41 results on '"Imaz, Inhar"'
Search Results
2. A Molecular Approach for Engineering Interfacial Interactions in Magnetic-Topological Insulator Heterostructures
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Cuxart, Marc G., Valbuena, Miguel Angel, Robles, Roberto, Moreno, César, Bonell, Frédéric, Sauthier, Guillaume, Imaz, Inhar, Xu, Heng, Nistor, Corneliu, Barla, Alessandro, Gargiani, Pierluigi, Valvidares, Manuel, Maspoch, Daniel, Gambardella, Pietro, Valenzuela, Sergio O., and Mugarza, Aitor
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Condensed Matter - Materials Science ,Condensed Matter - Mesoscale and Nanoscale Physics ,Physics - Chemical Physics - Abstract
Controlling interfacial interactions in magnetic/topological insulator heterostructures is a major challenge for the emergence of novel spin-dependent electronic phenomena. As for any rational design of heterostructures that rely on proximity effects, one should ideally retain the overall properties of each component while tuning interactions at the interface. However, in most inorganic interfaces interactions are too strong, consequently perturbing, and even quenching, both the magnetic moment and the topological surface states at each side of the interface. Here we show that these properties can be preserved by using ligand chemistry to tune the interaction of magnetic ions with the surface states. By depositing Co-based porphyrin and phthalocyanine monolayers on the surface of Bi$_2$Te$_3$ thin films, robust interfaces are formed that preserve undoped topological surface states as well as the pristine magnetic moment of the divalent Co ions. The selected ligands allow us to tune the interfacial hybridization within this weak interaction regime. These results, which are in stark contrast with the observed suppression of the surface state at the first quintuple layer of Bi$_2$Se$_3$ induced by the interaction with Co phthalocyanines, demonstrate the capability of planar metal-organic molecules to span interactions from the strong to the weak limit.
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- 2020
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3. Hf/porphyrin-based metal-organic framework PCN-224 for CO2 cycloaddition with epoxides
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Carrasco, Sergio, Orcajo, Gisela, Martínez, Fernando, Imaz, Inhar, Kavak, Safiyye, Arenas-Esteban, Daniel, Maspoch, Daniel, Bals, Sara, Calleja, Guillermo, and Horcajada, Patricia
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- 2023
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4. Supramolecular Fullerene Sponges as Catalytic Masks for Regioselective Functionalization of C60
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Fuertes-Espinosa, Carles, García-Simón, Cristina, Pujals, Míriam, Garcia-Borràs, Marc, Gómez, Laura, Parella, Teodor, Juanhuix, Judit, Imaz, Inhar, Maspoch, Daniel, Costas, Miquel, and Ribas, Xavi
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- 2020
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5. Metal- and covalent-organic framework mixed matrix membranes for CO2 separation: A perspective on stability and scalability
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Shan, Meixia, primary, Geng, Xiumei, additional, Imaz, Inhar, additional, Broto-Ribas, A., additional, Ortín-Rubio, Borja, additional, Maspoch, D., additional, Ansaloni, Luca, additional, Peters, Thijs A., additional, Tena, Alberto, additional, Boerrigter, Marcel E., additional, and Vermaas, David A., additional
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- 2023
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6. Net-clipping as a top-down approach for the prediction of topologies of MOFs built from reduced-symmetry linkers.
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Ortín-Rubio, Borja, Rostoll-Berenguer, Jaume, Vila, Carlos, Proserpio, Davide M., Guillerm, Vincent, Juanhuix, Judith, Imaz, Inhar, and Maspoch, Daniel
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- 2023
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7. Antibacterial Films Based on MOF Composites that Release Iodine Passively or Upon Triggering by Near-Infrared Light
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Han, Xu, Boix, Gerard, Balcerzak, Mateusz, Hernando Moriones, Oscar, Cano-Sarabia, Mary, Cortés Garmendia, M. Pilar, Bastús, Neus G., Puntes, Víctor, Llagostera Casas, Montserrat, Imaz, Inhar, Maspoch Comamala, Daniel, Ministerio de Economía y Competitividad (España), European Commission, Generalitat de Catalunya, China Scholarship Council, Polish National Agency for Academic Exchange, Ministerio de Ciencia e Innovación (España), and Agencia Estatal de Investigación (España)
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Photothermal ,Framework ,Metal-organic ,Triggered release ,Condensed Matter Physics ,Gold nanorods ,Electronic, Optical and Magnetic Materials ,Biomaterials ,Electrochemistry ,Antimicrobial ,metal-organic frameworks ,Composites ,Iodine - Abstract
Multidrug-resistant bacteria have become a global health problem for which new prophylactic strategies are now needed, including surface-coatings for hospital spaces and medical equipment. This work reports the preparation and functional validation of a metal-organic framework (MOF) based composite for the triggered controlled release of iodine, an antimicrobial element that does not generate resistance. It comprises beads of the iodophilic MOF UiO-66 containing encapsulated gold nanorods (AuNRs) coated with a silica shell. Irradiation of the AuNRs with near-infrared light (NIR) provokes a photothermal effect and the resultant heat actively liberates the iodine. After validating the performance of this composite, it is integrated into a polymer for the development of antibacterial films. This work assesses the adsorption of iodine into these composite films, as well as its passive long-term release and active light-triggered. Finally, this work validates the antibacterial activity of the composite films in vitro against gram-positive and gram-negative bacteria. The findings will surely inform the development of new prophylactic treatments., This work was supported by the Spanish MINECO (project RTI2018-095622-B-I00, RTI2018-099965-B-I00, AEI/FEDER, UE), the Catalan AGAUR (project 2017 SGR 238, 2017 SGR 1431), and the ERC, under the EU-FP7 (ERC-Co 615954). It was also funded by the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706). X.H. thanks the China Scholarship Council (CSC) for scholarship support (201804910551). M.B. thanks the Polish National Agency for Academic Exchange (contract no. PPN/BEK/2018/1/00094/U/00001). O.M. acknowledges financial support from the Spanish Ministry of Science and Innovation (MICINN) by FPI fellowship, resolved by the Agencia Estatal de Investigación (AEI) with reference (BES-2017-083043).
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- 2022
8. Synthesis, crystal structure and vibrational spectra characterization of MILa(PO 3) 4 ( MI=Na, Ag)
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Masloumi, Mohamed El, Imaz, Inhar, Chaminade, Jean-Pierre, Videau, Jean-Jacques, Couzi, Michel, Mesnaoui, Mohamed, and Maazaz, Mohamed
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- 2005
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9. A Self-Folding Polymer Film Based on Swelling Metal–Organic Frameworks
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Troyano, Javier, Carné-Sánchez, Arnau, Pérez-Carvajal, Javier, León-Reina, Laura, Imaz, Inhar, Cabeza-Diaz, Aurelio, and Maspoch, Daniel
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Metal–organic frameworks ,Conductores orgánicos ,Self-folding ,Composites ,Films ,Swelling behaviour - Abstract
Herein, we exploit the well-known swelling behaviour of metal–organic frameworks (MOFs) to create a selffolding polymer film. Namely, we show that incorporating crystals of the flexible MOF MIL-88A into a polyvinylidene difluoride (PVDF) matrix affords a polymer composite film that undergoes reversible shape transformations upon exposure to polar solvents and vapours. Since the self-folding properties of this film correlate directly with the swelling properties of the MIL-88A crystals, it selectively bends to certain solvents and its degree of folding can be controlled by controlling the relative humidity. Moreover, it shows a shapememory effect at relative humidity values from 60% to 90%. As proof of concept, we demonstrate that these composite films can lift cargo and can be used to assemble 3D structures from 2D patterns. Our strategy is a straightforward method for designing autonomous soft materials with folding properties that can be tuned by judicious choice of the constituent flexible MOF. Proyecto del MINECO MAT2013-41836-R y de la Junta de Andalucía P12-FQM-1656
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- 2018
10. Self-assembly of polyhedral metal–organic framework particles into three-dimensional ordered superstructures
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Avci, Civan, Imaz, Inhar, Carné-Sánchez, Arnau, Pariente, Jose Angel, Tasios, Nikos, Pérez-Carvajal, Javier, Alonso, Maria Isabel, Blanco, Alvaro, Dijkstra, M., López, Cefe, Maspoch, Daniel, Sub Soft Condensed Matter, Soft Condensed Matter and Biophysics, Sub Soft Condensed Matter, and Soft Condensed Matter and Biophysics
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Metal–organic frameworks ,Chemistry ,General Chemical Engineering ,Nanotechnology ,02 engineering and technology ,General Chemistry ,Self-assembly ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Photonic metamaterial ,Coordination chemistry ,Dodecahedron ,Octahedron ,Lattice (order) ,Optical materials ,Taverne ,Metal-organic framework ,0210 nano-technology ,Plasmon ,Photonic crystal - Abstract
Altres ajuts: Comunidad de Madrid project S2013/MIT-2740 (PHAMA_2.0). CERCA Programme/Generalitat de Catalunya Self-assembly of particles into long-range, three-dimensional, ordered superstructures is crucial for the design of a variety of materials, including plasmonic sensing materials, energy or gas storage systems, catalysts and photonic crystals. Here, we have combined experimental and simulation data to show that truncated rhombic dodecahedral particles of the metal-organic framework (MOF) ZIF-8 can self-assemble into millimetre-sized superstructures with an underlying three-dimensional rhombohedral lattice that behave as photonic crystals. Those superstructures feature a photonic bandgap that can be tuned by controlling the size of the ZIF-8 particles and is also responsive to the adsorption of guest substances in the micropores of the ZIF-8 particles. In addition, superstructures with different lattices can also be assembled by tuning the truncation of ZIF-8 particles, or by using octahedral UiO-66 MOF particles instead. These well-ordered, sub-micrometre-sized superstructures might ultimately facilitate the design of three-dimensional photonic materials for applications in sensing.
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- 2018
11. Magnetic anisotropy and electronic structure of molecular networks on topological insulators
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Cuxart, M. G., Valbuena, Miguel A., Bonell, Fréderic, Moreno, César, Cruz, Jorge, Xu, Heng, Imaz, Inhar, Maspoch, Daniel, Nistor, Corneliu, Gambardella, Pietro, Valenzuela, Sergio O., and Mugarza, Aitor
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Resumen del póster presentado al 1st Workshop Spain-Taiwan: "2D Materials and Interfaces for Spintronics", celebrado en Barcelona (España) del 23 al 25 de octubre de 2017., In topological insulators (TIs), long-range interactions between magnetic dopants mediated by the topological surface states can give rise to exotic phenomena such as the quantum anomalous Hall effect (QAHE) and dissipationless spin polarized edge currents. Such interactions, however, only occur under specific conditions of magnetic moment, anisotropy, and exchange coupling with the surrounding electron bath. Here we propose the use of metalorganic networks as an alternative strategy for tuning the electronic and magnetic interaction between the magnetic impurity and the substrate. The electronic and magnetic properties of TI surfaces modified by Brominated Cobalt tetraphenyl-porphyrin (4Br-CoTPP) networks are studied by combining Angle Resolved Photoemission Spectroscopy (ARPES) with X-Ray Magnetic Circular Dichroism (XMCD) measurements. ARPES measurements reveal that the topological surface state (TSS) is not quenched upon adsorption of slightly more than 1 ML 4Br-CoTPP in contrast with previous ARPES in Cobalt phthalocyanine/TI interfaces. The weaker interaction between the molecular layer and the substrate is confirmed by XMCD measurements where a strong in-plane magnetic moment is preserved. This ligand-mediated tuneability of interfacial interactions, together with the well-known capability of controlling magnetic anisotropy, makes the use of metalorganic molecules a promising route for engineering the electronic and magnetic properties of hybrid TI-based heterostructures.
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- 2017
12. Tuning the endocytosis mechanism of Zr-based metal-organic frameworks through linker functionalization
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Orellana-Tavra, Claudia, Haddad, Salame, Marshall, Ross J., Abánades Lázaro, Isabel, Boix, Gerard, Imaz, Inhar, Maspoch, Daniel, Forgan, Ross S., Fairen-Jimenez, David, Fairen Jimenez, David [0000-0002-5013-1194], and Apollo - University of Cambridge Repository
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Mmetabolic pathways ,drug delivery ,Drug delivery ,metabolic pathways ,endocytosis ,metal−organic frameworks ,Metal−organic frameworks ,Endocytosis ,Research Article - Abstract
A critical bottleneck for the use of metal-organic frameworks (MOFs) as drug delivery systems has been allowing them to reach their intracellular targets without being degraded in the acidic environment of the lysosomes. Cells take up particles by endocytosis through multiple biochemical pathways, and the fate of these particles depends on these routes of entry. Here, we show the effect of functional group incorporation into a series of Zr-based MOFs on their endocytosis mechanisms, allowing us to design an efficient drug delivery system. In particular, naphthalene-2,6-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid ligands promote entry through the caveolin -pathway, allowing the particles to avoid lysosomal degradation and be delivered into the cytosol and enhancing their therapeutic activity when loaded with drugs.
