WorldWideScience

Sample records for metal-organic coordination polymers

  1. A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal-Organic Framework Materials.

    Science.gov (United States)

    Einkauf, Jeffrey D; Clark, Jessica M; Paulive, Alec; Tanner, Garrett P; de Lill, Daniel T

    2017-05-15

    Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

  2. Self-assembly of metal-organic supramolecules: from a metallamacrocycle and a metal-organic coordination cage to 1D or 2D coordination polymers based on flexible dicarboxylate ligands.

    Science.gov (United States)

    Dai, Fangna; Dou, Jianmin; He, Haiyan; Zhao, Xiaoliang; Sun, Daofeng

    2010-05-03

    To assemble metal-organic supramolecules such as a metallamacrocycle and metal-organic coordination cage (MOCC), a series of flexible dicarboxylate ligands with the appropriate angle, 2,2'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(1)), 2,2'-(2,5-dimethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(2)), 2,2'-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(sulfanediyl)dinicotinic acid (H(2)L(3)), and 2,2'-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(4)), have been designed and synthesized. Using these flexible ligands to assemble with metal ions, six metal-organic supramolecules, Cd(2)(L(1))(2)(dmf)(4)(H(2)O)(2).H(2)O (1), Mn(3)((1)L(2))(2)((2)L(2))(dmf)(2)(H(2)O)(2).5dmf (2), Cu(4)(L(3))(4)(H(2)O)(4).3dmf (3), Cu(4)(L(4))(4)(dmf)(2)(EtOH)(2).8dmf.6H(2)O (4), Mn(4)(L(4))(4)(dmf)(4)(H(2)O)(4).6dmf.H(2)O (5), and Mn(3)(L(4))(3)(dmf)(4).2dmf.3H(2)O (6), possessing a rectangular macrocycle, MOCCs or their extensions, and 1D or 2D coordination polymers, have been isolated. All complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, and thermogravimetric analysis. Complex 1 is a discrete rectangular macrocycle, while complex 2 is a 2D macrocycle-based coordination polymer in which the L(2) ligand adopts both syn and anti conformations. Complexes 3-5 are discrete MOCCs in which two binuclear metal clusters are engaged by four organic ligands. The different geometries of the secondary building units (SBUs) and the axial coordinated solvates on the SBUs result in their different symmetries. Complex 6 is a 1D coordination polymer, extended from a MOCC made up of two metal ions and three L(4) ligands. All of the flexible dicarboxylate ligands adopt a syn conformation except that in complex 2, indicating that the syn conformational ligand is helpful for the formation of a metallamacrocycle and a MOCC. The magnetic properties of complexes 5

  3. Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers

    Directory of Open Access Journals (Sweden)

    Yann Garcia

    2011-10-01

    Full Text Available The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs and metal-organic frameworks (MOFs are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution.

  4. Aerogels of 1D Coordination Polymers: From a Non-Porous Metal-Organic Crystal Structure to a Highly Porous Material

    Directory of Open Access Journals (Sweden)

    Adrián Angulo-Ibáñez

    2016-01-01

    Full Text Available The processing of an originally non-porous 1D coordination polymer as monolithic gel, xerogel and aerogel is reported as an alternative method to obtain novel metal-organic porous materials, conceptually different to conventional crystalline porous coordination polymer (PCPs or metal-organic frameworks (MOFs. Although the work herein reported is focused upon a particular kind of coordination polymer ([M(μ-ox(4-apy2]n, M: Co(II, Ni(II, the results are of interest in the field of porous materials and of MOFs, as the employed synthetic approach implies that any coordination polymer could be processable as a mesoporous material. The polymerization conditions were fixed to obtain stiff gels at the synthesis stage. Gels were dried at ambient pressure and at supercritical conditions to render well shaped monolithic xerogels and aerogels, respectively. The monolithic shape of the synthesis product is another remarkable result, as it does not require a post-processing or the use of additives or binders. The aerogels of the 1D coordination polymers are featured by exhibiting high pore volumes and diameters ranging in the mesoporous/macroporous regions which endow to these materials the ability to deal with large-sized molecules. The aerogel monoliths present markedly low densities (0.082–0.311 g·cm−3, an aspect of interest for applications that persecute light materials.

  5. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    Science.gov (United States)

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

  6. Recovery of metals from simulant spent lithium-ion battery as organophosphonate coordination polymers in aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Perez, Emilie; Andre, Marie-Laure; Navarro Amador, Ricardo [ICSM, Institut de Chimie Séparative de Marcoule, UMR 5257, CEA/CNRS/ENSCM/UM, Bât 426, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Hyvrard, François; Borrini, Julien [SARPI VEOLIA, Direction Technique et Innovations, Zone portuaire de Limay-Porcheville, 427 route du Hazay, 78520 Limay (France); Carboni, Michaël, E-mail: michael.carboni@cea.fr [ICSM, Institut de Chimie Séparative de Marcoule, UMR 5257, CEA/CNRS/ENSCM/UM, Bât 426, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Meyer, Daniel [ICSM, Institut de Chimie Séparative de Marcoule, UMR 5257, CEA/CNRS/ENSCM/UM, Bât 426, BP 17171, 30207 Bagnols-sur-Cèze cedex (France)

    2016-11-05

    Highlights: • Original waste disposal strategies for battery. • Precipitation of metals as coordination polymers. • Organo-phosphonate coordination polymers. • Selective extraction of manganese or co-precipitation of manganese/cobalt. • The recycling process give a promising application on any waste solution. - Abstract: An innovative approach is proposed for the recycling of metals from a simulant lithium-ion battery (LIBs) waste aqueous solution. Phosphonate organic linkers are introduced as precipitating agents to selectively react with the metals to form coordination polymers from an aqueous solution containing Ni, Mn and Co in a hydrothermal process. The supernatant is analyzed by ICP-AES to quantify the efficiency and the selectivity of the precipitation and the materials are characterized by Scanning Electron Microscopy (SEM), Powder X-Ray Diffraction (PXRD), Thermogravimetric Analyses (TGA) and nitrogen gas sorption (BET). Conditions have been achieved to selectively precipitate Manganese or Manganese/Cobalt from this solution with a high efficiency. This work describes a novel method to obtain potentially valuable coordination polymers from a waste metal solution that can be generalized on any waste solution.

  7. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Energy Technology Data Exchange (ETDEWEB)

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  8. Porphyrin coordination polymer nanospheres and nanorods

    Science.gov (United States)

    Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

    2012-12-04

    A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

  9. Exploring 3D non-interpenetrated metal-organic framework with malonate-bridged Co(II) coordination polymer: structural elucidation and theoretical study

    Science.gov (United States)

    Hossain, Anowar; Mandal, Tripti; Mitra, Monojit; Manna, Prankrishna; Bauzá, Antonio; Frontera, Antonio; Seth, Saikat Kumar; Mukhopadhyay, Subrata

    2017-12-01

    A Co(II)-based coordination polymer with tetranuclear cobalt(II)-malonate cluster has been easily generated by aqueous medium self-assembly from Cobalt(II) chloride hexahydrate and malonic acid. The structure exhibits a non-interpenetrating, highly undulating two-dimensional (2D) bi-layer network with (4,4) topology. The crystal structure is composed of infinite interdigitated 2D metal-organic bi-layers which extended to an intricate 3D framework through the interbilayer hydrogen bonds. We have studied energetically by means of Density Functional Theory (DFT) calculations the H-bonding interactions that connect the 2D metal-organic bi-layers. The finite theoretical models have been used to compute conventional O‒H•••O and unconventional C‒H•••O interactions which plays a key role to build 3D architecture.

  10. Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

    Science.gov (United States)

    Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2013-04-10

    Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

  11. Room temperature synthesis of a Zn(II) metal-organic coordination polymer for dye removal

    Energy Technology Data Exchange (ETDEWEB)

    Abbasi, Alireza, E-mail: aabbasi@khayam.ut.ac.ir [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Gharib, Maniya; Najafi, Mahnaz [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Janczak, Jan [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, PO Box 1410, 50-950 Wrocław (Poland)

    2016-03-15

    A new one-dimensional (1D) coordination polymer, [Zn(4,4′-bpy)(H{sub 2}O){sub 4}](ADC)·4H{sub 2}O (1) (4,4′-bpy=4,4′-bipyridine and H{sub 2}ADC=acetylenedicarboxylic acid), was synthesized at room temperature. The crystal structure of the coordination polymer was determined by single-crystal X-ray diffraction analysis. Compound 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The catalytic activity of 1 was evaluated in the color removal of Bismarck brown as a representative of dye pollutant in water under mild conditions. Coordination polymer 1 exhibited good catalytic activity and stability in the decolorization of Bismarck brown and could be easily recovered and reused for at least three cycles. - Graphical abstract: A new 1D coordination polymer as catalyst for the degradation of Bismarck brown aqueous solution. - Highlights: • A 1D coordination polymer has been synthesized at room temperature. • The prepared compound was utilized for color removal of Bismarck brown dye. • Good catalytic activity and stability in the dye decolorization has been found.

  12. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    International Nuclear Information System (INIS)

    Shi, Fa-Nian; Rosa Silva, Ana; Bian, Liang

    2015-01-01

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi 2 O(1,3,5-BTC) 2 ] n (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi 4 O 2 (COO) 12 clusters which are further connected to Mn(COO) 6 fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4 13 .6 2 )(4 13 .6 8 )(4 16 .6 5 )(4 18 .6 10 )(4 22 .6 14 )(4 3 ) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles

  13. Design and characterization of metal-thiocyanate coordination polymers

    OpenAIRE

    Savard, Didier

    2018-01-01

    This thesis focuses on exploring the synthesis and chemical reactivity of thiocyanate-based building blocks of the type [M(SCN)x]y- for the synthesis of coordination polymers. A series of potassium, ammonium, and tetraalkylammonium metal isothiocyanate salts of the type Qy[M(SCN)x] were synthesized and structurally characterized. Most of the salts were revealed to be isostructural and classic Werner complexes, but for (Et4N)3[Fe(NCS)6] and (n-Bu4N)3[Fe(NCS)6], a solid-state size-dependent cha...

  14. Room temperature synthesis of a Zn(II) metal-organic coordination polymer for dye removal

    Science.gov (United States)

    Abbasi, Alireza; Gharib, Maniya; Najafi, Mahnaz; Janczak, Jan

    2016-03-01

    A new one-dimensional (1D) coordination polymer, [Zn(4,4‧-bpy)(H2O)4](ADC)·4H2O (1) (4,4‧-bpy=4,4‧-bipyridine and H2ADC=acetylenedicarboxylic acid), was synthesized at room temperature. The crystal structure of the coordination polymer was determined by single-crystal X-ray diffraction analysis. Compound 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The catalytic activity of 1 was evaluated in the color removal of Bismarck brown as a representative of dye pollutant in water under mild conditions. Coordination polymer 1 exhibited good catalytic activity and stability in the decolorization of Bismarck brown and could be easily recovered and reused for at least three cycles.

  15. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Fa-Nian, E-mail: fshi@ua.pt [School of Science, Shenyang University of Technology, 110870 Shenyang (China); Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Rosa Silva, Ana [Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Bian, Liang [Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, Xinjiang (China)

    2015-05-15

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi{sub 2}O(1,3,5-BTC){sub 2}]{sub n} (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi{sub 4}O{sub 2}(COO){sub 12} clusters which are further connected to Mn(COO){sub 6} fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4{sup 13}.6{sup 2})(4{sup 13}.6{sup 8})(4{sup 16}.6{sup 5})(4{sup 18}.6{sup 10})(4{sup 22}.6{sup 14})(4{sup 3}) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles.

  16. Nanostructural self-organization and dynamic adaptation of metal-polymer tribosystems

    Science.gov (United States)

    Mashkov, Yu. K.

    2017-02-01

    The results of investigating the effect of nanosize modifiers of a polymer matrix on the nanostructural self-organization of polymer composites and dynamic adaptation of metal-polymer tribosystems, which considerably affect the wear resistance of polymer composite materials, have been analyzed. It has been shown that the physicochemical nanostructural self-organization processes are developed in metal-polymer tribosystems with the formation of thermotropic liquid-crystal structures of the polymer matrix, followed by the transition of the system to the stationary state with a negative feedback that ensures dynamic adaptation of the tribosystem to given operating conditions.

  17. Luminescent lanthanide coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Ma, L.; Evans, O.R.; Foxman, B.M.; Lin, W.

    1999-12-13

    One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate){sub 3}(H{sub 2}O){sub 2} (Ln = Ce, Pr, Nd, Sm, Eu, Tb; 1a-f) were synthesized by treating nitrate or perchlorate salts of Ln(III) with 4-pyridinecarboxaldehyde under hydro(solvo)thermal conditions. Single-crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate){sub 2}-Ln and Ln-(carboxylate){sub 4}-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite-chain structure with one chelating carboxylate group on each metal center. In both structures, the lanthanide centers also bind to two water molecules to yield an eight-coordinate, square antiprismatic geometry. The pyridine nitrogen atoms of the isonicotinate groups do not coordinate to the metal centers in these lanthanide(III) complexes; instead, they direct the formation of Ln(III) coordination polymers via hydrogen bonding with coordinated water molecules. Photoluminescence measurements show that Tb(isonicotinate){sub 3}(H{sub 2}O){sub 2} is highly emissive at room temperature with a quantum yield of {approximately}90%. These results indicate that highly luminescent lanthanide coordination polymers can be assembled using a combination of coordination and hydrogen bonds. Crystal data for 1a: monoclinic space group P2{sub 1}/c, a = 9.712(2) {angstrom}, b = 19.833(4) {angstrom}, c = 11.616(2) {angstrom}, {beta} = 111.89(3){degree}, Z = 4. Crystal data for 1f: monoclinic space group C2/c, a = 20.253(4) {angstrom}, b = 11.584(2) {angstrom}, c = 9.839(2) {angstrom}, {beta} = 115.64(3){degree}, Z = 8.

  18. A novel self-assembly with zinc porphyrin coordination polymer for enhanced photocurrent conversion in supramolecular solar cells

    International Nuclear Information System (INIS)

    Cao, Jing; Liu, Jia-Cheng; Deng, Wen-Ting; Li, Ren-Zhi; Jin, Neng-Zhi

    2013-01-01

    Graphical abstract: An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells. - Highlights: • A novel assembly with acetohydrazide porphyrin coordination polymer. • The assembly based on porphyrin is prepared as parallel sample. • Coordination polymer-based assembly shows enhanced photoelectronic behavior. • A series of different organic acid ligands as anchoring groups are prepared. - Abstract: In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO 2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO 2 electrode surface in supramolecular solar cells

  19. Inorganic Metal Oxide/Organic Polymer Nanocomposites And Method Thereof

    Science.gov (United States)

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-11-16

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal in organic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophilic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the material, providing superb mixing of the component phases in the energetic nanocomposite.

  20. Surface grafting of a dense and rigid coordination polymer based on tri-para-carboxy-polychlorotriphenylmethyl radical and copper acetate

    KAUST Repository

    Mugnaini, Veró nica; Paradinas, Markos; Shekhah, Osama; Roques, Nans; Ocal, Carmen; Wö ll, Christof H.; Veciana, Jaume

    2013-01-01

    The step-by-step method is here presented as suitable to anchor on appropriately functionalized gold surfaces a metal-organic coordination polymer based on a non-planar trigonal tri-para-carboxy-polychlorotriphenylmethyl radical derivative and copper acetate. The structural characteristics of the grafted coordination polymer are derived during the step-wise growth from the real time changes in refractive index and oscillation frequency. The film thickness, as measured by scanning force microscopy, combined with the mass uptake value from the quartz crystal microbalance, are used to estimate an average density of the grafted metal-organic coordination polymer that suggests the formation of a dense and rather rigid thin film. This journal is © 2013 The Royal Society of Chemistry.

  1. Synthesis, Structure and Properties of Two Novel 2D Zinc(II) Coordination Polymers based on Fluconazole and Benzene Carboxylic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Ganghong; Tang, Jingniu; Xu, Wenjia; Liang, Peng; Huang, Zhongjing [Guangxi University for Nationalities, Nanning (China)

    2013-12-15

    The design and synthesis of coordination polymers have aroused great interest owing to their intriguing aesthetic structures and potential applications in nonlinear optics, gas storage, ion exchange, luminescence, magnetism and catalysis. Self-assembly of bridging organic ligands (connectors) and multi-connected metal ions can give rise to various types of interesting coordination polymers. Since metal ion Zn(II) with d{sup 10} electronic configuration permits a variety of coordination numbers and geometries which are not dependent on ligand field stabilization but on ligand size and charge, it is well suited for the construction of various coordination polymers. Its borderline hardness allows the coordination of N, O and S donor atoms.

  2. Homochiral coordination polymers with helixes and metal clusters based on lactate derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Zhong-Xuan, E-mail: xuzhongxuan4201@163.com [Department of Chemistry, Zunyi Normal College, Zunyi, Guizhou 563002 (China); Ma, Yu-Lu [School of Chemical Science and Technology, Yunnan University, Kunming 650091 (China); Lv, Guo-ling [Department of Chemistry, Zunyi Normal College, Zunyi, Guizhou 563002 (China)

    2017-05-15

    Utilizing the lactic acid derivatives (R)-4-(1-carboxyethoxy)benzoic acid (denoted: (R)-H{sub 2}CBA) and (S)-4-(1-carboxyethoxy)benzoic acid (denoted: (S)-H{sub 2}CBA)as chiral linkers to self-assemble with 4, 4′-bipyridine (denoted: BIP) and Cd(II) ions, a couple of three-dimensional homochiral coordination polymers, namely [Cd{sub 3}((R)-CBA){sub 3} (BIP){sub 2}(H{sub 2}O)]·xGuest (1-D) and [Cd{sub 3}((S)-CBA){sub 3}(BIP){sub 2}(H{sub 2}O)]·xGuest (1-L), have been synthesized under solvothermal reaction condition. Single crystal X-ray diffraction analysis reveals the two complexes contain single helical chains based on enantiopure ligands and cadmium clusters. Moreover, some physical characteristics such as PXRD, thermal stability, solid-state circular dichroism (CD) and luminescent were also investigated. - Graphical abstract: Utilizing enantiomeric lactic acid derivatives (R)-H{sub 2}CBA and (S)-H{sub 2}CBA to assemble with Cd{sup 2+} ions and ancillary BIP ligands, a couple of 3D homochiral coordination polymers with metal clusters and helical chains have been prepared by hydrothermal reaction. - Highlights: • Chiral lactic acid derivative. • Enantiomeric coordination polymer. • Helical chain. • Trinuclear cadmium cluster.

  3. Synthesis, Crystal Structure and Luminescent Property of A Novel Cd(II) Coordination Polymer with Bis-imidazole Ligand

    International Nuclear Information System (INIS)

    Zhou, Yong Hong

    2013-01-01

    The key to the successful design of metal-organic coordination polymers is the judicious selection of organic ligand. Recently, polydentate aromatic nitrogen heterocyclic ligands with five-membered rings have been well-studied in the construction of supramolecular structure for their N-coordinated sites apt to coordinating to transition metals. Similar to six-membered N-heterocyclic ligands, the azole-based five-membered N-heterocyclic ligands, such as imidazoles, triazoles and tetrazoles have been extensively employed in the construction of various coordination polymers with diverse topologies and interesting properties. The bis(azole) ligands in which N-donor azole rings (imidazole, triazole, or tetrazole) are separated by alkyl, (CH 2 ) n , spacers are good choices for flexible bridging ligands. The conformational flexibility of the spacers makes the ligands adaptable to various coordination networks with one-, two-, and three dimensional structures

  4. coordination polymers derived from two different bis-pyridyl-bis-am

    Indian Academy of Sciences (India)

    Abstract. Three new Ni(II) coordination polymers exhibiting different 1D and 2D framework structures ... separation, magnetism, ion exchange and so on.5 8 ... of the coordination geometries of metal ions, which ... Cu(II)/Co(II)/Cd(II) coordination polymers containing ..... tion, the concentration of MB and RhB (C) versus reac-.

  5. Natural Gas Purification Using a Porous Coordination Polymer with Water and Chemical Stability

    NARCIS (Netherlands)

    Duan, J.; Jin, W.; Krishna, R.

    2015-01-01

    Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we

  6. One-Pot Synthesis of Co-Based Coordination Polymer Nanowire for Li-Ion Batteries with Great Capacity and Stable Cycling Stability

    Science.gov (United States)

    Wang, Peng; Lou, Xiaobing; Li, Chao; Hu, Xiaoshi; Yang, Qi; Hu, Bingwen

    2018-06-01

    Nanowire coordination polymer cobalt-terephthalonitrile (Co-BDCN) was successfully synthesized using a simple solvothermal method and applied as anode material for lithium-ion batteries (LIBs). A reversible capacity of 1132 mAh g-1 was retained after 100 cycles at a rate of 100 mA g-1, which should be one of the best LIBs performances among metal organic frameworks and coordination polymers-based anode materials at such a rate. On the basis of the comprehensive structural and morphology characterizations including fourier transform infrared spectroscopy, 1H NMR, 13C NMR, and scanning electron microscopy, we demonstrated that the great electrochemical performance of the as-synthesized Co-BDCN coordination polymer can be attributed to the synergistic effect of metal centers and organic ligands, as well as the stability of the nanowire morphology during cycling.[Figure not available: see fulltext.

  7. Studies on dielectric properties of ferrocenylhydrazone coordinated polymers irradiated by γ-rays

    International Nuclear Information System (INIS)

    Lin Yun; Chen Jie; Lin Zhanru

    2007-01-01

    The three ferrocenylhydrazone coordinated metal polymers were synthesized (PZM). The effect of the 60 Co γ irradiation on microwave dielectric properties and their temperature-dielectric properties were studies. It has been found that the dielectric parameters (ε', tgδ) of coordinated polymers increase along with the absorbed doses and coordinated metals in order Cu, Co, Ni, However, the dependent curves of dielectric parameters on arise-down temperature are universal. On the other hand, the small changes in chemical structure before and after irradiation were confirmed by IR differential spectrometry and SEM. It is possible to make such coordinated polymers as a multifunctional polymeric material with optical, electric and magnetic properties, which may be potentially used in microwave communication. (authors)

  8. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    International Nuclear Information System (INIS)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-01-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg 2+ , Ca 2+ and Ba 2+ ) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO) 4 , which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (4 4 ·6 2 ) 3 (4 9 ·6 6 ) 2 . The calcium compound consists of 1D infinite “Ca-O” inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D “Ba-O” inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions’ influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies. - Graphical abstract: Three alkaline

  9. Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Wei [Univ. of New Mexico, Albuquerque, NM (United States); Xiang, Guolei [Univ. of Cambridge (United Kingdom); Shang, Jin [Univ. of Hong Kong (China); Guo, Jimin [Univ. of New Mexico, Albuquerque, NM (United States); Motevalli, Benyamin [Monash Univ., Clayton, VIC (Australia); Durfee, Paul [Univ. of New Mexico, Albuquerque, NM (United States); Agola, Jacob Ongudi [Univ. of New Mexico, Albuquerque, NM (United States); Coker, Eric N. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Brinker, C. Jeffrey [Univ. of New Mexico, Albuquerque, NM (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2018-02-22

    Here, a novel strategy for the versatile functionalization of the external surface of metal-organic frameworks (MOFs) has been developed based on the direct coordination of a phenolic-inspired lipid molecule DPGG (1,2-dipalmitoyl-sn-glycero-3-galloyl) with metal nodes/sites surrounding MOF surface. X-ray diffraction and Argon sorption analysis prove that the modified MOF particles retain their structural integrity and porosity after surface modification. Density functional theory calculations reveal that strong chelation strength between the metal sites and the galloyl head group of DPGG is the basic prerequisite for successful coating. Due to the pH-responsive nature of metal-phenol complexation, the modification process is reversible by simple washing in weak acidic water, showing an excellent regeneration ability for water-stable MOFs. Moreover, the colloidal stability of the modified MOFs in the nonpolar solvent allows them to be further organized into 2 dimensional MOF or MOF/polymer monolayers by evaporation-induced interfacial assembly conducted on an air/water interface. Lastly, the easy fusion of a second functional layer onto DPGG-modified MOF cores, enabled a series of MOF-based functional nanoarchitectures, such as MOFs encapsulated within hybrid supported lipid bilayers (so-called protocells), polyhedral core-shell structures, hybrid lipid-modified-plasmonic vesicles and multicomponent supraparticles with target functionalities, to be generated. for a wide range of applications.

  10. Reversible, high molecular weight palladium and platinum coordination polymers based on phosphorus ligands

    NARCIS (Netherlands)

    Paulusse, J.M.J.; Huijbers, J.P.J.; Sijbesma, R.P.

    2005-01-01

    A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for the formation of linear coordination polymers

  11. Reversible, High Molecular Weight Palladium and Platinum Coordination Polymers Based on Phosphorus Ligands

    NARCIS (Netherlands)

    Paulusse, Jos Marie Johannes; Huijbers, Jeroen P.J.; Sijbesma, Rint P.

    2005-01-01

    A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for the formation of linear coordination polymers

  12. Highly effective synthesis of a cobalt(ii) metal-organic coordination polymer by using continuous flow chemistry.

    Science.gov (United States)

    Gong, Chunhua; Zhang, Junyong; Zeng, Xianghua; Xie, Jingli

    2016-12-20

    The coordination polymer [Co 2 L 4 (H 2 O) 2 ]·CH 3 CN·H 2 O (HL = (E)-2-[2-(4-chlorophenyl)vinyl]-8-hydroxyquinoline) has been achieved with 95% yield by using an Asia flow synthesis system (chip reactor). Compared with the conventional batch-type methods such as diffusion, reflux and solvothermal reactions, higher yielding reactions carried out in a flow reactor have demonstrated that this technique is a powerful strategy to obtain coordination compounds.

  13. A polythreaded Ag(I) coordination polymer: A rare three-dimensional Pseudo-polyrotaxana constructed from the same components

    Energy Technology Data Exchange (ETDEWEB)

    Im, Han Su; Lee, Eunji; Lee, Shim Sung; Kim, Tae Ho; Park, Ki Min [Research Institute of Natural Science and Dept. of Chemistry, Gyeongsang National University, Jinju (Korea, Republic of); Moon, Suk Hee [Dept. of Food and Nutrition, Kyungnam College of Information and Technology, Busan (Korea, Republic of)

    2017-01-15

    In supramolecular chemistry, a lot of mechanically poly-threaded coordination polymers, such as polyrotaxanes, based on self-assembly of organic ligands and transition metal ions have attracted great attention over the past two decades because of their fascinating architectures as well as their potential application in material science. Among them, 1D + 2D → 3D pseudo-polyrotaxane constructed by the penetration of 1D coordination polymer chains into 1D channels formed by parallel stacking of 2D porous coordination layers is a quite rare topology. Until now, only a few examples of 1D + 2D → 3D pseudo-polyrotaxanes have been reported.

  14. A polythreaded Ag(I) coordination polymer: A rare three-dimensional Pseudo-polyrotaxana constructed from the same components

    International Nuclear Information System (INIS)

    Im, Han Su; Lee, Eunji; Lee, Shim Sung; Kim, Tae Ho; Park, Ki Min; Moon, Suk Hee

    2017-01-01

    In supramolecular chemistry, a lot of mechanically poly-threaded coordination polymers, such as polyrotaxanes, based on self-assembly of organic ligands and transition metal ions have attracted great attention over the past two decades because of their fascinating architectures as well as their potential application in material science. Among them, 1D + 2D → 3D pseudo-polyrotaxane constructed by the penetration of 1D coordination polymer chains into 1D channels formed by parallel stacking of 2D porous coordination layers is a quite rare topology. Until now, only a few examples of 1D + 2D → 3D pseudo-polyrotaxanes have been reported

  15. Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers

    Directory of Open Access Journals (Sweden)

    James S. Wright

    2015-03-01

    Full Text Available A family of one-dimensional coordination polymers, [Ag4(O2C(CF22CF34(phenazine2(arenen]·m(arene, 1 (arene = toluene or xylene, have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF22CF34(phenazine2], 2a and/or 2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF22CF34(phenazine2(toluene]·2(toluene, a phase containing toluene coordinated to Ag(I in an unusual μ:η1,η1 manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations.

  16. Homo- and heterodinuclear coordination polymers based on a tritopic cyclam bis-terpyridine unit: Structure and rheological properties

    Energy Technology Data Exchange (ETDEWEB)

    Qu, Li; Fan, Jiangxia; Ren, Yong; Xiong, Kun [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010 (China); Yan, Minhao, E-mail: yanminhao@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010 (China); Tuo, Xianguo, E-mail: tuoxg@swust.edu.cn [Laboratory of National Defense for Radioactive Waste and Environmental Security, Southwest University of Science and Technology, Mianyang 621010 (China); Terech, Pierre [SPrAM, UMR CEA/CNRS/UJF-Grenoble 1, INAC, Grenoble F-38054 (France); Royal, Guy [Université Joseph Fourier Grenoble I, Département de Chimie Moléculaire, UMR CNRS-5250, Institut de Chimie Moléculaire de Grenoble, FR CNRS-2607, BP 53, 38041 Grenoble Cedex 9 (France)

    2015-03-01

    An innovative coordination polymer based on a tritopic ligand having the bis-terpyridine cyclam (CHTT) unit is explored. Homo- or heteronuclear 1D coordination polymers can be formed with bivalent metal ions such as Co(II) and Ni(II) in solvent DMF. Creep-recovery curves of the (Co{sup II}){sub 2}CHTT gels formed from 1D coordination polymers were analyzed with the Burgers model and demonstrated an original self-healing property, unusual in the class of molecular gels. The influence of the metal type was studied through the structural features using small-angle neutron scattering (SANS) experiments. In gels, the corresponding network involves genuine fibers (R ≈ 35 Å), bundles of these fibers and also a fraction of finite size aggregates (rods with aspect ratio f ≈ 3–5). We found that the distribution of these latter structural components is sensitive to the metal ions type. Such tritopic 1D coordination polymers exhibit a range of original structural features and a facile control of the developed structures in solutions and gels by tuning their thermodynamic parameters. The versatility associated to the intrinsic dynamic ability of the systems should pave the way to original properties for molecular devices. - Graphical abstract: A tritopic ligand with a bis-terpyridine cyclam (CHTT) unit can form homo- and heterobinuclear coordination polymers with bivalent metal ions in DMF. Gels exhibit a remarkable self-healing property while structures of solutions and gels are studied by small-angle neutron scattering. - Highlights: • Homo- and heteronuclear coordination polymers based on innovative tritopic ligand. • The gels formed from the coordination polymers demonstrated self-healing property. • Influence of the metal type was studied through the structural properties by SANS. • Versatility of the singular system present original properties for molecular device.

  17. Synthesis of f metal coordination polymers: properties and conversion into inorganic solids

    International Nuclear Information System (INIS)

    Demars, Thomas

    2012-01-01

    Coordination polymers (CP) are of great academic and industrial interest due to flexible structure and composition and offer prospects for original chemical (catalysis, soft-hard materials conversion..) and physical properties (magnetism, optics..). The major interest of these studies is to check the transfer of the structure, meso-structure and composition from the CP to the ceramic via a thermal treatment. In this context, this thesis describes studies on conversion of coordination polymers obtained by self-assembly of 4f and 5f metal ions with 2,5-dihydroxy-1,4-benzoquinone (DHBQ). Aqueous and anhydrous synthetic ways were developed, which yielded different kinds of CPs (4f, 4f-4f, 4f-5f); solid solutions were obtained with the mixed compounds. The products were characterized and their behaviour under thermal treatment was studied. The main results show that the DHBQ-based precursors obtained by aqueous way have a micrometric meso-structure, formed by the assembly of micro-crystalline subunits which all posses the same crystallographic structure. The study of the assembly of the meso-structure allowed controlling the morphology of the elementary grain (cylinder, cube, disk...) with very good size distribution. The implementation of anhydrous systems in a controlled atmosphere allowed yielded a wider range of micro-structural parameters (surface area, porosity...). For all CP-type compounds, the thermal conversion to ceramic has barely altered the morphology of the materials. The microstructural aspects could be controlled via the method of synthesis. (author) [fr

  18. Understanding the origins of metal-organic framework/polymer compatibility.

    Science.gov (United States)

    Semino, R; Moreton, J C; Ramsahye, N A; Cohen, S M; Maurin, G

    2018-01-14

    The microscopic interfacial structures for a series of metal-organic framework/polymer composites consisting of the Zr-based UiO-66 coupled with different polymers are systematically explored by applying a computational methodology that integrates density functional theory calculations and force field-based molecular dynamics simulations. These predictions are correlated with experimental findings to unravel the structure-compatibility relationship of the MOF/polymer pairs. The relative contributions of the intermolecular MOF/polymer interactions and the flexibility/rigidity of the polymer with respect to the microscopic structure of the interface are rationalized, and their impact on the compatibility of the two components in the resulting composite is discussed. The most compatible pairs among those investigated involve more flexible polymers, i.e. polyvinylidene fluoride (PVDF) and polyethylene glycol (PEG). These polymers exhibit an enhanced contact surface, due to a better adaptation of their configuration to the MOF surface. In these cases, the irregularities at the MOF surface are filled by the polymer, and even some penetration of the terminal groups of the polymer into the pores of the MOF can be observed. As a result, the affinity between the MOF and the polymer is very high; however, the pores of the MOF may be sterically blocked due to the strong MOF/polymer interactions, as evidenced by UiO-66/PEG composites. In contrast, composites involving polymers that exhibit higher rigidity, such as the polymer of intrinsic microporosity-1 (PIM-1) or polystyrene (PS), present interfacial microvoids that contribute to a decrease in the contact surface between the two components, thus reducing the MOF/polymer affinity.

  19. An Unusual Pseudo-Coordination Polymer of Dithia-18-Crown-6 with Heavy Metal

    International Nuclear Information System (INIS)

    Kang, Gyeongchan; Park, Inhyeok; Lee, Shimsung

    2012-01-01

    The assembly reactions of 1,10-dithia-18-crown-6 (L) with mercury(II) and/or cadmium(II) salts provide metallosupramolecules with the unusual arrangement due to the formation of the mercury(II) halides (chloride and iodide) clusters which locate outside the macrocyclic cavity. In the reaction with mercury(II) chloride, we were able to isolate the 1D pseudo-coordination polymer 1 which resembles the ivy leaves. In 1, it is considered that the 1D zigzag array of Hg-Cl-Hg-Cl chain as a leaf-stem and the macrocyclic complexes as leaves. While, from the reaction of mercury(II) iodide and cadmium(II) iodide mixture, the discrete complex 2 with two macrocyclic cadmium(II) complex cation parts and one mercury(II) iodide cluster anion part was isolated. In both cases, each metal center is seven-coordinate, being bound to all the donors of L, with its seventh site being occupied by one halide atom, adopting a distorted monocapped trigonal prism

  20. An Unusual Pseudo-Coordination Polymer of Dithia-18-Crown-6 with Heavy Metal

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Gyeongchan [Yeosu High School, Yeosu (Korea, Republic of); Park, Inhyeok; Lee, Shimsung [Gyeongsang National Univ., Jinju (Korea, Republic of)

    2012-11-15

    The assembly reactions of 1,10-dithia-18-crown-6 (L) with mercury(II) and/or cadmium(II) salts provide metallosupramolecules with the unusual arrangement due to the formation of the mercury(II) halides (chloride and iodide) clusters which locate outside the macrocyclic cavity. In the reaction with mercury(II) chloride, we were able to isolate the 1D pseudo-coordination polymer 1 which resembles the ivy leaves. In 1, it is considered that the 1D zigzag array of Hg-Cl-Hg-Cl chain as a leaf-stem and the macrocyclic complexes as leaves. While, from the reaction of mercury(II) iodide and cadmium(II) iodide mixture, the discrete complex 2 with two macrocyclic cadmium(II) complex cation parts and one mercury(II) iodide cluster anion part was isolated. In both cases, each metal center is seven-coordinate, being bound to all the donors of L, with its seventh site being occupied by one halide atom, adopting a distorted monocapped trigonal prism.

  1. Mussel-inspired histidine-based transient network metal coordination hydrogels

    Science.gov (United States)

    Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

    2013-01-01

    Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

  2. Titanium coordination compounds: from discrete metal complexes to metal–organic frameworks

    KAUST Repository

    Assi, Hala

    2017-05-24

    Owing to their promise in photocatalysis and optoelectronics, titanium based metal–organic frameworks (MOFs) are one of the most appealing classes of MOFs reported to date. Nevertheless, Ti-MOFs are still very scarce because of their challenging synthesis associated with a poor degree of control of their chemistry and crystallization. This review aims at giving an overview of the recent progress in this field focusing on the most relevant existing titanium coordination compounds as well as their promising photoredox properties. Not only Ti-MOFs but also Ti-oxo-clusters will be discussed and particular interest will be dedicated to highlight the different successful synthetic strategies allowing to overcome the still “unpredictable” reactivity of titanium ions, particularly to afford crystalline porous coordination polymers.

  3. Molecularly Imprinted Polymer/Metal Organic Framework Based Chemical Sensors

    Directory of Open Access Journals (Sweden)

    Zhenzhong Guo

    2016-10-01

    Full Text Available The present review describes recent advances in the concept of molecular imprinting using metal organic frameworks (MOF for development of chemical sensors. Two main strategies regarding the fabrication, performance and applications of recent sensors based on molecularly imprinted polymers associated with MOF are presented: molecularly imprinted MOF films and molecularly imprinted core-shell nanoparticles using MOF as core. The associated transduction modes are also discussed. A brief conclusion and future expectations are described herein.

  4. Strategies, linkers and coordination polymers for high-performance sorbents

    Science.gov (United States)

    Matzger, Adam J.; Wong-Foy, Antek G.; Lebel, Oliver

    2015-09-15

    A linking ligand compound includes three bidentate chemical moieties distributed about a central chemical moiety. Another linking ligand compound includes a bidentate linking ligand and a monodentate chemical moiety. Coordination polymers include a plurality of metal clusters linked together by residues of the linking ligand compounds.

  5. Structures and Spectroscopy Studies of Two M(II-Phosphonate Coordination Polymers Based on Alkaline Earth Metals (M = Ba, Mg

    Directory of Open Access Journals (Sweden)

    Kui-Rong Ma

    2013-01-01

    Full Text Available The two examples of alkaline-earth M(II-phosphonate coordination polymers, [Ba2(L(H2O9]·3H2O (1 and [Mg1.5(H2O9]·(L-H21.5·6H2O (2 (H4L = H2O3PCH2N(C4H8NCH2PO3H2, N,N′-piperazinebis(methylenephosphonic acid, (L-H2 = O3PH2CHN(C4H8NHCH2PO3 have been hydrothermally synthesized and characterized by elemental analysis, FT-IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Compound 1 possesses a 2D inorganic-organic alternate arrangement layer structure built from 1D inorganic chains through the piperazine bridge, in which the ligand L−4 shows two types of coordination modes reported rarely at the same time. In 1, both crystallographic distinct Ba(1 and Ba(2 ions adopt 8-coordination two caps and 9-coordination three caps triangular prism geometry structures, respectively. Compound 2 possesses a zero-dimensional mononuclear structure with two crystallographic distinct Mg(II ions. Free metal cations   [MgO6]n2+ and uncoordinated anions (L-H2n2- are joined together by static electric force. Results of photoluminescent measurement indicate three main emission bands centered at 300 nm, 378.5 nm, and 433 nm for 1 and 302 nm, 378 nm, and 434.5 nm for 2 (λex=235 nm, respectively. The high energy emissions could be derived from the intraligand π∗-n transition stations of H4L (310 nm and 382 nm, λex=235 nm, while the low energy emission (>400 nm of 1-2 may be due to the coordination effect with metal(II ions.

  6. Meso-Helical Ag(I) Coordination Polymer Based on a Pyridylimidazole Ligand

    International Nuclear Information System (INIS)

    Kang, Youngjin; Kim, Jinho; Lee, Eunji; Park, Ki-Min; Moon, Suk-Hee

    2016-01-01

    In the fields of material science and metallosupramolecular chemistry, coordination polymers with various helical types have been extensively explored because of their charming structures, and their potential applications in material chemistry. Among them, meso-helical coordination polymers consisting of achiral 1D strands, which are generally constructed by a crystallographic inversion symmetry, are relatively rare. The coordination polymer 1 exhibits a rare one-dimensional meso-helical chain topology constructed by its internal inversion symmetry. The skeleton of this meso-helical chain is preserved up to 300°C. The complexation of silver(I) ion to the free pyim ligand give rise to the enhanced photoluminescence intensity and slightly blue-shifted emission maximum, originated from intraligand (IL) π[BOND]π* transition and rigidochromic effect. Further exploration of complexation of this ligand with other transition metal ions is currently in progress

  7. Bismuth-, Tin-, and Lead-Containing Metal-Organic Materials: Synthesis, Structure, Photoluminescence, Second Harmonic Generation, and Ferroelectric Properties

    Science.gov (United States)

    Wibowo, Arief Cahyo

    Metal-Organic Materials (MOMs) contain metal moieties and organic ligands that combine to form discrete (e.g. metal-organic polyhedra, spheres or nanoballs, metal-organic polygons) or polymeric structures with one-, two-, or three-dimensional periodicities that can exhibit a variety of properties resulting from the presence of the metal moieties and/or ligand connectors in the structure. To date, MOMs with a range of functional attributes have been prepared, including record-breaking porosity, catalytic properties, molecular magnetism, chemical separations and sensing ability, luminescence and NLO properties, multiferroic, ferroelectric, and switchable molecular dielectric properties. We are interested in synthesizing non-centrosymmetric MOM single crystals possessing one of the ten polar space groups required for non-linear optical properties (such as second harmonic generation) and ferroelectric applications. This thesis is divided into two main parts: materials with optical properties, such as photoluminescence and materials for targeted applications such as second harmonic generation and ferroelectric properties. This thesis starts with an introduction describing material having centrosymmetric, non-polar space groups, single crystals structures and their photoluminescence properties. These crystals exhibit very interesting and rare structures as well as interesting photoluminescence properties. Chapters 2-5 of this thesis focus on photoluminescent properties of new MOMs, and detail the exploratory research involving the comparatively rare bismuth, lead, and tin coordination polymers. Specifically, the formation of single white-light emitting phosphors based on the combination of bismuth or lead with pyridine-2,5-dicarboxylate is discussed (Chapter 2). The observation of a new Bi2O2 layer and a new Bi4O 3 chain in bismuth terephthalate-based coordination polymers is presented in Chapter 3, while the formation of diverse structures of tin-based coordination

  8. Nanorods of a new metal-biomolecule coordination polymer showing novel bidirectional electrocatalytic activity and excellent performance in electrochemical sensing.

    Science.gov (United States)

    Yang, Jiao; Zhou, Bo; Yao, Jie; Jiang, Xiao-Qing

    2015-05-15

    Metal organic coordination polymers (CPs), as most attractive multifunctional materials, have been studied extensively in many fields. However, metal-biomolecule CPs and CPs' electrochemical properties and applications were studied much less. We focus on this topic aiming at electrochemical biosensors with excellent performance and high biocompatibility. A new nanoscaled metal-biomolecule CP, Mn-tyr, containing manganese and tyrosine, was synthesized hydrothermally and characterized by various techniques, including XRD, TEM, EDS, EDX mapping, elemental analysis, XPS, and IR. Electrode modified with Mn-tyr showed novel bidirectional electrocatalytic ability toward both reduction and oxidation of H2O2, which might be due to Mn. With the assistance of CNTs, the sensing performance of Mn-tyr/CNTs/GCE was improved to a much higher level, with high sensitivity of 543 mA mol(-1) L cm(-2) in linear range of 1.00×10(-6)-1.02×10(-4) mol L(-1), and detection limit of 3.8×10(-7) mol L(-1). Mn-tyr/CNTs/GCE also showed fast response, high selectivity, high steadiness and reproducibility. The excellent performance implies that the metal-biomolecule CPs are promising candidates for using in enzyme-free electrochemical biosensing. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

    International Nuclear Information System (INIS)

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-Li

    2013-01-01

    Three new metal-organic coordination polymers [Co(4-bbc) 2 (bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H 2 O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H 2 pdc=3,5-pyridinedicarboxylic acid, 1,4-H 2 ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co II ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3 2 ·4·5·6 2 ·7 4 ) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphical abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated

  10. Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene ligand

    Science.gov (United States)

    Shao, Min; Li, Ming-Xing; Lu, Li-Ruo; Zhang, Heng-Hua

    2016-09-01

    Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu3(CN)3(tib)]n (1), [Cu4(CN)4(tib)]n (2), and [Cu2(CN)2(tib)]n (3), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ2-cyanides and a μ3-cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250-350 °C. Complexes 1-3 show similar orange emission band at 602 nm originating from LMCT mechanism.

  11. Coordination Polymer Gels by Electron Beam

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ji Ha; Cho, Young Je; Jung, Jong Hwa [Gyeongsang National Univ., Jinju (Korea, Republic of)

    2011-07-01

    Hydrogenation of a pyridine derivative possessing tetrazole moieties as end groups, without long alkyl chain groups, results in the formation of a Mg(NO{sub 3}){sub 2} coordination polymer gel. The polymer exhibits a strong fluorescence enhancement upon gel formation. 1 can also be gloated with a variety of magnesium anions such as SO{sub 4}{sup 2-}, NO{sub 3}{sup -}, Cl{sup -}, Br{sup -} and I{sup -}, indicating that the coordination polymer gel formation of 1 does not strongly depends on anions. The Seam and ABM images of Mg{sup 2+} coordination polymer gel 1 display a flabbier network with several micrometers long, widths in the range 60-70 nm and thicknesses of about 3 nm. In addition, photophysical studies show that the hydrogel exhibits a typical {pi}-{pi} transition and gives rise to high fluorescence behavior. The coordination polymer hydrogel exhibits viscoelastic behavior as evidenced from the rheological studies.

  12. A two-dimensional zinc(II) coordination polymer based on mixed dimethyl succinate and bipyridine ligands: synthesis, structure, thermostability and luminescence properties.

    Science.gov (United States)

    Liu, Yang; Feng, Yong Lan; Fu, Wei Wei

    2016-04-01

    From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self-assembly process. Multicarboxylate ligands are of particular interest due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of dicarboxylate-based coordination polymers of transition metals has been developed through the grafting of N-containing organic linkers into carboxylate-bridged transition metal networks. A new luminescent two-dimensional zinc(II) coordination polymer containing bridging 2,2-dimethylsuccinate and 4,4'-bipyridine ligands, namely poly[[aqua(μ2-4,4'-bipyridine-κ(2)N:N')bis(μ3-2,2-dimethylbutanedioato)-κ(4)O(1),O(1'):O(4):O(4');κ(5)O(1):O(1),O(4):O(4),O(4')-dizinc(II)] dihydrate], {[Zn2(C6H8O4)2(C10H8N2)(H2O)]·2H2O}n, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2-dimethylsuccinate ligands link linear tetranuclear Zn(II) subunits into one-dimensional chains along the c axis. 4,4'-Bipyridine acts as a tethering ligand expanding these one-dimensional chains into a two-dimensional layered structure. Hydrogen-bonding interactions between the water molecules (both coordinated and free) and carboxylate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic-organic photoactive materials.

  13. Two Zn coordination polymers with meso-helical chains based on mononuclear or dinuclear cluster units

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Ling, E-mail: qinling@hfut.edu.cn [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China); Jiangsu Engineering Technology Research Center of Environmental Cleaning Materials (CEM), School of Environmental Sciences and Engineering, Nanjing University of Information Science and Technology (China); State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (China); Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China)

    2016-07-15

    Two zinc coordination polymers {[Zn_2(TPPBDA)(oba)_2]·DMF·1.5H_2O}{sub n} (1), {[Zn(TPPBDA)_1_/_2(tpdc)]·DMF}{sub n} (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymers have been investigated in detail. - Graphical abstract: Two zinc coordination polymers have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. In addition, the photoluminescent properties for TPPBDA ligand under different status and coordination polymers have been investigated in detail. Display Omitted - Highlights: • Two Zn coordination polymers based on mononuclear or dinuclear cluster units have been synthesized. • Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. • Compound 2 is a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. • The photoluminescent properties for TPPBDA with different state and two coordination polymers have been investigated.

  14. Metal-containing radiation-sensitive polymers

    International Nuclear Information System (INIS)

    Lee, A.Y.

    1986-01-01

    The copolymers of methyl methacrylate with alkali metal salts (Na, K, and Cs) of methacrylic acid have been prepared by saponification K, and Cs) of methylacrylic acid have been prepared by saponification of the homopolymer poly(methyl methacrylate), PMMA. Low degrees of hydrolysis have been achieved by a heterogeneous system, and from the infrared spectra it has been confirmed that the ester groups of the methyl methacrylates are directly converted to the metal salts of methacrylic acid. These ionomers exhibit pseudo high molecular weights in gel permeation chromatogram, but no appreciable increase in intrinsic viscosities is observed in comparison to PMMA. The coordinated inorganic polymers poly[(dithio-2,2'-diacetato)bis(dimethylsulfoxide)dioxouranium(VI)] and poly[{methylenebis(thio)-2,2'-bis(acetato)}bis(dimethylsulfoxide)dioxouranium(VI)]have been synthesized in dimethyl sulfoxide solution with about 90% yield. The degree of polymerization and the number of average molecular weights of these polymers have been assessed by high resolution nuclear magnetic resonance, with which the acetato end group to the bridging ligand group ratios have been determined. The polymers bridging ligand group ratios have been determined. The polymers have been characterized by employing various techniques: infrared spectra, thermal gravimetric analysis, 13 C solid state nuclear magnetic resonance, and gel permeation chromatography. The prepared polymer samples have been subjected to various doses of 137 Cs gamma radiation under which the polymers predominantly undergo chain scission. The radiation sensitivities of the polymers are assessed by G values which are obtained from gel permeation chromatograms. These uranyl polymers exhibit unusually high G values

  15. Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

    International Nuclear Information System (INIS)

    Cui, Zhongping; Qi, Ji; Xu, Xinxin; Liu, Lu; Wang, Yi

    2013-01-01

    To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer composite material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future

  16. New 3-D coordination polymers based on semi-rigid V-shape tetracarboxylates

    International Nuclear Information System (INIS)

    Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning; Yu, Jie-Hui; Zhang, Ping; Xu, Ji-Qing

    2015-01-01

    Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N′-donor ligands yielded three new coordination polymers as [Cu 4 (fph) 2 (bpe) 3 (H 2 O) 2 ]·2H 2 O (fph=4,4′-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co 2 (fph)(bpa) 2 (H 2 O) 2 ]·3H 2 O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H 2 O)(H 2 oph)(bpa)] (oph=4,4′-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu 2+ ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co 2+ ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1–3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors. - Graphical abstract: Structures of three semi-rigid V-shape tetracarboxylate-based coordination polymers were reported, and their magnetic properties were investigated. - Highlights: • Structures of three tetracarboxylate-based coordination polymers were reported. • Role of organic bases in metal–tetracarboxylate compounds was discussed. • Characters of V-shape and semi-rigidity for tetracarboxylate play a key role in crystal growth. • Their magnetic properties were investigated

  17. New 3-D coordination polymers based on semi-rigid V-shape tetracarboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Qianjin Road 2699, Changchun 130012, Jilin (China); Yu, Jie-Hui, E-mail: jhyu@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Qianjin Road 2699, Changchun 130012, Jilin (China); Zhang, Ping, E-mail: zhangping@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); Xu, Ji-Qing [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Qianjin Road 2699, Changchun 130012, Jilin (China)

    2015-03-15

    Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N′-donor ligands yielded three new coordination polymers as [Cu{sub 4}(fph){sub 2}(bpe){sub 3}(H{sub 2}O){sub 2}]·2H{sub 2}O (fph=4,4′-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co{sub 2}(fph)(bpa){sub 2}(H{sub 2}O){sub 2}]·3H{sub 2}O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H{sub 2}O)(H{sub 2}oph)(bpa)] (oph=4,4′-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu{sup 2+} ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co{sup 2+} ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1–3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors. - Graphical abstract: Structures of three semi-rigid V-shape tetracarboxylate-based coordination polymers were reported, and their magnetic properties were investigated. - Highlights: • Structures of three tetracarboxylate-based coordination polymers were reported. • Role of organic bases in metal–tetracarboxylate compounds was discussed. • Characters of V-shape and semi-rigidity for tetracarboxylate play a key role in crystal growth. • Their magnetic properties were investigated.

  18. Crystal Structures and Physical Properties of Ag(I) Coordination Polymers with Unsymmetrical Dipyridyl Ligand

    International Nuclear Information System (INIS)

    Lee, Eunji; Ryu, Hyunsoo; Park, Kimin

    2013-01-01

    Three Ag(I) coordination polymers with the formula [Ag(L)]·(X)·(DMSO) n (X = ClO 4 (1), BF 4 (2), and PF 6 (3), and L = dipyridyl ligand) were prepared and characterized fully their structures. All three compounds are isostructures and stable 2-D honeycomb type coordination polymers, in which 1-D zigzag chains with -(Ag-L)- motif are linked by the argentophilic interactions and the π···π stacking interactions between pyridine rings. The investigation on photophysical properties of all compounds shows that the nature of emission can be attributed to the metal-to-ligand charge transfer as well as the formation of the polymeric structures with restriction of the flexibility of the free ligand. Based on the present solid state results, further investigation on the development and characterization of new coordination polymers using flexible unsymmetrical ligand is in progress. During last two decades, silver coordination polymers based on dipyridyl type ligands have attracted particular interest because of the various intriguing architectures caused by a variety of coordination geometry of Ag(I) ion as well as their potential applications as functional materials

  19. Thin films of metal-organic compounds and metal nanoparticle

    Indian Academy of Sciences (India)

    Thin films of metal-organic compounds and metal nanoparticle-embedded polymers for nonlinear optical applications. S Philip Anthony Shatabdi Porel D ... Thin films based on two very different metal-organic systems are developed and some nonlinear optical applications are explored. A family of zinc complexes which ...

  20. Polymer complexes.. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

    Science.gov (United States)

    El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.

    2003-02-01

    The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [( 11)+( 12)] in the paper and in mononuclear polymer complexes ( 1)-( 5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX 2 and KPtCl 4 in the presence of N-heterocyclic base consisting of polymer complexes ( 9)+( 10), and in monouclear compounds ( 6)-( 8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds ( 13)+( 14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

  1. Synthesis and Molecular Structures of Two [1,4-bis(3-pyridyl)-2,3-diazo-1,3-butadiene]-dichloro-Zn(II) Coordination Polymers

    OpenAIRE

    Lee, Gene-Hsiang; Wang, Hsin-Ta

    2006-01-01

    Two novel coordination polymers with 3D metal-organic frameworks (MOFs) have been synthesized by reacting 1,4-bis(3-pyridyl)-2,3-diazo-1,3-butadiene (L) with zinc dichloride. Both compounds have the same repeating unit consisting of a distorted tetrahedral Zn(II) center coordinated by two chlorides and two pyridyl nitrogen atoms of two bridging bismonodentate L ligands, however, different structural conformations have been found, one forming a helical chain and the other producing a square-wa...

  2. Crystal structures of coordination polymers from CaI2 and proline

    Directory of Open Access Journals (Sweden)

    Kevin Lamberts

    2015-06-01

    Full Text Available Completing our reports concerning the reaction products from calcium halides and the amino acid proline, two different solids were found for the reaction of l- and dl-proline with CaI2. The enantiopure amino acid yields the one-dimensional coordination polymer catena-poly[[aqua-μ3-l-proline-tetra-μ2-l-proline-dicalcium] tetraiodide 1.7-hydrate], {[Ca2(C5H9NO25(H2O]I4·1.7H2O}n, (1, with two independent Ca2+ cations in characteristic seven- and eightfold coordination. Five symmetry-independent zwitterionic l-proline molecules bridge the metal sites into a cationic polymer. Racemic proline forms with Ca2+ cations heterochiral chains of the one-dimensional polymer catena-poly[[diaquadi-μ2-dl-proline-calcium] diiodide], {[Ca(C5H9NO22(H2O2]I2}n, (2. The centrosymmetric structure is built by one Ca2+ cation that is bridged towards its symmetry equivalents by two zwitterionic proline molecules. In both structures, the iodide ions remain non-coordinating and hydrogen bonds are formed between these counter-anions, the amino groups, coordinating and co-crystallized water molecules. While the overall composition of (1 and (2 is in line with other structures from calcium halides and amino acids, the diversity of the carboxylate coordination geometry is quite surprising.

  3. Coordination polymers: trapping of radionuclides and chemistry of tetravalent actinides (Th, U) carboxylates

    International Nuclear Information System (INIS)

    Falaise, Clement

    2014-01-01

    The use of nuclear energy obviously raises the question of the presence of radionuclides in the environment. Currently, their mitigation is a major issue associated with nuclear chemistry. This thesis focuses on both the trapping of radionuclides by porous solids called Metal-Organic Frameworks (MOF) and the crystal chemistry of the carboxylate of tetravalent actinides (AnIV). The academic knowledge of the reactivity of carboxylate of AnIV could help the understanding of actinides speciation in environment. We focused on the sequestration of iodine by aluminum based MOF. The functionalization (electron-donor group) of the MOF drastically enhances the iodine capture capacity. The removal of light actinides (Th and U) from aqueous solution was also investigated as well as the stability of (Al)-MOF under γ radiation. More than twenty coordination polymers based on tetravalent actinides have been synthesized and characterized by single crystal X-ray diffraction. The use of controlled hydrolysis promotes the formation of coordination polymers exhibiting polynuclear cluster ([U 4 ], [Th 6 ], [U 6 ] and [U 38 ]). In order to understand the formation of the largest cluster, the ex-situ study of the solvo-thermal synthesis of compound {U 38 } has also been investigated. (author)

  4. Mechanical properties of metal-organic frameworks: An indentation study on epitaxial thin films

    Science.gov (United States)

    Bundschuh, S.; Kraft, O.; Arslan, H. K.; Gliemann, H.; Weidler, P. G.; Wöll, C.

    2012-09-01

    We have determined the hardness and Young's modulus of a highly porous metal-organic framework (MOF) using a standard nanoindentation technique. Despite the very low density of these films, 1.22 g cm-3, Young's modulus reaches values of almost 10 GPa for HKUST-1, demonstrating that this porous coordination polymer is substantially stiffer than normal polymers. This progress in characterizing mechanical properties of MOFs has been made possible by the use of high quality, oriented thin films grown using liquid phase epitaxy on modified Au substrates.

  5. White-emissive tandem-type hybrid organic/polymer diodes with (0.33, 0.33) chromaticity coordinates.

    Science.gov (United States)

    Guo, Tzung-Fang; Wen, Ten-Chin; Huang, Yi-Shun; Lin, Ming-Wei; Tsou, Chuan-Cheng; Chung, Chia-Tin

    2009-11-09

    This study reports fabrication of white-emissive, tandem-type, hybrid organic/polymer light-emitting diodes (O/PLED). The tandem devices are made by stacking a blue-emissive OLED on a yellow-emissive phenyl-substituted poly(para-phenylene vinylene) copolymer-based PLED and applying an organic oxide/Al/molybdenum oxide (MoO(3)) complex structure as a connecting structure or charge-generation layer (CGL). The organic oxide/Al/MoO(3) CGL functions as an effective junction interface for the transport and injection of opposite charge carriers through the stacked configuration. The electroluminescence (EL) spectra of the tandem-type devices can be tuned by varying the intensity of the emission in each emissive component to yield the visible-range spectra from 400 to 750 nm, with Commission Internationale de l'Eclairage chromaticity coordinates of (0.33, 0.33) and a high color rendering capacity as used for illumination. The EL spectra also exhibit good color stability under various bias conditions. The tandem-type device of emission with chromaticity coordinates, (0.30, 0.31), has maximum brightness and luminous efficiency over 25,000 cd/m(2) and approximately 4.2 cd/A, respectively.

