Escultura urbana. Chillida: el arquitecto del vacío

La arquitectura y la escultura han estado ligadas desde sus inicios hace ya miles de años. Esta relación ha ido evolucionando a lo largo de la historia. Es en el siglo pasado cuando ambas disciplinas, y en general todas las artes, evolucionan y transforman los conceptos de lo que hasta entonces se entendía como ‘arquitectura’ y ‘escultura’ desdibujando los límites que previamente las diferenciaban de forma clara. En este trabajo de investigación se estudiará, a través de la obra del escultor Eduardo Chillida, la transgresión de los límites entre ambas disciplinas. Se analizará el trabajo escultórico del autodenominado ‘arquitecto del vacío’ y su relación, no solo con la arquitectura como tal, sino también con la ciudad y su repercusión urbana. De este modo se espera encontrar las claves proyectuales que el artista utilizaba para su creación y que de alguna manera se puedan extrapolar a la proyectación arquitectónica.Architecture and sculpture have been linked since their beginnings thousands of years ago. This relationship has evolved throughout history. It was in the last century when both disciplines, and in general all the arts, evolved and transformed the concepts of what was previously understood as ‘architecture’ and ‘sculpture’, blurring the limits that previously clearly differentiated them. This research project will study, through the work of the sculptor Eduardo Chillida, the transgression of the limits between the two disciplines. It will analyse the sculptural work of the self-styled ‘architect of the void’ and his relationship, not only with architecture as such, but also with the city and its urban repercussions. In this way it is hoped to find the design keys that the artist used for his creations and which can be extrapolated in some way to architectural design.Universidad de Sevilla. Grado en Fundamentos de la Arquitectur

Prevention of Bone Loss in a Model of Postmenopausal Osteoporosis through Adrenomedullin Inhibition

Despite recent advances in the understanding and treatment options for osteoporosis, this condition remains a serious public health issue. Adrenomedullin (AM) is a regulatory peptide with reported activity on bone remodeling. To better understand this relationship we built an inducible knockout for AM. An outstanding feature of knockout mice is their heavier weight due, in part, to the presence of denser bones. The femur of knockout animals was denser, had more trabeculae, and a thicker growth plate than wild type littermates. The endocrine influence of AM on bone seems to be elicited through an indirect mechanism involving, at least, the regulation of insulin, glucose, ghrelin, and calcitonin gene-related peptide (CGRP). To confirm the data we performed a pharmacological approach using the AM inhibitor 16311 in a mouse model of osteoporosis. Ovariectomized females showed significant bone mass loss, whereas ovariectomized females treated with 16311 had similar bone density to sham operated females. In conclusion, we propose the use of AM inhibitors for the treatment of osteoporosis and other conditions leading to the loss of bone mass

Autoecología y distribución potencial de la encina (Quercus ilex subsp. ballota (Desf.) Samp.) en la zona norte de Monegros

