Caracterización fundamental de superficies metálicas a condiciones relevantes para la catálisis

Heterogeneous catalysis involves chemisorption, reactions of chemisorbed species, and desorption of the products formed. The enthalpies and entropies for these elementary steps and their transition states provide the thermodynamic context that allows rigorous interpretations of the rates and selectivities of chemical reactions mediated by surfaces. The measurement of rates and/or thermodynamic properties at conditions relevant for catalysts and in the absence of mass and heat transport limitations are required for the proper reactor and catalyst design. Different challenging examples are provided, in which chemical rates and/or thermodynamic properties are measured under rigorous kinetic or thermodynamic conditions, giving information regarding the nature of the active metal surfaces and their role at reaction conditions. Among the cases to be presented are the alkane oxidation reactions on noble metals, Pd-PdO phase transition and its consequences for catalysis, and the surface characterization of metals by H2 chemisorption at elevated temperatures. Alkane-O2 (CH4 and C2H6) reactions are highly exothermic and tend to occur within the length scale of conductive or convective heat and mass transfer, which lead to severe gradients within undiluted catalyst pellets and reactors. Extensive dilution within the pellets and reactor has been used to get kinetic and isotopic data for Alkane-O2 reactions on supported Pt, Rh and Pd. These data have shown that CO and H2 do not form via direct alkane partial oxidation but instead via sequential combustion-reforming pathways. Alkane-O2 reactants form CO2 and H2O on Pt in three kinetic regimes (KR), each with distinct rate equations, kinetically-relevant steps, most abundant surface intermediates (MASI), and cluster size effects. Transitions among these regimes are determined by the prevalent steady-state coverages of chemisorbed oxygen (O*), which are given by O2 pressure when O2 dissociation is equilibrated and by O2 to Alkane ratios when it is irreversible. Mechanistic interpretations remain valid for other metals such as Pd, and the difference in reactivity among metals is correlated to O* binding strengths when O* is involved in the kinetically-relevant steps. On Pd and Rh, however, the clusters undergo phase transition to PdO and RhO2, leading to an additional kinetic regime characterized by an abrupt increase in reactivity caused by the transition from metal to oxide. Ex-situ O2 uptake measurements, at equilibrium, were performed to correlate the oxygen content during the phase transition with the measured rates at reaction conditions. Another example is given by the use of dissociative H2 chemisorption methods at conditions relevant for catalysis as a thermodynamic probe instead of mere site counting technique, in which differential enthalpies and entropies of adsorption are obtain to probe the non-uniformity of cluster surfaces. H-atoms formed via H2 dissociation are attractive titrants because of the reversible nature of the adsorption processes and the well-defined adsorption stoichiometry, but also because of the ubiquitous involvement of H-atoms in hydrogenation-dehydrogenation catalysis.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Therapy and diagnosis of Alzheimer’s disease: from discrete metal complexes to metal–organic frameworks

Alzheimer’s disease (AD) is a neurodegenerative disorder affecting 44 million people worldwide. Although many issues (pathogenesis, genetics, clinical features, and pathological aspects) are still unknown, this disease is characterized by noticeable hallmarks such as the formation of b-amyloid plaques, hyperphosphorylation of tau proteins, the overproduction of reactive oxygen species, and the reduction of acetylcholine levels. There is still no cure for AD and the current treatments are aimed at regulating the cholinesterase levels, attenuating symptoms temporarily rather than preventing the AD progression. In this context, coordination compounds are regarded as a promissing tool in AD treatment and/or diagnosis. Coordination compounds (discrete or polymeric) possess several features that make them an interesting option for developing new drugs for AD (good biocompatibility, porosity, synergetic effects of ligand–metal, fluorescence, particle size, homogeneity, monodispersity, etc.). This review discusses the recent progress in the development of novel discrete metal complexes and metal–organic frameworks (MOFs) for the treatment, diagnosis and theragnosis of AD. These advanced therapies for AD treatment are organized according to the target: Ab peptides, hyperphosphorylated tau proteins, synaptic dysfunction, and mitochondrial failure with subsequent oxidative stressMOFSEIDON project (PID2019- 104228RB-100, MCI/AEI/FEDER)AgroMOFs project (TED2021-132440B-I00)MCIN/AEI/10.13039/50110 0011033NextGenerationEU/PRTRMargarita Salas contract 401Ministerio de Universidades and Next GenerationB- FQM-394, ProyExcel_00105ProyExcel_00386Consejería de Universidad, Investigación e Innovación de la Junta de AndalucíaGrant (RYC2021-032522-I)MCIN/AEI/10.13039/ 50110001103

