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Space cooling and heating, ventilation, and air conditioning (HVAC) accountsfor roughly 10% of global electricity use and are responsible for ca. 1.13gigatonnes of CO2emissions annually. Adsorbent-based HVAC technologieshave long been touted as an energy-efficient alternative to traditionalrefrigeration systems. However, thus far, no suitable adsorbents have beendeveloped which overcome the drawbacks associated with traditional sorbentmaterials such as silica gels and zeolites. Metal-organic frameworks (MOFs)offer order-of-magnitude improvements in water adsorption and regenerationenergy requirements. However, the deployment of MOFs in HVACapplications has been hampered by issues related to MOF powderprocessing. Herein, three high-density, shaped, monolithic MOFs (UiO-66,UiO-66-NH2, and Zr-fumarate) with exceptional volumetric gas/vapor uptakeare developed - solving previous issues in MOF-HVAC deployment. Themonolithic structures across the mesoporous range are visualized usingsmall-angle X-ray scattering and lattice-gas models, giving accuratepredictions of adsorption characteristics of the monolithic materials. It is alsodemonstrated that a fragile MOF such as Zr-fumarate can be synthesized inmonolithic form with a bulk density of 0.76 gcm-3without losing anyadsorption performance, having a coefficient of performance (COP) of 0.71with a low regeneration temperature (≤100°C).

Herein, we describe for the first time the synthesis of the highly porous Hf-tetracarboxylate porphyrin-based metal-organic framework (MOF) (Hf)PCN-224(M) (M = H2, Co2+). (Hf)PCN-224(H2) was easily and efficiently prepared following a simple microwave-assisted procedure with good yields (56–67%; space-time yields: 1100–1270 kg m−3·day−1), high crystallinity and phase purity by using trifluoromethanesulfonic acid and benzoic acid as modulators in less than 30 min. By simply introducing a preliminary step (10 min), 5,10,15,20-(tetra-4-carboxyphenyl)porphyrin linker (TCPP) was quantitatively metalated with Co2+ without additional purification and/or time consuming protection/deprotection steps to further obtain (Hf)PCN-224(Co). (Hf)PCN-224(Co) was then tested as catalyst in CO2 cycloaddition reaction with different epoxides to yield cyclic carbonates, showing the best catalytic performance described to date compared to other PCNs, under mild conditions (1 bar CO2, room temperature, 18–24 h). Twelve epoxides were tested, obtaining from moderate to excellent conversions (35–96%). Moreover, this reaction was gram scaled-up (x50) without significant loss of yield to cyclic carbonates. (Hf)PCN-224(Co) maintained its integrity and crystallinity even after 8 consecutive runs, and poisoning was efficiently reverted by a simple thermal treatment (175 °C, 6 h), fully recovering the initial catalytic activity.

Demand continues for processing methods to shape covalent organic frameworks (COFs) into macroscopic objects that are needed for their practical applications. Herein, a simple compression method to prepare large-scale, free-standing homogeneous and porous imine-based COF-membranes with dimensions in the centimeter range and excellent mechanical properties is reported. This method entails the compression of imine-based COF-aerogels, which undergo a morphological change from an elastic to plastic material. The COF-membranes fabricated upon compression show good performances for the separation of gas mixtures of industrial interest, N2/CO2 and CH4/CO2. It is believed that the new procedure paves the way to a broader range of COF-membranes., This work was supported by the Spanish MINECO (PID2019-106268GB-C31, PID2019-106268GB-C32, PCI2018-093081, and RTI2018-095622-B-I00), the Catalan AGAUR (project 2017 SGR 238), and through the “María de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M). It was also funded by the CERCA Program/Generalitat de Catalunya. ICN2 was supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706). Y.C. and D.Z. acknowledge the National Research Foundation Singapore (NRF2018-NRF-ANR007 POCEMON) and the Ministry of Education – Singapore (MOE2018-T2-2-148, MOE2019-T2-1-093) for their financial support of this project.

