Catalytically Active Imine-based Covalent Organic Frameworks for Detoxification of Nerve Agent Simulants in Aqueous Media

A series of imine-based covalent organic frameworks decorated in their cavities with di erent alkynyl, pyrrolidine, and N-methylpyrrolidine functional groups have been synthetized. These materials exhibit catalytic activity in aqueous media for the hydrolytic detoxification of nerve agents, as exemplified with nerve gas simulant diisopropylfluorophosphate (DIFP). These preliminary results suggest imine-based covalent organic frameworks (COFs) as promising materials for detoxification of highly toxic molecules.MINECO (MAT2016-77608-C3-1-P and 2-P, CTQ2017-84692-R) and EU FEDER fundin

Layer-by-Layer Integration of Zirconium Metal-Organic Frameworks onto Activated Carbon Spheres and Fabrics with Model Nerve Agent Detoxification Properties

This research was funded by the Directorate for Planning, Technology, and Innovation (SDG PLATIN) from the Directorate General of Armaments and Material (DGAM) of the Spanish Ministry of Defense, COINCIDENTE Program exp. 1003219007500—NBQD2. The authors also acknowledge EU Feder funding, MINECO (CTQ2017-84692-R and PID2020-113608RB-I00), Universidad de Granada (Plan Propio de Investigación), and Junta de Andalucia (P18-RT-612). Funding for open access charge: Universidad de Granada/CBUA.We report the controlled synthesis of thin films of prototypical zirconium metal-organic frameworks [Zr6O4(OH)4(benzene-1,4-dicarboxylate-2-X)6] (X = H, UiO-66 and X = NH2, UiO-66-NH2) over the external surface of shaped carbonized substrates (spheres and textile fabrics) using a layer-by-layer method. The resulting composite materials contain metal-organic framework (MOF) crystals homogeneously distributed over the external surface of the porous shaped bodies, which are able to capture an organophosphate nerve agent simulant (diisopropylfluorophosphate, DIFP) in competition with moisture (very fast) and hydrolyze the P-F bond (slow). This behavior confers the composite material self-cleaning properties, which are useful for blocking secondary emission problems of classical protective equipment based on activated carbon.CBUADirectorate General of Armaments and MaterialDirectorate for Planning, Technology, and InnovationSpanish Ministry of Defense 1003219007500Universidad de Granad

The Carbonation of Wollastonite: A Model Reaction to Test Natural and Biomimetic Catalysts for Enhanced CO2 Sequestration

One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO2 capture and storage (CCS). Here, we studied the different steps of wollastonite (CaSiO3) carbonation (silicate dissolution -> carbonate precipitation) as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA), a natural enzyme that catalyzes the reversible hydration of CO2(aq), and biomimetic metal-organic frameworks (MOFs). Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl)-specific). CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS.This research was funded by the Spanish Government (grants CGL2015-70642-R, CGL2015-73103-EXP, CTQ2017-84692-R), EU FEDER funding, the University of Granada (“Unidad Científica de Excelencia” UCE-PP2016-05) and the Junta de Andalucía (grant P11-RNM-7550 and Research Group RNM-179). We thank the personnel of the Centro de Instrumentación Científica (CIC) of the University of Granada for their help during TG-DSC, FESEM, -XRD, and ICP-OES analyses

Materiales autolimpiables basados en composites de polímeros de coordinación porosos

El vertiginoso desarrollo tecnológico e industrial de las últimas décadas está llevando consigo una emisión descontrolada de gases nocivos para el medio ambiente, cuyos efectos ya se pueden observar. La alarma social que esto ha despertado hace que gran parte de la comunidad científica esté centrando sus esfuerzos en el desarrollo de sistemas eficaces para neutralizar estas emisiones. Uno de los ejemplos prototípicos de compuestos tóxicos son los agentes de guerra química (Chemical Warfare Agents, CWAs). Es importante resaltar que son los compuestos químicos conocidos de mayor toxicidad y suponen una gran amenaza social debido a la relativa facilidad con la que grupos terroristas o gobiernos sin escrúpulos pueden llevar a cabo su fabricación y almacenamiento. Entre los tipos de CWAs destacan los llamados agentes nerviosos, compuestos organofosforados que dañan el sistema nervioso central; y los agentes vesicantes, compuestos organosulfurados que provocan quemaduras en la piel y mucosas. El origen de la toxicidad de estos compuestos se encuentra relacionado con la reactividad de los enlaces P-X y C-X (X= F, Cl, O, S), la volatilidad de estos compuestos y la baja polaridad del esqueleto esqueleto orgánico que permite su fácil penetración a través de la piel y mucosas.Tesis Univ. Granada

Adsorbentes autolimpiables de compuestos orgánicos volátiles tóxicos

Número de publicación: 2 677 143Número de solicitud: 201631713Adsorbentes autolimpiables de compuestos orgánicos volátiles tóxicos. La invención describe un material adsorbente que comprende un catalizador activo en degradación hidrolítica de contaminantes basado en hidróxido de zirconio dopado con compuestos de litio y/o magnesio de naturaleza básica, que no son tóxicos ni corrosivos y presentan propiedades autolimpiables siendo capaz de descontaminar aire, agua o superficies contaminadas con un agente de guerra química o insecticida o un compuesto análogo.Universidad de GranadaMinisterio de Defens

