Three-Dimensional Phthalocyanine Metal-Catecholates for High Electrochemical Carbon Dioxide Reduction.

The synthesis of a new anionic 3D metal-catecholate framework, termed MOF-1992, is achieved by linking tetratopic cobalt phthalocyanin-2,3,9,10,16,17,23,24-octaol linkers with Fe3(-C2O2-)6(OH2)2 trimers into an extended framework of roc topology. MOF-1992 exhibits sterically accessible Co active sites together with charge transfer properties. Cathodes based on MOF-1992 and carbon black (CB) display a high coverage of electroactive sites (270 nmol cm-2) and a high current density (-16.5 mA cm-2; overpotential, -0.52 V) for the CO2 to CO reduction reaction in water (faradaic efficiency, 80%). Over the 6 h experiment, MOF-1992/CB cathodes reach turnover numbers of 5800 with turnover frequencies of 0.20 s-1 per active site

Copper-based MOF, Cu 3 (SDBA) 2 (HSDBA), as a catalyst for efficient reduction of 4-nitrophenol in the presence of sodium borohydride

International audienceHerein, we report the synthesis of the copper-based MOF, Cu3(SDBA)2(HSDBA), using a solvothermal method. The physicochemical properties of the as-prepared sample were examined by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier-transform infrared and UV-vis spectroscopy techniques, and thermal analysis. Cu3(SDBA)2(HSDBA) was then investigated as a catalyst for the reduction of 4-nitrophenol (4-NP) in the presence of sodium borohydride (NaBH4) at 25 °C, and related kinetics and thermodynamics analyses were carried out. In a nutshell, it can be emphasized that, under our conditions, the Cu3(SDBA)2(HSDBA) catalyst is able to completely reduce 4-NP to 4-aminophenol (4-AP) in a very short time such as 20 s. Additionally, Cu3(SDBA)2(HSDBA) can be re-used for seven successive cycles without obvious change in its catalytic activity

Structure-directing and template roles of aromatic molecules in the self-assembly formation process of 3D holmium-succinate MOFs

Two new holmium-succinate frameworks have been synthesized by hydrolysis in situ of the succinylsalicylic acid under different hydrothermal conditions. Compound 1, [Ho2(C4H4O4) 3(H2O)2]•0.33(C7H 6O3), Pī space group, has a novel structure composed by 1D-SBUs consisting of [HoO9] chains of polyhedra linked by the succinate ligands giving a 3D framework. Compound 2, [Ho2(C 4H4O4)3(H2O) 2], also belonging to the Pī space group, has a denser structure. The role of the in-situ-generated salicylic acid on formation of both structures is studied by means of a synthesis design methodology. A topological study of the new holmium succinate compounds in comparison with the previously reported 3D holmium-succinate framework is performed here.Fil: Bernini, Maria Celeste. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Snejko, Natalia. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Gutierrez Puebla, Enrique. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Brusau, Elena Virginia. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; ArgentinaFil: Narda, Griselda Edith. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Monge, M. Ángeles. Instituto de Ciencia de Materiales de Madrid; Españ

Magneto-optical activity in organic thin film materials

© 2016 IOP Publishing Ltd. A series of CF3-capped phenylacetylenes with varying symmetry is obtained by a conventional palladium-catalyzed cross-coupling protocol. The phenylacetylene targets form thin films both, liquid crystalline (LC) and crystalline in nature depending on their molecular structure. The magneto-optical activity of the resulting organic material is extraordinarily high as proved by Faraday rotation spectroscopy on thin film devices.journal_title: Smart Materials and Structures article_type: lett article_title: Magneto-optical activity in organic thin film materials copyright_information: © 2016 IOP Publishing Ltd date_received: 2016-06-23 date_accepted: 2016-10-27 date_epub: 2016-11-10status: publishe

Unusual Magnetic Behaviors and Electronic Configurations Driven by Diverse Co(II) or Mn(II) MOF Architectures