Figure S1. Effect of rHDL-rApoJ or free rApoJ treatment in the levels of mouse ApoJ in brain homogenates and plasma from treated mice, determined by ELISA. Data are expressed as the mean ± SEM. N = 3–4/group. Figure S2. Effect of rHDL-rApoJ or free rApoJ treatment in the expression of full-length APP protein and the processing of APP through α-, β-, and γ secretases. a) Representative Western blots showing the relative amount of full-length APP, sAPPα, sAPPβ, and CTF-APP. Relative quantification of b) full-length APP, c) sAPPα, d) sAPPβ, and e) CTF-APP levels after treatments. Data are expressed as the mean ± SEM. N = 6/group. Table S1. List of abbreviation of tested inflammatory molecules by multiplexed ELISA. (DOCX 302 kb)

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

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.

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.

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.

Resumen del trabajo presentado al VIII International Congress on Analytical Nanoscience and Nanotechnology, celebrado en Barcelona (España) del 3 al 5 de julio de 2017., Despite the strong advances in the field of sensing and analytical techniques, the specific and fast control of a large number of environmental pollutants is still challenging. This is mainly due to the lack of analytical tools which, in addition to being fast, accurate and reliable, have an affordable cost and, more importantly, bare selective. For this reason, we have developed a novel photonic nanosensor, using a new class of nanoporous materials, the so-called Metal-Organic Frameworks (MOFs), as receptors for the rapid and selective detection of carbon dioxide as a control parameter for environmental monitoring. The nanosensor transducer is based on highly sensitive heteromodal waveguides and the receptors are transparent nanoZIF-8, made by zinc ions clusters coordinated by four imidazolate rings. The MOF layer is deposited by spin-coating and permanently attached to the sensor surface through a PDMS layer (Figure 1). Preliminary results show a limit of detection around 1% of CO2 and selectivity for CO2 versus N2. Each measure-regeneration cycle takes less than a minute. The process is reversible and the sensor surface is stable for more than one month.

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.

Resumen del póster presentado al CIBERDEM Annual Meeting, celebrado en Cerdanyola del Vallès, Barcelona (España) del 11 al 13 de mayo de 2016.-- et al., Currently, the aetiology of type 1 diabetes mellitus (T1DM) remains unknown and strategies to cure this disease are not available. To prevent and cure T1DM, a sine qua non condition is the arrest of the autoimmune β-cell destruction. An ideal immunotherapy should restore immunological self-tolerance, avoiding systemic side effects and allowing islet regeneration. A physiological strategy to avoid autoimmunity is apoptosis. Apoptotic cells are a source of autoantigens, and when they are phagocytosed, induce tolerance and promote cell replacement. Based on these features, liposomes mimicking apoptotic β-cells have been created as immunotherapy for T1DM. Liposomes are vesicles clinically used for drug delivery and are safe and biocompatible. Liposomes rich in phosphatidylserine (PS), a membrane component exposed during apoptosis and the main signal for phagocytosis, were loaded with β-cell autoantigens. PS-liposomes showed multivesicular morphology and optimal size for phagocytosis. PS-liposome induced tolerogenic dendritic cells (tolDCs), capable of inducing self-tolerance. TolDCs display low levels of costimulatory molecules, secrete prostaglandin E2, a lipid mediator with suppressive function, and impair autoreactive T cell proliferation. The tolerogenic potential of PS-liposomes has been confirmed in non-obese diabetic (NOD) mice, the spontaneous model of T1DM. When administered to prediabetic NOD mice, PS-liposome signal was detected in lymph nodes, spleen and pancreas. Importantly, a single dose of PS-liposomes administered at pre-clinical stage, arrests β-cell destruction, reduces insulitis, and permanently prevents T1D. PS-liposome treatment results in a fast expansion of antigen-specific T cells that could prove to possess regulatory function. Therefore, PS-liposomes mimicking apoptotic β-cells can be an effective antigen-specific immunotherapy, constituting a promising strategy to arrest autoimmunity in T1DM and other autoimmune diseases., Work supported by ISCiii (FIS PI12/00195, PI15/00198). European patent filed.

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.