  6. Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

    KAUST Repository

    Barankova, Eva

    2017-06-01

    Since the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good chemical and thermal stability, recent commercial availability and attractive pore size. The aim of this work is to develop convenient methods for growing ZIF thin layers on polymer supports to obtain defect-free ZIF membranes with good gas separation properties. We present new approaches for ZIF membranes preparation on polymers. We introduce zinc oxide nanoparticles in the support as a secondary metal source for ZIF-8 growth. Initially the ZnO particles were incorporated into the polymer matrix and later on the surface of the polymer by magnetron sputtering. In both cases, the ZnO facilitated to create more nucleation opportunities and improved the ZIF-8 growth compared to the synthesis without using ZnO. By employing the secondary seeded growth method, we were able to obtain thin (900 nm) ZIF-8 layer with good gas separation performance. Next, we propose a metal-chelating polymer as a suitable support for growing ZIF layers. Defect-free ZIF-8 films with a thickness of 600 nm could be obtained by a contra-diffusion method. ZIF-8 membranes were tested for permeation of hydrogen and hydrocarbons, and one of the highest selectivities reported so far for hydrogen/propane, and propylene/propane was obtained. Another promising method to facilitate the growth of MOFs on polymeric supports is the chemical functionalization of the support surface with functional groups, which can complex metal ions and which can covalently bond the MOF crystals. We functionalized the surface of a common porous polymeric membrane with amine groups, which took part in the reaction to form ZIF-8 nanocrystals. We observed an enhancement in adhesion between the ZIF layer and the support. The effect of parameters of the contra-diffusion experiment

  7. Supramolecular Coordination Assemblies Constructed From Multifunctional Azole-Containing Carboxylic Acids

    Directory of Open Access Journals (Sweden)

    Yuheng Deng

    2010-05-01

    Full Text Available This paper provides a brief review of recent progress in the field of metal coordination polymers assembled from azole-containing carboxylic acids and gives a diagrammatic summary of the diversity of topological structures in the resulting infinite metal-organic coordination networks (MOCNs. Azole-containing carboxylic acids are a favorable kind of multifunctional ligand to construct various metal complexes with isolated complexes and one, two and three dimensional structures, whose isolated complexes are not the focus of this review. An insight into the topology patterns of the infinite coordination polymers is provided. Analyzed topologies are compared with documented topologies and catalogued by the nature of nodes and connectivity pattern. New topologies which are not available from current topology databases are described and demonstrated graphically.

  8. Semi-metallic polymers

    DEFF Research Database (Denmark)

    Bubnova, Olga; Khan, Zia Ullah; Wang, Hui

    2014-01-01

    Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report...... that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being...... a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics....

  9. Coordination Polymers of N, Nʼ-di-(8-Hydroxyquinolinolyl- 5-methyl-N, N-diethyl-1,3-propane diamine (QEPD

    Directory of Open Access Journals (Sweden)

    Asha D. Patel

    2010-01-01

    Full Text Available Coordination polymers containing a novel bis(oxine bidentate ligand, namely N,Nʼ-di(8-hydroxyquinolinolyl-5-methyl-N,Nʼ-diethyl-1,3-propane diamine (QEPD have been prepared with the metal ions Zn(II, Cu(II, Ni(II, Co(II and Mn(II. The novel bis-(bidentate ligand was synthesized by condensation of 5-chloromethyl-8-hydroxyquinoline hydrochloride with N,Nʼ-diethyl-1,2- propane diamine in the presence of a base catalyses. All of these coordination polymers and the parent ligand were characterized by elemental analyses, IR spectral and diffuse reflectance spectral studies. The thermal stability and number- average molecular weights (Mn¯ of all of the coordination polymers were determined by thermogravimetric analyses and non-aqueous conductometric titrations, respectively. In addition, all of the coordination polymers have been characterized by their magnetic susceptibilities.

  10. Syntheses, crystal structures, and properties of new metal-5-bromonicotinate coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenjie [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052 (China); Li, Guoting [Department of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011 (China); Lv, Lulu; Zhao, Hong [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052 (China); Wu, Benlai, E-mail: wbl@zzu.edu.cn [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052 (China)

    2015-05-15

    Four metal–5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (1), [Ni(Brnic){sub 2}]{sub n} (2), [Ni(Brnic)(bpy)(H{sub 2}O){sub 2}]{sub n}·n(Brnic)·4.5nH{sub 2}O (3), and [Co{sub 2}(Brnic){sub 3}(bpy){sub 2}(OH)]{sub n}·nH{sub 2}O (4) have been synthesized and structurally characterized (bpy=4,4′-bipyridine). Complex 1 has corrugated (4,4) sheets formed by μ-Brnic ligands and planar nodes Fe(II). As for 2–4, they all built up from Brnic-bridged dinuclear subunits, but have very different structure features. Complex 2 is a twin-like polymer with (4,4) layers formed by twin paddle-wheel [Ni{sub 2}(Brnic){sub 4}] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni{sub 2}(Brnic){sub 2}] and trigons [Co{sub 2}(Brnic){sub 3}(OH)], 6{sup 3}-topological cationic layers with nanosized grids of 3 and chiral ladder-type double chains of 4 formed, respectively. Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules 1–4. The thermostabilities of all compounds have been discussed in detail. Moreover, the magnetic investigations of 2 and 4 indicate that there exist antiferromagnetic interactions in the paddle-wheel [Ni{sub 2}(Brnic){sub 4}] and trigon [Co{sub 2}(Brnic){sub 3}(OH)] cores, respectively. - Highlights: • Four novel metal–5-bromonicotinate coordination polymers have been synthesized. • Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules. • Antiferromagnetic interactions in nickel(II) paddle-wheel and cobalt(II) trigon cores were observed.

  11. Advances in Solid-State Transformations of Coordination Bonds: From the Ball Mill to the Aging Chamber

    Directory of Open Access Journals (Sweden)

    Cristina Mottillo

    2017-01-01

    Full Text Available Controlling the formation of coordination bonds is pivotal to the development of a plethora of functional metal-organic materials, ranging from coordination polymers, metal-organic frameworks (MOFs to metallodrugs. The interest in and commercialization of such materials has created a need for more efficient, environmentally-friendly routes for making coordination bonds. Solid-state coordination chemistry is a versatile greener alternative to conventional synthesis, offering quantitative yields, enhanced stoichiometric and topological selectivity, access to a wider range of precursors, as well as to molecules and materials not readily accessible in solution or solvothermally. With a focus on mechanochemical, thermochemical and “accelerated aging” approaches to coordination polymers, including pharmaceutically-relevant materials and microporous MOFs, this review highlights the recent advances in solid-state coordination chemistry and techniques for understanding the underlying reaction mechanisms.

  12. Two novel metal-organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

    Science.gov (United States)

    Niu, Qing-Jun; Zheng, Yue-Qing; Zhou, Lin-Xia; Zhu, Hong-Lin

    2015-07-01

    Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H2en)[Co3(H2zdn)2(ox)(H2O)2] (1) and Cd2(H2zdn)(ox)0.5(H2O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H5zdn; oxalic acid=H2ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O-P-O units of H5zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property.

  13. Three dimensional nano-assemblies of noble metal nanoparticle-infinite coordination polymers as specific oxidase mimetics for degradation of methylene blue without adding any cosubstrate.

    Science.gov (United States)

    Wang, Lihua; Zeng, Yi; Shen, Aiguo; Zhou, Xiaodong; Hu, Jiming

    2015-02-07

    Novel three-dimensional (3D) nano-assemblies of noble metal nanoparticle (NP)-infinite coordination polymers (ICPs) are conveniently fabricated through the infiltration of HAuCl4 into hollow Au@Ag@ICPs core-shell nanostructures and its replacement reaction with Au@Ag NPs. The present 3D nano-assemblies exhibit highly efficient and specific intrinsic oxidase-like activity even without adding any cosubstrate.

  14. Synthesis and characterization of a multifunctional inorganic-organic hybrid mixed-valence copper(I/II) coordination polymer: {[CuCN][Cu(isonic)2]}n

    Science.gov (United States)

    Liu, Dong-Sheng; Chen, Wen-Tong; Ye, Guang-Ming; Zhang, Jing; Sui, Yan

    2017-12-01

    A new multifunctional mixed-valence copper(I/II) coordination polymer, {[CuCN][Cu(isonic)2]}n(1) (Hisonic = isonicotinic acid), was synthesized by treating isonicotinic acid and 5-amino-tetrazolate (Hatz = 5-amino-tetrazolate) with copper(II) salts under hydrothermal conditions, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound exhibit noncentrosymmetric polar packing arrangement. It is three-dimensional (3D) framework with (3,5)-connected 'seh-3' topological network constructed from metal organic framework {[Cu(isonic)2]}n and the inorganic linear chain{Cu(CN)}n subunits. A remarkable feature of 1 is the rhombic open channels that are occupied by a linear chain of {Cu(CN)}n. Impressively compound 1 displays not only a second harmonic generation (SHG) response, but also a ferroelectric behavior and magnetic properties.

  15. A series of novel metal–organic coordination polymers constructed from the new 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole spacer and aromatic carboxylates: Synthesis, crystal structures, and luminescence properties

    International Nuclear Information System (INIS)

    Sun, Jiayin; Zhang, Daojun; Wang, Li; Zhang, Renchun; Wang, Junjie; Zeng, Ying; Zhan, Jinling; Xu, Jianing; Fan, Yong

    2013-01-01

    Using bifunctional organic ligand 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (HL) and different aromatic carboxylates as secondary ligands, four novel metal-organic coordination polymers, [Zn(L)(1,4-bdc) 0.5 ] (1), [Zn 1.5 (L)(2,5-pydc)] (2), [Zn(HL)(1,2,4,5-btec) 0.5 ] (3), and [Cd(HL)(1,2,4,5-btec) 0.5 ] (4) (1,4-bdc, 1,4-benzenedicarboxylate; 2,5-pydc, 2,5-pyridinedicarboxylate; 1,2,4,5-btec, 1,2,4,5-benzenetetracarboxylate) have been successfully synthesized and analyzed. Compound 1 features the 2D [Zn(L)] n layers built by μ 3 -L bridging ligands and Zn(II) ions, which are further linked by pillared 1,4-bdc 2− ligands to form a 2-fold interpenetrating dmc framework. The 3D network of compound 2 can be simplified as a rare 2-nodal (3,6)-connected rtl (rutile) topology. Compound 3 possesses a 2D layer structure which is accomplished by connecting ladder-chains to L ligands. Compound 4 exhibits 2D [Cd(1,2,4,5-btec)] layers with infinite Cd–O–Cd rods and the adjacent 2D networks are further pillared by L with terminal bidentate coordination mode to generate the final 3D structure. The solid-state luminescent studies show that compounds 1–4 display intense fluorescent emissions. - Graphical abstract: Using bifunctional organic ligand 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (HL) and different aromatic carboxylates as secondary ligands, four novel metal-organic coordination polymers have been obtained. All compounds show good luminescence properties at room temperature. Display Omitted - Highlights: • Four Zn(II)/Cd(II)-MOCPs have been successfully prepared with the rigid bifunctional ligand 5-(4-imidazol -1-yl-phenyl) -2H-tetrazole and different aromatic carboxylates mixed ligands. • Compound 2 is a 2-nodal rtl (rutile) net and compound 4 is a binodal (5, 6)-connected net with yav topology. • Compounds 1-4 display intense fluorescent emissions at room temperature

  16. Solvent induced synthesis, structure and properties of coordination polymers based on 5-hydroxyisophthalic acid as linker and 1,10-phenanthroline as auxiliary ligand

    International Nuclear Information System (INIS)

    Kariem, Mukaddus; Yawer, Mohd; Sheikh, Haq Nawaz

    2015-01-01

    Three new coordination polymers [Mn(hip)(phen) (H_2O)]_n (1), [Co(hip)(phen) (H_2O)]_n (2), and [Cd(hip) (phen) (H_2O)]_n (3) (H_2hip=5-hydroxyisophthalic acid; phen=1,10-phenanthroline) have been synthesized by solvo-hydrothermal method using diethyl formamide-water (DEF-H_2O) as solvent system. Single-crystal X-ray diffraction analysis reveals that all three coordination polymers 1, 2 and 3 crystallize in monoclinic space group P2/n. Metal ions are inter-connected by hydroxyisophthalate anions forming zig-zag 1D chain. 1D chains are further inter-connected by hydrogen bonding and π–π stacking interactions leading to 3D supramolecular architecture. Hydrogen-bonding and π–π stacking provide thermal stability to polymers. Compounds 1 and 2 are paramagnetic at room temperature and variable temperature magnetic moment measurements revealed weak ferromagnetic interactions between metal ions at low temperature. Compound 3 exhibits excellent photoluminescence with large Stokes shift. - Graphical abstract: 1D helical chains of coordination polymers were synthesized by solvo-hydrothermal reaction of 5-hydroxyisopthalic acid and 1,10-phenanthroline with MnCl_2·4H_2O / CoCl_2·6H_2O / Cd(NO_3)_2·6H_2O. - Highlights: • Solvent induced synthesis of three coordination polymers with 1D zig-zag structure. • Crystal structures of coordination polymers are reported and discussed. • 1,10-Phenanthroline influences magnetic and luminescent properties of polymers. • Coordination polymer of Cd is luminescent exhibiting large Stokes shift.

  17. Synthesis of biocidal polymers containing metal NPs using an electron beam

    International Nuclear Information System (INIS)

    Choi, Kwonyong; Kim, Seong-Eun; Kim, Hee-Yeon; Yoon, Jeyong; Lee, Jong-Chan

    2012-01-01

    Metal containing antibacterial polymers were prepared by the polymerization of methylmethacrylate and methacrylic acid with copper or zinc. When the thin film of the polymers coated on a glass was irradiated with an electron beam, nanoparticles were obtained. It was found that these polymers exhibited a potent antibacterial activity against the Gram-negative bacteria, Escherichia coli. The metal containing polymers showed a 99.999% (5.0 logs) reduction in E. coli at a contact time of 12 h. In addition, polymers had a good antifouling effect against marine organisms. - Graphical abstract: Biocidal activity of Cu nanoparticle/polymer composite film against Gram-negative bacteria. Highlights: ► Metal containing antibacterial polymers were prepared with copper. ► Using the electron beam, nanoparticles were obtained. ► It was found that these polymers exhibited potent biocidal activity against E. coli. ► The metal containing polymers showed a 99.999% reduction of E. coli.

  18. Two multi-dimensional frameworks constructed from zinc coordination polymers with pyridine carboxylic acids

    International Nuclear Information System (INIS)

    Guo Yuanyuan; Ma Pengtao; Wang Jingping; Niu Jingyang

    2011-01-01

    Two novel zinc coordination polymers [Zn 2 (H 2 O)L(MoO 4 )] n (1) and [Zn 4 (PO 4 ) 2 L'(H 2 O)] n (2) (H 2 L=2,2'-bipyridine-6.6'-dicarboxylic acid, H 2 L'=2,2'-bipyridine-4,4'-dicarboxylic acid) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV spectra, single-crystal X-ray diffraction and thermogravimetric analyses. Structural analyses indicate that 1 represents a 2-D sheet structure built by dimeric [Zn 2 L(H 2 O)] 2+ units and MoO 4 2- groups whereas 2 displays an interesting 3-D framework constructed by tetranuclear zinc clusters, L' 2- ligands and PO 4 3- groups. Examination of UV spectra suggests that both 1 and 2 can stably exist in the pH range of 2.45-5.45 and 3.01-8.55 in aqueous solution, respectively. The room-temperature solid-state photoluminescence of 1 and 2 are derived from the intra-ligands π-π* transitions of H 2 L and H 2 L' ligands and the ligand-to-metal-charge-transfer transitions. - Graphical Abstract: Two new transition metal coordination polymers, namely, [Zn 2 (H 2 O)L 1 (MoO 4 )] n (1), [Zn 4 (PO 4 ) 2 L 2 (H 2 O)] n (2) (H 2 L 1 =2,2'-bipyridine-6,6'-dicarboxylic acid, H 2 L 2 =2,2'-bipyridine-4,4'-dicarboxylic acid) have been hydrothermally synthesized. 1 represents a 2-D sheet structure while 2 represents 3-D network. Highlights: →Two new transition metal coordination polymers have been hydrothermally synthesized. → The two compounds have been characterized by elemental analyses, IR, UV spectra, single-crystal X-ray diffraction, thermogravimetric analyses and photoluminescence. → Compound 1 represents a 2-D sheet structure while 2 represents 3-D network.

  19. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    International Nuclear Information System (INIS)

    Arıcı, Mürsel; Zafer Yeşilel, Okan; Büyükgüngör, Orhan

    2017-01-01

    Four coordination polymers including, [Co(µ-Htbip) 2 (µ-dib)] n (1), [Co(µ-tbip)(µ-dmib) 0.5 ] n (2), [Zn 2 (µ-tbip)(µ 3 -tbip)(µ-dmib) 1.5 ] n (3) and [Cd(µ 3 -tbip)(µ-dib) 0.5 (H 2 O)] n (4) (tbip: 5-tert-butylisophthalate, dib: 1,4-bis(imidazol-1yl)benzene, dmib: 1,4-bis(imidazol-1yl)-2,5-dimethylbenzene), were hydrothermally synthesized and characterized by elemental analysis, IR spectra, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). The structural diversity is observed depending on ligands and coordination number of metal centers in the synthesized complexes. The tbip ligand displayed five different coordination modes in its complexes. In 1 and 2, complex 1 is 3D framework with the dia topology while complex 2 has 2D structure with the sql topology depending on coordination geometries of Co ions. Complex 3 is 3D framework with the fsh 4,6-conn topology and complex 4 has 2D 4-connected sql topology. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in methanol could be used as a fluorescent sensor for the detection of acetone. Moreover, thermal and optical properties of the complexes were also studied. - Graphical abstract: Four coordination polymers were hydrothermally synthesized and characterized by various techniques. The complexes showed the structural diversity depending on ligands and coordination number of metal centers. The tbip ligand displayed four different coordination modes in its complexes. In 1 and 2, complexes 1 and 2 are 3D and 2D structures with the dia and sql topologies depending on coordination geometries of Co ions, respectively. Complexes 3 and 4 are 3D and 2D structures with the fsh 4,6-conn and sql topology, respectively. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in methanol could be used as a fluorescent sensor for the

  20. Series of coordination polymers based on 4-(5-sulfo-quinolin-8-yloxy) phthalate and bipyridinyl coligands: Structure diversity and properties

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xun [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Liu, Jing [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Li, Jin; Ma, Lu-Fang [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Wang, Li-Ya, E-mail: wlya@lynu.edu.cn [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473601 (China); Ng, Seik-Weng [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 80203 (Saudi Arabia); Qin, Guo-Zhan [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China)

    2015-10-15

    Reactions between later metal salts and conjugational N-hetrocyclic sulfonate/ carboxylic acid under the presence of bipyridyl auxiliary ligands afforded a series of manganese, nickel, zinc, silver, cadmium coordination polymers bearing with phenyl pendant arm attached to quinoline skeletons, and they have been characterized by elements analysis, thermogravimetry, infrared spectroscopy and single-crystal X-ray diffraction studying. The series of polymers show interesting structural diversity in coordination environment, dimensions and topologies. They are all built from 2-D networks constructed from metal cluster through sulfonate or carboxylate groups, as the secondary building unit (SBU). The thermalgravimetric analyses show that they display framework stabilities in solid state. Variable-temperature magnetic susceptibility studies reveal the existence of antiferromagnetic interactions between adjacent Mn (II) ions in 1, and ferromagnetic interactions between Ni(II) ions for 2, respectively. The photo-luminescence properties of 3-5 have also been investigated systemically. - Highlights: • A series of coordination polymers based on later transition metal ions have been obtained. • They contain conjugational N-hetrocyclic sulfonate-carboxylic acid and bipyridyl auxiliary ligands. • They have been characterized systemically. • They exhibit structure diversity and interesting properties.

  1. Preparation of PbS and PbO nanopowders from new Pb(II)(saccharine) coordination polymers

    International Nuclear Information System (INIS)

    Aslani, Alireza; Musevi, Seyid Javad; Şahin, Ertan; Yilmaz, Veysel T.

    2014-01-01

    Highlights: • The complex of compounds “[Pb(H 2 O)(μ-OAc)(μ-sac)] n ” are synthesized at nano and bulk size structurally diverse and show interesting three-dimensional coordination polymers. • Reduction of the particle size of the coordination polymers to a few dozen nanometers results in lower thermal stability when compared to the single crystalline samples. • This study demonstrates that the metal–organic framework may be suitable precursors for the preparation of nanoscale materials with interesting morphologies. - Abstract: Nanopowders and single crystal of new Pb(II) three-dimensional coordination polymer, [Pb(H 2 O)(μ-OAc)(μ-sac)] n “PASAC” were synthesized by a sonochemical and branched tube methods (Yılmaz et al., Z. Anorg. Allg. Chem. 629 (2003) 172). The new nano-structures of Pb(II) coordination polymer were characterized by X-ray crystallography analysis, scanning electron microscopy (SEM), X-ray powder diffraction (XRD), surface analysis (BET), and IR spectroscopy. The crystal structure of these compounds consists of three-dimensional polymeric units. The thermal stability of compounds was studied by thermal gravimetric analysis (TGA) and differential thermal analyses (DTA). PbS and PbO nano-structures were obtained by calcinations of the nano-structures of this coordination polymer at 600 °C

  2. Solvent induced synthesis, structure and properties of coordination polymers based on 5-hydroxyisophthalic acid as linker and 1,10-phenanthroline as auxiliary ligand

    Energy Technology Data Exchange (ETDEWEB)

    Kariem, Mukaddus; Yawer, Mohd; Sheikh, Haq Nawaz, E-mail: hnsheikh@rediffmail.com

    2015-11-15

    Three new coordination polymers [Mn(hip)(phen) (H{sub 2}O)]{sub n} (1), [Co(hip)(phen) (H{sub 2}O)]{sub n} (2), and [Cd(hip) (phen) (H{sub 2}O)]{sub n} (3) (H{sub 2}hip=5-hydroxyisophthalic acid; phen=1,10-phenanthroline) have been synthesized by solvo-hydrothermal method using diethyl formamide-water (DEF-H{sub 2}O) as solvent system. Single-crystal X-ray diffraction analysis reveals that all three coordination polymers 1, 2 and 3 crystallize in monoclinic space group P2/n. Metal ions are inter-connected by hydroxyisophthalate anions forming zig-zag 1D chain. 1D chains are further inter-connected by hydrogen bonding and π–π stacking interactions leading to 3D supramolecular architecture. Hydrogen-bonding and π–π stacking provide thermal stability to polymers. Compounds 1 and 2 are paramagnetic at room temperature and variable temperature magnetic moment measurements revealed weak ferromagnetic interactions between metal ions at low temperature. Compound 3 exhibits excellent photoluminescence with large Stokes shift. - Graphical abstract: 1D helical chains of coordination polymers were synthesized by solvo-hydrothermal reaction of 5-hydroxyisopthalic acid and 1,10-phenanthroline with MnCl{sub 2}·4H{sub 2}O / CoCl{sub 2}·6H{sub 2}O / Cd(NO{sub 3}){sub 2}·6H{sub 2}O. - Highlights: • Solvent induced synthesis of three coordination polymers with 1D zig-zag structure. • Crystal structures of coordination polymers are reported and discussed. • 1,10-Phenanthroline influences magnetic and luminescent properties of polymers. • Coordination polymer of Cd is luminescent exhibiting large Stokes shift.

  3. Synthesis of new water-soluble metal-binding polymers: Combinatorial chemistry approach. 1998 annual progress report

    International Nuclear Information System (INIS)

    Kurth, M.J.; Miller, R.B.; Sawan, S.; Smith, B.F.

    1998-01-01

    '(1) Develop rapid discovery and optimization approaches to new water-soluble chelating polymers for use in Polymer Filtration (PF) systems, and (2) evaluate the concept of using water and organic soluble polymers as new solid supports for combinatorial synthesis. Polymer Filtration (PF), which uses water-soluble metal-binding polymers to sequester metal ions in dilute solution with ultrafiltration (UF) to separate the polymers, is a new technology to selectively remove or recover hazardous and valuable metal ions. Future directions in PF must include rapid development, testing, and characterization of new metal-binding polymers. Thus, the authors are building upon and adapting the combinatorial chemistry approach developed for rapid molecule generation for the drug industry to the rapid development of new chelating polymers. The authors have focused on four areas including the development of: (1) synthetic procedures, (2) small ultrafiltration equipment compatible with organic- and aqueous-based combinatorial synthesis, (3) rapid assay techniques, and (4) polymer characterization techniques.'

  4. Four Novel Zn (II Coordination Polymers Based on 4′-Ferrocenyl-3,2′:6′,3′′-Terpyridine: Engineering a Switch from 1D Helical Polymer Chain to 2D Network by Coordination Anion Modulation

    Directory of Open Access Journals (Sweden)

    Lufei Xiao

    2017-11-01

    Full Text Available Four novel ZnII coordination polymers, [(ZnCl22(L2]n (1, [(ZnBr22(L2]n (2, and [(ZnI22(L2]n (3 and {[Zn(SCN2]1.5(L3}n (4, have been synthesized based on 4′-ferrocenyl-3,2′:6′,3′′-terpyridine with ZnII ions and different coordination anions under similar ambient conditions. Their structures have been confirmed using single crystal X-ray diffraction analysis, showing that complexes 1–3 are one-dimensional (1D double-stranded metal ion helical polymer chains and complex 4 is of a two-dimensional (2D network. The structural transformations of them from a 1D polymer chain to a 2D network under the influence of the coordination anions has been systematic investigated. Furthermore, the optical band gaps have been measured by optical diffuse reflectance spectroscopy, revealing that the ligand and the complexes should have semiconductor properties.

  5. Imidazole and Triazole Coordination Chemistry for Antifouling Coatings

    Directory of Open Access Journals (Sweden)

    Markus Andersson Trojer

    2013-01-01

    Full Text Available Fouling of marine organisms on the hulls of ships is a severe problem for the shipping industry. Many antifouling agents are based on five-membered nitrogen heterocyclic compounds, in particular imidazoles and triazoles. Moreover, imidazole and triazoles are strong ligands for Cu2+ and Cu+, which are both potent antifouling agents. In this review, we summarize a decade of work within our groups concerning imidazole and triazole coordination chemistry for antifouling applications with a particular focus on the very potent antifouling agent medetomidine. The entry starts by providing a detailed theoretical description of the azole-metal coordination chemistry. Some attention will be given to ways to functionalize polymers with azole ligands. Then, the effect of metal coordination in azole-containing polymers with respect to material properties will be discussed. Our work concerning the controlled release of antifouling agents, in particular medetomidine, using azole coordination chemistry will be reviewed. Finally, an outlook will be given describing the potential for tailoring the azole ligand chemistry in polymers with respect to Cu2+ adsorption and Cu2+→Cu+ reduction for antifouling coatings without added biocides.

  6. Diagnostics of transparent polymer coatings of metal items

    Science.gov (United States)

    Varepo, L. G.; Ermakova, I. N.; Nagornova, I. V.; Kondratov, A. P.

    2017-08-01

    The methods of visual and instrumental express diagnostics of safety critical defects and non-uniform thickness of transparent mono- and multilayer polyolefin surface coating of metal items are analyzed in the paper. The instrumental diagnostics method relates to colorimetric measuring based on effects, which appear in the polarized light for extrusion polymer coatings. A color coordinates dependence (in the color system CIE La*b*) on both HDPE / PVC coating thickness fluctuation values (from average ones) and coating interlayer or adhesion layer delaminating is shown. A variation of color characteristics in the polarized light at a liquid penetration into delaminated polymer layers is found. Measuring parameters and critical uncertainties are defined.

  7. Homochiral coordination polymers constructed from aminocarboxylate derivates: Effect of bipyridine on the amidation reaction

    International Nuclear Information System (INIS)

    Chen Jianshan; Sheng Tianlu; Hu Shengmin; Xiang Shengchang; Fu Ruibiao; Zhu Qilong; Wu Xintao

    2012-01-01

    Using aminocarboxylate derivates (S)-N-(4-cyanobenzoic)-glutamic acid (denoted as cbg, 1a) and (S)-N-(4-nitrobenzoic)-glutamic acid (denoted as nbg, 1b) as chiral ligands, five new homochiral coordination polymers formulated as [Cu(cbg)(H 2 O) 2 ] n (3), [Cu(cbop) 2 (4,4′-bipy)(H 2 O)] n (4) (cbop=(S)-N-(4-cyanobenzoic)-5-oxoproline, 4,4′-bipy=4,4′-bipyridine), {[Cu(nbop) 2 (4,4′-bipy)]·4H 2 O} n (5) (nbop=(S)-N-(4-nitrobenzoic)-5-oxoproline), {[Cd(nbop) 2 (4,4′-bipy)]·2H 2 O} n (6), and [Ni(nbop) 2 (4,4′-bipy)(H 2 O) 2 ] n (7) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction study reveals that the original chirality of aminocarboxylate derivates is maintained in all these complexes. Complexes 3, 4, and 7 are one-dimensional infinite chain coordination polymers, while complexes 5 and 6 possess two-dimensional network structures. In situ cyclization of 1a and 1b was taken place in the formation of complexes 4–7, which may be due to the competition of 4,4′-bipyridine with chiral ligands during the coordination process. Preliminary optical behavior investigation indicates that ligands 1a, 1b, and complexes 6, 7 are nonlinear optical active. - Graphical abstract: Using aminocarboxylate derivates as chiral ligands, five new homochiral coordination polymers possessing second harmonic generation activities have been hydrothermally synthesized. Highlights: ► Two new chiral aminocarboxylate derivates were firstly synthesized. ► Five new homochiral metal organic complexes were obtained hydrothermally based on these ligands. ► Intramolecular amidation was taken place on the aminocarboxylate derivates during the formation of these complexes. ► In situ amidation may be due to the impact of 4,4′-bipyridine. ► The homochiral complexes are nonlinear optical active.

  8. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Arıcı, Mürsel, E-mail: marici@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Zafer Yeşilel, Okan [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Büyükgüngör, Orhan [Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun (Turkey)

    2017-05-15

    Four coordination polymers including, [Co(µ-Htbip){sub 2}(µ-dib)]{sub n} (1), [Co(µ-tbip)(µ-dmib){sub 0.5}]{sub n} (2), [Zn{sub 2}(µ-tbip)(µ{sub 3}-tbip)(µ-dmib){sub 1.5}]{sub n} (3) and [Cd(µ{sub 3}-tbip)(µ-dib){sub 0.5} (H{sub 2}O)]{sub n} (4) (tbip: 5-tert-butylisophthalate, dib: 1,4-bis(imidazol-1yl)benzene, dmib: 1,4-bis(imidazol-1yl)-2,5-dimethylbenzene), were hydrothermally synthesized and characterized by elemental analysis, IR spectra, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). The structural diversity is observed depending on ligands and coordination number of metal centers in the synthesized complexes. The tbip ligand displayed five different coordination modes in its complexes. In 1 and 2, complex 1 is 3D framework with the dia topology while complex 2 has 2D structure with the sql topology depending on coordination geometries of Co ions. Complex 3 is 3D framework with the fsh 4,6-conn topology and complex 4 has 2D 4-connected sql topology. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in methanol could be used as a fluorescent sensor for the detection of acetone. Moreover, thermal and optical properties of the complexes were also studied. - Graphical abstract: Four coordination polymers were hydrothermally synthesized and characterized by various techniques. The complexes showed the structural diversity depending on ligands and coordination number of metal centers. The tbip ligand displayed four different coordination modes in its complexes. In 1 and 2, complexes 1 and 2 are 3D and 2D structures with the dia and sql topologies depending on coordination geometries of Co ions, respectively. Complexes 3 and 4 are 3D and 2D structures with the fsh 4,6-conn and sql topology, respectively. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in

  9. Anion-Dependent Exocyclic Mercury(II) Coordination Polymers of Bis-dithiamacrocycle

    Energy Technology Data Exchange (ETDEWEB)

    Siewe, Arlette Deukam; Kim, Seul Gi; Choi, Kyu Seong [Kyungnam University, Changwon (Korea, Republic of); Lee, Shim Sung [Gyeongsang National University, Jinju (Korea, Republic of)

    2014-09-15

    Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}-Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}- macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies outside the cavity is six-coordinate with a distorted octahedral geometry, being bound to four adjacent ligands via monodentate Hg-S bonds and two remaining sites are occupied by two terminal chlorido ligands to form a fishnet-like 2D structure. When reacting with mercury(II) iodide, L afforded a 1D coordination polymer [Hg{sub 2}(L)I{sub 4}]·CHCl{sub 3}n in which each exocyclic Hg atom is four-coordinate, being bound to two sulfur donors from different ligands doubly bridging the ligand molecules in a head-to-tail mode. The coordination sphere in 3 is completed by two iodo terminal ligands, adopting a distorted tetrahedral geometry. On reacting with mercury(II) perchlorate, L forms solvent-coordinated 1D coordination polymer ([Hg{sub 2}(L)(DMF){sub 6}](ClO{sub 4}){sub 4}·2DMF)n instead of the anion-coordination. In 4, the Hg atom is five-coordinate, being bound to two sulfur donors from two different ligands doubly bridging the ligand molecules in a side-by-side mode to form a ribbon-like 1D structure.. The three remaining coordination sites in 4 are completed by three DMF molecules in a monodentate manner. Consequently, the different structures and connectivity patterns for the observed exocyclic coordination polymers depending on the anions used are influenced not only by the coordination ability of the anions but also by anion sizes macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies

  10. Liquid metals as electrodes in polymer light emitting diodes

    NARCIS (Netherlands)

    Andersson, G.G.; Gommans, H.H.P.; Denier van der Gon, A.W.; Brongersma, H.H.

    2003-01-01

    We demonstrate that liquid metals can be used as cathodes in light emitting diodes (pLEDs). The main difference between the use of liquid cathodes and evaporated cathodes is the sharpness of the metal–polymer interface. Liquid metal cathodes result in significantly sharper metal–organic interfaces

  11. Coordination Polymer Modified Separator for Mitigating Polysulfide Shuttle Effect in Lithium-Sulfur Batteries

    KAUST Repository

    Wan, Yi

    2017-11-19

    The development of the new cathode and anode materials of Lithium-Ion Batteries (LIBs) with high energy density and outstanding electrochemical performance is of substantial technological importance due to the ever-increasing demand for economic and efficient energy storage system. Because of the abundance of element sulfur and high theoretical energy density, Lithium-Sulfur (Li-S) batteries have become one of the most promising candidates for the next-generation energy storage system. However, the shuttling effect of electrolyte-soluble polysulfides severely impedes the cell performance and commercialization of Li-S batteries, and significant progress have been made to mitigate this shuttle effect in the past two decades. Coordination polymers (CPs) or Metal-organic Frameworks (MOFs) have been attracted much attention by virtue of their controllable porosity, nanometer cavity sizes and high surface areas, which supposed to be an available material in suppressing polysulfide migration. In this thesis, we investigate different mechanisms of mitigating polysulfide diffusion by applying a layer of MOFs (including Y-FTZB, ZIF-7, ZIF-8, and HKUST-1) on a separator. We also fabricate a new free-standing 2D coordination polymer Zn2(Benzimidazolate)2(OH)2 with rich hydroxyl (OH-) groups by using a simple, scalable and low cost method at air/water surface. Our results suggest that the chemical stability, the cluster morphology and the surface function groups of MOFs shows a greater impact on minimizing the shuttling effect in Li-S batteries, other than the internal cavity size in MOFs. Meanwhile, the new design of 2D coordination polymer efficiently mitigate the shuttling effect in Li-S battery resulting in a largely promotion of the battery capacity to 1407 mAh g-1 at 0.1 C and excellent cycling performance (capacity retention of 98% after 200 cycles at 0.25C). Such excellent cell performance is mainly owing to the fancying physical and chemical structure controllability

  12. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Baoxia [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Huang, Yankai [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhu, Xu; Hao, Yuanqiang [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Ding, Yujie [College of Biochemical Engineering, Anhui Polytechnic University, Wuhu 241000 (China); Wei, Wei; Wang, Qi [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Qu, Peng, E-mail: qupeng0212@163.com [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Xu, Maotian, E-mail: xumaotian@sqnc.edu.cn [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China)

    2016-03-17

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg{sup 2+} detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb{sup 3+} from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg{sup 2+} into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg{sup 2+}. As a kind of Hg{sup 2+} nanosensor, the probe exhibited excellent selectivity for Hg{sup 2+} and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg{sup 2+} in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg{sup 2+} was achieved based on time-resolved spectroscopy.

  13. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

    International Nuclear Information System (INIS)

    Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

    2016-01-01

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg"2"+ detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb"3"+ from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg"2"+ into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg"2"+. As a kind of Hg"2"+ nanosensor, the probe exhibited excellent selectivity for Hg"2"+ and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg"2"+ in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg"2"+ was achieved based on time-resolved spectroscopy.

  14. Lanthanide Organophosphate Spiro Polymers: Synthesis, Structure, and Magnetocaloric Effect in the Gadolinium Polymer.

    Science.gov (United States)

    Gupta, Sandeep K; Bhat, Gulzar A; Murugavel, Ramaswamy

    2017-08-07

    Spirocyclic lanthanide organophosphate polymers, {[Ln(dipp)(dippH)(CH 3 OH)(H 2 O) 2 ](CH 3 OH) 2 } n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11)], have been prepared from the reaction of Ln(NO 3 ) 3 ·xH 2 O with sterically hindered 2,6-diisopropylphenyl phosphate (dippH 2 ) using aqueous NaOH as the base. The one-dimensional chainlike lanthanide (III) organophosphate coordination polymers have been characterized with the aid of analytical and spectroscopic methods. The single crystal structure determination of polymers (2-5 and 7-11) reveals that in these compounds the hydrophobic organic groups of the phosphate provide a protective coating for the inorganic lanthanide phosphate polymeric chain. The encapsulation of inorganic lanthanide phosphate core, which has very low solubility product, within the organic groups assists in the facile crystallization of the polymers. The di- and monoanionic organophosphate ligands dipp 2- and dippH - display [2.111] and [2.110] binding modes, respectively, in 2-5 and 7. However, they exhibit only [2.110] binding mode in the case of 8-11. This results in the formation of two different types of polymers. While the lighter rare-earth metal ions in 2-5 and 7 display eight coordinate biaugmented trigonal prismatic geometry, the heavier rare-earth metal ions in 9-11 exhibit a seven coordinate capped trigonal prismatic environment. The Tb(III) ion in 8 displays distorted pentagonal bipyramidal geometry. Magnetic studies reveal the presence of weak antiferromagnetic interactions between the Ln(III) ions through the organophosphate ligand. The isotropic Gd(III) polymer 7 exhibits a maximum entropy change of 17.83 J kg -1 K -1 for a field change of 7.0 T at 2.5 K, which is significant considering the high molecular weight of the organophosphate ligand. These polymers represent the first family of any structurally characterized rare-earth organophosphate polymers derived from monoesters

  15. Organic-Inorganic Hybrid Polymers as Adsorbents for Removal of Heavy Metal Ions from Solutions: A Review

    Science.gov (United States)

    Samiey, Babak; Cheng, Chil-Hung; Wu, Jiangning

    2014-01-01

    Over the past decades, organic-inorganic hybrid polymers have been applied in different fields, including the adsorption of pollutants from wastewater and solid-state separations. In this review, firstly, these compounds are classified. These compounds are prepared by sol-gel method, self-assembly process (mesopores), assembling of nanobuilding blocks (e.g., layered or core-shell compounds) and as interpenetrating networks and hierarchically structures. Lastly, the adsorption characteristics of heavy metals of these materials, including different kinds of functional groups, selectivity of them for heavy metals, effect of pH and synthesis conditions on adsorption capacity, are studied. PMID:28788483

  16. Polymer/metal nanocomposites for biomedical applications.

    Science.gov (United States)

    Zare, Yasser; Shabani, Iman

    2016-03-01

    Polymer/metal nanocomposites consisting of polymer as matrix and metal nanoparticles as nanofiller commonly show several attractive advantages such as electrical, mechanical and optical characteristics. Accordingly, many scientific and industrial communities have focused on polymer/metal nanocomposites in order to develop some new products or substitute the available materials. In the current paper, characteristics and applications of polymer/metal nanocomposites for biomedical applications are extensively explained in several categories including strong and stable materials, conductive devices, sensors and biomedical products. Moreover, some perspective utilizations are suggested for future studies. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Syntheses, structural analyses and luminescent property of four alkaline-earth coordination polymers

    International Nuclear Information System (INIS)

    Zhang, Sheng; Qu, Xiao-Ni; Xie, Gang; Wei, Qing; Chen, San-Ping

    2014-01-01

    Four alkaline-earth coordination polymers, [Ba(Pzdc)(H 2 O)] n (1), [Ba(Pzdc)] n (2), [AgSr(Pzdc)(NO 3 )(H 2 O)] n (3), [Ag 2 Ca(Pzdc) 2 (H 2 O)] n (4) (H 2 Pzdc=2, 3-pyrazinedicarboxylic acid) have been synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 afford 2D layer networks generated by one-dimensional chains containing the [Ba 2 O 11 N] units. Compound 3 is of 2D mixed-metal coordination network formed by one-dimensional chain units, while 4 is of a 3D heterometallic framework. Interestingly, 1 and 2 can undergo reversible SCSC structural transformation upon dehydration/rehydration of coordinated water molecules. In addition, the π–π stacking interactions dominate fluorescent properties of compounds 1 and 2. - Graphical abstract: Four new coordination polymers [Ba(Pzdc)(H 2 O)] n (1), [Ba(Pzdc)] n (2), [AgSr(Pzdc)(NO 3 )(H 2 O)] n (3), [Ag 2 Ca(Pzdc) 2 (H 2 O)] n (4) (H 2 Pzdc=2, 3-pyrazinedicarboxylic acid) have been synthesized. Compounds 1–3 display 2D topology structures and compound 4 exhibits a 3D topology structure. Fortunately, 1 and 2 undergo reversible dehydration/rehydration of coordinated water molecules. Display Omitted - Highlights: • All structures are generated by 1D chains. • 1 and 2 show reversible dehydration/rehydration of coordinated water molecules. • The π–π stacking interactions dominate fluorescent properties of compounds 1 and 2

  18. Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

    Science.gov (United States)

    Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

    2011-11-30

    The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Coordination-chemistry control of proton conductivity in the iconic metal-organic framework material HKUST-1.

    Science.gov (United States)

    Jeong, Nak Cheon; Samanta, Bappaditya; Lee, Chang Yeon; Farha, Omar K; Hupp, Joseph T

    2012-01-11

    HKUST-1, a metal-organic framework (MOF) material containing Cu(II)-paddlewheel-type nodes and 1,3,5-benzenetricarboxylate struts, features accessible Cu(II) sites to which solvent or other desired molecules can be intentionally coordinated. As part of a broader investigation of ionic conductivity in MOFs, we unexpectedly observed substantial proton conductivity with the "as synthesized" version of this material following sorption of methanol. Although HKUST-1 is neutral, coordinated water molecules are rendered sufficiently acidic by Cu(II) to contribute protons to pore-filling methanol molecules and thereby enhance the alternating-current conductivity. At ambient temperature, the chemical identities of the node-coordinated and pore-filling molecules can be independently varied, thus enabling the proton conductivity to be reversibly modulated. The proton conductivity of HKUST-1 was observed to increase by ~75-fold, for example, when node-coordinated acetonitrile molecules were replaced by water molecules. In contrast, the conductivity became almost immeasurably small when methanol was replaced by hexane as the pore-filling solvent. © 2011 American Chemical Society

  20. A supramolecular miktoarm star polymer based on porphyrin metal complexation in water.

    Science.gov (United States)

    Hou, Zhanyao; Dehaen, Wim; Lyskawa, Joël; Woisel, Patrice; Hoogenboom, Richard

    2017-07-25

    A novel supramolecular miktoarm star polymer was successfully constructed in water from a pyridine end-decorated polymer (Py-PmDEGA) and a metalloporphyrin based star polymer (ZnTPP-(PEG) 4 ) via metal-ligand coordination. The Py-PmDEGA moiety was prepared via a combination of reversible addition-fragmentation chain transfer polymerization (RAFT) and subsequent aminolysis and Michael addition reactions to introduce the pyridine end-group. The ZnTPP(PEG) 4 star-polymer was synthesized by the reaction between tetrakis(p-hydroxyphenyl)porphyrin and toluenesulfonyl-PEG, followed by insertion of a zinc ion into the porphyrin core. The formation of a well-defined supramolecular AB 4 -type miktoarm star polymer was unambiguously demonstrated via UV-Vis spectroscopic titration, isothermal titration calorimetry (ITC) and diffusion ordered NMR spectroscopy (DOSY).

  1. A multi-functional coordination polymer coexisting spontaneous chirality resolution and weak ferromagnetism

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiu-Hua, E-mail: xhli.univ@gmail.com [College of Chemistry and Chemical Engineering, Fujian Normal University, Fuzhou, 350117 Fujian (China); Zhang, Qi [School of Life Science, Changchun Normal University, Changchun, 130032 Jilin (China); Hu, Ping [Southampton Management School, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom)

    2014-10-15

    A multifunctional homochiral coordination polymer, [Co(H{sub 2}O)(BDC)(4,4′-BPY)]∙3H{sub 2}O (1) (H{sub 2}BDC=1,2-benzenedicarboxylate and 4,4′-BPY=4,4′-bipyridine), has been successfully isolated from Co(II) ions and mixed ligands (1,2-benzenedicarboxylate and 4,4′-bipyridine). Complex 1, which exhibits spontaneous chirality resolution and weak ferromagnetism, is built by chiral helices interconnected via end-to-end 4,4′-BPY bridges into a two-dimensional (2D) layer structure. - Graphical abstract: A 2D cobalt coordination polymer compound showing spontaneous chirality resolution and weak ferromagnetism. - Highlights: • A new 2D cobalt mix-ligand coordination polymer complex has been synthesized. • The cobalt coordination polymer complex shows spontaneous chirality resolution in solid state. • The cobalt coordination polymer complex displays dominant and weak intrachain ferromagnetic interactions.

  2. A multi-functional coordination polymer coexisting spontaneous chirality resolution and weak ferromagnetism

    International Nuclear Information System (INIS)

    Li, Xiu-Hua; Zhang, Qi; Hu, Ping

    2014-01-01

    A multifunctional homochiral coordination polymer, [Co(H 2 O)(BDC)(4,4′-BPY)]∙3H 2 O (1) (H 2 BDC=1,2-benzenedicarboxylate and 4,4′-BPY=4,4′-bipyridine), has been successfully isolated from Co(II) ions and mixed ligands (1,2-benzenedicarboxylate and 4,4′-bipyridine). Complex 1, which exhibits spontaneous chirality resolution and weak ferromagnetism, is built by chiral helices interconnected via end-to-end 4,4′-BPY bridges into a two-dimensional (2D) layer structure. - Graphical abstract: A 2D cobalt coordination polymer compound showing spontaneous chirality resolution and weak ferromagnetism. - Highlights: • A new 2D cobalt mix-ligand coordination polymer complex has been synthesized. • The cobalt coordination polymer complex shows spontaneous chirality resolution in solid state. • The cobalt coordination polymer complex displays dominant and weak intrachain ferromagnetic interactions

  3. Metallacyclopentadienes: structural features and coordination in transition metal complexes

    International Nuclear Information System (INIS)

    Dolgushin, Fedor M; Yanovsky, Aleksandr I; Antipin, Mikhail Yu

    2004-01-01

    Results of structural studies of polynuclear transition metal complexes containing the metallacyclopentadiene fragment are overviewed. The structural features of the complexes in relation to the nature of the substituents in the organic moiety of the metallacycles, the nature of the transition metals and their ligand environment are analysed. The main structural characteristics corresponding to different modes of coordination of metallacyclopentadienes to one or two additional metal centres are revealed.

  4. Synthesis of new water-soluble metal-binding polymers: Combinatorial chemistry approach. 1997 mid-year progress report

    International Nuclear Information System (INIS)

    Smith, B.F.

    1997-01-01

    'The first objective of this research is to develop rapid discovery and optimization approaches to new water-soluble chelating polymers. A byproduct of the development approach will be the new, selective, and efficient metal-binding agents. The second objective is to evaluate the concept of using water and organic soluble polymers as new solid supports for combinatorial synthesis. The technology under development, Polymer Filtration (PF), is a technique to selectively remove or recover hazardous and valuable metal ions and radionuclides from various dilute aqueous streams. Not only can this technology be used to remediate contaminated soils and solid surfaces and treat aqueous wastes, it can also be incorporated into facilities as a pollution prevention and waste minimization technology. Polymer Filtration uses water-soluble metal-binding polymers to sequester metal ions in dilute solution. The water-soluble polymers have a sufficiently large molecular size that they can be separated and concentrated using commercial ultrafiltration technology. Water, small organic molecules, and unbound metals pass freely through the ultrafiltration membrane while concentrating the metal-binding polymer. The polymers can then be reused by changing the solution conditions to release the metal ions. The metal-ions are recovered in concentrated form for recycle or disposal using a diafiltration process. The water-soluble polymer can be recycled for further aqueous-stream processing. To advance Polymer Filtration technology to the selectivity levels required for DOE needs. fixture directions in Polymer Filtration must include rapid development, testing, and characterization of new metal-binding polymers. The development of new chelating molecules can be equated to the process of new drugs or new materials discovery. Thus, the authors want to build upon and adapt the combinatorial chemistry approaches developed for rapid molecule generation for the drug industry to the rapid

  5. Synthesis, crystal structure, and magnetic properties of two-dimensional divalent metal glutarate/dipyridylamine coordination polymers, with a single crystal-to-single crystal transformation in the copper derivative

    International Nuclear Information System (INIS)

    Montney, Matthew R.; Supkowski, Ronald M.; Staples, Richard J.; LaDuca, Robert L.

    2009-01-01

    Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4'-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)] n (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a '5+1' extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)] n neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure of 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses. - Graphical abstract: The coordination polymers [M(glu)(dpa)] n (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)] n chains linked through dpa tethers. Antiferromagnetic coupling is observed for 2 and 3, while ferromagnetism is predominant in 1. Compound 3 undergoes a thermally induced single crystal-to-single crystal transformation from an acentric to a centrosymmetric space group

  6. New trends in the optical and electronic applications of polymers containing transition-metal complexes.

    Science.gov (United States)

    Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei

    2012-04-13

    Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A two-dimensional layered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating mixed multidentate N- and O-donor ligands.

    Science.gov (United States)

    Huang, Qiu-Ying; Su, Ming-Yang; Meng, Xiang-Ru

    2015-06-01

    The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{μ2-1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κ(2)N(3):N(4)}(μ4-butanedioato-κ(4)O(1):O(1'):O(4):O(4'))(μ2-butanedioato-κ(2)O(1):O(4))dicadmium], [Cd(C4H4O4)(C9H8N6)]n, each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) ligands. Cd(II) ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.

  8. Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water

    International Nuclear Information System (INIS)

    Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

    2011-01-01

    Highlights: ► A novel type of functionalized MOF for heavy metal removal. ► Functionalization of MOF by a facile coordination-based postsynthetic strategy. ► Thiol-functionalization of MOF has been realized for the first time. ► Enhanced removal of Hg 2+ by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu 3 (BTC) 2 (H 2 O) 3 ] n (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu 3 (BTC) 2 ] n samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with –SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N 2 sorption–desorption isothermal. Significantly, the thiol-functionalized [Cu 3 (BTC) 2 ] n exhibited remarkably high adsorption affinity (K d = 4.73 × 10 5 mL g −1 ) and high adsorption capacity (714.29 mg g −1 ) for Hg 2+ adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg 2+ under the same condition.

  9. 21 CFR 888.3560 - Knee joint patellofemorotibial polymer/metal/polymer semi-constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint patellofemorotibial polymer/metal... Devices § 888.3560 Knee joint patellofemorotibial polymer/metal/polymer semi-constrained cemented prosthesis. (a) Identification. A knee joint patellofemorotibial polymer/metal/polymer semi-constrained...

  10. Antimicrobial Polymers with Metal Nanoparticles

    Science.gov (United States)

    Palza, Humberto

    2015-01-01

    Metals, such as copper and silver, can be extremely toxic to bacteria at exceptionally low concentrations. Because of this biocidal activity, metals have been widely used as antimicrobial agents in a multitude of applications related with agriculture, healthcare, and the industry in general. Unlike other antimicrobial agents, metals are stable under conditions currently found in the industry allowing their use as additives. Today these metal based additives are found as: particles, ions absorbed/exchanged in different carriers, salts, hybrid structures, etc. One recent route to further extend the antimicrobial applications of these metals is by their incorporation as nanoparticles into polymer matrices. These polymer/metal nanocomposites can be prepared by several routes such as in situ synthesis of the nanoparticle within a hydrogel or direct addition of the metal nanofiller into a thermoplastic matrix. The objective of the present review is to show examples of polymer/metal composites designed to have antimicrobial activities, with a special focus on copper and silver metal nanoparticles and their mechanisms. PMID:25607734

  11. 21 CFR 888.3550 - Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint patellofemorotibial polymer/metal/metal... § 888.3550 Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis. (a) Identification. A knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis is a device...

  12. Syntheses, structural analyses and luminescent property of four alkaline-earth coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Sheng; Qu, Xiao-Ni; Xie, Gang; Wei, Qing; Chen, San-Ping, E-mail: sanpingchen@126.com

    2014-02-15

    Four alkaline-earth coordination polymers, [Ba(Pzdc)(H{sub 2}O)]{sub n} (1), [Ba(Pzdc)]{sub n} (2), [AgSr(Pzdc)(NO{sub 3})(H{sub 2}O)]{sub n} (3), [Ag{sub 2}Ca(Pzdc){sub 2}(H{sub 2}O)]{sub n} (4) (H{sub 2}Pzdc=2, 3-pyrazinedicarboxylic acid) have been synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 afford 2D layer networks generated by one-dimensional chains containing the [Ba{sub 2}O{sub 11}N] units. Compound 3 is of 2D mixed-metal coordination network formed by one-dimensional chain units, while 4 is of a 3D heterometallic framework. Interestingly, 1 and 2 can undergo reversible SCSC structural transformation upon dehydration/rehydration of coordinated water molecules. In addition, the π–π stacking interactions dominate fluorescent properties of compounds 1 and 2. - Graphical abstract: Four new coordination polymers [Ba(Pzdc)(H{sub 2}O)]{sub n} (1), [Ba(Pzdc)]{sub n} (2), [AgSr(Pzdc)(NO{sub 3})(H{sub 2}O)]{sub n} (3), [Ag{sub 2}Ca(Pzdc){sub 2}(H{sub 2}O)]{sub n} (4) (H{sub 2}Pzdc=2, 3-pyrazinedicarboxylic acid) have been synthesized. Compounds 1–3 display 2D topology structures and compound 4 exhibits a 3D topology structure. Fortunately, 1 and 2 undergo reversible dehydration/rehydration of coordinated water molecules. Display Omitted - Highlights: • All structures are generated by 1D chains. • 1 and 2 show reversible dehydration/rehydration of coordinated water molecules. • The π–π stacking interactions dominate fluorescent properties of compounds 1 and 2.

  13. 21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

  14. Organic thin film transistors and polymer light-emitting diodes patterned by polymer inking and stamping

    International Nuclear Information System (INIS)

    Li Dawen; Guo, L Jay

    2008-01-01

    To fully realize the advantages of organic flexible electronics, patterning is very important. In this paper we show that a purely additive patterning technique, termed polymer inking and stamping, can be used to pattern conductive polymer PEDOT and fabricate sub-micron channel length organic thin film transistors. In addition, we applied the technique to transfer a stack of metal/conjugated polymer in one step and fabricated working polymer light-emitting devices. Based on the polymer inking and stamping technique, a roll-to-roll printing for high throughput fabrication has been demonstrated. We investigated and explained the mechanism of this process based on the interfacial energy consideration and by using the finite element analysis. This technique can be further extended to transfer more complex stacked layer structures, which may benefit the research on patterning on flexible substrates

  15. Self-organization in metal complexes

    International Nuclear Information System (INIS)

    Radecka-Paryzek, W.

    1999-01-01

    Inorganic self-organization involves the spontaneous generation of well-defined supramolecular architectures from metal ions and organic ligands. The basic concept of supramolecular chemistry is a molecular recognition. When the substrate are metal ions, recognition is expressed in the stability and selectivity of metal ion complexation by organic ligands and depends on the geometry of the ligand and on their binding sites that it contains. The combination of the geometric features of the ligand units and the coordination geometries of the metal ions provides very efficient tool for the synthesis of novel, intriguing and highly sophisticated species such as catenanes, box structures, double and triple helicates with a variety of interesting properties. The article will focus on the examples of inorganic self-organization involving the templating as a first step for the assembly of supramolecular structures of high complexity. (author)

  16. Structural diversity and fluorescence properties of three 2-sulfoterephthalate Cd{sup II}/Zn{sup II} coordination polymers employing 1,4-bisbenzimidazole

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Yixia, E-mail: renyixia1@163.com; Chai, Hongmei; Tang, Long; Hou, Xiangyang; Wang, Jijiang

    2016-02-15

    Three novel coordination polymers, namely, [Cd(2-Hstp)(1,4-bbi)(H{sub 2}O){sub 2}]·3H{sub 2}O (1), [Cd{sub 1.5}(2-stp)(1,4-bbi)(H{sub 2}O){sub 2}]·H{sub 2}O (2) and [Zn{sub 2}(2-stp)(μ{sub 2}-OH)(1,4-bbi){sub 1.5}(H{sub 2}O)]·6H{sub 2}O (3) (2-H{sub 3}stp is equal to 2-sulfoterephthalate and 1,4-bisbenzimidazole is equal to 1,4-bbi), have been synthesized by hydrothermal reaction. The structural analyses show that 1 and 2 possess different structural features despite the same raw materials, which are 1D chain structure featuring 6-member-water H-bonds cluster and 3D bbi-pillared wavy-like layer framework, respectively. As changing the metal ion to zinc ion, 3 exhibits 3D stp-pillared layer architecture, which discovers the effect of the central metal ions on the formation of metal–organic frameworks. The fluorescence studies show that the emissions of the coordination polymers are attributed to the ligand π–π* transition, which means they could be potential fluorescence materials. - Graphical abstract: Three new Cd{sup II}/Zn{sup II} 2-sulfoterephthalate (2-H{sub 3}stp) complexes with 1,4-bisbenzimidazole (1,4-bbi) are described. Complex 1 exhibits one-dimensional chain-like structure, 2 is a three-dimensional bbi-pillared wavy-like layer framework, while 3 is a three-dimensional stp-pillared layer architecture. Fluorescence spectra exhibit the π–π* transition of two organic ligands. - Highlights: • Three Cd{sup II}/Mn{sup II} 2-sulfoterephthalate complexes containing 1,4-bisbenzimidazole. • Different structural features despite the same raw materials for 1 and 2. • Fluorescence spectra exhibit the π–π* transition of organic ligands.

  17. Application of hybrid organic/inorganic polymers as coatings on metallic substrates

    Science.gov (United States)

    Augustinho, T. R.; Motz, G.; Ihlow, S.; Machado, R. A. F.

    2016-09-01

    Acrylic polymers, particularly poly (methyl methacrylate) (PMMA), have certain specific properties, such as good film formation, transparency, and good mechanical properties, which have been widely used in paints, coatings and adhesives. However, the limited chemical and physical stability of these pure polymers limits their applications when exposed to hostile conditions, as in ship hulls, for example. A suitable way to enhance PMMA properties is the addition of silicon polymers with very good protective characteristics. In this study, a PMMA and HTT 1800 (commercial silazane) copolymer were applied on metallic substrate and compared to pure PMMA and HTT 1800. All the materials were applied as coatings. They were applied on stainless steel via dip-coating to investigate the coating properties. Thermal cycling was employed to analyze coating durability at high temperatures (50 °C to 600 °C). Optical microscopy (OM) and scanning electron microscopy (SEM) were used to characterize the coated surfaces, and the adhesion of pure PMMA, pure HTT 1800 and PMMA/HTT 1800 coatings on metallic substrate was investigated by Cross-Cut-Test (ASTM D 3359). The sessile drop method was used to determine the contact angle. PMMA coatings presented complete degradation from 250 °C, while hybrid coatings of PMMA and HTT 1800 have good protection until 400 °C. The adherence of the coating on metallic substrate showed improvement in all synthesized materials when compared to pure PMMA, obtaining the best adherence possible. The contact angle test showed that the hydrophobicity of the hybrid coatings is higher than that of the pure coatings.

  18. Antifungal activity of water-stable copper-containing metal-organic frameworks

    Science.gov (United States)

    Bouson, Supaporn; Krittayavathananon, Atiweena; Phattharasupakun, Nutthaphon; Siwayaprahm, Patcharaporn; Sawangphruk, Montree

    2017-10-01

    Although metal-organic frameworks (MOFs) or porous coordination polymers have been widely studied, their antimicrobial activities have not yet been fully investigated. In this work, antifungal activity of copper-based benzene-tricarboxylate MOF (Cu-BTC MOF), which is water stable and industrially interesting, is investigated against Candida albicans, Aspergillus niger, Aspergillus oryzae and Fusarium oxysporum. The Cu-BTC MOF can effectively inhibit the growth rate of C. albicans and remarkably inhibit the spore growth of A. niger, A. oryzae and F. oxysporum. This finding shows the potential of using Cu-BTC MOF as a strong biocidal material against representative yeasts and moulds that are commonly found in the food and agricultural industries.