Five novel metal organic frameworks were obtained by hydrosolvothermal reactions using the hexafluorisopropylidenebis(benzoic) acid (H2hfipbb) as linker and Co(II) or Mn(II) ions as connectors. [Co2(Hhfipbb)-(TEA)], compound 1 (TEA = triethanolamine trianion) with a threedimensional (3D) framework, and a tpu net; [Co1.5(hfipbb)2]·HN(CH2CH3)3 and [Co3(hfipbb)2]·2{HN(CH2CH3)3}, compounds 2 and 2-a, respectively, both with two-dimensional structure, sql topologies, and different layer packings. Compounds 3 and 4, having the general formula [M2(hfipbb)2]·C7H8,where M = Co (3) or Mn (4), have 3D frameworks with an sqc topology. A deep analysis of the magnetic measurements reveals different striking magnetic behaviors resulting from diverse secondary building unit and framework architectures. Compound 1 presents canted antiferromagnetic chains, compound 2 contains ferromagnetic linear trimeric clusters, and compound 3 exhibits ferromagnetic chains. For the three compounds, a 3D canted antiferromagnetic structure takes place at ∼8 K by means of weak magnetic interactions between the mentioned magnetic units. Such long-range magnetic order is precluded with the application of a high enough magnetic field. Compound 4 evidenced intrachain antiferromagnetic interactions.Depto. de Química InorgánicaFac. de Ciencias QuímicasTRUEpu

Unusual Magnetic Behaviors and Electronic Configurations Driven by Diverse Co(II) or Mn(II) MOF Architectures

Five novel metal organic frameworks were obtained by hydrosolvothermal reactions using the hexafluorisopropylidenebis(benzoic) acid (H2hfipbb) as linker and Co(II) or Mn(II) ions as connectors. [Co2(Hhfipbb)- (TEA)], compound 1 (TEA = triethanolamine trianion) with a threedimensional (3D) framework, and a tpu net; [Co1.5(hfipbb)2]·HN(CH2CH3)3 and [Co3(hfipbb)2]·2{HN(CH2CH3)3}, compounds 2 and 2-a, respectively, both with two-dimensional structure, sql topologies, and different layer packings. Compounds 3 and 4, having the general formula [M2(hfipbb)2]·C7H8, where M = Co (3) or Mn (4), have 3D frameworks with an sqc topology. A deep analysis of the magnetic measurements reveals different striking magnetic behaviors resulting from diverse secondary building unit and framework architectures. Compound 1 presents canted antiferromagnetic chains, compound 2 contains ferromagnetic linear trimeric clusters, and compound 3 exhibits ferromagnetic chains. For the three compounds, a 3D canted antiferromagnetic structure takes place at ∼8 K by means of weak magnetic interactions between the mentioned magnetic units. Such long-range magnetic order is precluded with the application of a high enough magnetic field. Compound 4 evidenced intrachain antiferromagnetic interactions.Fil: Bernini, Maria Celeste. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Investigaciones En Tecnología Química; Argentina. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Romero de Paz, Julio. Universidad Complutense de Madrid; EspañaFil: Snejko, Natalia. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Sáez Puche, Regino. Universidad Complutense de Madrid; EspañaFil: Gutierrez Puebla, Enrique. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Monge, Maria Angeles . Instituto de Ciencia de Materiales de Madrid; Españ

Gestational diabetes reduces adenosine transport in human placental microvascular endothelium, an effect reversed by insulin

Gestational diabetes mellitus (GDM) courses with increased fetal plasma adenosine concentration and reduced adenosine transport in placental macrovascular endothelium. Since insulin modulates human equilibrative nucleoside transporters (hENTs) expression/activity, we hypothesize that GDM will alter hENT2-mediated transport in human placental microvascular endothelium (hPMEC), and that insulin will restore GDM to a normal phenotype involving insulin receptors A (IR-A) and B (IR-B). GDM effect on hENTs expression and transport activity, and IR-A/IR-B expression and associated cell signalling cascades (p42/44 mitogen-activated protein kinases (p42/44) and Akt) role in hPMEC primary cultures was assayed. GDM associates with elevated umbilical whole and vein, but not arteries blood adenosine, and reduced hENTs adenosine transport and expression. IR-A/IR-B mRNA expression and p42/44/Akt ratios ('metabolic phenotype') were lower in GDM. Insulin reversed GDM-reduced hENT2 expression/activity, IR-A/IR-B mRNA expression and p42/44/Akt ratios to normal pregnancies ('mitogenic phenotype'). It is suggested that insulin effects required IR-A and IR-B expression leading to differential modulation of signalling pathways restoring GDM-metabolic to a normal-mitogenic like phenotype. Insulin could be acting as protecting factor for placental microvascular endothelial dysfunction in GDM