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- 2017
13. Magnetic dopants on the surface of 2D heavy metal alloys and topological insulators
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Valbuena, Miguel A., Cuxart, M. G., Robles, Roberto, Schirone, S., Moreno, César, Bonell, Fréderic, Godey, Sylvie, Cruz, Jorge, Xu, Heng, Imaz, Inhar, Maspoch, Daniel, Nistor, Corneliu, Gambardella, Pietro, and Mugarza, Aitor
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Resumen del trabajo presentado al 1st Workshop Spain-Taiwan: "2D Materials and Interfaces for Spintronics", celebrado en Barcelona (España) del 23 al 25 de octubre de 2017.-- et al., Spin-Orbit Coupling (SOC) is at the origin of important new phenomena in materials such as heavy metal surface alloys with strong Rashba interaction and topological insulators (TIs), both with evident and promising applications in spintronics. Of special relevance are the emergent phenomena derived from the magnetic interactions in ferromagnetic (FM)/SOC interfaces. The Rashba and topological surface states can be used efficiently for reversing the magnetization of FM thin films by charge currents via spin transfer torque and for spin to charge conversion as a result of an inverse Edelstein effect. Besides, in topological insulators (TIs), long-range interactions between magnetic dopants mediated by the topological surface states can give rise to exotic phenomena such as the quantum anomalous Hall effect and dissipationless spin polarized edge currents. Despite their experimental demonstrations, an atomistic understanding of these phenomena is still missing. In this work we present a systematic experimental investigation on the magnetic properties in model FM/SOC interfaces. In a first step we will use 3d transition metals (TM) adatoms as magnetic dopants on the substitutional BiAg2 surface alloy grown on Ag(111). Through the controlled deposition of a series of TM impurities at cryogenic temperatures we systematically study different magnetic configurations. The influence of the SOC interaction, impurity adsorption sites and surface structure on the magnetic anisotropy is analyzed correlating experimental (XMCD) and theoretical (DFT) data. On the other side, we try to overcome the experimental difficulties of controlling the magnetic ground state and anisotropy of 3d transition metal impurities by using metalorganic molecular networks (porphyrin based) as an alternative strategy for tuning the electronic and magnetic interaction between the dopant and the TI substrate. Here, depending on the transition metal ion, the ligand field related to the organic molecular structure and the molecular charge, the magnetic moment and anisotropy can be consequently manipulated.
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- 2017
14. Influence of chemical doping and molecular organization on the electronic properties of 2D organic thin films
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Hieulle, Jeremy, Robles, Roberto, Cruz, Jorge, Imaz, Inhar, Maspoch, Daniel, Moreno, César, and Mugarza, Aitor
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Resumen del póster presentado a la 10th Conferencia Fuerzas y Túnel, celebrada en Girona (España) del 5 al 7 de septiembre de 2016., Designing functional devices based on organic films require a detailed knowledge of the mechanisms that govern their electronic properties. Therefore, it is of prime importance to understand the close relationship existing between the molecular organization of an organic film and its electronic structure. Additionally, the doping of organic semiconductors by using electron donor species like alkali atoms constitutes an effective strategy to improve the performance of organic optoelectronic devices and fabricating materials with exotic electronic properties, such as organic superconductors. Here, we investigate the influence of chemical doping and molecular organization on the electronic properties of a metal-porphyrin derivative (CoTPPBr) by using low-temperature scanning tunneling microscopy (LT-STM) and spectroscopy (STS) techniques. During this work, we observed that the CoTPPBr molecule forms a square self-assembled structure on the Au(111) substrate, similar to what it is generally observed for metalloporphyrin derivatives. In contrast, new self-assembled networks based on the CoTPPBr molecule were seen on the Ag(111) substrate. Additionally, a covalently bound architecture was formed on both substrates after a thermally activated de-bromination reaction. As a consequence, a shift of the HOMO and LUMO orbitals toward higher energies is observed on the silver substrate but not on the gold. Furthermore, a strong modification of the electronic properties of the metal-organic film upon chemical doping was observed using alkali atoms. After doping, the d-levels suffer a drastic change and according to the STS spectra near the Fermi level this has strong consequences to the magnetic state of the molecule. The results presented here give some insights in the realization of covalent metalorganic networks with desired electronic properties.
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- 2016
15. Nanoestructures metal·lobiomoleculars
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Rubio-Martínez, Marta, Imaz, Inhar, Puigmartí-Luis, Josep, and Maspoch, Daniel
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La miniaturització de materials metal·lorgànics a escala nanomètrica és una estratègia emergent per al desenvolupament de noves nanoestructures d'una gran diversitat composicional, estructural i morfològica. Aquests nous nanomaterials, molts d'ells porosos, poden presentar un ventall variat de propietats i, en conseqüència, poden ser utilitzats en diverses àrees tecnològiques, sigui en l'emmagatzematge o la separació de gasos i catàlisis, sigui per formar nous sensors, nanotransportadors de fàrmacs i agents de contrast. Immersos en el desenvolupament d'aquestes nanoestructures, el nostre grup de recerca està actualment desenvolupant una nova aproximació basada en l'ús de biomolècules com a lligands orgànics que, coordinades amb ions metàl·lics, permetin la creació de nanoarquitectures metal·lobiomoleculars. Aquestes nanoestructures combinaran les propietats dels nanomaterials metal·lorgànics (per exemple, la porositat) amb les propietats intrínseques de les biomolècules, com ara la biocompatibilitat, el reconeixement selectiu o la quiralitat. En aquesta comunicació s'exposaran els últims avanços efectuats en el desenvolupament de noves metodologies sintètiques i el seu ús per sintetitzar les primeres nanoestructures metal·lobiomoleculars formades per aminoàcids com l'àcid aspàrtic (Asp) i la cisteïna (Cys)., The miniaturization of metal-organic materials to the nanoscale is an emerging strategy for the development of new nanostructures with tailored compositions, structures and morphologies. These new nanomaterials, many of which are porous, may have a wide range of properties and consequently show promise for many practical applications, such as gas storage or separation, catalysis, sensors, drug-delivery and contrast agents. With this aim, our research group is currently developing a new approach using biomolecules to coordinate metal ions and create metal-biomolecule nanoarchitectures. These new bioinspired nanostructures will combine the properties of more conventional metal-organic nanomaterials (e. g. porosity) with the intrinsic characteristics of the biomolecules, such as biocompatibility, chirality and selective recognition capabilities. This paper presents the latest advances in the development of new synthesis methodologies and their use in producing the first metal-biomolecule nanostructures based on amino acids, such as aspartic acid (Asp) and cysteine (Cys).
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- 2012
16. Effect of crystalline disorder on quantum tunneling in the single-molecule magnet Mn12 benzoate
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Carbonera, Chiara, Luis, Fernando, Sánchez-Marcos, J., Camón, Agustín, Chaboy, Jesús, Ruiz Molina, Daniel, Imaz, Inhar, Ministerio de Ciencia e Innovación (España), Diputación General de Aragón, German Research Foundation, and German Academic Exchange Service
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10 páginas, 9 figuras, 1 tabla.-- PACS number(s): 75.45.+j, 75.50.Xx, 75.60.Jk, 75.50.Kj.-- et al., We report a detailed study of the effects that crystalline disorder has on the magnetic relaxation and quantum tunneling of Mn12 benzoate clusters. Thanks to the absence of interstitial molecules in the crystal structure of this molecular compound, we have been able to isolate the influence of long-range crystalline disorder. For this, we compare results obtained under two extreme situations: a crystalline sample and a nearly amorphous material. The results show that crystalline disorder affects little the anisotropy, magnetic relaxation, and quantum tunneling of these materials. It follows that disorder is not a necessary ingredient for the existence of magnetic quantum tunneling. The results unveil, however, a subtle influence of crystallinity via the modification of the symmetry of dipole-dipole interactions. The faster tunneling rates measured for the amorphous material are accounted for by a narrower distribution of dipolar bias in this material, as compared with the crystalline sample., This work has been partly funded by Grants No. MAT2009-13977-C03, No. MAT2008-06542- C04, and No. CSD2007-00010 from the Spanish Ministerio de Ciencia e Innovación, and NABISUP from DGA. We acknowledge funding from Acción Integrada under Grant No. HA2006-0051 and the Network of Excellence MAGMANet. J.v.S and S.D. acknowledge the financial support of the Deutsche Forschungsgemeinschaft (DFG) and the DAAD. Ch.C. and I.I. acknowledge the Spanish Ministerio de Ciencia e Innovación.
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- 2010
17. Sponge-like molecular cage for purification of fullerenes
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García-Simón, Cristina, primary, Garcia-Borràs, Marc, additional, Gómez, Laura, additional, Parella, Teodor, additional, Osuna, Sílvia, additional, Juanhuix, Jordi, additional, Imaz, Inhar, additional, Maspoch, Daniel, additional, Costas, Miquel, additional, and Ribas, Xavi, additional
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- 2014
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18. Metallo-organic system for the encaspsulation and release of compounds of interest, method for obtaining same and uses thereof
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Ruiz Molina, Daniel, Maspoch, Daniel, and Imaz, Inhar
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Fecha de solicitud: 05-11-2009.- Titular: Consejo Superior de Investigaciones Científicas (CSIC), The present invention describes a metallo-organic system that includes: a metal ion salt or complex; at least one organic ligand; and a substance of interest to be encapsulated, belonging to the group comprising a biological entity, a drug, a vaccine, a diagnostic contrast agent, a marker, an organic compound, an inorganic compound, a metallo-organic compound or a nanomaterial or nanodevices. Also described is the method for obtaining same and the uses thereof for the release and/or protection and/or storage of said substances in the pharmaceutical, chemical, environmental, medical and industrial sectors., La presente invención describe un sistema metallo-organic que incluya: una sal del ion metálico o complejo por lo menos un ligand orgánico y una sustancia del interés de ser encapsulado, perteneciendo al grupo comprendiendo una entidad biológica, un fármaco, una vacuna, un agente de contraste del diagnóstico, un marcador, un compuesto orgánico, un compuesto inorgánico, un compuesto metallo-organic o un nanomaterial o nanodevices. También descrito es el método para obtener mismo y los usos de eso para la liberación y/o la protección y/o almacenamiento de las sustancias dichas en el farmacéutico, el producto químico, el ambiental, médico y los sectores industriales.
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- 2009
19. New insights into the thermal stability of Mn12 clusters: The case of complex [Mn12O12(O2CC≡CH)16(H2O)4]·3H2O and its thermolysis derived [Mn3(O2CC≡CH)6(H2O)4]·2H2O complex
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Gómez-Segura, Jordi, Campo, Javier, Imaz, Inhar, Wurst, Klaus, Veciana, Jaume, Gerbier, Philippe, Ruiz Molina, Daniel, Generalitat de Catalunya, Ministerio de Ciencia e Innovación (España), Gobierno de Aragón, Conseil régional, Languedoc-Roussillon, CSIC-ICN Centro de Investigación en Nanociencia y Nanotecnología (CIN2), Région Midi-Pyrénées, and European Commission
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Two novel Mn12 derivatives [Mn12O12(O2CC≡CH)16(H2O)4]·3H2O (1) and [Mn12O12(O2CC≡C6H5)16(H2O)4]·3H2O (2) have been prepared and characterized. Magnetic measurements confirm that both function as single-molecule magnets (SMM), showing frequency-dependent out-of-phase AC susceptibility signals and magnetization hysteresis curves. Thermal stability studies of both complexes were first conducted in the solid state. While complex 1 undergoes a sudden exothermal decomposition at Tonset = 118 °C, complex 2 exhibits a higher stability. Thermolysis reaction of 1 was hence assessed in solution to yield dark red crystals of a two-dimensional MnII-based co-ordination polymer [Mn3(O2CC≡CH)6(H2O)4]·2H2O (3), which corresponds to an extended sheet-like structure that crystallizes in the monoclinic space group P2 1/n; a = 9.2800(2) Å, b = 9.4132(2) Å, c = 14.9675(3) Å, β = 99.630(1)°, and Z = 2. Finally, the magnetic properties of complex 3 have been studied on an oriented single crystal over two different orientations of the reciprocal vector versus the external field., This work was supported by the Spanish government under MAT 2002–0043, the Generalitat de Catalunya under XI2002-9, the Gobierno de Aragon under the project Nanomateria and the EU under the NoE Magmanet. P. G. is grateful to the Region Languedoc-Roussillon for its financial support through the Communeaute de Travail des Pyrénées network DeNaMol. D. R.-M. also wants to thank Prof. David Hendrickson for fruitful discussions on the chemistry of Mn12 clusters and the Institut Catala de Nanotecnologia for financial support.
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- 2007
20. Bis(hexafluoroacetylacetonato)manganese(II) complex of 1,1-dimethyl-2,5-bis-(3-N-tert-butyl-N-phenylaminoxyl) -3,4-diphenylsilolacyclopentadiene
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ROQUES, Nans, GERBIER, Philippe, IMAZ, Inhar, GUIONNEAU, Philippe, SUTTER, Jean-Pascal, Chimie moléculaire et organisation du solide (CMOS), Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
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[CHIM.ORGA]Chemical Sciences/Organic chemistry ,Nitroxide radical ,[CHIM.CRIS]Chemical Sciences/Cristallography ,Silole ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,Manganese adduct - Abstract
International audience; Crystals of the 1st bis-adduct of 2,5-bis[3-(tert-butylaminoxyl)phenyl]-1,1-dimethyl-3,4-diphenylsilole with bis(hexafluoroacetylacetonato)manganese(II) are monoclinic, space group P21/n; Z = 2. The Mn atom lies on a crystallog. inversion center and is bound to two chelating hexafluoroacetylacetonate ligands and two monodentate nitroxide groups in a distorted octahedral configuration. The silole ligands present a propeller-like arrangement of the benzene rings around the Si-contg. five-membered ring. The dihedral angles between the complexed nitroxides and the benzene rings to which they are bound are smaller than those found in the free ligand.
