Auto-ensamblaje de unidades porfirínicas para la obtención de dispositivos supramoleculares

40 p. : il.[spa]Las entidades supramoleculares basadas en el auto-ensamblaje de metaloporfirinas son ejemplos paradigmáticos de la gran eficiencia de los nanodispositivos empleados por los seres vivos para el almacenamiento y el transporte de energía y masa. Por ello, se constituyen en un modelo de referencia para el desarrollo de nuevos materiales que realicen éstas y otras, aún inexploradas, funciones. Mientras los biosistemas metaloporfírinicos operan en disolución, la preparación de materiales traslada la problemática de su síntesis al estado sólido. Así, la obtención de entidades supramoleculares puede realizarse en base a varias estrategias de diseño sintético. Una de ellas consiste en la conexión de las esferas de coordinación metaloporfirínicas con otros metalocentros. El abanico de compuestos que puede ser utilizado para realizar estas combinaciones es inagotable y en el mismo destacan los metalocentros basados en ligandos dipiridínicos. En lo que a metodologías de síntesis se refiere, los sistemas porfírinicos obtenidos hasta el momento se han preparado tanto por vías clásicas en disolución como por métodos hidrotermales. Con estos antecedentes, el trabajo de investigación que se presenta en esta memoria se circunscribe en una nueva línea de investigación con la que se pretende abordar la síntesis y caracterización de dispositivos supramoleculares basados en el autoensamblaje de unidades porfírinicas para el almacenamiento y transporte de energía y masa. Para ello, un primer enfoque ha consistido en el uso de biometales de la primera serie de transición combinados con porfirinas de distintas características y varios ligandos dipirídínicos. Asimismo, se ha introducido la calefacción por microondas como metodología de síntesis alternativa. Los primeros resultados, que aquí se recogen, han desembocado en la obtención del compuesto [Fe(P-ca)], donde P-ca-3 es el anión trivalente de la meso-tetra-4-carboxifenilporfirina. Este compuesto presenta una estructura quiral de capas onduladas que se unen a través de enlaces de hidrógeno dando lugar a un entramado 3D que preserva la quiralidad. Este agrupamiento covalente 2D representa un esqueleto origen, a partir del cual se prevé la preparación de nuevos compuestos.[eng]Supramolecular entities based on self-assembly of metalloporphyrins are paradigmatic examples of the great efficiency of the nanodevices used by living things for the storage and transport of energy and mass. Therefore, they constitute reference models for the development of new materials that make these and other yet unexplored functions. While metalloporphyrin systems operate in solution, the preparation of materials moves the problem to the solid state synthesis. Thus, obtaining supramolecular entities may be based on various strategies of synthetic design. One of them consists in connecting the spheres of coordination metalloporphyrins with other metalocenters. The range of compounds that can be used for these combinations is endless and in it the metalocenters based on dipyridinic ligands do highlight. In relation to the synthesis methods, it should be remarked that porphyrin systems obtained so far have been prepared both by classic solution ways and by hydrothermal methods. Taking into account the above mentioned aspects, the research work here presented corresponds to a new line of research focused to the synthesis and characterization of supramolecular devices based on the self-assembly of porphyrin units for storage and transport of energy and mass. With this purpouse, a first approach has been the use of biometals of the first transition series combined with porphyrins with different characteristics and various dipyridinic ligands. Microwave heating has also been introduced as an alternative for synthesis. The first results, here collected, correspond to the compound [Fe (P-ca)], where P-ca-3 is the trivalent anion of meso-tetra-4-carboxyphenyl porphyrin. This compound has a chiral structure of wavy layers linked through hydrogen bonds resulting in a 3D framework that preserves chirality. This 2D covalent array represents an origin skeleton, from which the preparation of new compounds is planned.Ministerio de Educación y Ciencia MAT2007-60400, Gobierno Vasco IT-177-0

Sare metal-organikoetan oinarritutako farmakoen liberazio sistemak: biomolekulak atxikitzeko funtzionalizazio-estrategiak

