Hollow Microcrystals of Copper Hexafluoroacetylacetonate-Pyridine Derivative Adducts via Supercritical CO2 Recrystallization

An innovative crystallization process, based in the use of the eco-friendly supercritical carbon dioxide (scCO2) solvent, is presented for the production of coordination compounds macrocrystals of general formula [Cu(hfacac)2(dPy)2], with intriguing prismatic hollow structures and single polymorphic forms. On the contrary, conventional solvents yielded compact microstructures. Studied pyridine derivatives (dPy) were 4-phenylpyridine, PhPy; 4-benzylylpyridine, BzPy; and 4-acetylpyridine, AcPy. In the specific case of the [Cu(hfacac)2(AcPy)2] adduct, the use of scCO2 as a solvent allows obtaining a pure polymorph, while the conventional solvent trials yielded a mixture of two polymorphs. Four new crystalline structures have been resolved from single crystal X-ray diffraction. All the structures consist in mononuclear complexes connected through intermolecular interactions, including H···H, H···O, F···F, C-F···Caromatic and/or C-F··· interactions, generating bidimensional networks that determine their crystallization mode in scCO2.This work was partially financed by the Spanish National Plan of Research CTQ2014-56324 and Severo Ochoa SEV-2015-0496, and by the Generalitat de Catalunya 2014SGR377. A. López-Periago acknowledges the RyC-2012-11588 contract. ALBA synchrotron is acknowledged for the provision of beamtime.Peer Reviewe

Exploring a novel preparation method of 1D metal organic frameworks based on supercritical CO2

The preparation of copper(II) one-dimensional MOFs using an eco-efficient method is reported here. This method is based exclusively on using supercritical CO2 as a solvent, without the addition of any other additive or co-solvent. Neutral acetylacetonate copper complexes and two linear linkers, namely, the bidentate 4,4¿-bipyridine and 4,4¿-trimethylenedipyridine molecules, were reacted under compressed CO2 at 60 °C and 20 MPa for periods of 4 or 24 h. The success achieved in the synthesis of the different studied 1D-MOFs was related to the solubility of the reagents in supercritical CO2. The reaction yield of the synthesized coordination polymers via the supercritical route was close to 100% because both the reactants were almost completely depleted in the performed experiments. © The Royal Society of Chemistry 2015.This work was partially financed by EU COST project MP1202 OC-2011-2-10820 and by the Generalitat de Catalunya 2014SGR377. A. López-Periago acknowledges the RyC-2012- 11588 contract. We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)Peer Reviewe

Novel Zn(II) coordination polymers based on the natural molecule bisdemethoxycurcumin

This article introduces a new family of coordination polymers (CPs) that contains a renewable curcumin derivative, the bisdemethoxycurcumin (BDMC), coordinated to Zn(II) centers. The reaction between BDMC and zinc acetate, performed under mild conditions in ethanol, provides a new 1D phase termed BDMCZn-1. In addition, dimensionality and porosity of this network have been expanded by studying the reaction occurring between three species, the BDMC, the Zn(II), and a ditopic colinker: 1,2-bis(4-pyridyl)ethylene, 1,3-bis(4-pyridyl)propane, or 4,4′-bipyridine. In total, seven new CPs are presented, named BDMCZn-x. The structures of five of them were elucidated by single-crystal X-ray diffraction. Moreover, we show that the combination of the latest technique with solid-state 13C nuclear magnetic resonance is a powerful tool set to analyze the coordination modes of the BDMC, providing insight into the two unresolved structures. In the achievement of the new CPs, we further discuss the coordination capacity of BDMC, the relevance of solvents, and supramolecular interactions

Facile, fast and green synthesis of a highly porous calcium-syringate bioMOF with intriguing triple bioactivity

A facile, fast and green strategy based on ethanol is utilized to prepare a new bioMOF, namely, CaSyr-1, with particular characteristics of full biocompatibility given by using just calcium and syringic acid, the latter being a phenolic natural product found in fruits and vegetables, permanent porosity with an outstanding surface area >1000 m2 g−1, and a micropore diameter of 1.4 nm close to mesopore values. Collectively, these data establish CaSyr-1 as one of the most porous bioMOFs reported to date, with high molecular adsorption capacity. The CaSyr-1 adsorptive behavior is revised here through the reversible adsorption of CO2 and the encapsulation of bioactive ingredients in the structure. Remarkably, CaSyr-1 enables the development of triple therapeutic entities, involving bioactive Ca2+, syringic acid and an impregnated drug