  19. Facile construction of terpridine-based metallo-polymers in hydrogels, crystals and solutions directed by metal ions.

    Science.gov (United States)

    Li, Yajuan; Guo, Jiangbo; Dai, Bo; Geng, Lijun; Shen, Fengjuan; Zhang, Yajun; Yu, Xudong

    2018-07-01

    Driven by tunable metal-ligand interactions, a polydentate ligand TC containing terpyridine and carboxylic acid units was developed to construct metallo-polymers that showed multiple aggregation modes with controlled macroscopic properties. In the presence of different kind of Zn 2+ ions or NaOH, TC could form metallo-polymers via π-π stacking and metal-ligand interaction that further trapped water molecules, resulting in hydrogels and crystals. Moreover, these TC/Zn 2+ hydrogels could transform to soluble and fluorescent aggregates in the presence of NaOH due to the formation of binuclear metallo-polymers with enhanced ICT emission. The metal-ligand interactions tuned by different metal salts in gels, crystals, and sols were also studied and illustrated in detail, it was also proved that water was an essential linker for constructing Na + -based metallo-polymers from the TC/NaOH crystal data. This work demonstrated the engineered coordination pathways in generating controllable hydrogels and metallo-polymers for the first time, which led to novel approach for facilely constructing a number of hydrogels with tailorable macroscopic properties. Copyright © 2018 Elsevier Inc. All rights reserved.

  20. Preparation and evaluation of open-tubular capillary column combining a metal-organic framework and a brush-shaped polymer for liquid chromatography.

    Science.gov (United States)

    Chen, Kai; Zhang, Lingyi; Zhang, Weibing

    2018-03-30

    In this work, an open-tubular capillary liquid-phase column was prepared by modifying chain polymer on the inner surface of capillary and chemical bonding of metal organic frameworks, NH 2 -UiO-66, to the brushes of chain polymer (poly(glycidyl methacrylate)). Besides advantages of facial preparation and good permeability, the chain polymer effectively increases the modification amount of NH 2 -UiO-66 nanoparticles to increase the phase ratio of open-tubular capillary column and enhance the interactions with analytes. The results of scanning electron microscope energy-dispersive X-ray spectra indicated that NH 2 -UiO-66 nanoparticles were successfully bonded to the chain polymer. Because of the hydrophobic interaction and hydrogen bonding interaction between the analytes and the ligand of NH 2 -UiO-66, different analytes were well separated on the NH 2 -UiO-66-modified poly(glycidyl methacrylate) capillary (1.12 m × 25 μm id × 365 μm od) with the high absolute column efficiency reaching 121 477 plates, benefiting from an open-tubular column and low mass transfer resistance provided by polymer brush and metal-organic framework crystal. The relative standard deviations of the retention time for run-to-run, day-to-day, and column-to-column (n = 3) runs are below 4.28%, exhibiting good repeatability. Finally, the column was successfully applied to separation of flavonoids in licorice. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis and Molecular Structures of Two [1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene]-dichloro-Zn(II Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Hsin-Ta Wang

    2006-08-01

    Full Text Available Two novel coordination polymers with 3D metal-organic frameworks (MOFs have been synthesized by reacting 1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene (L with zinc dichloride. Both compounds have the same repeating unit consisting of a distorted tetrahedral Zn(II center coordinated by two chlorides and two pyridyl nitrogen atoms of two bridging bismonodentate L ligands, however, different structural conformations have been found, one forming a helical chain and the other producing a square-wave chain. The intermolecular C−H···Cl hydrogen bonds in 1 and 2 play important roles in the formation of three-dimensional coordination polymers. Compound 1 crystallized in an orthorhombic space group Pna21 with a = 7.9652(3, b = 21.4716(7, c = 8.2491(3Å, V = 1410.81(9 Å 3 and Z = 4. Compound 2 crystallized in a monoclinic space group P21/n with a = 9.1752(3, b = 14.5976(4, c = 10.3666(3 Å , β = 98.231(2°, V = 1374.16(7 Å 3 and Z = 4.

  2. Chemistry of the metal-polymer interfacial region.

    Science.gov (United States)

    Leidheiser, H; Deck, P D

    1988-09-02

    In many polymer-metal systems, chemical bonds are formed that involve metal-oxygen-carbon complexes. Infrared and Mössbauer spectroscopic studies indicate that carboxylate groups play an important role in some systems. The oxygen sources may be the polymer, the oxygen present in the oxide on the metal surface, or atmospheric oxygen. Diffusion of metal ions from the substrate into the polymer interphase may occur in some systems that are cured at elevated temperatures. It is unclear whether a similar, less extensive diffusion occurs over long time periods in systems maintained at room temperature. The interfacial region is dynamic, and chemical changes occur with aging at room temperature. Positron annihilation spectroscopy may have application to characterizing the voids at the metal-polymer interface.

  3. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    Science.gov (United States)

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

  4. Removal and recovery of toxic metal ions from aqueous waste sites using polymer pendant ligands

    International Nuclear Information System (INIS)

    Fish, D.

    1996-01-01

    The purpose of this project is to investigate the use of polymer pendant ligand technology to remove and recover toxic metal ions from DOE aqueous waste sites. Polymer pendant lgiands are organic ligands, anchored to crosslinked, modified divinylbenzene-polystyrene beads, that can selectively complex metal ions. The metal ion removal step usually occurs through a complexation or ion exchange phenomena, thus recovery of the metal ions and reuse of the beads is readily accomplished

  5. Metals in proteins: correlation between the metal-ion type, coordination number and the amino-acid residues involved in the coordination.

    Science.gov (United States)

    Dokmanić, Ivan; Sikić, Mile; Tomić, Sanja

    2008-03-01

    Metal ions are constituents of many metalloproteins, in which they have either catalytic (metalloenzymes) or structural functions. In this work, the characteristics of various metals were studied (Cu, Zn, Mg, Mn, Fe, Co, Ni, Cd and Ca in proteins with known crystal structure) as well as the specificity of their environments. The analysis was performed on two data sets: the set of protein structures in the Protein Data Bank (PDB) determined with resolution metal ion and its electron donors and the latter was used to assess the preferred coordination numbers and common combinations of amino-acid residues in the neighbourhood of each metal. Although the metal ions considered predominantly had a valence of two, their preferred coordination number and the type of amino-acid residues that participate in the coordination differed significantly from one metal ion to the next. This study concentrates on finding the specificities of a metal-ion environment, namely the distribution of coordination numbers and the amino-acid residue types that frequently take part in coordination. Furthermore, the correlation between the coordination number and the occurrence of certain amino-acid residues (quartets and triplets) in a metal-ion coordination sphere was analysed. The results obtained are of particular value for the identification and modelling of metal-binding sites in protein structures derived by homology modelling. Knowledge of the geometry and characteristics of the metal-binding sites in metalloproteins of known function can help to more closely determine the biological activity of proteins of unknown function and to aid in design of proteins with specific affinity for certain metals.

  6. Selective metal-vapor deposition on solvent evaporated polymer surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, Koji; Tsujioka, Tsuyoshi, E-mail: tsujioka@cc.osaka-kyoiku.ac.jp

    2015-12-31

    We report a selective metal-vapor deposition phenomenon based on solvent printing and evaporation on polymer surfaces and propose a method to prepare fine metal patterns using maskless vacuum deposition. Evaporation of the solvent molecules from the surface caused large free volumes between surface polymer chains and resulted in high mobility of the chains, enhancing metal-vapor atom desorption from the surface. This phenomenon was applied to prepare metal patterns on the polymer surface using solvent printing and maskless metal vacuum deposition. Metal patterns with high resolution of micron scale were obtained for various metal species and semiconductor polymer substrates including poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] and poly(3-hexylthiophene-2,5-diyl). - Highlights: • Selective metal-vapor deposition using solvent evaporation on polymer was attained. • Metal patterns with high resolution were obtained for various metal species. • This method can be applied to achieve fine metal-electrodes for polymer electronics.

  7. Synthesis, characterization and applications of polymer-metal ...

    Indian Academy of Sciences (India)

    Abstract. 4-Acryloxy acetophenone was prepared and subjected to suspension polymerization with divinyl- benzene as a cross-linking agent. The resulting network polymer was ligated with benzoyl hydrazone. The functional polymer was treated with metal ions [Cu(II), Fe(II)]. The polymer-metal complexes obtained.

  8. Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg{sup 2+} from water

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Fei [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Qiu, Ling-Guang, E-mail: lgqiu@ahu.edu.cn [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Zhu, Jun-Fa [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China)

    2011-11-30

    Highlights: Black-Right-Pointing-Pointer A novel type of functionalized MOF for heavy metal removal. Black-Right-Pointing-Pointer Functionalization of MOF by a facile coordination-based postsynthetic strategy. Black-Right-Pointing-Pointer Thiol-functionalization of MOF has been realized for the first time. Black-Right-Pointing-Pointer Enhanced removal of Hg{sup 2+} by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu{sub 3}(BTC){sub 2}(H{sub 2}O){sub 3}]{sub n} (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu{sub 3}(BTC){sub 2}]{sub n} samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N{sub 2} sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu{sub 3}(BTC){sub 2}]{sub n} exhibited remarkably high adsorption affinity (K{sub d} = 4.73 Multiplication-Sign 10{sup 5} mL g{sup -1}) and high adsorption capacity (714.29 mg g{sup -1}) for Hg{sup 2+} adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg{sup 2+} under the same condition.

  9. Solvent induced synthesis, structure and properties of coordination polymers based on 5-hydroxyisophthalic acid as linker and 1,10-phenanthroline as auxiliary ligand

    Science.gov (United States)

    Kariem, Mukaddus; Yawer, Mohd; Sheikh, Haq Nawaz

    2015-11-01

    Three new coordination polymers [Mn(hip)(phen) (H2O)]n (1), [Co(hip)(phen) (H2O)]n (2), and [Cd(hip) (phen) (H2O)]n (3) (H2hip=5-hydroxyisophthalic acid; phen=1,10-phenanthroline) have been synthesized by solvo-hydrothermal method using diethyl formamide-water (DEF-H2O) as solvent system. Single-crystal X-ray diffraction analysis reveals that all three coordination polymers 1, 2 and 3 crystallize in monoclinic space group P2/n. Metal ions are inter-connected by hydroxyisophthalate anions forming zig-zag 1D chain. 1D chains are further inter-connected by hydrogen bonding and π-π stacking interactions leading to 3D supramolecular architecture. Hydrogen-bonding and π-π stacking provide thermal stability to polymers. Compounds 1 and 2 are paramagnetic at room temperature and variable temperature magnetic moment measurements revealed weak ferromagnetic interactions between metal ions at low temperature. Compound 3 exhibits excellent photoluminescence with large Stokes shift.

  10. Modular assembly of low-dimensional coordination architectures on metal surfaces

    International Nuclear Information System (INIS)

    Stepanow, Sebastian; Lin, Nian; Barth, Johannes V

    2008-01-01

    The engineering of highly organized molecular architectures has attracted strong interest because of its potential for novel materials and functional nanoscopic devices. An important factor in the development, integration, and exploitation of such systems is the capability to prepare them on surfaces or in nanostructured environments. Recent advances in supramolecular design on metal substrates provide atomistic insight into the underlying self-assembly processes, mainly by scanning tunneling microscopy observations. This review summarizes progress in noncovalent synthesis strategies under ultra-high vacuum conditions employing metal ions as coordination centers directing the molecular organization. The realized metallosupramolecular compounds and arrays combine the properties of their constituent metal ions and organic ligands, and present several attractive features: their redox, magnetic and spin-state transitions. The presented exemplary molecular level studies elucidate the arrangement of organic adsorbates on metal surfaces, demonstrating the interplay between intermolecular and molecule-substrate interactions that needs to be controlled for the fabrication of low-dimensional structures. The understanding of metallosupramolecular organization and metal-ligand interactions on solid surfaces is important for the control of structure and concomitant function

  11. Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

    Science.gov (United States)

    Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

    2016-04-25

    Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Three luminescent d{sup 10} metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu{sup 2+} ion and nitrobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Wei-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China); Institute of Functional Materials, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Liu, Ping; Liang, Yu-Tong; Cui, Lin; Xi, Zheng-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China); Wang, Yao-Yu, E-mail: wyaoyu@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China)

    2015-08-15

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL{sub 2}]{sub n} (1) and ([ML{sub 2}]·(H{sub 2}O)){sub n} (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu{sup 2+} ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed. - Graphical abstract: Three luminescent d{sup 10} metal coordination polymers with helical-layer based on 4-((2-methyl-1H-imidazol-1-yl)methyl)benzoic acid have been obtained. Compound 1 shows high selective detecting for Cu{sup 2+} ion in aqueous and nitrobenzene. - Highlights: • Three coordination polymers with chiral helical-layer have been obtained. • 1 Can luminescent detect Cu{sup 2+} ion in aqueous media and nitrobenzene. • Racemic mixture or mesomer compounds can be obtained by controlling the reaction conditions.

  13. (1-Butyl-4-methyl-pyridinium)[Cu(SCN)2]: a coordination polymer and ionic liquid.

    Science.gov (United States)

    Spielberg, Eike T; Edengeiser, Eugen; Mallick, Bert; Havenith, Martina; Mudring, Anja-Verena

    2014-04-25

    The compound (C4C1py)[Cu(SCN)2], (C4C1py = 1-Butyl-4-methyl-pyridinium), which can be obtained from CuSCN and the ionic liquid (C4C1py)(SCN), turns out to be a new organic-inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)2](-) units, in which the thiocyanates bridge the copper ions in a μ1,3-fashion. The resulting one-dimensional chains run along the a axis, separated by the C4C1py counterions. Powder X-ray diffraction not only confirms the single-crystal X-ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature-dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100 °C point towards the formation of polyanionic chain fragments in the melt. Solid-state UV/Vis spectroscopy shows a broad absorption band around 18,870 cm(-1) (530 nm) and another strong one below 20,000 cm(-1) (<500 nm). The latter is attributed to the d(Cu(I))→π*(SCN)-MLCT (metal-to-ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15,870 cm(-1) (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Hydrothermal syntheses, crystal structures, and photophysical properties of two coordination polymers with mixed ligands

    Science.gov (United States)

    Yan, Li; Liu, Chun-Ling

    2017-10-01

    Two novel metal-organic coordination polymers [Cd(ipdt)(m-BDC)·3H2O]n (1) and [Pb(mip)2(NTC) ·2H2O]n (2) [ipdt = 2,6-Dimethoxy-4-(1H-1,3,7,8-tetraaza-cyclopenta[l]phenanthren-2-yl)-phenol, mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, m-BDC = isophthalic acid, NTC = nicotinic acid] have been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 exhibits two-dimensional (2D) layer architecture, and 2 shows 1D chain architecture. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. The luminescent properties for the ligand ipdt, mip and complexes 1-2 are also discussed in detail, which should be acted as potential luminescent material.

  15. One Dimensional Coordination Polymer of Zn(II) for Developing Multifunctional Nanoparticles.

    Science.gov (United States)

    Agarwal, Rashmi A

    2017-10-16

    A variety of nanoparticles (NPs) including Ag, Au, Pd, Cr and mixed Cu/Fe have been synthesized in a non-activated (without solvent removal) one dimensional coordination polymer (CP) of Zn(II) via two different mechanisms, acid formation and redox activity of the framework. Main driving force to grow these NPs within the cavities of CP is the presence of free oxygens of one of the monodentate carboxylate groups of BDC ligand. These free oxygens act as anchoring sites for the metal ions of the metal precursors. Chemical and physical characteristics of the NPs within the framework have been evaluated by the high resolution transmission electron microscopic (HRTEM) images. Excluding Ag(0) and Pd(0) other NPs are present as combinations of their elemental as well as oxide forms (Au/Au 2 O 3 , Cr/Cr 2 O 3 /CrO 2 and Cu/Cu 2 O, Fe/FeO). Synthesized Ag NPs within the framework show remarkable antibacterial efficacy at extremely low concentrations. Ag, Au and Cu/Fe NPs show ferromagnetic properties within the framework at room temperature. This polymer has potential to sequester highly toxic Cr(VI) to non toxic Cr(0), Cr(III) and Cr(IV) species.

  16. A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal$-$Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Jacob A. [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Petersen, Brenna M. [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Kormos, Attila [Hungarian Academy of Sciences, Budapest (Hungary); Echeverría, Elena [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy; Chen, Yu-Sheng [Univ. of Chicago, Argonne, IL (United States). ChemMatCARS, Center for Advanced Radiation Sources; Zhang, Jian [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry

    2017-02-28

    Here, we describe a new strategy to generate non-coordinating anions using zwitterionic metal–organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4]$-$) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of MnIII- and FeIII-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels–Alder cycloaddition of aldehydes with dienes. Lastly, this work paves a new way to design functional MOFs for tunable chemical catalysis.

  17. Recyclable Cu(II)-Coordination Crosslinked Poly(benzimidazolyl pyridine)s as High-Performance Polymers.

    Science.gov (United States)

    Wang, Cheng; Yang, Li; Chang, Guanjun

    2018-03-01

    Crosslinked high-performance polymers have many industrial applications, but are difficult to recycle or rework. A novel class of recyclable crosslinking Cu(II)-metallo-supramolecular coordination polymers are successfully prepared, which possess outstanding thermal stability and mechanical property. More importantly, the Cu 2+ coordination interactions can be further removed via external pyrophosphate to recover the linear polymers, which endow the crosslinking polymers with recyclability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis, crystal structure and luminescent properties of one 3D Cd(II) coordination polymer [Cd(H3BPTC)2(bpy)]n (H4BPTC = 1,1'-biphenyl-2,2',6,6'-tetracarboxylic acid, bpy = 4,4'-bipyridine).

    Science.gov (United States)

    Mei, Chong-Zhen; Shan, Wen-Wen; Liu, Bing-Tao

    2011-10-15

    A new 3D metal-organic coordination polymer [Cd(H(3)BPTC)(2)(bpy)](n) (1) (H(4)BPTC = 1,1'-biphenyl-2,2',6,6'-tetracarboxylic acid, bpy =4,4'-bipyridine) has been synthesized and characterized by single X-ray diffraction and IR spectroscopy. The one-dimensional metal-organic chains of the title complex, namely [Cd(H(3)BPTC)(2)](n), are held together through hydrogen bonding and bridging "second" ligand 4,4'-bpy to give a three-dimensional metal-organic network. The thermal stability of complex 1 was studied by thermal gravimetric (TG) and differential thermal analysis (DTA). Compound 1 exhibits photoluminescence with an emission maximum at ca. 380 nm upon excitation at ca. 251 nm. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Coordination compounds of metals with imidazoles and benzimidazoles

    International Nuclear Information System (INIS)

    Novikova, G.A.; Molodkin, A.K.; Kukalenko, S.S.

    1988-01-01

    Methods of preparation, composition and structure of UO 2 2+ , Th 4+ , Mo 3+ , Cd 2+ , Ln 3+ metal ion complexes with imidazoles and benzimidazoles are considered in reviews of native and foreign literature of up to 1985. Complexes are customarily prepared by direct interaction of ligands with inorganic salts in different organic solvents. Complex composition is defined by the nature of complexing metal and inorganic salt anion, ligand volume and basicity, as well as solvent characteristics. Effect of R substituent in imidazole and benzimidazole side chain on composition of coordination compounds is considered

  20. Pyrolysis of Helical Coordination Polymers for Metal-Sulfide-Based Helices with Broadband Chiroptical Activity.

    Science.gov (United States)

    Hirai, Kenji; Yeom, Bongjun; Sada, Kazuki

    2017-06-27

    Fabrication of chiroptical materials with broadband response in the visible light region is vital to fully realize their potential applications. One way to achieve broadband chiroptical activity is to fabricate chiral nanostructures from materials that exhibit broadband absorption in the visible light region. However, the compounds used for chiroptical materials have predominantly been limited to materials with narrowband spectral response. Here, we synthesize Ag 2 S-based nanohelices derived from helical coordination polymers. The right- and left-handed coordination helices used as precursors are prepared from l- and d-glutathione with Ag + and a small amount of Cu 2+ . The pyrolysis of the coordination helices yields right- and left-handed helices of Cu 0.12 Ag 1.94 S/C, which exhibit chiroptical activity spanning the entire visible light region. Finite element method simulations substantiate that the broadband chiroptical activity is attributed to synergistic broadband light absorption and light scattering. Furthermore, another series of Cu 0.10 Ag 1.90 S/C nanohelices are synthesized by choosing the l- or d-Glu-Cys as starting materials. The pitch length of nanohelicies is controlled by changing the peptides, which alters their chiroptical properties. The pyrolysis of coordination helices enables one to fabricate helical Ag 2 S-based materials that enable broadband chiroptical activity but have not been explored owing to the lack of synthetic routes.

  1. Coordination Nature of 4-Mercaptoaniline to Sn(II Ion: Formation of a One Dimensional Coordination Polymer and Its Decomposition to a Mono Nuclear Sn(IV Complex

    Directory of Open Access Journals (Sweden)

    Eon S. Burkett

    2014-12-01

    Full Text Available The coordination of the bifunctional ligand 4-mercaptoaniline with aqueo us tin(II metal ion was studied. A coordination polymer was synthesized when an aqueous solution of SnCl2 was treated with 4-MA. The crystalline material is stable under atmospheric conditions retaining its oxidation state. However, when submerged in a solution saturated with oxygen, the compound oxidizes to a mononuclear tin(IV complex. Both the compounds were characterized by single crystal X-ray diffraction studies. Although the structure of the tin(IV complex was previously reported, crystal structure of this compound was redetermined.

  2. Polymer filtration: A new technology for selective metals recovery

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.F.; Robison, T.W.; Cournoyer, M.E.; Wilson, K.V.; Sauer, N.N.; Mullen, K.I.; Lu, M.T.; Jarvinen, J.J.

    1995-04-01

    Polymer Filtration (PF) was evaluated for the recovery of electroplating metal ions (zinc and nickel) from rinse waters. Polymer Filtration combines the use of water-soluble metal-binding polymers and ultrafiltration to concentrate metal ions from dilute rinse water solutions. The metal ions are retained by the polymers; the smaller, unbound species freely pass through the ultrafiltration membrane. By using this process the ultrafiltered permeate more than meets EPA discharge limits. The metal ions are recovered from the concentrated polymer solution by pH adjustment using diafiltration and can be recycled to the original electroplating baths with no deleterious effects on the test panels. Metal-ion recovery is accomplished without producing sludge.

  3. Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties.

    Science.gov (United States)

    Bendjellal, Nassima; Trifa, Chahrazed; Bouacida, Sofiane; Boudaren, Chaouki; Boudraa, Mhamed; Merazig, Hocine

    2018-02-01

    In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ 2 N,N')bis(μ-3-phenylprop-2-enoato-κ 3 O,O':O)calcium(II)], [Ca(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (1), and poly[(1,10-phenanthroline-κ 2 N,N')(μ 3 -3-phenylprop-2-enoato-κ 4 O:O,O':O')(μ-3-phenylprop-2-enoato-κ 3 O,O':O)barium(II)], [Ba(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (2), and characterized them by FT-IR and UV-Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C-H...O hydrogen bonds and π-π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297-1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.

  4. 21 CFR 888.3358 - Hip joint metal/polymer/metal semi-constrained porous-coated uncemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint metal/polymer/metal semi-constrained... Devices § 888.3358 Hip joint metal/polymer/metal semi-constrained porous-coated uncemented prosthesis. (a) Identification. A hip joint metal/polymer/metal semi-constrained porous-coated uncemented prosthesis is a device...

  5. Chemical metallization of KMPR photoresist polymer in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Zeb, Gul [MiQro Innovation Collaborative Centre (C2MI), 45, boul. de l' Aéroport, Bromont, QC, J2L 1S8 (Canada); Mining & Materials Engineering, McGill University, 3610,University Street, Montreal, QC, H3A 0C5 (Canada); Duong, Xuan Truong [Department of Mechanical Engineering, Ecole polytechnique de Montréal, Montréal, QC, H3C 3T5 (Canada); Thai Nguyen University of Technology, 3-2 Street, Thai Nguyen City (Viet Nam); Vu, Ngoc Pi; Phan, Quang The; Nguyen, Duc Tuong; Ly, Viet Anh [Thai Nguyen University of Technology, 3-2 Street, Thai Nguyen City (Viet Nam); Salimy, Siamak [ePeer Review LLC, 145 Pine Haven Shores Rd, Suite 1000-X, Shelburne, VT 05482 (United States); Le, Xuan Tuan, E-mail: xuantuan.le@teledyne.com [MiQro Innovation Collaborative Centre (C2MI), 45, boul. de l' Aéroport, Bromont, QC, J2L 1S8 (Canada); Thai Nguyen University of Technology, 3-2 Street, Thai Nguyen City (Viet Nam)

    2017-06-15

    Highlights: • Electroless deposition of Ni-B film on KMPR photoresist polymer insulator with excellent adhesion has been achieved. • This metallization has been carried out in aqueous solutions at low temperature. • Polyamine palladium complexes grafts serve as seeds for the electroless plating on KMPR. • This electroless metallization process is simple, industrially feasible, chromium-free and environment-friendly. - Abstract: While conventional methods for preparing thin films of metals and metallic alloys on insulating substrates in the field of microelectromechanical systems (MEMS) include vapor deposition techniques, we demonstrate here that electroless deposition can be considered as an alternate efficient approach to metallize the surface of insulating substrates, such as KMPR epoxy photoresist polymer. In comparison with the physical and chemical vapor deposition methods, which are well-established for metallization of photoresist polymers, our electroless nickel plating requires only immersing the substrates into aqueous solutions in open air at low temperatures. Thin films of nickel alloy have been deposited electrolessly on KMPR surface, through a cost-effective and environmental chromium-free process, mediated through direct grafting of amine palladium complexes in aqueous medium. This covalent organic coating provides excellent adhesion between KMPR and the nickel film and allows better control of the palladium catalyst content. Covalent grafting and characterization of the deposited nickel film have been carried out by means of Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy techniques.

  6. Mechanics of metal-catecholate complexes: The roles of coordination state and metal types

    Science.gov (United States)

    Xu, Zhiping

    2013-01-01

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications. PMID:24107799

  7. Gas adsorption/separation properties of metal directed self-assembly of two coordination polymers with 5-nitroisophthalate

    Energy Technology Data Exchange (ETDEWEB)

    Arıcı, Mürsel [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Keskin, Seda [Department of Chemical and Biological Engineering, Koç University, İstanbul (Turkey); Şahin, Onur [Scientific and Technological Research Application and Research Center, Sinop University, 57010 Sinop (Turkey)

    2014-02-15

    Two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Thermal properties of the complexes showed that both complexes were stable over 320 °C. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. - Graphical abstract: In this study, two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. Display Omitted - Highlights: • Two new coordination polymers with 5-nitroisophthalate and 1,2-bis(4-pyridyl)ethane. • Atomically detailed simulation studies of the complexes. • Complex 2 can be proposed as molecular sieve to separate CO{sub 2} from CH{sub 4} at low pressures.

  8. Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

    Science.gov (United States)

    Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2012-09-17

    Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

  9. Gold nanoparticles modified with coordination compounds of metals: synthesis and application

    International Nuclear Information System (INIS)

    Beloglazkina, Elena K; Majouga, Alexander G; Romashkina, Renata B; Zyk, Nikolai V; Zefirov, Nikolai S

    2012-01-01

    The data on the preparation methods and applications of gold nanoparticles with coordinated metal ions on the surfaces are generalized. The currently available data on the interaction of metal ions with gold nanoparticles modified with organic (particularly, sulfur-containing) ligands comprising terminal chelating groups are considered in detail as well as the applications of such modified nanoparticles. The bibliography includes 141 references.

  10. A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

    Science.gov (United States)

    Rao, B. Narasimha; Suvarna, R. Padma

    2016-05-01

    Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

  11. Diffusion Control in the in Situ Synthesis of Iconic Metal-Organic Frameworks within an Ionic Polymer Matrix.

    Science.gov (United States)

    Lim, Jungho; Lee, Eun Ji; Choi, Jae Sun; Jeong, Nak Cheon

    2018-01-31

    Ionic polymers that possess ion-exchangeable sites have been shown to be a greatly useful platform to fabricate mixed matrices (MMs) where metal-organic frameworks (MOFs) can be in situ synthesized, although the in situ synthesis of MOF has been rarely studied. In this study, alginate (ALG), an anionic green polymer that possesses metal-ion-exchangeable sites, is employed as a platform of MMs for the in situ synthesis of iconic MOFs, HKUST-1, and MOF-74(Zn). We demonstrate for the first time that the sequential order of supplying MOF ingredients (metal ion and deprotonated ligand) into the alginate matrix leads to substantially different results because of a difference in the diffusion of the MOF components. For the examples examined, whereas the infusion of BTC 3- ligand into Cu 2+ -exchanged ALG engendered the eggshell-shaped HKUST-1 layers on the surface of MM spheres, the infusion of Cu 2+ ions into BTC 3- -included alginate engendered the high dispersivity and junction contact of HKUST-1 crystals in the alginate matrix. This fundamental property has been exploited to fabricate a flexible MOF-containing mixed matrix membrane by coincorporating poly(vinyl alcohol). Using two molecular dyes, namely, methylene blue and rhodamine 6G, further, we show that this in situ strategy is suitable for fabricating an MOF-MM that exhibits size-selective molecular uptake.

  12. Deformation limits of polymer coated metal sheets

    NARCIS (Netherlands)

    Van Den Bosch, M.J.W.J.P.; Schreurs, P.J.G; Geers, M.G.D.

    2005-01-01

    Polymer coated metals are increasingly used by the packaging and automotive industry. During industrial deformation processes (drawing, roll-forming, bending etc.) the polymer-metal laminate is highly deformed at high deformation rates. These forming conditions can affect the mechanical integrity

  13. Chemical metallization of KMPR photoresist polymer in aqueous solutions

    Science.gov (United States)

    Zeb, Gul; Duong, Xuan Truong; Vu, Ngoc Pi; Phan, Quang The; Nguyen, Duc Tuong; Ly, Viet Anh; Salimy, Siamak; Le, Xuan Tuan

    2017-06-01

    While conventional methods for preparing thin films of metals and metallic alloys on insulating substrates in the field of microelectromechanical systems (MEMS) include vapor deposition techniques, we demonstrate here that electroless deposition can be considered as an alternate efficient approach to metallize the surface of insulating substrates, such as KMPR epoxy photoresist polymer. In comparison with the physical and chemical vapor deposition methods, which are well-established for metallization of photoresist polymers, our electroless nickel plating requires only immersing the substrates into aqueous solutions in open air at low temperatures. Thin films of nickel alloy have been deposited electrolessly on KMPR surface, through a cost-effective and environmental chromium-free process, mediated through direct grafting of amine palladium complexes in aqueous medium. This covalent organic coating provides excellent adhesion between KMPR and the nickel film and allows better control of the palladium catalyst content. Covalent grafting and characterization of the deposited nickel film have been carried out by means of Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy techniques.

  14. Gas Phase Sensing of Alcohols by Metal Organic Framework–Polymer Composite Materials

    Science.gov (United States)

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0–100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing

  15. Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

    International Nuclear Information System (INIS)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil

    2012-01-01

    We rationally designed and synthesized metallopolymers with organic 1,4-benzenedicarboxylic acid (BDC) linkers with different lengths of oxyethylene side chains in order to examine the influence of side chains on the coordination characteristics. While in a previous report the BDC linkers with alkyl side chains were found to form three-dimensional (3D) isoreticular metal-organic framework (IRMOF) structures or one-dimensional (1D) coordination polymeric structures with short -O(CH 2 ) 6 CH 3 or long -O(CH 2 ) 9 CH 3 side chains, respectively, new BDC linkers with oxyethylene side chains of the same lengths, -(OCH 2 CH 2 ) 2 CH 3 and -(OCH 2 CH 2 ) 3 CH 3 , form only 3D IRMOF structures. This result is attributed to the higher flexibility and smaller volume of oxyethylene side chains compared to alkyl side chains

  16. Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

    Directory of Open Access Journals (Sweden)

    Samantha Russell

    2015-11-01

    Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

  17. Chemical Reactions Catalyzed by Metalloporphyrin-Based Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Kelly Aparecida Dias de Freitas Castro

    2013-06-01

    Full Text Available The synthetic versatility and the potential application of metalloporphyrins (MP in different fields have aroused researchers’ interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs, contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2- or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions.

  18. Amorphous infinite coordination polymer microparticles: a new class of selective hydrogen storage materials

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, You-Moon; Heo, Jungseok; Mirkin, Chad A [Department of Chemistry, International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, IL (United States); Armatas, Gerasimos S [Department of Chemistry, Northwestern University, Evanston, IL (United States); Kanatzidis, Mercouri G [Materials Science Division, Argonne National Laboratory, Argonne, IL (United States)

    2008-06-04

    A new class of micrometer-sized amorphous infinite coordination particles is selectively prepared from the coordination chemistry of a metallo-salen building block and Zn{sup 2+} ions. The particles show moderately high H{sub 2} uptake and almost no N{sub 2} adsorption, even though they are amorphous and do not have the well-defined channels typically used to explain such selectivity in metal-organic framework systems. (Abstract Copyright [2008], Wiley Periodicals, Inc.)

  19. Graphene-Reinforced Metal and Polymer Matrix Composites

    Science.gov (United States)

    Kasar, Ashish K.; Xiong, Guoping; Menezes, Pradeep L.

    2018-06-01

    Composites have tremendous applicability due to their excellent capabilities. The performance of composites mainly depends on the reinforcing material applied. Graphene is successful as an efficient reinforcing material due to its versatile as well as superior properties. Even at very low content, graphene can dramatically improve the properties of polymer and metal matrix composites. This article reviews the fabrication followed by mechanical and tribological properties of metal and polymer matrix composites filled with different kinds of graphene, including single-layer, multilayer, and functionalized graphene. Results reported to date in literature indicate that functionalized graphene or graphene oxide-polymer composites are promising materials offering significantly improved strength and frictional properties. A similar trend of improved properties has been observed in case of graphene-metal matrix composites. However, achieving higher graphene loading with uniform dispersion in metal matrix composites remains a challenge. Although graphene-reinforced composites face some challenges, such as understanding the graphene-matrix interaction or fabrication techniques, graphene-reinforced polymer and metal matrix composites have great potential for application in various fields due to their outstanding properties.

  20. Neutron powder diffraction of metal-organic frameworks for ...

    Indian Academy of Sciences (India)

    We review recent structural studies that we have undertaken aimed at elucidating the fundamental properties of metal-organic framework materials and their interactions with hydrogen. We have shown that exposing coordinatively unsaturated metal centers can greatly enhance the hydrogen binding energy and that they ...

  1. Synthesis, crystal structure and DFT calculations of a new Hg (II) metal-organic polymer

    Czech Academy of Sciences Publication Activity Database

    Mirtamizdoust, B.; Roodsari, M.S.; Shaabani, B.; Dušek, Michal; Fejfarová, Karla

    2016-01-01

    Roč. 15, č. 3 (2016), s. 257-266 ISSN 1024-1221 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : mercury (II) iodide * coordination polymer * square planar * tetrahedral geometry * density functional calculation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.565, year: 2016

  2. Fluid Structure Interaction Analysis in Manufacturing Metal/Polymer Macro-Composites

    International Nuclear Information System (INIS)

    Baesso, R.; Lucchetta, G.

    2007-01-01

    Polymer Injection Forming (PIF) is a new manufacturing technology for sheet metal-polymer macro-composites, which results from the combination of injection moulding and sheet metal forming. This process consists on forming the sheet metal according to the boundary of the mould cavity by means of the injected polymer. After cooling, the polymer bonds permanently to the metal resulting in a sheet metal-polymer macro-composite product. Comparing this process to traditional ones (where the polymeric and metal parts are joined together after separate forming) the main advantages are both reduction of production costs and increase of part quality. This paper presents a multi-physics numerical simulation of the process performed in the Ansys/CFX environment

  3. The architecture of metal coordination groups in proteins.

    Science.gov (United States)

    Harding, Marjorie M

    2004-05-01

    A set of tables is presented and a survey given of the architecture of metal coordination groups in a representative set of protein structures from the Protein Data Bank [Bernstein et al. (1977), J. Mol. Biol. 112, 535-542; Berman et al. (2000), Nucleic Acids Res. 28, 235-242]. The structures have been determined to a resolution of 2.5 A or better; the metals considered are Ca, Mg, Mn, Fe, Cu, Zn, Na and K, with particular emphasis on Ca and Zn and the exclusion of haem groups and Fe/S clusters; the proteins are a representative set in which none has more than 30% sequence identity with any other. In them the metal is coordinated by several donor groups from different amino-acid residues in the protein chain and often also by water or other small molecules. The tables, for approximately 600 metal coordination groups, include information on the conformations of the protein chain in the region around the metal and reliability indicators. They illustrate the wide variety of coordination numbers, chelate-loop sizes and other properties and the different characteristics of different metals. They show that glycine has a particular significance in the position adjacent to a donor residue, especially in Ca coordination groups. They also show that metal coordination does not appear to lead to significant distortions of the torsion angles phi, psi from their normally allowed values. Very few metal coordination groups occur more than once in the representative set and when they do they are usually related in fold and function; they have similar but not necessarily identical conformations. However, individual chelate loops, for example Zn(-C-X-X'-C-), in which both cysteines are coordinated to Zn through S, and X and X' are any amino acids, are repeated frequently in many different and unrelated proteins. Not all chelate loops with the same composition have the same conformation, but for smaller loops there are usually one or two strongly preferred and well defined

  4. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando

    2016-07-07

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  5. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

    2016-01-01

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  6. Anion-Controlled Architecture and Photochromism of Naphthalene Diimide-Based Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Jian-Jun Liu

    2018-02-01

    Full Text Available Three new cadmium coordination polymers, namely [Cd(NO32(DPNDI(CH3OH]·CH3OH (1, [Cd(SCN2(DPNDI] (2, and [Cd(DPNDI2(DMF2]·2ClO4 (3 (DPNDI = N,N-di(4-pyridyl-1,4,5,8-naphthalene diimide, DMF = N,N-dimethylformamide have been synthesized by reactions of DPNDI with Cd(NO32, Cd(SCN2, and Cd(ClO42, respectively. Compound 1 is a one-dimensional coordination polymer with strong lone pair-π interactions between the coordinated NO3− anions and the imide ring of DPNDI; while 2 is a two-dimensional network with a (4, 4 net topology. In the case of 3, due to the presence of uncoordinated perchlorate counter ions, it exhibits a non-interpenetrated square-grid coordination polymer containing one-dimensional rhomboid channels. The structural diversity in these compounds is attributed to different coordination abilities and geometries of counter anions. Due to the presence of electron-deficient NDI moiety, the photochromic behavior of these compounds was studied. Interestingly, only compounds 1 and 3 exhibit color changes under light irradiation. The influence of the anions on the photochromism process of the NDI-based materials has been discussed.

  7. Immobilization of metals in contaminated soils using natural polymer-based stabilizers.

    Science.gov (United States)

    Tao, Xue; Li, Aimin; Yang, Hu

    2017-03-01

    Three low-cost natural polymer materials, namely, lignin (Ln), carboxymethyl cellulose, and sodium alginate, were used for soil amendment to immobilize lead and cadmium in two contaminated soil samples collected from a mining area in Nanjing, China. The remediation effects of the aforementioned natural polymers were evaluated by toxicity characteristic leaching procedure (TCLP) and sequential extractions. The stabilizers could lower the bioavailability of Pb and Cd in the contaminated soils, and the amount of the exchangeable forms of the aforementioned two metals were reduced evidently. TCLP results showed that the leaching concentrations of Pb and Cd were decreased by 5.46%-71.1% and 4.25%-49.6%, respectively, in the treated soils. The contents of the organic forms of the two metals both increased with the increase in stabilizer dose on the basis of the redistribution of metal forms by sequential extractions. These findings were due to the fact that the abundant oxygen-containing groups on the polymeric amendments were effective in chelating and immobilizing Pb and Cd, which have been further confirmed from the metal adsorptions in aqueous solutions. Moreover, Ln achieved the greatest effect among the three polymers under study because of the former's distinct three-dimensional molecular structure, showing the preferential immobilization of Pb over Cd in soils also. Thus, the above-mentioned natural polymers hold great application potentials for reducing metal ion entry into the food chain at a field scale. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Three-dimensional tetranuclear Cd(II) coordination network based on a 1,3-alternate calix[4]arene derivative

    International Nuclear Information System (INIS)

    Lee, Eun Ji; Ju, Hui Yeong; Park, Ki Min; Moon, ASuk Hee; Kang, Young Jin

    2015-01-01

    Polynuclear coordination polymers can exhibit more intriguing network topologies and better functionalities than those of common complexes because they have metal-cluster nodes for the construction of multidimensional frameworks and the potential applications induced by collaborative activities between metal ions. New tetranuclear Cd(II) coordination polymer 1 based on 1,3-alternate calix arene derivative (H_4 CTA) with four carboxyl pendant arms has been synthesized by the solvo thermal reaction at 110 .deg. C for 2 days. Compound 1 shows a 3-D framework consisting of tetranuclear Cd(II) cluster core as a metal-cluster node and 1,3-alternate H_4CTA as a multidentate linker. The coordination polymer 1 displays intense blue emission, implying that this tetranuclear Cd(II) coordination polymer could be a suitable material in the area of luminescence research

  9. Polymer-supported metals and metal oxide nanoparticles: synthesis, characterization, and applications

    International Nuclear Information System (INIS)

    Sarkar, Sudipta; Guibal, E.; Quignard, F.; SenGupta, A. K.

    2012-01-01

    Metal and metal oxide nanoparticles exhibit unique properties in regard to sorption behaviors, magnetic activity, chemical reduction, ligand sequestration among others. To this end, attempts are being continuously made to take advantage of them in multitude of applications including separation, catalysis, environmental remediation, sensing, biomedical applications and others. However, metal and metal oxide nanoparticles lack chemical stability and mechanical strength. They exhibit extremely high pressure drop or head loss in fixed-bed column operation and are not suitable for any flow-through systems. Also, nanoparticles tend to aggregate; this phenomenon reduces their high surface area to volume ratio and subsequently reduces effectiveness. By appropriately dispersing metal and metal oxide nanoparticles into synthetic and naturally occurring polymers, many of the shortcomings can be overcome without compromising the parent properties of the nanoparticles. Furthermore, the appropriate choice of the polymer host with specific functional groups may even lead to the enhancement of the properties of nanoparticles. The synthesis of hybrid materials involves two broad pathways: dispersing the nanoparticles (i) within pre-formed or commercially available polymers; and (ii) during the polymerization process. This review presents a broad coverage of nanoparticles and polymeric/biopolymeric host materials and the resulting properties of the hybrid composites. In addition, the review discusses the role of the Donnan membrane effect exerted by the host functionalized polymer in harnessing the desirable properties of metal and metal oxide nanoparticles for intended applications.

  10. PREPARATION OF A POLYMER ARTICLE FOR SELECTIVE METALLIZATION

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention relates to the field of selective metallization, and in particular to preparing a polymer article for selective metallization by submerging the article in a first liquid, and while submergedirradiate the article by a laser beam the area of the article on which the metal...... is to be deposited. An activation step, prior to the selective metallization, comprises submerging the article in an activation liquid for depositing seedparticles in the selected area. The irradiation of the selected area is proportionate so as to cause a temporary meltingof the polymer in the surface...... of the selected area of the polymer article. The invention is advantageous in that the preparation may be performed with a relatively high scan rate across the polymer article, and in that a quite limited use of toxic chemicals....

  11. Enhancement of oxygen reduction at Fe tetrapyridyl porphyrin by pyridyl-N coordination to transition metal ions

    International Nuclear Information System (INIS)

    Maruyama, Jun; Baier, Claudia; Wolfschmidt, Holger; Bele, Petra; Stimming, Ulrich

    2012-01-01

    One of the promising candidates as noble-metal-free electrode catalysts for polymer electrolyte fuel cells (PEFCs) is a carbon material with nitrogen atoms coordinating iron ions embedded on the surface (Fe-N x moiety) as the active site, although the activity is insufficient compared to conventional platinum-based electrocatalysts. In order to obtain fundamental information on the activity enhancement, a simple model of the Fe-N x active site was formed by adsorbing 5,10,15,20-Tetrakis(4-pyridyl)-21H,23H-porphine iron(III) chloride (FeTPyPCl) on the basal plane of highly oriented pyrolytic graphite (HOPG), and cathodic oxygen reduction was investigated on the surface in 0.1 M HClO 4 . The catalytic activity for oxygen reduction was enhanced by loading transition metal ions (Co 2+ , Ni 2+ , Cu 2+ ) together with FeTPyPCl. The X-ray photoelectron spectrum of the surface suggested that the metal was coordinated by the pyridine-N. The enhancement effect of the transition metals was supported by two different measurements: oxygen reduction at HOPG in 0.1 M HClO 4 dissolving FeTPyPCl and the metal ions; oxygen reduction in 0.1 M HClO 4 at the subsequently well-rinsed and dried HOPG. The ultraviolet–visible spectrum for the solution also suggested the coordination between the pyridyl-N and the metal ions. The oxygen reduction enhancement was attributed to the electronic interaction between the additional transition metal and the Fe center of the porphyrin through the coordination bonds. These results implied that the improvement of the activity of the noble-metal-free catalyst would be possible by the proper introduction of the transition metal ions around the active site.

  12. Ion conducting polymers and polymer blends for alkali metal ion batteries

    Science.gov (United States)

    DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

    2017-08-29

    Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

  13. Self-Templated Stepwise Synthesis of Monodispersed Nanoscale Metalated Covalent Organic Polymers for In Vivo Bioimaging and Photothermal Therapy.

    Science.gov (United States)

    Shi, Yanshu; Deng, Xiaoran; Bao, Shouxin; Liu, Bei; Liu, Bin; Ma, Ping'an; Cheng, Ziyong; Pang, Maolin; Lin, Jun

    2017-09-05

    Size- and shape-controlled growth of nanoscale microporous organic polymers (MOPs) is a big challenge scientists are confronted with; meanwhile, rendering these materials for in vivo biomedical applications is still scarce. In this study, a monodispersed nanometalated covalent organic polymer (MCOP, M=Fe, Gd) with sizes around 120 nm was prepared by a self-templated two-step solution-phase synthesis method. The metal ions (Fe 3+ , Gd 3+ ) played important roles in generating a small particle size and in the functionalization of the products during the reaction with p-phenylenediamine (Pa). The resultant Fe-Pa complex was used as a template for the subsequent formation of MCOP following the Schiff base reaction with 1,3,5-triformylphloroglucinol (Tp). A high tumor suppression efficiency for this Pa-based COP is reported for the first time. This study demonstrates the potential use of MCOP as a photothermal agent for photothermal therapy (PTT) and also provides an alternative route to fabricate nano-sized MCOPs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Mercury coordination polymers with flexible ethane-1,2-diyl-bis-(pyridyl-3-carboxylate): Synthesis, structures, thermal and luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Vallejos, Javier [Departamento de Química, Universidad Católica del Norte, Av. Angamos 0610, Antofagasta (Chile); Brito, Iván, E-mail: ivanbritob@yahoo.com [Departamento de Quimica, Universidad de Antofagasta, Av. Angamos 601, Antofagasta (Chile); Cárdenas, Alejandro [Departamento de Física, Universidad de Antofagasta, Av. Angamos 601, Antofagasta (Chile); Llanos, Jaime [Departamento de Química, Universidad Católica del Norte, Av. Angamos 0610, Antofagasta (Chile); Bolte, Michael [Institut für Anorganische Chemie der Goethe—Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main (Germany); López-Rodríguez, Matías [Instituto de Bio-Orgánica “Antonio González”, Universidad de La Laguna, Astrofísico Francisco Sánchez N° 2, La Laguna, Tenerife (Spain)

    2015-03-15

    The reaction of the flexible ligand, ethane-1,2-diyl-bis-(pyridyl-3-carboxylate), (L) with HgI{sub 2} and HgBr{sub 2} salts under the same experimental conditions leads to the formation of two coordination polymers with different motifs: ([Hg(L)(Br{sub 2})]){sub n}(1) and ([Hg(L)(I{sub 2})]){sub n}(2). In both compounds, the ligand, (L) acts in a μ2-N:N′-bidentate fashion to link HgBr{sub 2} and HgI{sub 2} units to form a linear and helical chain motif, along [1 0 0] for (1) and [0 0 1] for (2). The ethylene moiety of (L) has gauche and trans conformation in compounds (1) and (2), respectively. The flexible conformation of L produces differences in the optical and crystal properties of the two compounds. - Graphical abstract: This work demonstrates how the HgX{sub 2} units are coordinates by bi-dentate ligand forming polymeric coordination complexes by self-assembly of both chemical units.- Highlights: • News 1-D d{sup 10} transition metal coordination polymers. • The photoluminescent properties have been measured. • The thermal properties have been measured.

  15. Syntheses, structures, electrochemistry and catalytic oxidation degradation of organic dyes of two new coordination polymers derived from Cu(II) and Mn(II) and 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene

    Energy Technology Data Exchange (ETDEWEB)

    Song, Ming; Mu, Bao; Huang, Ru-Dan, E-mail: huangrd@bit.edu.cn

    2017-02-15

    Two new coordination polymers (CPs), namely, [Cu{sub 2}(ttbz)(H{sub 2}btc){sub 2}(OH)]{sub n} (1) and [Mn(ttbz){sub 2}(H{sub 2}O){sub 2}]{sub n} (2) (Httbz =1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene, H{sub 3}btc =1,3,5-benzenetricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a (3,5,5,5)-connected 2D layer with a Schläfli symbol of (3·4{sup 2})(3·4{sup 4}0.5{sup 2}0.6{sup 3})(3{sup 2}0.4{sup 4}0.5{sup 2}0.6{sup 2})(3{sup 2}0.4{sup 4}0.5{sup 3}0.6), in which the ttbz{sup -} ligand can be described as μ{sub 5}-bridge, linking Cu(II) ions into a 2D layer and H{sub 2}btc{sup -} ions play a supporting role in complex 1. The ttbz{sup -} ligand in complex 2 represents the bridging coordination mode, connecting two Mn(II) ions to form the infinite 1D zigzag chains, respectively, which are further connected by two different types of hydrogen bonds to form a 3D supramolecular. Furthermore, catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated at room temperature in aqueous solutions, indicating these complexes may be applicable to color removal in a textile wastewater stream and practical applications in areas of electrocatalytic reduction toward nitrite, respectively. - Graphical abstract: Two new coordination polymers based on different structural characteristics have been hydrothermally synthesized by the mixed ligands. The catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated. - Highlights: • The organic ligand containing the tetrazolyl group and triazolyl group with some advantages has been used. • Two new coordination polymers with different structural characteristics has been discussed in detail. • Catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated.

  16. Computational design of metal-organic frameworks with paddlewheel-type secondary building units

    Science.gov (United States)

    Schwingenschlogl, Udo; Peskov, Maxim V.; Masghouni, Nejib

    We employ the TOPOS package to study 697 coordination polymers containing paddlewheel-type secondary building units. The underlying nets are analyzed and 3 novel nets are chosen as potential topologies for paddlewheel-type metal organic frameworks (MOFs). Dicarboxylate linkers are used to build basic structures for novel isoreticular MOF series, aiming at relatively compact structures with a low number of atoms per unit cell. The structures are optimized using density functional theory. Afterwards the Grand Canonical Monte Carlo approach is employed to generate adsorption isotherms for CO2, CO, and CH4 molecules. We utilize the universal forcefield for simulating the interaction between the molecules and hosting MOF. The diffusion behavior of the molecules inside the MOFs is analyzed by molecular dynamics simulations.

  17. Gas-phase synthesis of magnetic metal/polymer nanocomposites

    Science.gov (United States)

    Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

    2014-12-01

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  18. Reversible Mechanochemistry of a PdII Coordination Polymer

    NARCIS (Netherlands)

    Paulusse, Jos Marie Johannes; Sijbesma, Rint P.

    2004-01-01

    Breaking up and making up: The ultrasonic cleavage of high-molecular-weight linear coordination polymers of phosphane telechelic polytetrahydrofuran and palladium dichloride in dilute solution is a reversible process (see picture). Sonication for 1 h led to a decrease in the weight-averaged

  19. Solvothermal Synthesis, Crystal Structure, and Magnetic Properties of [Co3(SDA)3(DMF)2]: 2-D Layered Metal-organic Framework Derived from 4,4'-Stilbenedicarboxylic Acid (H2SDA)

    International Nuclear Information System (INIS)

    Park, Gyung Se; Kim, Hyun Uk; Kim, Ki Moon; Lee, Gang Ho; Park, Sang Kyu

    2006-01-01

    A new 2-D coordination polymer has been synthesized and characterized by using a novel 4,4'-stilbene dicarboxylic acid and Co(ClO 4 ) 2 ·6H 2 O. The title complex has an unique Co 3 pin-wheel cluster in which central Co has octahedral geometry and two surrounding Co have tetrahedral geometry. The Co 3 pin-wheel clusters, the building unit, are linked through carboxylate oxygens to generate a 2-D layered coordination polymer in ABCABC packing mode. Variable-temperature magnetic susceptibility data of the title compound confirms the high spin splitting of Co with S=3/2. Syntheses of MOF by using SDA and other transition metal ions, Zn, Cd, and Mn, are on progress in this lab. Metal-organic frameworks (MOF) have attracted much more attention in the past decade owing to their various intriguing framework topologies and potential applications as functional materials in gas storage, separation, and catalysis. Because high framework stability is fundamental and essential property for many practical applications, multi-dentate linkers such as carboxylates have been extensively investigated for the formation of more rigid frameworks due to their ability to aggregate metal ions into M-O-C clusters called secondary building units (SBUs) rather than N-bound organic linkers such as 4,4-bipyridine (bipy)

  20. Syntheses, structures, and magnetic properties of cobalt(II) and nickel(II) coordination polymers based on a V-shaped ligand

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Shuang [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China); Yi, Fei-Yan [The School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Li, Guanghua [State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Yu, Yang [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China); Wang, Jing-yuan, E-mail: jywang@mail.ipc.ac.cn [Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences, 29 Zhongguancun East Road, Haidian District, Beijing 100190 (China); Liu, Dan, E-mail: liudan2007@ciac.ac.cn [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China); Song, Shu-Yan [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China)

    2017-06-15

    Two coordination polymers [Co{sub 2}(TA)(4,4′-bipy){sub 2}(H{sub 2}O){sub 2}]·H{sub 2}O (1) and [Ni{sub 2}(TA)(4,4′-bipy){sub 2}(H{sub 2}O){sub 4}]·3H{sub 2}O (2) were prepared by hydrothermal reactions of MCl{sub 2}·6H{sub 2}O (M = Co, Ni) with a V-shaped ligand TDPA (3,3′,4,4′-thiodiphthalic anhydride) and a I-shaped N-donor co-ligand (4,4′-bipy). They were characterized by elemental analyses, thermogravinetric analyses, and magnetic behavior. As is expected, TDPA hydrolyzes into the corresponding tetra-carboxylate acid H{sub 4}TA (3,3′,4,4′-thiodiphthalic acid) during the reactions. Co{sub 2} dimer and Ni mononuclear center are connected into two-dimensional (2D) layers by H{sub 4}TA and 4,4′-bipy bridge in 1 and 2, respectively. The most amazing feature is that 1 and 2 exhibit interesting spin-canting metamagnetism and weak ferromagnetic behavior, respectively, with the critical Néel temperature of T{sub N} =4 K for 1 and T{sub N} =13 K for 2, based on variable temperature magnetic susceptibility measurements. In low mono- or dinuclear metal system, such magnetic behaviors have rare been observed. Furthermore, complex 1 will be a potential metamagnet material. - Graphical abstract: Two Co(II) and Ni(II) coordination polymers were synthesized by hydrothermal reactions from a V-shape ligand (3,3′,4,4′-thiodiphthalic anhydride) and a I-shape ligand (4,4′-bipy), which were characterized by single crystal X-ray diffraction, elemental analyses, thermogravinetric analyses, and magnetic behavior, and exhibit interesting spin-canting metamagnetism and weak ferromagnetic behavior, respectively. - Highlights: • Two Co(II) and Ni(II) coordination polymers were successfully synthesized. • Co(II) coordination polymer shows an interesting spin-canting metamagnetism. • Ni(II) coordination polymer exhibits a weak ferromagnetic behavior.

  1. Metallization of Various Polymers by Cold Spray

    Science.gov (United States)

    Che, Hanqing; Chu, Xin; Vo, Phuong; Yue, Stephen

    2018-01-01

    Previous results have shown that metallic coatings can be successfully cold sprayed onto polymeric substrates. This paper studies the cold sprayability of various metal powders on different polymeric substrates. Five different substrates were used, including carbon fiber reinforced polymer (CFRP), acrylonitrile butadiene styrene (ABS), polyether ether ketone (PEEK), polyethylenimine (PEI); mild steel was also used as a benchmark substrate. The CFRP used in this work has a thermosetting matrix, and the ABS, PEEK and PEI are all thermoplastic polymers, with different glass transition temperatures as well as a number of distinct mechanical properties. Three metal powders, tin, copper and iron, were cold sprayed with both a low-pressure system and a high-pressure system at various conditions. In general, cold spray on the thermoplastic polymers rendered more positive results than the thermosetting polymers, due to the local thermal softening mechanism in the thermoplastics. Thick copper coatings were successfully deposited on PEEK and PEI. Based on the results, a method is proposed to determine the feasibility and deposition window of cold spraying specific metal powder/polymeric substrate combinations.

  2. Three-dimensional tetranuclear Cd(II) coordination network based on a 1,3-alternate calix[4]arene derivative

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eun Ji; Ju, Hui Yeong; Park, Ki Min [Dept. of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju (Korea, Republic of); Moon, ASuk Hee [Dept. of Food and Nutrition, Kyungnam College of Inform ation and Technology, Busan (Korea, Republic of); Kang, Young Jin [Div. of cience Education, Kangwon National University, Chuncheon (Korea, Republic of)

    2015-08-15

    Polynuclear coordination polymers can exhibit more intriguing network topologies and better functionalities than those of common complexes because they have metal-cluster nodes for the construction of multidimensional frameworks and the potential applications induced by collaborative activities between metal ions. New tetranuclear Cd(II) coordination polymer 1 based on 1,3-alternate calix arene derivative (H{sub 4} CTA) with four carboxyl pendant arms has been synthesized by the solvo thermal reaction at 110 .deg. C for 2 days. Compound 1 shows a 3-D framework consisting of tetranuclear Cd(II) cluster core as a metal-cluster node and 1,3-alternate H{sub 4}CTA as a multidentate linker. The coordination polymer 1 displays intense blue emission, implying that this tetranuclear Cd(II) coordination polymer could be a suitable material in the area of luminescence research.