Para conocer la autoecología y distribución potencial de la encina (Quercus ilex subsp. ballota (Desf.) Samp.) en la zona norte de Monegros se ha cartografiado la distribución de la encina y sus especies asociadas, analizando 37 parcelas con presencia de esta especie. Se han analizado las relaciones entre variables dasométricas de los encinares y variables ambientales, edáficas y climáticas, mediante análisis de correlaciones, y se ha utilizado el análisis canónico de correspondencias para estudiar las relaciones entre las especies vegetales descritas en los encinares y aquellas variables ambientales. A partir del mapa de suelos de la zona, se han definido como áreas potenciales para la encina las que presentan suelos similares a los de las parcelas con presencia actual de esta especie, y como áreas de exclusión las afectadas por salinidad-sodicidad, las que presentan suelos erosionados desarrollados sobre lutitas, y las formaciones de ribera. Las condiciones climáticas a escala de parcela indican un clima semiárido con precipitaciones de 400 - 500 mm, y déficits hídricos entre 364 y 741 mm. Los suelos asociados se clasifican, principalmente, como Torriorthents lítico-xéricos y Petrocalcids cálcicos. Son suelos bien drenados, no salinos, con una proporción de arena superior al 30 % en la fracción fina, y profundidad enraizable de 8 - 70 cm. Las masas de encina presentan áreas basimétricas de 1.1 - 27.6 m2.ha-1, diámetros medios de 3.9 - 27.7 cm y alturas dominantes de 3.0 - 10.7 m, y aparece regenerado de esta especie en un 81 % de las parcelas. La cartografía muestra que más del 60 % de la zona de estudio podría ser un hábitat apto para la encina.In order to understand the ecology and potential distribution of holm oak (Quercus ilex subsp. Ballota (Desf.) Samp.) in North Monegros we mapped the present distribution of this and associated species. We also studied 37 plots in which Q. ilex is present analyzing the relations between the characteristics of the stands and the plant species recorded and the biophysical variables. On the basis of the soil map of the area, the potential distribution of holm oak in North Monegros was defined as that occupied by soils similar to those described in plots with actual presence of this species. The areas where it may be excluded were defined as those with saline-sodic soils, with eroded soils on lutites, or river banks. Mean annual rainfall was estimated at 400 - 500 mm, mean annual temperature at 12.9 - 16.8 ºC, with an accumulated mean annual moisture deficit of 364 - 741 mm. The most frequent soil taxa described were Lithic-xeric Torriorthents (31 %) and Calcic Petrocalcids (11 %). Soils were well-drained, non-saline, had a sand concentration higher than 30 %, and a rootable depth of 8-70 cm. The Q. ilex stands had a basal area of 1.1 - 27.6 m2.ha-1, a mean diameter of 3.9 - 27.7 cm, and a dominant height of 3.0 - 10.7 m, and regeneration of this species was present in 81 % of the plots. The Q. ilex potential distribution map shows that over 60 % of the study area may be a suitable habitat for this species

Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol

This is the peer-reviewed version of the following article: Troyano, J., Perles, J., Amo‐Ochoa, P., Martínez, J. I., Concepción Gimeno, M., Fernández‐Moreira, V., ... & Delgado, S. (2016). Luminescent Thermochromism of 2D Coordination Polymers Based on Copper (I) Halides with 4‐Hydroxythiophenol. Chemistry–A European Journal, 22(50), 18027-18035., which has been published in final form at https://doi.org/10.1002/chem.201603675. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-ArchivingSolvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3X(HT)2]n(X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu−S, Cu−X and Cu−Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ3-bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4-mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materialsThis work was supported by MICINN (MAT2013-46753-C2-1-P). JIM acknowledges funding from the ERC-Synergy Program (Grant ERC-2013-SYG-610256 NANOCOSMOS) and computing resources from CTI-CSIC

Control and Simplicity in the Nanoprocessing of Semiconducting Copper-Iodine Double Chain Coordination Polymers

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.8b00364Two coordination polymers (CPs), based on Cu(I)-I double zig-zag chains bearing isonicotinic acid or 3-chloroisonicotinic acid as terminal ligands with molecular recognition capabilities, have been synthesized and fully characterized. Both compounds present extended networks with supramolecular interactions directed by the formation of H-bonds between the complementary carboxylic groups, giving supramolecular sheets. The chloro substituent allows establishing additional Cl···Cl supramolecular interactions that reinforce the stability of the supramolecular sheets. These CPs are semiconductor materials; however, the presence of chlorine produces slight changes in the I-Cu-I chains, generating a worse overlap in the Cu-I orbitals, thus determining a decrease in its electrical conductivity value. These experimental results have also been corroborated by theoretical calculations using the study of the morphology of the density of states and 3D orbital isodensities, which determine that conductivity is mostly produced through the Cu-I skeleton and is less efficient in the case of the chloro derivative compound. A fast and efficient bottom-up approach based on the self-assembly of the initial building blocks and the low solutibility of these CPs has proved very useful for the production of nanostructuresWe thank the Spanish MINECO (projects MAT2016-75883-C2-2-P, CTQ2017-87201-P, and fellowship BES-2015-071534) and the Generalitat Valenciana (PrometeoII/2014/076 project) for financial suppor

Innovative Microstructural Transformation upon CO2 Supercritical Conditions on Metal-Nucleobase Aerogel and Its Use as Effective Filler for HPLC Biomolecules Separation

This work contributes to enlightening the opportunities of the anisotropic scheme of non-covalent interactions present in supramolecular materials. It provides a top-down approach based on their selective disruption that herein has been employed to process a conventional microcrystalline material to a nanofibrillar porous material. The developed bulk microcrystalline material contains uracil-1-propionic acid (UPrOH) nucleobase as a molecular recognition capable building block. Its crystal structure consists of discrete [Cu(UPrO)2 (4,4′-bipy)2 (H2 O)] (4,4′-bipy=4,4′-bipyridine) entities held together through a highly anisotropic scheme of non-covalent interactions in which strong hydrogen bonds involving coordinated water molecules provide 1D supramolecular chains interacting between them by weaker interactions. The sonication of this microcrystalline material and heating at 45 °C in acetic acid–methanol allows partial reversible solubilization/recrystallization processes that promote the cross-linking of particles into an interlocked platelet-like micro-particles metal–organic gel, but during CO2 supercritical drying, the microcrystalline particles undergo a complete morphological change towards highly anisotropic nanofibers. This unprecedented top-down microstructural conversion provides a nanofibrillar material bearing the same crystal structure but with a highly increased surface area. Its usefulness has been tested for HPLC separation purposes observing the expected nucleobase complementarity-based separation.We thank the grant CTQ2017-87201-P funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” for financial support; and Generalidat Valenciana (Prometeo/2019/076). We thank the grant PID2019-108028GB-C22 and PID2019-108028GB-C21 funded by MCIN/AEI 10.13039/501100011033.We thank the grant FEDERPID2020-118422-GB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” for financial support; and the Basque Government (Grupos IT908-16)

Reversible transformation between Cu(i)-thiophenolate coordination polymers displaying luminescence and electrical properties

A one-dimensional [Cu6I3(TP)3(MeCN)2]n (1) coordination polymer (CP) has been prepared by the direct reaction between CuI and a thiophenol (TP) ligand. The reversible conversion reaction between 1 and the homoleptic 1D-CP [Cu(TP)]n (2) is observed in acetonitrile upon controlling the CuI ratio. Interestingly, CPs 1 and 2 are multifunctional materials showing both luminescence and electrical properties. Photoluminescence measurements reveal that 1 and 2 are emissive in the blue and the red regions, respectively. Additionally, both materials show electrical conductivity at room temperature (1.2 × 10-8 for 1 and 3.7 × 10-4 S cm-1 for 2) indicating a semiconductor behaviour. DFT calculations have been used to rationalise these observationsThis work was supported in part by MICINN (grant MAT2016-77608-C3-1-P

