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

Inorganic mesoporous silicas as vehicles of two novel anthracene-based ruthenium metalloarenes

Version aceptada / Accepted versionTwo novel anthracene-based half-sandwich organometallic Ru(II) compounds, namely, [Ru(p-cymene)(L1)Cl2] (1) and [Ru(p-cymene)(L2)Cl2] (2) (L1 = 1-(anthracen-9-yl)-N-(pyridin-3-ylmethyl)methanamine; L2 = 1-(anthracen-9-yl)-N-(pyridin-4-ylmethyl)methanamine) have been synthesized and characterized. We demonstrate that the fluorescence properties of these complexes are highly affected by the linking position of the anthracene unit, as only 2 shows fluorescence emission in the blue region. Regarding their biological activity, both ruthenium metallodrugs show interaction with different biological targets such as S-donor amino acids (cysteine) and proteases (cysteine cathepsin B). Moreover, 1 and 2 show in vitro cytotoxicity against HL-60 cancer cell line (IC50 = 84.5 and 87.0 μM for 1 and 2, respectively), with cell death occurring via apoptosis. Further studies have shown that diffusion into cells is the main mechanism of metallodrug uptake. Finally, as a proof of concept, these ruthenium complexes have been successfully encapsulated into MCM-41 and SBA-15 mesoporous silicas using two different incorporation strategies (impregnation and grinding).The Spanish Ministry of Economy and Competitiveness and UE Feder Program (projects CTQ2014-53486R and CRM Juan de la Cierva Contract), Junta de Andalucía (project P09-FQM-4981 and SR postdoctoral contract), CEI BioTic Granada (project CEI2015-MP-BS39) and COST action CM1105 are gratefully acknowledged for generous funding

Dual removal and selective recovery of phosphate and an organophosphorus pesticide from water by a Zr-based metal-organic framework

The authors express their thanks for the financial support provided by the Marie Sklodowska-Curie Individual Fellowships (H2020-MSCA-IF-2019-EF-ST-888972-PSustMOF, F.J.C.; H2020-MSCA-IF-2016-GF-749359-EnanSET, N.M.P.) within the European Union H2020 programme and EU FEDER. MINECO (CTQ2017-84692-R, PID2020-113608RB-I00, PEJ2018-004022-A), Universidad de Granada (Plan Propio de Investigacion and Programa Operativo FEDER Andalucia 2014-2020: B-FQM-364-UGR18), Junta de Andalucia (P18-RT-612) and 2020 Post-doctoral Junior Leadere-Retaining Fellowship, la Caixa Foundation (ID 100010434 and fellowship code LCF/BQ/PR20/11770014, N.M.P.) are also acknowledged for funding. Funding for open access charge: Universidad de Granada / CBUA.Zr-based metal-organic framework [Zr6(m3-O)4(m3-OH)4(OH)4(H2O)4(1,3,6,8-tetrakis(p-benzoate)pyrene) 2] (NU-1000) has been successfully used to remove phosphate and fenamiphos (an organophosphorus pesticide) from water solutions. In order to approach practical conditions, these studies have been performed under dynamic conditions and in the presence of relevant interferences, such as hydrogen carbonate. The results show that NU-1000 is able to adsorb 0.19 mol/mol of phosphate, reaching a plateau after 20 min, while 0.89 mol/mol fenamiphos is captured after 120 min. Afterward, a three-step strategy has been designed, allowing quantitative recovery of both phosphate anions and fenamiphos, separately, and ulterior adsorbent regeneration. Noteworthy, after this treatment, NU-1000 maintains a good performance toward the dual removal and selective desorption of phosphate and fenamiphos for at least two additional cycles.Marie Sklodowska-Curie Individual Fellowships within the European Union H2020 programme H2020-MSCA-IF-2019-EF-ST-888972-PSustMOF H2020-MSCA-IF-2016-GF-749359-EnanSETEuropean CommissionMINECO CTQ2017-84692-R PID2020-113608RB-I00 PEJ2018-004022-AUniversidad de Granada (Plan Propio de Investigacion and Programa Operativo FEDER Andalucia 2014-2020) B-FQM-364-UGR18Junta de Andalucia P18-RT-6122020 Post-doctoral Junior Leadere-Retaining Fellowship, la Caixa Foundation 100010434 LCF/BQ/PR20/11770014Universidad de Granada / CBU

