Functional conductive nanomaterials via polymerisation in nano-channels: PEDOT in a MOF.

Reactions inside the pores of metal-organic frameworks (MOFs) offer potential for controlling polymer structures with regularity to sub-nanometre scales. We report a wet-chemistry route to poly-3,4-ethylenedioxythiophene (PEDOT)-MOF composites. After a two-step removal of the MOF template we obtain unique and stable macroscale structures of this conductive polymer with some nanoscale regularity.The project is funded through the European Research Council (ERC) grant (grant number: EMATTER 280078). AKC thanks the Ras Al Khaimah Center for Advanced Materials (RAK-CAM). JDWM and MF acknowledge funding through a Discovery Grant from The Natural Sciences and Engineering Research Council of Canada (NSERC). TW thanks the China Scholarship Council (CSC) for funding and the Engineering and Physical Sciences Research Council of the UK (EPSRC) Centre for Doctoral Training in Sensor Technologies and Applications (grant number: EP/L015889/1) for support. SH acknowledges the Alexander von Humboldt Foundation for funding. SS is funded through a scholarship from the Cambridge Overseas Trust. JSB thanks the Isaac Newton Trust for financial support for the FEI Tecnait TEM. The authors would also like to show the gratitude to Phenom-World for the use of the Phenom Pro X SEM and Dr Suman-Lata Sahonta for the help with Raman spectroscopy.This is the final version of the article. It first appeared from the Royal Society of Chemistry at http://dx.doi.org/10.1039/c6mh00230g

Hydrolysis of Dipeptides Catalyzed by a Zirconium(IV)-Substituted Lindqvist Type Polyoxometalate

The hydrolysis of a series of unactivated dipeptides in the presence of a zirconium(IV)-substituted Lindqvist type polyoxometalate, (Me 4 N) 2 [W 5 O 18 Zr(H 2 O) 3 ] (designated as ZrW 5 ), was studied by kinetic experiments and NMR spectroscopy. Among the dipeptides examined, those with the X-Ser amino acid sequence were most effectively hydrolyzed. The kinetics of the hydrolysis of histidylserine (His-Ser) was studied in detail; a rate constant of 95.3 (± 0.1) × 10 -7 s -1 (pD 7.4 and 60 °C) in the presence of an equimolar amount of ZrW 5 was calculated. The binding of His-Ser to ZrW 5 was examined by UV/Vis, 1 H, 13 C, and 183 W NMR spectroscopy, and the data indicate that at physiological pD His-Ser chelates the Zr IV through its imidazole nitrogen, amine nitrogen, and amide carbonyl oxygen. In the presence of ZrW 5 , the pD profile of k obs is bell-shaped, with a maximum reaction rate at pD 7.5. At high pD values an inactive complex is formed as a result of the deprotonation of the amide nitrogen, resulting in inhibition of His-Ser hydrolysis. The effects of pH, temperature, inhibitors, and ionic strength on the hydrolysis rate constant were also investigated, and a full account of the mechanism of this novel reaction is given. The hydrolysis of dipeptides in the presence of a zirconium(IV)-substituted Lindqvist type polyoxometalate was investigated. Of the dipeptides studied, His-Ser was most effectively hydrolyzed, with a first-order rate constant of 9.53 × 10 -6 s -1 at pD 7.4 and 60 °C. The binding of His-Ser to the Zr complex and the effect of pH, temperature, inhibitors, and ionic strength on the rate constant were examined. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.status: publishe

Convenient synthesis of Cu-3(BTC)(2) encapsulated Keggin heteropolyacid nanomaterial for application in catalysis

Nanomaterial of Cu-3(BTC)(2) (BTC = benzene tricarboxylic acid) incorporating Keggin heteropolyacid conveniently prepared at room temperature and recovered by freeze drying outperforms ultrastable Y zeolite in acid catalysed esterification reaction

Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework

HKUST-1 is one of the popular metal-organic frameworks (MOFs). The formation of this MOF is significantly accelerated by adding Keggin polyoxometalate anions to the synthesis solution. In this paper the chemistry behind this observation was investigated. Upon addition of Keggin type H 3PW12O40 heteropolyacid the speciation of Cu2+ cations in ethanol:H2O mixture drastically changes. Combining EPR and XANES measurements with accurate pH measurements and prediction of Cu2+ hydrolysis provides strong evidence for surface induced hydrolysis and consequent dimerisation of monomeric Cu2+ species on Keggin ions in acidic conditions. This enables paddle wheel formation, hence explaining the instantaneous precipitation of Cu 3(BTC)2 at room temperature and the systematic encapsulation of Keggin ions in its pores.Fil: Bajpe, Sneha R.. Katholikie Universiteit Leuven; BélgicaFil: Breynaert, Eric. Katholikie Universiteit Leuven; BélgicaFil: Mustafa, Danilo. Katholikie Universiteit Leuven; BélgicaFil: Jobbagy, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Maes, André. Katholikie Universiteit Leuven; BélgicaFil: Martens, Johan A.. Katholikie Universiteit Leuven; BélgicaFil: Kirschhock, Christine E. A.. Katholikie Universiteit Leuven; Bélgic

Copper Benzene Tricarboxylate Metal–Organic Framework with Wide Permanent Mesopores Stabilized by Keggin Polyoxometallate Ions

Porous solids with organized multiple porosity are of scientific and technological importance for broadening the application range from traditional areas of catalysis and adsorption/separation to drug release and biomedical imaging. Synthesis of crystalline porous materials offering a network of uniform micro- and mesopores remains a major scientific challenge. One strategy is based on variation of synthesis parameters of microporous networks, such as, for example, zeolites or metal–organic frameworks (MOFs). Here, we show the rational development of an hierarchical variant of the microporous cubic Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylate) HKUST-1 MOF having strictly repetitive 5 nm wide mesopores separated by uniform microporous walls in a single crystal structure. This new material coined COK-15 (COK = Centrum voor Oppervlaktechemie en Katalyse) was synthesized via a dual-templating approach. Stability was enhanced by Keggin type phosphotungstate (HPW) systematically occluded in the cavities constituting the walls between the mesopores

Copper Benzene Tricarboxylate Metal–Organic Framework with Wide Permanent Mesopores Stabilized by Keggin Polyoxometallate Ions

Porous solids with organized multiple porosity are of scientific and technological importance for broadening the application range from traditional areas of catalysis and adsorption/separation to drug release and biomedical imaging. Synthesis of crystalline porous materials offering a network of uniform micro- and mesopores remains a major scientific challenge. One strategy is based on variation of synthesis parameters of microporous networks, such as, for example, zeolites or metal–organic frameworks (MOFs). Here, we show the rational development of an hierarchical variant of the microporous cubic Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylate) HKUST-1 MOF having strictly repetitive 5 nm wide mesopores separated by uniform microporous walls in a single crystal structure. This new material coined COK-15 (COK = Centrum voor Oppervlaktechemie en Katalyse) was synthesized via a dual-templating approach. Stability was enhanced by Keggin type phosphotungstate (HPW) systematically occluded in the cavities constituting the walls between the mesopores

CCDC 1047056: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 1047055: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures