y proyección

Fac. de Estudios EstadísticosFALSEsubmitte

CSF Chitinase 3–Like 2 Is Associated With Long-term Disability Progression in Patients With Progressive Multiple Sclerosis

Multiple Sclerosis; ChitinaseEsclerosis múltiple; QuitinasaEsclerosi múltiple; QuitinasaObjective This study aimed to identify long-term prognostic protein biomarkers associated with disease progression in patients with progressive multiple sclerosis (MS). Methods CSF samples were collected from a discovery cohort of 28 patients with progressive MS who participated in a clinical trial with interferon beta. Patients were classified into high and low disability progression phenotypes according to numeric progression rates (NPR) and step-based progression rates (SPR) after a mean follow-up time of 12 years. Protein abundance was measured by shotgun proteomics. Selected proteins from the discovery cohort were quantified by parallel reaction monitoring in CSF samples from an independent validation cohort of 41 patients with progressive MS classified also into high and low disability progression phenotypes after a mean follow-up time of 7 years. Results Of 2,548 CSF proteins identified in the discovery cohort, 10 were selected for validation based on their association with long-term disability progression: SPATS2-like protein, chitinase 3–like 2 (CHI3L2), plasma serine protease inhibitor, metallothionein-3, phospholipase D4, beta-hexosaminidase, neurexophilin-1, adipocyte enhancer-binding protein 1, cathepsin L1, and lipopolysaccharide-binding protein. Only CHI3L2 was validated, and patients with high disability progression exhibited significantly higher CSF protein levels compared with patients with low disability progression (p = 0.03 for NPR and p = 0.02 for SPR). CHI3L2 levels showed good performance to discriminate between high and low disability progression in patients with progressive MS (area under the curve 0.73; sensitivity 90% and specificity 63%). Conclusions Although further confirmatory studies are needed, we propose CSF CHI3L2 as a prognostic protein biomarker associated with long-term disability progression in patients with progressive MS.This work was funded by grants from the International Progressive MS Alliance (grant no. PA0020), Asociación Esclerosis Múltiple (EME)—Red Española de Esclerosi múltiple (REEM), REEM (RD16/0015/002 and RD16/0015/003) cofunded by the Instituto de Salud Carlos III and Fondo Europeo de Desarrollo Regional (FEDER, Otra manera de hacer Europa)

Serum micrornas as tool to predict early response to benralizumab in severe eosinophilic asthma

Severe eosinophilic asthma poses a serious health and economic problem, so new therapy approaches have been developed to control it, including biological drugs such as benralizumab, which is a monoclonal antibody that binds to IL-5 receptor alpha subunit and depletes peripheral blood eosinophils rapidly. Biomarkers that predict the response to this drug are needed so that microRNAs (miRNAs) can be useful tools. This study was performed with fifteen severe eosinophilic asthmatic patients treated with benralizumab, and serum miRNAs were evaluated before and after treatment by semi-quantitative PCR (qPCR). Patients showed a clinical improvement after benralizumab administration. Additionally, deregulation of miR-1246, miR-5100 and miR-338-3p was observed in severe asthmatic patients after eight weeks of therapy, and a correlation was found between miR-1246 and eosinophil counts, including a number of exacerbations per year in these severe asthmatics. In silico pathway analysis revealed that these three miRNAs are regulators of the MAPK signaling pathway, regulating target genes implicated in asthma such as NFKB2, NFATC3, DUSP1, DUSP2, DUSP5 and DUSP16. In this study, we observed an altered expression of miR-1246, miR-5100 and miR-338-3p after eight weeks of benralizumab administration, which could be used as early response markers.This manuscript was funded by Fondo de Investigación Sanitaria–FIS and FEDER (Fondo Europeo de Desarrollo Regional) [PI15/00803, PI18/00044, and FI16/00036], CIBER de Enfermedades Respiratorias (CIBERES), Merck Health Foundation funds, and Ministerio de Ciencia, Innovación y Universidades (RTC-2017-6501-1

Serum neurofilament light chain levels predict long-term disability progression in patients with progressive multiple sclerosis

© Author(s) (or their employer(s)) 2022. No commercial re-use. See rights and permissions. Published by BMJ.Objective : There is a lack of sensitive and specific biomarkers for use in progressive multiple sclerosis (MS). The study aimed to assess the potential of serum neurofilament light chain (sNfL) levels as biomarker of disability progression in patients with progressive MS. Methods: We performed a prospective observational cohort study in 51 patients with progressive MS who participated in a 2-year phase II single-centre, randomised, double-blind, placebo-controlled trial of interferon-beta. Mean (SD) follow-up duration was 13.9 (6.2) years. Levels of sNfL were measured using a single molecule array immunoassay at baseline, 1, 2 and 6 years. Univariable and multivariable analyses were carried out to evaluate associations between sNfL levels and disability progression at short term (2 years), medium term (6 years) and long term (at the time of the last follow-up). Results: A sNfL cut-off value of 10.2¿pg/mL at baseline discriminated between long-term progressors and non-progressors with a 75% sensitivity and 67% specificity (adjusted OR 7.8; 95%¿CI 1.8 to 46.4; p=0.01). Similar performance to discriminate between long-term progressors and non-progressors was observed using age/body mass index-adjusted sNfL Z-scores derived from a normative database of healthy controls. A cut-off increase of 5.1¿pg/mL in sNfL levels between baseline and 6 years also discriminated between long-term progressors and non-progressors with a 71% sensitivity and 86% specificity (adjusted OR 49.4; 95%¿CI 4.4 to 2×103; p=0.008). Conclusions: sNfL can be considered a prognostic biomarker of future long-term disability progression in patients with progressive MS. These data expand the little knowledge existing on the role of sNfL as long-term prognostic biomarker in patients with progressive MS.Postprint (author's final draft