Reducing the Anaerobic Digestion Model No. 1 for its application to an industrial wastewater treatment plant treating winery effluent wastewater

International audienceThe Anaerobic Digestion Model No. 1 (ADM1) is a complex model which is widely accepted as a common platform for anaerobic process modeling and simulation. However, it has a large number of parameters and states that hinder its calibration and use in control applications. A principal component analysis (PCA) technique was extended and applied to simplify the ADM1 using data of an industrial wastewater treatment plant processing winery effluent. The method shows that the main model features could be obtained with a minimum of two reactions. A reduced stoichiometric matrix was identified and the kinetic parameters were estimated on the basis of representative known biochemical kinetics (Monod and Haldane). The obtained reduced model takes into account the measured states in the anaerobic wastewater treatment (AWT) plant and reproduces the dynamics of the process fairly accurately. The reduced model can support on-line control, optimization and supervision strategies for AWT plants

Autentificación de carnes procedentes de aves de caza y de la avicultura alternativa por PCR-RFLP

Sin resume

Role of hydrazone substituents in determining the nuclearity and antibacterial activity of Zn(II) complexes with pyrazolone-based hydrazones

Hydrazones and their metal derivatives are very important compounds in medicinal chemistry due to their reported variety of biological activities, such as antibacterial, antifungal and anticancer action. Five hydrazone- pyrazolone ligands H2Ln (n = 1–5) were prepared and fully characterized and their tautomerism was investigated in the solid state and solution. Five zinc(II) complexes 1–5 of composition [Zn(HLn)2] (n = 1 and 2), [Zn(HLn)2(H2O)2] (n = 3 and 5) and [Zn(HL4)2]n were synthesized and characterized by elemental analysis, IR, 1H, 19F, 13C, and 15N NMR spectroscopy, and ESI mass spectrometry. In addition, the structures of two ligands and three complexes were determined by single-crystal X-ray diffraction. The ligands H2L2 and H2L4 exist both in the NH,NH tautomeric form. Complexes 1 and 2 are mononuclear compounds, while complex 4 is a one-dimensional coordination compound. Density functional theory (DFT) calculations were carried out on proligands, their anions and all zinc complexes, confirming the experimental results, supporting IR and NMR assignments and giving proofs of the mononuclear diaqua structure of complexes 3 and 5. The antibacterial activity of the free ligands and the Zn(II) complexes was established against Escherichia coli and Staphylococcus aureus, and a strong efficiency has been found for Zn(II) complexes, particularly for the polynuclear 4 and the mononuclear diaqua complex 5, the latter containing a ligand with aliphatic and fluorinated substituents able to compromise the permeability of and disrupt the bacterial cell membrane.University of Camerino (Italy)European Commission PRIMA19_00246Ministry of Education, Universities and Research (MIUR)POR Marche FSEInstituto de Salud Carlos IIISpanish Government PGC2018-093443-B-I0

Copper Glufosinate-Based Metal−Organic Framework as a Novel Multifunctional Agrochemical