  3. Syntheses and structures of three heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid

    International Nuclear Information System (INIS)

    Fang, Wei-Hui; Yang, Guo-Yu

    2014-01-01

    Three lanthanide–transition-metal coordination polymers, namely, [Er 2 L 6 (H 2 O)][Cu 2 I 2 ] (1), [ErL 3 ][CuI] (2), and [Dy 2 L 6 (BPDC) 0.5 (H 2 O) 4 ][Cu 3 I 2 ] (3) (HL=4-pyridin-3-yl-benzoic acid, H 2 BPDC=4,4′-biphenyldicarboxylic acid) have been made by reacting Ln 2 O 3 and CuI with HL at different temperatures under hydrothermal conditions. All the complexes are characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction, respectively. 1–3 all construct from dimeric (Ln 2 ) and (Cu 2 ) units and exhibit two types of the structural features: 1 is a two-dimensional layer, 2–3 are three-dimensional frameworks. Interestingly, the in situ formation of the BPDC ligand is found in the structure of 3. The distinct architectures of these complexes indicated that the reaction temperature plays an important role in the formation of higher dimensional coordination polymers. - Graphical abstract: By hydrothermal reaction of lanthanide oxide, copper halide, and 4-pyridin-3-yl-benzoic ligand at different temperatures, a series of 1-D to 3-D 3d–4f coordination polymers, namely [ErL 3 (H 2 O) 2 ][CuI], [Er 2 L 6 (H 2 O)][Cu 2 I 2 ], [ErL 3 ][CuI], and [Dy 2 L 6 (BPDC) 0.5 (H 2 O) 4 ][Cu 3 I 2 ], have been made, respectively. - Highlights: • Three novel heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid have been hydrothermally synthesized. • Mixed dinuclear motifs of (Ln 2 ) and (Cu 2 ) serve as secondary building units to generate 2-D layer and 3-D frameworks. • It is proved that higher temperature is apt to permit construction of high dimensional architectures

  4. Polymer waveguide couplers based on metal nanoparticle–polymer nanocomposites

    International Nuclear Information System (INIS)

    Signoretto, M; Suárez, I; Chirvony, V S; Martínez-Pastor, J; Abargues, R; Rodríguez-Cantó, P J

    2015-01-01

    In this work Au nanoparticles (AuNPs) are incorporated into poly(methyl methacrylate) (PMMA) waveguides to develop optical couplers that are compatible with planar organic polymer photonics. A method for growing AuNPs (of 10 to 100 nm in size) inside the commercially available Novolak resist is proposed with the intention of tuning the plasmon resonance and the absorption/scattering efficiencies inside the patterned structures. The refractive index of the MNP–Novolak nanocomposite (MNPs: noble metal nanoparticles) is carefully analysed both experimentally and numerically in order to find the appropriate fabrication conditions (filling factor and growth time) to optimize the scattering cross section at a desired wavelength. Then the nanocomposite is patterned inside a PMMA waveguide to exploit its scattering properties to couple and guide a normal incident laser light beam along the polymer. In this way, light coupling is experimentally demonstrated in a broad wavelength range (404–780 nm). Due to the elliptical shape of the MNPs the nanocomposite demonstrates a birefringence, which enhances the coupling to the TE mode up to efficiencies of around 1%. (paper)

  5. Polymer-Derived In- Situ Metal Matrix Composites Created by Direct Injection of a Liquid Polymer into Molten Magnesium

    Science.gov (United States)

    Sudarshan; Terauds, Kalvis; Anilchandra, A. R.; Raj, Rishi

    2014-02-01

    We show that a liquid organic precursor can be injected directly into molten magnesium to produce nanoscale ceramic dispersions within the melt. The castings made in this way possess good resistance to tensile deformation at 673 K (400 °C), confirming the non-coarsening nature of these dispersions. Direct liquid injection into molten metals is a significant step toward inserting different chemistries of liquid precursors to generate a variety of polymer-derived metal matrix composites.

  6. Polymer-assisted metal deposition (PAMD): a full-solution strategy for flexible, stretchable, compressible, and wearable metal conductors.

    Science.gov (United States)

    Yu, You; Yan, Casey; Zheng, Zijian

    2014-08-20

    Metal interconnects, contacts, and electrodes are indispensable elements for most applications of flexible, stretchable, and wearable electronics. Current fabrication methods for these metal conductors are mainly based on conventional microfabrication procedures that have been migrated from Si semiconductor industries, which face significant challenges for organic-based compliant substrates. This Research News highlights a recently developed full-solution processing strategy, polymer-assisted metal deposition (PAMD), which is particularly suitable for the roll-to-roll, low-cost fabrication of high-performance compliant metal conductors (Cu, Ni, Ag, and Au) on a wide variety of organic substrates including plastics, elastomers, papers, and textiles. This paper presents i) the principles of PAMD, and how to use it for making ii) flexible, stretchable, and wearable conductive metal electrodes, iii) patterned metal interconnects, and d) 3D stretchable and compressible metal sponges. A critical perspective on this emerging strategy is also provided. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Combined use of polymer composites and metals in engineering structures

    International Nuclear Information System (INIS)

    Hoa, S.V.

    2002-01-01

    Polymer matrix composites have found many applications in the construction of light weight structures such as those in aircrafts, automobiles, sports equipment etc. This is because these materials possess high stiffness, high strength and low densities. In applications of polymer matrix composites in the light weight structures, the polymer composites are however, not used by themselves alone in most cases. Usually the polymer composites are used in conjunction with some metal components. The metal components are used either to provide means for joining the composite components or the composites are used to repair the cracked metal structures. The synergistic effect of both metals and composites can provide excellent performance with good economy. This paper presents a few applications where polymer composites are used in conjunction with metals in engineering structures. (author)

  8. Coordination compounds of rare-earth metals with organic ligands for electroluminescent diodes

    International Nuclear Information System (INIS)

    Katkova, M A; Bochkarev, Mikhail N; Vitukhnovsky, Alexey G

    2005-01-01

    Data on lanthanide coordination compounds with organic ligands used in the design of electroluminescent diodes are summarised and systematically represented. The molecular and electronic structures and spectroscopic characteristics of these compounds are considered. A comparative analysis of the properties of organic electroluminescent diodes with different compositions of emitting and conductive layers is presented.

  9. Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

    KAUST Repository

    Cadiau, Amandine; Belmabkhout, Youssef; Adil, Karim; Bhatt, Prashant; Pillai, Renjith S.; Shkurenko, Aleksander; Martineau-Corcos, Charlotte; Maurin, Guillaume; Eddaoudi, Mohamed

    2017-01-01

    fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas

  10. Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

    Science.gov (United States)

    Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

    2015-08-01

    Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Rare earth niobate coordination polymers

    Science.gov (United States)

    Muniz, Collin N.; Patel, Hiral; Fast, Dylan B.; Rohwer, Lauren E. S.; Reinheimer, Eric W.; Dolgos, Michelle; Graham, Matt W.; Nyman, May

    2018-03-01

    Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. Here we described the synthesis of a heterometallic rare-earth coordination compound ((CH3)2SO)3(RE)NbO(C2O4)3((CH3)2SO) = dimethylsulfoxide, DMSO, (C2O2= oxalate), (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb). The structure was obtained from single crystal X-ray diffraction of the La analogue. The Nb˭O and DMSO terminal-bonding character guides assembly of an open framework structure with noncentrosymmetric RE-coordination geometry, and large spacing between the RE centers. A second structure was observed by PXRD for the smaller rare earths (Dy, Ho, Er, Yb); this structure has not yet been determined. The materials were further characterized using FTIR, and photoluminescence measurements. Characteristic excitation and emission transitions were observed for RE = Nd, Sm, Eu, and Tb. Quantum yield (QY) measurements were performed by exciting Eu and Tb analoges at 394 nm (QY 66%) and 464 nm (QY 71%) for Eu; and 370 nm (QY=40%) for Tb. We attribute the high QY and bright luminescence to two main structure-function properties of the system; namely the absence of water in the structure, and absence of concentration quenching.

  12. Solvent-free porous framework resulted from 3D entanglement of 1D zigzag coordination polymer

    KAUST Repository

    Kole, Goutam Kumar Umar; Cairns, Amy J.; Eddaoudi, Mohamed; Vittal, Jagadese J.

    2010-01-01

    A solvent-free porous metal organic framework is constructed by the 3D entanglement of 1D zigzag coordination polymeric chains. The role of solvents and the effect of reaction conditions on such unique entanglement are addressed. © 2010 The Royal

  13. Metal selective co-ordinative self-assembly of π-donors

    Indian Academy of Sciences (India)

    Metal selective co-ordinative nanostructures were constructed by the supramolecular ... observed an anomalous binding of metal ion to the core sulphur groups causing redox changes in the TTF ... attention on metal-assisted co-ordinative self-assembly ..... M TTF-Py in 1:1 CHCl3: MeCN and (c) photographs showing visual.

  14. Preparation and evaluation of open-tubular capillary columns modified with metal-organic framework incorporated polymeric porous layer for liquid chromatography.

    Science.gov (United States)

    Zhu, Manman; Zhang, Lingyi; Chu, Zhanying; Wang, Shulei; Chen, Kai; Zhang, Weibing; Liu, Fan

    2018-07-01

    An open tubular capillary liquid phase chromatographic column (1 m × 25 µm i.d.× 375 µm o.d.) was prepared by incorporating metal organic framework particles modified with vancomycin directly into zwitterionic polymer coating synthesized by the copolymerization of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide and N,N'-methylenebisacrylamide. The incorporation of IRMOF-3 (isoreticular metal organic framework-3) particles improved selectivity of zwitterionic polymer coating with absolute column efficiency reaching 79900 plates for p-xylene. Besides strong hydrophilic interaction, the separation of neutral, basic, and acidic compounds demonstrates that π-π stacking interaction and the coordination effect of unsaturated Zn 2+ of MOF also contribute to separation of various analytes. The RSD values (run-to-run, day-to-day, column-to-column, n = 3) of retention time of neutral compounds were less than 0.71%, 0.69% and 3.08% respectively, suggesting good repeatability. In addition, the column was applied to the analysis of the trypsin digest of bovine serum albumin, revealing the potential in separating biological samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. In situ ligand generation for novel Mn(II) and Ni(II) coordination polymers with disulfide ligand: Solvothermal syntheses, structures and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Han, Yinfeng, E-mail: hanyinfeng@gmail.com; Wang, Chang' an; Zheng, Zebao; Sun, Jiafeng; Nie, Kun; Zuo, Jian; Zhang, Jianping

    2015-07-15

    Two coordination polymers, ([Mn{sub 2}(L1){sub 2}(μ{sub 2}-H{sub 2}O)(H{sub 2}O){sub 4}]·5H{sub 2}O){sub n}1 and ([Ni(L1)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n}2 (H{sub 2}L1=2,2′-dithiobisnicotinic acid), were prepared by the solvothermal reactions of the Mn(II) or Ni(II) ions with 2-mercaptonanicotinic acid. In 1, the [Mn{sub 2}(COO){sub 4}] units are connected by the 2,2′-dithiobisnicotinic dianion to form a two-dimensional (4,4)-connected network. In 2, the adjacent Ni(II) ions are connected by the carboxyl groups of the 2,2′-dithiobisnicotinic dianion to form an one-dimensional inorganic rod-shaped chain [Ni(COO){sub 2}]{sub n}, which are further interconnected by the 2,2′-dithiobisnicotinic ligand, giving rise to a two-dimensional framework. Variable-temperature magnetic susceptibilities of 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent metal ions. - Graphical abstract: Two 2D coordination polymers were synthesized by transition-metal/in-situ oxidation of 2-mercaptonicotinic acid. The compounds pack into 2D frameworks by the carboxyl groups of 2,2′-dithiobisnicotinic dianion and exhibit overall weak antiferromagnetic coupling. - Highlights: • Two 2D coordination polymers containing 2,2′-dithiobisnicotinic dianion. • In situ oxidation and dehydro coupling reaction of 2-mercaptonbenzoic acid. • Two compounds display weak antiferromagnetic exchanges.

  16. Metal{Polymer Hybrid Materials For Flexible Transparent Conductors

    Science.gov (United States)

    Narayanan, Sudarshan

    The field of organic electronics, till recently a mere research topic, is currently making rapid strides and tremendous progress into entering the mainstream electronics industry with several applications and products such as OLED televisions, curved displays, wearable devices, flexible solar cells, etc. already having been commercialized. A major component in these devices, especially for photovoltaic applications, is a transparent conductor used as one of the electrodes, which in most commercial applications are highly doped wide bandgap semiconducting oxides also called Transparent Conducting Oxides (TCOs). However, TCOs exhibit inherent disadvantages such as limited supply, brittle mechanical properties, expensive processing that present major barriers for the more widespread economic use in applications such as exible transparent conductors, owing to which suitable alternative materials are being sought. In this context we present two approaches in realizing alternative TCs using metal-polymer hybrid materials, with high figures of merit that are easily processable, reasonably inexpensive and mechanically robust as well. In this context, our first approach employs laminated metal-polymer photonic bandgap structures to effectively tune optical and electrical properties by an appropriate design of the material stack, factoring in the effect of the materials involved, the number of layers and layer properties. We have found that in the case of a four-bilayer Au/polystyrene (AujPS) laminate structure, an enhancement in optical transmittance of ˜ 500% in comparison to a monolithic A film of equivalent thickness, can be achieved. The high conductivity (˜ 106 O--1cm--1) of the metallic component, Au in this case, also ensures planar conductivity; metallic inclusions in the dielectric polymer layer can in principle give rise to out-of-plane conductivity as well enabling a fully functional TC. Such materials also have immense potential for several other applications

  17. Fabrication of a PANI/CPs composite material: a feasible method to enhance the photocatalytic activity of coordination polymers.

    Science.gov (United States)

    Xu, Xin-Xin; Cui, Zhong-Ping; Qi, Ji; Liu, Xiao-Xia

    2013-03-21

    To improve the photocatalytic activity of a coordination polymer in the visible light region, polyaniline (PANI) was loaded onto its surface through a facile in situ chemical oxidation polymerization process. The resulting PANI loaded coordination polymer composite materials with excellent stability exhibit significantly higher photocatalytic activities than the pure coordination polymer photocatalyst on the degradation of methyl orange (MO) under visible light irradiation. This enhancement can be ascribed to the introduction of PANI on the surface of the coordination polymer, which leads to efficient separation of photogenerated electron-hole pairs as well as a significant expansion of the photoresponse region. Finally, we discussed the influence of acidity on the morphology and photocatalytic activity of the composite material. An optimal condition to obtain the PANI loaded coordination polymer composite material with excellent photocatalytic activity has been obtained.

  18. A Metal Chelating Porous Polymeric Support: The Missing Link for a Defect-free Metal-Organic Framework Composite Membrane

    KAUST Repository

    Barankova, Eva

    2017-02-06

    Since the discovery of size-selective metal-organic frameworks (MOFs), researchers have tried to incorporate these materials into gas separation membranes. Impressive gas selectivities were found, but these MOF membranes were mostly made on inorganic supports, which are generally too bulky and expensive for industrial gas separation. Forming MOF layers on porous polymer supports is industrially attractive but technically challenging. Two features to overcome these problems are described: 1) a metal chelating support polymer to bind the MOF layer, and 2) control of MOF crystal growth by contra-diffusion, aiming at a very thin nanocrystalline MOF layer. Using a metal chelating polythiosemicarbazide (PTSC) support and adjusting the metal and organic ligand concentrations carefully, a very compact ZIF-8 (ZIF=zeolitic imidazolate framework) layer was produced that displayed interference colors because of its smooth surface and extreme thinness-within the range of visible light. High performances were measured in terms of hydrogen/propane (8350) and propylene/propane (150) selectivity.

  19. Crystal chemistry of uranyl carboxylate coordination networks obtained in the presence of organic amine molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mihalcea, Ionut; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2014-03-15

    Three uranyl isophthalates (1,3-bdc) and two uranyl pyromellitates (btec) of coordination-polymer type were hydrothermally synthesized (200 C for 24 h) in the presence of different amine-based molecules [1,3-diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N-dimethylformamide]. (UO{sub 2}){sub 2}(OH){sub 2}(H{sub 2}O)(1,3-bdc).H{sub 2}O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H{sub 2}O molecules. The compounds (UO{sub 2}){sub 1.5}(H{sub 2}O)(1,3-bdc){sub 2}.0.5H{sub 2}dap.1.5H{sub 2}O (2) and UO{sub 2}(1,3-bdc){sub 1.5}.0.5H{sub 2}dap.2H{sub 2}O (3) consist of discrete uranyl-centered hexagonal bipyramids connected to each other by a ditopic linker to form a single-layer network for 2 or a double-layer network for 3. The protonated diamine molecules are located between the uranyl-organic sheets and balance the negative charge of the layered sub-networks. The phase (UO{sub 2}){sub 2}O(btec).2Hdma.H{sub 2}O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO{sub 2}(btec).2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non-bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen-bond network. The different illustrations show the structural diversity of uranyl-organic coordination polymers with organic

  20. Multifunctional fluorescent sensing of chemical and physical stimuli using smart riboflavin-5'-phosphate/Eu3+ coordination polymers.

    Science.gov (United States)

    Xue, Shi-Fan; Zhang, Jing-Fei; Chen, Zi-Han; Han, Xin-Yue; Zhang, Min; Shi, Guoyue

    2018-07-05

    A novel type of stimuli-responsive fluorescent polymers has been developed via the self-assembly of riboflavin-5'-phosphate (RiP) as ligand and europium (III) (Eu 3+ ) as central metal ion coordinated with the ligand. The as-prepared RiP/Eu 3+ coordination polymers (RiP/Eu 3+ CPs) are smart and multifunctional for respectively responding to chemical and physical stimuli, in which RiP acts as the stimuli-responsive fluorescent signal indicator. For sensing chemical stimuli, 2,6-pyridinedicarboxylic acid (DPA, an anthrax biomarker) having higher bonding force towards Eu 3+ can grab it from smart RiP/Eu 3+ CPs through competition reaction, resulting in the release of RiP for highly sensitive and selective DPA monitoring in a mix-and-read fluorescent enhancement format, and the detection limit is as low as 41.5 nM. Density functional theory (DFT) calculations has been also performed to verify the DPA sensing principle. For sensing physical stimuli, the smart RiP/Eu 3+ CPs can be acting as a novel sensory probe for the determination of temperature from 10 °C to 40 °C based on the thermal-induced disruption of the binding between Eu 3+ and RiP and the disassembly of the smart RiP/Eu 3+ CPs accompanying with the recovery of the fluorescence of RiP. This work establishes an effective platform for multifunctional sensing of chemical and physical stimuli utilizing both smart lanthanide nanoscale coordination polymers (LNCPs) and novel sensing strategies. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Water molecule-enhanced CO2 insertion in lanthanide coordination polymers

    International Nuclear Information System (INIS)

    Luo Liushan; Huang Xiaoyuan; Wang Ning; Wu Hongyan; Chen Wenbin; Feng Zihao; Zhu Huiping; Peng Xiaoling; Li Yongxian; Huang Ling; Yue Shantang; Liu Yingliang

    2009-01-01

    Two new lanthanide coordination polymers H 2 N(CH 3 ) 2 .[Eu III 2 (L 1 ) 3 (L 2 )] (1, L 1 =isophthalic acid dianion, L 2 =formic acid anion) and [La III (2,5-PDC)(L 2 )](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L 2 ) is not contained in the stating materials, but arises from the water molecule-enhanced CO 2 insertion during the solvothermal process. Both of the two compounds exhibit complicated three dimensional sandwich-like frameworks. - Graphical abstract: Two new lanthanide coordination polymers involving water molecule-enhanced CO 2 insertion resulting in the formation of formic anion and dimethylammonium cation were synthesized under solvothermal conditions.

  2. Selectivity in inter polymer complexation involving phenolic copolymer, poly electrolytes, non-ionic polymers and transition metal ions

    International Nuclear Information System (INIS)

    Vasheghani Farahani, B.; Hosseinpour Rajabi, F.

    2006-01-01

    Selectivity in inter polymer complex formation involving a typical four-component phenolic copolymer (ρ-chloro phenol-ρ-aminophenol-ρ-toluidine-ρ-cresol- HCHO copolymer), poly electrolytes such as polyethylene imine and polyacrylic acid, a non-ionic homopolymer polyvinyl pyrrolidone, and some transition metal ions (e.g., Cu (II), Ni (11)) have been studied in dimethylformamide-methanol solvents mixture. The coordinating groups of phenolic copolymer form complexes through hydrogen bonding and ion-dipole interactions. The different stages of interactions have been studied by several experimental techniques, e.g., viscometry, potentiometry and conductometry. Some schemes have been suggested to explain the mode of interaction between these components

  3. Coordination polymers with the chiral ligand N-p-tolylsulfonyl-L-glutamic acid: Influence of metal ions and different bipyridine ligands on structural chirality

    International Nuclear Information System (INIS)

    He Rong; Song Huihua; Wei Zhen; Zhang Jianjun; Gao Yuanzhe

    2010-01-01

    Four new polymers, namely [Ni(-tsgluO)(2,4'-bipy) 2 (H 2 O) 2 ] n .5nH 2 O (1), [Co(-tsgluO)(2,4'-bipy) 2 (H 2 O) 2 ] n .5nH 2 O (2), [Ni(-tsgluO)(4,4'-bipy)] n .0.5nH 2 O (3), and [Co(-tsgluO)(4,4'-bipy)] n .0.5nH 2 O (4), where tsgluO 2- =(+)-N-p-tolylsulfonyl-L-glutamate dianion, 2,4'-bipy=2,4'-bipyridine, and 4,4'-bipy=4,4'-bipyridine, have been prepared and structurally characterized. Compounds 1 and 2 are isostructural and mononuclear, and crystallize in the acentric monoclinic space group Cc, forming 1D chain structures. Compound 3 is also mononuclear, but crystallizes in the chiral space group P2 1 , forming a homochiral 2D architecture. In contrast to the other complexes, compound 4 crystallizes in the space group P-1 and is composed of binuclear [Co 2 O 6 N 2 ] n 4- units, which give rise to a 2D bilayer framework. Moreover, compounds 1, 2, and 4 self-assemble to form 3D supramolecular structures through π-π stacking and hydrogen-bonding interactions, while compound 3 is further hydrogen-bonded to form 3D frameworks. We have demonstrated the influence of the central metal and bipyridine ligands on the framework chirality of the coordination complexes. - Graphical abstract: Four novel polymers based on a chiral ligand were prepared and structurally characterized; it represents the first series of investigations about the effect of central metals and bipyridine ligands on framework chirality.

  4. Selective removal of heavy metal ions by disulfide linked polymer networks

    Energy Technology Data Exchange (ETDEWEB)

    Ko, Dongah [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark); Lee, Joo Sung [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Patel, Hasmukh A. [Department of Chemistry, Northwestern University, Evanston, IL 60208 (United States); Jakobsen, Mogens H. [Department of Micro and Nano technology, Technical University of Denmark, Ørsteds Plads, 345B, 2800 Kgs. Lyngby (Denmark); Hwang, Yuhoon [Department of Environmental Engineering, Seoul National University of Science and Technology, 232 Gongreung-ro, Nowon-gu, Seoul 01811 (Korea, Republic of); Yavuz, Cafer T. [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Hansen, Hans Chr. Bruun [Department of Plant and Environmental Sciences, University of Copenhagen, Frederiksberg, Thorvaldsensvej 40, 1871 Frederiksberg C (Denmark); Andersen, Henrik R., E-mail: henrik@ndersen.net [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark)

    2017-06-15

    Highlights: • Disulfide/thiol polymer networks are promising as sorbent for heavy metals. • Rapid sorption and high Langmuir affinity constant (a{sub L}) for stormwater treatment. • Selective sorption for copper, cadmium, and zinc in the presence of calcium. • Reusability likely due to structure stability of disulfide linked polymer networks. - Abstract: Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions–copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

  5. Selective removal of heavy metal ions by disulfide linked polymer networks

    DEFF Research Database (Denmark)

    Ko, Dongah; Sung Lee, Joo; Patel, Hasmukh A.

    2017-01-01

    Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has...... a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal...... sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions―copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water....

  6. Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

    International Nuclear Information System (INIS)

    Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E.; Chan, Benny C.; Lill, Daniel T. de

    2015-01-01

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C 6 H 2 O 5 )(C 6 H 3 O 5 )(H 2 O)] n (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented. - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted

  7. Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E. [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States); Chan, Benny C. [Department of Chemistry, The College of New Jersey, 2000 Pennington Road, Ewing, NJ 08628 (United States); Lill, Daniel T. de, E-mail: ddelill@fau.edu [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States)

    2015-05-15

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C{sub 6}H{sub 2}O{sub 5})(C{sub 6}H{sub 3}O{sub 5})(H{sub 2}O)]{sub n} (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented. - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted.

  8. Synthesis and characterization of two new zinc(II) coordination polymers with bidentate flexible ligands: Formation of a 2D structure with (44.62)-sql topology

    Science.gov (United States)

    Lalegani, Arash; Khaledi Sardashti, Mohammad; Gajda, Roman; Woźniak, Krzysztof

    2017-12-01

    Zinc(II) coordination polymers [Zn(bip)2(NCS)2]n (1) and [Zn(μ-bbd)(N3)2]n (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd) and 1,3-bis(imidazolyl)propane (bip), mono-anionic NCS- or N3-ligand and zinc(II) chloride salts. The results of the X-ray analyses demonstrate that in the structure of 1, the zinc(II) ion is located on an inversion center and exhibits an ZnN6 octahedral arrangement while, in the structure of 2, the zinc(II) ion adopts an ZnN4 tetrahedral geometry. In the polymer 1, the NCS groups are terminally N-bonded to the metal center and the each bip with anti-gauche conformation acts as bridging connecting four zinc(II) ions to form a two-dimensional network with a sql [point symbol (44.62)] topology while, in the polymer 1, the N3 groups are terminally bonded to the metal center and each bbd with anti-anti-anti conformation acts as bridging ligand connecting two zinc(II) ions to form a one-dimensional zig-zag chain. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analyses of polymers were also presented.

  9. Polymer Surface Engineering for Efficient Printing of Highly Conductive Metal Nanoparticle Inks.

    Science.gov (United States)

    Agina, Elena V; Sizov, Alexey S; Yablokov, Mikhail Yu; Borshchev, Oleg V; Bessonov, Alexander A; Kirikova, Marina N; Bailey, Marc J A; Ponomarenko, Sergei A

    2015-06-10

    An approach to polymer surface modification using self-assembled layers (SALs) of functional alkoxysilanes has been developed in order to improve the printability of silver nanoparticle inks and enhance adhesion between the metal conducting layer and the flexible polymer substrate. The SALs have been fully characterized by AFM, XPS, and WCA, and the resulting printability, adhesion, and electrical conductivity of the screen-printed metal contacts have been estimated by cross-cut tape test and 4-point probe measurements. It was shown that (3-mercaptopropyl)trimethoxysilane SALs enable significant adhesion improvements for both aqueous- and organic-based silver inks, approaching nearly 100% for PEN and PDMS substrates while exhibiting relatively low sheet resistance up to 0.1 Ω/sq. It was demonstrated that SALs containing functional -SH or -NH2 end groups offer the opportunity to increase the affinity of the polymer substrates to silver inks and thus to achieve efficient patterning of highly conductive structures on flexible and stretchable substrates.

  10. Synthesis of non-toxic As and Cr nanoparticles through redox activity of highly flexible layered coordination polymer of Ni(II)

    Science.gov (United States)

    Agarwal, Rashmi A.

    2018-03-01

    A simple method for the sequestration of As(III) and Cr(VI) from water has been demonstrated by utilizing a highly flexible porous coordination polymer (PCP) of Ni(II) in its as synthesized form or without solvent removal. This PCP reduces the high toxicity of As(III) and Cr(VI) ions into non-toxic As(0) and Cr/Cr2O3/CrO2 (zero, tri and tetravalent) nanoparticles (NPs) within its pores, and this is characterized by powder x-ray diffraction, x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis. The high functionality of this polymer is due to the presence of monodentate carboxylate groups of a benzenetricarboxylate linker, which provide anchoring sites to the metal ions of the metal precursors. Due to the highly oxidising nature of these toxic ions, a redox reaction takes place between the framework metal ions and toxic metal ions, which is explained by an electron paramagnetic resonance study. This is the first report to synthesize non-toxic, as well as useful, NPs of As and Cr from their highly toxic ions within the cavities of a PCP for remediation of the toxic waste stream and contaminated waste water.

  11. Synthesis of non-toxic As and Cr nanoparticles through redox activity of highly flexible layered coordination polymer of Ni(II).

    Science.gov (United States)

    Agarwal, Rashmi A

    2018-03-09

    A simple method for the sequestration of As(III) and Cr(VI) from water has been demonstrated by utilizing a highly flexible porous coordination polymer (PCP) of Ni(II) in its as synthesized form or without solvent removal. This PCP reduces the high toxicity of As(III) and Cr(VI) ions into non-toxic As(0) and Cr/Cr 2 O 3 /CrO 2 (zero, tri and tetravalent) nanoparticles (NPs) within its pores, and this is characterized by powder x-ray diffraction, x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis. The high functionality of this polymer is due to the presence of monodentate carboxylate groups of a benzenetricarboxylate linker, which provide anchoring sites to the metal ions of the metal precursors. Due to the highly oxidising nature of these toxic ions, a redox reaction takes place between the framework metal ions and toxic metal ions, which is explained by an electron paramagnetic resonance study. This is the first report to synthesize non-toxic, as well as useful, NPs of As and Cr from their highly toxic ions within the cavities of a PCP for remediation of the toxic waste stream and contaminated waste water.

  12. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    Science.gov (United States)

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis, crystal structure and luminescence properties of lanthanide coordination polymers with a new semirigid bridging thenylsalicylamide ligand

    International Nuclear Information System (INIS)

    Song, Xue-Qin; Wang, Li; Zhao, Meng-Meng; Wang, Xiao-Run; Peng, Yun-Qiao; Cheng, Guo-Quan

    2013-01-01

    Two new lanthanide coordination polymers based on a semirigid bridging thenylsalicylamide ligand ([Ln 2 L 3 (NO 3 ) 6 ]·(C 4 H 8 O 2 ) 2 ) ∞ were obtained and characterized by elemental analysis, X-ray diffraction, IR and TGA measurements. The two compounds are isostructure and possess one dimensional trapezoid ladder-like chain built up from the connection of isolated LnO 3 (NO 3 ) 3 polyhedra (distorted monocapped antisquare prism) through the ligand. The photoluminescence analysis suggest that there is an efficient ligand-to-Ln(III) energy transfer in Tb(III) complex and the ligand is an efficient “antenna” for Tb(III). From a more general perspective, the results demonstrated herein provide the possibility of controlling the formation of the desired lanthanide coordination structure to enrich the crystal engineering strategy and enlarge the arsenal for developing excellent luminescent lanthanide coordination polymers. - Graphical abstract: We present herein one dimensional lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display interesting structures but also possess strong luminescence properties. Display Omitted - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit interesting structures. • The luminescent properties of Tb(III) complexes are discussed in detail

  14. Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

    Science.gov (United States)

    Das, Saikat; Xu, Shixian; Ben, Teng; Qiu, Shilun

    2018-05-16

    Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Synthesis, functionalization, and applications of metal-organic frameworks in biomedicine.

    Science.gov (United States)

    Chen, Wei; Wu, Chunsheng

    2018-02-13

    Metal-organic frameworks (MOFs), also known as coordination polymers, have attracted extensive research interest in the past few decades due to their unique physical structures and potentially vast applications. In this review, we outline the recent progress in the synthesis, functionalization and applications of MOFs in biomedicine, mainly focusing on two promising, yet challenging areas, i.e., drug delivery and biosensing applications. A major challenge is the proper functionalization of MOFs with demanding properties suitable for biomedical applications. Extensive studies on MOFs in biomedicine have led to substantial progress in the control of key properties of MOFs such as toxicity, size and shape, and biological stability. Due to their flexible composition, pore size and easy functionalization properties, MOFs can be utilized as key components for the development of various functional systems, and their applications in drug delivery and biosensing are reviewed. Future trends and perspectives in these research areas are also outlined.

  16. Synthesis and Preliminary Characterization of a PPE-Type Polymer Containing Substituted Fullerenes and Transition Metal Ligation Sites

    Directory of Open Access Journals (Sweden)

    Corinne A. Basinger

    2015-01-01

    Full Text Available A substituted fullerene was incorporated into a PPE-conjugated polymer repeat unit. This subunit was then polymerized via Sonogashira coupling with other repeat units to create polymeric systems approaching 50 repeat units (based on GPC characterization. Bipyridine ligands were incorporated into some of these repeat units to provide sites for transition metal coordination. Photophysical characterization of the absorption and emission properties of these systems shows excited states located on both the fullerene and aromatic backbone of the polymers that exist in a thermally controlled equilibrium. Future work will explore other substituted polyaromatic systems using similar methodologies.

  17. Thermostability and photophysical properties of mixed-ligand carboxylate/benzimidazole Zn(II)-coordination polymers

    International Nuclear Information System (INIS)

    Barros, Bráulio Silva; Chojnacki, Jaroslaw; Macêdo Soares, Antonia Alice; Kulesza, Joanna; Lourenço da Luz, Leonis; Júnior, Severino Alves

    2015-01-01

    The reaction between Zn(NO 3 ) 2 ·6H 2 O or Zn(CH 3 COO) 2 ·2H 2 O and isophthalic acid (1,3-H 2 bdc) in the presence of benzimidazole (Hbzim) in dimethylformamide (DMF)/ethanol (EtOH)/H 2 O solvent mixture at room temperature yielded two structurally different coordination polymers: [Zn 2 (1,3-bdc) 2 (Hbzim) 2 ] (1) and [Zn 2 (1,3-bdc)(bzim) 2 ] (2). (1) is a 2D-layered framework with a molecule of benzimidazole coordinated to the Zn center, whereas (2) is a 3D framework with benzimidazolate species acting as a co-ligand and bridging two Zn(II) ions. Reactions performed at 90 °C led to the formation of coordination polymers structurally similar to (2), independently of the Zn(II) source used. In the absence of benzimidazole, the reaction between ZnAc 2 .2H 2 O and 1,3-H 2 bdc at 90 °C resulted in the formation of (3), a 3D coordination polymer Zn(HCOO) 3 (Me 2 NH 2 + ). It was observed that the thermostability and the photophysical properties of (1) and (2) are strongly dependent on the coordination modes and packing of benzimidazole in the solid state. These materials present photoluminescence in the wide range of the spectrum, from UV to IR. A full understanding of a physical process occurring in these intriguing systems, including complete energy level diagrams with possible transitions were provided. - Graphical abstract: Display Omitted - Highlights: • Structurally different Zn(II)-coordination polymers were prepared. • The formation of frameworks was counter anion and temperature dependent. • Photoluminescence in the wide range of the spectrum, from UV to IR was observed. • Thermostability and luminescence depended on bzim packing in the structure

  18. Redox-active porous coordination polymer based on trinuclear pivalate: Temperature-dependent crystal rearrangement and redox-behavior

    Energy Technology Data Exchange (ETDEWEB)

    Lytvynenko, Anton S. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, Kiev 03028 (Ukraine); Kiskin, Mikhail A., E-mail: mkiskin@igic.ras.ru [N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 31, GSP-1, 119991 Moscow (Russian Federation); Dorofeeva, Victoria N.; Mishura, Andrey M.; Titov, Vladimir E.; Kolotilov, Sergey V. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, Kiev 03028 (Ukraine); Eremenko, Igor L.; Novotortsev, Vladimir M. [N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 31, GSP-1, 119991 Moscow (Russian Federation)

    2015-03-15

    Linking of trinuclear pivalate Fe{sub 2}NiO(Piv){sub 6} (Piv=O{sub 2}CC(CH{sub 3}){sub 3}) by 2,6-bis(4-pyridyl)-4-(1-naphthyl)pyridine (L) resulted in formation of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)·Solv, which was characterized in two forms: DMSO solvate Fe{sub 2}NiO(Piv){sub 6}(L)(DMSO)·2.5DMSO (1) or water solvate Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) (2). X-ray structure of 1 was determined. Crystal lattice of 1 at 160 K contained open channels, filled by captured solvent, while temperature growth to 296 K led to the crystal lattice rearrangement and formation of closed voids. Redox-behavior of 2 was studied by cyclic voltammetry for a solid compound, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. The presence of pores in desolvated sample Fe{sub 2}NiO(Piv){sub 6}(L) was confirmed by the measurements of N{sub 2} and H{sub 2} adsorption at 77 K. Potential barriers of the different molecules diffusion through pores were estimated by the means of molecular mechanics. - Graphical abstract: Redox-behavior of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) was studied by cyclic voltammetry in thin film, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. Potential barriers of different molecules diffusion through pores were estimated by the means of molecular mechanics. - Highlights: • Porous 1D coordination polymer was synthesized. • Temperature growth led to pores closing due to crystal lattice rearrangement. • Redox-activity of ligand preserved upon incorporation into coordination polymer. • Redox-properties of solid coordination polymer were studied in thin film. • Diffusion barriers were evaluated by molecular mechanics.

  19. Four thiophene-pyridyl-amide-based Zn{sup II}/Cd{sup II} coordination polymers: Assembly, structures, photocatalytic properties and fluorescent recognition for Fe{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiu-Li; Wu, Xiao-Mei; Liu, Guo-Cheng; Li, Qiao-Min; Lin, Hong-Yan; Wang, Xiang

    2017-05-15

    By tuning metal ions and combining with different dicarboxylates, four new semi-rigid thiophene-bis-pyridyl-bis-amide-based coordination polymers, namely, [Zn(3-bptpa)(1,3-BDC)]·DMA·2H{sub 2}O (1), [Zn(3-bptpa)(5-MIP)] (2), [Cd(3-bptpa)(1,3-BDC)]·2H{sub 2}O (3) and [Cd(3-bptpa)(5-MIP)]·4H{sub 2}O (4) (3-bptpa=N,N′-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide, 1,3-H{sub 2}BDC=1,3-benzenedicarboxylic acid, 5-H{sub 2}MIP=5-methylisophthalic acid, DMA=N,N-dimethylacetamide), were solvothermally/hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analyses, IR spectra, UV–vis diffuse-reflectance spectra (DRS), powder X-ray diffraction (PXRD) and thermal gravimetric analyses (TG). The structural analysis reveals that Zn-complexes 1 and 2 are similar 2D networks. While Cd-complexes 3 and 4 exhibit similar 2-fold interpenetrating 3D α-Po frameworks with the (4{sup 12}·6{sup 3}) topology. The photocatalytic properties for the degradation of methylene blue (MB) under ultraviolet light irradiation of the title complexes have been investigated in detail. Furthermore, the luminescent sensing behaviors for metal cations of 1–4 have been studied, the results indicate that 3 is an excellent fluorescent probe, with high sensitivity, selectivity, and simple regeneration, for environmentally relevant Fe{sup 3+} ions. - Graphical abstract: Four Zn{sup II}/Cd{sup II} coordination polymers with a thiophene-pyridyl-amide ligand have been prepared. The photocatalytic activities and fluorescent sensing properties for metal ions of the title complexes have been investigated. - Highlights: • Four coordination polymers with thiophene-pyridyl-amide ligands have been obtained. • The central metal ions play an important role in the formation of the frameworks. • The photoluminescent sensing and the photocatalytic properties have been investigated.

  20. 21 CFR 888.3350 - Hip joint metal/polymer semi-constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint metal/polymer semi-constrained cemented... HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3350 Hip joint metal/polymer semi-constrained cemented prosthesis. (a) Identification. A hip joint metal/polymer semi...

  1. 21 CFR 888.3120 - Ankle joint metal/polymer non-constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ankle joint metal/polymer non-constrained cemented... HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3120 Ankle joint metal/polymer non-constrained cemented prosthesis. (a) Identification. An ankle joint metal/polymer non...

  2. Coordination compounds of metals with imidazoles and benzimidazoles. [Metals: V, Th, Mo, Cd, rare earths, etc

    Energy Technology Data Exchange (ETDEWEB)

    Novikova, G A; Molodkin, A K; Kukalenko, S S

    1988-12-01

    Methods of preparation, composition and structure of UO/sub 2//sup 2+/, Th/sup 4+/, Mo/sup 3+/, Cd/sup 2+/, Ln/sup 3+/ metal ion complexes with imidazoles and benzimidazoles are considered in reviews of native and foreign literature of up to 1985. Complexes are customarily prepared by direct interaction of ligands with inorganic salts in different organic solvents. Complex composition is defined by the nature of complexing metal and inorganic salt anion, ligand volume and basicity, as well as solvent characteristics. Effect of R substituent in imidazole and benzimidazole side chain on composition of coordination compounds is considered.

  3. 21 CFR 888.3110 - Ankle joint metal/polymer semi-constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ankle joint metal/polymer semi-constrained... Ankle joint metal/polymer semi-constrained cemented prosthesis. (a) Identification. An ankle joint metal/polymer semi-constrained cemented prosthesis is a device intended to be implanted to replace an ankle...

  4. Ionochromic effects and structures of metalated poly(p-phenylenevinylene) polymers incorporating 2,2'-bipyridines

    International Nuclear Information System (INIS)

    Chen, L.X.; Jager, W.J.H.; Gosztola, D.J.; Niemczyk, M.P.; Wasielewski, M.R.

    2000-01-01

    The effects of metal ion chelation to the 2,2'-bipyridine (bpy) groups on the photophysics and exciton dynamics of two conjugated polymers 1 and 2 in solution are investigated. The structures of polymers 1 and 2 have 2,2'-bipyridyl-5-vinylene units that alternate with one and three 2,5-bis(n-decyloxy)-1,4-phenylenevinylene monomer units, respectively. The photophysics and exciton dynamics of metalated polymers 1 and 2 are compared to those of the metal-free polymers (Chen et al. J. Phys. Chem. A 1999, 103, 4341-4351). The origins of ionochromic effects due the metal ion chelation were studied using both steady-state and transient optical spectroscopy, and the results indicate that both conformational flattening and participation of Jr electrons from the metal in the π-conjugation of the polymer backbone play important roles in metal ion binding induced red shifts in absorption and photoluminescence spectra. The photoluminescence properties of the metalated polymers are determined by the metal ion electronic structures, where the closed shell Zn 2+ -bound polymer 2 has an increased photoluminescence quantum yield and the corresponding open shell Ni 2+ - or Fe 3+ -bound polymers have quenched photoluminescence due to spin-orbit coupling. The dual character of metalated polymer 2 as a conjugated polymer and as a metal-bpy complex is discussed. In addition, the structures of metal ion binding sites are studied via X-ray absorption fine structure (XAFS) and are related to the photophysical properties of the metalated polymers

  5. Metal ion separations with proton-ionizable Lariat Ethers and their polymers

    International Nuclear Information System (INIS)

    Bartsch, R.A.

    1993-01-01

    The preparation of novel and specific organic complexing agents may lead to the development of new separation systems for aqueous metal ions. Thus the introduction of highly lipophilic oximes led to the current utilization of these compounds as commercial extractants for the hydrometallurgy of nonferrous metals. Crown ethers (macrocyclic polyethers) have been employed in the laboratory-scale solvent extraction of alkali-metal, alkaline-earth, and other metal cations into organic phases. Attachment of side arms to crown ethers gives lariat ethers. The presence of one or more potential coordination sites in the side arm of the lariat ether may produce substantial changes in the selectivity and efficiency of metal ion complexation. It has been demonstrated that concomitant transfer of an aqueous phase anion into the organic medium is not required for metal ion extraction. This factor is of immense importance to potential practical applications of these proton-ionizable crown ethers in which the common, hard, aqueous phase anions would be involved. Another advantage of proton-ionizable lariat ethers is the ease with which extracted metal ions may be stripped from the organic phase by shaking with aqueous mineral acid. Thus both metal ion extraction and stripping are facilitated by pendent proton-ionizable groups. Most of the hazardous metal ion species in the Hanford Site tank wastes are members of the alkali-metal, alkaline-earth, lanthanide, and actinide families. These hard metal ion species prefer association with hard donor atoms, such as oxygens. Therefore, crown and lariat ethers are well-suited for complexation with such metal ion species

  6. Bridging-ligand-substitution strategy for the preparation of metal-organic polyhedra

    Science.gov (United States)

    Li, Jian-Rong; Zhou, Hong-Cai

    2010-10-01

    Metal-organic polyhedra-discrete molecular architectures constructed through the coordination of metal ions and organic linkers-have recently attracted considerable attention due to their intriguing structures, their potential for a variety of applications and their relevance to biological self-assembly. Several synthetic routes have been investigated to prepare these complexes. However, to date, these preparative methods have typically been based on the direct assembly of metal ions and organic linkers. Although these routes are convenient, it remains difficult to find suitable reaction conditions or to control the outcome of the assembly process. Here, we demonstrate a synthetic strategy based on the substitution of bridging ligands in soluble metal-organic polyhedra. The introduction of linkers with different properties from those of the initial metal-organic polyhedra can thus lead to new metal-organic polyhedra with distinct properties (including size and shape). Furthermore, partial substitution can also occur and form mixed-ligand species that may be difficult to access by means of other approaches.

  7. Electric Transport Phenomena of Nanocomposite Organic Polymer Thin Films

    Science.gov (United States)

    Jira, Nicholas C.; Sabirianov, Ildar; Ilie, Carolina C.

    We discuss herein the nanocomposite organic thin film diodes for the use of plasmonic solar cells. This experimental work follows the theoretical calculations done for plasmonic solar cells using the MNPBEM toolbox for MatLab. These calculations include dispersion curves and amount of light scattering cross sections for different metallic nanoparticles. This study gives us clear ideas on what to expect from different metals, allowing us to make the best choice on what to use to obtain the best results. One specific technique for light trapping in thin films solar cells utilizes metal nanoparticles on the surface of the semiconductor. The characteristics of the metal, semiconductor interface allows for light to be guided in between them causing it to be scattered, allowing for more chances of absorption. The samples were fabricated using organic thin films made from polymers and metallic nanoparticles, more specifically Poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate) copolymer and silver or gold nanoparticles. The two fabrication methods applied include spin coating and Langmuir-Blodgett technique. The transport properties are obtained by analyzing the I-V curves. We will also discuss the resistance, resistivity, conductance, density of charge carriers. SUNY Oswego SCAC Grant.

  8. Physical masking process for integrating micro metallic structures on polymer substrate

    DEFF Research Database (Denmark)

    Islam, Mohammad Aminul; Hansen, Hans Nørgaard

    2009-01-01

    plasmon devices need micro metallic structures on a polymer substrate with an uniform metal layer thickness in the nanometer range. A well known fabrication process to achieve such metallic surface pattern on polymer substrate is photolithography which involves an expensive mask and toxic chemicals......Integration of micro metallic structures in polymer devices is a broad multi-disciplinary research field, consisting of various combinations of mechanical, chemical and physical fabrication methods. Each of the methods has its specific advantages and disadvantages. Some applications like surface....... The current study shows a novel approach for fabricating thin micro metallic structures on polymer substrates using a simple physical mask and a PVD equipment. The new process involves fewer process steps, it is cost effective and suitable for high volume industrial production. Current study suggests...

  9. Three two-dimensional coordination polymers constructed from transition metals and 2,3-norbornanedicarboxylic acid: Hydrothermal synthesis, crystal structures and photocatalytic properties

    Science.gov (United States)

    Zhang, Jia; Wang, Chong-Chen

    2017-02-01

    Three novel coordination polymers based on transition metals like Co(II), Cu(II) and Mn(II), namely [Co2(bpy)2(nbda)2(H2O)2]·2H2O (denoted as BUC-1), [Cu2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-2), [Mn2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-3), (where bpy = 4,4‧-bipyridine, H2nbda = 2,3-norbornanedicarboxylic acid, BUC = Beijing University of Civil Engineering and Architecture), were synthesized under hydrothermal conditions, and characterized by CNH elemental analyses (EA), Fourier Transform infrared spectroscopy (FTIR), and single crystal X-ray diffraction (SCXRD). BUC 1-3 were isostructural and crystallized in the monoclinic space group C2/c, in which the corresponding metal atoms were linked by typical bidentate bpy ligands into two adjacent 1D [M1(bpy)]n2n+ and [M2(bpy)]n2n+ (M = Co(II), Cu(II), Mn(II)), further joined by versatile nbda2- ligands into 2D [M2(bpy)2(nbda)2]n sheets. Finally, three-dimensional supramolecular frameworks were constructed with the aid of the intermolecular hydrogen bonding interactions. BUC 1-3 exhibited different photocatalytic degradation ability to decompose methylene blue (MB) and methyl orange (MO) under UV light irradiation. Additionally, a possible photocatalytic mechanism HOMO-LUMO was proposed and discussed, which was further confirmed by radicals trapping experiments using isopropanol as radical scavenger.

  10. m-Carboranylphosphinate as Versatile Building Blocks To Design all Inorganic Coordination Polymers.

    Science.gov (United States)

    Oleshkevich, Elena; Viñas, Clara; Romero, Isabel; Choquesillo-Lazarte, Duane; Haukka, Matti; Teixidor, Francesc

    2017-05-15

    The first examples of coordination polymers of manganese(II) and a nickel(II) complex with a purely inorganic carboranylphosphinate ligand are reported, together with its exhaustive characterization. X-ray analysis revealed 1D polymeric chains with carboranylphosphinate ligands bridging two manganese(II) centers. The reactivity of polymer 1 with water and Lewis bases has also been studied.

  11. Solvent-free porous framework resulted from 3D entanglement of 1D zigzag coordination polymer

    KAUST Repository

    Kole, Goutam Kumar Umar

    2010-01-01

    A solvent-free porous metal organic framework is constructed by the 3D entanglement of 1D zigzag coordination polymeric chains. The role of solvents and the effect of reaction conditions on such unique entanglement are addressed. © 2010 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

  12. Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties

    Directory of Open Access Journals (Sweden)

    Matasebia T. Munie

    2011-10-01

    Full Text Available Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM2(qox]n·nH2O (2, trans-[Co(tmhd2(qox]n (3, trans-[Ni(tmhd2(qox]n (4, where DBM− = dibenzoylmethanate, tmhd− = 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ along the polymer backbone, λ = wavelength (Ǻ, A = amplitude (Ǻ, x = distance (Ǻ along the polymer axis, provides a method to approximate and visualize the polymer structures.

  13. Synthesis, vibrational spectrometry and thermal characterizations of coordination polymers derived from divalent metal ions and hydroxyl terminated polyurethane as ligand

    Science.gov (United States)

    Laxmi; Khan, Shabnam; Kareem, Abdul; Zafar, Fahmina; Nishat, Nahid

    2018-01-01

    A series of novel coordination polyurethanes [HTPU-M, where M = Mn(II) 'd5', Ni(II) 'd8', and Zn(II) 'd10'] have been synthesized to investigate the effect of divalent metal ions coordination on structure, thermal and adsorption properties of low molecular weight hydroxyl terminated polyurethane (HTPU). HTPU-M have been synthesized in situ where, sbnd OH group of HTPU (synthesized by the condensation polymerization reaction of ethylene glycol (EG) and toluene diisocyanate (TDI) in presence of catalyst) on condensation polymerization with metal acetate in presence of acid catalyst synthesized HTPU-M followed by coordination of metal ions with hetero atoms. The structure, composition and geometry of HTPU-M have been confirmed by vibrational spectrometry (FTIR), 1H NMR, elemental analysis and UV-Visible spectroscopy. Morphological structures of HTPU-M were analyzed by X-Ray Diffraction analysis (XRD), Field Emission Scanning Electron Microscope (FE-SEM) with Energy Dispersive X-ray spectroscopy (EDX) and High Resolution Transmission Electron Microscope (HR-TEM) techniques. The thermal degradation pattern and thermal stability of HTPU-M in comparison to HTPU was investigated by thermal-gravimetric (TG)/differential thermal (DT), analyses along with Integral procedure decomposition temperature (IPDT) by Doyle method. The molecular weight of HTPU was determined by gel permeation chromatography (GPC). The preliminary adsorption/desorption studies of HTPU-M for Congo red (CR) was studied by batch adsorption techniques. The results indicated that HTPU-M have amorphous, layered morphology with higher number of nano-sized grooves in comparison to HTPU. Coordination of metal to HTPU plays a key role in enhancing the thermal stability [HTPU-Ni(II) > HTPU-Mn(II) > HTPU-Zn(II) > HTPU]. The HTPU-M can be utilized for industrial waste water treatment by removing environmental pollutants.

  14. Three-dimensional iron(ii) porous coordination polymer exhibiting carbon dioxide-dependent spin crossover.

    Science.gov (United States)

    Shin, Jong Won; Jeong, Ah Rim; Jeoung, Sungeun; Moon, Hoi Ri; Komatsumaru, Yuki; Hayami, Shinya; Moon, Dohyun; Min, Kil Sik

    2018-04-24

    We report a three-dimensional Fe(ii) porous coordination polymer that exhibits a spin crossover temperature change following CO2 sorption (though not N2 sorption). Furthermore, single crystals of the desolvated polymer with CO2 molecules at three different temperatures were characterised by X-ray crystallography.

  15. Corrosion at the Polymer-Metal Interface in Artificial Seawater Solutions

    Directory of Open Access Journals (Sweden)

    Amelia M. Anderson-Wile

    2012-01-01

    Full Text Available Polymer components for liquid sealing applications are employed in a variety of potentially corrosive environments, such as seawater. Frequently, corrosion of the metal is found at or adjacent to the rubber-metal interface rather than at a noncontact area. The corrosion of different metal alloys (titanium, bronze, nickel, aluminum, 316 stainless steel, and 4130 steel in combination with rubber O-rings (Buna-N and EPDM of varying internal diameters and cross-sectional shapes in seawater over a period of four years is described herein. The corrosion of some metals (i.e., 4130 stainless steel was found to be accelerated through interaction with Buna-N rubber O-rings. Theories to account for corrosion at the polymer-metal interface, especially with respect to polymer composition and O-ring size and shape, are discussed.

  16. Synthesis by plasma of polymer-metal materials

    International Nuclear Information System (INIS)

    Fernandez R, G.

    2004-01-01

    The objective of this work is the design of an experimental set-up to synthesize polymer- metal composites by plasma with versatility in the conditions of synthesis. The main components are a vacuum system capable to reach up to 10 -2 mbar and valves and accessories to control the pressure in the system. In order to generate the electrical discharges and the plasma, an electrical circuit with an inductive connection at 13.56 MHz of frequency was constructed. The electric field partially ionizes the reactor atmosphere where the polymer-metal composites were synthesized. The reactor has two metallic electrodes, one in front of the other, where the particles electrically charged collide against the electrodes producing ablation on them. The polymer-metal composites were synthesized by means of an inductive connection at 13.56 MHz. Aniline, 3-chlorine-ethylene and electrodes of silver (Ag) and copper (Cu) were used in a cylindrical reactor coupled with an external coil to generate glow discharges. The average pressures were 6.15 X 10 -1 and 5.2 X 10 -1 mbar for the synthesis of Poly aniline (P An) and Poly chloroethylene (PE-CI), respectively. The synthesis was performed during 60 and 180 minutes for P An and PE-CI, respectively. The polymers were formed, as films, with an average thickness of 6.42 μm for P An and, in the case of PE-CI, with an approximately growing rate of 14 ηm/W. The power in the syntheses was 30, 50, 70 and 90 W for P An and 50, 100, 120, 140 170, and 200 W for PE-CI. The characterization of the polymer-metal composites was done by energy dispersive spectroscopy to study the composition and the relation of the elements involved in the synthesis. The morphology of the films was studied by means of scanning electron microscopy. The infrared analysis (IR) was done to study the chemicals bonds and the structure of these polymers. Another important study in these materials was the behavior of the electrical conductivity (σ), which was complemented

  17. Interfacial delamination in polymer coated metal sheet : a numerical-experimental study

    NARCIS (Netherlands)

    van den Bosch, M.

    2007-01-01

    An increasing amount of products are nowadays made of polymer coated metal sheet. Polymer coated metal has several advantages compared to traditionally Sn (tin) coated metal, such as costs savings and a more environmental friendly production process. Beverage and food cans are formed by draw-redraw

  18. Inkjet-Printed Organic Transistors Based on Organic Semiconductor/Insulating Polymer Blends.

    Science.gov (United States)

    Kwon, Yoon-Jung; Park, Yeong Don; Lee, Wi Hyoung

    2016-08-02

    Recent advances in inkjet-printed organic field-effect transistors (OFETs) based on organic semiconductor/insulating polymer blends are reviewed in this article. Organic semiconductor/insulating polymer blends are attractive ink candidates for enhancing the jetting properties, inducing uniform film morphologies, and/or controlling crystallization behaviors of organic semiconductors. Representative studies using soluble acene/insulating polymer blends as an inkjet-printed active layer in OFETs are introduced with special attention paid to the phase separation characteristics of such blended films. In addition, inkjet-printed semiconducting/insulating polymer blends for fabricating high performance printed OFETs are reviewed.

  19. Porous Organic Polymers for CO2 Capture

    KAUST Repository

    Teng, Baiyang

    2013-05-01

    Carbon dioxide (CO2) has long been regarded as the major greenhouse gas, which leads to numerous negative effects on global environment. The capture and separation of CO2 by selective adsorption using porous materials proves to be an effective way to reduce the emission of CO2 to atmosphere. Porous organic polymers (POPs) are promising candidates for this application due to their readily tunable textual properties and surface functionalities. The objective of this thesis work is to develop new POPs with high CO2 adsorption capacities and CO2/N2 selectivities for post-combustion effluent (e.g. flue gas) treatment. We will also exploit the correlation between the CO2 capture performance of POPs and their textual properties/functionalities. Chapters Two focuses on the study of a group of porous phenolic-aldehyde polymers (PPAPs) synthesized by a catalyst-free method, the CO2 capture capacities of these PPAPs exceed 2.0 mmol/g at 298 K and 1 bar, while keeping CO2/N2 selectivity of more than 30 at the same time. Chapter Three reports the gas adsorption results of different hyper-cross-linked polymers (HCPs), which indicate that heterocyclo aromatic monomers can greatly enhance polymers’ CO2/N2 selectivities, and the N-H bond is proved to the active CO2 adsorption center in the N-contained (e.g. pyrrole) HCPs, which possess the highest selectivities of more than 40 at 273 K when compared with other HCPs. Chapter Four emphasizes on the chemical modification of a new designed polymer of intrinsic microporosity (PIM) with high CO2/N2 selectivity (50 at 273 K), whose experimental repeatability and chemical stability prove excellent. In Chapter Five, we demonstrate an improvement of both CO2 capture capacity and CO2/N2 selectivity by doping alkali metal ions into azo-polymers, which leads a promising method to the design of new porous organic polymers.

  20. 21 CFR 888.3565 - Knee joint patellofemorotibial metal/polymer porous-coated uncemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint patellofemorotibial metal/polymer... Devices § 888.3565 Knee joint patellofemorotibial metal/polymer porous-coated uncemented prosthesis. (a) Identification. A knee joint patellofemorotibial metal/polymer porous-coated uncemented prosthesis is a device...

  1. A first principles study of energetics and electronic structural responses of uranium-based coordination polymers to Np incorporation

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Saumitra [Melbourne Univ., VIC (Australia). Australian Research Council Centre of Excellence for Advanced Molecular Imaging; Becker, Udo [Michigan Univ., Ann Arbor, MI (United States). Dept. of Earth and Environmental Sciences

    2018-04-01

    Recently developed coordination polymers (CPs) and metal organic frameworks (MOFs) may find applications in areas such as catalysis, hydrogen storage, and heavy metal immobilization. Research on the potential application of actinide-based CPs (An-CP/MOFs) is not as advanced as transition metal-based MOFs. In order to modify their structures necessary for optimizing thermodynamic and electronic properties, here, we described how a specific topology of a particular actinide-based CP or MOF responds to the incorporation of other actinides considering their diverse coordination chemistry associated with the multiple valence states and charge-balancing mechanisms. In this study, we apply a recently developed DFT-based method to determine the relative stability of transuranium incorporated CPs in comparison to their uranium counterpart considering both solid and aqueous state sources and sinks to understand the mechanism and energetics of charge-balanced Np{sup 5+} incorporation into three uranium-based CPs. The calculated Np{sup 5+} + H{sup +} incorporation energies for these CPs range from 0.33 to 0.52 eV, depending on the organic linker, when using the solid oxide Np source Np{sub 2}O{sub 5} and U sink UO{sub 3}. Incorporation energies of these CPs using aqueous sources and sinks increase to 2.85-3.14 eV. The thermodynamic and structural analysis in this study aides in determining, why certain MOF topologies and ligands are selective for some actinides and not for others. This means that once this method is extended across a variety of CPs with their respective linker molecules and different actinides, it can be used to identify certain CPs with certain organic ligands being specific for certain actinides. This information can be used to construct CPs for actinide separation. This is the first determination of the electronic structure (band structure, density of states) of these uranium- and transuranium-based CPs which may eventually lead to design CPs with certain

  2. A first principles study of energetics and electronic structural responses of uranium-based coordination polymers to Np incorporation

    International Nuclear Information System (INIS)

    Saha, Saumitra; Becker, Udo

    2018-01-01

    Recently developed coordination polymers (CPs) and metal organic frameworks (MOFs) may find applications in areas such as catalysis, hydrogen storage, and heavy metal immobilization. Research on the potential application of actinide-based CPs (An-CP/MOFs) is not as advanced as transition metal-based MOFs. In order to modify their structures necessary for optimizing thermodynamic and electronic properties, here, we described how a specific topology of a particular actinide-based CP or MOF responds to the incorporation of other actinides considering their diverse coordination chemistry associated with the multiple valence states and charge-balancing mechanisms. In this study, we apply a recently developed DFT-based method to determine the relative stability of transuranium incorporated CPs in comparison to their uranium counterpart considering both solid and aqueous state sources and sinks to understand the mechanism and energetics of charge-balanced Np 5+ incorporation into three uranium-based CPs. The calculated Np 5+ + H + incorporation energies for these CPs range from 0.33 to 0.52 eV, depending on the organic linker, when using the solid oxide Np source Np 2 O 5 and U sink UO 3 . Incorporation energies of these CPs using aqueous sources and sinks increase to 2.85-3.14 eV. The thermodynamic and structural analysis in this study aides in determining, why certain MOF topologies and ligands are selective for some actinides and not for others. This means that once this method is extended across a variety of CPs with their respective linker molecules and different actinides, it can be used to identify certain CPs with certain organic ligands being specific for certain actinides. This information can be used to construct CPs for actinide separation. This is the first determination of the electronic structure (band structure, density of states) of these uranium- and transuranium-based CPs which may eventually lead to design CPs with certain optical or catalytic

  3. Aluminum based metal-organic framework-polymer monolith in solid-phase microextraction of penicillins in river water and milk samples.

