Características clínicas, complicaciones secundarias y apoyos en personas con lesión medular traumática en Asturias

Background and objective: Traumatic spinal cord injury is a supervening and often devastating event due to functional loss, secondary complications and lack of curative treatment. It is posed as a personal, health and social challenge. The objective of the study is to describe the epidemiological, clinical and support characteristics of people with traumatic spinal cord injury in the Principality of Asturias.Materials and method: Observational, descriptive and cross-sectional study. The population comprised people with traumatic spinal cord injury admitted for any reason at the Central University Hospital of Asturias from January 1, 2005 to January 31, 2015.Results: The number of cases was 92. 76.9% were men. The average age was 48.5 years old and the average age when the injury occurred was 40.2 years old. The most frequent causes were accidents: traffic, labor and fortuitous. The most frequent type of injury: according to limb involvement, paraplegia with 38.5%; according to the extension, the incomplete lesion with 52.6%; according to the neurological level, the dorsal lesion with 45.4% and according to the classification scale of the American Spinal Injury Association (ASIA), the ASIA A lesion with 50.7%. As most frequent secondary complications: 68.7% have neurogenic bladder, 60.2% neurogenic bowel, 46.5% pressure ulcers, 46.4% spasticity and 30.1% neuropathic pain.Conclusions: There is a high prevalence of secondary complications in spinal cord injury, being necessary to join efforts in the prevention and treatment of them.Introducción: La lesión medular traumática es un acontecimiento sobrevenido y frecuentemente devastador debido a la pérdida funcional, a las complicaciones secundarias y a la inexistencia de tratamiento curativo. Se plantea como un reto personal, sanitario y social. El objetivo del estudio es describir las características epidemiológicas, clínicas y los apoyos utilizados de las personas con lesión medular traumática del Principado de Asturias.Materiales y método: Estudio observacional, descriptivo y transversal. La población estuvo conformada por personas con lesión medular traumática ingresadas por cualquier causa en el Hospital Universitario Central de Asturias del 1 de enero de 2005 al 31 de enero de 2015.Resultados: El número de casos fue 92. Un 76,9% eran hombres. La edad media fue 48,5 años y la edad media cuando se produjo la lesión 40,2 años. Las causas más frecuentes fueron los accidentes: de tráfico, laborales y fortuitos. El tipo de lesión más frecuente: según afectación de miembros, la paraplejia con un 38,5%; según la extensión, la lesión incompleta con un 52,6%; según el nivel neurológico, la lesión dorsal con un 45,4% y según la escala de clasificación de la American Spinal Injury Association (ASIA), la lesión ASIA A con un 50,7%. Como complicaciones secundarias más frecuentes: el 68,7% presenta vejiga neurógena, el 60,2% intestino neurógeno, el 46,5 úlceras por presión, 46,4% espasticidad y el 30,1% dolor neuropático. Conclusiones: Existe una alta prevalencia de complicaciones secundarias en la lesión medular, siendo necesario aunar esfuerzos en la prevención y tratamiento de las mismas

General aspects in the use of graphenes in catalysis

[EN] This perspective is aimed at presenting some issues that, in our opinion, have still to be better addressed in the field of graphenes as catalysts. After an introductory section, the article comments on how the number of layers present on the catalyst, termed frequently as graphene, could be in some cases in contradiction with good practices about what should be or not considered as graphene. It will also be commented that some of the characterization tools that are employed in some cases for graphenes as catalysts, like specific surface area measurements based on isothermal gas adsorption on powders or XRD patterns are not well suited to characterizing graphenes. The potential role of impurities and structural defects in graphene catalysis has been highlighted showing the importance of providing exhaustive analysis of the materials. This perspective includes a final section with our view on future progress and wider consensus in the use of graphene in catalysis.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2014-53292-R) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2013/014). SN is thankful for financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016). Financial support by Fundacion Ramon Areces (XVII Concurso Nacional para la adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia).Navalón Oltra, S.; Herance, JR.; Alvaro Rodríguez, MM.; García Gómez, H. (2018). General aspects in the use of graphenes in catalysis. Materials Horizons (Online). 5(3):363-378. https://doi.org/10.1039/c8mh00066bS3633785

Generating and optimizing the catalytic activity in UiO-66 for aerobic oxidation of alkenes by post-synthetic exchange Ti atoms combined with ligand substitution