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- 2006
21. Sur la mise en oeuvre de composés de coordination tétraédriques pour l'élaboration d'architectures supramoléculaires nanoporeuses : synthèse, caractérisation et propriétés zéolitiques d'édifices hétérométalliques ou hybrides
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IMAZ, Inhar, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB), Université Sciences et Technologies - Bordeaux I, and Sutter Jean-Pascal
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Physico-Chimie de la Matière Condensée ,Coordination polymers ,Matériaux Supramoléculaires ,Matériau microporeux hétérométalliques ,Brique moléculaire {M(oxalate)4}4 ,Supramolecular materials ,Liaison Hydrogène ,Adsorption ,[CHIM.MATE]Chemical Sciences/Material chemistry ,Molecular building blocks {M(oxalate)4}4 ,Polymères de coordination ,H-bond ,Heterometallic microporous materials - Abstract
The preparation of micro-porous metal-organic frameworks has been envisaged by assemblage of pre-formed tetrahedral coordination compounds involved as primary building units. A typical example of such a building block is (M(oxalate)4)4- (with M = UIV, ZrIV, etc...) but the tetrahedral (Zr(chloranilate)4)4- and (Zr(dihydrobenzoquinolate)4)4- complexes have been envisaged as well. Their assemblage with either metal ions by the means of coordination bonds or organic cations through charge-assisted H-bond lead to a series of structurally characterized 2-D and 3-D supramolecular nano-porous architectures. This approach permitted the synthesis of rare examples of heterometallic open frameworks. These structures display channels with apertures up to 12 Å x 8 Å which are emptied from solvates at mild temperatures without affecting the chemical scaffolds which integrity is maintained up to 250-300°C. A certain degree of flexibility of the coordination polymers upon guest release is suggested by the temperature dependence of the powder X-ray patterns and N2 sorption experiments, but reversible and selective sorption of small molecules has been observed suggesting these open-frameworks to behave like sponges. The flexibility of the framework upon guest release is illustrated by the crystal structures of the hydrated and dehydrated phases of [K4(Zr(dhbq)4)] (dhbq = dihydrobenzoquinolate). Finally, the different sorption measurements (BET, Langmuir) show that these supramolecular porous materials are promising adsorbents; preliminary results show that they might be envisaged for hydrogen.; Cette thèse est dédiée à la synthèse et à la caractérisation d'une famille inédite d'édifices métallo-organiques micro-poreux. La voie de synthèse explorée se fonde sur des briques moléculaires tétrahédriques préformées dont un exemple type est (M(oxalate)4)4- (où M = UIV, ZrIV, etc...). Les complexes tétraédriques (Zr(dihydrobenzoquinolate)4)4- et (Zr(chloranilate)4)4- sont également décrits. Les structures de plusieurs architectures supramoléculaires 2-D et 3-D parcourues par des canaux dont la section peut atteindre 8 Å x 12 Å, sont décrites. Des polymères de coordination hétérométalliques (U-Mn), (U-Cd), (Zr-Mn) ou encore (U-Gd) sont obtenus par association d'une brique avec un ion de métal de transition ou de terre-rare. Mais ces briques permettent aussi la formation de réseaux hybrides par assemblage avec des cations organiques au travers de liaisons-Hydrogène robustes. La diffraction des rayons X sur poudre et mono-cristal a mis en évidence la stabilité de ces édifices vis à vis d'un cycle désorption-adsorption mais aussi, pour certains, leur flexibilité. La déformation réversible de l'édifice est illustrée au travers des structures hydratées et déshydratées du réseau [K4(Zr(dhbq)4)] (dhbq = dihydrobenzoquinolate).Des mesures de sorption (BET, Langmuir) montrent que ces structures sont ouvertes. Un des édifices décrit adsorbe H2 et permet d'envisager cette famille de matériaux supramoléculaires pour le stockage de l'hydrogène.
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- 2005
22. Femtolitre chemistry assisted by microfluidic pen lithography
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Carbonell, Carlos, primary, Stylianou, Kyriakos C., additional, Hernando, Jordi, additional, Evangelio, Emi, additional, Barnett, Sarah A., additional, Nettikadan, Saju, additional, Imaz, Inhar, additional, and Maspoch, Daniel, additional
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- 2013
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23. {2,5-Bis[3-(tert-butylaminoxyl)phenyl]-1,1-dimethyl-3,4-diphenylsilole-κO}bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)manganese(II)
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Roques, Nans, primary, Gerbier, Philippe, additional, Imaz, Inhar, additional, Guionneau, Philippe, additional, and Sutter, Jean-Pascal, additional
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- 2006
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24. Synthesis, crystal structure and vibrational spectra characterization of MILa(PO3)4 (MI=Na, Ag)
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Masloumi, Mohamed El, primary, Imaz, Inhar, additional, Chaminade, Jean-Pierre, additional, Videau, Jean-Jacques, additional, Couzi, Michel, additional, Mesnaoui, Mohamed, additional, and Maazaz, Mohamed, additional
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- 2005
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25. Synthesis, crystal structure and vibrational spectra characterization of M ILa(PO3)4 (M I=Na, Ag)
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Masloumi, Mohamed El, Imaz, Inhar, Chaminade, Jean-Pierre, Videau, Jean-Jacques, Couzi, Michel, Mesnaoui, Mohamed, and Maazaz, Mohamed
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- *
CHEMICAL structure , *LANTHANUM compounds , *SPECTRUM analysis , *X-ray diffraction - Abstract
Abstract: The single crystals of lanthanum metaphosphate MLa(PO3)4 (M=Na, Ag) have been synthesized and studied by a combination of X-ray crystal diffraction and vibrational spectroscopy. The sodium and silver compounds crystallize in the same monoclinic P21/n space group ( factor group) with the following respective unit cell dimensions: , , , , , and , , , , , . This three-dimensional framework is built of twisted zig-zag chains running along a direction and made up of PO4 tetrahedra sharing two corners, connected to the LaO8 and NaO7 or AgO7 polyhedra by common oxygen atoms to the chains. The infrared and Raman vibrational spectra have been investigated. A group factor analysis leads to the determination of internal modes of (PO3)− anion in the phosphate chain. [Copyright &y& Elsevier]
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- 2005
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26. {2,5-Bis[3-( tert-butylaminoxyl)phenyl]-1,1-dimethyl-3,4-diphenylsilole-κ O}bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)manganese(II).
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Roques, Nans, Gerbier, Philippe, Imaz, Inhar, Guionneau, Philippe, and Sutter, Jean-Pascal
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PHYSICAL & theoretical chemistry ,MANGANESE ,BENZENE ,ETHANES ,HYDROGEN bonding ,MOLECULAR association - Abstract
In the structure of the first bis-adduct of 2,5-bis[3-( tert-butylaminoxyl)phenyl]-1,1-dimethyl-3,4-diphenylsilole with bis(hexafluoroacetylacetonato)manganese(II), [Mn(C
5 HF6 O2 )2 (C38 H42 N2 O2 Si)2 ], the Mn atom lies on a crystallographic inversion centre and is bound to two chelating hexafluoroacetylacetonate ligands and two monodentate nitroxide groups in a distorted octahedral configuration. The silole ligands present a propeller-like arrangement of the benzene rings around the Si-containing five-membered ring. The dihedral angles between the complexed nitroxides and the benzene rings to which they are bound are smaller than those found in the free ligand. [ABSTRACT FROM AUTHOR]- Published
- 2006
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27. Sequential Deconstruction–Reconstruction of Metal–Organic Frameworks: An Alternative Strategy for Synthesizing (Multi)-Layered ZIF Composites
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Amirali Yazdi, Elise Bernoud, Daniel Maspoch, Civan Avci, Inhar Imaz, Víctor F. Puntes, Màrius Tarrés, Neus G. Bastús, Xavi Ribas, Ministerio de Economía y Competitividad (España), Generalitat de Catalunya, European Commission, European Research Council, Yazdi, Amirali, Bastús, Neus G., Imaz, Inhar, Ribas, Xavi, Maspoch, Daniel, Yazdi, Amirali [0000-0001-9420-8504], Bastús, Neus G. [0000-0002-3144-7986], Imaz, Inhar [0000-0002-0278-1141], Ribas, Xavi [0000-0002-2850-4409], and Maspoch, Daniel [0000-0003-1325-9161]
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Materials science ,Composite number ,Crystal growth ,02 engineering and technology ,Metal−organic frameworks ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Cascade catalysis ,0104 chemical sciences ,ZIF composites ,Crystal ,Inorganic nanoparticles ,Etching ,Particle ,General Materials Science ,Metal-organic framework ,Composite material ,0210 nano-technology ,Nanoscopic scale ,Zeolitic imidazolate framework - Abstract
Here, we report the synthesis of (multi)-layered zeolitic imidazolate framework (ZIF-8/-67) composite particles via a sequential deconstruction–reconstruction process. We show that this process can be applied to construct ZIF-8-on-ZIF-67 composite particles whose cores are the initially etched particles. In addition, we demonstrate that introduction of functional inorganic nanoparticles (INPs) onto the crystal surface of etched particles does not disrupt ZIF particle reconstruction, opening new avenues for designing (multi)-layered ZIF-on-INP-on-ZIF composite particles comprising more than one class of inorganic nanoparticles. In these latter composites, the location of the inorganic nanoparticles inside each single metal–organic framework particle as well as of their separation at the nanoscale (20 nm) is controlled. Preliminary results show that (multi)-layered ZIF-on-INP-on-ZIF composite particles comprising a good sequence of inorganic nanoparticles can potentially catalyze cascade reactions., This work was supported by the EU FP7 ERC-Co 615954, the Spanish MINECO (projects PN MAT2015-65354-C2-1-R, MAT2015-70725-R, and CTQ2016-77989-P), and the Catalan AGAUR (projects 2014 SGR 80, 2014 SGR 612 and 2014 SGR 862). It was also funded by the CERCA Program/Generalitat de Catalunya. N.G.B. acknowledges financial support by MINECO through the Ramon y Cajal program (RYC-2012-10991). ICN2 acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program under Grant SEV-2013-0295.
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- 2018
28. Zigzag ligands for transversal design in reticular chemistry : unveiling new structural opportunities for metal-organic frameworks
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Vincent Guillerm, Thais Grancha, Daniel Maspoch, Inhar Imaz, Judith Juanhuix, European Research Council, European Commission, Generalitat de Catalunya, Ministerio de Economía y Competitividad (España), Guillerm, Vincent [0000-0003-3460-223X], Imaz, Inhar [0000-0002-0278-1141], Maspoch, Daniel [0000-0003-1325-9161], Guillerm, Vincent, Imaz, Inhar, Maspoch, Daniel, Catalan Institute of Nanoscience and Nanotechnology (ICN2), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC)-Barcelona Institute of Science and Technology (BIST), Instituto de Ciencia Molecular (ICMol), Universitat de València (UV), ALBA Synchrotron light source [Barcelone], Centre d'Investigació en Nanociència i Nanotecnologia (ICN-CSIC), and Universitat Autònoma de Barcelona (UAB)
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Nanotechnology ,02 engineering and technology ,Transversal designs ,[CHIM.INOR]Chemical Sciences/Inorganic chemistry ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Catalysis ,Organic ligands ,Colloid and Surface Chemistry ,Metalorganic frameworks (MOFs) ,[CHIM.CRIS]Chemical Sciences/Cristallography ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,ComputingMilieux_MISCELLANEOUS ,Chemistry ,General Chemistry ,[CHIM.MATE]Chemical Sciences/Material chemistry ,021001 nanoscience & nanotechnology ,3. Good health ,0104 chemical sciences ,Metal organic framework ,Zigzag ,Transversal design ,Transversal (combinatorics) ,Reticular connective tissue ,Metal-organic framework ,0210 nano-technology - Abstract
Herein we describe the topological influence of zigzag ligands in the assembly of Zr(IV) metal–organic frameworks (MOFs). Through a transversal design strategy using reticular chemistry, we were able to synthesize a family of isoreticular Zr(IV)-based MOFs exhibiting the bcu—rather than the fcu—topology. Our findings underscore the value of the transversal parameter in organic ligands for dictating MOF architectures., This work was supported by the EU FP7 ERC-Co 615954, the Spanish MINECO (project PN MAT2015-65354-C2-1-R), and the Catalan AGAUR (project 2014 SGR 80). It was also funded by the CERCA Program/Generalitat de Catalunya. ICN2 acknowledges the support of MINECO through the Severo Ochoa Centers of Excellence Program, under Grant SEV-2013-0295. V.G. is grateful to the Generalitat de Catalunya for a Beatriu de Pinos fellowship (2014 BP-B 00155) (Marie Curie Fellowship, EU-funded project ITHACA).