Aluminum Doped MCM-41 Nanoparticles as Platforms for the Dual Encapsulation of a CO-Releasing Molecule and Cisplatin

Accepted version/ Versión aceptadaMesoporous silica Al-MCM-41 nanoparticles have been used, for the first time, as vehicles for the single and dual encapsulation of the cationic CO-releasing molecule (CORM) [Mn(1,4,7-triazacyclononane)(CO)3]+ (ALF472+) and the well-known antineoplastic drug, cis-[PtCl2(NH3)2] (cisplatin). Thus, two new hybrid materials, namely, ALF472@Al-MCM-41 and ALF472-cisplatin@Al-MCM-41, have been isolated and fully characterized. The results reveal that the presence of CORM molecules enhances cisplatin loading 3-fold, yielding a cargo of 0.45 mmol g–1 of ALF472+ and 0.12 mmol g–1 of the platinum complex for ALF472-cisplatin@Al-MCM-41. It is worth noting that ALF472@Al-MCM-41 shows a good dispersion in phosphate buffered saline solution, while the dual hybrid material slightly aggregates in this simulated physiological medium (hydrodynamic size: 112 ± 23 and 336 ± 50 nm, respectively). In addition, both hybrid materials (ALF472@Al-MCM-41 and ALF472-cisplatin@Al-MCM-41) behave as photoactive CO-releasing materials, delivering 0.25 and 0.11 equiv of CO, respectively, after 24 h and exhibiting a more controlled CO delivery than that of the free CORM. Finally, metal leaching studies have confirmed the good retention capacity of Al-MCM-41 toward the potentially toxic manganese fragments (86% of retention after 72 h) as well as the low release of cisplatin (ca. 7% after 72 h).The Spanish Ministry of Economy and Competitivity and UE Feder Program (Projects CTQ2014-53486R and CRM Juan de la Cierva Contract), University of Granada (CRM Reincorporación Plan Propio), Junta de Andalucía (Project P09-FQM-4981 and S.R. postdoctoral contract), and COST action CM1105 are gratefully acknowledged for generous funding. The authors thank Alfama Inc. for providing ALF472. We thank Helia Jeremias and Helena Laronha for the synthesis and purification of ALF472 batches. The NMR data were acquired at CERMAX (Centro de Ressonância Magnética António Xavier), which is a member of the National NMR network

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

Green synthesis of zirconium MOF-808 for simultaneous phosphate recovery and organophosphorus pesticide detoxification in wastewater

MCIN/AEI/10.13039/501100011033 (Project PID2020-113608RBI00), FEDER/Junta de Andalucia-Consejeria de Economia y Conocimiento (Project B-FQM-364-UGR18) and FEDER/Junta de Andalucia-Consejeria de Transformacion Economica, Industria, Conocimiento y Universidades (Project P20_00672 and P18RT-612) and the University of Granada (Project PPJIA2021.20) are acknowledged for funding. F. J. C. is thankful for the.nancial support provided by the Marie Sklodowska-Curie Individual Fellowship (H2020-MSCA-IF-2019-EF-ST-888972 PSustMOF) within the European Union H2020 programme and EU FEDER. L. G. thanks MCIN for her contract (Garant ' ia Juvenil en I+D+i, PEJ 2018-004022-A). Funding for open access charge: Universidad de Granada/CBUA.Agricultural wastewater posseses serious threats to the environment and human health. In this work, we report a green microwave assisted synthesis of MOF-808 with tuned particle size. These materials have been proved to simultaneously degrade a toxic pesticide and capture phosphate from water over several cycles. The adsorbed phosphate can be further recovered, favoring a P-circular economy.MCIN/AEI PID2020-113608RBI00FEDER/Junta de Andalucia-Consejeria de Economia y Conocimiento B-FQM-364-UGR18 FEDER/Junta de Andalucia-Consejeria de Transformacion Economica, Industria, Conocimiento y Universidades P20_00672 P18RT-612University of Granada PPJIA2021.20European Commission 888972MCIN PEJ 2018-004022-AUniversidad de Granada/CBU

Silk fibroin nanoparticles as biocompatible nanocarriers of a novel light-responsive CO-prodrug

