Catalytic activity of Pt and Pd in gaseous reactions of H2 and CH4 oxidation at low pressures

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Influence of saddle-splay deformation on lyotropic chromonic liquid crystals confined between two coaxial cylinders

ABSTRACT

A striking feature of lyotropic chromonic liquid crystals confined in cylinder model exhibit double-twist director configurations. Evidence suggests that saddle-splay deformation is among the most important factors for the distortions of director. Previous researches limit the director to distort at a fixed plane (r-? plane) by using specific boundary conditions such as degenerate planar anchoring condition. In this work, we consider lyotropic chromonic liquid crystals confined between two coaxial cylinders with free-surface boundary conditions and Rapini-Papoular-type anchoring conditions. By using finite-difference iterative method to solve the numerical solution of Euler equation, we find that saddle-splay deformation leads to double-twist director configurations under free-surface boundary conditions, which consist of the result under degenerate planar anchoring conditions. Furthermore, at Rapini-Papoular-type anchoring conditions, saddle-splay deformation has a great influence on the director in the radial direction (r direction) and the director distorts in three-dimensional space. Remarkably, our method provides a more accurate theory basis for the measured values of saddle-splay elastic constant K_24。     

Extraordinary transport behavior of gases in isothermally annealed poly(4‐methyl‐1‐pentene) membranes

Poly(4‐methyl‐1‐pentene) (PMP) membranes were modified through isothermal annealing to investigate the change of their crystalline structure and rigid and mobile amorphous fractions (RAF and MAF), assuming a three‐phase model, affected the gas transport behavior. The crystalline structure was characterized by wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS) techniques, and the free volume properties were analyzed by positron annihilation lifetime spectroscopy. Compared with the pristine membrane, the annealed membranes show higher crystallinity; the crystals undergo partial structural change from form III to form I. The lamellar crystal thickness, rigid amorphous fraction thickness, and long period in the lamellar stacks increase with crystallinity. The annealed PMP membranes exhibit higher permeability due to the increase in larger size free volumes in MAF and higher selectivity due to the increase in smaller size free volumes in RAF, respectively. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2368–2376     

The structures of the isomorphous potassium and rubidium salts of 4‐nitrobenzoic acid and an overview of the metal complex stereochemistries of the alkali metal salt series with this ligand

4‐Nitrobenzoic acid (PNBA) has proved to be a useful ligand for the preparation of metal complexes but the known structures of the alkali metal salts of PNBA do not include the rubidium salt. The structures of the isomorphous potassium and rubidium polymeric coordination complexes with PNBA, namely poly[μ₂‐aqua‐aqua‐μ₃‐(4‐nitrobenzoato)‐potassium], [K(C₇H₄N₂O₂)(H₂O)₂]_n, (I), and poly[μ₃‐aqua‐aqua‐μ₅‐(4‐nitrobenzoato)‐rubidium], [Rb(C₇H₄N₂O₂)(H₂O)₂]_n, (II), have been determined. In (I), the very distorted KO₆ coordination sphere about the K⁺ centres in the repeat unit comprise two bridging nitro O‐atom donors, a single bridging carboxylate O‐atom donor and two water molecules, one of which is bridging. In Rb complex (II), the same basic MO₆ coordination is found in the repeat unit, but it is expanded to RbO₉ through a slight increase in the accepted Rb—O bond‐length range and includes an additional Rb—O_carboxylate bond, completing a bidentate O,O′‐chelate interaction, and additional bridging Rb—O_nitro and Rb—O_water bonds. The comparative K—O and Rb—O bond‐length ranges are 2.7352 (14)–3.0051 (14) and 2.884 (2)–3.182 (2) Å, respectively. The structure of (II) is also isomorphous, as well as isostructural, with the known structure of the nine‐coordinate caesium 4‐nitrobenzoate analogue, (III), in which the Cs—O bond‐length range is 3.047 (4)–3.338 (4) Å. In all three complexes, common basic polymeric extensions are found, including two different centrosymmetric bridging interactions through both water and nitro groups, as well as extensions along c through the para‐related carboxylate group, giving a two‐dimensional structure in (I). In (II) and (III), three‐dimensional structures are generated through additional bridges involving the nitro and water O atoms. In all three structures, the two water molecules are involved in similar intra‐polymer O—H...O hydrogen‐bonding interactions to both carboxylate and water O‐atom acceptors. A comparison of the varied coordination behaviour of the full set of Li–Cs salts with 4‐nitrobenzoic acid is also made.     

A three‐dimensional coordination polymer based on the Zn4(μ3‐OH)2 unit: poly[[(μ4‐benzene‐1,4‐dicarboxylato)bis(μ3‐benzene‐1,4‐dicarboxylato)bis(μ3‐hydroxido)bis(1,10‐phenanthroline‐5,6‐dione)tetrazinc] dihydrate]

The title compound, {[Zn₄(C₈H₄O₄)₃(OH)₂(C₁₂H₆N₂O₂)₂]·2H₂O}_n, has been prepared hydrothermally by the reaction of Zn(NO₃)₂·6H₂O with benzene‐1,4‐dicarboxylic acid (H₂bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H₂O. In the crystal structure, a tetranuclear Zn₄(OH)₂ fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN₂O₄] octahedron and a [ZnO₄] tetrahedron bridged by a μ₃‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN₂O₄] octahedron. The two crystallographically independent bdc²⁻ ligands are fully deprotonated and adopt μ₃‐κO:κO′:κO′′ and μ₄‐κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four Zn^II cations, respectively, from two Zn₄(OH)₂ units. The Zn₄(OH)₂ fragment connects six neighbouring tetranuclear units through four μ₃‐bdc²⁻ and two μ₄‐bdc²⁻ ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn₄(OH)₂ units are considered as 6‐connected nodes and the bdc²⁻ ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn₄(OH)₂ unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ₄‐bdc²⁻ ligands.     