[EN] The catalytic activity for the aerobic epoxidation of cyclooctene of UiO-66 has been introduced by post synthetic ion exchange of Zr4+ by Ti4+ at the nodes and the performance optimized by nitro substitution in the terephthalate ligand. In this way a TON value of 16,600 (1660 considering Zr + Ti content) was achieved, comparing favorably with the highest catalytic activity reported in homogeneous for the same reaction (10,000 for gamma-SiW10{(Fe3+(OH2)}(O-38(6-)). Kinetic studies have shown that the most likely reactive oxygen species involved in the oxidation is superoxide, with hydroxyl radicals also contributing to the reaction. UiO-66(Zr-5.4 Ti-0.6)-NO2 is stable under catalytic conditions, being used six times without any change in the conversion temporal profile and in the X-ray diffractogram. The scope of UiO-66(Zr-5.4 Ti-0.6)-NO2 promoted aerobic oxidation of alkenes was expanded by including smaller rings cycloalkenes, as well as acyclic and aryl conjugated alkenes. (C) 2018 Elsevier Inc. All rights reserved.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2014-53292-R and CTQ2015-69563-CO2-14) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2017/018). SN thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016).Santiago-Portillo, A.; Navalón Oltra, S.; Alvaro Rodríguez, MM.; García Gómez, H. (2018). Generating and optimizing the catalytic activity in UiO-66 for aerobic oxidation of alkenes by post-synthetic exchange Ti atoms combined with ligand substitution. Journal of Catalysis. 365:450-463. https://doi.org/10.1016/j.jcat.2018.07.032S45046336

A model to enable indirect manufacturing options transactions between organisations: An application to the ceramic industry

En los contextos actuales de competitividad es ampliamente aceptado y probado que la colaboración entre empresas conduce muchas veces a mejores resultados. Además, la industria cerámica española debe mejorar y reducir los costes de sus procesos de fabricación para así poder competir con los productos de menor coste que provienen principalmente de países asiáticos. En este sentido, este trabajo presenta los resultados de aplicar un modelo innovador para facilitar el trasvase indirecto de opciones de fabricación entre dos empresas fabricantes cerámicas competidoras que comparten un mismo proveedor de productos, cuando una de ellas necesita más capacidad de fabricación de la que reservó en base a sus previsiones de demanda y la otra tiene un excedente. Así, se desarrollan una serie de mecanismos decisionales los cuales proporcionan los valores que deben tomar ciertos parámetros para aumentar el beneficio de todos los participantes en el proceso. Dichos parámetros están gobernados por el proveedor común de esmaltes, quien juega el rol de intermediario entre los fabricantes cerámicos y quien determina hasta qué punto es beneficioso el trasvase y bajo qué condiciones debe realizarse el mismo. Con la aplicación de este modelo se alcanzan mejores resultados empresariales tanto económicos como de nivel de servicio.In the current competitive contexts, it is widely accepted and proved that inter-enterprise collaboration lead in many occasions to better results. The Spanish ceramic industry must improve, dropping its manufacturing costs in order to be able to compete with low cost products coming from Asia. In this sense, this work presents the main results obtained from applying an innovative model, which facilitates the transfer of manufacturing options between two ceramic enterprises that share a common supplier in the scenario where one of them needs more manufacturing capacity than the one booked according to its demand forecast and the another need less. Then, some decisional mechanisms are applied, which output the values for certain parameters in order to augment the benefit of all the three participants. With the application of this model better organisational results both economic and of service level are achievedRodríguez Rodríguez, R.; Gómez-Gasquet, P.; Oltra Badenes, RF. (2014). Modelo de trasvase indirecto de opciones de fabricación entre organizaciones: Una aplicación a la industria cerámica. Boletín de la Sociedad Española de Cerámica y Vidrio. 53(6):275-278. doi:10.3989/cyv.2014S27527853

Influence of the organic linker substituent on the catalytic activity of MIL-101(Cr) for the oxidative coupling of benzylamines to imines

[EN] MIL-101(Cr) having substituents at the terephthalate linker (X = H, NO2, SO3H, Cl, CH3 and NH2) promotes the aerobic oxidation of benzylamines to the corresponding N-benzylidene benzylamines at different rates. MIL-101(Cr)¿NO2 was the most active catalyst, about 6-fold more active than the parent MIL-101(Cr). MIL-101(Cr)¿NO2 does not deactivate significantly upon five consecutive reuses, does not leach the metal to the solution and maintains its crystallinity. MIL-101(Cr)¿NO2 is active for a wide range of benzylamines including para-substituted, heterocyclic benzylamines and di- and tribenzylamines.Financial support by the Spanish Ministry of Economy and Competitiveness (CTQ 2015-69153-CO2-1, CTQ2014-53292-R, Severo Ochoa) and Generalitat Valenciana (Prometeo 2013014) is gratefully acknowledged.Santiago-Portillo, A.; Blandez, JF.; Navalón Oltra, S.; Alvaro Rodríguez, MM.; García Gómez, H. (2017). Influence of the organic linker substituent on the catalytic activity of MIL-101(Cr) for the oxidative coupling of benzylamines to imines. Catalysis Science & Technology. 7(6):1351-1362. https://doi.org/10.1039/c6cy02577cS135113627

MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes

[EN] A series of MIL-101(Cr)-X functionalized with electron withdrawing (NO2, SO3H or Cl) or electron donor (NH2 or CH3) groups has been tested for the solvent-free oxidative coupling of thiophenol to disulfides. No byproducts were observed. A relationship between the catalytic activity of these MOFs with the substituent meta Hammet constant on the terephthalate ligand and with their redox potential was found, MIL-101(Cr)-NO2 being the most active catalyst. NO2-substituted MIL-101 is also more efficient than the parent MIL-101(Cr) to promote the aerobic desulfurization of dibenzothiophenes in n-dodecane or commercial Diesel as solvent. No byproduct formation was observed. Mechanistic studies reveal that MIL-101(Cr)-NO2 is acting as heterogeneous catalyst in thiophenol oxidation and as radical initiator for the aerobic desulfurization. For both reactions, the catalyst can be reused without deactivation, maintaining its crystallinity and with negligible metal leaching.Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. S.N. thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovacion y Universidades CTQ-2018 RTI2018-099482-A-I00 project and Generalitat Valenciana grupos de investigacion consolidables 2019 (AICO2019/214 project).Vallés-García, C.; Santiago-Portillo, A.; Alvaro Rodríguez, MM.; Navalón Oltra, S.; García Gómez, H. (2020). MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes. 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K., Allendorf, M., Van Duyne, R. P., & Hupp, J. T. (2011). Metal–Organic Framework Materials as Chemical Sensors. Chemical Reviews, 112(2), 1105-1125. doi:10.1021/cr200324tHorcajada, P., Gref, R., Baati, T., Allan, P. K., Maurin, G., Couvreur, P., … Serre, C. (2011). Metal–Organic Frameworks in Biomedicine. Chemical Reviews, 112(2), 1232-1268. doi:10.1021/cr200256vWu, Y., Song, X., Li, S., Zhang, J., Yang, X., Shen, P., … Xiao, G. (2018). 3D-monoclinic M–BTC MOF (M = Mn, Co, Ni) as highly efficient catalysts for chemical fixation of CO2 into cyclic carbonates. Journal of Industrial and Engineering Chemistry, 58, 296-303. doi:10.1016/j.jiec.2017.09.040Wu, Y., Song, X., Xu, S., Zhang, J., Zhu, Y., Gao, L., & Xiao, G. (2019). 2-Methylimidazole Modified Co-BTC MOF as an Efficient Catalyst for Chemical Fixation of Carbon Dioxide. Catalysis Letters, 149(9), 2575-2585. doi:10.1007/s10562-019-02874-9Wu, Y., Song, X., Zhang, J., Xu, S., Gao, L., Zhang, J., & Xiao, G. (2019). Mn-based MOFs as efficient catalysts for catalytic conversion of carbon dioxide into cyclic carbonates and DFT studies. Chemical Engineering Science, 201, 288-297. doi:10.1016/j.ces.2019.02.032Wu, Y., Song, X., Zhang, J., Xu, S., Xu, N., Yang, H., … Xiao, G. (2018). Zn2(C9H3O6)(C4H5N2)(C4H6N2)3 MOF as a highly efficient catalyst for chemical fixation of CO2 into cyclic carbonates and kinetic studies. Chemical Engineering Research and Design, 140, 273-282. doi:10.1016/j.cherd.2018.10.034Chughtai, A. H., Ahmad, N., Younus, H. A., Laypkov, A., & Verpoort, F. (2015). Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. Chemical Society Reviews, 44(19), 6804-6849. doi:10.1039/c4cs00395kDhakshinamoorthy, A., Opanasenko, M., Čejka, J., & Garcia, H. (2013). Metal organic frameworks as heterogeneous catalysts for the production of fine chemicals. 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Chemical Society Reviews, 38(5), 1248. doi:10.1039/b807083kValvekens, P., Vermoortele, F., & De Vos, D. (2013). Metal–organic frameworks as catalysts: the role of metal active sites. Catalysis Science & Technology, 3(6), 1435. doi:10.1039/c3cy20813cYoon, M., Srirambalaji, R., & Kim, K. (2011). Homochiral Metal–Organic Frameworks for Asymmetric Heterogeneous Catalysis. Chemical Reviews, 112(2), 1196-1231. doi:10.1021/cr2003147Kholdeeva, O. A. (2016). Liquid-phase selective oxidation catalysis with metal-organic frameworks. Catalysis Today, 278, 22-29. doi:10.1016/j.cattod.2016.06.010Chen, Y. F., Babarao, R., Sandler, S. I., & Jiang, J. W. (2010). Metal−Organic Framework MIL-101 for Adsorption and Effect of Terminal Water Molecules: From Quantum Mechanics to Molecular Simulation. Langmuir, 26(11), 8743-8750. doi:10.1021/la904502hJhung, S. H., Lee, J.-H., Yoon, J. W., Serre, C., Férey, G., & Chang, J.-S. (2007). 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Engineering Active Sites in Reduced Graphene Oxide: Tuning the Catalytic Activity for Aerobic Oxidation

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, 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/acssuschemeng.9b02237."[EN] The influence of the graphene oxide (GO) reduction method on the activity of the resulting reduced graphene oxide (rGO) for the aerobic oxidation of benzylamine is reported. Starting from GO obtained by the Hummers method, a series of rGO samples were obtained either by chemical (hydroquinone (HQ), hydrazine (HZ) or ascorbic acid (ASC)) or by thermal reduction were prepared. Analytical and spectroscopic techniques provide evidence showing that chemical reducing agents reduce GO with different functional groups that influence the catalytic activity of the resulting rGO for the activation of molecular oxygen in benzylamine oxidation. The highest activity in the aerobic oxidation of benzylamine at 80 degrees C was found for the rGO-HQ1 sample prepared using HQ as a reducing agent. It is proposed that HQ introduces hydroquinone/p-benzoquinone-like moieties on the graphene sheet that act as active sites in the oxidation reaction. This proposal is supported by the activity of HQand/or p-benzoquinone as organocatalysts and by selective masking of oxygen-functional groups present in the most active rGO sample. The most active rGO sample exhibited good reusability and stability in five consecutive uses. Selective quenching experiments revealed that hydroperoxyl radicals are the primary reactive oxygen species generated in the system.Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. S.N. thanks financial support by the Fundacion RamOn Areces (XVIII Concurso Nacional para la Adjudication de Ayudas a la Investigation en Ciencias de la Vida y de la Materia, 2016) and Ministerio de Ciencia, Innovation y Universidades RTI2018-099482-A-I00 project and Generalitat Valenciana (grupos de investigation consolidables 2019, AICO/2019/214). A.D. thanks the University Grants Commission, New Delhi, for the award of an Assistant Professorship under its Faculty Recharge Programme. A.D. also thanks the Department of Science and Technology, India, for the financial support through Extramural Research Funding (EMR/2016/006500).Espinosa-López, JC.; Alvaro Rodríguez, MM.; Dhakshinamoorthy, A.; Navalón Oltra, S.; García Gómez, H. (2019). Engineering Active Sites in Reduced Graphene Oxide: Tuning the Catalytic Activity for Aerobic Oxidation. ACS Sustainable Chemistry & Engineering. 7(19):15948-15956. https://doi.org/10.1021/acssuschemeng.9b02237S159481595671

Tuning the Microenvironment of Gold Nanoparticles Encapsulated within MIL-101(Cr) for the Selective Oxidation of Alcohols with O-2: Influence of the Amino Terephthalate Linker

This is the peer reviewed version of the following article: Chem. Eur. J. 2019, 25, 9280 9286, which has been published in final form at https://doi.org/10.1002/chem.201901361. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] This manuscript reports a comparative study of the catalytic performance of gold nanoparticles (NPs) encapsulated within MIL-101(Cr) with or without amino groups in the terephthalate linker. The purpose is to show how the amino groups can influence the microenvironment and catalytic stability of incorporated gold nanoparticles. The first influence of the presence of this substituent is the smaller particle size of Au NPs hosted in MIL-101(Cr)-NH2 (2.45 +/- 0.19 nm) compared with the parent MIL-101(Cr)-H (3.02 +/- 0.39 nm). Both materials are highly active to promote the aerobic alcohol oxidation and exhibit a wide substrate scope. Although both catalysts can achieve turnover numbers as high as 10(6) for the solvent-free aerobic oxidation of benzyl alcohol, Au@MIL-101(Cr)-NH2 exhibits higher turnover frequency values (12 000 h(-1)) than Au@MIL-101(Cr)-H (6800 h(-1)). Au@MIL-101(Cr)-NH2 also exhibits higher catalytic stability, being recyclable for 20 times with coincident temporal conversion profiles, in comparison with some decay observed in the parent Au@MIL-101(Cr)-H. Characterization by transmission electron microscopy of the 20-times used samples shows a very minor particle size increase in the case of Au@MIL-101(Cr)-NH2 (2.97 +/- 0.27 nm) in comparison with the Au@MIL-101(Cr)-H analog (5.32 +/- 0.72 nm). The data presented show the potential of better control of the microenvironment to improve the performance of encapsulated Au nanoparticles.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, CTQ2015-65963-CQ-R1 and CTQ2014-53292-R) is gratefully acknowledged. 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