Methodological improvements in the final project of Civil Engineering Degree

The final project of an engineering degree represents a test of maturity where students must crossexamine all the contents studied in the degree which adds technical difficulties. Traditionally the students are supervised by only one teacher and they usually also take a previous course in the writing of the project. Currently, the program of the Civil Engineering Degree contemplates this activity in the last semester with an allocation of 18 credits. The hardest difficulty noted by students and teachers is the short time estimated for writing it. A teaching innovation project is presented herein which aims to define a working protocol in order to help the student in a more efficient and close way during the development of the task. Among the methodological changes introduced, it should be highlighted the tutoring by professors from different areas of knowledge instead of only one professor as it was traditionally done. Thus, coordination mechanisms must be implemented to guarantee the achievement of the proposed objectives. The innovation project also helps to identify tasks that can be advanced in time and gain time for the effective drafting of the project. Some other solutions found will be presented as well as a comparison of the results obtained along this year with those of the former methodology

A Career in Catalysis: Avelino Corma

As one of the most influential scientists in the field of heterogeneous catalysis and materials science, Prof. Avelino Corma has made significant contributions in many diverse fields, spanning over solid catalysts for petrochemistry, solid catalysts for production of fine chemicals, synthesis of microporous and mesoporous materials, development of inorganic-organic hybrid materials, supported metal catalysts (from isolated metal atoms to nanoclusters and nanoparticles) and photochemistry with solid materials. These experimental approaches are complemented with characterization of solid materials with advanced spectroscopy and microscopy techniques as well as theoretical calculations/modeling. The aim of this Account is to overview Avelino's distinguished scientific career and highlight the most remarkable achievements made in his research activities during >40 years. We attempt to show the evolution of Avelino's research topics in his group throughout his career and the approaches that Avelino has chosen to tackle the challenges encountered. The research paradigm developed by Avelino and his team can be inspiring to the researchers in the field of materials science who are striving to translate the knowledge generated in fundamental studies into practical applications for addressing the new scientific challenges encountered in building a sustainable world

Procalcitonin is not sufficiently reliable to be the sole marker of neonatal sepsis of nosocomial origin

BACKGROUND: It has recently been suggested that serum procalcitonin (PCT) is of value in the diagnosis of neonatal sepsis, with varying results. The aim of this prospective multicenter study was to assess the usefulness of PCT as a marker of neonatal sepsis of nosocomial origin. METHODS: One hundred infants aged between 4 and 28 days of life admitted to the Neonatology Services of 13 acute-care teaching hospitals in Spain over 1-year with clinical suspicion of neonatal sepsis of nosocomial origin were included in the study. Serum PCT concentrations were determined by a specific immunoluminometric assay. The reliability of PCT for the diagnosis of nosocomial neonatal sepsis at the time of suspicion of infection and at 12–24 h and 36–48 h after the onset of symptoms was calculated by receiver-operating characteristics (ROC) curves. The Youden's index (sensitivity + specificity - 1) was used for determination of optimal cutoff values of the diagnostic tests in the different postnatal periods. Sensitivity, specificity, and the likelihood ratio of a positive and negative result with the 95% confidence interval (CI) were calculated. RESULTS: The diagnosis of nosocomial sepsis was confirmed in 61 neonates. Serum PCT concentrations were significantly higher at initial suspicion and at 12–24 h and 36–48 h after the onset of symptoms in neonates with confirmed sepsis than in neonates with clinically suspected but not confirmed sepsis. Optimal PCT thresholds according to ROC curves were 0.59 ng/mL at the time of suspicion of sepsis (sensitivity 81.4%, specificity 80.6%); 1.34 ng/mL within 12–24 h of birth (sensitivity 73.7%, specificity 80.6%), and 0.69 ng/mL within 36–48 h of birth (sensitivity 86.5%, specificity 72.7%). CONCLUSION: Serum PCT concentrations showed a moderate diagnostic reliability for the detection of nosocomial neonatal sepsis from the time of suspicion of infection. PCT is not sufficiently reliable to be the sole marker of sepsis, but would be useful as part of a full sepsis evaluation