Sare metal-organikoetan (MoF, metal-organic framework, ingelesez) oinarritutako farmakoen liberazio kontrolaturako erabiltzen diren sistemak (DDS, drug delivery system, ingelesez) orain arte erabilitako sistema tradizionalek aurkezten dituzten mugak gainditzeko gai dira. Izan ere, haien izaera hibridoa dela eta, bai sistema ez-organiko bai organiko tradizionalek aurkezten dituzten abantailak batzeko gai dira, eta haien desabantailak murrizten dituzte. Lan honetan, DDSak sortzeko kontuan hartu beharreko ezaugarriak azaldu eta gero, MoF sareek DDS gisa erabiltzeko aurkezten dituzten ezaugarri nabarmenenak aipatuko dira. Azkenik, MoF egituretan biomolekulen atxikipen eta/ edo askapen kontrolatua lortzeko erabiltzen diren bost funtzionalizazio-estrategia nagusiak aztertuko dira.; Drug delivery systems (DDSs) based on metal-organic frameworks (MOFs) overcome the limits shown by conventionally used drug delivery systems. Due to their hybrid inorganic-organic nature, MOFs are able to combine the advantages shown by inorganic and organic based conventional DDSs, while minimising their drawbacks. In this work, after explaining the general characteristics that DDS systems must fullfil, the key properties of MOFs for their use as DDSs are discussed. More specifically, the five most used functionalization strategies to achieve a controled incorporation and/or release of biomolecules within MOF structures will be explained

MOF@IL composite materials as Pd(II) supports for heterogeneous organocatalytic reactions

Comunicación Oral realizada en World Congress & Expo on Chemical Engineering & Catalysis (23-24 julio 2018, Osaka, Japón)Metal-Organic Frameworks (MOFs) have experienced a rapid emerge in the last two decades because they offer unique advantages for many applications due to their ordered structures, high thermal stability, tunable chemical functionality, ultra-high porosity and the availability of hundreds of well characterized structures.[1] Among the properties that they may present, they have shown interesting activity as heterogeneous catalysts.[2] Additionally, MOFs could be excellent supports for active catalytic species, due to their porous nature, in order to obtain heterogeneous and reusable catalysts,[3] providing superb opportunities to tackle with reactions that requires more than one type of active centre.[4] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] ionic liquid (BMIM= 1-Butyl-3-methylimidazolium). Then, the insertion of palladium was made in basic media by the formation of a Pd organometallic complex with the N-heterocyclic carbine from the IL. The material was tested as heterogeneous catalyst for several organocatalytic reactions such as Suzuki-Miyaura and Sonogashira cross-coupling reactions, amine alkylation… The different conversion and selectivity results obtained for each type of reaction have allowed analyzing what is the role of each of the metals (Cu and Pd) in each reaction. References [1] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science, 2013, 341(6149), 1230444-01–12; J. Adams, D. Pendlebury, Materials Science & Technology, Thomson Reuters, 2011. [2] P. García-García, M. Müller, A. Corma, Chem. Sci. 2014, 5, 2979–3007; J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su, Chem. Soc. Rev. 2014, 43, 6011–6061. [3] P. Valvekens, F. Vermoortele, D. D. Vos, Catal. Sci. Technol. 2013, 3, 1435–1445; E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias, M. I. Arriortua, Eur. J. Inorg. Chem. 2015, 2015, 4699–4707. [4] D. Saha, R. Sen, T. Maity, S. Koner, Langmuir, 2013, 29, 3140–3151.Aknowledgements: This work has been financially supported by the “Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R (AEI/FEDER, UE)), the “Gobierno Vasco” (Basque University Research System Group, IT-630-13 and Dept. of Economic Development and Competitiveness, ELKARTEK program, LISOL (KK-2016/00095) projects), which we gratefully acknowledge. The authors thank the technicians of SGIker (UPV/EHU)

Characterization of cobalt based TPP-bipy coordination polymer

Comunicación a congreso: Póster presentado en The 4th EuCheMS Chemistry Congress (4ECC), Prague, Czech Republic, August 26–30, 2012Metalloporphyrin systems are one of the cornerstones on which the existence of life is based, as major biochemical, enzymatic and photochemical functions depend on the special properties of the tetrapyrrolic macrocycle. The possibility of introducing porphyrin units into MOFs (metal-organic frameworks) increases the variety of new materials based on these macrocycles. During the last years, cobalt porphyrins are well-known to be prominent catalysts for oxygen reduction reactions (ORR) and in order to obtain materials which provide new properties our research group is working with different combinations of metalloporphyrins and organic ligands. The work herein presented aims to the characterization of [CoTPP(bipy)]·[CoTPP]0.22·TPP0.78 (TPP= meso-tetraphenylporphyrin and bipy = 4,4´-bipyridine) compound in order to know the thermal, electronic and catalytic properties of these new porphyrin-based coordination polymer.Ministerio de Ciencia e Innovación (MAT2010-15375) y Gobierno Vasco (Basque University System Research Groups, IT-177-07