A three‐dimensional cadmium(II) coordination polymer with unequal homochiral double‐stranded concentric helical chains

A homochiral helical three‐dimensional coordination polymer, poly[[(μ₂‐acetato‐κ³O,O′:O)(hydroxido‐κO)(μ₄‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁵N¹,O:N²:N⁴:N⁵)(μ₃‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁴N¹,O:N²:N⁴:N⁵)dicadmium(II)] 0.75‐hydrate], {[Cd₂(C₇H₅N₆O)₂(CH₃COO)(OH)]·0.75H₂O}_n, was synthesized by the reaction of cadmium acetate, N‐(1H‐tetrazol‐5‐yl)isonicotinamide (H‐NTIA), ethanol and H₂O under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Cd^II cations, two deprotonated 5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ide (NTIA⁻) ligands, one acetate anion, one hydroxide anion and three independent partially occupied water sites. The two Cd^II cations, with six‐coordinated octahedral and seven‐coordinated pentagonal bipyramidal geometries are located on general sites. The tetrazole group of one symmetry‐independent NTIA⁻ ligand links one of the independent Cd^II cations into 6₁ helical chains, while the other NTIA⁻ ligand links the other independent Cd^II cations into similar but unequal 6₁ helical chains. These chains, with a pitch of 24.937 (5) Å, intertwine into a double‐stranded helix. Each of the double‐stranded 6₁ helices is further connected to six adjacent helical chains through an acetate μ₂‐O atom and the tetrazole group of the NTIA⁻ ligand into a three‐dimensional framework. The helical channel is occupied by the isonicotinamide groups of NTIA⁻ ligands and two helices are connected to each other through the pyridine N and carbonyl O atoms of isonicotinamide groups. In addition, N—H...O and O—H...N hydrogen bonds exist in the complex.     

A three‐dimensional anionic metal–dicyanamide network in poly[ethyltriphenylphosphonium [tri‐μ2‐dicyanamidato‐cadmium(II)]]

The title compound, (C₂₀H₂₀P)[Cd(C₂N₃)₃], consists of ethyltriphenylphosphonium (EtPh₃P⁺) cations filling voids in a three‐dimensional anionic cadmium dicyanamide network. In the structure, each Cd^II atom is connected to six neighbouring Cd^II atoms through six separate dicyanamide ligands, forming cube‐shaped cages. The three‐dimensional anionic network encloses a solvent‐accessible void space of 1851 ų, amounting to 69.3% of the unit‐cell volume. Each cage accommodates only one EtPh₃P⁺ cation.     

A three‐dimensional cadmium coordination polymer based on 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene and benzene‐1,3,5‐tricarboxylic acid

The Cd^II three‐dimensional coordination poly[[[μ₄‐1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene]bis(μ₃‐5‐carboxybenzene‐1,3‐dicarboxylato)dicadmium(II)] dihydrate], {[Cd₂(C₉H₄O₆)₂(C₈H₁₀N₆)]·2H₂O}_n , (I), has been synthesized by the hydrothermal reaction of Cd(NO₃)₂·4H₂O, benzene‐1,3,5‐tricarboxylic acid (1,3,5‐H₃BTC) and 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene (1,4‐btbe). The IR spectrum suggests the presence of protonated carboxylic acid, deprotonated carboxylate and triazolyl groups. The purity of the bulk sample was confirmed by elemental analysis and X‐ray powder diffraction. Single‐crystal X‐ray diffraction analysis reveals that the Cd^II ions adopt a five‐coordinated distorted trigonal–bipyramidal geometry, coordinated by three O atoms from three different 1,3,5‐HBTC²⁻ ligands and two N atoms from two different 1,4‐btbe ligands; the latter are situated on centres of inversion. The Cd^II centres are bridged by 1,3,5‐HBTC²⁻ and 1,4‐btbe ligands into an overall three‐dimensional framework. When the Cd^II centres and the tetradentate 1,4‐btbe ligands are regarded as nodes, the three‐dimensional topology can be simplified as a binodal 4,6‐connected network. Thermogravimetric analysis confirms the presence of lattice water in (I). Photoluminescence studies imply that the emission of (I) may be ascribed to intraligand fluorescence.     

Three‐dimensional printed magnetophoretic system for the continuous flow separation of avian influenza H5N1 viruses

As a result of the low concentration of avian influenza viruses in samples for routine screening, the separation and concentration of these viruses are vital for their sensitive detection. We present a novel three‐dimensional printed magnetophoretic system for the continuous flow separation of the viruses using aptamer‐modified magnetic nanoparticles, a magnetophoretic chip, a magnetic field, and a fluidic controller. The magnetic field was designed based on finite element magnetic simulation and developed using neodymium magnets with a maximum intensity of 0.65 T and a gradient of 32 T/m for dragging the nanoparticle–virus complexes. The magnetophoretic chip was designed by SOLIDWORKS and fabricated by a three‐dimensional printer with a magnetophoretic channel for the continuous flow separation of the viruses using phosphate‐buffered saline as carrier flow. The fluidic controller was developed using a microcontroller and peristaltic pumps to inject the carrier flow and the viruses. The trajectory of the virus–nanoparticle complexes was simulated using COMSOL for optimization of the carrier flow and the magnetic field, respectively. The results showed that the H5N1 viruses could be captured, separated, and concentrated using the proposed magnetophoretic system with the separation efficiency up to 88% in a continuous flow separation time of 2 min for a sample volume of 200 μL.