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- 2018
29. The photothermal effect in MOFs: covalent post-synthetic modification of MOFs mediated by UV-Vis light under solvent-free conditions
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Daniel Maspoch, Inhar Imaz, Jordi Espín, Luis Garzón-Tovar, Gerard Boix, European Commission, Ministerio de Economía y Competitividad (España), Generalitat de Catalunya, Espín, Jordi [0000-0001-6381-6259], Garzón-Tovar, Luis [0000-0003-0253-4041], Boix, Gerard [0000-0001-8431-4813], Imaz, Inhar [0000-0002-0278-1141], Maspoch, Daniel [0000-0003-1325-9161], Espín, Jordi, Garzón-Tovar, Luis, Boix, Gerard, Imaz, Inhar, and Maspoch, Daniel
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02 engineering and technology ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Aldehyde ,Catalysis ,Turn (biochemistry) ,Ultraviolet visible spectroscopy ,Cascade reaction ,Materials Chemistry ,Irradiation ,chemistry.chemical_classification ,Photothermal effect ,fungi ,Metals and Alloys ,General Chemistry ,021001 nanoscience & nanotechnology ,3. Good health ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry ,Covalent bond ,Reagent ,Ceramics and Composites ,0210 nano-technology - Abstract
Here, we report the covalent post-synthetic modification (CPSM) of MOFs using the photothermal effect. Specifically, we subjected mixtures of a photothermally active MOF and another reagent to irradiation with a UV-Vis lamp. This caused the MOF to heat up, which in turn caused the other reagent to melt and subsequently react with the functional groups on the walls of the MOF pores. We have exploited this dual function of MOFs as both heater and host for CPSMs to achieve rapid formation of amides from the reaction of representative MOFs (UiO-66-NH2 or MIL-101-NH2-(Al)) with anhydrides under solvent-free conditions. In addition, this approach enables more complex CPSMs in MOFs such as the formation of amides in UiO-66-NH2 by using an aldehyde through a cascade reaction., This work was supported by the EU FP7 ERC-Co 615954, the Spanish MINECO (project PN MAT2015-65354-C2-1-R), and the Catalan AGAUR (project 2014 SGR 80). It was also funded by the CERCA Programme/Generalitat de Catalunya. ICN2 acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Programme under Grant SEV-2013-0295. J. E. acknowledges the MINECO for the FPI fellowship.
- Published
- 2018
30. Multifunctional Composites made of Metal-Organic Frameworks and Inorganic Nanoparticles
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Boix, Gerard, Maspoch Comamala, Daniel, Imaz, Inhar, and Maspoch, Daniel
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Compòsits ,Nanopartícules ,Ciències Experimentals ,Nanopartículas ,Nanoparticles ,Estructura metall-orgànica ,Estructura metal-orgánica ,Metal-organic frameworks ,Compósitos ,Composites - Abstract
Tesis doctoral presentada para la obtención del título de Doctor en Química por la Universidad Auónoma de Barcelona., [EN] The present PhD thesis has been dedicated to the study, development and implementation of composite materials made of Metal-Organic Frameworks (MOFs) and Inorganic Nanoparticles (INPs) with enhanced functionalities not achievable by the constituent materials alone. In Chapter 1, a brief review of the state of the art in the field of porous crystalline materials is presented, from their conception to actual successful application in the industrial field. This Chapter offers a quick look to the most relevant concepts for the design and synthesis of this class of materials, as well as their most promising exploitable functionalities. Especial emphasis has been given in presenting works that successfully combine MOFs with other functional materials in order to compensate shortcomings of the individual constituents, or complement their strengths. The aim of this chapter is to contextualize the reader to the work presented in this thesis. In Chapter 2, the general and specific objectives of this Thesis are described. In Chapter 3, a composite material synthetized through spray drying for water remediation applications is presented. This material, shaped in the form of microbeads, combines a MOF from the UiO-66 family and CeO2 INPs. Both materials are known for their capabilities for the removal of various heavy metals from water. The synthetized composite microbeads are tested to assess their adsorptive capabilities in several experiments including ones simulating real water samples from polluted rivers. Furthermore, the material is incorporated into a continuous-flow fixed bed filtration system prototype where breakthrough and regeneration experiments are performed Finally, to prove the versatility of the synthetic method utilized for the formation of the beads an additional magnetic composite is developed by simultaneously incorporating CeO2 and Fe3O4 INPs into UiO-66-(SH)2. In Chapter 4, one of the materials presented in the previous chapter, UiO-66 microbeads with encapsulated CeO2 INPs, is integrated into a millimetre-sized polymer granule for water remediation applications. This study is carried out with a product-minded view. All the experiments where performed in a jug-filter commercialized by Brita® by replacing the original contents of the adsorption cartridge with our material. The water remediation experiments were carried out following the American National Standards Institute (ANSI) guideline 53-2019, "Drinking Water Treatment Units - Health Effects Standard". This is the same standard commercial product must fulfill in the USA. To the best of our knowledge this was the first time a MOF-based material was evaluated under internationally recognized water remediation standards. The aim of the work presented in this chapter was to bring MOF adsorbents one step closer to real-life water remediation applications. In Chapter 5, a spray-dried composite material combining UiO-66 MOF and silica-coated gold nanorods for the capture and release of Iodine is presented. When irradiated with the appropriate wavelength of light, the encapsulated gold nanorods generate heat thanks to the photothermal effect triggering the release of the adsorbed Iodine. We aim to utilize this triggered release to utilize our material in antibacterial applications. After validating the performance of this composite, we integrate it into a polymer film. We perform a complete study of the iodine adsorption and triggered release of the films as well as in vitro antibacterial experiments against gram positive and negative bacteria., [CA] La present tesi doctoral ha estat dedicada a l'estudi, desenvolupament i implementació de materials compòsits fets d'estructures organometàl·liques (MOFs) i nanopartícules inorgàniques (INPs) amb funcionalitats augmentades que no són possibles d'obtenir pels materials constituents sols. En el Capítol 1 es presenta un breu resum de l'estat actual del camp dels materials porosos cristal·lins. Des de la seva concepció, a casos on són aplicats exitosament en el camp de la indústria. Aquest capítol ofereix un cop d'ull als conceptes més importants per la síntesi i disseny d'aquesta classe de materials, així com les seves funcionalitats més útils. S'ha posat especial èmfasi en presentar treballs que combinen de forma exitosa MOFs amb altres materials funcionals per tal de compensar els desavantatges dels constituents individuals, o potenciar els seus punts forts. L'objectiu d'aquest capítol es el de contextualitzar el lector en el treball presentat en aquesta tesi. En el Capítol 2 es descriuen els objectius específics i generals d'aquesta tesi. En el Capítol 3 es presenta un material compòsit sintetitzat a través d'assecat per esprai aplicat a la purificació d'aigua. Aquest material, estructurat en forma de microperles, combina un MOF de la família del UiO-66 i INPs de CeO2. Tots dos materials són coneguts per la seva capacitat d'extraure diferents metalls pesants de l'aigua. Les microperles compòsit sintetitzades han estat provades per avaluar les seves capacitats absortives en multitud d'experiments incloent uns que simulaven mostres reals de rius contaminats. A més a més, el material estudiat és incorporat a un sistema de flux continuo en un prototip de columna de filtració de llit empacat fix per efectuar experiments de corbes d'esgotat i regeneració del material. Finalment, i per tal de demostrar la versatilitat de la síntesi d'assecat per esprai, vam desenvolupar microperles magnètiques mitjançant la incorporació simultània de INPs de CeO2 i Fe3O4 dintre de UiO-66-(SH)2. En el Capítol 4 s'integra un dels materials presentats en el capítol anterior, les microperles de UiO-66 amb INPs de CeO2 encapsulades en l'interior, dintre grànuls polimèrics de mida mil·limètrica per la purificació d'aigua. Aquest estudi està efectuat des del punt de vista no només d'estudi, sinó també de desenvolupar un producte. Tots els experiments estan efectuats utilitzant una gerra filtrant comercialitzada per Brita® en la qual els continguts del filtre original són reemplaçats pel nostre material. A més a més, els experiments de purificació es van efectuar seguint l'estàndard del "American National Standards Institute (ANSI) 53-2019, "Drinking Water Treatment Units - Health Effects Standard". Aquest és el estàndard que els productes comercials tenen que complir als EUA. Que nosaltres sapiguem, aquesta és la primera vegada que un material basat en MOFs és avaluat seguint les directrius d'un estàndard per la filtració d'aigua internacionalment reconegut. L'objectiu de la feina presentada és el d'acostar els materials basats en MOF a aplicacions reals de purificació d'aigua. En el Capítol 5, es presenta un material compòsit sintetitzat mitjançant assecat per esprai que combina el MOF UiO-66 amb nanobarres d'or recobertes amb una capa de sílice per la captura i alliberament de iode. Quan sún irradiades amb la freqüència de llum correcta, les nanobarres encapsulades generen calor gràcies a l'efecte fototèrmic, fet que indueix l'alliberament controlat del iode encapsulat. El nostre objectiu és utilitzar aquest alliberament controlat del nostre compòsit per aplicacions antibacterianes. Després de validar les propietats d'aquest compòsit, l'integrem amb un polímer per generar una membrana. Finalment, fem un estudi complet de l'adsorció i alliberament controlat de iode de les membranes així com experiments in vitro amb bacteris gram positiu i negatiu., [ES] La presente tesis doctoral ha estado dedicada al estudio, desarrollo e implementación de materiales compuestos hechos de estructuras organometálicas (MOFs) y nanopartículas inorgánicas (INPs) con funcionalidades aumentadas que no son posibles de obtener por los materiales constituyentes solos. En el Capítulo 1 se presenta un breve resumen del estado actual del campo de los materiales porosos cristalinos. Desde su concepción, a casos donde son aplicados exitosamente en el campo de la industria. Este capítulo ofrece un vistazo a los conceptos más importantes para la síntesis y diseño de esta clase de materiales, así como sus funcionalidades más útiles. Se ha prestado especial atención en presentar trabajos que combinen de forma exitosa MOFs con otros materiales funcionales con tal de compensar las desventajas de los constituyentes individuales, o potenciar sus puntos fuertes. El objetivo de este capítulo es el de contextualizar el lector en el trabajo presentado en esta tesis. En el Capítulo 2 se describen los objetivos específicos y generales de esta tesis. En el Capítulo 3 se presenta un material compuesto sintetizado a través de secado por espray aplicado a la purificación de agua. Este material, estructurado en forma de microperlas, combina un MOF de la familia del UiO-66 y INPs de CeO2. Los dos materiales son conocidos por su capacidad de extraer diferentes metales pesados del agua. Las microperlas compuestas sintetizadas han estado probadas para evaluar sus capacidades adsorbentes en multitud de experimentos incluyendo unos en que simulaban muestras reales de ríos contaminados. Además, el material estudiado es incorporado a un sistema de flujo continuo en un prototipo de columna de filtración de lecho fijo empaquetado para efectuar experimentos de corvas de agotamiento y regeneración del material. Finalmente, y para demostrar la versatilidad de la síntesis de secado por espray, desarrollamos microperlas magnéticas mediante la incorporación simultánea de INPs de CeO2 y Fe3O4 dentro de UiO-66-(SH)2 En el Capítulo 4 se integra uno de los materiales presentados en el capítulo anterior, las microperlas de UiO-66 con INPs de CeO2 encapsuladas en su interior, dentro de gránulos poliméricos de tamaño milimétrico para la purificación de agua. Este trabajo no está efectuado solo desde un punto de vista de estudio, sino también de desarrollo de un producto. Todos los experimentos están efectuados utilizando una jarra filtrante comercializada por Brita® en la que los contenidos del filtro original son reemplazados por nuestro material. Además, los experimentos de purificación se efectuaron siguiendo el estándar de la American National Standards Institute (ANSI) 53-2019, "Drinking Water Treatment Units - Health Effects Standard". Este es el mismo estándar que los productos comerciales deben cumplir en los EUA. Que nosotros sepamos, esta es la primera vez que un material basado en MOFs es evaluado siguiendo las directrices de un estándar para la filtración de agua reconocido internacionalmente. El objetivo del trabajo presentado es el de acercar los materiales basados en MOFs a aplicaciones reales de purificación de agua. En el Capítulo 5, se presenta un material compuesto sintetizado mediante secado por spray que combina el MOF UiO-66 con nanobarras de oro recubiertas de una capa de sílice para la captura y liberación de iodo. Cuando son irradiadas con la frecuencia de luz correcta, las nanobarras encapsuladas generan calor gracias al efecto fototérmico, hecho que induce la liberación controlada del iodo encapsulado. Nuestro objetivo es utilizar esta liberación controlada de nuestro compuesto para aplicaciones antibacterianas. Después de validar las propiedades de estos compuestos, los integramos en un polímero para generar una membrana. Finalmente, hacemos un estudio completo de la adsorción y liberación controlada de iodo de las membranas, así como experimentos in vitro con bacteria gram positivas y negativas.