Metalloporphyrin-based MOFs: First Cobalt Based TPPS-bipy Coordination Network

Poster presentado en el congreso: Third International Conference on Multifunctional, Hybrid and Nanomaterials (3-7 March 2013, Sorrento, Italy)Supramolecular entities based on self-assembly of metalloporphyrins are paradigmatic examples of the great efficiency of the nanodevices used by natural systems in photosynthesis, oxygen transport, electron transfer and catalysis. Thus, porphyrin catalysts are well-known to be highly efficient in many catalytic reactions and, during the last years, a great effort has been devoted to the immobilization of distinct types of catalysts on solids. In this sense, recent strategy consists of the immobilization of catalysts in MOFs (metal-organic frameworks). In our group we have started exploring the possibility of using metalloporphyrins both as structural units in MOFs and catalyst, in the same compound.Ministerio de Ciencia e Innovación (MAT2010-15375) y Gobierno Vasco (Basque University System Research Groups, IT-177-07

Crystal structure and characterization of a new μ-oxo bridged iron porphyrin

Comunicacion a congreso: Póster presentado en VIII Reunión Científica de Bioinorgánica – Bioburgos 2013 (Burgos, 7 al 10 de julio de 2013)Metalloporphyrin systems are one of the cornerstones on which the existence of life is based, as major biochemical, enzymatic and photochemical functions depend on the special properties of the tetrapyrrolic macrocycle. Supramolecular entities based on self-assembly of those macrocycles are paradigmatic examples of the great efficiency of the nanodevices used by natural systems in photosynthesis, oxygen transport, electron transfer and catalysis, and our group is working with different combinations of metalloporphyrins in order to obtain new compounds that are able to mimicking the functions of those complexes. The work herein presented aims to the characterization of [(FeTCPP)2O] (TCPP= meso-tetracarboxyphenylporphyrin) compound in order to analyse the crystal structure and thermal, spectroscopic and catalytic properties of this new porphyrin-based coordination polymer. Even if there are some other examples of μ-oxo bridged iron porphyrins, this is the first one with TCPP.Ministerio de Ciencia e Innovación (MAT2010-15375) y Gobierno Vasco (Basque University System Research Groups, IT-630-13

Self-assembly of metallated TPP porphyrin by external dipyridyl ligands

Póster presentado en: XXII International Congress and General Assembly of the International Union of Crystallography (UICr), 22–30 Agosto 2011. Madrid, EspañaSupramolecular entities based on self-assembly of metalloporphyrins are paradigmatic examples of the great efficiency of the nanodevices used by natural systems in photosynthesis, oxygen transport, electron transfer and catalysis. Therefore, they constitute reference models for the development of new materials that make these, and other yet unexplored, functions. While metalloporphyrin biosystems operate in solution, the preparation of materials based on these macrocycles moves the problem to the solid state synthesis. Thus, obtaining supramolecular entities may be approached by different strategies of synthetic design. One of them consists on the use of external dipyridyl ligands to assemble the metallated porphyrin units. In this aspect, the range of compounds that can be used is endless. In this context, our research group is working with different combinations of organic ligands and metalloporphyrins, and the work herein presented corresponds to the compound [FeTPP(bipy)] (TPP=meso-tetraphenylporphyrin and bipy=4,4´-bipyridine), obtained by solvothermal synthesis. The crystal structure of [FeTPP(bipy)] consists of 1D chains of alternating FeTPP and bipy molecules bonded to the axial positions of the coordination sphere. These chains are sustained by π-π stacking between the phenyl rings at about 5 Å. So far, very few compounds with TPP and bipy have been described, of which only one is really a 1D coordination polymer, being all others isolated dimers. It is also remarkable that, as far as we know, this is the first structure with these ligands based on Fe, one of the most important metals in porphyrin biosystems.Ministerio de Ciencia e Innovación (MAT2010-15375) and the Gobierno Vasco (Basque University System Research Groups, IT-177-07

Ionic liquids in the control of the poly(vinylidene fluoride-co- hexafluoropropylene) membranes morphology [Poster]

Poster presentado en: New Materials for a Better life! 2017 Workshop, 27/10/2017, Facultad de Ciencia y Tecnología, Universidad del País VascoThe development of polymer membranes with tailored micro-morphology and wettability are a demand in the areas of filtration, sensors or tissue engineering, among others. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is a thermoplastic copolymer and one of the most interesting polymers to be used in these areas due to its good mechanical and thermal properties, biocompatibility and low density. The control of the morphology on this material is crucial for its performance. However, for the moment this is a complicated task and is mostly restricted to the use of solvent evaporation (SE) and non-solvent-induced phase separation (NIPS) techniques. In this way, this work consists in a systematic study of the use of ionic liquids in the control of these membranes properties. Ionic liquids are molten salts with melting points lower than 100 °C, which stand out for their good properties, such as high good thermal stability, low vapor pressure, nonflammability and their ability to act as solvents of various materials and they have already been studied for the control of morphology in certain materials. In this work, the production and the characterization of PVDF-HFP@ionic liquid composite membranes using different ionic liquids (Diethylmethylammonium trifluoromethanesulfonate, 1-Methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-Methylimidazolium chloride) and methodologies (solvent evaporation temperature) are described in detail. The results demonstrate how aspects such as morphology, wettability or mechanical properties change depending on the production methodology employed and on the type of used ionic liquid. In view of the results, it is concluded that the morphology of a polymer composite can be tuned by use ILs and this control of the morphology could open up new possibilities for their use in different applications.“Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R(AEI/FEDER, UE)). “Gobierno Vasco” ( KK-2016/00095-LISOL, program Elkartek)

Ionic liquids in the control of the poly(vinylidene fluoride-co- hexafluoropropylene) membranes morphology [Poster]

Poster presentado en: New Materials for a Better life! 2017 Workshop, 27/10/2017, Facultad de Ciencia y Tecnología, Universidad del País VascoThe development of polymer membranes with tailored micro-morphology and wettability are a demand in the areas of filtration, sensors or tissue engineering, among others. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is a thermoplastic copolymer and one of the most interesting polymers to be used in these areas due to its good mechanical and thermal properties, biocompatibility and low density. The control of the morphology on this material is crucial for its performance. However, for the moment this is a complicated task and is mostly restricted to the use of solvent evaporation (SE) and non-solvent-induced phase separation (NIPS) techniques. In this way, this work consists in a systematic study of the use of ionic liquids in the control of these membranes properties. Ionic liquids are molten salts with melting points lower than 100 °C, which stand out for their good properties, such as high good thermal stability, low vapor pressure, nonflammability and their ability to act as solvents of various materials and they have already been studied for the control of morphology in certain materials. In this work, the production and the characterization of PVDF-HFP@ionic liquid composite membranes using different ionic liquids (Diethylmethylammonium trifluoromethanesulfonate, 1-Methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-Methylimidazolium chloride) and methodologies (solvent evaporation temperature) are described in detail. The results demonstrate how aspects such as morphology, wettability or mechanical properties change depending on the production methodology employed and on the type of used ionic liquid. In view of the results, it is concluded that the morphology of a polymer composite can be tuned by use ILs and this control of the morphology could open up new possibilities for their use in different applications.“Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R(AEI/FEDER, UE)). “Gobierno Vasco” ( KK-2016/00095-LISOL, program Elkartek)

Ionic liquids in the control of the poly(vinylidene fluoride-co-hexafluoropropylene) membranes morphology

Presentada en NALS 2017 Conference on Nanomaterials applied to Lifesciences in Gijón, Spain, 13-15 December 2017The development of polymer membranes with tailored micro-morphology and wettability are a demand in the areas of filtration, sensors or tissue engineering, among others. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is a thermoplastic copolymer and one of the most interesting polymers to be used in these areas due to its good mechanical and thermal properties, biocompatibility and low density. The control of the morphology on this material is crucial for its performance [1]. However, for the moment this is a complicated task and is mostly restricted to the use of solvent evaporation (SE) and non-solvent-induced phase separation (NIPS) techniques. In this way, this work consists in a systematic study of the use of ionic liquids in the control of these membranes properties. Ionic liquids are molten salts with melting points lower than 100 °C, which stand out for their good properties, such as high good thermal stability, low vapor pressure, nonflammability and their ability to act as solvents of various materials and they have already been studied for the control of morphology in certain materials [2-3]. In this work, the production and the characterization of PVDF-HFP@ionic liquid composite membranes using different ionic liquids (Diethylmethylammonium trifluoromethanesulfonate, 1-Methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-Methylimidazolium chloride) and methodologies (solvent evaporation temperature) are described in detail. The results demonstrate how aspects such as morphology, wettability or mechanical properties change depending on the production methodology employed and on the type of used ionic liquid. In view of the results, it is concluded that the morphology of a polymer composite can be tuned by use ILs and this control of the morphology could open up new possibilities for their use in different applications