Version aceptada /Accepted version[Mn(CO)3(2,2’-bipyridine)(PPh3)](ClO4) (1), a novel photoactive CO- releasing molecule, has been prepared and fully characterized. Besides, silk fibroin nanoparticles (SFNs) have been used, for the first time, as vehicles of 1 leading to the hybrid material 1@SFNs that shows an enhanced CO-delivery.The Spanish Ministry of Economy and Competitivity, the UE FEDER Program (CTQ2017-84692-R), University of Granada (C. R. Maldonado, Reincorporación Plan Propio, I. Romero-García, Beca de Iniciación a la Investigación Plan Propio), and the ERDF/FEDER Operative Programme of the Region of Murcia (Project No. 14-20-01) are gratefully acknowledged for generous funding. This study was partially supported by the “Unidad de Excelencia de Química Aplicada a Biomedicina y Medioambiente” (University of Granada). The research contract of Dr A. Abel Lozano-Pérez was partially supported (80%) by the ERDF/FEDER Operative Programme of the Region of Murcia (Project No. 14-20-01). The authors also thank Prof. Meseguer-Olmo and Dr M. J. Yáñez-Gascón (UCAM, Murcia, Spain) for their help during FESEM image acquisition

Organophosphate Detoxification and Acetylcholinesterase Reactivation Triggered by Zeolitic Imidazolate Framework Structural Degradation

Organophosphate (OP) toxicity is related to inhibition of acetylcholinesterase (AChE) activity, which plays a key role in the neurotransmission process. In this work, we report the ability of different zinc zeolitic imidazolate frameworks (ZIFs) to behave as potential antidotes against OP poisoning. The Zn−L coordination bond (L = purine, benzimidazole, imidazole, or 2-methylimidazole) is sensitive to the G-type nerve agent model compounds diisopropylfluorophosphate (DIFP) and diisopropylchlorophosphate, leading to P−X (X = F or Cl) bond breakdown into nontoxic diisopropylphosphate. P−X hydrolysis is accompanied by ZIF structural degradation (Zn−imidazolate bond hydrolysis), with the concomitant release of the imidazolate linkers and zinc ions representing up to 95% of ZIF particle dissolution. The delivered imidazolate nucleophilic attack on the OP@AChE adduct gives rise to the recovery of AChE enzymatic function. P−X bond breakdown, ZIF structural degradation, and AChE reactivation are dependent on imidazolate linker nucleophilicity, framework topology, and particle size. The best performance is obtained for 20 nm nanoparticles (NPs) of Zn(2-methylimidazolate)2 (sod ZIF-8) exhibiting a DIFP degradation half-life of 2.6 min and full recovery of AChE activity within 1 h. 20 nm sod ZIF-8 NPs are not neurotoxic, as proven by in vitro neuroblastoma cell culture viability tests.Spanish MCIN/AEI/10.13039/501100011033 (project PID2020-113608RB-I00; TED2021-129886B-C41)NATO Science for Peace and Security Programme under grant no. G5889-“SARS-CoV-2 Multi-Messenger Monitoring for Occupational Health & Safety-SARS 3M”Plan Propio de Investigación-Universidad de Granada for a predoctoral fellowshipFEDER/Junta de Andalucía-Consejería de Economía, Conocimiento, Empresas y Universidad (Project C-EXP-056-UGR23)Universidad de Granada for covering the Open Access Article Publication Charg

Nanoscaled zinc pyrazolate metal-Organic frameworks as drug-Delivery systems

This work describes synthesis at the nanoscale of the isoreticular metal–organic framework (MOF) series ZnBDP_X, based on the assembly of ZnII metal ions and the functionalized organic spacers 1,4-bis(1H-pyrazol-4-yl)-2-X-benzene (H2BDP_X; X = H, NO2, NH2, OH). The colloidal stability of these systems was evaluated under different relevant intravenous and oral-simulated physiological conditions, showing that ZnBDP_OH nanoparticles exhibit good structural and colloidal stability probably because of the formation of a protein corona on their surface that prevents their aggregation. Furthermore, two antitumor drugs (mitroxantrone and [Ru(p-cymene)Cl2(pta)] (RAPTA-C) where pta = 1,3,5-triaza-7-phospaadamantane) were encapsulated within the pores of the ZnBDP_X series in order to investigate the effect of the framework functionalization on the incorporation/delivery of bioactive molecules. Thus, the loading capacity of both drugs within the ZnBDP_X series seems to directly depend on the surface area of the solids. Moreover, ligand functionalization significantly affects both the delivery kinetics and the total amount of released drug. In particular, ZnBDP_OH and ZnBDP_NH2 matrixes show a slower rate of delivery and higher percentage of release than ZnBDP_NO2 and ZnBDP_H systems. Additionally, RAPTA-C delivery from ZnBDP_OH is accompanied by a concomitant and progressive matrix degradation due to the higher polarity of the BPD_OH ligand, highlighting the impact of functionalization of the MOF cavities over the kinetics of delivery.The Spanish Ministry of Economy and Competitivity and UE Feder Program (Projects CTQ2011-22787/PPQ and CTQ2014-53486R), Junta de Andalucía (Project P09-FQM-4981 and a predoctoral grant to S.R.), and COST action CM1105 are gratefully acknowledged for generous funding. P.H. and C.S. acknowledge CNRS, Université of Versailles St. Quentin, and the Labex Nanosaclay (Reference ANR-10-LABX-0035) for financial support

Anales de Edafología y Agrobiología Tomo 33 Número 11-12

Efecto de la etiolación en la rizogénesis de Castanea sativa Mili., por A. M. Vieitez y E. Vieitez.-- Efecto de los déficits hídricos en el contenido en hidratos de carbono y en la producción de tubérculos de patata (Solanum tuberosum L.), por M. Sánchez-Díaz, J. Salaverri y J. Grau.--Inhibición de la síntesis de caoiinita vor diversos extractos acuosos de restos vegetales, por F. Guitián Ojea y V. Coladas Calvo.-- Gibsita en suelos sobre granitos del sistema central, por M. Sánchez Camazano.-- El nematodo de los cítricos, Tylenchulus semipenetrans Cobb., en España, por M. P. Alvira.-- Estudio de la migración de arcilla en Jos suelos «Praderas arenosas gris-amarillentas desarrollados sobre las areniscas de Tacuarembo (Uruguay), por A. van Wambeke y D. Barrera Saquieres.-- Crecimiento y materia seca en maíz (Zea mays L.), por Benito Sánchez y Gerardo.-- Regulación de la NADH-nitrato reductasa de Chlamydomonas reinhardi: inactivación reversible in vivo e in vitro, por J. L. Barea, F. M. Sosa y T. Ortega.-- Andosuelos desarrollados sobre íihtas en Ulzama (Navarra), por J. Iñiguez y E. Barragán.-- Mineralogía de las terrazas del río Duero desde Gormaz hasta Peñafiel, por M. A. Hoyos Guerrero, S. Leguey y J. Rodríguez Martínez.-- Estudio de suelos desarrollados sobre rocas cristalinas. I. Zona Ojén-Mijas, por J. Fernándes, J. lñgues y J. Aguilar.-- Estudio de suelos desarrollados sobre rocas cristalinas. II. Zona de Antequera, por J. Fernándes, J. lñiguez y J. Aguilar.—Notas.-- Fallecimiento del Consejero de Número del Patronato Excmo. Sr. D. Miguel Odriozola Pietá.-- El Prof. Primo Yúfera, nuevo Presidente del C. S. I. C.-- Nombramiento de Consejeros de Número.-- Nombramiento de Presidente y Secretario de la División de Ciencias.-- Cese del Presidente del Patronato Alonso de Herrera.-- Propuesta de nuevo Presidente del Patronato Alonso de Herrera.-- Cambio de nombre del Instituto de Investigaciones Geológicas, Edafológicas y Agrobiológicas de Galicia.-- Nombramiento de representante del Patronato Alonso de Herrera» en el Consejo de Dirección del I.N.I. A.-- Cambio en la dirección del Jardín Botánico.-- Nombramiento de Vocales del Crida de la Coruña.-- Nombramiento de Vicedirector del Instituto de Alimentación y Productividad Animal .-- Vocales del Consejo Técnico Administrativo de la Estación Experimental La Mayora.-- Becas ofrecidas por el I. N. I. A.-- Nuevo Prof. Agregado de la Universidad Autónoma de Madrid.-- Autorizaciones para impartir docencia.-- Congresos, reuniones y desplazamientos al extranjero y nacionales.-- Reunión del Grupo de Trabajo de Normalización de Métodos Analíticos.-- La micromorfología del suelo en Polonia.-- Real Academia de Farmacia.-- Instituto Palinológico de León.-- BibliografíaPeer reviewe