- Published
- 2022
31. Self-Assembly of Colloidal Metal-Organic Framework Particles into Multidimensional Superstructures
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Liu, Yang, Maspoch Comamala, Daniel, Imaz, Inhar, Busqué Sánchez, Félix, Maspoch, Daniel, and Busqué, Félix
- Subjects
Ciències Experimentals ,Marcs metàlico-orgànics ,Estructuras metálicas orgánicas ,Metal-organic frameworks - Abstract
[EN] The aim of the present PhD Thesis has been the exploration of Metal-Organic Frameworks (MOFs) as a potential source of polyhedral for the assembly of a new generation of materials. The discovery of thousands of MOFs over the past 25 years has created a huge pool of highly porous, crystalline particles that encompass most known polyhedral shapes. The research presented in this Thesis hopes to dip in this pool, opening up new avenues to synthesize new porous self-assembled materials with original structures that will give access to new photonic properties The Thesis is organized into two parts. Chapter 1 constitutes the first part where the reader will find an introduction of the self-assembly field, with a brief description of the different interactions that are involved in self-assembly processes, and of different self-assembled systems and synthetic strategies. This Chapter continues with a brief introduction to MOFs, from an historical perspective to their representative applications. We have also pay attention on the few examples in which MOF particles have already been used to generate self-assembled superstructures. The second part of this Thesis contains a description of the general and specific objectives. Then, in Chapter 3, we will briefly describe and discuss the different results obtained during this Thesis. The detailed results will be found in the three publications reproduced in Chapters 5, 6 and Appendix. The publication in Chapter 5 focuses on the use of the polyhedral shape of MOF particles to direct the assembly of colloidal clusters through colloidal fusion. Thanks to the geometry of colloidal MOF particles, colloidal clusters with well-defined geometries can be prepared by controlling the attachment of a single polystyrene particle on each face of the polyhedral MOF particle. Following this approach, we show the synthesis of six-coordinated (6-c) octahedral, 8-c cubic, and 12-c cuboctahedral clusters using cubic ZIF-8, octahedral UiO-66, and rhombic dodecahedral ZIF-8 core particles, respectively. The second publication in Chapter 6 is related to a new template-free method to self-assemble (111)-, (100)-, and (110)-oriented face-centered cubic supercrystals of the ZIF-8 particles by adjusting the amount of surfactant. This publication explains how the orientation of self-assembly of ZIF-8 can be controlled by adjusting the nature and the amount of surfactant. We also describe that the photonic property of these supercrystals depends on their growth orientation. The last study found in Appendix presents the assembly of supraparticles using polyhedral MOF particles, which expands the type of self-assemblies made of colloidal MOF particles. This study includes the confinement synthesis of supraparticles of four types of polyhedral MOF particles: cubic, truncated rhombic dodecahedral, and rhombic dodecahedral ZIF-8 particles as well as octahedral UiO-66 particles. We also study the relationship between the ordered structure of the different supraparticles and their structural coloration., [CA] La present Tesi Doctoral ha tingut com a objectiu investigar el potencial dels Metall-Organic Frameworks (MOFs) com a font de partícules polièdriques per ser acoblades i donar lloc a una nova generació de materials autoassemblats. Des del seu descobriment fa uns 25 anys, el descobriment de milers de MOF ha generat un ampli catàleg de partícules cristal·lines altament poroses que engloben la majoria de les formes polièdriques. La investigació presentada en aquesta Tesi té com a propòsit aprofitar aquest ampli catàleg de partícules polièdriques per fabricar nous materials autoassemblats porosos amb estructures originals i que presentin noves propietats fotòniques. La Tesi s'estructura en dues parts. El Capítol 1 compon la primera part, en la qual el lector trobarà una introducció al camp de l'autoassemblat, amb una breu descripció de les interaccions involucrades, els diferents tipus d'autoassemblat i les diferents estratègies sintètiques. El capítol continua amb una breu introducció als MOFs des dels seus orígens fins a les aplicacions potencials. En aquesta secció, s'ha fet especial èmfasi en els pocs exemples de la literatura en els quals partícules de MOFs han estat usades per generar estructures autoassemblades. La segona part de la Tesi comença amb el Capítol 2, on es defineixen els objectius generals i específics. A continuació, al Capítol 3, es descriuen de manera concisa els diferents resultats obtinguts durant aquesta Tesi. Els resultats detallats es podran trobar a les tres publicacions reproduïdes als Capítols 5, 6 i Apèndix. La publicació del Capítol 5 descriu l'ús de la forma polièdrica de les partícules de MOF per dirigir l'acoblament de clústers col·loïdals a través de la fusió col·loïdal. S'ha estudiat com, gràcies a aquesta forma polièdrica, es poden construir clústers amb diferents geometries controlant la interacció d'una sola partícula esfèrica de poliestirè a cadascuna de cares dels políedres de MOF. Amb aquesta estratègia, s'han pogut obtenir clústers octaèdrics hexacoordinats (6-c), cúbics (8-c) i cuboctaèdrics (12-c) a partir de partícules de ZIF-8 cúbiques, d'UiO-66 octaèdriques i de ZIF-8 rombododecaèdriques. A la segona publicació, inclosa al Capítol 6, es descriu una nova metodologia "sense ús de plantilla" per a l'acte assemblat orientat a les adreces (111)-, (100)-, and (110) de supercristalls de partícules de ZIF -8, amb simetria cúbica centrada a les cares. Aquesta publicació explica com només ajustant la naturalesa i la quantitat de surfactant es pot controlar l'orientació de l'autoassemblat de partícules de ZIF-8. També es descriu la correlació entre les propietats fotòniques i lorientació del supercristall. L'última estudi, reproduïda a l'apèndix, s'ha centrat en l'acoblament de suprapartícules esfèriques usant les partícules polièdriques de MOF, expandint així els tipus d'autoassemblats d'aquest tipus de partícules. Aquesta publicació inclou l'assemblatge en esfera confinada de quatre tipus de partícules de MOF: partícules de ZIF-8 cúbiques, rombododecaèdriques truncades i rombododecaèdriques, i partícules d'UiO-66 octaèdriques. També s'ha estudiat la relació entre l'estructura ordenada de les diferents suprapartícules i la coloració estructural., [ES] La presente Tesis Doctoral ha tenido como objetivo investigar el potencial de los Metal-Organic Frameworks (MOFs) como fuente de partículas poliédricas para ser ensambladas y dar lugar a una nueva generación de materiales auto-ensamblados. Desde su descubrimiento hace unos 25 años, el descubrimiento de miles de MOFs ha generado un amplio catálogo de partículas cristalinas altamente porosas que engloban la mayoría de las formas poliédricas. La investigación presentada en esta Tesis tiene como propósito aprovechar este amplio catálogo de partículas poliédricas para fabricar nuevos materiales auto-ensamblados porosos con estructuras originales y que presenten nuevas propiedades fotónicas. La Tesis se estructura en dos partes. El Capítulo 1 compone la primera parte, en la cual el lector encontrará una introducción al campo del auto-ensamblado, con una breve descripción de las interacciones involucradas, los diferentes tipos de auto-ensamblado y las diferentes estrategias sintéticas. El capítulo continua con una breve introducción a los MOFs desde sus orígenes hasta sus aplicaciones potenciales. En esta sección, se ha hecho especial énfasis en los pocos ejemplos de la literatura en los cuales partículas de MOFs han sido usadas para generar estructuras auto-ensambladas. La segunda parte de la Tesis se inicia con el Capítulo 2, donde se definen los objetivos generales y específicos. A continuación, en el Capítulo 3, se describen de una manera concisa los diferentes resultados obtenidos durante esta Tesis. Los resultados detallados se podrán encontrar en las tres publicaciones reproducidas en los Capítulos 5, 6 y Apéndice. La publicación del Capítulo 5 describe el uso de la forma poliédrica de las partículas de MOF para dirigir el ensamblaje de clústeres coloidales a través de la fusión coloidal. Se ha estudiado como, gracias a esta forma poliédrica, se pueden construir clústeres con diferentes geometrías controlando la interacción de una sola partícula esférica de poliestireno en cada una de caras de los poliedros de MOF. Con esta estrategia, se han podido obtener clústeres octaédricos hexacoordinados (6-c), cúbicos (8-c) y cuboctaédricos (12-c) a partir de partículas de ZIF-8 cúbicas, de UiO-66 octaédricas y de ZIF-8 rombododecaédricas. En la segunda publicación, incluida en el Capítulo 6, se describe una nueva metodología "sin uso de plantilla" para el auto ensamblado orientado en las direcciones (111)-, (100)-, and (110) de supercristales de partículas de ZIF-8, con simetría cúbica centrada en las caras. Esta publicación explica como sólo ajustando la naturaleza y la cantidad de surfactante se puede controlar la orientación del auto-ensamblado de partículas de ZIF-8. También se describe la correlación entre las propiedades fotónicas y la orientación del supercristal. La última estudio, reproducida en el Apéndice, se ha centrado en el ensamblado de suprapartículas esféricas usando las partículas poliédricas de MOF, expandiendo así los tipos de auto-ensamblados de este tipo de partículas. Esta publicación incluye el ensamblaje en esfera confinada de cuatro tipos de partículas de MOF: partículas de ZIF-8 cúbicas, rombododecaédricas truncadas y rombododecaédricas, y partículas de UiO-66 octaédricas. También se ha estudiado la relación entre la estructura ordenada de las diferentes suprapartículas y su coloración estructural.
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- 2022
32. Engineering Stöber Silica Nanoparticles : Insights into the Growth Mechanism and Development of Silica-Based Nanostructures for Multimodal Imaging
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Moriones Botero, Oscar Hernando, Puntes, Víctor, Gómez Bastús, Neus, and Imaz, Inhar
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Nanotecnología ,Nanopartícules ,Ciències Experimentals ,Nanotecnologia ,Nanopartículas ,Nanoparticules ,Nanotechnology ,Silica ,Silice - Abstract
Aprofitant l'experiència del grup Inorganic Nanoparticles (ING) de l'ICN2, que té com a gran expertesa en la producció de nanopartícules col·loïdals altament monodisperses, aquesta tesi té com a objectiu fabricar una nanoestructura híbrida complexa inorgànica-orgànica utilitzant sílice com a material de suport, aplicant mètodes sintètics de química en líquid, per al desenvolupament d'un agent de contrast multifuncional amb propietats adequades per aplicar-lo en imatge mèdica. Per això s'han abordat tres objectius principals: en primer lloc, l'estudi del mecanisme de nucleació i creixement de les NPs de SiO2 per controlar amb precisió la mida de les partícules. En segon lloc, una modificació sistemàtica de la superfície i el nucli de les nanopartícules de sílice, per tal de preparar nanopartícules a base de sílice amb propietats òptiques funcionals i, en tercer lloc, explotar la funcionalitat dels híbrids de sílice preparats per al desenvolupament duna nanoestructura complexa multicapa híbrida amb capacitats dimatge multimodal. Aprovechando la experiencia del grupo Inorganic Nanoparticles (ING) del ICN2, que tiene como gran experticia en la producción de nanopartículas coloidales altamente monodispersas, esta tesis tiene como objetivo fabricar una nanoestructura híbrida compleja inorgánica-orgánica utilizando sílice como material de soporte, aplicando métodos sintéticos de química en líquido, para el desarrollo de un agente de contraste multifuncional con propiedades adecuadas para su aplicación en imagen médica. Para ello se han abordado tres objetivos principales: en primer lugar, el estudio del mecanismo de nucleación y crecimiento de las NPs de SiO2 para controlar con precisión el tamaño de las partículas. En segundo lugar, una modificación sistemática de la superficie y el núcleo de las nanopartículas de sílice, con el fin de preparar nanopartículas a base de sílice con propiedades ópticas funcionales y, en tercer lugar, explotar la funcionalidad de los híbridos de sílice preparados para el desarrollo de una nanoestructura compleja multicapa híbrida con capacidades de imagen multimodal. In this regard, taking advantage of the expertise in the group on the production of highly monodisperse colloidal nanoparticles, this thesis aims to fabricate an inorganic-organic complex hybrid nanostructure using silica as supporting material, by applying wet chemistry synthetic methods, for the development of a multifunctional contrast agent with adequate properties for their application in medical imaging. For that purpose, three main objectives have been addressed: first, the study of the mechanism of nucleation and growth of the SiO2 NPs in order to precisely control the size of the particles. Second, a systematically surface and core modification of the silica nanoparticles, in order to prepare silica-based nanoparticles with functional optical properties and third, exploiting the functionality of the prepared silica hybrids for the development of a hybrid multilayer complex nanostructure with multimodal imaging capabilities
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- 2022
33. Nanoengineering composites made of metal- and covalent- organic frameworks and inorganic nanoparticles using encapsulation techniques
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Yazdi, Amirali, Maspoch Comamala, Daniel, Puntes, Víctor, Imaz, Inhar, Hernando Campos, Jordi, and Universitat Autònoma de Barcelona. Departament de Química
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Nanopartícules inorgàniques ,Nanopartículas inorgánicas ,Inorganic nanoparticles ,Xdes metal-orgánicas ,Covalent-organic frameworks ,Ciències Experimentals ,Xarxes orgàniques-covalents ,Xarxes metal·lorgàniques ,Redes organicas-covalentes ,Metal-organic frameworks - Abstract
La presente tesis doctoral se ha enfocado en el diseño y la síntesis de un nuevo tipo de materiales compuestos basados en metal-organic frameworks (MOFs) o covalent-organic frameworks (COFs) y nanopartículas inorgánicas y el uso de estos materiales compuestos para la catálisis heterogénea. En el primer capítulo se introduce la familia de materiales compuestos dispersos en/sobre diferentes materiales haciendo especial énfasis en aquellos construidos con MOFs y COFs. En el capítulo 2 se presentan los objetivos generales de la tesis doctoral. En el capítulo 3 se muestran los resultados del artículo “The influence of the MOF shell thickness on the catalytic performance of composites made of inorganic (hollow) nanoparticles encapsulated into MOFs” publicado en 2016 en la revista Catalysis Science & Technology. En el mismo se reporta la encapsulación de nanopartículas huecas de Platino y Paladio en el ZIF-8 formando así una serie de materiales compuestos en los cuales el espesor de la cáscara de ZIF-8 era modulada de manera sistemática. En el capítulo 4, nanopartículas híbridas de tipo núcleo-coraza de Au/CeO2 dispersadas en microesféras de UiO-66 han sintetizados usando el método se atomización por secado con flujo continuo. Las propiedades catalíticas combinadas en una única partícula de los nanocristales de CeO2 y Au y la capacidad protectora de las microesféras porosas de UiO-66 hacen que estos materiales compuestos muestren resultados interesantes como catalizadores para la reacción de reducción de monóxido de Carbono. (T50 = 72 °C; T100 = 100 °C) con alta reusabilidad. Los resultados obtenidos han sido incluidos en el artículo. “Core-shell Au/CeO2 nanoparticles supported in UiO-66 beads exhibiting full CO conversion at 100 °C” publicado en la revista Journal of Materials Chemistry A en 2017. Finalmente, en el capítulo 5, hemos demostrado que usando un método en dos pasos se pueden funcionalizar COFs confinando en ellos nanopartículas. La reacción directa entre el 1,3,5-tris(4-aminofenil)benceno y el 1,3,5-benzenetricarbaldehído en presencia de una variedad de nanopartículas metalícas o de óxidos de metal resulta en la encapsulación de estas nanopartículas en un polímero amorfo de iminas-enlazadas con forma de esfera. El Post-tratamiento de estas esferas con ácido acético en reflujo conduce a la obtención de esferas cristalinas de COFs basados en iminas. Además materiales compuestos basados en COF y nanopartículas de Au y Pd han demostrado ser catalíticamente activas. Estos resultados han sido publicados en el artículo “Confining Functional Nanoparticles into Colloidal Imine-Based COF Spheres by a Sequential Encapsulation-Crystallization Method” publicado en la revista Chemistry a European Journal en 2017. The present PhD Thesis has been dedicated to the design and synthesis of a new type of composites of metal-organic frameworks (MOFs) or covalent-organic frameworks (COFs) with inorganic nanoparticles (iNPs) and the use of these composites for heterogeneous catalysis. In the first chapter, we introduce the family of composites made by supporting iNPs on/in different materials, focusing on those constructed with MOFs and COFs. Then, the general objectives of the Thesis are described in Chapter 2. Chapter 3 shows the results in “The influence of the MOF shell thickness on the catalytic performance of composites made of inorganic (hollow) nanoparticles encapsulated into MOFs”, Catalysis Science & Technology (2016). Herein, we report the encapsulation of hollow Pt or Pd nanoparticles (NPs) into ZIF-8, making a series of composites in which the ZIF-8 shell thickness has been systematically varied. By using these composites as catalysts for the reduction of 4-nitrophenol and Eosin Y, we show that the MOF shell thickness plays a key role in the catalytic performance of this class of composites. In Chapter 4, hybrid core-shell Au/CeO2 NPs dispersed in UiO-66 shaped into microspherical beads are created using the spray-drying continuous-flow method. The combined catalytic properties of nanocrystalline CeO2 and Au in a single particle and the support and protective function of porous UiO-66 beads make the resulting composites show good performances as catalysts for CO oxidation (T50 = 72 °C; T100 = 100 °C) and recyclability. The results are included in the manuscript entitled “Core-shell Au/CeO2 nanoparticles supported in UiO-66 beads exhibiting full CO conversion at 100 °C”, Journal of Materials Chemistry A (2017). Finally, in Chapter 5, we demonstrated a two-step method that enables imparting new functionalities to COFs by nanoparticle confinement. The direct reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde in the presence of a variety of metallic/metal-oxide nanoparticles resulted in the embedding of the nanoparticles in amorphous and nonporous imine-linked polymer organic spheres. Post-treatment reactions of these polymers with acetic acid under reflux led to crystalline and porous imine-based COF- hybrid spheres. Interestingly, porous imine-based COF-hybrids with Au and Pd NPs were found to be catalytically active. These results have been reported in the publication entitled “Confining Functional Nanoparticles into Colloidal Imine-Based COF Spheres by a Sequential Encapsulation-Crystallization Method”. Chemistry a European Journal (2017).
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- 2018
34. Confining Reactions in a Droplet: Synthesis of MOFs, COFs and Composites using Spray-Drying
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Garzón Tovar, Luis Carlos, Maspoch Comamala, Daniel, Imaz, Inhar, Busqué Sánchez, Félix, and Universitat Autònoma de Barcelona. Departament de Química
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Covalent-organic frameworks ,Ciències Experimentals ,Spray-drying ,Redes metal-orgánicas ,Xarxes orgàniques-couvalents ,Redes organicas-covalentes ,Metal-organic frameworks ,Xarxes metall-orgàniques - Abstract
Una nueva era en la química de los materiales inició con el descubrimiento de las redes Metal-Orgánicas (MOFs, por sus siglas en inglés) y las redes Orgánicas-Covalentes (COFs, por sus siglas en inglés). En particular, la introducción de la química reticular representó una estrategia revolucionaria que proporcionó a los químicos infinitas oportunidades para diseñar y construir nuevos materiales funcionales con propiedades excepcionales, como su alta porosidad, alta flexibilidad estructural / composicional y bajas densidades (para COF). De hecho, estas propiedades convierten a los MOFs y a los COFs en materiales prometedores para múltiples aplicaciones de interés comercial, que incluyen almacenamiento y separación de gases, catálisis, administración de fármacos, baterías térmicas y sistemas de refrigeración. Estas posibilidades han promovido un ritmo de expansión rápido y explosivo en este campo y, como resultado, la academia y la industria han comenzado a proponer varias iniciativas para la comercialización de estos materiales porosos. Sin embargo, a pesar de estos esfuerzos, la comunidad científica también ha reconocido que el uso de estos materiales podría verse limitado por los desafíos relacionados con sus métodos de producción a gran escala, ya que normalmente se necesitan condiciones severas para sintetizarlos. En este sentido, nuevas estrategias para su síntesis se han desarrollado recientemente. En particular, el método de secado por pulverización ha surgido como una tecnología prometedora para la síntesis de MOF a gran escala. Sin embargo, el secado por pulverización todavía está en sus etapas iniciales y, por lo tanto, hay muchos desafíos que deben superarse. En esta tesis, hemos desarrollado nuevas estrategias para sintetizar MOFs. En particular, hemos desarrollado un nuevo método para la síntesis de MOFs basados en unidades de construcción secundarias. También, hemos demostrado que el método de secado por atomización acoplado a un sistema de flujo-continuo puede ser usado no solo para sintetizar MOFs, sino también para incorporar especies funcionales. De este modo, se introduce una nueva ruta para la síntesis de materiales compuestos. En esta tesis, se extiende el uso de la técnica de secado por pulverización a la química covalente. De esta manera, se muestra que diferentes iminas pueden ser sintetizadas a partir de reacciones de condensación entre aldehídos y aminas. Además, también demostramos que los MOFs pueden ser fácilmente modificados. De esta manera, usando la técnica de secado por pulverización, mostramos la modificación post-sintética de dos MOFs, el amino-terminal UiO-66-NH2 y el aldehído-terminal ZIF-90. Además, también se demuestra que las reacciones de condensación pueden extenderse para la síntesis de COFs. Así, demostramos que superestructuras esféricas creadas a partir del ensamblaje de nanocristales de COF pueden ser obtenidas en un proceso de dos pasos, que incluye el secado por pulverización seguido de una transformación amorfo-cristalino del material. Además, se demuestra como las superestructuras resultantes pueden ser utilizadas para encapsular diferentes materiales, tales como moléculas fluorescentes y nanopartículas magnéticas. A new age in materials chemistry started with the discovery of Metal-Organic Frameworks and Covalent-Organic frameworks. In particular, the introduction of reticular chemistry represented a revolutionary strategy that gave chemists infinite opportunities toward the design and construction of novel functional materials with exceptional properties, such as their high porosity, high structural/compositional flexibility and low densities (for COFs). Indeed, these properties render MOFs and COFs as promising materials for multiple applications of commercial interest, including gas storage and separation, catalysis, sensing, drug delivery, water harvesting and adsorptive heat transformation systems. These possibilities have promoted a rapid and explosive pace of expansion in this field and as a result, academia and industry have begun to propose several initiatives towards the commercialization of these porous materials. However, despite these efforts, the scientific community has also recognized that the use of these materials could be limited by the challenges pertaining to their production methods at large scale since harsh conditions are usually needed to synthesize them. In this sense, novel approaches for their synthesis have been developed recently. In particular, the spray-drying method has emerged as a promising technology for the synthesis of MOFs at large scale. However, spray-drying is still in its embryonic stage and therefore, there are many challenges that need to be overcome. In this Thesis, we have developed new strategies to synthesize MOFs. In particular, we describes a new methodology based on coupling two processes —spray-drying and continuous flow— for continuous synthesis of MOFs assembled from high-nuclearity secondary building units (SBUs). In addition, we demonstrated that the spray-drying-continuous flow method can be used not only to synthesize MOF superstructures but also to incorporate functional species, thereby providing a new route for the synthesis of MOF-based composites. In this thesis, we extend the use of spray-drying technique to covalent chemistry. To this end, we show that different imines can be synthesized from Schiff-base condensation reactions between discrete aldehydes and amines using the spray-drying. We also show that this chemistry can be extended to post-synthetically modify MOFs. For example, we show the post-synthetic modification of two MOFs, the amine-terminated UiO-66-NH2 and the aldehyde-terminated ZIF-90. Moreover, we demonstrate that the Schiff-base condensation reactions can be extended to the synthesis of COFs. Thus, we prove that spherical superstructures made from the assembly of imine-based COF nanocrystals can be obtained by combining the spray-drying technique with a dynamic covalent chemistry process. In addition, we show that this methodology enables the integration of other functional materials such as dyes and magnetic nanoparticles into these superstructures forming COF-based composites.
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- 2018
35. Janus-type and Molecular MOF-based composites
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Ayala Hernández, Abraham, Maspoch Comamala, Daniel, Imaz, Inhar, and Universitat Autònoma de Barcelona. Departament de Química
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Ciències Experimentals - Abstract
La presente Tesis está enfocada al estudio, desarrollo e implementación de nuevas metodologías de síntesis de estructuras metal-orgánicas (MOFs) basadas en compuestos multifuncionales. El trabajo de investigación de esta Tesis se desarrolló en dos líneas de investigación: i) por un lado, la síntesis de partículas metálicas Janus con MOFs y su funcionalización parcial para aplicaciones en eliminación de metales pesados, aplicaciones de auto movilidad y fluorescencia, ii) por otro lado la incorporación de moléculas activas en MOFs a través de la creación controlada de defectos, estudiando la formación del MOF así como su posible aplicación en eliminación de metales pesados En el capítulo uno, nosotros revisamos la evolución en el campo de los MOFs a partir de un desarrollo histórico, y la presentación de las principales estrategias de síntesis, así como las propiedades y aplicaciones. También, nosotros presentamos especial atención en las metodologías actuales para la miniaturización de MOFs, las mejoras en las propiedades y posibles aplicaciones. También mencionamos la importancia de las posibilidades de crear compuestos de MOF combinando las propiedades intrínsecas de MOFs y otros materiales funcionales, por ejemplo, materiales magnéticos, materiales fluorescentes y catalíticos. En el capítulo dos, se describen los objetivos de la Tesis. En el tercer capítulo, se presenta el trabajo llevado a cabo en la síntesis de partículas de tipo Janus basados en MOFs. Una vez introducidos los conceptos de partículas de tipo Janus y la manera de sintetizados se presenta el trabajo experimental llevado a cabo. Este trabajo se basa en la evaporación controlada y selectiva de metales sobre parte de la superficie de MOFs. Esta metodología novedosa se organiza en diferentes pasos: i) Síntesis de MOFs nanoscópicos de tamaño controlado, ii) Deposición controlada en superficie de una monocapa de nanocristales de MOF dispersos, iii) Evaporación sobre las monocapas de nanocristales de MOFs de nanocapas de metal, iv) Separación de las superficies de los MOFs y obtención de las nanopartículas de Janus. La versatilidad de esta metodología nos ha permitido sintetizar diferentes compuestos de partículas Janus metal@MOFs, así como evaluar las propiedades magnéticas, fluorescentes, y catalíticas. En el capítulo cuatro se describe otro de tipo de composites basados en MOFs y moléculas orgánicas funcionales. Este estudio consiste en introducir moléculas orgánicas funcionales creando defectos dentro de la estructura. En particular, se ha estudiado la capacidad de insertar la molécula xylenol orange; molécula con grupos coordinantes fuertes de tipo carboxílato con capacidad de capturar metales pesados. Se ha estudiado el mecanismo de incoprporación del XO dentro del MOF y su influencia en la formación del MOF, sus propiedades finales y la capacidad de eliminación de metales pesados del composite final fueron evaluados., The present Thesis has been dedicated to the study, development, and implementations of new methodologies synthesize Metal Organic Frameworks (MOFs) based multifunctional composites. Accordingly, two main lines of work can be distinguished through the lecture of this Thesis: i) the synthesis of Janus metal@MOFs particles and their partial functionalization for applications in removal of heavy metal ions, application in self-propelled and fluorescence; ii) the incorporation of active molecules into the MOFs through of creating controlled defects, and the use of the resulting composites in the removal of heavy metal ions. In the Chapter 1, we review the evolution of the field of the MOFs including a brief historical introduction and the presentation of the main synthetic routes, properties and applications. We pay special attention to the current methodologies to synthesis MOFs and their miniaturization and their improvements of their properties and their possible applications. We mention the importance of the possibilities as well to create MOF composites combining the intrinsic properties of MOFs and other functional materials (i.e. magnetic materials, fluorescence, catalytic). In Chapter 2, cites the general and specific objectives of this PhD Thesis. Chapter 3 describes the methodology used for the synthesis of Janus metallic@MOFs particles. This methodology is based on the selective evaporation of metallic components on the MOFs surfaces and is carried out in different steps: i) synthesis of MOFs and their control size; ii) fabrication of MOFs monolayers on surfaces through the controlled deposition based on solvent evaporation; iii) evaporation of metal components through the electron bean evaporation technique, iv) detachment of the MOFs from the surfaces obtaining the Janus metallic@MOFs nanoparticles. The versatility of this methodology has allowed us to synthesis different MOF based composites, and in addition, we present the magnetic, fluorescence and catalytic properties that were evaluated in different Janus metallic@MOFs nanoparticles. In chapter 4, we explored another kind of composites based on the combination of MOFs and organic functional molecules. We studied the incorporation of functional molecules into the MOFs creating defects into the network of the MOFs. In particular, we evaluated the incorporating of Xylenol Orange (XO) that has coordinative carboxylic groups and a strong capacity to chelate heavy metal ions. We studied the mechanism of the integration of XO into the MOF and their influence on the formation of the MOF, and in addition, we evaluated the final properties and specially the capacity to remove heavy metal ions.
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- 2017
36. Metal-Organic Frameworks made of amino acids and adenine: chirality and hydrochromism
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Burneo Saavedra, Iván Patricio, Maspoch Comamala, Daniel, Imaz, Inhar, Hernando, Jordi, and Universitat Autònoma de Barcelona. Departament de Química
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Materiales porosos ,Chinality ,Ciències Experimentals ,Amino acidos ,Amino acids ,Porous materials ,Materias porosos ,Quinalitat ,Quinalidad - Abstract
La presente Tesis ha sido enfocada en la síntesis de Polímeros de Coordinación (CPs) y Metal-organic frameworks (MOFs) a partir de ligandos basados en biomoléculas para la obtención de materiales nuevos y funcionales. Sobre esta premisa, la Tesis aborda dos líneas de investigación principales que han sido desarrolladas para alcanzar los objetivos propuestos: i) estudiar la influencia de la razón enantioméricos de dos ligandos quirales sobre la estructura y quiralidad en Metal-Organic Frameworks, y ii) el diseño y la síntesis de nuevos polímeros de coordinación basados en adenina, ligandos aromáticos tetracarboxílicos y metales de transición. En el Capítulo 1, mostramos un breve resumen a cerca de la química, los métodos de síntesis y las aplicaciones actuales de CPs/MOFs, como, por ejemplo, absorción de gases o catálisis, con énfasis en aquellos en los cuales se usan biomoléculas como bloques de construcción. Posteriormente, en el Capítulo 2, describimos los objetivos generales de nuestra tesis. El Capítulo 3 describe la importancia de la quiralidad como una importante propiedad en CPs/MOFs, y resume los resultados obtenido y publicados en el artículo “The influence of the enantiomeric ratio of an organic ligand on the structure and chirality of metal–organic frameworks”, Chemical Communications, 2014, 50, 13829-13832. En este trabajo, hemos mostrado la importancia de la razón enantiomérica como variable relevante en la síntesis de MOFs porosos, y que puede ser tomada en cuenta como variable con resultados sorprendentes, la cual vii nos ha permitido obtener materiales porosos variando la razón enantiomérica. En el Capítulo 4, hemos tratado de desarrollar nuevos polímeros de coordinación basados en adenina usando ácidos aromáticos tetracarboxílicos, como ligandos auxiliares y Co(II). Lo resultados han sido publicados en el artículo titulado “Two New Adenine-based Co(II) Coordination Polymers: Synthesis, Crystal Structure, Coordination Modes and Reversible Hydrochromic Behavior”, Crystal Growth and Design, 2015, 15, 3182–3189, donde hemos aprovechado de los cinco sitios potenciales de coordinación y mostrado la importancia de adenina como ligando rígido en la síntesis de polímeros funcionales., The present Thesis has been addressed to the synthesis of bio-related metal-organic frameworks and coordination polymers as novel and functional materials. On the basis of the above, two main lines were developed to reach the objectives proposed: i) study the influence of enantiomeric ratio of two chiral ligands over the structure and chirality in Metal-Organic Frameworks, and ii) the design and synthesis of novel coordination polymers based in nucleobase-adenine, aromatic tetracarboylate ligands and transition metals. In Chapter 1, we showed a brief review about Coordination Polymers (CPs)/Metal-Organic Frameworks (MOFs), their chemistry, synthetic methods and their current applications, as gas adsorption or catalysis, with emphasis in ones which use biomolecules as building blocks for the construction of coordination polymers. Then, general objectives of this Thesis are described in Chapter 2. Chapter 3 describes the importance of chirality as an important property in CPs/MOFs, and summarized the results obtained and reported in the article “The influence of the enantiomeric ratio of an organic ligand on the structure and chirality of metal–organic frameworks”, Chemical Communications, 2014, 50, 13829-13832. In this work, we showed the importance of enantiomeric ratio as relevant variable in the synthesis of porous metal-organic frameworks, and as it might be introduced as variable with surprising results, which enabled us to obtain a porous material varying the enantiomeric ratio. v In Chapter 4, we aimed to develop new adenine-based coordination polymers using aromatic tetracarboxylic acids, as auxiliary linker and Co(II). We showed in the article titled “Two New Adenine-based Co(II) Coordination Polymers: Synthesis, Crystal Structure, Coordination Modes and Reversible Hydrochromic Behavior”, Crystal Growth and Design, 2015, 15, 3182–3189, where we took advantage of its five potential coordination sites for metal binding, showing the relevance of adenine as rigid linker in the synthesis of functional coordination polymers.
- Published
- 2017
37. Design and Synthesis of Submicron Diagnostic Systems Based on Coordination Polymers
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Aríñez Soriano, Javier, Maspoch, Daniel, Imaz, Inhar, Hernando, Jordi, and Universitat Autònoma de Barcelona. Departament de Química
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CA ,Ciències Experimentals ,MOF ,MRI - Published
- 2016
38. A new synthetic method for nanoscale metal-organic frameworks and their application as contrast agents for magnetic resonance imaging
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Carné Sánchez, Arnau, Maspoch Comamala, Daniel, Imaz, Inhar, Busqué Sánchez, Félix, and Universitat Autònoma de Barcelona. Departament de Química
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Metalorganics ,Biomedicine ,Ciències Experimentals ,Nanotecnologia ,Metal·lorgànics ,Nanotechnology ,Biomedicina - Abstract
La present Tesis ha estat dedicada a la síntesis de materials Metal·lorgànics a la nanoescala (NMOFs, fent servir l’acrònim anglès) i l’estudi de les seves potencials aplicacions com a Agents de Contrast (AC) en Imatgeria per Ressonància Magnètica. En conseqüència, dos línies de treball es distingeixen al llarg de la lectura d’aquesta Tesis: (ii) el desenvolupament de una nova metodologia per a sintetitzar NMOFs, i (ii) la síntesis de nous NMOFs que puguin complir els requeriments específics per tal de ser utilitzats com a AC. En el primer capítol, revisem la evolució que ha viscut el camp dels MOFs, des de els seus antecedents que van fer possible el seu descobriment fins a les seves aplicacions actuals i les seves noves perspectives. Prestem especial atenció a les actuals metodologies emprades per a sintetitzar NMOFs, i al adveniment de noves aplicacions aparegudes gràcies a la seva mida nanoscòpica. El en Capítol 3 descrivim la validació de la tècnica coneguda com Spray-Drying (SD) com a nova metodologia per sintetitzar NMOFs i les superestructures buides que se’n deriven. S’estudia l’impacte dels principals paràmetres experimentals en la síntesi del NMOFs així com les diferents modalitats de usatge que ofereix la tècnica. Precisament, la versatilitat de la tècnica ens ha permès sintetitzar un ampli ventall de NMOFs pertanyent a les subfamílies més representatives. El Capítol 4 explica les possibilitats de utilitzar la tècnica de SD per a combinar NMOFs amb altres especies funcionals per tal de sintetitzar compòsits basats en MOFs. Demostrem com les superestructures buides de NMOFs poden ser utilitzades per a encapsular diferents materials, tals com cristalls de NaCl, molècules fluorescents i nanopartícules magnètiques. A més, també demostrem com cristalls de NMOFs poden ser fàcilment encapsulats en matrius polimèriques mitjançant la tècnica de SD. La varietat de compòsits basats en MOFs que es pot obtenir utilitzant la tècnica de SD permet ampliar el ventall d’aplicacions dels NMOFs. En el capítol 5 es descriu la segona línia de treball que conforma la present Tesis doctoral referent a la síntesis de una nova generació de NMOFs amb propietats de AC. La estratègia consisteix en utilitzar lligands heterocíclics emprats en la síntesis dels AC moleculars, els quals presenten una gran afinitat per als ions de Gd(III). El lligand heterocíclic DOTP s’utilitza per l’assemblatge de un MOF bimetàl·lic i porós. Aquest MOF és miniaturitzat a la nanoescala per a forma dispersions col·loïdals estables; és estable en medi fisiològic, en cultiu cel·lular i no presenta citotoxicitat. A més, presenta unes propietats de AC interessants, com ho demostra la relaxativitat mesurada a camp magnètic alt (r1 = 5 mM-1·s-1 a 500 MHz) i una relaxativitat màxima a 40 MHz de 15 mM-1·s-1, la qual es manté constant al llarg de un ampli ventall de pH., The present Thesis has been dedicated to the synthesis of nanoscale Metal-Organic Frameworks (NMOFs) and the study of their potential application as Contrast Agents (CAs). Accordingly, two main lines of work can be distinguished through the lecture of this Thesis: i) the development of a novel synthetic methodology to synthesise NMOFs; and ii) the synthesis of new NMOFs that meet the specific requirements for their use as CAs. In the first Chapter, we review the evolution of the field of MOFs, from their antecedents that made their discovery possible to their current applications and prospects. We pay special attention to the current methodologies to synthesise MOFs at the nanoscale, and the advent of new applications resulting from their small size. Chapter 3 describes the validation of the Spray-Drying (SD) technique as a new methodology to synthesise NMOFs and their related hollow superstructures. The impact of the main experimental parameters on the synthesis of NMOFs is given as well as the different modes of operations that the SD technique offers for their synthesis. The versatility of the technique has allowed us to synthesise a wide panel of NMOFs belonging to the most representative subfamilies. In Chapter 4 the possibilities of combining NMOFs with other functional species using the SD technique to synthesise MOF-based composites is explained. We show how the MOF-based hollow superstructures can be used to encapsulate different materials, including NaCl crystals, dyes and FeOx inorganic nanoparticles (INPs). Furthermore, we also prove that NMOFs can also be easily encapsulated within functional matrices, such as polymers, by SD. Finally, we demonstrate that the unique capabilities of the SD to create MOF-based composites can be exploited to further expand the applications of NMOFs. In the second axis of this Thesis, Chapter 5 describes the synthesis of a new generation of NMOFs with CA properties. The strategy consists on using heterocyclic ligands currently employed in the synthesis of molecular CAs, which possess high chelating capabilities towards Gd(III) ions. The macrocyclic ligand DOTP is used to assemble a porous, heterometallic MOF. This MOF is miniaturizable down to the nanoscale to form stable colloids; is stable in physiological saline solution and cell culture media; and is not cytotoxic. It shows interesting relaxometric properties with a r1 at high field (500 MHz) of 5 mM-1·s-1 and a maximum in r1 of 15 mM-1·s-1 at 40 MHz, which remains constant over a wide pH range and increases with temperature.