Bacterial cellulose/graphene oxide aerogels with enhanced dimensional and thermal stability

We present a novel method for processing bacterial cellulose/graphene oxide (BC/GO) aerogels with multifunctional properties. The addition of a small amount of dimethyl sulfoxide (DMSO) to the aqueous dispersion of the nanomaterials during the gelification process affected the water freezing temperature of the system and thereby affecting the porous structure of the aerogel obtained after liophilization. The possibility to obtain small and elongated pore with axial orientation allowed a significant improvement of the structural stability of the aerogels. Moreover, the aerogels reduction by thermal treatment with ammonia gas induced crosslinking between the different nanophases, thus given an incremental factor for the mechanical performance of the aerogels under harsh conditions. The resulting aerogels also showed significant improvements in terms of thermal stability and electrical conductivity. These multifunctional BC/GO aerogels present high potential as sustainable and ecological alternative materials for lightweight packaging, filters for atmosphere and water treatment, or energy applications.in publicatio

Impact of the “Law on promotion of personal autonomy and care for people dependent” in population with severe mental disorder

Law 39/2006, known as Dependence Law, has generated skepticism since its approval, for being focused on dependancy and barely promoting personal autonomy, treating it as a secondary issue. As it relates to people with severe mental disorder, a major concern to mental health professional organizations and family associations has been the compatibility of the law with the services provided by the National health service and whether the established selection criteria for qualifying for the service fits the needs of this group. This article reflects the work done across several Spanish autonomous regions by different professionals in an attempt to convince the administration to make the necessary adjustment to suit the characteristics of people with serious mental disorders. After discussing its strengths and weaknesses, it outlines three different ways to offset their risks in three different regions, Extremadura, Andalucia and Madrid. Finally it addresses the key aspects of the law which need to be worked on, in order to become a benefit for people with severe mental disorder, and not a barrierLa Ley 39/2006, conocida como Ley de Dependencia, ha generado, desde su aprobación, desconfianza por estar enfocada a la atención a la dependencia, siendo la promoción de la autonomía personal un elemento apenas desarrollado y secundario. En el caso de las personas con trastorno mental grave, lo que mayor preocupación ha causado a las organizaciones de profesionales de la salud mental y a las asociaciones de familiares ha sido la compatibilidad de dicha Ley con las prestaciones del Sistema Nacional de Salud y si el baremo establecido se ajustaba a las necesidades de este colectivo. Este artículo recoge el trabajo realizado desde diferentes comunidades autónomas por diferentes profesionales en un intento de, tras un análisis de la Ley, plantear a la administración responsable de la misma el necesario ajuste para adaptarla a las características de las personas con trastorno mental grave. Se analizan, en primer lugar, sus fortalezas y debilidades. Posteriormente se exponen tres formas diferentes de contrarrestar sus riesgos, en tres comunidades autónomas diferentes, Extremadura, Andalucía y Madrid. Finalmente se dan las claves de los aspectos de la Ley sobre los que hay que seguir trabajando para que sea una oportunidad para las personas con trastorno mental grave, y no una barrer

Binary supercritical CO2 solvent mixtures for the synthesis of 3D metal-organic frameworks

Efficient and sustainable synthesis of MOFs, as nano or microcrystalline powder, is crucial for the development of new applications for these compounds. For this purpose, the synthesis of Zn2þ, Cu2þ and Fe3þ-based MOFs was attempted in this study by using a binary medium consisting of supercritical CO2 mixed with an ionic liquid (emimBF4 or emimBr). In comparison with conventional solvothermal and ionothermal synthesis, MOFs were herein obtained under mild reaction conditions, i.e. 200 bar and 65 C, after relatively short reaction periods (<10 h). To explore the described synthesis method as a generic procedure for the preparation of three-dimensional MOFs, different linkers of the imidazole and carboxylic acid families were tested. Widely investigated MOFs, such as ZIF-8 and HKUST-1, were prepared along with the complex mesoporous MIL-100(Fe). The structure and composition of the synthesized materials were determined by X-ray powder diffraction and elemental analysis. N2 adsorption at low temperature was used to assess the textural properties.This work was partially financed by the Spanish National Plan of Research CTQ2014-56324-CO2-P1 and MAT2014-53500-R, the Generalitat de Catalunya 2014SGR377 and Fundaci on Iberdrola. Authors acknowledge financial support from the Spanish Ministry of Economy and Competitiveness through the “Severo Ochoa” Programme for Centers of Excellence in R&D (SEV-2015-0496). A. L opez-Periago acknowledges the RyC-2012-11588 contract.Peer reviewe