    Science.gov (United States)

    Lirio, Stephen; Liu, Wan-Ling; Lin, Chen-Lan; Lin, Chia-Her; Huang, Hsi-Ya

    2016-01-08

    In this study, aluminum based metal-organic framework (Al-MOF)-organic polymer monoliths were prepared via microwave-assisted polymerization of ethylene dimethacrylate (EDMA), butyl methacrylate (BMA) with different weight percentages of Al-MOF (MIL-53; 37.5-62.5%) and subsequently utilized as sorbent in solid-phase microextraction (SPME) of penicillins (penicillin G, penicillin V, oxacillin, cloxacillin, dicloxacillin, nafcillin). The Al-MOF-polymer was characterized using Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and SEM-energy-dispersive X-ray spectroscopy (SEM-EDS) to clarify the retained crystalline structure well as the homogeneous dispersion of Al-MOF (MIL-53) in polymer monolith. The developed Al-MOF-polymer (MIL-53) monolithic column was evaluated according to its extraction recovery of penicillins. Several parameters affecting the extraction recoveries of penicillins using fabricated Al-MOF-polymer (MIL-53) monolithic column including different MIL-53 weight percentages, column length, pH, desorption solvent, and mobile phase flow rate were investigated. For comparison, different Al-based MOFs (MIL-68, CYCU-4 and DUT-5) were fabricated using the optimized condition for MIL-53-polymer (sample matrix at pH 3, 200μL desorption volume using methanol, 37.5% of MOF, 4-cm column length at 0.100mLmin(-1) flow rate). Among all the Al-MOF-polymers, MIL-53(Al)-polymer still afforded the best extraction recovery for penicillins ranging from 90.5 to 95.7% for intra-day with less than 3.5% relative standard deviations (RSDs) and inter-day precision were in the range of 90.7-97.6% with less than 4.2% RSDs. Meanwhile, the recoveries for column-to-column were in the range of 89.5-93.5% (<3.4% RSDs) while 88.5-90.5% (<5.8% RSDs) for batch-to-batch (n=3). Under the optimal conditions, the limit of detections were in the range of 0.06-0.26μgL(-1) and limit of quantifications between 0.20 and 0.87

  4. Superconductivity in a copper(II)-based coordination polymer with perfect kagome structure

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xing; Liu, Liyao; Xu, Wei; Zhu, Daoben [Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing (China); University of Chinese Academy of Sciences, Beijing (China); Zhang, Shuai [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing (China); Yu, Lei [Department of Chemistry, University of Kentucky, Lexington, KY (United States); Chen, Genfu [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing (China); University of Chinese Academy of Sciences, Beijing (China); Collaborative Innovation Center of Quantum Matter, Beijing (China)

    2018-01-02

    A highly crystalline copper(II) benzenehexathiolate coordination polymer (Cu-BHT) has been prepared. The two-dimensional kagome structure has been confirmed by powder X-ray diffraction, high-resolution transmission electron microscopy, and high-resolution scanning transmission electron microscopy. The as-prepared sample exhibits bulk superconductivity at about 0.25 K, which is confirmed by the zero resistivity, AC magnetic susceptibility, and specific heat measurements. Another diamagnetic transition at about 3 K suggests that there is a second superconducting phase that may be associated with a single layer or few layers of Cu-BHT. It is the first time that superconductivity has been observed in a coordination polymer. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. 21 CFR 888.3530 - Knee joint femorotibial metal/polymer semi-constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint femorotibial metal/polymer semi... § 888.3530 Knee joint femorotibial metal/polymer semi-constrained cemented prosthesis. (a) Identification. A knee joint femorotibial metal/polymer semi-constrained cemented prosthesis is a device intended...

  6. 21 CFR 888.3540 - Knee joint patellofemoral polymer/metal semi-constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint patellofemoral polymer/metal semi... § 888.3540 Knee joint patellofemoral polymer/metal semi-constrained cemented prosthesis. (a) Identification. A knee joint patellofemoral polymer/metal semi-constrained cemented prosthesis is a two-part...

  7. 21 CFR 888.3520 - Knee joint femorotibial metal/polymer non-constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint femorotibial metal/polymer non... § 888.3520 Knee joint femorotibial metal/polymer non-constrained cemented prosthesis. (a) Identification. A knee joint femorotibial metal/polymer non-constrained cemented prosthesis is a device intended to...

  8. Rational assembly of Pb(II)/Cd(II)/Mn(II) coordination polymers based on flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Gao-Shan [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Liu, Chong-Bo, E-mail: cbliu@nchu.edu.cn [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Liu, Hong [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Robbins, Julianne; Zhang, Z. John [School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Yin, Hong-Shan [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Wen, Hui-Liang [State Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047 (China); Wang, Yu-Hua [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China)

    2015-05-15

    Six new coordination polymers, namely, [Pb(L)(H{sub 2}O)] (1), [Pb(L)(phen)] (2), [Pb{sub 2}(L){sub 2}(4,4′-bipy){sub 0.5}] (3), [Cd(L)(phen)] (4), [Cd(L)(4,4′-bipy)]·H{sub 2}O (5) and [Mn(L)(4,4′-bipy)]·H{sub 2}O (6) have been synthesized by the hydrothermal reaction of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) with Pb(II)/Cd(II)/Mn(II) in the presence of ancillary ligands 4,4′-bipyridine (4,4′-bipy) or 1,10-phenanthroline (phen). Complexes 1 and 4–6 exhibit 2-D structures, and complexes 2–3 display 3-D frameworks, of which L{sup 2−} ligands join metal ions to single-stranded helical chains of 1, 3–6 and double-stranded helical chains of 2. Complexes 2 and 3 also contain double-stranded Metal–O helices. Topology analysis reveals that complexes 1 and 4 both represent 4-connected sql net, 2 represents 6-connected pcu net, 3 exhibits a novel (3,12)-connected net, while 5 and 6 display (3,5)-connected gek1 net. The six complexes exhibit two kinds of inorganic–organic connectivities: I{sup 0}O{sup 2} for 1, 4–6, and I{sup 1}O{sup 2} for 2–3. The photoluminescent properties of 4–5 and the magnetic properties of 6 have been investigated. - Graphical abstract: Six new Pb(II)/Cd(II)/Mn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent and magnetic properties have been investigated. - Highlights: • Six novel M(II) coordination polymers with 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid and N-donor ligands. • Complexes 1–6 show diverse intriguing helical characters. • The luminescent properties of complexes 1–5 were investigated. • Complex 6 shows antiferromagnetic coupling.

  9. Vacuum-based surface modification of organic and metallic substrates

    Science.gov (United States)

    Torres, Jessica

    Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous

  10. Inkjet-Printed Organic Transistors Based on Organic Semiconductor/Insulating Polymer Blends

    Science.gov (United States)

    Kwon, Yoon-Jung; Park, Yeong Don; Lee, Wi Hyoung

    2016-01-01

    Recent advances in inkjet-printed organic field-effect transistors (OFETs) based on organic semiconductor/insulating polymer blends are reviewed in this article. Organic semiconductor/insulating polymer blends are attractive ink candidates for enhancing the jetting properties, inducing uniform film morphologies, and/or controlling crystallization behaviors of organic semiconductors. Representative studies using soluble acene/insulating polymer blends as an inkjet-printed active layer in OFETs are introduced with special attention paid to the phase separation characteristics of such blended films. In addition, inkjet-printed semiconducting/insulating polymer blends for fabricating high performance printed OFETs are reviewed. PMID:28773772

  11. Investigations of the polymer/magnetic interface of organic spin-valves

    Energy Technology Data Exchange (ETDEWEB)

    Morley, N.A., E-mail: n.a.morley@sheffield.ac.uk [Department of Materials Science and Engineering, University of Sheffield, Mappin Street, Sheffield S1 3JD (United Kingdom); Dost, R.; Lingam, A.S.V. [Department of Materials Science and Engineering, University of Sheffield, Mappin Street, Sheffield S1 3JD (United Kingdom); Barlow, A.J. [National EPSRC XPS Users’ Service, School of Mechanical and Systems Engineering, Newcastle University, Newcastle upon Tyne NE1 7RU (United Kingdom)

    2015-12-30

    Graphical abstract: - Highlights: • Metal carbide and sulphide species are detected at a polymer–magnetic interface. • Top magnetic electrodes on P3HT have uniaxial anisotropy. • Top magnetic electrodes on PBTTT are isotropic. - Abstract: This work investigates the top interface of an organic spin-valve, to determine the interactions between the polymer and top magnetic electrode. The polymers studied are regio-regular poly(3-hexylthiophene) (RR-P3HT) and poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and the magnetic top electrodes are NiFe and Fe. X-ray photoelectron spectroscopy (XPS) is used to determine the bonding at the interface, along with the extent of how oxidised the magnetic layers are, while atomic force microscopy (AFM) is used to determine the surface roughness. A magneto-optic Kerr effect (MOKE) magnetometer is used to study the magnetic properties of the top electrode. It is shown that at the organic–magnetic interface the magnetic atoms interact with the polymer, as metallic–sulphide and metallic-carbide species are present at the interface. It is also shown that the structure of the polymer influences the anisotropy of the magnetic electrode, such that the magnetic electrodes grown on RR-P3HT have uniaxial anisotropy, while those grown on PBTTT are isotropic.

  12. Nano-Sized Zero Valent Iron and Covalent Organic Polymer Composites for Azo Dye Remediation

    DEFF Research Database (Denmark)

    Mines, Paul D.; Byun, Jeehye; Hwang, Yuhoon

    2014-01-01

    . In this study, the effect of various covalent organic polymers (COPs) as effective supporting materials for nZVI for optimal pollutant degradation was assessed. These COPs demonstrate promising results for the ability to adsorb and remove carbon dioxide, yielding the notion that they are capable of groundwater...... in chlorinated organics, heavy metals, and various other groundwater contaminants....

  13. Assembly of three new POM-based Ag(I) coordination polymers with antibacterial and photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Xin-Xin; Luo, Yu-Hui [Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, PR China (China); Lu, Chen [School of Pharmaceutical and Life Sciences,Changzhou University, Changzhou, Jiangsu 213164 (China); Chen, Xin, E-mail: xinchen@cczu.edu.cn [School of Pharmaceutical and Life Sciences,Changzhou University, Changzhou, Jiangsu 213164 (China); Zhang, Hong, E-mail: zhangh@nenu.edu.cn [Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, PR China (China)

    2015-12-15

    Three new silver coordination polymers, namely, {Ag_3(bpy)_6[PW_1_2O_4_0]} (1), {Ag_5(H_2biim)_2(Hbiim-NO_2)_2[PW_1_2O_4_0]} (2), {Ag_7(pytz)_4[PW_1_2O_4_0]} (3) (bpy=2,2′-bipyridine, H{sub 2}biim=2,2′-biimidazole, pytz=4-(1H-tetrazol-5-yl)pyridine), have been synthesized under hydrothermal condition. Compound 1 shows a 3D supramolecular framework based on 0D moieties. Compound 2 exhibits an attractive 2D biologic screw axis. Compound 3 displays a 3D structure, which consists of Ag(I)···π interactions, π···π stacking and weak Ag···Ag interactions. It is noteworthy that nitration happens to compound 2 during the hydrothermal condition, which is quite rare. Through contrasting the antibacterial activities of gram negative and gram positive bacteria, we find compounds 1–3 have better antibacterial property in gram negative bacteria than gram positive bacteria. In addition, compounds 1–3 also exhibit efficiency of photocatalytic decomposition of organic dyes. Those compounds may be used as potential multifunctional materials in wastewater treatment, because they not only can kill bacteria but also degrade organic pollutants. - Highlights: • Three new silver coordination polymers have been synthesized under hydrothermal condition. • Due to different coordination modes of rigid N-donor ligands, structures of the title compounds vary from 0D to 3D frameworks. • It is noteworthy that nitration happens to compound 2 during the hydrothermal condition, which is quite rare. • In addition, these compounds exhibit efficiency of photocatalytic decomposition of dyes and antibacterial activities.

  14. Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

    Science.gov (United States)

    Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

    2015-02-24

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

  15. Polymer-noble metal nanocomposites: Review

    CSIR Research Space (South Africa)

    Folarin, OM

    2011-09-01

    Full Text Available because of their multi-functionality, ease of process-ability, potential for large-scale manufacturing, significantly lighter than metals, ease of synthesis when compared to the oxide/noble metal multi-layers (Gass et al., 2006; Lee et al., 2003.... their easy aggregation arising from their high surface free energy (Lee et al., 2006). In the design of nanocomposites, one must consider the properties of the polymer matrix as well as the stability of the nanoparticles and more importantly...

  16. Formation of Rosette-Shaped Cd(II) Thiolate Coordination Polymer in Aqueous Solution and Conversion to CdS by Calcination

    International Nuclear Information System (INIS)

    Han, Sung June; Lee, Myung Han; Jeon, Young Jin

    2010-01-01

    We have synthesized rosette-shaped Cd-MSA CPs by a reaction between Cd(II) ions and MSA in aqueous solution and calcined the obtained CPs to obtain CdS microstructures. Upon calcination, the morphology of the CPs does not undergo any significant change, but the particle diameter decreases by 74%. This indicates that our strategy can be used for the synthesis of CPs from other metal thiolates as well. We expect this strategy to be suitable for the preparation of important metal chalcogenide nanostructures and microstructures that can be used in future applications. Coordination polymers (CPs) have attracted considerable attention because of their potential applications in gas storage, catalysis, ion exchange, separation, biomedicine, etc. For use in the above mentioned applications, the structure and morphology of these CPs have been controlled by judicious choice of metals, ligands, and reaction conditions. Recently, Oh and coworkers have reported that CPs can be successfully converted into metal oxides by calcination without causing any significant change in their morphology

  17. Five new Zn(II) and Cd(II) coordination polymers constructed by 3,5-bis-oxyacetate-benzoic acid: Syntheses, crystal structures, network topologies and luminescent properties

    International Nuclear Information System (INIS)

    Jiang Xianrong; Yuan Hongyan; Feng Yunlong

    2012-01-01

    Five Zn(II) and Cd(II) coordination polymers, [Zn 2 (BOABA)(bpp)(OH)]·0.5H 2 O (1), [Cd 3 (BOABA) 2 (bpp) 2 (H 2 O) 6 ]·2H 2 O (2), [Cd 3 (BOABA) 2 (2,2′-bipy) 3 (H 2 O) 4 ]·5.5H 2 O (3), [CdNa(BOABA)(H 2 O)] 2 ·H 2 O (4) and [Cd 2 (BOABA)(bimb)Cl(H 2 O) 2 ]·H 2 O (5) (H 3 BOABA=3,5-bis-oxyacetate-benzoic acid, bpp=1,3-bi(4-pyridyl)propane, 2,2′-bipy=2,2′-bipyridine, bimb=1,4-bis(imidazol-1′-yl)butane), have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and TG analyses. 1 is an uninodal 4-connected 2D square grid network based on binuclear zinc clusters. 2 is 2D wavelike layer structure and further linked by hydrogen bonds into the final 3D (5,6,6)-connected topology network. 3 is 3-connected 2D topology network and the 2,2′-bipy ligands decorate in two different types. 4 is a (4,8)-connected 2D topology network with heterocaryotic {Cd 2 Na 2 } clusters and BOABA 3– ligands. 5 can be rationalized as a (3,10)-connected 3D topology network with tetranuclear {Cd 4 Cl 2 } clusters and BOABA 3– ligands. Meanwhile, photoluminescence studies revealed that these five coordination polymers display strong fluorescent emission bands in the solid state at room temperature. - Graphical abstract: Five new d 10 metal(II) coordination polymers based on H 3 BOABA ligand were obtained and characterized. They display different topological structures and luminescent properties. Highlights: ► Five d 10 metal(II) polymers based on 3,5-bis-oxyacetate-benzoic acid were obtained. ► The polymers were structurally characterized by single-crystal X-ray diffraction. ► Polymers 1–5 display different topological structures. ► They show strong fluorescent emission bands in the solid state.

  18. Synthesis, characterizations and catalytic studies of a new two-dimensional metal-organic framework based on Co-carboxylate secondary building units

    Science.gov (United States)

    Bagherzadeh, Mojtaba; Ashouri, Fatemeh; Đaković, Marijana

    2015-03-01

    A metal-organic framework [Co3(BDC)3(DMF)2(H2O)2] was synthesized and structurally characterized. X-ray single crystal analysis revealed that the framework contains a 2D polymeric chain through coordination of 1,4-benzenedicarboxylic acid linker ligand to cobalt centers. The polymer crystallize in monoclinic P21/n space group with a=13.989(3) Å, b=9.6728(17) Å, c=16.707(3) Å, and Z=2. The polymer features a framework based on the perfect octahedral Co-O6 secondary building units. The catalytic activities of [Co3(BDC)3(DMF)2(H2O)2]n for olefins oxidation was conducted. The heterogeneous catalyst could be facilely separated from the reaction mixture, and reused three times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active species leaching into reaction solution was detected.

  19. Metal-organic framework tethering PNIPAM for ON-OFF controlled release in solution.

    Science.gov (United States)

    Nagata, Shunjiro; Kokado, Kenta; Sada, Kazuki

    2015-05-21

    A smart metal-organic framework (MOF) exhibiting controlled release was achieved by modification with a thermoresponsive polymer (PNIPAM) via a surface-selective post-synthetic modification technique. Simple temperature variation readily switches "open" (lower temperature) and "closed" (higher temperature) states of the polymer-modified MOF through conformational change of PNIPAM grafted onto the MOF, resulting in controlled release of the included guest molecules such as resorufin, caffeine, and procainamide.

  20. Metal-polymer composites comprising nanostructures and applications thereof

    Science.gov (United States)

    Wang, Hsing-Lin [Los Alamos, NM; Jeon, Sea Ho [Dracut, MA; Mack, Nathan H [Los Alamos, NM

    2011-08-02

    Metal-polymer composites, and methods of making and use thereof, said composites comprising a thermally-cured dense polyaniline substrate; an acid dopant; and, metal nanostructure deposits wherein the deposits have a morphology dependent upon the acid dopant.

  1. Coordination polymer nanobamboos of {Fe(x)In(1-x)}-MIL-88B: induced formation of a virtual In-MIL-88B.

    Science.gov (United States)

    Park, Shin Ae; Lee, Hee Jung; Cho, Yea Jin; Choi, Sora; Oh, Moonhyun

    2014-05-05

    A precise fabrication of nanobamboo structures made from hybrid coordination polymers of the type {Fex In1-x }-MIL-88B is demonstrated. The compositions of the hybrid coordination polymer nanobamboos of {Fex In1-x }-MIL-88B (x=0.06, 0.19, or 0.75) are regulated by altering the amount of metal ions used in the reactions. Interestingly, the formation of a virtual In-MIL-88B (precise structure, {Fe0.06 In0.94 }-MIL-88B), which cannot be created in a typical reaction, is induced by the assistance of a Fe-MIL-88B structure. The a and c cell parameters of {Fe0.06 In0.94 }-MIL-88B are calculated at 10.95 and 19.86 Å, respectively. These values of {Fe0.06 In0.94 }-MIL-88B are larger than those of pure Fe-MIL-88B owing to the large ionic size of In(3+) within the framework. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Reactivity and morphology of vapor-deposited Al/polymer interfaces for organic semiconductor devices

    International Nuclear Information System (INIS)

    Demirkan, K.; Mathew, A.; Weiland, C.; Opila, R. L.; Reid, M.

    2008-01-01

    The chemistry and the morphology of metal-deposited organic semiconductor interfaces play a significant role in determining the performance and reliability of organic semiconductor devices. We investigated the aluminum metallization of poly(2-methoxy-5,2 ' -ethyl-hexyloxy-phenylene vinylene) (MEH-PPV), polystyrene, and ozone-treated polystyrene surfaces by chemical (x-ray and ultraviolet photoelectron spectroscopy) and microscopic [atomic force microscopy, scanning electron microscopy (SEM), focused ion beam (FIB)] analyses. Photoelectron spectroscopy showed the degree of chemical interaction between Al and each polymer; for MEH-PPV, the chemical interactions were mainly through the C-O present in the side chain of the polymer structure. The chemical interaction of aluminum with polystyrene was less significant, but it showed a dramatic increase after ozone treatment of the polystyrene surface (due to the formation of exposed oxygen sites). Results showed a strong relationship between the surface reactivity and the condensation/sticking of the aluminum atoms on the surface. SEM analysis showed that, during the initial stages of the metallization, a significant clustering of aluminum takes place. FIB analysis showed that such clustering yields a notably porous structure. The chemical and the morphological properties of the vapor-deposited Al on organic semiconductor surfaces makes such electrical contacts more complicated. The possible effects of surface chemistry and interface morphology on the electrical properties and reliability of organic semiconductor devices are discussed in light of the experimental findings

  3. Removal of Chromophoric Dissolved Organic Matter and Heavy Metals in a River-Sea System: Role of Aquatic Microgel Formation

    Science.gov (United States)

    Shiu, R. F.; Lee, C. L.

    2016-12-01

    Dissolved organic carbon (DOC) polymers are complex and poorly understood mixture of organic macromolecules in environment system. Portions of these polymers spontaneously form microgels that play key roles in many biogeochemical reactions, including mediating aggregation processes, element cycling, and pollutant mobility. However, the detailed interaction of microgels-heterogeneous materials in aquatic systems is still lacking. Insight into the interaction between surrounding materials and microgels from different types of aquatic DOC polymers are extremely important, as it is crucial in determining the fate and transport of these materials. Here, we use riverine and marine DOC polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit too much difference in size ( 3-5 μm) and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had the sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of pollutant.

  4. Diketopyrrolopyrrole Polymers for Organic Solar Cells.

    Science.gov (United States)

    Li, Weiwei; Hendriks, Koen H; Wienk, Martijn M; Janssen, René A J

    2016-01-19

    Conjugated polymers have been extensively studied for application in organic solar cells. In designing new polymers, particular attention has been given to tuning the absorption spectrum, molecular energy levels, crystallinity, and charge carrier mobility to enhance performance. As a result, the power conversion efficiencies (PCEs) of solar cells based on conjugated polymers as electron donor and fullerene derivatives as electron acceptor have exceeded 10% in single-junction and 11% in multijunction devices. Despite these efforts, it is notoriously difficult to establish thorough structure-property relationships that will be required to further optimize existing high-performance polymers to their intrinsic limits. In this Account, we highlight progress on the development and our understanding of diketopyrrolopyrrole (DPP) based conjugated polymers for polymer solar cells. The DPP moiety is strongly electron withdrawing and its polar nature enhances the tendency of DPP-based polymers to crystallize. As a result, DPP-based conjugated polymers often exhibit an advantageously broad and tunable optical absorption, up to 1000 nm, and high mobilities for holes and electrons, which can result in high photocurrents and good fill factors in solar cells. Here we focus on the structural modifications applied to DPP polymers and rationalize and explain the relationships between chemical structure and organic photovoltaic performance. The DPP polymers can be tuned via their aromatic substituents, their alkyl side chains, and the nature of the π-conjugated segment linking the units along the polymer chain. We show that these building blocks work together in determining the molecular conformation, the optical properties, the charge carrier mobility, and the solubility of the polymer. We identify the latter as a decisive parameter for DPP-based organic solar cells because it regulates the diameter of the semicrystalline DPP polymer fibers that form in the photovoltaic blends with

  5. A two-dimensional CdII coordination polymer: poly[diaqua[μ3-5,6-bis(pyridin-2-ylpyrazine-2,3-dicarboxylato-κ5O2:O3:O3,N4,N5]cadmium

    Directory of Open Access Journals (Sweden)

    Monserrat Alfonso

    2016-09-01

    Full Text Available The reaction of 5,6-bis(pyridin-2-ylpyrazine-2,3-dicarboxylic acid with cadmium dichloride leads to the formation of the title two-dimensional coordination polymer, [Cd(C16H8N4O4(H2O2]n. The metal atom is sevenfold coordinated by one pyrazine and one pyridine N atom, two water O atoms, and by two carboxylate O atoms, one of which bridges two CdII atoms to form a Cd2O2 unit situated about a centre of inversion. Hence, the ligand coordinates to the cadmium atom in an N,N′,O-tridentate and an O-monodentate manner. Within the polymer network, there are a number of O—H...O hydrogen bonds present, involving the water molecules and the carboxylate O atoms. There are also C—H...N and C—H...O hydrogen bonds present. In the crystal, the polymer networks lie parallel to the bc plane. They are aligned back-to-back along the a axis with the non-coordinating pyridine rings directed into the space between the networks.

  6. A new three-dimensional bis(benzimidazole)-based cadmium(II) coordination polymer

    Science.gov (United States)

    Hao, Shao Yun; Hou, Suo Xia; Hao, Zeng Chuan; Cui, Guang Hua

    2018-01-01

    A new coordination polymer (CP), formulated as [Cd(L)(DCTP)]n (1) (L = 1,1‧-(1,4-butanediyl)bis(2-methylbenzimidazole), H2DCTP = 2,5-dichloroterephthalic acid), was synthesized under hydrothermal conditions and the performance as luminescent probe was also investigated. Single-crystal X-ray diffraction reveals CP 1 is a 3D 3-fold interpenetrated dia network with large well-defined pores. It is found that CP 1 revealed highly sensitive luminescence sensing for Fe3 + ions in acetonitrile solution with a high quenching efficiency of KSV = 2541.238 L·mol- 1 and a low detection limit of 3.2 μM (S/N = 3). Moreover, the photocatalytic efficiency of 1 for degradation of methylene blue could reach 82.8% after 135 min. Therefore, this coordination polymer could be viewed as multifunctional material for selectively sensing Fe3 + ions and effectively degrading dyes.

  7. Lanthanide coordination polymers based on multi-donor ligand containing pyridine and phthalate moieties: Structures, luminescence and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xun [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Liu, Lang [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450002 (China); College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Wang, Li-Ya, E-mail: wlya@lynu.edu.cn [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473601 (China); Song, Hong-Liang; Qiang Shi, Zhi; Wu, Xu-Hong [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Ng, Seik-Weng [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 80203 (Saudi Arabia)

    2013-10-15

    A new family of five lanthanide-organic coordination polymers incorporating multi-functional N-hetrocyclic dicarboxylate ligand, namely, [Ln{sub 2}(Hdpp){sub 2}(dpp){sub 2}]{sub n}Ln=Pr(1), Eu(2), Gd(3), Dy(4), Er(5) (H{sub 2}dpp=1-(3, 4-dicarboxyphenyl) pyridin-4-ol) have been fabricated successfully through solvothermal reaction of 1-(3,4-dicarboxyphenyl)-4-hydroxypyridin-1-ium chloride with trivalent lanthanide salts, and have been characterized systematically. The complexes 1–5 are isomorphous and isostructural. They all feature three dimensional (3D) frameworks based on the interconnection of 1D double chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 4+} basic carboxylate as secondary building unit (SBU). The results of magnetic analysis shows the same bridging fashion of carboxylic group in this case results in the different magnetic properties occurring within lanthanide polymers. Moreover, the Eu(III) and Dy(III) complexes display characteristic luminescence emission in the visible regions. - Graphical abstract: A new family of lanthanide-organic frameworks incorporating multi-donor twisted ligand has been fabricated successfully, and has been characterized systematically. The complexes 1–5 are isostructural, and all feather three dimensional (3D) frameworks based on the interconnection of 1D double stride chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 2+} basic carboxylate as secondary building unit (SBU). Display Omitted - Highlights: • New family of lanthanide–organic coordination polymers incorporating multifunctional N-hetrocyclic dicarboxylate ligand has been fabricated. • They have been characterized systematically. • They all feather three dimensional frameworks based on the binuclear moiety of [Ln{sub 2}(Hdpp){sub 2}]{sup 2+}. • The Eu(III) and Dy(III) analogues exhibit intense photoluminescence.

  8. Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

    International Nuclear Information System (INIS)

    Gavrilov, Konstantin N; Bondarev, Oleg G; Polosukhin, Aleksei I

    2004-01-01

    The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

  9. Two novel metal–organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

    International Nuclear Information System (INIS)

    Niu, Qing-Jun; Zheng, Yue-Qing; Zhou, Lin-Xia; Zhu, Hong-Lin

    2015-01-01

    Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H 2 en)[Co 3 (H 2 zdn) 2 (ox)(H 2 O) 2 ] (1) and Cd 2 (H 2 zdn)(ox) 0.5 (H 2 O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H 5 zdn; oxalic acid=H 2 ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O–P–O units of H 5 zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property. - Graphical abstract: Linked by oxalate, two zoledronate-based metal–organic frameworks are synthesized, which exhibits the different frameworks. Magnetism and luminescent properties have been studied. The weak antiferromagnetic coupling is conducted in 1. - Highlights: • Compound 1 and 2 are first linked by oxalate anion based on zoledronic acid. • Compound 1 generates a classic “dia Diamond” (6 6 ) topology. • Compound 2 exhibits a (4 4 ·6 2 )(4 4 ·6 6 ) topology. • Magnetism and luminescent properties of 1 and 2 have been studied, respectively

  10. Organic light emitting diodes on ITO-free polymer anodes

    Energy Technology Data Exchange (ETDEWEB)

    Fehse, Karsten; Schwartz, Gregor; Walzer, Karsten; Leo, Karl [Institut fuer Angewandte Photophysik, TU Dresden, D-01062 Dresden (Germany)

    2007-07-01

    The high material cost of indium, being the main component of the commonly used indium-tin-oxide anodes (ITO) in organic light emitting diodes (OLEDs), is an obstacle for the production of efficient low-cost OLEDs. Therefore, new anode materials are needed for large scale OLED production. Recently, we demonstrated that the polymer PEDOT:PSS can substitute ITO as anode. Another highly conductive polymer is polyaniline (PANI) that provides 200 S/cm with a work function of 4.8 eV. In this study, we use PANI as anode for OLEDs (without ITO layer underneath the polymer) with electrically doped hole- and electron transport layers and intrinsic materials in between. Fluorescent blue (Spiro-DPVBi) as well as phosphorescent green (Ir(ppy){sub 3}) and red emitters (Ir(MDQ){sub 2}(acac)) were used for single colour and white OLEDs. Green single and double emission OLEDs achieve device efficiencies of 34 lm/W and 40.7 lm/W, respectively. The white OLED shows a power efficiency of 8.9 lm/W at 1000 cd/m{sup 2} with CIE coordinates of (0.42/0.39).

  11. Development of artificial muscles based on electroactive ionomeric polymer-metal composites.

    Science.gov (United States)

    Hirano, Laos A; Escote, Márcia T; Martins-Filho, Luiz S; Mantovani, Gerson L; Scuracchio, Carlos H

    2011-05-01

    This work contextualizes the research of materials that can be applied as artificial muscles. The main motivation of this research is the importance of the development of mechatronic systems for the replacement of traditional devices of actuation and motion based on rotational electrical motors by other devices that reproduce biological muscle movements. Electroactive polymers (EAPs) are materials that respond to electric stimuli with shape and/or dimension changes, and accomplish movements that are smooth enough to mimic biological muscles. Among EAPs, the ionomeric polymer-metal composites (IPMCs) are an interesting alternative to biomimetic devices due to large displacements when submitted to low applied voltage. This article presents a brief review of IPMCs, a sample preparation procedure, and some electromechanical experimental results. We also discuss the applicability of this technology in medical devices and as artificial muscles. © 2011, Copyright the Authors. Artificial Organs © 2011, International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.

  12. Adhesion along metal-polymer interfaces during plastic deformation

    NARCIS (Netherlands)

    van Tijum, R.; Vellinga, W. P.; De Hosson, J. Th. M.

    In this paper a numerical study is presented that concentrates on the influence of the interface roughness that develops during plastic deformation of a metal, on the work of adhesion and on the change of interface energy upon contact with a glassy polymer. The polymer coating is described with a

  13. Estimation of strength parameters of small-bore metal-polymer pipes

    Science.gov (United States)

    Shaydakov, V. V.; Chernova, K. V.; Penzin, A. V.

    2018-03-01

    The paper presents results from a set of laboratory studies of strength parameters of small-bore metal-polymer pipes of type TG-5/15. A wave method was used to estimate the provisional modulus of elasticity of the metal-polymer material of the pipes. Longitudinal deformation, transverse deformation and leak-off pressure were determined experimentally, with considerations for mechanical damage and pipe bend.

  14. Reversible light-controlled conductance switching of azobenzene-based metal/polymer nanocomposites

    International Nuclear Information System (INIS)

    Pakula, Christina; Zaporojtchenko, Vladimir; Strunskus, Thomas; Faupel, Franz; Zargarani, Dordaneh; Herges, Rainer

    2010-01-01

    We present a new concept of light-controlled conductance switching based on metal/polymer nanocomposites with dissolved chromophores that do not have intrinsic current switching ability. Photoswitchable metal/PMMA nanocomposites were prepared by physical vapor deposition of Au and Pt clusters, respectively, onto spin-coated thin poly(methylmethacrylate) films doped with azo-dye molecules. High dye concentrations were achieved by functionalizing the azo groups with tails and branches, thus enhancing solubility. The composites show completely reversible optical switching of the absorption bands upon alternating irradiation with UV and blue light. We also demonstrate reversible light-controlled conductance switching. This is attributed to changes in the metal cluster separation upon isomerization based on model experiments where analogous conductance changes were induced by swelling of the composite films in organic vapors and by tensile stress.

  15. Organic ferroelectric memory devices with inkjet-printed polymer electrodes on flexible substrates

    KAUST Repository

    Bhansali, Unnat Sampatraj

    2013-05-01

    Drop-on-demand piezoelectric inkjet-printing technique has been used to fabricate a functional cross-bar array of all-organic ferroelectric memory devices. The polymer-ferroelectric-polymer device consists of a ferroelectric copolymer P(VDF-TrFE) film sandwiched between inkjet-patterned, continuous, orthogonal lines of PEDOT:PSS polymer as the bottom and top electrodes. These devices exhibit well-saturated hysteresis curves with a maximum remnant polarization (Pr) = 6.7 μC/cm2, coercive field (E c) = 55 MV/m and a peak capacitance density of 45 nF/cm2. Our polarization fatigue measurements show that these devices retain ∼100% and 45% of their initial Pr values after 103 and 10 5 stress cycles, respectively. The overall performance and polarization retention characteristics of these ferroelectric capacitors with inkjet-printed polymer electrodes are comparable to metal and spin-cast polymer electrodes suggesting their potential use in large-area flexible electronics. © 2013 Elsevier Ltd. All rights reserved.

  16. Cohesion and coordination effects on transition metal surface energies

    Science.gov (United States)

    Ruvireta, Judit; Vega, Lorena; Viñes, Francesc

    2017-10-01

    Here we explore the accuracy of Stefan equation and broken-bond model semiempirical approaches to obtain surface energies on transition metals. Cohesive factors are accounted for either via the vaporization enthalpies, as proposed in Stefan equation, or via cohesive energies, as employed in the broken-bond model. Coordination effects are considered including the saturation degree, as suggested in Stefan equation, employing Coordination Numbers (CN), or as the ratio of broken bonds, according to the bond-cutting model, considering as well the square root dependency of the bond strength on CN. Further, generalized coordination numbers CN bar are contemplated as well, exploring a total number of 12 semiempirical formulations on the three most densely packed surfaces of 3d, 4d, and 5d Transition Metals (TMs) displaying face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. Estimates are compared to available experimental surface energies obtained extrapolated to zero temperature. Results reveal that Stefan formula cohesive and coordination dependencies are only qualitative suited, but unadvised for quantitative discussion, as surface energies are highly overestimated, favoring in addition the stability of under-coordinated surfaces. Broken-bond cohesion and coordination dependencies are a suited basis for quantitative comparison, where square-root dependencies on CN to account for bond weakening are sensibly worse. An analysis using Wulff shaped averaged surface energies suggests the employment of broken-bond model using CN to gain surface energies for TMs, likely applicable to other metals.

  17. Water linked 3D coordination polymers: Syntheses, structures and applications

    Science.gov (United States)

    Singh, Suryabhan; Bhim, Anupam

    2016-12-01

    Three new coordination polymers (CPs) based on Cd and Pb, [Cd(OBA)(μ-H2O)(H2O)]n1, [Pb(OBA)(μ-H2O)]n2 [where OBA=4,4'-Oxybis(benzoate)] and [Pb(SDBA)(H2O)]n.1/4DMF 3 (SDBA=4,4'-Sulfonyldibenzoate), have been synthesized and characterized. The single crystal structural studies reveal that CPs 1 and 2 have three dimensional structure. A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. Compound 3 has a supramolecular 3D structure involving water molecule and hydrogen bonds. A structural transformation is observed when 3 was heated at 100 °C or kept in methanol, forming [Pb(SDBA)]n4. Compound 4 is used as supporting matrix for palladium nanoparticles, PdNPs@4. The PdNPs@4 exhibits good catalytic activity toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH4 at room temperature. Luminescence studies revealed that all CPs could be an effective sensor for nitroaromatic explosives.

  18. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    Science.gov (United States)

    Arıcı, Mürsel; Zafer Yeşilel, Okan; Büyükgüngör, Orhan

    2017-05-01

    Four coordination polymers including, [Co(μ-Htbip)2(μ-dib)]n (1), [Co(μ-tbip)(μ-dmib)0.5]n (2), [Zn2(μ-tbip)(μ3-tbip)(μ-dmib)1.5]n (3) and [Cd(μ3-tbip)(μ-dib)0.5 (H2O)]n (4) (tbip: 5-tert-butylisophthalate, dib: 1,4-bis(imidazol-1yl)benzene, dmib: 1,4-bis(imidazol-1yl)-2,5-dimethylbenzene), were hydrothermally synthesized and characterized by elemental analysis, IR spectra, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). The structural diversity is observed depending on ligands and coordination number of metal centers in the synthesized complexes. The tbip ligand displayed five different coordination modes in its complexes. In 1 and 2, complex 1 is 3D framework with the dia topology while complex 2 has 2D structure with the sql topology depending on coordination geometries of Co ions. Complex 3 is 3D framework with the fsh 4,6-conn topology and complex 4 has 2D 4-connected sql topology. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in methanol could be used as a fluorescent sensor for the detection of acetone. Moreover, thermal and optical properties of the complexes were also studied.

  19. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  20. Metal-organic cooperative catalysis in C-H and C-C bond activation and its concurrent recovery.

    Science.gov (United States)

    Park, Young Jun; Park, Jung-Woo; Jun, Chul-Ho

    2008-02-01

    The development of an efficient catalytic activation (cleavage) system for C-H and C-C bonds is an important challenge in organic synthesis, because these bonds comprise a variety of organic molecules such as natural products, petroleum oils, and polymers on the earth. Among many elegant approaches utilizing transition metals to activate C-H and C-C bonds facilely, chelation-assisted protocols based on the coordinating ability of an organic moiety have attracted great attention, though they have often suffered from the need for an intact coordinating group in a substrate. In this Account, we describe our entire efforts to activate C-H or C-C bonds adjacent to carbonyl groups by employing a new concept of metal-organic cooperative catalysis (MOCC), which enables the temporal installation of a 2-aminopyridyl group into common aldehydes or ketones in a catalytic way. Consequently, a series of new catalytic reactions such as alcohol hydroacylation, oxo-ester synthesis, C-C triple bond cleavage, hydrative dimerization of alkynes, and skeletal rearrangements of cyclic ketones was realized through MOCC. In particular, in the quest for an optimized MOCC system composed of a Wilkinson's catalyst (Ph 3P) 3RhCl and an organic catalyst (2-amino-3-picoline), surprising efficiency enhancements could be achieved when benzoic acid and aniline were introduced as promoters for the aldimine formation process. Furthermore, a notable accomplishment of C-C bond activation has been made using 2-amino-3-picoline as a temporary chelating auxiliary in the reactions of unstrained ketones with various terminal olefins and Wilkinson's catalyst. In the case of seven-membered cyclic ketones, an interesting ring contraction to five- or six-membered ones takes place through skeletal rearrangements initiated by the C-C bond activation of MOCC. On the other hand, the fundamental advances of these catalytic systems into recyclable processes could be achieved by immobilizing both metal and organic

  1. Characterisation of polymers, 1

    CERN Document Server

    Crompton, Roy

    2008-01-01

    This essential guide to Polymer Characterisation is a complete compendium of methodologies that have evolved for the determination of the chemical composition of polymers. This 478-page book gives an up-to-date and thorough exposition of the state-of-the-art theories and availability of instrumentation needed to effect chemical and physical analysis of polymers. This is supported by approximately 1200 references. Volume 1 covers the methodology used for the determination of metals, non-metals and organic functional groups in polymers, and for the determination of the ratio in which different m

  2. Metal-free, single-polymer device exhibits resistive memory effect

    KAUST Repository

    Bhansali, Unnat Sampatraj; Khan, Yasser; Cha, Dong Kyu; Almadhoun, Mahmoud N.; Li, Ruipeng; Chen, Long; Amassian, Aram; Odeh, Ihab N.; Alshareef, Husam N.

    2013-01-01

    All-polymer, write-once-read-many times resistive memory devices have been fabricated on flexible substrates using a single polymer, poly(3,4- ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). Spin-cast or inkjet-printed films of solvent-modified PEDOT:PSS are used as electrodes, while the unmodified or as-is PEDOT:PSS is used as the semiconducting active layer. The all-polymer devices exhibit an irreversible but stable transition from a low resistance state (ON) to a high resistance state (OFF) at low voltages caused by an electric-field-induced morphological rearrangement of PEDOT and PSS at the electrode interface. However, in the metal-PEDOT:PSS-metal devices, we have shown a metal filament formation switching the device from an initial high resistance state (OFF) to the low resistance state (ON). The all-PEDOT:PSS memory device has low write voltages (<3 V), high ON/OFF ratio (>10 3), good retention characteristics (>10 000 s), and stability in ambient storage (>3 months). © 2013 American Chemical Society.

  3. Metal-free, single-polymer device exhibits resistive memory effect

    KAUST Repository

    Bhansali, Unnat Sampatraj

    2013-12-23

    All-polymer, write-once-read-many times resistive memory devices have been fabricated on flexible substrates using a single polymer, poly(3,4- ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). Spin-cast or inkjet-printed films of solvent-modified PEDOT:PSS are used as electrodes, while the unmodified or as-is PEDOT:PSS is used as the semiconducting active layer. The all-polymer devices exhibit an irreversible but stable transition from a low resistance state (ON) to a high resistance state (OFF) at low voltages caused by an electric-field-induced morphological rearrangement of PEDOT and PSS at the electrode interface. However, in the metal-PEDOT:PSS-metal devices, we have shown a metal filament formation switching the device from an initial high resistance state (OFF) to the low resistance state (ON). The all-PEDOT:PSS memory device has low write voltages (<3 V), high ON/OFF ratio (>10 3), good retention characteristics (>10 000 s), and stability in ambient storage (>3 months). © 2013 American Chemical Society.

  4. Coagulation and flocculation of dissolved organic substances with organic polymers

    OpenAIRE

    Kvinnesland, Thomas

    2002-01-01

    Coagulation of natural organic matter (NOM) in water is a well-established process, enabling or enhancing the removal of these substances by different particle separation processes. The dominating coagulating agents used are, however, inorganic salts of iron (Fe3+) and aluminium (Al3+). The primary use of organic polymers is as flocculating agents for already coagulated aggregates. However, in recent years the use of cationic organic polymers have received increasing attent...

  5. Synthesis, characterisation and catalytic activity of 4, 5-imidazoledicarboxylate ligated Co(II) and Cd(II) metal-organic coordination complexes

    Science.gov (United States)

    Gangu, Kranthi Kumar; Maddila, Suresh; Mukkamala, Saratchandra Babu; Jonnalagadda, Sreekantha B.

    2017-09-01

    Two mono nuclear coordination complexes, namely, [Co(4,5-Imdc)2 (H2O)2] (1) and [Cd(4,5-Imdc)2(H2O)3]·H2O (2) were constructed using Co(II) and Cd(II) metal salts with 4,5-Imidazoledicarboxylic acid (4,5-Imdc) as organic ligand. Both 1, 2 were structurally characterized by single crystal XRD and the results reveal that 1 belongs to P21/n space group with unit cell parameters [a = 5.0514(3) Å, b = 22.5786(9) Å, c = 6.5377(3) Å, β = 111.5°] whereas, 2 belongs to P21/c space group with unit cell parameters [a = 6.9116(1) Å, b = 17.4579(2) Å, c = 13.8941(2) Å, β = 97.7°]. While Co(II) in 1 exhibited a six coordination geometry with 4,5-Imdc and water molecules, Cd(II) ion in 2 showed a seven coordination with the same ligand and solvent. In both 1 and 2, the hydrogen bond interactions with mononuclear unit generated 3D-supramolecular structures. Both complexes exhibit solid state fluorescent emission at room temperature. The efficacy of both the complexes as heterogeneous catalysts was examined in the green synthesis of six pyrano[2,3,c]pyrazole derivatives with ethanol as solvent via one-pot reaction between four components, a mixture of aromatic aldehyde, malononitrile, hydrazine hydrate and dimethyl acetylenedicarboxylate. Both 1 and 2 have produced pyrano [2,3,c]pyrazoles in impressive yields (92-98%) at room temperature in short interval of times (<20 min), with no need for any chromatographic separations. With good stability, ease of preparation and recovery plus reusability up to six cycles, both 1 and 2 prove to be excellent environmental friendly catalysts for the value-added organic transformations using green principles.

  6. New coordination polymers from 1D chain, 2D layer to 3D framework constructed from 1,2-phenylenediacetic acid and 1,3-bis(4-pyridyl)propane flexible ligands

    International Nuclear Information System (INIS)

    Xin Lingyun; Liu Guangzhen; Wang Liya

    2011-01-01

    The hydrothermal reactions of Cd, Zn, or Cu(II) acetate salts with H 2 PHDA and BPP flexible ligands afford three new coordination polymers, including [Cd(PHDA)(BPP)(H 2 O)] n (1), [Zn(PHDA)(BPP)] n (2), and [Cu 2 (PHDA) 2 (BPP)] n (3) (H 2 PHDA=1,2-phenylenediacetic acid, BPP=1,3-bis(4-pyridyl)propane). The single-crystal X-ray diffractions reveal that all three complexes feature various metal carboxylate subunits extended further by the BPP ligands to form a diverse range of structures, displaying a remarked structural sensitivity to metal(II) cation. Complex 1 containing PHDA-bridged binuclear cadmium generates 1D double-stranded chain, complex 2 results in 2D→2D interpenetrated (4,4) grids, and complex 3 displays a 3D self-penetrated framework with 4 8 6 6 8 rob topology. In addition, fluorescent analyses show that both 1 and 2 exhibit intense blue-violet photoluminescence in the solid state. - Graphical Abstract: We show diverse supramolecular frameworks based on the same ligands (PHDA and BPP) and different metal acetate salts including 1D double-stranded chain, 2D → 2D twofold interpenetrated layer, and 3D self-penetration networks. Highlights: → Three metal(II = 2 /* ROMAN ) coordination polymers were synthesized using H 2 PHDA and BPP. → The diversity of structures show a remarked sensitivity to metal(II) center. → Complexes show the enhancement of fluorescence compared to that of free ligand.

  7. Use of Hydrophilic Insoluble Polymers in the Restoration of Metal-Contaminated Soils

    Directory of Open Access Journals (Sweden)

    Guiwei Qu

    2009-01-01

    Full Text Available To develop cost-effective techniques that contribute to phytostabilization of severely metal-contaminated soils is a necessary task in environmental research. Hydrophilic insoluble polymers have been used for some time in diapers and other hygienic products and to increase the water-holding capacity of coarse-textured soils. These polymers contain groups, such as carboxyl groups, that are capable of forming bonds with metallic cations, thereby decreasing their bioavailability in soils. The use of polyacrylate polymers as soil amendments to restore metal-contaminated soils has been investigated in the Technical University of Lisbon since the late nineties. Plant growth and plant nutrients concentrations, extractable levels of metals in soil, and soil enzyme activities were used to monitor the improvement in soil quality following the application of these polymers. In contaminated soils, hydrophilic insoluble polymers can create microcosms that are rich in water and nutrients (counterions but only contain small concentrations of toxic elements; the conditions of these microenvironments are favorable to roots and microorganisms. In this paper we described the most relevant information available about this topic.

  8. Use of Hydrophilic Insoluble Polymers in the Restoration of Metal-Contaminated Soils

    International Nuclear Information System (INIS)

    Qu, G.; De Varennes, A.; Qu, G.

    2010-01-01

    To develop cost-effective techniques that contribute to phyto stabilization of severely metal-contaminated soils is a necessary task in environmental research. Hydrophilic insoluble polymers have been used for some time in diapers and other hygienic products and to increase the water-holding capacity of coarse-textured soils. These polymers contain groups, such as carboxyl groups, that are capable of forming bonds with metallic cations, thereby decreasing their bioavailability in soils. The use of polyacrylate polymers as soil amendments to restore metal-contaminated soils has been investigated in the Technical University of Lisbon since the late nineties. Plant growth and plant nutrients concentrations, extractable levels of metals in soil, and soil enzyme activities were used to monitor the improvement in soil quality following the application of these polymers. In contaminated soils, hydrophilic insoluble polymers can create microcosms that are rich in water and nutrients (counterions) but only contain small concentrations of toxic elements; the conditions of these micro environments are favorable to roots and microorganisms. In this paper we described the most relevant information available about this topic.

  9. Removal and recovery of metal ions from process and waste streams using polymer filtration

    International Nuclear Information System (INIS)

    Jarvinen, G.D.; Smith, B.F.; Robison, T.W.; Kraus, K.M.; Thompson, J.A.

    1999-01-01

    Polymer Filtration (PF) is an innovative, selective metal removal technology. Chelating, water-soluble polymers are used to selectively bind the desired metal ions and ultrafiltration is used to concentrate the polymer-metal complex producing a permeate with low levels of the targeted metal ion. When applied to the treatment of industrial metal-bearing aqueous process streams, the permeate water can often be reused within the process and the metal ions reclaimed. This technology is applicable to many types of industrial aqueous streams with widely varying chemistries. Application of PF to aqueous streams from nuclear materials processing and electroplating operations will be described

  10. A new one-dimensional NiII coordination polymer with a two-dimensional supramolecular architecture

    Directory of Open Access Journals (Sweden)

    Kai-Long Zhong

    2017-02-01

    Full Text Available A new one-dimensional NiII coordination polymer of 1,3,5-tris(imidazol-1-ylmethylbenzene, namely catena-poly[[aqua(sulfato-κOhemi(μ-ethane-1,2-diol-κ2O:O′[μ3-1,3,5-tris(1H-imidazol-1-ylmethylbenzene-κ3N3,N3′,N3′′]nickel(II] ethane-1,2-diol monosolvate monohydrate], {[Ni(SO4(C18H18N6(C2H6O20.5(H2O]·C2H6O2·H2O}n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The NiII cation is coordinated by three N atoms of three different 1,3,5-tris(imidazol-1-ylmethylbenzene ligands, one O atom of an ethane-1,2-diol molecule, by a sulfate anion and a water molecule, forming a distorted octahedral NiN3O3 coordination geometry. The tripodal 1,3,5-tris(imidazol-1-ylmethylbenzene ligands link the NiII cations, generating metal–organic chains running along the [100] direction. Adjacent chains are further connected by O—H...O hydrogen bonds, resulting in a two-dimensional supermolecular architecture running parallel to the (001 plane. Another water molecule and a second ethane-1,2-diol molecule are non-coordinating and are linked to the coordinating sulfate ions via O—H...O hydrogen bonds.

  11. Five new Zn(II) and Cd(II) coordination polymers constructed by 3,5-bis-oxyacetate-benzoic acid: Syntheses, crystal structures, network topologies and luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Xianrong; Yuan Hongyan [Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004 (China); Feng Yunlong, E-mail: sky37@zjnu.edu.cn [Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004 (China)

    2012-07-15

    Five Zn(II) and Cd(II) coordination polymers, [Zn{sub 2}(BOABA)(bpp)(OH)]{center_dot}0.5H{sub 2}O (1), [Cd{sub 3}(BOABA){sub 2}(bpp){sub 2}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O (2), [Cd{sub 3}(BOABA){sub 2}(2,2 Prime -bipy){sub 3}(H{sub 2}O){sub 4}]{center_dot}5.5H{sub 2}O (3), [CdNa(BOABA)(H{sub 2}O)]{sub 2}{center_dot}H{sub 2}O (4) and [Cd{sub 2}(BOABA)(bimb)Cl(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O (5) (H{sub 3}BOABA=3,5-bis-oxyacetate-benzoic acid, bpp=1,3-bi(4-pyridyl)propane, 2,2 Prime -bipy=2,2 Prime -bipyridine, bimb=1,4-bis(imidazol-1 Prime -yl)butane), have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and TG analyses. 1 is an uninodal 4-connected 2D square grid network based on binuclear zinc clusters. 2 is 2D wavelike layer structure and further linked by hydrogen bonds into the final 3D (5,6,6)-connected topology network. 3 is 3-connected 2D topology network and the 2,2 Prime -bipy ligands decorate in two different types. 4 is a (4,8)-connected 2D topology network with heterocaryotic {l_brace}Cd{sub 2}Na{sub 2}{r_brace} clusters and BOABA{sup 3-} ligands. 5 can be rationalized as a (3,10)-connected 3D topology network with tetranuclear {l_brace}Cd{sub 4}Cl{sub 2}{r_brace} clusters and BOABA{sup 3-} ligands. Meanwhile, photoluminescence studies revealed that these five coordination polymers display strong fluorescent emission bands in the solid state at room temperature. - Graphical abstract: Five new d{sup 10} metal(II) coordination polymers based on H{sub 3}BOABA ligand were obtained and characterized. They display different topological structures and luminescent properties. Highlights: Black-Right-Pointing-Pointer Five d{sup 10} metal(II) polymers based on 3,5-bis-oxyacetate-benzoic acid were obtained. Black-Right-Pointing-Pointer The polymers were structurally characterized by single-crystal X-ray diffraction. Black-Right-Pointing-Pointer Polymers 1-5 display different

  12. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  13. Polymer-supported reagents with enhanced metal ion recognition: Application to separations science

    International Nuclear Information System (INIS)

    Alexandratos, S.D.

    1993-01-01

    The design and development of polymer-supported reagents with ever-increasing specificities for targeted metal ions remains an important areas of research. The need for efficient separation schemes for both ions and molecules has been outlined in a report by the National Research Council (King) and will gain increased emphasis as environmental restoration is pursued. Polymer-supported reagents are unique in their ability to be applied in an environmentally benign manner to a host of challenges. Such reagents, in the form of beads, can be applied to continuous separation processes ranging from the removal of metal ions in water to the recovery of medicinal drugs produced through biotechnological means. The application of polymer-supported reagents to metal ion separations still requires developing a fundamental understanding of ligand-metal interactions, the role of the polymer in those interactions, and the methods of synthesizing such polymeric reagents in a readily applicable form. Ion exchange resins with sulfonic acid ligands are the prototypical polymer-supported reagents, and their properties have been exhaustively studied (Helfferich). The high acidity of the sulfonic acid group, however, precludes much selectivity, and it displays a very limited range of reaction free energy values with different metal ions (Boyd et al.). The carboxylic acid ligand, present in the acrylate resins, is more selective, though its weak acidity requires relatively high pH solutions for it to be effective. Research has thus been focused on the preparation of polymer-supported reagents with high levels of specificity for targeted metal ions

  14. Positron beam analysis of polymer/metal interfaces under stress

    NARCIS (Netherlands)

    Escobar Galindo, R.; van Veen, A.; Garcia, A.A.; Schut, H.; de Hosson, J.T.M.; Triftshauser, W; Kogel, G; Sperr, P

    2001-01-01

    The polymers Epoxy and Poly(Methyl MethAcrylate) spin coated on Interstitial Free (IF) steel were subjected to external stresses and studied using the Delft Variable Energy Positron (VEP) beam facility. The polymer/metal interface was identified using an S-W map. After tensile experiments vacancy

  15. 21 CFR 888.3390 - Hip joint femoral (hemi-hip) metal/polymer cemented or uncemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint femoral (hemi-hip) metal/polymer... § 888.3390 Hip joint femoral (hemi-hip) metal/polymer cemented or uncemented prosthesis. (a) Identification. A hip joint femoral (hemi-hip) metal/polymer cemented or uncemented prosthesis is a two-part...

  16. Inorganic nanostructure-organic polymer heterostructures useful for thermoelectric devices

    Energy Technology Data Exchange (ETDEWEB)

    See, Kevin C.; Urban, Jeffrey J.; Segalman, Rachel A.; Coates, Nelson E.; Yee, Shannon K.

    2017-11-28

    The present invention provides for an inorganic nanostructure-organic polymer heterostructure, useful as a thermoelectric composite material, comprising (a) an inorganic nanostructure, and (b) an electrically conductive organic polymer disposed on the inorganic nanostructure. Both the inorganic nanostructure and the electrically conductive organic polymer are solution-processable.

  17. Role of microgel formation in scavenging of chromophoric dissolved organic matter and heavy metals in a river-sea system

    International Nuclear Information System (INIS)

    Shiu, Ruei-Feng; Lee, Chon-Lin

    2017-01-01

    Highlights: • Different types of DOC polymers forming microgel were compared. • The assembly effectiveness of marine DOC was much higher than riverine DOC. • Types and sources of DOC polymers may control the aquatic microgel abundance. • An alternative route for CDOM and heavy metals removal is presented. • Ecological risk and fate assessments of pollutants may consider the microgel phase. - Abstract: We use riverine and marine dissolved organic carbon (DOC) polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit very much difference in size and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of hazardous materials.

  18. Role of microgel formation in scavenging of chromophoric dissolved organic matter and heavy metals in a river-sea system

    Energy Technology Data Exchange (ETDEWEB)

    Shiu, Ruei-Feng [Department of Marine Environment and Engineering, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Lee, Chon-Lin, E-mail: linnohc@fac.nsysu.edu.tw [Department of Marine Environment and Engineering, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Department of Public Health, College of Health Science, Kaohsiung Medical University, Kaohsiung, Taiwan (China); Asia-Pacific Ocean Research Center, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Research Center for Environmental Medicine, Kaohsiung Medical University, Kaohsiung, Taiwan (China)

    2017-04-15

    Highlights: • Different types of DOC polymers forming microgel were compared. • The assembly effectiveness of marine DOC was much higher than riverine DOC. • Types and sources of DOC polymers may control the aquatic microgel abundance. • An alternative route for CDOM and heavy metals removal is presented. • Ecological risk and fate assessments of pollutants may consider the microgel phase. - Abstract: We use riverine and marine dissolved organic carbon (DOC) polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit very much difference in size and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of hazardous materials.