- Published
- 2014
39. Coordination polymer nanofibers made of amino acids and peptides and their use as templates to synthesize inorganic nanoparticle superstructures
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Rubio Martínez, Marta, Maspoch Comamala, Daniel, Imaz, Inhar, Hernando Campos, Jordi, and Universitat Autònoma de Barcelona. Departament de Química
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Coordination polymers ,Biomolecules ,Ciències Experimentals ,Nanofibers - Abstract
La present Tesi Doctoral s'ha dedicat a explorar les capacitats de coordinació d’aminoàcids i pèptids per tal de desenvolupar nous Polimers de Coordinació (PCs) en forma de nanofibres a escala nanoemetrica, i poder utilitzar-los com a (doble) plantilla per la síntesi de superestructures fetes amb nanopartícules inorgàniques (INPs). Utilitzar PC en forma de nanofibres com a doble plantilla té l’avantatge de poder aprofitar tant les propietats de plantilla com les característiques inherents de reconeixement dels pèptids per tal de formar CPs. En el primer capítol es mostra una breu introducció als PC, centrant-se en l’ús de biomolècules. Aquest capítol inclou el treball titulat "Metal–biomolecule frameworks (MBioFs)", Chem. Commun (2011), on es fa una estesa i detallada descripció sobre aquests tipus de materials. A continuació, els objectius generals d'aquesta tesi es descriuen en el capítol 2. El Capítol 3 resumeix els resultats reportats en "Amino acid-based metal-organic nanofibers", J. Am. Chem. Soc. (2009). Aquí, es mostra la síntesi i caracterització de nanofibres de CP i gels construïts a partir de la coordinació d'amino àcids (L-o àcid D-aspàrtic, Asp) i ions metàl · lics (Cu (II) ions). Les nanofibres quirals de Cu(II)-Asp resultants s’han sintetitzat utilitzant tècniques de precipitació ràpida i de difusió lenta, amb les quals la longitud d’aquestes pot arribar fins a 1 centímetre. En el capítol 4, les nanofibres de Cu(II)-Asp s'han utilitzat com a cas-escenari de prova per explorar la tècnica de microfluídica (més precisament flux laminar) com a nou mètode sintètic per tal d'aconseguir un control més precís sobre l’assamblatge d'ions metàl·lics amb AA. S’ha demostrat que, a diferència dels procediments sintètics comuns, aquesta aproximació permet la síntesi en paral·lel amb un eminent nivell sobre el control de la coordinació, facilitant la formació de 1-D PC ensamblats a escala nanomètrica. A més de les nanofibres de Cu(II)-Asp, l’ús de la microfluidica ha permès la síntesis d’un segon tipus de nanofibres fetes amb aminoàcids, Ag(I)-Cisteina (Cys). S’ha confirmat que aquestes nanoestructures no es poden obtenir amb mètodes tradicionals com el de la precipitació ràpida dels dos components. Aquests resultats s'inclouen en el manuscrit "Coordination polymer nanofibers generated by microfluidic synthesis", J. Am. Chem. Soc. (2011). En un següent pas, el capítol 5 es centra en l'ús de les nanofibres de Ag (I)-Cys com a plantilles per tal de sintetitzar i acoblar NP inorgàniques en superestructures 1-D. En aquest capítol, primer es motra la síntesi de NPs de Ag2S ensamblades en 1-D exposant les nanofibres de Ag(I)-Cys sota un bombardeig d'electrons. A continuació, es mostra que aquestes plantilles sintetitzadades poden localitzar-se en posicions precises mitjançant la tecnologia de la microfluidica amb la incorporació de vàlvules de fluids microfabricades incorporades. La microfluídica permet orientar i localitzar la formació de les nanofibres de Ag (I)-Cys i a més, l'ús de vàlvules permet la immobilització de les fibres i poder utilitzar-les com a plantilles per a la síntesis de 1-D superestructures de NPs deAg. Aquestes superestructures s'han sintetitzat mitjançant la reducció (àcid ascòrbic) dels ions de Ag(I) que es troben dins de la plantilla. El nivell de control assolit amb la microfluídica ha permès que es puguin utilitzar més a fons aquestes superestructures de Ag NP com a segones plantilles per sintetitzar cristalls conductors de Ag (I)-tetracyanoquinodinmethane (TCNQ), permetent a més la mesura directe de les seves propietats de conductivitat. Tots aquests resultats estan inclosos en l'article presentat en el capítol 4 i en l'article titulat "Localized template growth of functional nanofibers from an metal-amino acid-supported framework in a microfluidic chip", ACS Nano 2014. Finalment, en el capítol 6, s'ha incrementat la complexitat dels PCs de Ag(I) fets a partir d'aminoàcids amb pèptids per tal d’explotar les característiques inherents de reconeixement que tenen els pèptids. S'ha sintetitzat una nova classe de plantilles metall-pèptid, cristalls de Ag(I)-DLL similars a cintes, amb els quals s'ha demostrat que poden ser utilitzats com a doble plantilla per a la síntesi i assamblatge de dos tipus de NPs inorgàniques, unes sobre la seva superfície (cara del cristall) i les altres dins de les seves estructures internes. En aquestes plantilles, les capacitats d'auto-assamblatge i reconeixement dels pèptids, i la reducció selectiva dels ions Ag(I) a Ag s'han explotat simultàniament per tal de controlar el creixement i l'assamblatge de més complexos multicomposicionals de superestructures amb NP inorgàniques. S'ha demostrat que aquests cinturons Ag(I)-DLL poden ser utilitzats com a dobles plantilles per crear llargues (> 100 µm) i polimetàl·liques superestructures conductores de Ag@AgNP i compostos multifuncionals de NPs de Fe3O4@Ag combinant les propietats magnètiques i conductores dels dos tipus de NPs. Aquests resultats han estat reportats en el manuscrit titulat "“Dual-template” Synthesis of one-dimensional conductive NP superstructures from coordination metal-peptide polymer crystals", Small (2013)., The present PhD Thesis has been dedicated to explore the coordination capabilities of amino acids and peptides to create novel nanoscale Coordination Polymers (CPs) in the form of nanofibers, and to use these nanofibers as (dual) scaffolds for the synthesis of superstructures made of inorganic nanoparticles (INPs). The use of CP nanofibers as dual scaffolds has taken advantage of the templating characteristics of CPs as well as the inherent recognition-template characteristics of the peptide that has been used to form the CP. In the first Chapter, we show a brief introduction to CPs, focusing on those constructed from biomolecules. This Chapter includes the review entitled "Metal–biomolecule frameworks (MBioFs)", Chem. Commun (2011), in which an extended, detailed description of this type of materials was reported. Then, the general objectives of this Thesis are described in Chapter 2. Chapter 3 summarizes the results reported in "Amino acid-based metal-organic nanofibers", J. Am. Chem. Soc.(2009). Here, we show the synthesis and characterization of CP nanofibers and gels built up from the coordination of amino acids (L- or D-aspartic acid, Asp) and metal ions (Cu(II) ions). The resulting chiral Cu(II)-Asp nanofibers have been synthesized using fast precipitation and slow diffusion techniques, from which their lenght could be extended up to 1 centimeter. In Chapter 4, Cu(II)-Asp nanofibers have been used as the test-case-scenario to explore microfluidics technology (more precisely, laminar flow) as a new synthetic approach to achieve precise control over the assembly of metal ions and amino acids. We have demonstrated that unlike common synthetic procedures, this approach enables parallel synthesis with an unprecedented level of control over the coordination pathway and facilitates the formation of 1D CP assemblies at the nanometer length scale. In addition to Cu(II)-Asp nanofibers, the use of microfluidics has allowed the synthesis of a second type of CP nanofibers made of amino acids Ag(I)-Cysteine (Cys) nanofibers. We have also confirmed that these nanostructures can not be synthesized with more traditional methods, such as fast mixing of both components. All these results are included in the manuscript entitled "Coordination polymer nanofibers generated by microfluidic synthesis", J. Am. Chem. Soc. (2011). In a next step, Chapter 5 focuses on the use of the Ag(I)-Cys nanofibers as templates to synthesize and assemble inorganic NPs into 1D superstructures. In this Chapter, we first show the synthesis of 1-D assemblies of Ag2S NPs by exposing the Ag(I)-Cys nanofibers to e-beam bombardment. We then show that this template synthesis can be localized at precise positions by using microfluidic technology with micro-engineered fluidic clamps incorporated. Microfluidics allows guiding and localizing the formation of Ag(I)-Cys nanofibers, whereas the use of clamps allows immobilizing these fibers and use them as templates to synthesize 1-D Ag NP superstructures. These superstructures have been synthesized via reduction (ascorbic acid) of the Ag(I) ions inside the scaffold structure. We anticipate that the level of control achieved with microfluidics has allowed us to further use these Ag NP superstructures as second templates to synthesize conductive Ag(I)-tetracyanoquinodinmethane (TCNQ) CP crystals, allowing also the direct measurement of their conductivity properties. All these results are included in the article presented in Chapter 4 and in the article entitled "Localized template growth of functional nanofibers from an metal-amino acid-supported framework in a microfluidic chip", ACS Nano 2014. Finally, in Chapter 6, we have increased the complexity of the Ag(I)-based CP from amino acids to peptides to exploit the inherent recognition-template characteristics of peptides. Here, we have synthesized a new class of metal-peptide scaffolds, Ag(I)-DLL belt-like crystals, that were proved to be used as dual-templates for the synthesis and assembly of two types of inorganic NPs, one on their surface (crystal face) and the other within their internal structures. In these CP scaffolds, the self-assembly and recognition capacities of peptides and the selective reduction of Ag(I) ions to Ag are simultaneously exploited to control the growth and assembly of more complex, multicompositional inorganic NP superstructures. We demonstrate that these Ag(I)-DLL belts could be applied as dual templates to create long (> 100 μm) conductive Ag@Ag NP superstructures and polymetallic, multifunctional Fe3O4@Ag NP composites that marry the magnetic and conductive properties of the two NP types. These results have been reported in the manuscript entitled "“Dual-template” Synthesis of one-dimensional conductive NP superstructures from coordination metal-peptide polymer crystals", Small (2013).
- Published
- 2014
40. Surface structuration of metal-organic frameworks using tip-based lithographies
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Carbonell Fernández, Carlos, Maspoch Comamala, Daniel, Imaz, Inhar, Pascual i Gainza, Jordi, and Universitat Autònoma de Barcelona. Departament de Física
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Metal-organic materials ,Probe based lithography ,Ciències Experimentals ,Materials metal-orgànics ,Litografia per sonda ,Nano-estructuració ,Nanostructuration - Abstract
La presente Tesis Doctoral se ha dedicado al estudio, desarrollo e implementación de métodos para la síntesis y micro- nanoestructuración de materiales metal-orgánicos porosos (MOFs, Metal-Organic Frameworks) sobre superficies. La importancia en la estructuración de MOFs con alta resolución radica en la necesidad de su integración en microdispositivos, especialmente de tipo sensor. En el primer capítulo se realiza una prospección bibliográfica sobre el estado del arte en MOFs, con una breve introducción histórica, las principales rutas sintéticas, propiedades y aplicaciones. Se introducen también los nano-MOFs (NMOFs) con sus particularidades tanto sintéticas como relativas a sus propiedades y aplicaciones. Este capítulo incluye el trabajo de revisión titulado “Nanoscale Metal-Organic Materials”, Chemical Society Reviews (2010) donde se da una descripción extensa y más genérica sobre materiales Metal-Orgánicos. El Capítulo 2 cita los objetivos generales y particulares de la presente Tesis Doctoral. En el Capítulo 3 se introduce la nanoestructuración de MOFs en superficie y se desarrolla un nuevo método para nanoestructurar un MOF en particular (HKUST-1) sobre superficies con precisión nanométrica y al nivel de monocristales. Además de desarrollar un nuevo y versátil método para nanoestructurar HKUST-1 en superficies, se estudia cómo influye la funcionalización de la superficie sobre el crecimiento, nucleación y orientación cristalina. Los resultados de este capítulo se incluyen en el artículo “Single-Crystal Metal-Organic Framework Arrays”, Journal of the American Chemical Society, (2011). A partir del análisis de los resultados y problemáticas aparecidas en el capítulo anterior, en el Capítulo 4 se desarrolla una nueva aproximación que permite ampliar el abanico de MOFs viables para su estructuración. Así, en este capítulo se estudian las características de la nueva aproximación basada en combinar reactivos en volúmenes del orden de los femtolitros (10-15 l) utilizando una sonda de nanolitografía por microfluídica. Se demuestra la habilidad para realizar diferentes reacciones químicas y bioquímicas confinadas en dicho rango de volúmenes. Más adelante se demuestra la utilidad de la nueva aproximación para estructurar MOFs diferentes en un espacio micrométrico de una superficie realizando química combinatoria. Finalmente, se demuestra que dicha aproximación se puede utilizar para la detección combinatoria de posibles nuevos materiales, en nuestro caso se descubren dos nuevos bioMOFs. Los resultados de este trabajo se incluyen en el artículo “Femtolitre Chemistry assisted by microfluidic pen lithography” Nature Communications, (2013)., The present PhD Thesis has been dedicated to the study, development and implementation of methods for the synthesis and nanostructuring of Metal-Organic Frameworks (MOFs) on surfaces. The importance in structuring MOFs with high resolution is the need for their integration into microdevices, especially sensors. In the first chapter a literature survey on the state of the art in MOFs, with a brief historical introduction, the main synthetic routes, properties and applications is given. Nano-MOFs (NMOFs) are also introduced with both synthetic and properties and application characteristics. This chapter includes the review paper entitled "Nanoscale Metal-Organic Materials", Chemical Society Reviews (2010) where an extensive and more generic description of Metal-Organic material is developed. Chapter 2 cites the general and specific objectives of this PhD thesis. In Chapter 3 nanostructuring of MOFs on surfaces is introduced and a new method to nanostructure a particular MOF (HKUST-1) on surfaces with nanometer precision even at the level of single crystals is developed. In addition to developing a new and versatile method for HKUST-1 surface nanoestructure, we study how the surface functionalization influences on the growth, nucleation and crystal orientation. The results of this chapter are included in the article "Single-Crystal Metal-Organic Framework Arrays", Journal of the American Chemical Society, (2011). From the analysis of the results and issues that appeared in the previous chapter, in Chapter 4 is developed a new approach that can extend the range of viable MOFs for structuring. Thus, in this chapter the characteristics of the new approach based on combining reagents in volumes on the order of femtoliters (10-15 l) using a nanolithography microfluidic probe is studied. It is demonstrated the ability to perform various confined chemical and biochemical reactions in this volume range. Also, the utility of the new approach to structure different MOFs in a space of a micrometer performing combinatorial chemistry surface is demonstrated. Finally, it is shown that this approach can be used for combinatorial detection of possible new materials, in our case two new bioMOFs are discovered. The results of this work are included in the article "Femtolitre Chemistry assisted by microfluidic pen lithography" Nature Communications, (2013).
- Published
- 2014
41. {2,5-Bis[3-(tert-butylaminoxyl)phenyl]-1,1-dimethyl-3,4-diphenylsilole-kappaO}bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)manganese(II).
- Author
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Roques N, Gerbier P, Imaz I, Guionneau P, and Sutter JP
- Abstract
In the structure of the first bis-adduct of 2,5-bis[3-(tert-butylaminoxyl)phenyl]-1,1-dimethyl-3,4-diphenylsilole with bis(hexafluoroacetylacetonato)manganese(II), [Mn(C5HF6O2)2(C38H42N2O2Si)2], the Mn atom lies on a crystallographic inversion centre and is bound to two chelating hexafluoroacetylacetonate ligands and two monodentate nitroxide groups in a distorted octahedral configuration. The silole ligands present a propeller-like arrangement of the benzene rings around the Si-containing five-membered ring. The dihedral angles between the complexed nitroxides and the benzene rings to which they are bound are smaller than those found in the free ligand.
- Published
- 2006
- Full Text
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