Resumen del trabajo presentado al X Congrés de la Societat Catalana d'Inmunologia: "Immunoteràpia contra el Càncer", session III: "From Innate to Adaptative Immunity"; celebrado en Barcelona (España) del 17 al 18 de noviembre de 2016.-- et al., Autoimmune diseases are caused by the destruction of the host’s own cells by autoreactive lymphocytes. There are nearly 100 autoimmune diseases, with increasing incidence and affecting around 5% of the population. Genetic and environmental factors contribute to autoimmunity but the triggering factors remain unknown, and current therapies are poorly effective and cause side effects. Therefore, new and safe approaches are required to arrest autoimmunity and allow target tissue regeneration. Based on apoptotic cells’ ability to induce self-tolerance after phagocytosis, liposomes that possess their inherent tolerogenic features have been designed. Liposomes are phospholipid bilayer vesicles that constitute a versatile system for modulation of immune responses. The herein reported liposomes are made of phosphatidylcholine, cholesterol, phosphatidylserine (PS) —the main 'eat me' signal exposed in the membrane of apoptotic cells—, and display a diameter greater than 500 nm to promote phagocytosis. Liposome’s ability to restore self-tolerance was tested in experimental models of autoimmune diseases: the non-obese diabetic (NOD) mouse for type 1 diabetes (T1D), and the experimental autoimmune encephalomyelitis (EAE)-induced mouse for multiple sclerosis (MS). Liposomes were generated encapsulating disease-specific autoantigens: insulin peptides for T1D and myelin-oligodendrocyte glycoprotein peptide for MS. Liposomes were efficiently engulfed by dendritic cells, inducing a tolerogenic phenotype and function. Liposomes were successful at arresting autoimmunity in vivo: T1D and EAE’s incidence was decreased and their onset delayed. Moreover, EAE’s severity was reduced. PS-Liposomes induced an antigen-specific CD4+ FoxP3+ and FoxP3– T cell response in the T1D model, and FoxP3– T lymphocytes correlated with minor clinical signs and hinted at belonging to Type 1 regulatory T cells in the MS model. This work validates PS-liposomes as a powerful tool for the re-establishment of tolerance. Working synergistically, autoantigen-loaded PS-liposomes co-deliver a double signal of tolerance and specificity to arrest autoimmune reactions in an effective and safe manner.

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).

7 páginas, 5 figuras., In this manuscript we demonstrate the spatially controlled immobilization of ferritin proteins by directly writing them on a wide range of substrates of technological interest. Optical and fluorescence microscopy, AFM and TOF-SIMS studies confirm the successful deposition of the protein on those surfaces. Control on nanostructure shape and size, by miniaturizing the dot-like features down to a 100 nm, demonstrates the particular capabilities of the DPN approach. Ultimately, this study gives the opportunity to design nanoparticle-based arrays regarding the growing interest in the use of nanoparticles as structural and functional elements for fabricating nanodevices. Herein, we demonstrate how the protein shell of ferritins can be removed by a simple heat-treatment process while maintaining the encapsulated inorganic nanoparticle intact on the same location of the nanoarray. As a result, this study establishes how direct-write DPN approach could give the opportunity to design not only protein-based nanoarrays but also nanoparticle-based nanoarrays with high-resolution and control., D. M. thanks the Ministerio de Ciencia y Tecnología for a RyC contract. A. L. thanks ARAID for financial support. R. de M. is indebted to MICINN for receiving a predoctoral FPU fellowship.

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.

Type 1 diabetes (T1D) is an autoimmune disease caused by the destruction of insulin-producing cells. Due to the ability of apoptotic cells clearance to induce tolerance, we previously generated liposomes rich in phophatidylserine (PS) –a feature of apoptotic cells– loaded with insulin peptides to mimic apoptotic beta-cells. PS-liposomes arrested autoimmunity in experimental T1D through the induction of tolerance. The aim of this study was to investigate the potential of several peptides from different T1D autoantigens encapsulated in (PS)-liposomes for T1D prevention and to assess its safety. T1D autoantigens (Insulin, C-peptide, GAD65 and IA2) were encapsulated in PS-liposomes. Liposomes were administered to the 'gold-standard' model for the study of autoimmune T1D, the Non-Obese Diabetic mouse, that spontaneously develop the disease. Safety and toxicity of liposomes were also determined. Only PS-liposomes encapsulating insulin peptides decrease T1D incidence in the Non-Obese Diabetic mouse model. Disease prevention correlates with a decrease in the severity of the autoimmune islet destruction driven by leukocytes. PS-liposomes neither showed toxic effect nor secondary complications. Among the here referred autoantigens, insulin peptides are the best candidates to be encapsulated in liposomes, like an artificial apoptotic cell, for the arrest of autoimmunity in T1D in a safe manner.

Type 1 diabetes (T1D) is an autoimmune disease caused by the destruction of insulin-producing cells. Due to the ability of apoptotic cells clearance to induce tolerance, we previously generated liposomes rich in phophatidylserine (PS) –a feature of apoptotic cells– loaded with insulin peptides to mimic apoptotic beta-cells. PS-liposomes arrested autoimmunity in experimental T1D through the induction of tolerance. The aim of this study was to investigate the potential of several peptides from different T1D autoantigens encapsulated in (PS)-liposomes for T1D prevention and to assess its safety. T1D autoantigens (Insulin, C-peptide, GAD65 and IA2) were encapsulated in PS-liposomes. Liposomes were administered to the 'gold-standard' model for the study of autoimmune T1D, the Non-Obese Diabetic mouse, that spontaneously develop the disease. Safety and toxicity of liposomes were also determined. Only PS-liposomes encapsulating insulin peptides decrease T1D incidence in the Non-Obese Diabetic mouse model. Disease prevention correlates with a decrease in the severity of the autoimmune islet destruction driven by leukocytes. PS-liposomes neither showed toxic effect nor secondary complications. Among the here referred autoantigens, insulin peptides are the best candidates to be encapsulated in liposomes, like an artificial apoptotic cell, for the arrest of autoimmunity in T1D in a safe manner.

This work bases on the solid?state study of a chiral ZnII?porphyrin derivative (5,10,15,20?tetra[(4?R,R,R,R)?methyl?2?phenoxy?propanoate, 1) building block and its achiral analogous (2). Here, foreseen the rich molecular recognition of the designed metallo?porphyrins (1 and 2) and tendency to crystallize, we recrystallized both using two sets of solvents (CH2Cl2/CH3OH and CH2Cl2/hexane). As a result, four different crystalline arrangements (1a?b, 2a?b, from 0D to 2D) were successfully achieved. We performed solid state studies for all the species, analysing the role played by chirality, solvent mixtures and surfaces (mica and HOPG), on the supramolecular arrangements. As for the combination of solvents and substrates we obtained a variety of micro?sized species, from vesicles to flower?shaped arrays, including geometrical microcrystals. Overall, our results emphasize the environmental susceptibility of metallo?porphyrins and how this feature must be taken into account in their design.

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.

The development of devices for sensing and monitoring CO2 levels is crucial for many fields such as food packaging and for human safety indoors. Herein the fabrication of an optical CO2 sensor by integration of a metal–organic framework (MOF) onto bimodal optical waveguides is reported. This sensor is constructed via self-assembly of a transparent film of zeolitic imidazolate framework-8 (ZIF-8) nanoparticles (size: 32 ± 5 nm) on the waveguides. The nanoZIF-8-based sensor exhibits a broad linear response, with limits of detection of 3130 ppm at room temperature and 774 ppm at 278 K. Furthermore, it is robust, selective, fast and reusable, and can be stored under humid conditions with no loss in performance., This work was supported by a grant from the Fundación Domingo Martínez (Ayuda a la Investigación 2016. Área de Aplicaciones Materiales), the Spanish MINECO (projects PN MAT2015-65354-C2-1-R and MAT2016-79053-P), the Catalan AGAUR (project 2014 SGR 80 and 2014 SGR 624), and the ERC, under the EU FP7 (ERC-Co 615954). It was also funded by the CERCA Program/Generalitat de Catalunya. This work also made use of the Spanish ICTS Network MICRONANOFABS, which is partially supported by MEINCOM. ICN2 and ICMAB acknowledge the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grants SEV-2013-0295 and SEV-2015-0496.