Pesticides are agrochemical compounds used to kill pests (insects, rodents, fungi, or unwanted plants), which are key to meet the world food demand. Regrettably, some important issues associated with their widespread/extensive use (contamination, bioaccumulation, and development of pest resistances) demand a reduction in the amount of pesticide applied in crop protection. Among the novel technologies used to combat the deterioration of our environment, metal−organic frameworks (MOFs) have emerged as innovative and promising materials in agroindustry since they possess several features (high porosity, functionalizable cavities, ecofriendly composition, etc.) that make them excellent candidates for the controlled release of pesticides. Moving toward a sustainable development, in this work, we originally describe the use of pesticides as building blocks for the MOF construction, leading to a new type of agricultural applied MOFs (or AgroMOFs). Particularly, we have prepared a novel 2D-MOF (namely, GR-MOF-7) based on the herbicide glufosinate and the widely used antibacterial and fungicide Cu2+. GR-MOF-7 crystallizes attaining a monoclinic P21/c space group, and the asymmetric unit is composed of one independent Cu2+ ion and one molecule of the Glu2− ligand. Considering the significant antibacterial activity of Cu-based compounds in agriculture, the potential combined bactericidal and herbicidal effect of GR-MOF-7 was investigated. GR-MOF-7 shows an important antibacterial activity against Staphylococcus aureus and Escherichia coli (involved in agricultural animal infections), improving the results obtained with its individual or even physical mixed precursors [glufosinate and Cu(NO3)2]. It is also an effective pesticide against germination and plant growth of the weed Raphanus sativus, an invasive species in berries and vines crops, demonstrating that the construction of MOFs based on herbicide and antibacterial/antifungal units is a promising strategy to achieve multifunctional agrochemicals. To the best of our knowledge, this first report on the synthesis of an MOF based on agrochemicals (what we have named AgroMOF) opens new ways on the safe and efficient MOF application in agriculture.project MOFseidon PID2019-104228RB-I00Juan de la Cierva incorporation JC2019-038894-I and Multifunctional Metallodrugs in Diagnosis and Therapy Network (MICIU) RED2018-102471-TComunidad de MadridEuropean Regional Development Fund-FEDER 2014-2020-OE REACTUEUniversidad de Granada/CBUAEuropean Union NextGenerationEU/PRT

Bis-Citrullinato Copper(II) Complex: Synthesis, Crystal Structure, and Non-Covalent Interactions

Citrulline (C6H13N3O3) is a non-protein amino acid found in watermelon. In physiological conditions, it is almost entirely present as a zwitterion, so its carboxylic and amine groups can act as Lewis donors, chelating metallic cations. In addition, Citrulline possesses a terminal ureide group of the aliphatic chain, which appears to be non-innocent. Although Citrulline is similar to other classical amino acids, only one coordination complex has been reported in the Cambridge Crystallographic Database. As part of our search for Casiopeina® analogs, we synthesized and characterized the copper bis-citrullinato complex, [Cu(Citr)2]n. The compound was described using UV-Vis, Infrared, and Raman spectroscopy, together with single-crystal X-ray diffraction. Computational tools were also used. The optimized structure, MEP map, IR and Raman spectra, and 1H and 13C chemical shifts were obtained with functional mPW1PW91 using 6-31G(d) basis set for N, O, C, and H atoms, and LANL2DZ basis set and ECP=LANL2DZ for the Cu atom. TD-mPW1PW91 calculations generated the UV-Vis spectrum. Finally, AIM and Hirshfeld surface analysis were used to examine noncovalent interactions. Previous investigations suggest Casiopeina®-like complexes can interact with DNA/RNA, creating potential anticancer chemicals. The [Cu(Citr)2]n complex’s polymeric nature and insolubility make it difficult for such purposes. However, the facile synthesis of D-Citrulline could be a novel way to find new applications for this interesting amino acid.PRODEP Academic Group (SEP, Mexico) BUAP-CA-263Ministerio de Universidades and Next Generation for the Margarita Salas contract (Spain) 401 100108444-VIEP 100256733-VIEP 100233622-VIE

La educación musical como herramienta para abordar las emociones en el aula de Infantil