Sólido MOF de titanio-hierro, procedimiento para su obtención y su uso para la degradación de compuestos

Número de publicación: 2844934. Número de solicitud: 202030047.El sólido MOF de titanio (IV) y hierro (111), MUV-17 (TiFe2), presenta fórmula general (1): [TjlVFeI1l2 (O)(L)2 (X)3]S, donde X es cada una igual o diferente seleccionada entre: 02-, OH-, H2 O, F, G, Br-, 1-, N03 -, CI04 -, BF4 -, SCN-, OH-, CH3COO-, C5H702 -, S042- y C032-, L es un ligando tricarboxílico y S es al menos una molécula de un disolvente polar seleccionado entre el grupo que consiste en N,N'-dimetilformamida, N,N'-dietilformamida, N,N'dimetilacetamida, N-metil-2-pirrolidona, metanol, etanol, isopropanol, n-propanol, agua y mezclas de los mismos. El sólido MOF de titanio (IV) y hierro (111) tiene actividad catalítica prolongada en el tiempo para degradar compuestos tóxicos. El procedimiento para su obtención comprende disolver los componentes en condiciones anaeróbicas. La invención también se refiere al uso del sólido MOF de titanio (IV) y hierro (111) como aditivo con propiedades detoxificadoras de compuestos tóxicos.Universidad de Granad

Torque teno virus load predicts opportunistic Infections after kidney transplantation but Is not associated with maintenance immunosuppression exposure

Measuring the non-pathogenic Torque Teno Virus (TTV) load allows assessing the net immunosuppressive state after kidney transplantation (KTx). Currently, it is not known how exposure to maintenance immunosuppression affects TTV load. We hypothesized that TTV load is associated with the exposure to mycophenolic acid (MPA) and tacrolimus. We performed a prospective study including 54 consecutive KTx. Blood TTV load was measured by an in-house PCR at months 1 and 3. Together with doses and trough blood levels of tacrolimus and MPA, we calculated the coefficient of variability (CV), time in therapeutic range (TTR) and concentration/dose ratio (C/D) of tacrolimus, and the MPA-area under the curve (AUC-MPA) at the third month. TTV load at the first and third month discriminated those patients at risk of developing opportunistic infections between months 1 and 3 (AUC-ROC 0.723, 95%CI 0.559-0.905, p = 0.023) and between months 3 and 6 (AUC-ROC 0.778, 95%CI 0.599-0.957, p = 0.028), respectively, but not those at risk of acute rejection. TTV load did not relate to mean tacrolimus blood level, CV, TTR, C/D and AUC-MPA. To conclude, although TTV is a useful marker of net immunosuppressive status after KTx, it is not related to exposure to maintenance immunosuppression.Funding: This research was funded by grants for Fondo de Investigaciones Sanitarias-ISCIII (PI20/01710) and RICORS (ISCIII RD21/0005/0010, “Financiado por la Unión Europea—NextGenerationEU,” Mecanismo para la Recuperación y la Resiliencia [MRR]). Acknowledgments: The authors are indebted to Consuelo Agüeros (Nephrology Research Laboratory, Hospital Marqués de Valdecilla-IDIVAL) for technician suppor

Safety of hospital discharge before return of bowel function after elective colorectal surgery

© 2020 BJS Society Ltd Published by John Wiley & Sons LtdBackground: Ileus is common after colorectal surgery and is associated with an increased risk of postoperative complications. Identifying features of normal bowel recovery and the appropriateness for hospital discharge is challenging. This study explored the safety of hospital discharge before the return of bowel function. Methods: A prospective, multicentre cohort study was undertaken across an international collaborative network. Adult patients undergoing elective colorectal resection between January and April 2018 were included. The main outcome of interest was readmission to hospital within 30 days of surgery. The impact of discharge timing according to the return of bowel function was explored using multivariable regression analysis. Other outcomes were postoperative complications within 30 days of surgery, measured using the Clavien–Dindo classification system. Results: A total of 3288 patients were included in the analysis, of whom 301 (9·2 per cent) were discharged before the return of bowel function. The median duration of hospital stay for patients discharged before and after return of bowel function was 5 (i.q.r. 4–7) and 7 (6–8) days respectively (P < 0·001). There were no significant differences in rates of readmission between these groups (6·6 versus 8·0 per cent; P = 0·499), and this remained the case after multivariable adjustment for baseline differences (odds ratio 0·90, 95 per cent c.i. 0·55 to 1·46; P = 0·659). Rates of postoperative complications were also similar in those discharged before versus after return of bowel function (minor: 34·7 versus 39·5 per cent; major 3·3 versus 3·4 per cent; P = 0·110). Conclusion: Discharge before return of bowel function after elective colorectal surgery appears to be safe in appropriately selected patients