  19. Charge Injection and Transport in Metal/Polymer Chains/Metal Sandwich Structure

    International Nuclear Information System (INIS)

    Hai-Hong, Li; Dong-Mei, Li; Yuan, Li; Kun, Gao; De-Sheng, Liu; Shi-Jie, Xie

    2008-01-01

    Using the tight-binding Su–Schrieffer–Heeger model and a nonadiabatic dynamic evolution method, we study the dynamic processes of the charge injection and transport in a metal/two coupled conjugated polymer chains/metal structure. It is found that the charge interchain transport is determined by the strength of the electric field and the magnitude of the voltage bias applied on the metal electrode. The stronger electric field and the larger voltage bias are both in favour of the charge interchain transport. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  20. Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Bhadbhade, Mohan [Mark Wainwright Analytical Centre, University of New South Wales, Kensington, NSW 2052 (Australia); Karatchevtseva, Inna [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Price, Jason R. [Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168 (Australia); Liu, Hao [Centre for Clean Energy Technology, School of Chemistry and Forensic Science, University of Technology Sydney, PO Box 123, Broadway, Sydney, NSW 2007 (Australia); Zhang, Zhaoming; Kong, Linggen [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Čejka, Jiří [Department of Mineralogy, National Museum, Václavské náměstí, 68, Prague 1, 115 79-CZ (Czech Republic); Lu, Kim; Lumpkin, Gregory R. [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia)

    2015-03-15

    Three new coordination polymers of uranium(VI) with pyromellitic acid (H{sub 4}btca) have been synthesized and structurally characterized. (ED)[(UO{sub 2})(btca)]·(DMSO)·3H{sub 2}O (1) (ED=ethylenediammonium; DMSO=dimethylsulfoxide) has a lamellar structure with intercalation of ED and DMSO. (NH{sub 4}){sub 2}[(UO{sub 2}){sub 6}O{sub 2}(OH){sub 6}(btca)]·~6H{sub 2}O (2) has a 3D framework built from 7-fold coordinated uranyl trinuclear units and btca ligands with 1D diamond-shaped channels (~8.5 Å×~8.6 Å). [(UO{sub 2}){sub 2}(H{sub 2}O)(btca)]·4H{sub 2}O (3) has a 3D network constructed by two types of 7-fold coordinated uranium polyhedron. The unique μ{sub 5}-coordination mode of btca in 3 enables the formation of 1D olive-shaped large channels (~4.5 Å×~19 Å). Vibrational modes, thermal stabilities and fluorescence properties have been investigated. - Graphical abstract: Table of content: three new uranium(VI) coordination polymers with pyromellitic acid (H{sub 4}btca) have been synthesized via room temperature and hydrothermal synthesis methods, and structurally characterized. Two to three dimensional (3D) frameworks are revealed. All 3D frameworks have unique 1D large channels. Their vibrational modes, thermal stabilities and photoluminescence properties have been investigated. - Highlights: • Three new coordination polymers of U(VI) with pyromellitic acid (H{sub 4}btca). • Structures from a 2D layer to 3D frameworks with unique 1D channels. • Unusual µ{sub 5}-(η{sub 1}:η{sub 2}:η{sub 1}:η{sub 2:}η{sub 1}) coordination mode of btca ligand. • Vibrational modes, thermal stabilities and luminescent properties reported.

  1. Morphology of polymer-based films for organic photovoltaics

    OpenAIRE

    Ruderer, Matthias A.

    2012-01-01

    In this thesis, polymer-based films are examined for applications in organic photovoltaics. Polymer-fullerene, polymer-polymer and diblock copolymer systems are characterized as active layer materials. The focus is on experimental parameters influencing the morphology formation of the active layer in organic solar cells. Scattering and imaging techniques provide a complete understanding of the internal structure on different length scales which is compared to spectroscopic and photovoltaic pr...

  2. Enhanced Nanotribology and Optimal Self-lubrication in Novel Polymer-Metal Composites

    Science.gov (United States)

    Seam, Alisha; Brostow, Witold; Olea-Mejia, Oscar

    2006-10-01

    Cheaper to produce, light-weight polymeric materials with improved micro and nano-scale tribological characteristics ar gradually replacing the heavier metals in gears, cams, ball-bearings, chains, and other critical machine components which operate under high stress, experience substantial sliding friction and wear, and require external lubrication regimes. Application of such high-performance synthetic materials in a whole range of machinery, manufacturing, aerospace and transportation industries would produce far reaching economic, energy conservation and environmental benefits. This paper devises and investigates a novel and previously untested method of developing self-lubricating and wear-resistant polymer based materials (PBMs) by blending a polymer with small proportions of a metallic additive. Tribological experiments establish that as increasing proportions of the metallic additive Iron (Fe) are added to the polymeric base polyethylene (PE), the friction and wear of the resulting composite (PE-Fe) experiences significant decline until an optimal value of 3 to 5 % Iron and then stabilize. Theoretical analysis reveals this phenomenon to likely be a result of the nano-structural formation of a lubricating oxide layer on surface of the polymer-metal composite. Furthermore, the oxide layer prevented significant degradation of the viscoelastic scratch-recovery of the base polymer, even with 10 percent metal additive (Fe) in the composite samples.

  3. Application of β-cyclodextrin polymers in separation of metal ions

    International Nuclear Information System (INIS)

    Kozlowski, C.A.; Kozlowska, J.

    2006-01-01

    In the present work the competitive transport of Cu(II), Co(II), Ni(II) and Zn(II) ions through the plasticized immobilized membranes was studied. β-cyclodextrin (β-CD) polymers have been used as macrocyclic ligands for separation of metal ions from dilute aqueous solutions by ion exchange methods, i.e. transport across polymer inclusion membranes and ion flotation process. β-CD polymers were prepared by cross-linking β-CD with alkenyl (nonenyl) succinic anhydride derivatives, phtalic and 3-nitrophtalic anhydride in anhydrous N,N-dimethylformamide (DMF) resulting in formation of Polymer A, B or C, respectively. In he case of cooper(II) flotation results obtained with the use of nonylphenol polyoxyethyl glycol ether as an non-anionic surfactant and β-CD polymers as complexation agent, show that the removal of metal decreases with higher molecular mass of β-CD polymers linked by phtalic or 3-nitrophtalic anhydrides. For both derivatives with pH increase the copper(II) removed increase. The highest flotation removal, i.e. 93% is observed for β-CD polymers synthesized at 100 o C with molar ratio CD : NaH : 3-nitrophtalic anhydride equal to 1 : 7 : 7

  4. POLYMER COMPOSITE FILMS WITH SIZE-SELECTED METAL NANOPARTICLES FABRICATED BY CLUSTER BEAM TECHNIQUE

    DEFF Research Database (Denmark)

    Ceynowa, F. A.; Chirumamilla, Manohar; Popok, Vladimir

    2017-01-01

    Formation of polymer films with size-selected silver and copper nanoparticles (NPs) is studied. Polymers are prepared by spin coating while NPs are fabricated and deposited utilizing a magnetron sputtering cluster apparatus. The particle embedding into the films is provided by thermal annealing...... after the deposition. The degree of immersion can be controlled by the annealing temperature and time. Together with control of cluster coverage the described approach represents an efficient method for the synthesis of thin polymer composite layers with either partially or fully embedded metal NPs....... Combining electron beam lithography, cluster beam deposition and thermal annealing allows to form ordered arrays of metal NPs on polymer films. Plasticity and flexibility of polymer host and specific properties added by coinage metal NPs open a way for different applications of such composite materials...

  5. 21 CFR 888.3510 - Knee joint femorotibial metal/polymer constrained cemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint femorotibial metal/polymer constrained... Knee joint femorotibial metal/polymer constrained cemented prosthesis. (a) Identification. A knee joint... of a knee joint. The device limits translation or rotation in one or more planes and has components...

  6. N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang Guilin, E-mail: glzhuang@zjut.edu.cn [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Chen Wulin [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Zheng Jun [Center of Modern Experimental Technology, Anhui University, Hefei 230039 (China); Yu Huiyou [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Wang Jianguo, E-mail: jgw@zjut.edu.cn [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China)

    2012-08-15

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H{sub 3}SIDA) and Ln(NO{sub 3}){sub 3} (Ln=La, 1; Pr, 2; Nd, 3; Gd, 4). Crystal structure analysis exhibits that lanthanide ions affect the coordination number, bond length and dimension of compounds 1-4, which reveal that their structure diversity can be attributed to the effect of lanthanide contraction. Furthermore, the combination of magnetic measure with quantum Monte Carlo(QMC) studies exhibits that the coupling parameters between two adjacent Gd{sup 3+} ions for anti-anti and syn-anti carboxylate bridges are -1.0 Multiplication-Sign 10{sup -3} and -5.0 Multiplication-Sign 10{sup -3} cm{sup -1}, respectively, which reveals weak antiferromagnetic interaction in 4. - Graphical abstract: Four lanthanide coordination polymers with N-(sulfoethyl) iminodiacetic acid were obtained under hydrothermal condition and reveal the weak antiferromagnetic coupling between two Gd{sup 3+} ions by Quantum Monte Carlo studies. Highlights: Black-Right-Pointing-Pointer Four lanthanide coordination polymers of H{sub 3}SIDA ligand were obtained. Black-Right-Pointing-Pointer Lanthanide ions play an important role in their structural diversity. Black-Right-Pointing-Pointer Magnetic measure exhibits that compound 4 features antiferromagnetic property. Black-Right-Pointing-Pointer Quantum Monte Carlo studies reveal the coupling parameters of two Gd{sup 3+} ions.

  7. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    International Nuclear Information System (INIS)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-01

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox) 0.5 (H 2 O)] n ·2n(H 2 O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H 2 sfpip)(ox)(H 2 O) 4 ] n ·2n(H 2 O) (Ln=Nd (8) Sm (9)), [H 2 ox=oxalic acid, H 3 sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H 3 sfpip resulted in two types of structures. Compounds 1–7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox 2− anions as linkers to bridge the adjacent layers. Compounds 8–9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1–9 were also investigated. - Graphical abstract: Nine new lanthanide coordination polymers have been synthesized under hydrothermal conditions. Compounds 1–7 exhibit a 3D tfz-d network. Compounds 8–9 display a 1D chain structure. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. - Highlights: • Nine lanthanide coordination polymers were prepared under hydrothermal conditions. • Their crystal structures have been determined. • The luminescence and thermal stabilities were studied in the solid state.

  8. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-15

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox){sub 0.5}(H{sub 2}O)]{sub n}·2n(H{sub 2}O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H{sub 2}sfpip)(ox)(H{sub 2}O){sub 4}]{sub n}·2n(H{sub 2}O) (Ln=Nd (8) Sm (9)), [H{sub 2}ox=oxalic acid, H{sub 3}sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H{sub 3}sfpip resulted in two types of structures. Compounds 1–7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox{sup 2−} anions as linkers to bridge the adjacent layers. Compounds 8–9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1–9 were also investigated. - Graphical abstract: Nine new lanthanide coordination polymers have been synthesized under hydrothermal conditions. Compounds 1–7 exhibit a 3D tfz-d network. Compounds 8–9 display a 1D chain structure. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. - Highlights: • Nine lanthanide coordination polymers were prepared under hydrothermal conditions. • Their crystal structures have been determined. • The luminescence and thermal stabilities were studied in the solid state.

  9. Chromium metal organic frameworks and synthesis of metal organic frameworks

    Science.gov (United States)

    Zhou, Hong-Cai; Liu, Tian-Fu; Lian, Xizhen; Zou, Lanfang; Feng, Dawei

    2018-04-24

    The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.

  10. Welding of a metal-polymer laminate

    NARCIS (Netherlands)

    Gower, H.L.

    2007-01-01

    The purpose of this work is to investigate the weldability of a metal polymer sandwich structure. The welding of the sandwich material proceeds first by welding of the skin layer. The material selected for this research is Steelite, a sandwich structure developed by Corus, with 0.12 mm thick mild

  11. Electroless formation of conductive polymer-metal nanostructured composites at boundary of two immiscible solvents. Morphology and properties

    International Nuclear Information System (INIS)

    Gniadek, Marianna; Donten, Mikolaj; Stojek, Zbigniew

    2010-01-01

    Formation of polypyrrole (PPy) with metallic inclusions was carried out at the interface between the aqueous phase containing an oxidizer and an organic solution of the monomer. A variety of the polymer-metal composites were obtained in the system. When the oxidizers were silver- and gold salts the obtained material contained from 4 to 9 at.% of metal. In the case of Ag + oxidant the structure of the metallic silver objects varied and included beads and ultra thin wires covered by polymer film, nanocrystals, micrometer cuboid monocrystals and microplates. Metallic gold practically appeared only in one structure-granules. The granules of Au incorporated into PPy were porous and made of very fine flat crystals of thickness in the nanometer range. The use of copper salts never led to the formation of metallic species in the composite. The influence of selected process parameters such as temperature and concentration of the reactants on the polymerization reaction was investigated. The composites with metallic nanoobjects were found to be better catalysts for the electrooxidation of ascorbic acids compared to pure polypyrrole. SEM, X-ray diffractometry, Raman spectroscopy and voltammetry were used in the investigation.

  12. Electroless formation of conductive polymer-metal nanostructured composites at boundary of two immiscible solvents. Morphology and properties

    Energy Technology Data Exchange (ETDEWEB)

    Gniadek, Marianna [Department of Chemistry, University of Warsaw, ul. Pasteura 1, 02-093 Warsaw (Poland); Donten, Mikolaj, E-mail: donten@chem.uw.edu.p [Department of Chemistry, University of Warsaw, ul. Pasteura 1, 02-093 Warsaw (Poland); Stojek, Zbigniew, E-mail: stojek@chem.uw.edu.p [Department of Chemistry, University of Warsaw, ul. Pasteura 1, 02-093 Warsaw (Poland)

    2010-11-01

    Formation of polypyrrole (PPy) with metallic inclusions was carried out at the interface between the aqueous phase containing an oxidizer and an organic solution of the monomer. A variety of the polymer-metal composites were obtained in the system. When the oxidizers were silver- and gold salts the obtained material contained from 4 to 9 at.% of metal. In the case of Ag{sup +} oxidant the structure of the metallic silver objects varied and included beads and ultra thin wires covered by polymer film, nanocrystals, micrometer cuboid monocrystals and microplates. Metallic gold practically appeared only in one structure-granules. The granules of Au incorporated into PPy were porous and made of very fine flat crystals of thickness in the nanometer range. The use of copper salts never led to the formation of metallic species in the composite. The influence of selected process parameters such as temperature and concentration of the reactants on the polymerization reaction was investigated. The composites with metallic nanoobjects were found to be better catalysts for the electrooxidation of ascorbic acids compared to pure polypyrrole. SEM, X-ray diffractometry, Raman spectroscopy and voltammetry were used in the investigation.

  13. Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

    2018-05-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

  14. Role of microgel formation in scavenging of chromophoric dissolved organic matter and heavy metals in a river-sea system.

    Science.gov (United States)

    Shiu, Ruei-Feng; Lee, Chon-Lin

    2017-04-15

    We use riverine and marine dissolved organic carbon (DOC) polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit very much difference in size and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of hazardous materials. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. A spin transition mechanism for cooperative adsorption in metal-organic frameworks

    Science.gov (United States)

    Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

    2017-10-01

    Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

  16. Chemical and structural changes at the ABS polymer-copper metal interface

    NARCIS (Netherlands)

    Kisin, S.; Scaltro, F.; Malanowski, P.; Varst, van der P.G.T.; With, de G.

    2007-01-01

    Creating oxygen containing moieties (hydroxyl or carbonyl) on polymer substrate surfaces is known to increase the adhesion strength of polymers to metals. However, we noticed adhesion increase with time even though no pre- or post-treatment of the polymer substrate was done. In the case of sputtered

  17. Design and construction of diverse structures of coordination polymers: Photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yu, E-mail: wuyuhlj@163.com [College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Lu, Lu [College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Feng, Jianshen [Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Li, Yulong; Sun, Yanchun [College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Ma, Aiqing, E-mail: maqandght@126.com [School of Pharmacy, Guangdong Medical University, Dongguan 523808 (China)

    2017-01-15

    The reaction of Cu(NO{sub 3}){sub 2}·3H{sub 2}O/Ni(NO{sub 3}){sub 2}·6H{sub 2}O with 4′-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2′:6′,4′′-terpyridine (H{sub 2}dbp) gave [Cu{sub 0.5}(Hdbp)]{sub n} (1) and [Ni(dbp)(H{sub 2}O)]{sub n} (2), while the reactions of Co(NO{sub 3}){sub 2}·6H{sub 2}O with H{sub 2}dbp in the presence of 4,4′-bipy and 2,2′-bpy generated [Co(dbp)(4,4′-bipy)]{sub n} (3) and ([Co(dbp)(2,2′-bipy)]{sub n}·H{sub 2}O) (4), respectively (4,4′-bipy=4.4′-pyridine and 2,2′-bipy=2,2′-bipyridine). X-Ray single-crystal analyses reveal that 1 contains a 1D double chain. 2 possesses a 3D architecture with (4.6{sup 2}0.8{sup 3}){sub 2} topology that is interpenetrated with each other to form a 2-fold network. In 3, the 2D [Co(dbp)]n sheets are pillared by 4,4′-bpy to form a 3D framework with 1D open channel. Compound 4 consists of a 1D ladder-like chain. The results showed that the structural diversity of the coordination polymers resulted from the different geometries of metal ions and effect of assistant ligands. Furthermore, the photocatalytic properties of 1–4 for degradation of the methyl violet (MV) have been examined. - Graphical abstract: The photocatalytic activity and selectivity of complexes 1–4 prove that they may be good and stable photocatalysts for degradation of organic dyes.

  18. A direct metal transfer method for cross-bar type polymer non-volatile memory applications

    International Nuclear Information System (INIS)

    Kim, Tae-Wook; Lee, Kyeongmi; Oh, Seung-Hwan; Wang, Gunuk; Kim, Dong-Yu; Jung, Gun-Young; Lee, Takhee

    2008-01-01

    Polymer non-volatile memory devices in 8 x 8 array cross-bar architecture were fabricated by a non-aqueous direct metal transfer (DMT) method using a two-step thermal treatment. Top electrodes with a linewidth of 2 μm were transferred onto the polymer layer by the DMT method. The switching behaviour of memory devices fabricated by the DMT method was very similar to that of devices fabricated by the conventional shadow mask method. The devices fabricated using the DMT method showed three orders of magnitude of on/off ratio with stable resistance switching, demonstrating that the DMT method can be a simple process to fabricate organic memory array devices

  19. Lanthanide metal-organic frameworks

    International Nuclear Information System (INIS)

    Cheng, Peng

    2015-01-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  20. Lanthanide metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Peng (ed.) [Nankai Univ., Tianjin (China). Dept. of Chemistry

    2015-03-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  1. Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

    KAUST Repository

    Barankova, Eva

    2017-01-01

    Since the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good

  2. Adaptive neuro-fuzzy control of ionic polymer metal composite actuators

    International Nuclear Information System (INIS)

    Thinh, Nguyen Truong; Yang, Young-Soo; Oh, Il-Kwon

    2009-01-01

    An adaptive neuro-fuzzy controller was newly designed to overcome the degradation of the actuation performance of ionic polymer metal composite actuators that show highly nonlinear responses such as a straightening-back problem under a step excitation. An adaptive control algorithm with the merits of fuzzy logic and neural networks was applied for controlling the tip displacement of the ionic polymer metal composite actuators. The reference and actual displacements and the change of the error with the electrical inputs were recorded to generate the training data. These data were used for training the adaptive neuro-fuzzy controller to find the membership functions in the fuzzy control algorithm. Software simulation and real-time experiments were conducted by using the Simulink and dSPACE environments. Present results show that the current adaptive neuro-fuzzy controller can be successfully applied to the reliable control of the ionic polymer metal composite actuator for which the performance degrades under long-time actuation

  3. Diketopyrrolopyrrole polymers for organic solar cells

    NARCIS (Netherlands)

    Li, Wei Wei; Hendriks, K.H.; Wienk, M.M.; Janssen, R.A.J.

    2016-01-01

    Conspectus Conjugated polymers have been extensively studied for application in organic solar cells. In designing new polymers, particular attention has been given to tuning the absorption spectrum, molecular energy levels, crystallinity, and charge carrier mobility to enhance performance. As a

  4. Building thiol and metal-thiolate functions into coordination nets: Clues from a simple molecule

    International Nuclear Information System (INIS)

    He Jun; Yang Chen; Xu Zhengtao; Zeller, Matthias; Hunter, Allen D.; Lin Jianhua

    2009-01-01

    The simple and easy-to-prepare bifunctional molecule 2,5-dimercapto-1,4-benzenedicarboxylic acid (H 4 DMBD) interacts with the increasingly harder metal ions of Cu + , Pb 2+ and Eu 3+ to form the coordination networks of Cu 6 (DMBD) 3 (en) 4 (Hen) 6 (1), Pb 2 (DMBD)(en) 2 (2) and Eu 2 (H 2 DMBD) 3 (DEF) 4 (3), where the carboxyl and thiol groups bind with distinct preference to the hard and soft metal ions, respectively. Notably, 1 features uncoordinated carboxylate groups and Cu 3 cluster units integrated via the thiolate groups into an extended network with significant interaction between the metal centers and the organic molecules; 2 features a 2D coordination net based on the mercapto and carboxylic groups all bonded to the Pb 2+ ions; 3 features free-standing thiol groups inside the channels of a metal-carboxylate-based network. This study illustrates the rich solid state structural features and potential functions offered by the carboxyl-thiol combination. - Graphical Abstract: Molecule 2,5-dimercapto-1,4-benzenedicarboxylic acid was reacted with Cu + , Pb 2+ and Eu 3+ ions to explore solid state networks with the rich structural features arising from the carboxyl-thiol combination.

  5. Incidental Polymorphism, Non-Isomorphic and Isomorphic Substitution in Calcium-Valine Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Kevin Lamberts

    2015-05-01

    Full Text Available Five coordination polymers with the stoichiometry CaX2(valine2(H2O2 (X = Cl, Br were obtained from the corresponding calcium halides and either racemic and enantiopure valine. In all cases the zwitterionic amino acid is exclusively O coordinated and the halides act as counteranions for the resulting one-dimensional cationic chains. The enantiopure chloride shows dimorphism; both forms differ in connectivity from the bromide. In contrast to this structural variability for L-valine, the derivatives of the racemic amino acid are isomorphous.

  6. Synthesis by plasma of polymer-metal materials; Sintesis por plasma de materiales polimero-metal

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez R, G

    2004-07-01

    The objective of this work is the design of an experimental set-up to synthesize polymer- metal composites by plasma with versatility in the conditions of synthesis. The main components are a vacuum system capable to reach up to 10{sup -2} mbar and valves and accessories to control the pressure in the system. In order to generate the electrical discharges and the plasma, an electrical circuit with an inductive connection at 13.56 MHz of frequency was constructed. The electric field partially ionizes the reactor atmosphere where the polymer-metal composites were synthesized. The reactor has two metallic electrodes, one in front of the other, where the particles electrically charged collide against the electrodes producing ablation on them. The polymer-metal composites were synthesized by means of an inductive connection at 13.56 MHz. Aniline, 3-chlorine-ethylene and electrodes of silver (Ag) and copper (Cu) were used in a cylindrical reactor coupled with an external coil to generate glow discharges. The average pressures were 6.15 X 10{sup -1} and 5.2 X 10{sup -1} mbar for the synthesis of Poly aniline (P An) and Poly chloroethylene (PE-CI), respectively. The synthesis was performed during 60 and 180 minutes for P An and PE-CI, respectively. The polymers were formed, as films, with an average thickness of 6.42 {mu}m for P An and, in the case of PE-CI, with an approximately growing rate of 14 {eta}m/W. The power in the syntheses was 30, 50, 70 and 90 W for P An and 50, 100, 120, 140 170, and 200 W for PE-CI. The characterization of the polymer-metal composites was done by energy dispersive spectroscopy to study the composition and the relation of the elements involved in the synthesis. The morphology of the films was studied by means of scanning electron microscopy. The infrared analysis (IR) was done to study the chemicals bonds and the structure of these polymers. Another important study in these materials was the behavior of the electrical conductivity ({sigma

  7. Neutral coordination polymers based on a metal-mono(dithiolene) complex: synthesis, crystal structure and supramolecular chemistry of [Zn(dmit)(4,4'-bpy)]n, [Zn(dmit)(4,4'-bpe)]n and [Zn(dmit)(bix)]n (4,4'-bpy = 4,4'-bipyridine, 4,4'-bpe = trans-1,2-bis(4-pyridyl)ethene, bix = 1,4-bis(imidazole-1-ylmethyl)-benzene.

    Science.gov (United States)

    Madhu, Vedichi; Das, Samar K

    2011-12-28

    This article describes a unique synthetic route that enables a neutral mono(dithiolene)metal unit, {Zn(dmit)}, to link with three different organic molecules, resulting in the isolation of a new class of neutral coordination polymers. The species {Zn(dmit)} coordinates with 4,4'-bipyridine (4,4'-bpy), trans-1,2-bis(4-pyridyl)ethene (4,4'-bpe) and 1,4-bis(imidazole-1-ylmethyl)-benzene (bix) as linkers giving rise to the formation of coordination polymers [Zn(dmit)(4,4'-bpy)](n) (1), [Zn(dmit)(4,4'-bpe)](n) (2) and [Zn(dmit)(bix)](n) (3) respectively. Compounds 1-3 were characterized by elemental analyses, IR, diffuse reflectance and single crystal X-ray diffraction studies. Compounds 1 and 3 crystallize in the monoclinic space group P2(1)/n, whereby compound 2 crystallizes in triclinic space group P1[combining macron]. In the present study, we chose three linkers 4,4'-bpy, 4,4'-bpe and bix (see , respectively, for their structural drawings), that differ in terms of their molecular dimensions. The crystal structures of compounds 1-3 are described here in terms of their supramolecular diversities that include π-π interactions, not only among aromatic stacking (compounds 1 and 3), but also between an aromatic ring and an ethylenic double bond (compound 2). The electronic absorption spectroscopy of compounds 1-3 support these intermolecular π-π interactions. This journal is © The Royal Society of Chemistry 2011

  8. Design, Synthesis and Characterization of Functional Metal-Organic Framework Materials

    KAUST Repository

    Alamer, Badriah

    2015-06-01

    Over the past few decades, vast majority of industrial and academic research throughout the world has witnessed the emergence of materials that can serve as ideal candidates for potential utility in desired applications, and these materials are known as Metal Organic Framework (MOFs). This exceptional new family of porous materials is fabricated by linkage of metal ions or clusters and organic linkers via strong bonds. MOFs have been awarded with remarkable interest and widely studied due to their inherent structural methodology (e.g. use of various metals, expanded library of organic building blocks with different geometry and functionality particularly frameworks designed from carboxylate organic linkers) and unquestionably unique structural and chemical features for many practical applications. (i.e. gas storage/separation, catalysis, drug delivery etc). Simply, metal organic frameworks epitomize the beauty of porous chemical structures. From a design perspective, the introduction of the Molecular Building Block (MBB) approach is actively being pursued pathway by researchers toward the construction of MOFs by employing inorganic building blocks and organic linkers and taking advantage of not only their multiple coordination modes and geometries but also the way in which they are reticulated to generate final framework. In this thesis, research studies will be directed toward (i) the investigation of the relationship between experimental parameters and synthesis of well-known fcu –MOF, (ii) rational design and synthesis of new rare earth (RE) based MOFs, (ii) isoreticular materials based on particular MBB ([M3O(RCO2)6]), M= p-and d-block metals, and (iv) zeolite- like metal organic framework assembled from single-metal ion based MBB ([MN2(CO2)4]) via 2-, 3-,and 4-connected organic linkers. Consequently, the porosity, chemical and thermal stability, and gas sorption properties will be evaluated and detailed.

  9. Radioisotope albedo method for measuring thickness of polymers coatings on metal basis

    International Nuclear Information System (INIS)

    Kapranov, B.I.; Myakin'kova, L.V.; Shaverin, V.A.

    1986-01-01

    Theoretical analysis of albedo thickness measuring of polymer coating-metal composite has been made and experimental studies of the range of tested thicknesses of polymer coating when different metal bases and radiation sources are used have been conducted. It is shown that the thickness of polymer coating on metal can be measured using backscattered γ-radiation in the energy range of 20-120 keV at the error 0.15-0.8 mm, at that, for thickness up to 23 mm the use of 147 Pm isotope can be defined as the optimum one; for thicknesses up to 40 mm 241 Am should be used; at thicknesses up to 60 mm - 57 Co. The AGAT-1 albedo gamma thickness gage, designed for measuring thickness of fiber glass coating up to 20 mm on metal base, is described

  10. Microwave-Assisted Synthesis of Nanoporous Aluminum-Based Coordination Polymers as Catalysts for Selective Sulfoxidation Reaction

    Directory of Open Access Journals (Sweden)

    Madhan Vinu

    2017-10-01

    Full Text Available A series of aluminum-based coordination polymers or metal–organic frameworks (Al–MOFs, i.e., DUT-4, DUT-5, MIL-53, NH2-MIL-53, and MIL-100, have been facile prepared by microwave (MW-assisted reactions and used as catalysts for selective sulfoxidation reactions. The MW-assisted synthesis drastically reduced the reaction time from few days to hours. The prepared MOFs have smaller and uniform particle sizes and better yield compared to conventional hydrothermal method. Furthermore, the Al–MOFs have been successfully demonstrated as catalysts in oxidation reaction of methyl phenyl sulfide with H2O2 as oxidant, even under mild conditions, with more than 95% conversion.

  11. Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Racimor, D

    2003-09-15

    The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

  12. Tellurium rings as electron pair donors in cluster compounds and coordination polymers; Tellurringe als Elektronenpaardonoren in Clusterverbindungen und Koordinationspolymeren

    Energy Technology Data Exchange (ETDEWEB)

    Guenther, Anja

    2011-11-08

    In this dissertation novel and already known molecular tellurium rings are presented in cluster compounds and quasi-one-dimensional coordination polymers. The cyclic, homonuclear units are always stabilized by coordination to electron-rich transition metal atoms, with the coordinating tellurium atoms acting as two-electron donors. As a synthesis route, the solid-state reaction in quartz glass vials was used uniformly. In addition to structural determination, the focus was on the characterization of the resulting compounds. For this purpose, resistance measurements were carried out on selected compounds, the magnetic behavior and the thermal degradation reactions were investigated and accompanying quantum chemical calculations were carried out. [German] In dieser Dissertation werden neuartige sowie bereits bekannte molekulare Tellurringe in Clusterverbindungen und quasi-eindimensionalen Koordinationspolymeren vorgestellt. Die Stabilisierung der zyklischen, homonuklearen Einheiten erfolgt dabei stets durch die Koordination an elektronenreiche Uebergangsmetallatome, wobei die koordinierenden Telluratome gegenueber diesen als Zwei-Elektronendonoren fungieren. Als Syntheseroute wurde dabei einheitlich auf die Festkoerperreaktion in Quarzglasampullen zurueckgegriffen. Neben der Strukturaufklaerung stand die Charakterisierung der erhaltenden Verbindungen im Fokus der Arbeit. Dazu wurden an ausgewaehlten Verbindungen Widerstandsmessungen durchgefuehrt, das magnetische Verhalten sowie die thermischen Abbaureaktionen untersucht und begleitende quantenchemische Rechnungen durchgefuehrt.

  13. Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II, Co(II, Ni(II, Cu(II, and Zn(II] metals

    Directory of Open Access Journals (Sweden)

    Nahid Nishat

    2016-09-01

    Full Text Available A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II, Co(II, Ni(II, Cu(II and Zn(II. All the polymeric compounds were characterized by (FT-IR spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA and antibacterial activities. Polymer complexes of Mn(II, Co(II and Ni(II show octahedral geometry, while polymer complexes of Cu(II and Zn(II show square planar and tetrahedral geometry, respectively. The TGA revealed that all the polymer metal complexes are more thermally stable than their parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM-D-5338-93 standards of biodegradable polymers by CO2 evolution method which says that coordination decreases biodegradability. The antibacterial activity was screened with the agar well diffusion method against some selected microorganisms. Among all the complexes, the antibacterial activity of the Cu(II polymer–metal complex showed the highest zone of inhibition because of its higher stability constant.

  14. Rapid, Selective Heavy Metal Removal from Water by a Metal-Organic Framework/Polydopamine Composite.

    Science.gov (United States)

    Sun, Daniel T; Peng, Li; Reeder, Washington S; Moosavi, Seyed Mohamad; Tiana, Davide; Britt, David K; Oveisi, Emad; Queen, Wendy L

    2018-03-28

    Drinking water contamination with heavy metals, particularly lead, is a persistent problem worldwide with grave public health consequences. Existing purification methods often cannot address this problem quickly and economically. Here we report a cheap, water stable metal-organic framework/polymer composite, Fe-BTC/PDA, that exhibits rapid, selective removal of large quantities of heavy metals, such as Pb 2+ and Hg 2+ , from real world water samples. In this work, Fe-BTC is treated with dopamine, which undergoes a spontaneous polymerization to polydopamine (PDA) within its pores via the Fe 3+ open metal sites. The PDA, pinned on the internal MOF surface, gains extrinsic porosity, resulting in a composite that binds up to 1634 mg of Hg 2+ and 394 mg of Pb 2+ per gram of composite and removes more than 99.8% of these ions from a 1 ppm solution, yielding drinkable levels in seconds. Further, the composite properties are well-maintained in river and seawater samples spiked with only trace amounts of lead, illustrating unprecedented selectivity. Remarkably, no significant uptake of competing metal ions is observed even when interferents, such as Na + , are present at concentrations up to 14 000 times that of Pb 2+ . The material is further shown to be resistant to fouling when tested in high concentrations of common organic interferents, like humic acid, and is fully regenerable over many cycles.

  15. “High-Throughput” Evaluation of Polymer-Supported Triazolic Appendages for Metallic Cations Extraction

    Directory of Open Access Journals (Sweden)

    Riadh Slimi

    2015-03-01

    Full Text Available The aim of this work was to find and use a low-cost high-throughput method for a quick primary evaluation of several metal extraction by substituted piperazines appendages as chelatants grafted onto Merrifield polymer using click-chemistry by the copper (I-catalyzed Huisgen’s reaction (CuAAC The polymers were tested for their efficiency to remove various metal ions from neutral aqueous solutions (13 cations studied: Li+, Na+, K+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Cd2+, Ba2+, Ce3+, Hg+ and Pb2+ using the simple conductimetric measurement method. The polymers were found to extract all metals with low efficiencies ≤40%, except for Fe3+ and Hg+, and sometimes Pb2+. Some polymers exhibited a selectively for K+, Cd2+ and Ba2+, with good efficiencies. The values obtained here using less polymer, and a faster method, are in fair correspondence (average difference ±16% with another published evaluation by atomic absorption spectroscopy (AAS.

  16. Cryochemistry of Metal Nanoparticles

    International Nuclear Information System (INIS)

    Sergeev, Gleb B.

    2003-01-01

    The interaction of metal atoms, clusters and nanoparticles with different organic and inorganic substances were studied at low temperature (10-40K). Combination of matrix isolation technique and preparative cryochemistry was applied for the investigation of activity and selectivity of metal particles of different size. Encapsulation of metal nanoparticles in polymers was studied. The metal-polymer films thus obtained exhibited satisfactory sensitivity to ammonia

  17. Cryochemistry of Metal Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sergeev, Gleb B. [Moscow State University, Laboratory of Low Temperature Chemistry, Chemistry Department (Russian Federation)], E-mail: gbs@kinet.chem.msu.ru

    2003-12-15

    The interaction of metal atoms, clusters and nanoparticles with different organic and inorganic substances were studied at low temperature (10-40K). Combination of matrix isolation technique and preparative cryochemistry was applied for the investigation of activity and selectivity of metal particles of different size. Encapsulation of metal nanoparticles in polymers was studied. The metal-polymer films thus obtained exhibited satisfactory sensitivity to ammonia.

  18. Cryochemistry of Metal Nanoparticles

    Science.gov (United States)

    Sergeev, Gleb B.

    2003-12-01

    The interaction of metal atoms, clusters and nanoparticles with different organic and inorganic substances were studied at low temperature (10-40K). Combination of matrix isolation technique and preparative cryochemistry was applied for the investigation of activity and selectivity of metal particles of different size. Encapsulation of metal nanoparticles in polymers was studied. The metal-polymer films thus obtained exhibited satisfactory sensitivity to ammonia.

  19. 21 CFR 888.3535 - Knee joint femorotibial (uni-compartmental) metal/polymer porous-coated uncemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint femorotibial (uni-compartmental) metal... Devices § 888.3535 Knee joint femorotibial (uni-compartmental) metal/polymer porous-coated uncemented prosthesis. (a) Identification. A knee joint femorotibial (uni-compartmental) metal/polymer porous-coated...

  20. Insight into the Broad Field of Polymer Nanocomposites: From Carbon Nanotubes to Clay Nanoplatelets, via Metal Nanoparticles

    Directory of Open Access Journals (Sweden)

    Cristina Stefanescu

    2009-11-01

    Full Text Available Highly ordered polymer nanocomposites are complex materials that display a rich morphological behavior owing to variations in composition, structure, and properties on a nanometer length scale. Metal-polymer nanocomposite materials are becoming more popular for applications requiring low cost, high metal surface areas. Catalytic systems seem to be the most prevalent application for a wide range of metals used in polymer nanocomposites, particularly for metals like Pt, Ni, Co, and Au, with known catalytic activities. On the other hand, among the most frequently utilized techniques to prepare polymer/CNT and/or polymer/clay nanocomposites are approaches like melt mixing, solution casting, electrospinning and solid-state shear pulverization. Additionally, some of the current and potential applications of polymer/CNT and/or polymer/clay nanocomposites include photovoltaic devices, optical switches, electromagnetic interference (EMI shielding, aerospace and automotive materials, packaging, adhesives and coatings. This extensive review covers a broad range of articles, typically from high impact-factor journals, on most of the polymer-nanocomposites known to date: polymer/carbon nanotubes, polymer/metal nanospheres, and polymer/clay nanoplatelets composites. The various types of nanocomposites are described form the preparation stages to performance and applications. Comparisons of the various types of nanocomposites are conducted and conclusions are formulated.

  1. Polymer-metal hybrid transparent electrodes for flexible electronics

    Science.gov (United States)

    Kang, Hongkyu; Jung, Suhyun; Jeong, Soyeong; Kim, Geunjin; Lee, Kwanghee

    2015-03-01

    Despite nearly two decades of research, the absence of ideal flexible and transparent electrodes has been the largest obstacle in realizing flexible and printable electronics for future technologies. Here we report the fabrication of ‘polymer-metal hybrid electrodes’ with high-performance properties, including a bending radius 95% and a sheet resistance solar cells that exhibit a high power conversion efficiency of 10% and polymer light-emitting diodes that can outperform those based on transparent conducting oxides.

  2. Hybrid polymer-inorganic photovoltaic cells

    NARCIS (Netherlands)

    Beek, W.J.E.; Janssen, R.A.J.; Merhari, L.

    2009-01-01

    Composite materials made from organic conjugated polymers and inorganic semiconductors such as metal oxides attract considerable interest for photovoltaic applications. Hybrid polymer-inorganic solar cells offer the opportunity to combine the beneficial properties of the two materials in charge

  3. 21 CFR 888.3310 - Hip joint metal/polymer constrained cemented or uncemented prosthesis.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint metal/polymer constrained cemented or... Hip joint metal/polymer constrained cemented or uncemented prosthesis. (a) Identification. A hip joint... replace a hip joint. The device prevents dislocation in more than one anatomic plane and has components...

  4. Disulfide polymer grafted porous carbon composites for heavy metal removal from stormwater runoff

    DEFF Research Database (Denmark)

    Ko, Dongah; Mines, Paul D.; Jakobsen, Mogens Havsteen

    2018-01-01

    The emerging concern of heavy metal pollution derived from stormwater runoff has triggered a demand for effective heavy metal sorbents. To be an effective sorbent, high affinity along with rapid sorption kinetics for environmental relevant concentrations of heavy metals is important. Herein, we...... have introduced a new composite suitable for trace metal concentration removal, which consists of cheap and common granular activated carbon covered with polymers containing soft bases, thiols, through acyl chlorination (DiS-AC). Material characterization demonstrated that the polymer was successfully...

  5. High Charge Carrier Mobility Polymers for Organic Transistors

    OpenAIRE

    Erdmann, Tim

    2017-01-01

    I) Introduction p-Conjugated polymers inherently combine electronic properties of inorganic semiconductor crystals and material characteristics of organic plastics due to their special molecular design. This unique combination has led to developing new unconventional optoelectronic technologies and, further, resulted in the evolution of semiconducting polymers (SCPs) as fundamental components for novel electronic devices, such as organic field-effect transistors (OFETs), organic light-emit...

  6. Thin metal electrodes for semitransparent organic photovoltaics

    KAUST Repository

    Lee, Kyusung

    2013-08-01

    We demonstrate semitransparent organic photovoltaics (OPVs) based on thin metal electrodes and polymer photoactive layers consisting of poly(3-hexylthiophene) and [6,6]-phenyl C61 butyric acid methyl ester. The power conversion efficiency of a semitransparent OPV device comprising a 15-nm silver (Ag) rear electrode is 1.98% under AM 1.5-G illumination through the indium-tin-oxide side of the front anode at 100 mW/cm2 with 15.6% average transmittance of the entire cell in the visible wavelength range. As its thickness increases, a thin Ag electrode mainly influences the enhancement of the short circuit current density and fill factor. Its relatively low absorption intensity makes a Ag thin film a viable option for semitransparent electrodes compatible with organic layers. © 2013 ETRI.

  7. Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Ogut, Serdar [Univ. of Illinois, Chicago, IL (United States)

    2017-09-11

    The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyes and metal-organic frameworks.

  8. Selective sensing of two novel coordination polymers based on tris(4-carboxylphenyl)phosphine oxide for organic molecules and Fe3+ and Hg2+ ions

    Science.gov (United States)

    Huo, Liangqin; Zhang, Jie; Gao, Lingling; Wang, Xiaoqing; Fan, Liming; Fang, Kegong; Hu, Tuoping

    2017-12-01

    Two novel coordination polymers, formulated as {[Zn(HTPO)(bib)]·4H2O}n (1), {[Cu3(TPO)2 (bib)3]·2DMF·0.5EtOH·0.5H2O}n (2) (H3TPO = tris(4-carboxylphenyl)phosphine oxide; bib = 1,4-bis(1H-imidazol-4-yl) benzene), have been synthesized under solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis (EA), IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD). Structural analysis reveals that complex 1 is a 2D 4-connected sheet with an intriguing 2D + 2D→2D network. Complex 2 displays a 3D 3,4-connected net with the point symbol of {103}2{106}3. Furthermore, the photoluminescence properties of 1 and 2 were investigated in the solid state and various solvent emulsions, the results show that 1 and 2 have better fluorescent recognition for organic molecules, Fe3+ and Hg2+ ions.

  9. Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes

    Directory of Open Access Journals (Sweden)

    Si Chen

    2016-01-01

    Full Text Available A well-defined amphiphilic core-shell polymer functionalized with bis(p-methoxy-phenylphosphinophenylphosphine (BMOPPP in the nanogel (NG core has been obtained by a convergent RAFT polymerization in emulsion. This BMOPPP@NG and the previously-reported TPP@NG (TPP = triphenylphosphine and core cross-linked micelles (L@CCM; L = TPP, BMOPPP having a slightly different architecture were loaded with [Rh(acac(CO2] or [RhCl(COD]2 to yield [Rh(acac(CO(L@Pol] or [RhCl(COD(L@Pol] (Pol = CCM, NG. The interparticle metal migration from [Rh(acac(CO(TPP@NG] to TPP@NG is fast at natural pH and much slower at high pH, the rate not depending significantly on the polymer architecture (CCM vs. NG. The cross-exchange using [Rh(acac(CO(BMOPPP@Pol] and [RhCl(COD(TPP@Pol] (Pol = CCM or NG as reagents at natural pH is also rapid (ca. 1 h, although slower than the equivalent homogeneous reaction on the molecular species (<5 min. On the other hand, the subsequent rearrangement of [Rh(acac(CO(TPP@Pol] and [RhCl(COD(TPP@Pol] within the TPP@Pol core and of [Rh(acac(CO(BMOPPP@Pol] and [RhCl(COD(BMOPPP@Pol] within the BMOPPP@Pol core, leading respectively to [RhCl(CO(TPP@Pol2] and [RhCl(CO(BMOPPP@Pol2], is much more rapid (<30 min than on the corresponding homogeneous process with the molecular species (>24 h.

  10. Conductive polymer/metal composites for interconnect of flexible devices

    Science.gov (United States)

    Kawakita, Jin; Hashimoto Shinoda, Yasuo; Shuto, Takanori; Chikyow, Toyohiro

    2015-06-01

    An interconnect of flexible and foldable devices based on advanced electronics requires high electrical conductivity, flexibility, adhesiveness on a plastic substrate, and efficient productivity. In this study, we investigated the applicability of a conductive polymer/metal composite to the interconnect of flexible devices. By combining an inkjet process and a photochemical reaction, micropatterns of a polypyrrole/silver composite were formed on flexible plastic substrates with an average linewidth of approximately 70 µm within 10 min. The conductivity of the composite was improved to 6.0 × 102 Ω-1·cm-1. From these results, it is expected that the conducting polymer/metal composite can be applied to the microwiring of flexible electronic devices.

  11. Plasma coatings of nitrogen polymers on metal prostheses of the circulatory system

    International Nuclear Information System (INIS)

    Gomez J, L. M.

    2016-01-01

    This work has a study about the synthesis of poly aniline, poly allylamine and poly pyrrole doped with iodine onto metallic surfaces similar to stents for the circulatory system. Ar, water and hydrogen peroxide plasmas were used for eroding, conditioning and synthesizing polymers that potentially reduce some rejection reactions when stents are implanted in the human body. Stents are small metallic meshes that applied inside collapsed arteries or veins enlarge the diameter and restore the blood flow, however the metallic surfaces usually cause rejection reactions that obstruct the veins again. To give solutions to this problem, in this work is studied the synthesis of biocompatible polymer coatings on the stents that resist the blood flow forming a biocompatible interface between metal and blood. The metallic substrates were eroded and chemically prepared with Ar, H_2O and/or H_2O_2 glow discharges on which the polymers were synthesized by plasma. The coatings were morphologically characterized by optical, scanning electron and atomic force microscopy, the chemical structure was studied by infrared and photoelectron X-ray spectroscopy. The hydrophilicity was studied measuring the advance static contact angle and the adhesion was evaluated indirectly with scanning electron microscopy after two months submerged in buffered phosphate solutions. The results indicate that the polymers grew following the superficial morphology; that the conditioning with Ar ions erode the substrates and that the conditioning with H_2O or H_2O_2 erodes and activates the surface generating oxygen bridges which help in the polymer-metal adhesion. The chemical structure of the polymeric coatings contain crosslinked structures that correspond to links between monomers with the participation of all atoms, states that suggest monomer fragmentation and oxidation and states that indicate oxygen bridges in the polymers. The coatings had contact angles close to 90 degrees where is located the line

  12. Gas Phase Sensing of Alcohols by Metal Organic Framework-Polymer Composite Materials

    NARCIS (Netherlands)

    Sachdeva, S.; Koper, S.J.H.; Sabetghadam Esfahani, A.; Soccol, Dimitri; Gravesteijn, Dirk J.; Kapteijn, F.; Sudholter, E.J.R.; Gascon Sabate, J.; de Smet, L.C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al)

  13. Gas Phase Sensing of Alcohols by Metal Organic Framework-Polymer Composite Materials

    NARCIS (Netherlands)

    Sachdeva, Sumit; Koper, Sander J.H.; Sabetghadam, Anahid; Soccol, Dimitri; Gravesteijn, Dirk J.; Kapteijn, Freek; Sudhölter, Ernst J.R.; Gascon, Jorge; Smet, De Louis C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in

  14. Ion Implantation of Polymers

    DEFF Research Database (Denmark)

    Popok, Vladimir

    2012-01-01

    The current paper presents a state-of-the-art review in the field of ion implantation of polymers. Numerous published studies of polymers modified by ion beams are analysed. General aspects of ion stopping, latent track formation and changes of structure and composition of organic materials...... are discussed. Related to that, the effects of radiothermolysis, degassing and carbonisation are considered. Specificity of depth distributions of implanted into polymers impurities is analysed and the case of high-fluence implantation is emphasised. Within rather broad topic of ion bombardment, the focus...... is put on the low-energy implantation of metal ions causing the nucleation and growth of nanoparticles in the shallow polymer layers. Electrical, optical and magnetic properties of metal/polymer composites are under the discussion and the approaches towards practical applications are overviewed....

  15. Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

    Science.gov (United States)

    Lee, Hosoowi; Jeong, Young-Hwan; Kim, Joo-Ho; Kim, Inhye; Lee, Eunji; Jang, Woo-Dong

    2015-09-30

    We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 μM) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased

  16. Coordination of cassava starch to metal ions and thermolysis of ...

    African Journals Online (AJOL)

    Cassava starch formed Werner-type complexes with ions of metals from the transition groups. This was proven by conductivity and electron paramagnetic resonance measurements. The coordination of starch to central metal ions influenced the thermal decomposition of starch. As a rule complexes started to decompose at ...

  17. A new (4, 6)-connected Cu(I) coordination polymer based on rare tetranuclear [Cu4I2] clusters: Synthesis, crystal structure, luminescent and photocatalytic properties

    Science.gov (United States)

    Cui, Li-Jing; Liu, Chun-Yan; Bian, Ming; Yu, Li-Jun

    2018-03-01

    A new Cu(I) coordination polymer, namely [Cu5I3(L)2]n (1 HL = 3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazolyl), was solvothermally synthesized using CuI, HL and NaI as the starting materials. Single crystal X-ray structural analysis shows that compound 1 features a (4, 6)-connected 3D framework employing rare tetranuclear [Cu4I2] clusters as building subunits. It exhibits intense metal-to-ligand luminescence and excellent photocatalytic activity on degradation of methylene blue (MB).

  18. Synthesis and characterization of metal ion-imprinted polymers

    Indian Academy of Sciences (India)

    2018-03-29

    Mar 29, 2018 ... polymers (CPs) were synthesized through the same method without using metal ion. Characterization of the ... tizanidine obtained from MMIP-NPs showed that signifi- .... C=C vari- able alkene stretching band at 1636 cm. −1.

  19. Metal-doped organic foam and method of making same. [Patent application

    Science.gov (United States)

    Rinde, J.A.

    Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  20. Unusual metal coordination chemistry from an amino-amide derivative of 4-nitrophenol, a surprising ligand

    DEFF Research Database (Denmark)

    McGinley, John; McKee, Vickie; Toftlund, Hans

    2009-01-01

    The simple ligand N-(2-aminoethyl)-2-hydroxy-5-nitrobenzamide () exhibits several coordination modes depending on the reaction conditions, acting as a zwitterion on its own or being ionic in the presence of acid and depending on the concentration of metal present in a reaction, it can coordinate...... to the metal in either a 1:1 or a 1:2 metal:ligand mode. Furthermore, the role of solvent plays an important role in these complexation reactions with both four and six coordinate copper complexes being obtained using water as solvent but only six coordinate copper complexes obtained using acetonitrile...

  1. Three d10 coordination polymers assembled from 3,5-bis(imidazole-1-yl)pyridine and different polycarboxylates: Syntheses, structures and luminescence properties

    Science.gov (United States)

    Pan, Jie; Zhang, Di; Xue, Zhen-Zhen; Wei, Li; Han, Song-De; Wang, Guo-Ming

    2017-11-01

    Three novel Zn(II)/Cd(II) coordination polymers, [Cd2(bip)2(m-bdc)2(H2O)2·3H2O]n (1), [Zn2(bip)2(p-bdc)2·2.5H2O]n (2) and [Zn(bip) (p-bdc)·3H2O]n (3), where bip = 3,5-bis(imidazole-1-yl)pyridine, m-H2bdc = 1,3-benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic acid, have been successfully synthesized under solvothermal conditions. The linkage of different ligands with Cd(II) ions in compound 1 affords a (3,5)-connected layer. Furthermore, 2D→3D parallel polycatenation occurs wherein the layers are polycatenated with the adjacent two parallel layers to form a 3D framework. In 2 and 3, the polycarboxylates act as pillars to combine the metal-bip chains, yielding the layered structures. These 2D networks are extended to the final 3D supramolecular architectures by π-π stacking interactions. The results show that bip can act as a versatile building block for the construction of various coordination polymers. Moreover, the fluorescent properties of 1-3 in the solid state at room temperature have been investigated.

  2. Cu(II) coordination polymers constructed by tetrafluoroterephthalic acid and varied imidazole-containing ligands: Syntheses, structures and properties

    Science.gov (United States)

    Liu, Kang; Sun, Yayong; Deng, Liming; Cao, Fan; Han, Jishu; Wang, Lei

    2018-02-01

    Six new copper(II) coordination polymers combining 2,3,5,6-tetrafluoroterephthalatic acid (H2tfBDC) and diverse imidazole-containing ligands, {[Cu(tfBDC)(1,2-bix)2]·2(H2O)}n (1), {Cu(tfBDC)(Im)2}n (2), {[Cu(1,4-bmimb)2(H2O)]·(tfBDC)·2(H2O)}n (3), {Cu(1,4-bimb)2(H2O)2·(tfBDC)}n (4), {[Cu(1,3-bix)2(H2O)2]·(tfBDC)·6(H2O)}n (5) and {[Cu(1,4-bix)2(H2O)2]·(tfBDC)·(1,4-bix)·4(H2O)}n (6) (1,2-bix = 1,2-bis(imidazole-1-ylmethyl)-benzene, Im = imidazole, 1,4-bmimb = 1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,4-bimb = 1,4-bis(imidazol-1-yl)-butane, 1,3-bix = 1,3-bis(imidazole-1-ylmethyl)-benzene, 1,4-bix = 1,4-bis(imidazole-1-ylmethyl)-benzene), have been obtained and structurally verified by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD), elemental analyses and infrared spectroscopy (IR). Single crystal X-ray diffraction analysis revealed that 1 is 2D 4-connected sql topology (point symbol: {44·62}) based on a single metal ion node. Compound 2 is characterized as an infinite 1D chain structure, which is further extended into a 2D layer through N-H···O hydrogen bonds and then a 3D supramolecular architecture via π···π stacking interactions. Note that 2 was prepared through an in situ ligand reaction in which N,N'-carbonyldiimidazole (cdi) broke up into imidazole ligand. Compound 3 possesses a 3D 4-fold interpenetrated architecture with 4-connected dia topology (Schläfli symbol: {66}) in which tfBDC2- is stabilized in the channel by hydrogen bonds. Compounds 4-6 are all linear 1D coordination polymers. In 4, the free tfBDC2- ligand acts as a μ4-bridge to link four coordinated water molecules from the chain to construct a 2D structure via hydrogen bonds. While in 5 and 6, the uncoordinated tfBDC2- ligands and multimeric water clusters is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O-H⋯O hydrogen bonding interactions. Moreover

  3. Artificial tongue based on metal-biomolecule coordination polymer nanoparticles.

    Science.gov (United States)

    Pu, Fang; Ran, Xiang; Ren, Jinsong; Qu, Xiaogang

    2016-02-25

    We construct an array-based recognition system (the so-called artificial tongue) through the self-assembly of nucleotides, dyes and lanthanide ions. Metal ions are selected as model analytes for verifying its discrimination ability. The work provides valuable insights into the application and development of biomolecule-based materials.

  4. Syntheses, crystal structures and luminescent properties of two new 1D d 1 coordination polymers constructed from 2,2'-bibenzimidazole and 1,4-benzenedicarboxylate

    International Nuclear Information System (INIS)

    Wen Lili; Li Yizhi; Dang Dongbin; Tian Zhengfang; Ni Zhaoping; Meng Qingjin

    2005-01-01

    Two novel interesting d 1 metal coordination polymers, [Zn(H 2 bibzim)(BDC)] n (1) and [Cd(H 2 bibzim)(BDC)] n (2) [H 2 bibzim=2,2'-bibenzimidazole, BDC=1,4-benzenedicarboxylate] have been synthesized under solvothermal conditions and structurally characterized. Both 1 and 2 are constructed from infinite neutral zigzag-like one-dimensional (1D) chains. The π-π interactions and interchain hydrogen-bonding interactions further extend the 1D arrangement to generate a 3D supramolecular architecture for 1 and 2. Both complexes have high thermal stability and display strong blue fluorescent emissions in the solid state upon photo-excitation at 365 nm at room temperature. They are the first two examples that 2,2'-bibenzimidazole has been introduced into the d 1 coordination polymeric framework

  5. Electrochemistry of conductive polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy.

    Science.gov (United States)

    Cho, Shin Hyo; Park, Su-Moon

    2006-12-28

    Electrical properties of contacts formed between conducting polymers and noble metal nanoparticles have been examined using current-sensing atomic force microscopy (CS-AFM). Contacts formed between electrochemically prepared pi-conjugated polymer films such as polypyrrole (PPy), poly(3-methylthiophene) (P3MeT), as well as poly(3,4-ethylenedioxythiophene) (PEDOT) and noble metal nanoparticles including platinum (Pt), gold (Au), and silver (Ag) have been examined. The Pt nanoparticles were electrochemically deposited on a pre-coated PPy film surface by reducing a platinum precursor (PtCl62-) at a constant potential. Both current and scanning electron microscopic images of the film showed the presence of Pt islands. The Au and Ag nanoparticles were dispersed on the P3MeT and PEDOT film surfaces simply by dipping the polymer films into colloid solutions containing Au or Ag particles for specified periods (5 to approximately 10 min). The deposition of Au or Ag particles resulted from either their physical adsorption or chemical bonding between particles and the polymer surface depending on the polymer. When compared with PPy, P3MeT and PEDOT showed a stronger binding to Au or Ag nanoparticles when dipped in their colloidal solutions for the same period. This indicates that Au and Ag particles are predominantly linked with the sulfur atoms via chemical bonding. Of the two, PEDOT was more conductive at the sites where the particles are connected to the polymer. It appears that PEDOT has better aligned sulfur atoms on the surface and is strongly bonded to Au and Ag nanoparticles due to their strong affinity to gold and silver. The current-voltage curves obtained at the metal islands demonstrate that the contacts between these metal islands and polymers are ohmic.

  6. Nano- and microsized cubic gel particles from cyclodextrin metal-organic frameworks.

    Science.gov (United States)

    Furukawa, Yuki; Ishiwata, Takumi; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2012-10-15

    Sweet cube o' mine: Bottom-up control of gel particles has been regarded as a great challenge. By employing internal cross-linking of cyclodextrin metal-organic frameworks, cubic sugar gels were formed with sharp edges that reflect the shape of the crystals. This enabled the fabrication of shape- and size-controlled polymer gels from porous crystals (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Qianqian; Han, Ying [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Lin, Hechun, E-mail: hclin@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Zhang, Yuanyuan; Duan, Chungang [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Peng, Hui, E-mail: hpeng@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, Shanxi 030006 (China)

    2017-03-15

    One dimensional coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO{sub 4}{sup 2-} ions to generate a 1-D chain, and all oxygen atoms in SO{sub 4}{sup 2-} groups are connected to three nearest Gd atoms in µ{sup 3}:η{sup 1}:η{sup 1}:η{sup 2} fashion. Gd, S and N from SO{sub 4}{sup 2-} and NO{sub 3}{sup -} are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH=7 T. - Graphical abstract: Coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] was obtained mediated by Bronsted acid Ionic Liquid, which presents a 1-D chains collected by SO{sub 4}{sup 2-} groups. Magnetic susceptibility of the polymer reveals weak antiferromagnetic interactions between the Gd(III) ions with the relatively large magneto-caloric effect of –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH= 7T.

  8. Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview.

    Science.gov (United States)

    Lofrano, Giusy; Carotenuto, Maurizio; Libralato, Giovanni; Domingos, Rute F; Markus, Arjen; Dini, Luciana; Gautam, Ravindra Kumar; Baldantoni, Daniela; Rossi, Marco; Sharma, Sanjay K; Chattopadhyaya, Mahesh Chandra; Giugni, Maurizio; Meric, Sureyya

    2016-04-01

    Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

    International Nuclear Information System (INIS)

    Jin, Jun-Cheng; Tong, Wen-Quan; Fu, Ai-Yun; Xie, Cheng-Gen; Chang, Wen-Gui; Wu, Ju; Xu, Guang-Nian; Zhang, Ya-Nan; Li, Jun; Li, Yong; Yang, Peng-Qi

    2015-01-01

    Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2 1 helical chains. While the Nd(III) ions are bridged through μ 2 -HIDC 2− and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2 1 helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2 1 helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature

  10. Coordination Driven Capture of Nicotine Inside a Mesoporous MOF.

    Science.gov (United States)

    Balestri, Davide; Capucci, Davide; Demitri, Nicola; Bacchi, Alessia; Pelagatti, Paolo

    2017-06-30

    Metal organic frameworks (MOFs) are a wide class of crystalline porous polymers studied in many fields, ranging from catalysis to gas storage. In the past few years, MOFs have been studied for the encapsulation of organic or organometallic molecules and for the development of potential drug carriers. Here, we report on the study of two structurally-related mesoporous Cu-MOFs, namely PCN-6 and PCN-6' (PCN stands for Porous Coordination Network), for nicotine trapping. Nicotine is a well-known alkaloid liquid molecule at room temperature, whose crystalline structure is still unknown. In this work, the loading process was monitored by electron ionization mass spectrometry by using a direct insertion probe (DIP-EI/MS), infrared (IR), and ultraviolet/visible (UV/VIS) analysis. Both nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric (TGA) analysis showed evidence that nicotine trapping reaches remarkable uptakes up to 40 wt %. In the case of PCN-6@nicotine, X-ray structural resolution revealed that the guest uptake is triggered by coordination of the pyridine ring of nicotine to the copper nuclei of the paddle-wheel units composing the framework of PCN-6.