El siguiente Trabajo Fin de Grado está centrado en dos temas cruciales en la educación infantil de los niños y niñas hoy en día: la educación musical y la educación emocional. En las siguientes páginas, se tratan los aspectos más teóricos de estos dos temas tan importantes y se analiza la relación que existe entre ambos. Por último se pretende llevar al aula una propuesta de intervención musical en la que las principales protagonistas sean las emociones. A través de esta propuesta los alumnos expresarán libremente de diferentes maneras las emociones que la música les inspire en cada momento. Este trabajo pretende fomentar el desarrollo de la educación musical en la etapa de Educación Infantil, así como guiar a los alumnos a conocer un poco más sus emociones y el respeto hacia las de los demás a través de una serie de actividades que componen una propuesta de intervención, en la que la música es el eje central de cada una de ellas.Grado en Educación Infanti

Técnicas de clustering aplicadas al análisis de trending topics en conjunto de tweets

Dado que los servicios de las redes sociales se expanden geográficamente desde hace varios años, cada vez en mayor medida, y penetran cada vez más en diversos segmentos de la población, el valor de la información que se genera en este tipo de plataformas en línea aumenta drásticamente. La comunicación e interacción en las redes sociales a menudo reflejan los acontecimientos y la dinámica de la vida real, por lo que el continuo aumento de usuario provoca que las redes sociales se conviertan en precisos sensores de los acontecimientos del mundo real. En este contexto, el tratamiento y procesamiento de toda esa información, capta un gran interés. Este hecho es el que ha inspirado el presente proyecto, centrado en la detección de temas emergentes, llamados Trending Topics en Twitter. Para ello se proponen y evalúan distintos algoritmos y estrategias de detección que nos permiten descubrir temas más generales o más específicos, según lo que más interese. Esto nos dará la capacidad de conocer los temas sobre los que se habla y saber cuáles de ellos y en qué momento captan un mayor interés por parte de los usuarios, lo que nos permitirá simular el posible comportamiento de Twitter en la tarea de la detección de Trending Topics.Ingeniería de Telecomunicació

Tris(2-Pyridylmethylamine)V(O)2 Complexes as Counter Ions of Diprotonated Decavanadate Anion: Potential Antineoplastic Activity

Projects funded this research: 100517029-VIEP2021 and 100233622-VIEP2021, and the PRODEP Academic Group BUAP-CA-263 (SEP, Mexico). Financial support was also provided by Junta de Andalusia (Spain), Project number FQM-394. NC, BM-V, and LN wish to thank CONACyT (Mexico) Ph.D. fellowship support numbers 390894, 593307, and 697889.The synthesis and theoretical-experimental characterization of a novel diprotanated decavanadate is presented here due to our search for novel anticancer metallodrugs. Tris(2-pyridylmethyl)amine (TPMA), which is also known to have anticancer activity in osteosarcoma cell lines, was introduced as a possible cationic species that could act as a counterpart for the decavanadate anion. However, the isolated compound contains the previously reported vanadium (V) dioxido-tpma moieties, and the decavanadate anion appears to be diprotonated. The structural characterization of the compound was performed by infrared spectroscopy and single-crystal X-ray diffraction. In addition, DFT calculations were used to analyze the reactive sites involved in the donoracceptor interactions from the molecular electrostatic potential maps. The level of theory mPW1PW91/6–31G(d)-LANL2DZ and ECP = LANL2DZ for the V atom was used. These insights about the compounds’ main interactions were supported by analyzing the noncovalent interactions utilizing the AIM and Hirshfeld surfaces approach. Molecular docking studies with small RNA fragments were used to assess the hypothesis that decavanadate’s anticancer activity could be attributed to its interaction with lncRNA molecules. Thus, a combination of three potentially beneficial components could be evaluated in various cancer cell lines.European CommissionPRODEP Academic Group (SEP, Mexico) BUAP-CA-263Junta de Andalusia (Spain) FQM-394Consejo Nacional de Ciencia y Tecnologia (CONACyT) 390894 593307 697889 SEP PRODEP BUAP-PTC_61