Supramolecular isomerism of metal-organic frameworks (MOFs) is known for several MOF structures, having direct implications on the properties of these materials. Although the synthesis of MOF isomers is mainly serendipitous in nature, achieving controlled formation of a target framework is highly relevant for practical applications. This work discusses the influence of additives and synthesis conditions on the formation of porous isomers containing Zn2+ as nodes and 2,5-dihydroxy-1,4-benzenedicarboxylate (dobdc4-) as a linker. Using solvent mixtures containing strongly coordinated molecules, e.g. N,N'-dimethylformamide (DMF) and N-methylpyrrolidone (NMP), facilitates the formation of porous structures of type [Zn2(dobdc)(S)x]·yS (S = DMF, NMP) which are built from dinuclear Zn2(O)2(CO2)3 secondary building units (SBUs) consisting of two different edge-sharing polyhedra with the Zn2+ ions in a unsaturated coordinative environment. In the presence of water, the Zn2+ dimers are converted to one-dimensional infinite Zn2+ chains, in which the number of Zn2+-linker bonds increases, therefore giving a hydrolytically more stable coordination environment. The full characterization of the isomers as well as their conversion to the most stable isomer is presented., This work is part of the Research Priority Area Sustainable Chemistry of the University of Amsterdam, http://suschem.uva.nl, and was funded by a TOP-PUNT grant from the NWO. It was also supported by Spanish MINECO (projects PN RTI2018-095622-B-I00), the Catalan AGAUR (project 2014 SGR 80), the ERC under the EU-FP7 (ERC-Co 615954), and the CERCA Program/Generalitat de Catalunya. ICN2 was supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706).

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).

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.

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.

Metal-organic frameworks (MOFs) assembled from multiple building blocks exhibit greater chemical complexity and superior functionality in practical applications. Herein, we report a new approach based on using prefabricated cavities to design isoreticular multicomponent MOFs from a known parent MOF. We demonstrate this concept with the formation of multicomponent HKUST-1 analogues, using a prefabricated cavity that comprises a cuboctahedral Rh(II) metal-organic polyhedron functionalized with 24 carboxylic acid groups. The cavities are reticulated in three dimensions via Cu(II)-paddlewheel clusters and (functionalized) 1,3,5-benzenetricarboxylate linkers to form three- and four-component HKUST-1 analogues., This work was supported by the Spanish MINECO (project RTI2018-095622-B-I00), the Catalan AGAUR (project 2017 SGR 238), the CERCA Program/Generalitat de Catalunya, and the MCIN/AEI/10.13039/501100011033 and by the European Union “NextGenerationEU”/PRTR (EUR2020-112294). We also thank CESGA Supercomputing center for technical support and computer time at the supercomputer Finisterrae III. ICN2 and ICMAB are supported by the Severo Ochoa program from the Spanish MINECO (grants SEV-2017-0706 and CEX2019-000917-S). The project that gave rise to these results received the support of a fellowship (LCF/BQ/PR20/11770011) from “la Caixa” Foundation (ID 100010434). A.E.P.-P. acknowledges a Ramón y Cajal fellowship (RYC2018-024328-I). With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

[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.

Under a Creative Commons license.-- et al., Herein we report the use of immunostimulant-loaded nanoliposomes (called NLc liposomes) as a strategy to protect fish against bacterial and/or viral infections. This work entailed developing a method for in vivo tracking of the liposomes administered to adult zebrafish that enables evaluation of their in vivo dynamics and characterisation of their tissue distribution. The NLc liposomes, which co-encapsulate poly(I:C) and LPS, accumulate in immune tissues and in immunologically relevant cells such as macrophages, as has been assessed in trout primary cell cultures. They protect zebrafish against otherwise lethal bacterial (Pseudomonas aeruginosa PAO1) and viral (Spring Viraemia of Carp Virus) infections regardless of whether they are administered by injection or by immersion, as demonstrated in a series of in vivo infection experiments with adult zebrafish. Importantly, protection was not achieved in fish that had been treated with empty liposomes or with a mixture of the free immunostimulants. Our findings indicate that stimulation of the innate immune system with co-encapsulated immunostimulants in nano-liposomes is a promising strategy to simultaneously improve the levels of protection against bacterial and viral infections in fish., The authors acknowledge financial support from Fundación Ramon Areces, AGL2012-33877 (MINECO, Spain) and Aposta (UAB). AR thanks Fundación Ramon Areces for a PhD fellowship and NR thanks MINECO for a Ramón y Cajal grant.