  11. Coordination Driven Capture of Nicotine Inside a Mesoporous MOF

    Directory of Open Access Journals (Sweden)

    Davide Balestri

    2017-06-01

    Full Text Available Metal organic frameworks (MOFs are a wide class of crystalline porous polymers studied in many fields, ranging from catalysis to gas storage. In the past few years, MOFs have been studied for the encapsulation of organic or organometallic molecules and for the development of potential drug carriers. Here, we report on the study of two structurally-related mesoporous Cu-MOFs, namely PCN-6 and PCN-6′ (PCN stands for Porous Coordination Network, for nicotine trapping. Nicotine is a well-known alkaloid liquid molecule at room temperature, whose crystalline structure is still unknown. In this work, the loading process was monitored by electron ionization mass spectrometry by using a direct insertion probe (DIP-EI/MS, infrared (IR, and ultraviolet/visible (UV/VIS analysis. Both nuclear magnetic resonance (NMR spectroscopy and thermogravimetric (TGA analysis showed evidence that nicotine trapping reaches remarkable uptakes up to 40 wt %. In the case of PCN-6@nicotine, X-ray structural resolution revealed that the guest uptake is triggered by coordination of the pyridine ring of nicotine to the copper nuclei of the paddle-wheel units composing the framework of PCN-6.

  12. Method of processing radiation-contaminated organic polymer materials

    International Nuclear Information System (INIS)

    Kobayashi, Yoshii.

    1980-01-01

    Purpose: To process radiation contaminated organic high polymer materials with no evolution of toxic gases, at low temperature and with safety by hot-acid immersion process using sulfuric acid-hydrogen peroxide. Method: Less flammable or easily flammable organic polymers contaminated with radioactive substances, particularly with long life actinoid are heated and carbonized in concentrated sulfuric acid. Then, aqueous 30% H 2 O 2 solution is continuously added dropwise as an oxidizing agent till the solution turns colourless. If the carbonization was insufficient, addition of H 2 O 2 solution is stopped temporarily and the carbonization is conducted again. Thus, the organic polymers are completely decomposed by the wet oxidization. Then, the volume of the organic materials to be discharged is decreased and the radioactive substances contained are simultaneously concentrated and collected. (Seki, T.)

  13. Sonochemical synthesis and characterization of a novel hetro-binuclear metal organic nano polymer based on picolinic acid ligand

    Science.gov (United States)

    Hayati, Payam; Souri, Bagher; Rezvani, Ali Reza; Morsali, Ali; Gutierrez, Angel

    2017-12-01

    Nanoparticles of one new lead and K coordination polymer (CP), {[Pb6(pyc)6(N3)7K].½H2O}n (1) Hpyc = picolinic acid ligand, has been synthesized by use of a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR) spectroscopy and elemental analyses. The single crystal X-ray data of compound 1 imply that the Pb ion is seven coordinated. The thermal stability of compound 1 has been studied by thermogravimetric (TG) and differential scanning calorimetry (DSC). The role of temperature, reaction time and ultrasound irradiation power on the size and morphfology of the nano-structured compound obtained from 1, have been investigated. Results indicate that an increase of temperature and sonication power and a decrease in time reaction led to a decrease of particle size.

  14. SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF A Zn(II COORDINATION POLYMER BASED ON 4,4’-BIPYRIDINE AND ACETATO

    Directory of Open Access Journals (Sweden)

    LI-HUA WANG

    2015-05-01

    Full Text Available A novel Zn(II coordination polymer, [Zn(bpy(acetato2]n (bpy = 4,4’-bipyridine, has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Zn(II coordination polymer is triclinic, space group P-1 with a = 8.046(3 Å, b = 9.161(3 Å, c = 10.663(3 Å, α = 109.769(4º, β = 99.966(5º, γ = 101.666(5º, V= 699.1(4 Å3, Z = 2, Dc = 1.614 mg·m-3, μ = 1.774 mm-1, F(000 = 348, and final R1 = 0.0541, ωR2 = 0.1605. X-ray diffraction analysis reveals that the Zn(II center is six-coordination with a N2O4 distorted octahedral coordination environment. The Zn(II complex forms 1D chain structure by the bridge of 4,4’-bipyridine and acetato.

  15. Effect of fractal silver electrodes on charge collection and light distribution in semiconducting organic polymer films

    Energy Technology Data Exchange (ETDEWEB)

    Chamousis, RL; Chang, LL; Watterson, WJ; Montgomery, RD; Taylor, RP; Moule, AJ; Shaheen, SE; Ilan, B; van de Lagemaat, J; Osterloh, FE

    2014-08-21

    Living organisms use fractal structures to optimize material and energy transport across regions of differing size scales. Here we test the effect of fractal silver electrodes on light distribution and charge collection in organic semiconducting polymer films made of P3HT and PCBM. The semiconducting polymers were deposited onto electrochemically grown fractal silver structures (5000 nm x 500 nm; fractal dimension of 1.71) with PEDOT:PSS as hole-selective interlayer. The fractal silver electrodes appear black due to increased horizontal light scattering, which is shown to improve light absorption in the polymer. According to surface photovoltage spectroscopy, fractal silver electrodes outperform the flat electrodes when the BHJ film thickness is large (>400 nm, 0.4 V photovoltage). Photocurrents of up to 200 microamperes cm(-2) are generated from the bulk heterojunction (BHJ) photoelectrodes under 435 nm LED (10-20 mW cm(-2)) illumination in acetonitrile solution containing 0.005 M ferrocenium hexafluorophosphate as the electron acceptor. The low IPCE values (0.3-0.7%) are due to slow electron transfer to ferrocenium ion and due to shunting along the large metal-polymer interface. Overall, this work provides an initial assessment of the potential of fractal electrodes for organic photovoltaic cells.

  16. Liquid metal-organic frameworks

    Science.gov (United States)

    Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.; Chapman, Karena W.; Keen, David A.; Bennett, Thomas D.; Coudert, François-Xavier

    2017-11-01

    Metal-organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields, covering engineering, physics, chemistry, biology and medicine. Until recently, research has focused almost entirely on crystalline structures, yet now a clear trend is emerging, shifting the emphasis onto disordered states, including `defective by design’ crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework. We combine in situ variable temperature X-ray, ex situ neutron pair distribution function experiments, and first-principles molecular dynamics simulations to study the melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.

  17. Three-Dimensional (3D) Printing of Polymer-Metal Hybrid Materials by Fused Deposition Modeling.

    Science.gov (United States)

    Fafenrot, Susanna; Grimmelsmann, Nils; Wortmann, Martin; Ehrmann, Andrea

    2017-10-19

    Fused deposition modeling (FDM) is a three-dimensional (3D) printing technology that is usually performed with polymers that are molten in a printer nozzle and placed line by line on the printing bed or the previous layer, respectively. Nowadays, hybrid materials combining polymers with functional materials are also commercially available. Especially combinations of polymers with metal particles result in printed objects with interesting optical and mechanical properties. The mechanical properties of objects printed with two of these metal-polymer blends were compared to common poly (lactide acid) (PLA) printed objects. Tensile tests and bending tests show that hybrid materials mostly containing bronze have significantly reduced mechanical properties. Tensile strengths of the 3D-printed objects were unexpectedly nearly identical with those of the original filaments, indicating sufficient quality of the printing process. Our investigations show that while FDM printing allows for producing objects with mechanical properties similar to the original materials, metal-polymer blends cannot be used for the rapid manufacturing of objects necessitating mechanical strength.

  18. Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy

    Science.gov (United States)

    Lin, Tao

    Organic molecules are envisioned as the building blocks for design and fabrication of functional devices in future, owing to their versatility, low cost and flexibility. Although some devices such as organic light-emitting diode (OLED) have been already applied in our daily lives, the field is still in its infancy and numerous challenges still remain. In particular, fundamental understanding of the process of organic material fabrication at a molecular level is highly desirable. This thesis focuses on the design and fabrication of supramolecular and macromolecular nanostructures on a Au(111) surface through self-assembly, polymerization and a combination of two. We used scanning tunneling microscopy (STM) as an experimental tool and Monte Carlo (MC) and kinetic Monte Carlo (KMC) simulations as theoretical tools to characterize the structures of these systems and to investigate the mechanisms of the self-assembly and polymerization processes at a single-molecular level. The results of this thesis consist of four parts as below: Part I addresses the mechanisms of two-dimensional multicomponent supramolecular self-assembly via pyridyl-Fe-terpyridyl coordination. Firstly, we studied four types of self-assembled metal-organic systems exhibiting different dimensionalities using specifically-designed molecular building blocks. We found that the two-dimensional system is under thermodynamic controls while the systems of lower dimension are under kinetic controls. Secondly, we studied the self-assembly of a series of cyclic supramolecular polygons. Our results indicate that the yield of on-surface cyclic polygon structures is very low independent of temperature and concentration and this phenomenon can be attributed to a subtle competition between kinetic and thermodynamic controls. These results shed light on thermodynamic and kinetic controls in on-surface coordination self-assembly. Part II addresses the two-dimensional supramolecular self-assembly of porphyrin

  19. A coordination polymer based magnetic adsorbent material for hemoglobin isolation from human whole blood, highly selective and recoverable

    Science.gov (United States)

    Zhang, Xiaoxing; Tan, Jipeng; Xu, Xinxin; Shi, Fanian; Li, Guanglu; Yang, Yiqiao

    2017-09-01

    A composite material has been obtained successfully through the loading of nanoscale coordination polymer on magnetic Fe3O4@SiO2 core-shell particle. In this composite material, coordination polymer nanoparticles distribute uniformly on Fe3O4@SiO2 and these two components are "tied" together firmly with chemical bonds. Adsorption experiments suggest this composite material exhibits very excellent selectivity to hemoglobin. But under the same condition, its adsorption to bovine serum albumin can almost be ignored. This selectivity can be attributed to the existence of hydrophobic interactions between coordination polymer nanoparticle and hemoglobin. For composite material, the hemoglobin adsorption process follows Langmuir model perfectly with high speed. The adsorbed hemoglobin can be eluted easily by sodium dodecyl sulfate stripping reagent with structure and biological activity of hemoglobin keeps well. The composite material was also employed to separate hemoglobin from human whole blood, which receives a very satisfactory result. Furthermore, magnetic measurement reveals ferromagnetic character of this composite material with magnetization saturation 3.56 emu g-1 and this guarantees its excellent magnetic separation performance from the treated solution.

  20. Electrospun Polymer Nanofibers Decorated with Noble Metal Nanoparticles for Chemical Sensing.

    Science.gov (United States)

    Chen, Chen; Tang, Yongan; Vlahovic, Branislav; Yan, Fei

    2017-12-01

    The integration of different noble metal nanostructures, which exhibit desirable plasmonic and/or electrocatalytic properties, with electrospun polymer nanofibers, which display unique mechanical and thermodynamic properties, yields novel hybrid nanoscale systems of synergistic properties and functions. This review summarizes recent advances on how to incorporate noble metal nanoparticles into electrospun polymer nanofibers and illustrates how such integration paves the way towards chemical sensing applications with improved sensitivity, stability, flexibility, compatibility, and selectivity. It is expected that further development of this field will eventually make a wide impact on many areas of research.

  1. Low band gap polymers for organic photovoltaics

    DEFF Research Database (Denmark)

    Bundgaard, Eva; Krebs, Frederik C

    2007-01-01

    Low band gap polymer materials and their application in organic photovoltaics (OPV) are reviewed. We detail the synthetic approaches to low band gap polymer materials starting from the early methodologies employing quinoid homopolymer structures to the current state of the art that relies...

  2. CFA-7: an interpenetrated metal-organic framework of the MFU-4 family.

    Science.gov (United States)

    Schmieder, Phillip; Grzywa, Maciej; Denysenko, Dmytro; Hambach, Manuel; Volkmer, Dirk

    2015-08-07

    The novel interpenetrated metal-organic framework CFA-7 (Coordination Framework Augsburg University-7), [Zn5Cl4(tqpt)3], has been synthesized containing the organic linker {H2-tqpt = 6,6,14,14-tetramethyl-6,14-dihydroquinoxalino[2,3-b]phenazinebistriazole}. Reaction of H2-tqpt and anhydrous ZnCl2 in N,N-dimethylformamide (DMF) yields CFA-7 as pseudo-cubic crystals. CFA-7 serves as precursor for the synthesis of isostructural frameworks with redox-active metal centers, which is demonstrated by postsynthetic metal exchange of Zn(2+) by different M(2+) (M = Co, Ni, Cu) ions. The novel framework is robust upon solvent removal and has been structurally characterized by single-crystal X-ray diffraction, TGA and IR spectroscopy, as well as gas sorption (Ar, CO2 and H2).

  3. Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

    International Nuclear Information System (INIS)

    Ogihara, Wataru; Sun Jiazeng; Forsyth, Maria; MacFarlane, Douglas R.; Yoshizawa, Masahiro; Ohno, Hiroyuki

    2004-01-01

    We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10 -4 to 10 -3 S cm -1 at room temperature. Gelation was found to cause little change in the 7 Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids

  4. Laccase Immobilization by Chelated Metal Ion Coordination Chemistry

    Directory of Open Access Journals (Sweden)

    Qingqing Wang

    2014-09-01

    Full Text Available In this work, amidoxime polyacrylonitrile (AOPAN nanofibrous membrane was prepared by a reaction between PAN nanofibers and hydroxylamine hydrochloride. The AOPAN nanofibrous membranes were used for four metal ions (Fe3+, Cu2+, Ni2+, Cd2+ chelation under different conditions. Further, the competition of different metal ions coordinating with AOPAN nanofibrous membrane was also studied. The AOPAN chelated with individual metal ion (Fe3+, Cu2+, Ni2+, Cd2+ and also the four mixed metal ions were further used for laccase (Lac immobilization. Compared with free laccase, the immobilized laccase showed better resistance to pH and temperature changes as well as improved storage stability. Among the four individual metal ion chelated membranes, the stability of the immobilized enzymes generally followed the order as Fe–AOPAN–Lac > Cu–AOPAN–Lac > Ni–AOPAN–Lac > Cd–AOPAN–Lac. In addition, the immobilized enzyme on the carrier of AOPAN chelated with four mixed metal ions showed the best properties.

  5. Assembly, Structure, and Functionality of Metal-Organic Networks and Organic Semiconductor Layers at Surfaces

    Science.gov (United States)

    Tempas, Christopher D.

    Self-assembled nanostructures at surfaces show promise for the development of next generation technologies including organic electronic devices and heterogeneous catalysis. In many cases, the functionality of these nanostructures is not well understood. This thesis presents strategies for the structural design of new on-surface metal-organic networks and probes their chemical reactivity. It is shown that creating uniform metal sites greatly increases selectivity when compared to ligand-free metal islands. When O2 reacts with single-site vanadium centers, in redox-active self-assembled coordination networks on the Au(100) surface, it forms one product. When O2 reacts with vanadium metal islands on the same surface, multiple products are formed. Other metal-organic networks described in this thesis include a mixed valence network containing Pt0 and PtII and a network where two Fe centers reside in close proximity. This structure is stable to temperatures >450 °C. These new on-surface assemblies may offer the ability to perform reactions of increasing complexity as future heterogeneous catalysts. The functionalization of organic semiconductor molecules is also shown. When a few molecular layers are grown on the surface, it is seen that the addition of functional groups changes both the film's structure and charge transport properties. This is due to changes in both first layer packing structure and the pi-electron distribution in the functionalized molecules compared to the original molecule. The systems described in this thesis were studied using high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy. Overall, this work provides strategies for the creation of new, well-defined on-surface nanostructures and adds additional chemical insight into their properties.

  6. Synthesis, Structural Characterization, and Antitumor Activity of a Ca(II Coordination Polymer Based on 1,6-Naphthalenedisulfonate and 4,4′-Bipyridyl

    Directory of Open Access Journals (Sweden)

    Xishi Tai

    2013-08-01

    Full Text Available A novel Ca(II coordination polymer, [CaL(4,4′-bipyridyl(H2O4]n (L = 1,6-naphthalenedisulfonate, was synthesized by reaction of calcium perchlorate with 1,6-naphthalenedisulfonic acid disodium salt and 4,4′-bipyridyl in CH3CH2OH/H2O. It was characterized by elemental analysis, IR, molar conductivity and thermogravimetric analysis. X-ray crystallography reveals that the Ca(II coordination polymer belongs to the orthorhombic system, with space group P212121. The geometry of the Ca(II ion is a distorted CaNO6 pengonal bipyramid, arising from its coordination by four water molecules, one nitrogen atom of 4,4′-bipyridyl molecule, and two oxygen atoms from two L ligands. The complex molecules form a helical chain by self-assembly. The antitumor activity of 1,6-naphthalenedisulfonic acid disodium salt and the Ca(II coordination polymer against human hepatoma smmc-7721 cell line and human lung adenocarcinoma A549 cell line reveals that the Ca(II coordination polymer inhibits cell growth of human lung adenocarcinoma A549 cell line with IC50 value of 27 μg/mL, and is more resistive to human lung adenocarcinoma A549 cell line as compared to 1,6-naphthalenedisulfonic acid disodium salt.

  7. Investigation of the potential of polymer-bound co-ordination compounds as catalysts for the photolytic production of hydrogen from water. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, J M; Clear, J M; Grayson, D H; Johnston, D S; Pepper, D C; Vos, J G

    1981-01-01

    Organic polymers containing polymer-bound complexes of the type (Ru(bpy)/sub 2/(PVP)X)/sup n+/ (n=1, X=Cl; n=2, X=CO,py,H/sub 2/O,PVP) have been prepared. Synthetic routes proceed either from preformed polymer and Ru(bpy)/sub 2/Cl/sub 2/ or (Ru(bpy)/sub 2/(OH/sub 2/)/sub 2/)/sup 2 +/ or via polymerization of the corresponding monomer complex. The dependence of the chemical and physical properties on the nature of the polymer backbone and on the loading of the metal complex on the polymer (the Ru:PVP) ratio has been studied. The complexes prepared from homo-PVP are soluble in methanol and aqueous acid but not in neutral water. Water-soluble complexes may be prepared from water-soluble copolymers. (Ru(bpy)/sub 2/(PVP)Cl)/sup +/ and (Ru(bpy)/sub 2/(PVP)/sub 2/)/sup 2 +/ luminesce strongly in methanol at 77/sup 0/K but not at room temperature. Their behavior upon irradiation in methanol solution is similar to that of the pyridine complexes (Ru(bpy)/sub 2/(py)X)/sup n+/ which undergo photosubstitution and photoanation. The rate and extent of these reactions, which eventually lead to removal of the complex from the polymer backbone, are sensitive to the Ru:PVP ratio, and evidence has been found for intrachain recombination of the (Ru(bpy)/sub 2/X)/sup n+/ fragment with the polymer. This leads to enhanced photostability of the polymer. The water-soluble (Ru(bpy)/sub 2/(PVP)(OH/sub 2/))/sup 2 +/ is rather photostable. Water-insoluble films of the polymeric complexes may be cast on glass slides. Under these conditions they are luminescent at room temperature. They are quite photostable upon irradiation, even in water, and there is little tendency for dissociation of the metal complex from the polymer.

  8. The use of polymer gel dosimetry to measure dose distribution around metallic implants

    International Nuclear Information System (INIS)

    Nagahata, Tomomasa; Yamaguchi, Hajime; Monzen, Hajime; Nishimura, Yasumasa

    2014-01-01

    A semi-solid polymer dosimetry system using agar was developed to measure the dose distribution close to metallic implants. Dosimetry of heterogeneous fields where electron density markedly varies is often problematic. This prompted us to develop a polymer gel dosimetry technique using agar to measure the dose distribution near substance boundaries. Varying the concentration of an oxygen scavenger (tetra-hydroxymethyl phosphonium chloride) showed the absorbed dose and transverse relaxation rate of the magnetic resonance signal to be linear between 3 and 12 Gy. Although a change in the dosimeter due to oxidization was observed in room air after 24 hours, no such effects were observed in the first 4 hours. The dose distribution around the metal implants was measured using agar dosimetry. The metals tested were a lead rod, a titanium hip joint, and a metallic stent. A maximum 30% dose increase was observed near the lead rod, but only a 3% increase in the absorbed dose was noted near the surface of the titanium hip joint and metallic stent. Semi-solid polymer dosimetry using agar thus appears to be a useful method for dosimetry around metallic substances. (author)

  9. [The use of polymer gel dosimetry to measure dose distribution around metallic implants].

    Science.gov (United States)

    Nagahata, Tomomasa; Yamaguchi, Hajime; Monzen, Hajime; Nishimura, Yasumasa

    2014-10-01

    A semi-solid polymer dosimetry system using agar was developed to measure the dose distribution close to metallic implants. Dosimetry of heterogeneous fields where electron density markedly varies is often problematic. This prompted us to develop a polymer gel dosimetry technique using agar to measure the dose distribution near substance boundaries. Varying the concentration of an oxygen scavenger (tetra-hydroxymethyl phosphonium chloride) showed the absorbed dose and transverse relaxation rate of the magnetic resonance signal to be linear between 3 and 12 Gy. Although a change in the dosimeter due to oxidization was observed in room air after 24 hours, no such effects were observed in the first 4 hours. The dose distribution around the metal implants was measured using agar dosimetry. The metals tested were a lead rod, a titanium hip joint, and a metallic stent. A maximum 30% dose increase was observed near the lead rod, but only a 3% increase in the absorbed dose was noted near the surface of the titanium hip joint and metallic stent. Semi-solid polymer dosimetry using agar thus appears to be a useful method for dosimetry around metallic substances.

  10. A new bismuth-based coordination polymer as an efficient visible light responding photocatalyst under white LED irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Ya-Jing; Zheng, Yue-Qing, E-mail: zhengyueqing@nbu.edu.cn; Wang, Jin-Jian; Zhou, Lin-Xia

    2017-02-15

    A new bismuth-based polymer, [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O (H{sub 2}pydc=pyridine-2,5-dicarboxylic acid, bpe=trans-bis(4-pyridyl) ethylene) has been hydrothermally synthesized. Transient photocurrent response and electrochemical impedance spectroscopy studies indicate that the synthesized polymer with efficient charge separation and transportation can be used as a potential photocatalyst. So we use it for the degradation of rhodamine B (RhB) dye wastewater under visible light. The comparative study on commercial Bi{sub 2}O{sub 3} shows [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O has the higher photocatalytic performance, with the degradation rate of 97% and 2% within 100 min for [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O and commercial Bi{sub 2}O{sub 3} respectively. Additionally, the five cycle reproducibility results of [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O implies that it can be used as a stable photocatalyst. - Graphical abstract: We report a new 1D coordination polymer [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O by a facile hydrothermal method. The Bi-CP shows good photoelectric property and photocatalytic activity for RhB degradation under visible white LED lamp irradiation. And the stability of the visible-light-responsive bismuth-based coordination polymer has also been examined. - Highlights: • A new Bi(III) coordination polymer is hydrothermally synthesized. • The Bi-CP shows good photoelectric and photocatalytic properties. • Bi-CP shows higher activity than the commercial Bi{sub 2}O{sub 3} for RhB degradation.

  11. Metal removal from aqueous media by polymer-assisted ultrafiltration with chitosan

    Directory of Open Access Journals (Sweden)

    Grégorio Crini

    2017-05-01

    Full Text Available Polymer assisted ultrafiltration (PAUF is a relatively new process in water and wastewater treatment and the subject of an increasing number of papers in the field of membrane science. Among the commercial polymers used, poly(ethyleneimine and poly(acrylic acid are the most popular to complex numerous metal ions. Recently, there is an increasing interest in the use of chitosan, a natural linear polymer, as chelating agent for complexing metals. Chitosan has a high potential in wastewater treatment mainly due to its polyelectrolyte properties at acidic pH. The objectives of this review are to present the PAUF process and to highlight the advantages gained from the use of chitosan in the process of complexation–ultrafiltration. For this, a PAUF-based literature survey has been compiled and is discussed. From these data, chitosan, a biopolymer that is non-toxic to humans and the environment, is found to be effective in removing metal ions and exhibits high selectivity. It might be a promising polyelectrolyte for PAUF purposes.

  12. SYNTHESIS, CHARACTERIZATION AND ANTITUMOR ACTIVITY OF A Ca (II COORDINATION POLYMER BASED ON 3-AMINO-2-PYRAZINECARBOXYLIC ACID

    Directory of Open Access Journals (Sweden)

    XI-SHI TAI

    2015-10-01

    Full Text Available A new Ca(II coordination polymer has been obtained by reaction of Ca(ClO42·H2O with 3-amino-2-pyrazinecarboxylic acid in CH3CH2OH/H2O. It was characterized by IR, 1HNMR, thermal analysis and X-ray single crystal diffraction analysis. X-ray analysis reveals that each Ca(II center is seven-coordination with a N2O5 distorted pentagonal bipyramidal coordination environment. The Ca(II ions are linked through the O atoms of 3-amino-2-pyrazinecarboxylic acid ligands to form 1D chain structure. And then a 3D network structure is constructed by hydrogen bonds and π-π stacking. The antitumor activity of 3-amino-2-pyrazinecarboxylic acid ligand and its Ca(II coordination polymer against human intestinal adenocarcinoma HCT-8 cells, lung adenocarcinoma HCT-116 cells and human lung adenocarcinoma A549 cells line have been investigated.

  13. Water linked 3D coordination polymers: Syntheses, structures and applications

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Suryabhan, E-mail: sbs.bhu@gmail.com; Bhim, Anupam

    2016-12-15

    Three new coordination polymers (CPs) based on Cd and Pb, [Cd(OBA)(μ-H{sub 2}O)(H{sub 2}O)]{sub n}1, [Pb(OBA)(μ-H{sub 2}O)]{sub n}2 [where OBA=4,4’-Oxybis(benzoate)] and [Pb(SDBA)(H{sub 2}O)]{sub n}.1/4DMF 3 (SDBA=4,4’-Sulfonyldibenzoate), have been synthesized and characterized. The single crystal structural studies reveal that CPs 1 and 2 have three dimensional structure. A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. Compound 3 has a supramolecular 3D structure involving water molecule and hydrogen bonds. A structural transformation is observed when 3 was heated at 100 °C or kept in methanol, forming [Pb(SDBA)]{sub n}4. Compound 4 is used as supporting matrix for palladium nanoparticles, PdNPs@4. The PdNPs@4 exhibits good catalytic activity toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH{sub 4} at room temperature. Luminescence studies revealed that all CPs could be an effective sensor for nitroaromatic explosives. - Graphical abstract: Three new CPs based on Cd and Pb, have been synthesized and characterized. A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. One of the CP is used as supporting matrix for palladium nanoparticles, PdNPs@4. The PdNPs@4 exhibits good catalytic activity toward the reduction of 4-nitrophenol. Luminescence studies shown that all CPs could be an effective sensor for nitroaromatic explosives. - Highlights: • Three new CPs based on Cd and Pb, have been synthesized and characterized. • A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. • One of the CP is used as supporting matrix for palladium nanoparticles, PdNPs@4. • Luminescence studies shown that all CPs could be an effective sensor for nitroaromatic explosives.

  14. Hybrid organic-inorganic rotaxanes and molecular shuttles.

    Science.gov (United States)

    Lee, Chin-Fa; Leigh, David A; Pritchard, Robin G; Schultz, David; Teat, Simon J; Timco, Grigore A; Winpenny, Richard E P

    2009-03-19

    The tetravalency of carbon and its ability to form covalent bonds with itself and other elements enables large organic molecules with complex structures, functions and dynamics to be constructed. The varied electronic configurations and bonding patterns of inorganic elements, on the other hand, can impart diverse electronic, magnetic, catalytic and other useful properties to molecular-level structures. Some hybrid organic-inorganic materials that combine features of both chemistries have been developed, most notably metal-organic frameworks, dense and extended organic-inorganic frameworks and coordination polymers. Metal ions have also been incorporated into molecules that contain interlocked subunits, such as rotaxanes and catenanes, and structures in which many inorganic clusters encircle polymer chains have been described. Here we report the synthesis of a series of discrete rotaxane molecules in which inorganic and organic structural units are linked together mechanically at the molecular level. Structural units (dialkyammonium groups) in dumb-bell-shaped organic molecules template the assembly of essentially inorganic 'rings' about 'axles' to form rotaxanes consisting of various numbers of rings and axles. One of the rotaxanes behaves as a 'molecular shuttle': the ring moves between two binding sites on the axle in a large-amplitude motion typical of some synthetic molecular machine systems. The architecture of the rotaxanes ensures that the electronic, magnetic and paramagnetic characteristics of the inorganic rings-properties that could make them suitable as qubits for quantum computers-can influence, and potentially be influenced by, the organic portion of the molecule.

  15. Salt-Driven Deposition of Thermoresponsive Polymer-Coated Metal Nanoparticles on Solid Substrates.

    Science.gov (United States)

    Zhang, Zhiyue; Maji, Samarendra; da Fonseca Antunes, André B; De Rycke, Riet; Hoogenboom, Richard; De Geest, Bruno G

    2016-06-13

    Here we report on a simple, generally applicable method for depositing metal nanoparticles on a wide variety of solid surfaces under all aqueous conditions. Noble-metal nanoparticles obtained by citrate reduction followed by coating with thermoresponsive polymers spontaneously form a monolayer-like structure on a wide variety of substrates in presence of sodium chloride whereas this phenomenon does not occur in salt-free medium. Interestingly, this phenomenon occurs below the cloud point temperature of the polymers and we hypothesize that salt ion-induced screening of electrostatic charges on the nanoparticle surface entropically favors hydrophobic association between the polymer-coated nanoparticles and a hydrophobic substrate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Metal–organic coordinated multilayer film formation: Quantitative analysis of composition and structure

    Energy Technology Data Exchange (ETDEWEB)

    Benson, Alexandra S.; Elinski, Meagan B.; Ohnsorg, Monica L.; Beaudoin, Christopher K.; Alexander, Kyle A.; Peaslee, Graham F.; DeYoung, Paul A.; Anderson, Mary E., E-mail: meanderson@hope.edu

    2015-09-01

    Metal–organic coordinated multilayers are self-assembled thin films fabricated by alternating solution–phase deposition of bifunctional organic molecules and metal ions. The multilayer film composed of α,ω-mercaptoalkanoic acid and Cu (II) has been the focus of fundamental and applied research with its robust reproducibility and seemingly simple hierarchical architecture. However, internal structure and composition have not been unambiguously established. The composition of films up to thirty layers thick was investigated using Rutherford backscattering spectrometry and particle induced X-ray emission. Findings show these films are copper enriched, elucidating a 2:1 ratio for the ion to molecule complexation at the metal–organic interface. Results also reveal that these films have an average layer density similar to literature values established for a self-assembled monolayer, indicating a robust and stable structure. The surface structures of multilayer films have been characterized by contact angle goniometry, ellipsometry, and scanning probe microscopy. A morphological transition is observed as film thickness increases from the first few foundational layers to films containing five or more layers. Surface roughness analysis quantifies this evolution as the film initially increases in roughness before obtaining a lower roughness comparable to the underlying gold substrate. Quantitative analysis of topographical structure and internal composition for metal–organic coordinated multilayers as a function of number of deposited layers has implications for their incorporation in the fields of photonics and nanolithography. - Highlights: • Layer-by-layer deposition is examined by scanning probe microscopy and ion beam analysis. • Film growth undergoes morphological evolution during foundational layer deposition. • Image analysis quantified surface features such as roughness, grain size, and coverage. • Molecular density of each film layer is found to

  17. Water-soluble metal-binding polymers with ultrafiltration: A technology for the removal, concentration, and recovery of metal ions from aqueous streams

    International Nuclear Information System (INIS)

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1997-01-01

    The use of water-soluble metal-binding polymers coupled with ultrafiltration (UF) is a technology under development to selectively concentrate and recover valuable or regulated metal-ions from dilute process or waste waters. The polymers have a sufficiently large molecular size that they can be separated and concentrated using commercially available UF technology. The polymers can then be reused by changing the solution conditions to release the metal-ions, which are recovered in a concentrated form for recycle or disposal. Pilot-scale demonstrations have been completed for a variety of waste streams containing low concentrations of metal ions including electroplating wastes (zinc and nickel) and nuclear waste streams (plutonium and americium). Many other potential commercial applications exist including remediation of contaminated solids. An overview of both the pilot-scale demonstrated applications and small scale testing of this technology are presented

  18. Water-soluble metal-binding polymers with ultrafiltration: A technology for the removal, concentration, and recovery of metal ions from aqueous streams

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1997-12-31

    The use of water-soluble metal-binding polymers coupled with ultrafiltration (UF) is a technology under development to selectively concentrate and recover valuable or regulated metal-ions from dilute process or waste waters. The polymers have a sufficiently large molecular size that they can be separated and concentrated using commercially available UF technology. The polymers can then be reused by changing the solution conditions to release the metal-ions, which are recovered in a concentrated form for recycle or disposal. Pilot-scale demonstrations have been completed for a variety of waste streams containing low concentrations of metal ions including electroplating wastes (zinc and nickel) and nuclear waste streams (plutonium and americium). Many other potential commercial applications exist including remediation of contaminated solids. An overview of both the pilot-scale demonstrated applications and small scale testing of this technology are presented.

  19. A family of entangled coordination polymers constructed from a flexible V-shaped long bicarboxylic acid and auxiliary N-donor ligands: Luminescent sensing

    International Nuclear Information System (INIS)

    Wang, Jun; Bai, Chao; Hu, Huai-Ming; Yuan, Fei; Xue, Gang-Lin

    2017-01-01

    Eight Zn(II)-based coordination polymers, namely, [Zn 2 L 2 (2,2’-bipy)] n ·nH 2 O (1), [Zn 2 L 2 (phen)] n ·nH 2 O (2), [ZnL(phen)(H 2 O)] n (3), [Zn 3 L 3 (4,4’-bipy)] n (4), [Zn 2 L 2 (4,4’-bipy) 2 ] n [Zn 2 L 2 (H 2 O) 2 ] n ·2nH 2 O (5), [Zn 4 L 4 (bpp) 2 ] n (6), [ZnL(bbi) 0.5 ] n (7), [ZnL(bpz)] n (8) (H 2 L=4,4’-([1,2-phenylenebis-(methylene)]bis(oxy))dibenzoic acid, 2,2’-bipy =2,2’-bipyridine, phen =1,10-phenanthroline, 4,4’-bpy=4,4’-bipyridine, bpp =1,3-bis(4-pyridyl)propane, bbi=1,4-bis(imidazol-1-yl)butane, bpz=3,3′,5,5′-tetramethyl-4,4′-bipyrazole), have been hydrothermally synthesized and structurally characterized. 1–8 display various coordination motifs with different entangled forms and conformations due to the effect of the assistant N-donor ligands. The photoluminescent properties of compounds 1–8 in solid state were studied. Interestingly, 3 exhibits highly efficient luminescent sensing for Cu 2+ cations and CrO 4 2- anions, as well as detection ability for the different organic solvents and nitro explosives. These results indicated that it could be utilized as a multi-responsive luminescent sensor. Furthermore, compound 3 also shows good chemical resistance to both acidity and alkalinity solutions with pH ranging from 2 to 13. Thus, multi-photofunctionality and fluorescent response to pH have been combined in the 3, which is the first example in the Zn-based hybrid materials. - Graphical abstract: Eight new Zn(II)-based coordination polymers constructed from a flexible V-shaped long bicarboxylic acid and different N-donor ligands have been hydrothermally synthesized through fixing the metal salts and the solvent systems. The photoluminescent properties of complexes 1−8 in solid state were studied. Interestingly, 3 exhibits highly efficient luminescent sensing for Cu 2+ cations and CrO 4 2- anions, as well as detection ability for the different organic solvents and nitro explosives, in which indicates it could be

  20. Metal-organic frameworks in mixed-matrix membranes for gas separation.

    Science.gov (United States)

    Tanh Jeazet, Harold B; Staudt, Claudia; Janiak, Christoph

    2012-12-14

    Mixed-matrix membranes (MMMs) with metal-organic frameworks (MOFs) as additives (fillers) exhibit enhanced gas permeabilities and possibly also selectivities when compared to the pure polymer. Polyimides (Matrimid®) and polysulfones are popular polymer matrices for MOF fillers. Presently investigated MOFs for MMMs include [Cu(SiF(6))(4,4'-BIPY)(2)], [Cu(3)(BTC)(2)(H(2)O)(3)] (HKUST-1, Cu-BTC), [Cu(BDC)(DMF)], [Zn(4)O(BDC)(3)] (MOF-5), [Zn(2-methylimidazolate)(2)] (ZIF-8), [Zn(purinate)(2)] (ZIF-20), [Zn(2-carboxyaldehyde imidazolate)(2)] (ZIF-90), Mn(HCOO)(2), [Al(BDC)(μ-OH)] (MIL-53(Al)), [Al(NH(2)-BDC)(μ-OH)] (NH(2)-MIL-53(Al)) and [Cr(3)O(BDC)(3)(F,OH)(H(2)O)(2)] (MIL-101) (4,4'-BIPY = 4,4'-bipyridine, BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, terephthalate). MOF particle adhesion to polyimide and polysulfone organic polymers does not represent a problem. MOF-polymer MMMs are investigated for the permeability of the single gases H(2), N(2), O(2), CH(4), CO(2) and of the gas mixtures O(2)/N(2), H(2)/CH(4), CO(2)/CH(4), H(2)/CO(2), CH(4)/N(2) and CO(2)/N(2) (preferentially permeating gas named first). Permeability increases can be traced to the MOF porosity. Since the porosity of MOFs can be tuned very precisely, which is not possible with polymeric material, MMMs offer the opportunity of significantly increasing the selectivity compared to the pure polymeric matrix. Additionally in most of the cases the permeability is increased for MMM membranes compared to the pure polymer. Addition of MOFs to polymers in MMMs easily yields performances similar to the best polymer membranes and gives higher selectivities than those reported to date for any pure MOF membrane for the same gas separation. MOF-polymer MMMs allow for easier synthesis and handability compared to pure MOF membranes.

  1. Treatment of heterogeneous mixed wastes: Enzyme degradation of cellulosic materials contaminated with hazardous organics and toxic and radioactive metals

    International Nuclear Information System (INIS)

    Vanderberg, L.A.; Foreman, T.M.; Attrep, M. Jr.; Brainard, J.R.; Sauer, N.

    1999-01-01

    The redirection and downsizing of the US Department of Energy's nuclear weapons complex requires that many facilities be decontaminated and decommissioned (D and D). At Los Alamos National Laboratory, much of the low-level radioactive, mixed, and hazardous/chemical waste volume handled by waste management operations was produced by D and D and environmental restoration activities. A combination of technologies--air stripping and biodegradation of volatile organics, enzymatic digestion of cellulosics, and metal ion extraction--was effective in treating a radiologically contaminated heterogeneous paint-stripping waste. Treatment of VOCs using a modified bioreactor avoided radioactive contamination of byproduct biomass and inhibition of biodegradation by toxic metal ions in the waste. Cellulase digestion of bulk cellulose minimized the final solid waste volume by 80%. Moreover, the residue passed TCLP for RCRA metals. Hazardous metals and radioactivity in byproduct sugar solutions were removed using polymer filtration, which employs a combination of water-soluble chelating polymers and ultrafiltration to separate and concentrate metal contaminants. Polymer filtration was used to concentrate RCRA metals and radioactivity into <5% of the original wastewater volume. Permeate solutions had no detectable radioactivity and were below RCRA-allowable discharge limits for Pb and Cr

  2. Synthesis and Applications of Inorganic/Organic-Polymer Nanocomposites

    Science.gov (United States)

    Goyal, Anubha

    This research work focuses on developing new synthesis routes to fabricate polymer nanocomposites tailored towards different applications. A simple, one-step method has been devised for synthesizing free-standing, flexible metal nanoparticle-polydimethylsiloxane films. This process simplifies prevalent methods to synthesize nanocomposites, in that here nanoparticles are created in situ while curing the polymer. This route circumvents the need for pre-synthesized nanoparticles, external reducing agents and stabilizers, thereby significantly reducing processing time and cost. The resulting nanocomposite also demonstrates enhancement in mechanical and antibacterial properties, with other envisaged applications in biomedical devices and catalysis. Applying the same mechanism as that used for the formation of bulk metalsiloxane nanocomposites, metal core-siloxane shell nanoparticles and siloxane nanowires were synthesized, with octadecylsilane as the precursor and in situ formed metal nanoparticles (gold, silver) as the catalyst. This method offers some unique advantages over the previously existing methods. This is a room temperature route which does not require high temperature refluxing or the use of pre-synthesized nanoparticles. Furthermore, this synthesis process gives a control over the shape of resulting nanocomposite structures (1-D wires or 0-D spherical particles). High thermal stability of polydimethylsiloxane (PDMS) makes it viable to alternatively synthesize metal nanoparticles in the polymer matrix by thermal decomposition process. This technique is generic across a range of metals (palladium, iron, nickel) and results in nanoparticles with a very narrow size distribution. Membranes with palladium nanoparticles demonstrate catalytic activity in ethylene hydrogenation reaction. Additionally, a new nanocomposite electrode has been developed for flexible and light-weight Li-ion batteries. Flexible films were prepared by the integration of the poly

  3. Coordination-induced formation of nanometer-scale infinite coordination polymer at room temperature and conversion to CuO nanoparticles

    Science.gov (United States)

    Mohammadikish, Maryam; Zafari, Zohreh

    2018-03-01

    In this work, the construction of CuO nanoparticles semiconductor utilizing infinite coordination polymers (ICPs) as precursor was investigated. After successful functionalization of salpn (salpn = N,N‧-Bis(salicylidene)-1,3-propanediamine) ligand with sodium thioglycolate, bi-thioglycolate functionalized salpn linker was obtained, which was further transformed into Cu-ICP nanoparticles by simple precipitation method in the presence of Cu2+ cations. The mechanism of morphology evolution was illustrated by systematic time dependent studies, which demonstrated the preparation of Cu-ICP nanoparticles in shortest possible time, 5 min. Photoluminescence spectra show the emission quenching of the bi-thioglycolate functionalized salpn linker due to coordination to copper ion. In addition, the copper oxide nanoparticles are fabricated by thermal decomposition of the Cu-ICP precursor which showed larger band gap compared to bulk counterpart.

  4. Synthesis and Structural Characterization of Magnesium Based Coordination Networks in Different Solvents

    Energy Technology Data Exchange (ETDEWEB)

    D Banerjee; J Finkelstein; A Smirnov; P Forster; L Borkowski; S Teat; J Parise

    2011-12-31

    Three magnesium based metal-organic frameworks, Mg{sub 3}(3,5-PDC){sub 3}(DMF){sub 3} {center_dot} DMF [1], Mg(3,5-PDC)(H{sub 2}O) {center_dot} (H{sub 2}O) [3], and Mg{sub 4}(3,5-PDC){sub 4}(DMF){sub 2}(H{sub 2}O){sub 2} {center_dot} 2DMF {center_dot} 4.5H{sub 2}O [4], and a 2-D coordination polymer, [Mg(3,5-PDC)(H{sub 2}O){sub 2}] [2] [PDC = pyridinedicarboxylate], were synthesized using a combination of DMF, methanol, ethanol, and water. Compound 1 [space group P2{sub 1}/n, a = 12.3475(5) {angstrom}, b = 11.1929(5) {angstrom}, c = 28.6734(12) {angstrom}, {beta} = 98.8160(10){sup o}, V = 3916.0(3) {angstrom}{sup 3}] consists of a combination of isolated and corner-sharing magnesium octahedra connected by the organic linkers to form a 3-D network with a 12.2 {angstrom} x 4.6 {angstrom} 1-D channel. The channel contains coordinated and free DMF molecules. In compound 2 [space group C2/c, a = 9.964(5) {angstrom}, b = 12.0694(6) {angstrom}, c = 7.2763(4) {angstrom}, {beta} = 106.4970(6){sup o}, V = 836.70(6) {angstrom}{sup 3}], PDC connects isolated seven coordinated magnesium polyhedra into a layered structure. Compound 3 [space group P6{sub 1}22, a = 11.479(1) {angstrom}, c = 14.735(3) {angstrom}, V = 1681.7(4) {angstrom}{sup 3}] (previously reported) contains isolated magnesium octahedra connected by the organic linker with each other forming a 3D network. Compound 4 [space group P2{sub 1}/c, a = 13.7442(14) {angstrom}, b = 14.2887(15) {angstrom}, c = 14.1178(14) {angstrom}, {beta} = 104.912(2){sup o}, V = 2679.2(5) {angstrom}{sup 3}] also exhibits a 3D network based on isolated magnesium octahedra with square cavities containing both disordered DMF and water molecules. The structural topologies originate due to the variable coordination ability of solvent molecules with the metal center. Water molecules coordinate with the magnesium metal centers preferably over other polar solvents (DMF, methanol, ethanol) used to synthesize the coordination networks. Despite

  5. Four Mixed-Ligand Zn(II Three-Dimensional Metal-Organic Frameworks: Synthesis, Structural Diversity, and Photoluminescent Property

    Directory of Open Access Journals (Sweden)

    Chih-Chieh Wang

    2017-11-01

    Full Text Available Assemblies of four three-dimensional (3D mixed-ligand coordination polymers (CPs having formulas, {[Zn2(bdc2(4-bpdh]·C2H5OH·2H2O}n (1, [Zn(bdc(4-bpdh]n (2, {[Zn2(bdc2(4-bpdh2]·(4-bpdh}n (3, and {[Zn(bdc(4-bpdh]·C2H5OH}n (4 (bdc2− = dianion of 1,4-benzenedicarboxylic acid, 4-bpdh = 2,5-bis(4-pyridyl-3,4-diaza-2,4-hexadiene have been synthesized and structurally characterized by single-crystal X-ray diffraction method. Structural determination reveals that the coordination numbers (geometry of Zn(II ions in 1, 2, 3, and 4 are five (distorted square-pyramidal (SP, six (distorted octahedral (Oh, five (trigonal-bipyramidal (TBP, and four (tetrahedral (Td, respectively, and are bridged by 4-bpdh with bis-monodentate coordination mode and bdc2− ligands with bis-bidentate in 1, chelating/bidentate in 2, bis-monodentate and bis-bidentate in 3, and bis-monodentate in 4, to generate two-fold interpenetrating 3D cube-like metal-organic framework (MOF with pcu topology, non-interpenetrating 3D MOF, two-fold interpenetrating 3D rectangular-box-like MOF with pcu topology and five-fold interpenetrating diamondoid-like MOF with dia topology, respectively. These different intriguing architectures indicate that the coordination numbers and geometries of Zn(II ions, coordination modes of bdc2− ligand, and guest molecules play important roles in the construction of MOFs and the formation of the structural topologies and interpenetrations. Thermal stabilities, and photoluminescence study of 1–4 were also studied in detail. The complexes exhibit ligands based photoluminescence properties at room temperature.

  6. Three-Dimensional (3D Printing of Polymer-Metal Hybrid Materials by Fused Deposition Modeling

    Directory of Open Access Journals (Sweden)

    Susanna Fafenrot

    2017-10-01

    Full Text Available Fused deposition modeling (FDM is a three-dimensional (3D printing technology that is usually performed with polymers that are molten in a printer nozzle and placed line by line on the printing bed or the previous layer, respectively. Nowadays, hybrid materials combining polymers with functional materials are also commercially available. Especially combinations of polymers with metal particles result in printed objects with interesting optical and mechanical properties. The mechanical properties of objects printed with two of these metal-polymer blends were compared to common poly (lactide acid (PLA printed objects. Tensile tests and bending tests show that hybrid materials mostly containing bronze have significantly reduced mechanical properties. Tensile strengths of the 3D-printed objects were unexpectedly nearly identical with those of the original filaments, indicating sufficient quality of the printing process. Our investigations show that while FDM printing allows for producing objects with mechanical properties similar to the original materials, metal-polymer blends cannot be used for the rapid manufacturing of objects necessitating mechanical strength.

  7. Cooperative loading of multisite receptors with lanthanide containers: an approach for organized luminescent metallopolymers.

    Science.gov (United States)

    Babel, Lucille; Guénée, Laure; Besnard, Céline; Eliseeva, Svetlana V; Petoud, Stéphane; Piguet, Claude

    2018-01-14

    Metal-containing (bio)organic polymers are materials of continuously increasing importance for applications in energy storage and conversion, drug delivery, shape-memory items, supported catalysts, organic conductors and smart photonic devices. The embodiment of luminescent components provides a revolution in lighting and signaling with the ever-increasing development of polymeric light-emitting devices. Despite the unique properties expected from the introduction of optically and magnetically active lanthanides into organic polymers, the deficient control of the metal loading currently limits their design to empirical and poorly reproducible materials. We show here that the synthetic efforts required for producing soluble multi-site host systems L k are largely overcome by the virtue of reversible thermodynamics for mastering the metal loading with the help of only two parameters: (1) the affinity of the luminescent lanthanide container for a single binding site and (2) the cooperative effect which modulates the successive fixation of metallic units to adjacent sites. When unsymmetrical perfluorobenzene-trifluoroacetylacetonate co-ligands (pbta - ) are selected for balancing the charge of the trivalent lanthanide cations, Ln 3+ , in six-coordinate [Ln(pbta) 3 ] containers, the explored anti-cooperative complexation processes induce nearest-neighbor intermetallic interactions twice as large as thermal energy at room temperature ( RT = 2.5 kJ mol -1 ). These values have no precedent when using standard symmetrical containers and they pave the way for programming metal alternation in luminescent lanthanidopolymers.

  8. Highly Sensitive Detection of UV Radiation Using a Uranium Coordination Polymer.

    Science.gov (United States)

    Liu, Wei; Dai, Xing; Xie, Jian; Silver, Mark A; Zhang, Duo; Wang, Yanlong; Cai, Yawen; Diwu, Juan; Wang, Jian; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

    2018-02-07

    The accurate detection of UV radiation is required in a wide range of chemical industries and environmental or biological related applications. Conventional methods taking advantage of semiconductor photodetectors suffer from several drawbacks such as sophisticated synthesis and manufacturing procedure, not being able to measure the accumulated UV dosage as well as high defect density in the material. Searching for new strategies or materials serving as precise UV dosage sensor with extremely low detection limit is still highly desirable. In this work, a radiation resistant uranium coordination polymer [UO 2 (L)(DMF)] (L = 5-nitroisophthalic acid, DMF = N,N-dimethylformamide, denoted as compound 1) was successfully synthesized through mild solvothermal method and investigated as a unique UV probe with the detection limit of 2.4 × 10 -7 J. On the basis of the UV dosage dependent luminescence spectra, EPR analysis, single crystal structure investigation, and the DFT calculation, the UV-induced radical quenching mechanism was confirmed. Importantly, the generated radicals are of significant stability which offers the opportunity for measuring the accumulated UV radiation dosage. Furthermore, the powder material of compound 1 was further upgraded into membrane material without loss in luminescence intensity to investigate the real application potentials. To the best of our knowledge, compound 1 represents the most sensitive coordination polymer based UV dosage probe reported to date.

  9. Polymer-Derived Silicoboron Carbonitride Foams for CO2 Capture: From Design to Application as Scaffolds for the in Situ Growth of Metal-Organic Frameworks.

    Science.gov (United States)

    Sandra, Fabien; Depardieu, Martin; Mouline, Zineb; Vignoles, Gérard L; Iwamoto, Yuji; Miele, Philippe; Backov, Rénal; Bernard, Samuel

    2016-06-06

    A template-assisted polymer-derived ceramic route is investigated for preparing a series of silicoboron carbonitride (Si/B/C/N) foams with a hierarchical pore size distribution and tailorable interconnected porosity. A boron-modified polycarbosilazane was selected to impregnate monolithic silica and carbonaceous templates and form after pyrolysis and template removal Si/B/C/N foams. By changing the hard template nature and controlling the quantity of polymer to be impregnated, controlled micropore/macropore distributions with mesoscopic cell windows are generated. Specific surface areas from 29 to 239 m(2)  g(-1) and porosities from 51 to 77 % are achieved. These foams combine a low density with a thermal insulation and a relatively good thermostructural stability. Their particular structure allowed the in situ growth of metal-organic frameworks (MOFs) directly within the open-cell structure. MOFs offered a microporosity feature to the resulting Si/B/C/N@MOF composite foams that allowed increasing the specific surface area to provide CO2 uptake of 2.2 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ligand design for site-selective metal coordination: synthesis of transition-metal complexes with η{sup 6}-coordination of the central ring of anthracene

    Energy Technology Data Exchange (ETDEWEB)

    Karslyan, Eduard E.; Borissova, Alexandra O.; Perekalin, Dmitry S. [Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow (Russian Federation)

    2017-05-08

    A polycyclic aromatic ligand for site-selective metal coordination was designed by using DFT calculations. The computational prediction was confirmed by experiments: 2,3,6,7-tetramethoxy-9,10-dimethylanthracene initially reacts with [(C{sub 5}H{sub 5})Ru(MeCN){sub 3}]BF{sub 4} to give the kinetic product with a [(C{sub 5}H{sub 5})Ru]{sup +} fragment coordinated at the terminal ring, which is then transformed into the thermodynamic product with coordination through the central ring. These isomeric complexes have markedly different UV/Vis spectra, which was explained by analysis of the frontier orbitals. At the same time, the calculations suggest that electrostatic interactions are mainly responsible for the site selectivity of the coordination. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Hybrid inorganic-organic adsorbents Part 1: Synthesis and characterization of mesoporous zirconium titanate frameworks containing coordinating organic functionalities.

    Science.gov (United States)

    Griffith, Christopher S; De Los Reyes, Massey; Scales, Nicholas; Hanna, John V; Luca, Vittorio

    2010-12-01

    A series of functional hybrid inorganic-organic adsorbent materials have been prepared through postsynthetic grafting of mesoporous zirconium titanate xerogel powders using a range of synthesized and commercial mono-, bis-, and tris-phosphonic acids, many of which have never before been investigated for the preparation of hybrid phases. The hybrid materials have been characterized using thermogravimetric analysis, diffuse reflectance infrared (DRIFT) and 31P MAS NMR spectroscopic techniques and their adsorption properties studied using a 153Gd radiotracer. The highest level of surface functionalization (molecules/nm2) was observed for methylphosphonic acid (∼3 molecules/nm2). The level of functionalization decreased with an increase in the number of potential surface coordinating groups of the phosphonic acids. Spectral decomposition of the DRIFT and 31P MAS NMR spectra showed that each of the phosphonic acid molecules coordinated strongly to the metal oxide surface but that for the 1,1-bis-phosphonic acids and tris-phosphonic acids the coordination was highly variable resulting in a proportion of free or loosely coordinated phosphonic acid groups. Functionalization of a porous mixed metal oxide framework with the tris-methylenephosphonic acid (ATMP-ZrTi-0.33) resulted in a hybrid with the highest affinity for 153Gd3+ in nitric acid solutions across a wide range of acid concentrations. The ATMP-ZrTi-0.33 hybrid material extracted 153Gd3+ with a Kd value of 1×10(4) in 0.01 M HNO3 far exceeding that of the other hybrid phases. The unfunctionalized mesoporous mixed metal oxide had negligible affinity for Gd3+ (KdATMP-ZrTi-0.33 hybrid phase for Gd3+ has been determined to be about 0.005 mmol/g in 0.01 M HNO3. This behavior and that of the other hybrid phases suggests that the surface-bound ATMP ligand functions as a chelating ligand toward 153Gd3+ under these acidic conditions.

  12. Thin films of metal-organic compounds and metal nanoparticle ...

    Indian Academy of Sciences (India)

    Optical limiting capability of the nanoparticle-embedded polymer film is demonstrated. Keywords. Polar crystal; uniaxial orientational order; thin film; second harmonic gen- eration; silver ... able content of metal nanoparticles would be of considerable value from an appli- ... polar chain and perpendicular to it [10].

  13. Metal-polymer nanocomposites for functional applications

    Energy Technology Data Exchange (ETDEWEB)

    Faupel, Franz; Zaporojtchenko, Vladimir; Strunskus, Thomas [Christian-Albrechts-Universitaet zu Kiel (Germany). Institut fuer Materialwissenschaft - Materialverbunde; Elbahri, Mady [Christian-Albrechts-Universitaet zu Kiel (Germany). Institut fuer Materialwissenschaft - Nanochemistry and Engineering

    2010-12-15

    Nanocomposites combine favorable features of the constituents on the nanoscale to obtain new functionalities. The present paper is concerned with the preparation of polymer-based nanocomposites consisting of metal nanoparticles in a polymer matrix and the resulting functional properties. Emphasis is placed on vapor phase deposition which inter alia allows the incorporation of alloy clusters with well defined composition and tailored filling factor profiles. Examples discussed here include optical composites with tuned particle surface plasmon resonances for plasmonic applications, magnetic high frequency materials with cut-off frequencies well above 1 GHz, sensors that are based on the dramatic change in the electronic properties near the percolation threshold, and antibacterial coatings which benefit from the large effective surface of nanoparticles and the increased chemical potential which both strongly enhance ion release. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Metallogels derived from silver coordination polymers of C3-symmetric tris(pyridylamide) tripodal ligands: synthesis of Ag nanoparticles and catalysis.

    Science.gov (United States)

    Paul, Mithun; Sarkar, Koushik; Dastidar, Parthasarathi

    2015-01-02

    By applying a recently developed crystal engineering rationale, four C3 symmetric tris(pyridylamide) ligands namely 1,3,5-tris(nicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(isonicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(nicotinamidomethyl)-2,4,6-trimethylbenzene, and 1,3,5-tris(isonicotinamidomethyl)-2,4,6-trimethylbenzene, which contain potential hydrogen-bonding sites, were designed and synthesized for generating Ag(I) coordination polymers and coordination-polymer-based gels. The coordination polymers thus obtained were characterized by single-crystal X-ray diffraction. The silver metallogels were characterized by transmission electron microscopy (TEM) and dynamic rheology. Upon exposure to visible light, these silver metallogels produced silver nanoparticles (AgNPs), which were characterized by TEM, powder X-ray diffraction, energy dispersive X-ray and X-ray photoelectron spectroscopy. These NPs were found to be effectively catalyzed the reduction of 4-nitrophenolate to 4-aminophenolate without the use of any exogenous reducing agent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Development of Speciality polymer to extract uranium from sea water

    International Nuclear Information System (INIS)

    Tabushi, Iwao

    1983-01-01

    Polymer adsorbents were designed to extract uranium efficiently from sea water. The unique coordination structure of uranyl ion was suggested from x-ray crystallography and determining factors influencing equilibrium constants were elucidated. A quantitative estimation of the ligand efficiency was obtained. Based on these considerations on the coordination chemistry of uranyl ion, new polymer adsorbents were prepared and found to show excellent adsorption characteristics. The macrocyclic ligands mimicking crystallographic structure of the complex: planer headentate, were found to show large equilibrium constants as well as high selectivities toward metal ions. Direct usage of sea current was proposed as a most economical way of treating a huge amount of sea water. The polymer adsorbent could recover uranium with large adsorption rate just by immersing the resin into Kuroshio. (author)

  16. Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

    International Nuclear Information System (INIS)

    Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming; Wu, Qing-Ran; Xie, Juan; Dong, Fa-Xin; Yang, Meng-Lin; Xue, Gang-Lin

    2014-01-01

    Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln 2 (Hpdc) 2 (C 2 O 4 )(H 2 O) 4 ] n ·2nH 2 O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H 3 pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H 3 pdc was decomposed into (ox) 2− with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2 1 /c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groups to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1–4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities. - Graphical abstract: Four 3D microporous lanthanide coordination polymers with reversible structural interconversion have been synthesized. They exhibit characteristic emission bands of the lanthanide ions and possess great thermal stability. - Highlights: • Four lanthanide coordination polymers have been hydrothermal synthesized. • There is an in situ reaction in 1 in which H 3 pdc was decomposed into (ox) 2− with the Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. • TGA and XRD studies reveal that upon hydration–dehydration, compounds 1–4 undergo a reversible structural interconversion process through a cooling-heating cycle. • Compounds 1–4 exhibit characteristic lanthanide-centered luminescence

  17. Polymer supported organic catalysts for O2 reduction in Li-O2 batteries

    International Nuclear Information System (INIS)

    Weng, Wei; Barile, Christopher J.; Du, Peng; Abouimrane, Ali; Assary, Rajeev S.; Gewirth, Andrew A.; Curtiss, Larry A.; Amine, Khalil

    2014-01-01

    Graphical abstract: - Abstract: A novel organic catalyst has been synthesized that contains an anthraquinone moiety supported on a polymer backbone. This oxygen reduction catalyst was successfully incorporated in the cathode of Li-O 2 batteries. The addition of the anthraquinone-based catalyst improved the cycleability of the Li-O 2 battery when cycled in a tetraethylene glycol dimethyl ether electrolyte. Computational studies coupled with a wide range of analytical techniques including differential electrochemical mass spectrometry, cyclic voltammetry, electrochemical impedence spectroscopy, and X-ray diffraction were used to interrogate the Li-O 2 battery with and without the organic catalyst present. This study suggests that organic catalysts may serve as light and inexpensive alternatives to the precious metals frequently used in Li-O 2 batteries

  18. Gas phase sensing of alcohols by Metal Organic Framework – polymer composite materials

    NARCIS (Netherlands)

    Sachdeva, S.; Koper, Sander J.H.; Sabetghadam, Anahid; Soccol, D.; Gravesteijn, Dirk J; Kapteijn, Freek; Sudholter, Ernst J.R.; Gascon, Jorge; de Smet, Louis C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in

  19. COORDINATION COMPOUNDS OF 3D-METALS ACETYLACETONATES WITH THIOSEMICARBAZIDE

    Directory of Open Access Journals (Sweden)

    T. V. Koksharova

    2015-03-01

    Full Text Available Coordination Compounds of 3d-Metals acetylacetonates with Thiosemicarbazide were synthesized. Their physical and chemical properties and structure were studied by conductometry, IR spectroscopy, electronic spectroscopy, magnetochemistry and thermo-gravimetricstudies. The complexes compositions correspond to the formulas Co(L2(Acac and M(L(Acac, where M = Cu, Ni, Zn, HL is thiosemicarbazide, HAcac is acetylacetone. All of them are nonelectrolytes. Thiosemicarbazide is deprotonated and coordinated through the nitrogen and sulphur atoms with the formation of four-membered ring in all cases. Acetylacetonate co-ordination mode does not change at acetylacetonates with Thiosemicarbazide interaction. Copper(II and nickel(II complexes have square-planar structure, and cobalt(III complex is octahedral.