Cathodoluminescence Characterization of Dilute Nitride GaNSbAs Alloys

The effects of ex situ annealing in N ambient and in situ annealing in As ambient on GaNSbAs/GaAs structures grown by molecular beam epitaxy were investigated by low temperature cross-sectional cathodoluminescence (CL). The amount and distribution of Sb was measured by energy dispersive spectroscopy (EDS). The cross-sectional CL analysis of all samples reveals a shift of the near band edge (NBE) emission along the growth axis, presumably associated with a non-uniform incorporation of Sb during the growth process, in agreement with the Sb distribution measured by EDS in the as-grown sample. The NBE emission in the annealed samples presents a redshift with respect to the as-grown sample. This effect might be explained by a redistribution/activation of N in the GaNSbAs lattice since the Sb distribution measured by EDS does not reveal significant changes, within the error margin, with respect to the as-grown sample. The in situ annealed in the As overpressure sample shows the best properties for solar cells applications, i.e., a NBE peak position close to 1.0 eV and the lowest full width at half maximum of this emission.Spanish Government (MINECO Project ENE2014- 56069-C4-4-R) and Junta de Castilla y Leo´n (VA293U13 and VA081U16 Projects). The Ministry of Economy and Competitiveness MINECO supports this work through Projects TEC2014-54260- C3-1-P, TEC2014-54260-C3-2-P, TEC2014-54260- C3-3-P, PCIN-2015-181-C02-01 and PCIN-2015- 181-C02-02

Cunning defects: Emission control by structural point defects on Cu(i)I double chain coordination polymers

The following version is an accepted manuscript in Journal of Materials Chemistry C 8.4 (2020): 1448-1458 and may be found at ttps://doi.org/10.1039/C9TC05185FThe direct reaction between CuI and 3,5-dichloropyridine, in acetonitrile at room temperature, gives rise to [Cu(Cl2-py)I]n (Cl2-py = 3,5-dichloropyridine), which consists of a Cu(i)-I double chain based coordination polymer (CP) grafted with 3,5-dichloropyridine. In this simple one-pot process, the modulation of the reaction conditions, i.e. slight variations in the CuI and Cl2-py ratio caused by in situ disproportion, can, however, produce significant changes in the physical properties of the materials. For instance, the reaction carried out in a 1 : 1 ratio under ambient conditions leads to compound 1, while compound 1′ is obtained upon a solvothermal process of stoichiometric reaction mixture, Cl2-py and CuI, which produces partial disproportion (<0.5% in weight) of the initial Cu(i). Interestingly, compounds 1 and 1′ show an identical chemical composition and structure as determined by both single crystal and powder X-ray diffraction. However, they display remarkable differences in the luminescence behavior, featuring broad emission bands centered at 515 and 670 nm and associated to photoluminescence quantum yields of 12 and 5% for 1 and 1′, respectively. Density functional theory (DFT) calculations allowed us to rationalize the nature of this rare behavior. This is attributed to structural defects related to the weaker coordination bond present in these structures that provoke the strong red-shifted emissionThe authors thank financial support from the Spanish Ministerio de Economıa y Competitividad (MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2010-20843-C02-01, CTQ2016-75816- C2-1P, MAT2016-75586-C4-4-P) and by EU-FEDER funds. JGP thanks to Servicios Generales de Apoyo a la Investigacion (SEGAI) at La Laguna University. J. I. M. acknowledges the financial support by the ‘‘Ramo´n y Cajal’’ Program of MINECO (Grant RYC-2015- 17730) and the EU via the ERC-Synergy Program (Grant ERC-2013- SYG-610256 NANOCOSMOS). J. C. E. acknowledges the financialsupport by the ‘‘FPI-MINECO’’ Program of MINECO (Grant BES2015-071534). R. D. C. acknowledges the program ‘‘Ayudas para la atraccio´n de talento investigador—Modalidad 1 of the Consejerı´a de Educacio´n, Juventud y Deporte—Comunidad de Madrid with the Reference No. 2016-T1/IND-1463.’’, Spanish MINECO for the Ramo´n y Cajal program (RYC-2016-20891), the Europa Excelencia program (ERC2019-092825), and HYNANOSC (RTI2018-099504-A-C22). R. D. C. also acknowledges the 2018 Leonardo Grant for Researchers and Cultural Creators from BBVA Foundation and the FOTOART-CM project funded by Madrid region under programm P2018/NMT-4367. J. F.-C. acknowledges the Marie Skłodowska-Curie Individual Fellowships (H2020-MSCA-IF-2017). This paper is dedicated to Dmitri Mendele´yev in honour of the 150th anniversary of the discovery of the periodic tabl