  20. Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Thangavelu, Sonia G. [Department; Butcher, Ray J. [Department; Cahill, Christopher L. [Department

    2015-06-09

    Thiophene 2,5-dicarboxylic acid (TDC) was reacted with uranyl acetate dihydrate and one (or none) of six N-donor chelating ligands (2,2'-bipyridine (BPY), 4,4'-dimethyl-2,2'-bipyridine (4-MeBPY), 5,5'-dimethyl-2,2'-bipyridine (5-MeBPY), 6,6'-dimethyl-2,2'-bipyridine (6-MeBPY), 4,4',6,6'-tetramethyl-2,2'-bipyridine (4,6-MeBPY), and tetrakis(2-pyridyl)pyrazine (TPPZ) to result in the crystallization of seven uranyl coordination polymers, which were characterized by their crystal structures and luminescence properties. The seven coordination polymers, Na2[(UO2)2(C6H2O4S)3]·4H2O (1), [(UO2)4(C6H2O4S)5(C10H8N2)2]·C10H10N2·3H2O (2), [(UO2)(C6H2O4S)(C12H12N3)] (3), [(UO2)(C6H2O4S)(C12H12N3)]·H2O (4), [(UO2)2(C6H2O4S)3]·(C12H14N2)·5H2O (5), [(UO2)3(CH3CO2)(C6H2O4S)4](C14H17N2)3·(C14H16N2)·H2O (6), and [(UO2)2(C6H2O4S)3](C24H18N6) (7), consist of either uranyl hexagonal bipyramidal or pentagonal bipyramidal coordination geometries. In all structures, structural variations in the local and global structures of 1–7 are influenced by the positions (or number) of methyl groups or pyridyl rings on the N-donor species, thus resulting in a wide diversity of structures ranging from single chains, double chains, or 2-D sheets. Direct coordination of N-donor ligands to uranyl centers is observed in the chain structures of 2–4 using BPY, 4-MeBPY, and 5-MeBPY, whereas the N-donor species participate as guests (as either neutral or charge balancing species) in the chain and sheet structures of 5–7 using 6-MeBPY, 4,6-MeBPY, and TPPZ, respectively. Compound 1 is the only structure that does not contain any N-donor ligands and thus crystallizes as a 2-D interpenetrating sheet. The luminescent properties of 1–7 are influenced by the direct coordination or noncoordination of N-donor species to uranyl centers. Compounds 2–4 exhibit typical UO22+ emission upon direct coordination of N-donors, but its absence is observed in 1

  1. Polymeric metal chelates with piperazine(bis)dithiocarbamate

    International Nuclear Information System (INIS)

    Larionov, S.V.; Kosareva, L.A.; Ikorskij, V.N.; Uskov, E.M.

    1982-01-01

    Roentgenoamorphous polymer chelates of Fe 3 , Co 2 , Ni 2 , Cu 2 , Zn 2 , Cd 2 , Pb 2 with tetradentate bridge ligand piperazine-(bis) dithiocarbamate have been synthesized. IR spectra in the region 200-400 cm - 1 point to coordination of sulphur atoms of groups CS 2- with metals. It is found that among the polymers synthesized CuLxH 2 O possesses the lowest electric resistance

  2. A new Pb{sup II}(ethylenediaminetetraacetate) coordination polymer with a two-dimensional layer structure

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, D., E-mail: iamzd@hpu.edu.cn; Zhang, R. H.; Li, F. F. [Henan Polytechnic University, Department of Physics and Chemistry (China)

    2016-12-15

    A new Pb{sup II}−edta{sup 4–} coordination polymer, Pb{sub 2}(edta)(H{sub 2}O){sub 0.76} (edta{sup 4–} = ethylenediaminetetraacetate) was synthesized under hydrothermal condition. Single crystal X-ray analysis reveals that it represents a novel two-dimensional (2D) Pb{sup 2+}–edta{sup 4–} layer structure with a (4,8{sup 2})-topology. Each edta{sup 4–} ligand employs its four carboxylate O and two N atoms to chelate one Pb{sup II} atom (hexa-coordinated) and connects five Pb{sup II} atoms (ennea-coordinated) via its four carboxylate groups to form 2D layer framework. Adjacent layers are packed into the overall structure through vander Waals interactions.

  3. Local coordination of polyvalent metal ions in molten halide mixtures

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    1989-07-01

    Ample experimental evidence is available in the literature on the geometry and the stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides. Recent schemes for classifying this evidence are discussed. Dissociation of tetrahedral halocomplexes in good ionic systems can be viewed as a classical Mott problem of bound-state stability in a conducting matrix. More generally, structural coordinates can be constructed from properties of the component elements, to separate out systems with long-lived fourfold or sixfold coordination and to distinguish between these. (author). 11 refs, 1 fig

  4. Investigation of over-moulded hybrid metal/polymer devices

    DEFF Research Database (Denmark)

    Tosello, Guido; Hansen, Hans Nørgaard; Tang, Peter Torben

    2006-01-01

    principles, in-process manufacturing technologies, as well as testing methodologies have to be established in order to be able to develop such integrated devices. In this paper an investigation of the bonding between miniaturized metal insert and a polymer matrix is presented. A special demonstrator...... was designed and manufactured by over-moulding and hot-embossing. The bonding strength between the insert and the plastic part was tested by means of a tensile test. A variety of parameters was studied in order to investigate their influence on the bonding: different polymeric and metallic materials, insert...

  5. A novel fabrication method for surface integration of metal structures into polymers (SIMSIP)

    Science.gov (United States)

    Carrion-Gonzalez, Hector

    Recently developed flexible electronics applications require that the thin metal films embedded on elastomer substrates also be flexible. These electronic systems are radically different in terms of performance and functionality than conventional silicon-based devices. A key question is whether the metal deposited on flexible films can survive large strains without rupture. Cumbersome macro-fabrication methods have been developed for functional and bendable electronics (e.g., interconnects) encapsulated between layers of polymer films. However, future electronic applications may require electronic flexible devices to be in intimate contact with curved surfaces (e.g., retinal implants) and to be robust enough to withstand large and repeated mechanical deformations. In this research, a novel technique for surface integration of metal structures into polymers (SIMSIP) was developed. Surface embedding, as opposed to placing metal on polymers, provides better adherence while leaving the surface accessible for contacts. This was accomplished by first fabricating the micro-scale metal patterns on a quartz or Teflon mother substrate, and then embedding them to a flexible polyimide thin film. The technique was successfully used to embed micro-metal structures of gold (Au), silver (Ag), and copper (Cu) into polyimide films without affecting the functional properties of the either the metals or the polymers. Experimental results confirm the successful surface-embedding of metal structures as narrow as 0.6 microm wide for different geometries commonly used in circuit design. Although similar approaches exist in literature, the proposed methodology provides a simpler and more reliable way of producing flexible circuits/electronics that is also suitable for high volume manufacturing. In order to demonstrate the flexibility of metal interconnects fabricated using the SIMSIP technique, multiple Au electrodes (5 microm and 2.5 microm wide) were tested using the X-theta bending

  6. Organic secondary ion mass spectrometry: sensitivity enhancement by gold deposition.

    Science.gov (United States)

    Delcorte, A; Médard, N; Bertrand, P

    2002-10-01

    Hydrocarbon oligomers, high-molecular-weight polymers, and polymer additives have been covered with 2-60 nmol of gold/cm2 in order to enhance the ionization efficiency for static secondary ion mass spectrometry (s-SIMS) measurements. Au-cationized molecules (up to -3,000 Da) and fragments (up to the trimer) are observed in the positive mass spectra of metallized polystyrene (PS) oligomer films. Beyond 3,000 Da, the entanglement of polymer chains prevents the ejection of intact molecules from a "thick" organic film. This mass limit can be overcome by embedding the polymer chains in a low-molecular-weight matix. The diffusion of organic molecules over the metal surfaces is also demonstrated for short PS oligomers. In the case of high-molecular-weight polymers (polyethylene, polypropylene, PS) and polymer additives (Irganox 1010, Irgafos 168), the metallization procedure induces a dramatic increase of the fingerprint fragment ion yields as well as the formation of new Aucationized species that can be used for chemical diagnostics. In comparison with the deposition of submonolayers of organic molecules on metallic surfaces, metal evaporation onto organic samples provides a comparable sensitivity enhancement. The distinct advantage of the metal evaporation procedure is that it can be used for any kind of organic sample, irrespective of thickness, opening new perspectives for "real world" sample analysis and chemical imaging by s-SIMS.

  7. Novel Metals and Metal Complexes as Platforms for Cancer Therapy

    OpenAIRE

    Frezza, Michael; Hindo, Sarmad; Chen, Di; Davenport, Andrew; Schmitt, Sara; Tomco, Dajena; Dou, Q. Ping

    2010-01-01

    Metals are essential cellular components selected by nature to function in several indispensable biochemical processes for living organisms. Metals are endowed with unique characteristics that include redox activity, variable coordination modes, and reactivity towards organic substrates. Due to their reactivity, metals are tightly regulated under normal conditions and aberrant metal ion concentrations are associated with various pathological disorders, including cancer. For these reasons, coo...

  8. Design and Control of Cooperativity in Spin-Crossover in Metal–Organic Complexes: A Theoretical Overview

    Directory of Open Access Journals (Sweden)

    Hrishit Banerjee

    2017-07-01

    Full Text Available Metal organic complexes consisting of transition metal centers linked by organic ligands, may show bistability which enables the system to be observed in two different electronic states depending on external condition. One of the spectacular examples of molecular bistability is the spin-crossover phenomena. Spin-Crossover (SCO describes the phenomena in which the transition metal ion in the complex under the influence of external stimuli may show a crossover between a low-spin and high-spin state. For applications in memory devices, it is desirable to make the SCO phenomena cooperative, which may happen with associated hysteresis effect. In this respect, compounds with extended solid state structures containing metal ions connected by organic spacer linkers like linear polymers, coordination network solids are preferred candidates over isolated molecules or molecular assemblies. The microscopic understanding, design and control of mechanism driving cooperativity, however, are challenging. In this review we discuss the recent theoretical progress in this direction.

  9. 1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide.

    Science.gov (United States)

    Wen, Li-Li; Dang, Dong-Bin; Duan, Chun-Ying; Li, Yi-Zhi; Tian, Zheng-Fang; Meng, Qing-Jin

    2005-10-03

    Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.

  10. Photoactive devices including porphyrinoids with coordinating additives

    Science.gov (United States)

    Forrest, Stephen R; Zimmerman, Jeramy; Yu, Eric K; Thompson, Mark E; Trinh, Cong; Whited, Matthew; Diev, Vlacheslav

    2015-05-12

    Coordinating additives are included in porphyrinoid-based materials to promote intermolecular organization and improve one or more photoelectric characteristics of the materials. The coordinating additives are selected from fullerene compounds and organic compounds having free electron pairs. Combinations of different coordinating additives can be used to tailor the characteristic properties of such porphyrinoid-based materials, including porphyrin oligomers. Bidentate ligands are one type of coordinating additive that can form coordination bonds with a central metal ion of two different porphyrinoid compounds to promote porphyrinoid alignment and/or pi-stacking. The coordinating additives can shift the absorption spectrum of a photoactive material toward higher wavelengths, increase the external quantum efficiency of the material, or both.

  11. Bioinspired phospholipid polymer biomaterials for making high performance artificial organs

    Directory of Open Access Journals (Sweden)

    K Ishihara

    2000-01-01

    Full Text Available Novel polymer biomaterials, which can be used in contact with blood, are prepared with strong inspiration from the surface structure of biomembrane. That is, the polymers with a phospholipid polar group in the side chain, 2-methacrylooyloxyethyl phosphorylcholine (MPC polymers were synthesized. The MPC polymers can inhibit surface-induced clot formation effectively, when they are in contact with blood even in the absence of an anticoagulant. This phenomenon was due to the reduction of plasma protein and suppression of denaturation of adsorbed proteins, that is the MPC polymers interact with blood components very mildly. As the molecular structure of the MPC polymer was easily designed by changing the monomer units and their composition, it could be applied to surface modification of artificial organs and biomedical devices for improving blood and tissue compatibility. Thus, the MPC polymers are useful polymer biomaterials for manufacturing high performance artificial organs and biomedical devices to provide safe medical treatments.

  12. Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

    Science.gov (United States)

    Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

    2016-08-15

    A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

  13. Singlet Exciton Lifetimes in Conjugated Polymer Films for Organic Solar Cells

    KAUST Repository

    Dimitrov, Stoichko

    2016-01-13

    The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact on the photocurrent generation by organic solar cell devices. However, very little is known about the material properties controlling the lifetimes of singlet excitons, with most of our knowledge originating from studies of small organic molecules. Herein, we provide a brief summary of the nature of the excited states in conjugated polymer films and then present an analysis of the singlet exciton lifetimes of 16 semiconducting polymers. The exciton lifetimes of seven of the studied polymers were measured using ultrafast transient absorption spectroscopy and compared to the lifetimes of seven of the most common photoactive polymers found in the literature. A plot of the logarithm of the rate of exciton decay vs. the polymer optical bandgap reveals a medium correlation between lifetime and bandgap, thus suggesting that the Energy Gap Law may be valid for these systems. This therefore suggests that small bandgap polymers can suffer from short exciton lifetimes, which may limit their performance in organic solar cell devices. In addition, the impact of film crystallinity on the exciton lifetime was assessed for a small bandgap diketopyrrolopyrrole co-polymer. It is observed that the increase of polymer film crystallinity leads to reduction in exciton lifetime and optical bandgap again in agreement with the Energy Gap Law.

  14. Ruthenium(ii)-polypyridyl zirconium(iv) metal-organic frameworks as a new class of sensitized solar cells.

    Science.gov (United States)

    Maza, W A; Haring, A J; Ahrenholtz, S R; Epley, C C; Lin, S Y; Morris, A J

    2016-01-01

    A series of Ru(ii)L 2 L' (L = 2,2'-bipyridyl, L' = 2,2'-bipyridine-5,5'-dicarboxylic acid), RuDCBPY, -containing zirconium(iv) coordination polymer thin films have been prepared as sensitizing materials for solar cell applications. These metal-organic framework (MOF) sensitized solar cells, MOFSCs, each are shown to generate photocurrent in response to simulated 1 sun illumination. Emission lifetime measurements indicate the excited state quenching of RuDCBPY at the MOF-TiO 2 interface is extremely efficient (>90%), presumably due to electron injection into TiO 2 . A mechanism is proposed in which RuDCBPY-centers photo-excited within the MOF-bulk undergo isotropic energy migration up to 25 nm from the point of origin. This work represents the first example in which a MOFSC is directly compared to the constituent dye adsorbed on TiO 2 (DSC). Importantly, the MOFSCs outperformed their RuDCBPY-TiO 2 DSC counterpart under the conditions used here and, thus, are solidified as promising solar cell platforms.

  15. A New 1D Chained Coordination Polymer: Synthesis, Crystal Structure, Antitumor Activity and Luminescent Property

    Directory of Open Access Journals (Sweden)

    Xi-Shi Tai

    2015-11-01

    Full Text Available A new 1D chained coordination polymer of Zn(II, {[Zn(L2(4,4′-bipy]·(H2O}n(1 (HL = N-acetyl-l-phenylalanine; 4,4′-bipy = 4,4′-bipyridine has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. Theresults show that each asymmetric unit of Zn(II complex belongs to monoclinic, space group P21 with a = 11.421(2 Å, b = 9.2213(17 Å, c = 15.188(3 Å,β = 106.112(3°, V = 1536.7(5 Å3, Z = 2, Dc = 1.444 g·cm−3, µ = 0.857 mm−1, F(000 = 696, and final R1 = 0.0439, ωR2 = 0.1013. The molecules form one-dimensional chained structure by its the bridging 4,4′-bipyridine ligands. The antitumor activities and luminescent properties of Zn(II coordination polymer have also been investigated.

  16. Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

    Energy Technology Data Exchange (ETDEWEB)

    Kanatzidis, Mercouri G.; Katsoulidis, Alexandros

    2016-10-18

    Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

  17. Centro-Apical Self-Organization of Organic Semiconductors in a Line-Printed Organic Semiconductor: Polymer Blend for One-Step Printing Fabrication of Organic Field-Effect Transistors.

    Science.gov (United States)

    Lee, Su Jin; Kim, Yong-Jae; Yeo, So Young; Lee, Eunji; Lim, Ho Sun; Kim, Min; Song, Yong-Won; Cho, Jinhan; Lim, Jung Ah

    2015-09-11

    Here we report the first demonstration for centro-apical self-organization of organic semiconductors in a line-printed organic semiconductor: polymer blend. Key feature of this work is that organic semiconductor molecules were vertically segregated on top of the polymer phase and simultaneously crystallized at the center of the printed line pattern after solvent evaporation without an additive process. The thickness and width of the centro-apically segregated organic semiconductor crystalline stripe in the printed blend pattern were controlled by varying the relative content of the organic semiconductors, printing speed, and solution concentrations. The centro-apical self-organization of organic semiconductor molecules in a printed polymer blend may be attributed to the combination of an energetically favorable vertical phase-separation and hydrodynamic fluids inside the droplet during solvent evaporation. Finally, a centro-apically phase-separated bilayer structure of organic semiconductor: polymer blend was successfully demonstrated as a facile method to form the semiconductor and dielectric layer for OFETs in one- step.

  18. Systematic design and research on a series of cadmium coordination polymers assembled due to tetracarboxylate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Lü, Lei; Mu, Bao; Li, Chang-Xia; Huang, Ru-Dan, E-mail: huangrd@bit.edu.cn

    2016-02-15

    A series of metal-organic frameworks (MOFs) have been prepared by tetracarboxylate ligands and Cd(II) ions under the hydrothermal or solvothermal conditions with the formulas of {[Cd_2(L_1)(H_2O)_4]·H_2O}{sub n} (1), {[(CH_3)_2NH_2]_2[Cd(L_1)]}{sub n} (2), [Cd(L{sub 2}){sub 0.5}(H{sub 2}O)]{sub n} (3), {[(CH_3)_2NH_2]_2 [Cd(L_2)]·2DMF}{sub n} (4), [Cd(L{sub 3}){sub 0.5}(H{sub 2}O)]{sub n} (5), {[Cd(L_3)_0_._5(H_2O)]·CH_3OH}{sub n} (6), {[(CH_3)_2NH_2]_2[Cd_3(L_4)_2]}{sub n} (7) (H{sub 4}L{sub 1}=[1,1′:4′,1″-terphenyl]-2,2″,5,5″-tetracarboxylic acid; H{sub 4}L{sub 2}=[1,1′:4′,1″-terphenyl]-2′,4,4″,5′-tetracarboxylic acid; H{sub 4}L{sub 3}=[1,1′:3′,1″-terphenyl]-2′,3,3″,5′-tetracarboxylic acid; H{sub 4}L{sub 4}=[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid), which are characterized by single-crystal X-ray diffraction, elemental analyses, IR, TGA and PXRD. Complex 1 exhibits a three-dimensional (3D) supramolecular framework based on two-dimensional (2D) coordination networks. Complexes 2 and 4 possess 3D framework based on the 1D right-handed helix channels. Complexes 3 and 7 are a 3D architecture containing two different channels. Isostructural complexes 5 and 6 display 3D framework. The different synthetic methods and coordination modes of the tetracarboxylates ligands have effect on formation of various MOFs. Moreover, the luminescent properties and N{sub 2} adsorption behaviors have been reported. - Graphical abstract: A series of cadmium(II) high-dimensional coordination polymers constructed from four different kinds of tetracarboxylate ligands have been successfully prepared under hydrothermal or solvothermal conditions. The effect of solvents, the coordination modes of the tetracarboxylates and positions of carboxylate groups on the architectures of complexes 1–7 have been investigated in detail. The luminescent properties of the part of complexes, N{sub 2} adsorption behaviors of complexes 2, 4–7 have

  19. Application of a silver–olefin coordination polymer as a catalytic curing agent for self-healing epoxy polymers

    International Nuclear Information System (INIS)

    Everitt, D T; Coope, T S; Trask, R S; Bond, I P; Wass, D F

    2015-01-01

    A silver–olefin based coordination polymer was prepared in a simple, one step process to act as an initiator to facilitate the ring-opening polymerization of epoxides. Thermal analysis found the complex to be capable of curing a range of commercially available epoxy resins used in the manufacture of conventional composite materials. Curing of the oligomeric diglycidyl ether bisphenol A resin, Epon 828, in combination with a non-toxic solvent, ethyl phenylacetate, was studied by differential scanning calorimetry. The mechanical characterization of the resultant cured polymers was conducted by single lap shear tests. Tapered double cantilever beam (TDCB) test specimens containing 2.5 pph of silver–olefin initiator, both with and without embedded microcapsules, were analyzed for their healing performance. Healing efficiency values were found to be strongly dependent on the applied healing temperature. A mean recovery of 74% fracture load was found in TDCB samples after being healed at 70 °C for 48 h. (paper)

  20. New transparent conductive metal based on polymer composite

    Energy Technology Data Exchange (ETDEWEB)

    Keshavarz Hedayati, Mehdi; Jamali, Mohammad [Nanochemistry and Nanoengineering, Institute for Materials Science, Faculty of Engineering, Christian-Albrechts-University, Kiel (Germany); Strunkus, Thomas; Zaporochentko, Vladimir; Faupel, Franz [Multicomponent Materials, Institute for Materials Science, Faculty of Engineering, Christian-Albrechts-University, Kiel (Germany); Elbahri, Mady [Nanochemistry and Nanoengineering, Institute for Materials Science, Faculty of Engineering, Christian-Albrechts-University, Kiel (Germany); Helmholtz-Zentrum Geesthacht GmbH, Institute of Polymer Research, Nanochemistry and Nanoengineering (Germany)

    2011-07-01

    Currently great efforts are made to develop new kind of transparent conductors (TCs) to replace ITO. In this regard different materials and composites have been proposed and studied including conductive polymers, carbon nanotubes (CNTs), metal grids, and random networks of metallic nanowires. But so far none of them could be used as a replacing material, since either they are either fragile and brittle or their electrical conductivity is below the typical ITO. Thin metallic films due to their high electrical conductivity could be one of the best replacing materials for ITO, however their poor transparency makes their application as TCs limited. Here we design and fabricate a new polymeric composite coating which enhances the transparency of the thin metal film up to 100% relative to the initial value while having a high electrical conductivity of typical metals. Therefore our proposed device has a great potential to be used as new transparent conductor.

  1. Polymer Solar Cells – Non Toxic Processing and Stable Polymer Photovoltaic Materials

    DEFF Research Database (Denmark)

    Søndergaard, Roar

    The field of polymer solar cell has experienced enormous progress in the previous years, with efficiencies of small scale devices (~1 mm2) now exceeding 8%. However, if the polymer solar cell is to achieve success as a renewable energy resource, mass production of sufficiently stable and efficient...... and development of more stable materials. The field of polymer solar cells has evolved around the use of toxic and carcinogenic solvents like chloroform, benzene, toluene, chlorobenzene, dichlorobenzene and xylene. As large scale production of organic solar cells is envisaged to production volumes corresponding...... synthesis of polymers carrying water coordinating side chains which allow for processing from semi-aqueous solution. A series of different side chains were synthesized and incorporated into the final polymers as thermocleavable tertiary esters. Using a cleavable side chain induces stability to solar cells...

  2. New twists and turns for actinide chemistry. Organometallic infinite coordination polymers of thorium diazide

    Energy Technology Data Exchange (ETDEWEB)

    Monreal, Marisa J.; Seaman, Lani A.; Goff, George S.; Michalczyk, Ryszard; Morris, David E.; Scott, Brian L.; Kiplinger, Jaqueline L. [Los Alamos National Laboratory, Los Alamos, NM (United States)

    2016-03-07

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge.

  3. Mesoporous stilbene-based lanthanide metal organic frameworks: synthesis, photoluminescence and radioluminescence characteristics.

    Science.gov (United States)

    Mathis Ii, Stephan R; Golafale, Saki T; Bacsa, John; Steiner, Alexander; Ingram, Conrad W; Doty, F Patrick; Auden, Elizabeth; Hattar, Khalid

    2017-01-03

    Ultra large pore isostructural metal organic frameworks (MOFs) which exhibit both photoluminescence and scintillation properties, were synthesized from trans-4,4'-stilbenedicarboxylic acid (H 2 L) and trivalent lanthanide (Ln) metal salts under solvothermal conditions (Ln = Er 3+ (1) and Tm 3+ (2)). This new class of mesoporous materials is a non-interpenetrating network that features ultra-large diamond shaped pores of dimensions with approximate cross-sectional dimensions of 28 Å × 12 Å. The fully deprotonated ligand, L, is isolated and rigidified as it serves as the organic linker component of the MOF structure. Its low density unit cells possess asymmetric units with two crystallographically independent Ln 3+ ions in seven coordinate arrangements. A distinct feature of the structure is the bis-bidentate carboxylate groups. They serve as a ligand that coordinates two Ln(iii) ions while each L connects four Ln(iii) ions yielding an exceptionally large diamond-shaped rectangular network. The structure exhibits ligand-based photoluminescence with increased lifetime compared to free stilbene molecules on exposure to UV radiation, and also exhibits strong scintillation characteristics, comprising of both prompt and delayed radioluminescence features, on exposure to ionizing radiation.

  4. International PolyScene-workshop on polymer electronics. Proceedings

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-07-01

    Topics of this proceedings are: RFID: tagging the opportunities and threats for polymer electronics; polymeric semiconductor development for thin film transistors; hole and electron transport in semiconducting polymers for organic electronics; a circuit based strategy for the development of polymer TFTS; towards a technology for all-polymer electronics; electrically doped organic semiconductors: physics and device applications; organic solar cells and photodetectors; organic solar cells: trends, challenges and positioning in the field of thin-film solar cell technologies; technical production of plastic solar cells: an overview; optical and ESR studies on polymer/fullerene composites for solar cells; targets for OTFT development for active matrix displays; reflective electroactive display (READ) technology and opportunities in printed devices; OFETs, OLEDs, OLDs: organic devices for future polytronic systems; design of active polymer materials and their application in electronic devices; blue emitting ALQ3 for full color organic displays; technologies for the reel-to-reel production of flexible polytronic systems; new developments in polyester films for flexible electronics; printed conductive polymer structures; non-lithographic patterning of polymer transistors; laser structuring- a method for polymer and metal patterning; direct printing of polymer transistor circuits; molecular design of interphases - the key for the development of reliable polymer based products; wafer level packaging - encapsulation of micro structures.

  5. Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts.

    Science.gov (United States)

    Miyamura, Hiroyuki; Sonoyama, Arisa; Hayrapetyan, Davit; Kobayashi, Shū

    2015-09-01

    While water-compatible Lewis acids have great potential as accessible and environmentally benign catalysts for various organic transformations, efficient immobilization of such Lewis acids while keeping high activity and without leaching of metals even under aqueous conditions is a challenging task. Self-assembled nanocomposite catalysts of organic polymers, carbon black, aluminum reductants, and scandium salts as heterogeneous water-compatible Lewis acid catalysts are described. These catalysts could be successfully applied to various C-C bond-forming reactions without leaching of metals. Scanning transmission electron microscopy analyses revealed that the nanocomposite structure of Al and Sc was fabricated in these heterogeneous catalysts. It is noted that Al species, which are usually decomposed rapidly in the presence of water, are stabilized under aqueous conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Structural diversity of a series of terpyridyl carboxylate coordination polymers: Luminescent sensor and magnetic properties

    Science.gov (United States)

    Yuan, Fei; Yuan, Chun-Mei; Hu, Huai-Ming; Wang, Ting-Ting; Zhou, Chun-Sheng

    2018-02-01

    Eleven new coordination polymers, [Zn2(ctpy)2(HCOO)2]n·3nH2O (1), [Zn2(ctpy)2(HCOO)2(H2O)2]n·nH2O (2), [Zn2(ctpy)2(H2O)4]n·2n(CH3COO)·nH2O (3), [Zn2(ctpy)2(CH3COO)2]n·nH2O (4), [Zn(ctpy)2]n·nH2O (5), [Zn2(ctpy)2(Hidc)(H2O)2]n(6), [Cd2(ctpy)4]n(7), [Cd2(ctpy)2(Hidc)]n(8), [Co2(ctpy)2(HCOO)2(H2O)2]n·nH2O (9), [Co(ctpy)(DMF)(ox)0.5]n(10), [Co(ctpy)(ox)0.5]n(11) and the closely related compound [Zn(ctpy)(ox)0.5]n·0.5nH2O (12) (Hctpy = 4‧-carboxy-4,2‧:6‧,4‧‧-terpyridine, H2ox = oxalic acid and H3idc = imidazole-4,5-dicarboxylic acid) have been synthesized by hydro(solvo)thermal reaction of 4‧-carboxy-4,2‧:6‧,4‧‧-terpyridine with divalent metal salts and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction. Compounds 1 and 4 have similar structure which demonstrate a two-fold interpenetrating 3D framework with a 3-connected utp topological net, which contains the same number of left and right-handed 21 helical chains. Compounds 2 and 9 are isostructural 2D layer with a 3-connected hcb topological net. Similar to 2, compound 3 also displays a 3-connected 2D hcb topological net. Compounds 5 and 10 are a 2D layer with a 4-connected sql topological net. Compound 6 shows a chiral 2D layer based on a 1D left- or right-handed helical chains, which are further extended into an achiral 2D + 2D→3D supramolecular network by hydrogen bonds with alternately arrangement. Compound 7 features an unusual 2-fold interpenetrating 3D coordination network which exhibits a new intriguing (3,5)-connected binodal topological net with the Schläfli symbol of (52·6)(53·63·73·8). Compound 8 shows a 2D→3D supramolecular structure based on (3,4)-connected 2D bilayers with the Schläfli symbol of (44·62). Compound 11 displays an unusual three-dimensional coordination network which exhibits an intriguing (3,8)-connected binodal new topological net with Schläfli symbol (42·62)2(42·623·83). Compound 12 features a two

  7. Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

    International Nuclear Information System (INIS)

    Barranco, V.; Carpentier, J.; Grundmeier, G.

    2004-01-01

    The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake φ, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma

  8. Polymer thin film as coating layer to prevent corrosion of metal/metal oxide film

    Science.gov (United States)

    Sarkar, Suman; Kundu, Sarathi

    2018-04-01

    Thin film of polymer is used as coating layer and the corrosion of metal/metal oxide layer is studied with the variation of the thickness of the coating layer. The thin layer of polystyrene is fabricated using spin coating method on copper oxide (CuO) film which is deposited on glass substrate using DC magnetron sputtering technique. Thickness of the polystyrene and the CuO layers are determined using X-ray reflectivity (XRR) technique. CuO thin films coated with the polystyrene layer are exposed to acetic acid (2.5 v/v% aqueous CH3COOH solution) environments and are subsequently analyzed using UV-Vis spectroscopy and atomic force microscopy (AFM). Surface morphology of the film before and after interaction with the acidic environment is determined using AFM. Results obtained from the XRR and UV-Vis spectroscopy confirm that the thin film of polystyrene acts as an anticorrosion coating layer and the strength of the coating depends upon the polymer layer thickness at a constant acid concentration.

  9. Method and apparatus for selective capture of gas phase analytes using metal .beta.-diketonate polymers

    Science.gov (United States)

    Harvey, Scott D [Kennewick, WA

    2011-06-21

    A process and sensor device are disclosed that employ metal .beta.-diketonate polymers to selectively capture gas-phase explosives and weaponized chemical agents in a sampling area or volume. The metal .beta.-diketonate polymers can be applied to surfaces in various analytical formats for detection of: improvised explosive devices, unexploded ordinance, munitions hidden in cargo holds, explosives, and chemical weapons in public areas.

  10. Polymer powder adhesion to metallic surface improvement with plasma

    International Nuclear Information System (INIS)

    Hladik, J.; Pichal, J.; Spatenka, P.; Pichal, J.; Spatenka, P.

    2008-01-01

    Useful method for corrosion prevention is coating of a base material with a suitable substance. It performs a barrier between the base material and its environment. Great attractions in this field have found polymers, among them polyethylenes (PE). Due to the low adhesion grade of unmodified polymer powder or granules the application of any modification process increasing the adhesion grade is crucial. At present there is no universal approach to polymer adhesion improvement and there have been employed various quite different techniques. Our research employed the PE adhesion improvement by plasma modification. There were used two plasma reactors - the microwave low pressure reactor and the atmospheric reactor employing dielectric barrier discharge (DBD). The adhesion of the powder was determined by measurement of strength force demanded for displacement of the PE-metal joint

  11. The iron member of the CPO-27 coordination polymer series: Synthesis, characterization, and intriguing redox properties

    DEFF Research Database (Denmark)

    Märcz, Matthias; Johnsen, Rune; Dietzel, Pascal D.C.

    2012-01-01

    The microporous coordination polymer CPO-27-Fe was synthesized from iron salts and 2,5-dihydroxyterephthalic acid by microwave assisted solvothermal synthesis. The crystal structures of the as-synthesized compounds were determined by Rietveld refinement from powder X-ray diffraction data using...

  12. Enantiopure Chiral Coordination Polymers Based on Polynuclear Paddlewheel Helices and Arsenyl Tartrate

    Directory of Open Access Journals (Sweden)

    Ángela Valentín-Pérez

    2018-03-01

    Full Text Available Herein, we report the preparation of chiral, one-dimensional coordination polymers based on trinuclear paddlewheel helices [M3(dpa4]2+ (M = Co(II and Ni(II; dpa = the anion of 2,2′-dipyridylamine. Enantiomeric resolution of a racemic mixture of [M3(dpa4]2+ complexes was achieved by chiral recognition of the respective enantiomer by [Δ-As2(tartrate2]2− or [Λ-As2(tartrate2]2− in N,N-dimethylformamide (DMF, affording crystalline coordination polymers formed from [(Δ-Co3(dpa4(Λ-As2(tartrate2]·3DMF (Δ-1, [(Λ-Co3(dpa4(Δ-As2(tartrate2]·3DMF (Λ-1, [(Δ-Ni3(dpa4(Λ-As2(tartrate2]·(4 − nDMF∙nEt2O (Δ-2 or [(Λ-Ni3(dpa4(Δ-As2(tartrate2]·(4 − nDMF∙nEt2O (Λ-2 repeating units. UV-visible circular dichroism spectra of the complexes in DMF solutions demonstrate the efficient isolation of optically active species. The helicoidal [M3(dpa4]2+ units that were obtained display high stability towards racemization as shown by the absence of an evolution of the dichroic signals after several days at room temperature and only a small decrease of the signal after 3 h at 80 °C.

  13. Adhesion and adhesion changes at the copper metal-(acrylonitrile-butadiene-styrene) polymer interface

    NARCIS (Netherlands)

    Kisin, S.; Varst, van der P.G.T.; With, de G.

    2007-01-01

    It is known that the adhesive strength of metallic films on polymer substrates often changes in the course of time. To study this effect in more detail, the adhesion energy of sputtered and galvanically strengthened copper coatings on acrylonitrile–butadiene–styrene polymer substrate was determined

  14. Selective removal/recovery of RCRA metals from waste and process solutions using polymer filtration trademark technology

    International Nuclear Information System (INIS)

    Smith, B.F.

    1997-01-01

    Resource Conservation and Recovery Act (RCRA) metals are found in a number of process and waste streams at many DOE, U.S. Department of Defense, and industrial facilities. RCRA metals consist principally of chromium, mercury, cadmium, lead, and silver. Arsenic and selenium, which form oxyanions, are also considered RCRA elements. Discharge limits for each of these metals are based on toxicity and dictated by state and federal regulations (e.g., drinking water, RCRA, etc.). RCRA metals are used in many current operations, are generated in decontamination and decommissioning (D ampersand D) operations, and are also present in old process wastes that require treatment and stabilization. These metals can exist in solutions, as part of sludges, or as contaminants on soils or solid surfaces, as individual metals or as mixtures with other metals, mixtures with radioactive metals such as actinides (defined as mixed waste), or as mixtures with a variety of inert metals such as calcium and sodium. The authors have successfully completed a preliminary proof-of-principle evaluation of Polymer Filtration trademark (PF) technology for the dissolution of metallic mercury and have also shown that they can remove and concentrate RCRA metals from dilute solutions for a variety of aqueous solution types using PF technology. Another application successfully demonstrated is the dilute metal removal of americium and plutonium from process streams. This application was used to remove the total alpha contamination to below 30 pCi/L for the wastewater treatment plant at TA-50 at Los Alamos National Laboratory (LANL) and from nitric acid distillate in the acid recovery process at TA-55, the Plutonium Facility at LANL (ESP-CP TTP AL16C322). This project will develop and optimize the PF technology for specific DOE process streams containing RCRA metals and coordinate it with the needs of the commercial sector to ensure that technology transfer occurs

  15. Selective removal/recovery of RCRA metals from waste and process solutions using polymer filtration{trademark} technology

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.F. [Los Alamos National Lab., NM (United States)

    1997-10-01

    Resource Conservation and Recovery Act (RCRA) metals are found in a number of process and waste streams at many DOE, U.S. Department of Defense, and industrial facilities. RCRA metals consist principally of chromium, mercury, cadmium, lead, and silver. Arsenic and selenium, which form oxyanions, are also considered RCRA elements. Discharge limits for each of these metals are based on toxicity and dictated by state and federal regulations (e.g., drinking water, RCRA, etc.). RCRA metals are used in many current operations, are generated in decontamination and decommissioning (D&D) operations, and are also present in old process wastes that require treatment and stabilization. These metals can exist in solutions, as part of sludges, or as contaminants on soils or solid surfaces, as individual metals or as mixtures with other metals, mixtures with radioactive metals such as actinides (defined as mixed waste), or as mixtures with a variety of inert metals such as calcium and sodium. The authors have successfully completed a preliminary proof-of-principle evaluation of Polymer Filtration{trademark} (PF) technology for the dissolution of metallic mercury and have also shown that they can remove and concentrate RCRA metals from dilute solutions for a variety of aqueous solution types using PF technology. Another application successfully demonstrated is the dilute metal removal of americium and plutonium from process streams. This application was used to remove the total alpha contamination to below 30 pCi/L for the wastewater treatment plant at TA-50 at Los Alamos National Laboratory (LANL) and from nitric acid distillate in the acid recovery process at TA-55, the Plutonium Facility at LANL (ESP-CP TTP AL16C322). This project will develop and optimize the PF technology for specific DOE process streams containing RCRA metals and coordinate it with the needs of the commercial sector to ensure that technology transfer occurs.

  16. Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

    Energy Technology Data Exchange (ETDEWEB)

    Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Nozarian, Kimia; Babadi, Susan Soleymani; Noorizadeh, Siamak [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Motamedi, Hossein [Department of Biology, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Mayer, Peter [LMU München Department Chemie, Butenandtstr 5-13, D-81377 München (Germany); Bruno, Giuseppe [Dipartimento di Chimica Inorganica, Università di Messina, Vill. S. Agata, Salita Sperone 31, 98166 Messina (Italy); Rudbari, Hadi Amiri [Faculty of Chemistry, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of)

    2017-05-15

    Two new compounds namely [Cu(SCN)(µ-L)]{sub n} (1) and ([Ag (µ{sub 2}-L)](ClO{sub 4})){sub n} (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS{sub 2}N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, the adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS{sub 4} tetrahedral geometry with 4-membered Ag{sub 2}S{sub 2} rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. - Graphical abstract: Two new Cu(I) and Ag(I) coordination polymers have been have been synthesized by one-pot reactions. Copper complex has a 2D non-covalent structure, but silver compound is a 3D coordination compound. These compounds have effective antibacterial activity. - Highlights: • Cu(I) and Ag(I) based coordination polymers

  17. Radiation crosslinking of polymers with segregated metallic particles. Final report, June 1, 1971--September 30, 1973

    International Nuclear Information System (INIS)

    Corneliussen, R.D.; Kamel, I.; Kusy, R.P.

    1973-01-01

    Through the past four years of research, a new approach to fabricating conductive polymer/metal composites has been developed. This approach consists of compacting mixtures of polymer and metal powders and then stabilizing the composite through radiation-induced crosslinking. The result is a mechanically strong, conductive materials consisting of two intertwining networks. One is a massive network consisting of fused crosslinked, large (greater than 100 μ) polymer particles while the other is a fine network of small, metallic particles (greater than 10 μ). Nine different systems including crystalline, amorphous, and rubbery polymers were studied. Processing at this time is limited to compression molding in a closed die because of network stability problems. Costs for processing were estimated at about $6.00/lb compared to $50.00 and up for commercial material based on random networks. (U.S.)

  18. Use of X-ray fluorescence for metal determination in polymers

    International Nuclear Information System (INIS)

    Guidorizzi, Lorenza

    1996-01-01

    X-Ray fluorescence spectrometry was used to determine metals and non-metals in polyester polymers. The greatest advantage of this technique over others like Atomic Absorption or Plasma Emission is that no sample previous treatment (like calcination or acid digestion) is required. Other advantage of this method is its fastness allowing a complete analysis in just few minutes. On the other hand, this method requires metals higher than 15 ppm. Below those values there is a loss of the analysis' precision. Another advantage of this technique is the possibility of making qualitative metal analysis, scanning unknown samples and identifying the found peaks automatically. (author)

  19. Organic-inorganic perovskites containing trivalent metal halide layers: the templating influence of the organic cation layer.

    Science.gov (United States)

    Mitzi, D B

    2000-12-25

    Thin sheetlike crystals of the metal-deficient perovskites (H2AEQT)M2/3I4 [M = Bi or Sb; AEQT = 5,5"'-bis-(aminoethyl)-2,2':5',2'':5'',2'''-quaterthiophene] were formed from slowly cooled ethylene glycol/2-butanol solutions containing the bismuth(III) or antimony(III) iodide and AEQT.2HI salts. Each structure was refined in a monoclinic (C2/m) subcell, with the lattice parameters a = 39.712(13) A, b = 5.976(2) A, c = 6.043(2) A, beta = 92.238(5) degrees, and Z = 2 for M = Bi and a = 39.439(7) A, b = 5.952(1) A, c = 6.031(1) A, beta = 92.245(3) degrees, and Z = 2 for M = Sb. The trivalent metal cations locally adopt a distorted octahedral coordination, with M-I bond lengths ranging from 3.046(1) to 3.218(3) A (3.114 A average) for M = Bi and 3.012(1) to 3.153(2) A (3.073 A average) for M = Sb. The new organic-inorganic hybrids are the first members of a metal-deficient perovskite family consisting of (Mn+)2/nV(n-2)/nX4(2-) sheets, where V represents a vacancy (generally left out of the formula) and the metal cation valence, n, is greater than 2. The organic layers in the AEQT-based organic-inorganic hybrids feature edge-to-face aromatic interactions among the rigid, rodlike quaterthiophene moieties, which may help to stabilize the unusual metal-deficient layered structures.

  20. A family of entangled coordination polymers constructed from a flexible V-shaped long bicarboxylic acid and auxiliary N-donor ligands: Luminescent sensing

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China); College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Bai, Chao [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China); Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China); Yuan, Fei; Xue, Gang-Lin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China)

    2017-05-15

    Eight Zn(II)-based coordination polymers, namely, [Zn{sub 2}L{sub 2}(2,2’-bipy)]{sub n}·nH{sub 2}O (1), [Zn{sub 2}L{sub 2}(phen)]{sub n}·nH{sub 2}O (2), [ZnL(phen)(H{sub 2}O)]{sub n} (3), [Zn{sub 3}L{sub 3}(4,4’-bipy)]{sub n} (4), [Zn{sub 2}L{sub 2}(4,4’-bipy){sub 2}]{sub n} [Zn{sub 2}L{sub 2}(H{sub 2}O){sub 2}]{sub n}·2nH{sub 2}O (5), [Zn{sub 4}L{sub 4}(bpp){sub 2}]{sub n} (6), [ZnL(bbi){sub 0.5}]{sub n} (7), [ZnL(bpz)]{sub n} (8) (H{sub 2}L=4,4’-([1,2-phenylenebis-(methylene)]bis(oxy))dibenzoic acid, 2,2’-bipy =2,2’-bipyridine, phen =1,10-phenanthroline, 4,4’-bpy=4,4’-bipyridine, bpp =1,3-bis(4-pyridyl)propane, bbi=1,4-bis(imidazol-1-yl)butane, bpz=3,3′,5,5′-tetramethyl-4,4′-bipyrazole), have been hydrothermally synthesized and structurally characterized. 1–8 display various coordination motifs with different entangled forms and conformations due to the effect of the assistant N-donor ligands. The photoluminescent properties of compounds 1–8 in solid state were studied. Interestingly, 3 exhibits highly efficient luminescent sensing for Cu{sup 2+} cations and CrO{sub 4}{sup 2-} anions, as well as detection ability for the different organic solvents and nitro explosives. These results indicated that it could be utilized as a multi-responsive luminescent sensor. Furthermore, compound 3 also shows good chemical resistance to both acidity and alkalinity solutions with pH ranging from 2 to 13. Thus, multi-photofunctionality and fluorescent response to pH have been combined in the 3, which is the first example in the Zn-based hybrid materials. - Graphical abstract: Eight new Zn(II)-based coordination polymers constructed from a flexible V-shaped long bicarboxylic acid and different N-donor ligands have been hydrothermally synthesized through fixing the metal salts and the solvent systems. The photoluminescent properties of complexes 1−8 in solid state were studied. Interestingly, 3 exhibits highly efficient luminescent sensing for Cu{sup 2

  1. Metal-Organic Framework of Lanthanoid Dinuclear Clusters Undergoes Slow Magnetic Relaxation

    Directory of Open Access Journals (Sweden)

    Hikaru Iwami

    2017-01-01

    Full Text Available Lanthanoid metal-organic frameworks (Ln-MOFs can adopt a variety of new structures due to the large coordination numbers of Ln metal ions, and Ln-MOFs are expected to show new luminescence and magnetic properties due to the localized f electrons. In particular, some Ln metal ions, such as Dy(III and Tb(III ions, work as isolated quantum magnets when they have magnetic anisotropy. In this work, using 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB as a ligand, two new Ln-MOFs, [Dy(TATB(DMF2] (1 and [Tb(TATB(DMF2] (2, were obtained. The Ln-MOFs contain Ln dinuclear clusters as secondary building units, and 1 underwent slow magnetic relaxation similar to single-molecule magnets.

  2. Lanthanide co-ordination frameworks: Opportunities and diversity

    International Nuclear Information System (INIS)

    Hill, Robert J.; Long, De-Liang; Hubberstey, Peter; Schroeder, Martin; Champness, Neil R.

    2005-01-01

    Significant successes have been made over recent years in preparing co-ordination framework polymers that show macroscopic material properties, but in the vast majority of cases this has been achieved with d-block metal-based systems. Lanthanide co-ordination frameworks also offer attractive properties in terms of their potential applications as luminescent, non-linear optical and porous materials. However, lanthanide-based systems have been far less studied to date than their d-block counterparts. One possible reason for this is that the co-ordination spheres of lanthanide cations are more difficult to control and, in the absence of design strategies for lanthanide co-ordination frameworks, it is significantly more difficult to target materials with specific properties. However, this article highlights some of the exciting possibilities that have emerged from the earliest investigations in this field with new topological families of compounds being discovered from relatively simple framework components, including unusual eight, seven and five-connected framework systems. Our own research, as well as others, is leading to a much greater appreciation of the factors that control framework formation and the resultant observed topologies of these polymers. As this understanding develops targeting particular framework types will become more straightforward and the development of designed polyfunctional materials more accessible. Thus, it can be seen that lanthanide co-ordination frameworks have the potential to open up previously unexplored directions for materials chemistry. This article focuses on the underlying concepts for the construction of these enticing and potentially highly important materials

  3. A review of modelling the interaction between natural organic matter and metal cations

    International Nuclear Information System (INIS)

    Falck, W.E.

    1989-01-01

    This report reviews techniques available to model the interaction between natural organic matter (mainly fulvic and humic acids) and protons and metal cations. A concise definition of natural organic matter is given and their properties are outlined. These materials are macromolecules which exhibit a polyelectrolyte character owing to numerous dissociable functional groups which are attached to their carbon backbone or from integral parts of the structure. The polyelectrolyte character is thought to be responsible for their conformation, hydrogen bonding or bridging by metal cations between subunits being important mechanisms. Environmental parameters like pH and ionic strength thus will have profound effects on the conformation of natural organic matter, the properties of which can change from being a flexible polymer to being a rigid gel. Binding mechanisms and binding strengh are discussed and an overview of relevant techniques of investigation is given. This work is part of the Commission's Mirage project - Phase 2, research area Geochemistry of actinides and fission products in natural aquifer systems

  4. Nitrogen-doped graphitic hierarchically porous carbon nanofibers obtained via bimetallic-coordination organic framework modification and their application in supercapacitors.

    Science.gov (United States)

    Yao, Yuechao; Liu, Peng; Li, Xiaoyan; Zeng, Shaozhong; Lan, Tongbin; Huang, Haitao; Zeng, Xierong; Zou, Jizhao

    2018-05-17

    Herein, N-doped graphitic hierarchically porous carbon nanofibers (NGHPCF) were prepared by electrospinning the composite of bimetallic-coordination metal-organic frameworks and polyacrylonitrile, followed by a pyrolysis and acid wash process. Control over the N content, specific surface area, and degree of graphitization of NGHPCF materials has been realized by adjusting the Co/Zn metal coordination content as well as the pyrolysis temperature. The obtained NGHPCF with a high specific surface area (623 m2 g-1) and nitrogen content (13.83 wt%) exhibit a high capacitance of 326 F g-1 at 0.5 A g-1. In addition, the capacitance of 170 F g-1 is still maintained at a high current density (40 A g-1); this indicates a high capacitance retention capability. Furthermore, a superb energy density (9.61 W h kg-1) is obtained with a high power density (62.4 W kg-1) using an organic electrolyte. These results fully illustrate that the prepared NGHPCF binder-free electrodes are promising candidates for high-performance supercapacitors.

  5. Zn-based porous coordination solid as diclofenac sodium carrier

    Science.gov (United States)

    Lucena, Guilherme Nunes; Alves, Renata Carolina; Abuçafy, Marina Paiva; Chiavacci, Leila Aparecida; da Silva, Isabel Cristiane; Pavan, Fernando Rogério; Frem, Regina Célia Galvão

    2018-04-01

    Drug delivery systems produced with biocompatible components can be used to reduce adverse effects and improve therapy efficacy. Most of the carrier materials reported in the literature show poor drug loading and rapid release. However, porous hybrid solids, such as metal-organic frameworks, are well suited to serve as carriers for delivery and imaging applications. In this work, a luminescent and nontoxic porous Zn(II) coordination polymer with 4,4‧-biphenyl-dicarboxylic acid (BPDC) and adenine linkers (BioMOF-Zn) was synthesized by a solvothermal process and characterized by PXRD, TGA, SEM-FEG, and FTIR. Nitrogen adsorption measurements revealed the presence of micropores as well as mesopores in the framework after activation of the material. The blue-emitting BioMOF-Zn exhibited an outstanding loading capacity (1.72 g g-1) and satisfactory release capability (56% after two days) for diclofenac sodium.

  6. Synthesis, structure and fluorescence properties of a novel 3D Sr(II) coordination polymer

    Science.gov (United States)

    Tan, Yu-Hui; Xu, Qing; Gu, Zhi-Feng; Gao, Ji-Xing; Wang, Bin; Liu, Yi; Yang, Chang-Shan; Tang, Yun-Zhi

    2016-09-01

    Solvothermal reaction of 2,2‧-bipyridine-5,5‧-dicarboxylic acid (H2bpdc) and SrCl2 affords a novel coordination polymer [Sr(Hbpdc)2]n1. X-ray structure determination shows that 1 exhibits a novel three-dimensional network. The unique Sr II cation sits on a two-fold axis and coordinated by four O-atom donors from four Hbptc- ligands and four N-atom donors from two Hbptc- ligands in distorted dodecahedral geometry. In 1 each Sr II cation connects to six different Hbptc- ligands and each Hbptc- ligand bridges three different Sr II cations which results in the formation of a three-dimensional polymeric structure. Corresponding to the free ligand, the fluorescent emission of complex 1 display remarkable "Einstain" shifts, which may be attributed to the coordination interaction of Sr atoms, thus reduce the rigidity of pyridyl rings.

  7. Coordination kinetics of different metal ions with the amidoximated polyacrylonitrile nanofibrous membranes and catalytic behaviors of their complexes

    Energy Technology Data Exchange (ETDEWEB)

    Li, Fu; Dong, Yong Chun; Kang, Wei Min; Cheng, Bowen; Qu, Xiang; Cui, Guixin [School of Textiles, Tianjin Polytechnic University, Tianjin (China)

    2016-12-15

    Two transition metal ions (Fe{sup 3+} and Cu{sup 2+}) and a rare earth metal ion (Ce{sup 3+}) were selected to coordinate with amidoximated polyacrylonitrile (PAN) nanofibrous membrane for preparing three metal modified PAN nanofibrous membrane complexes (M-AO-n-PANs, M = Fe, Cu, or Ce) as the heterogeneous Fenton catalysts for the dye degradation in water under visible irradiation. The coordination kinetics of three metal ions with modified PAN nanofibrous membranes was studied and the catalytic properties of the resulting complexes were also compared. The results indicated that increasing metal ion concentrations in solution or higher coordination temperature led to a significant increase in metal content, particularly in Fe and Cu contents of the complexes. Their coordination process could be described using Langmuir isotherm and pseudo-second-order kinetic equations. Moreover, Fe-AO-n-PAN had the best photocatalytic efficiency for the dye degradation in acidic medium, but a lower photocatalytic activity than Cu-AO-n-PAN in alkali medium.

  8. Zn(II) coordination polymer of an in situ generated 4-pyridyl (4Py) attached bis(amido)phosphate ligand, [PO2(NH4Py)2]- showing preferential water uptake over aliphatic alcohols.

    Science.gov (United States)

    Gupta, Arvind K; Nagarkar, Sanjog S; Boomishankar, Ramamoorthy

    2013-08-14

    Two polymorphic 2D-coordination polymers of composition [ZnL(HCO2)]∞ were synthesized from an in situ generated ligand [PO2(NH(4)Py)2](-) (L(-)). The ligand L(-) was generated by a facile metal-assisted P-N bond hydrolysis reaction from the corresponding phosphonium salt 1, [P(NH(4)Py)4]Cl, or from the neutral phosphoric triamide 2, [PO(NH(4)Py)3]. The de-solvated sample of the polymer [ZnL(HCO2)]∞ features polar micropores and shows a type I isotherm for CO2 sorption whereas a type II behaviour was observed for N2. The vapour sorption isotherm of the de-solvated sample of [ZnL(HCO2)]∞ shows preferential adsorption of water vapour over aliphatic alcohols.

  9. A Simple Approach to Enhance the Water Stability of a Metal-Organic Framework.

    Science.gov (United States)

    Shih, Yung-Han; Kuo, Yu-Ching; Lirio, Stephen; Wang, Kun-Yun; Lin, Chia-Her; Huang, Hsi-Ya

    2017-01-01

    A facile method to improve the feasibility of water-unstable metal-organic frameworks in an aqueous environment has been developed that involves imbedding in a polymer monolith. The effect of compartment type during polymerization plays a significant role in maintaining the crystalline structure and thermal stability of the MOFs, which was confirmed by powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA), respectively. The MOF-polymer composite prepared in a narrow compartment (column, ID 0.8 mm) has better thermal and chemical stability than that prepared in a broad compartment (vial, ID 7 mm). The developed MOF-polymer composite was applied as an adsorbent in solid-phase microextraction of nine non-steroidal anti-inflammatory drugs (NSAIDs) and could be used for extraction more than 30 times, demonstrating that the proposed approach has potential for industrial applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Uranyl oxo activation and functionalization by metal cation coordination

    International Nuclear Information System (INIS)

    Arnold Polly, L.; Pecharman, A. F.; Hollis, E.; Parsons, S.; Love, J. B.; Yahia, A.; Maron, L.; Yahia, A.; Maron, L.

    2010-01-01

    The oxo groups in the uranyl ion [UO 2 ] 2+ - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  11. Gas transport in metal organic framework–polyetherimide mixed matrix membranes: The role of the polyetherimide backbone structure

    NARCIS (Netherlands)

    Hegde, Maruti; Shahid, S.; Norder, Ben; Dingemans, Theo J.; Nijmeijer, Dorothea C.

    2015-01-01

    We report on how the morphology of the polymer matrix, i.e. amorphous vs. semi-crystalline, affects the gas transport properties in a series of mixed matrix membranes (MMMs) using Cu3(BTC)2 as the metal organic framework (MOF) filler. The aim of our work is to demonstrate how incorporation of

  12. Gas transport in metal organic framework-polyetherimide mixed matrix membranes: The role of the polyetherimide backbone structure

    NARCIS (Netherlands)

    Hegde, Maruti; Shahid, Salman; Norder, Ben; Dingemans, T.J.; Nijmeijer, Kitty

    2015-01-01

    We report on how the morphology of the polymer matrix, i.e. amorphous vs. semi-crystalline, affects the gas transport properties in a series of mixed matrix membranes (MMMs) using Cu3(BTC)2 as the metal organic framework (MOF) filler. The aim of our work is to demonstrate how incorporation of

  13. Selective micro metallization of polymers for biomedical and medical application

    DEFF Research Database (Denmark)

    Islam, Mohammad Aminul; Hansen, Hans Nørgaard; Tang, Peter Torben

    Integration of micro/nano metallic structures in polymer devices is a broad multi-disciplinary research field, consisting of various combinations of mechanical, chemical and physical fabrication methods. Some of these combinations have been known for years and other combinations or methods are ve...

  14. Ion induced modification of polymers at energies between 100 keV and 1 GeV applied for optical waveguides and improved metal adhesion

    International Nuclear Information System (INIS)

    Rueck, D.M.

    2000-01-01

    Polymers are a class of materials widely used for a broad field of applications. Ion irradiation ranging from several eV to GeV is a quite efficient tool to modify the properties of polymers like wettability, optical properties, adhesion between metal and polymer surfaces. In this paper ion induced chemical changes of polymers will be discussed in relation to the modified macroscopic properties. In the field of optical telecommunication, polymers are discussed as a new class of materials for the fabrication of passive optical devices. Ion irradiation is a promising method to generate structures with a modified index of refraction, which is necessary for the guidance of light with different wavelengths in optical devices. Modified optical properties of different polymers under ion irradiation will be discussed. Analytical investigations like infrared measurements and measurement of the outgassing reaction products during irradiation will be discussed to interpret the chemical changes of the polymers. Metallization of polymers is of interest in several fields of application like for multilayer systems in microtechnology or casings for radiation shielding for example. Ion beam mixing at low energies is a promising method to improve the metal/polymer adhesion. Also ion irradiation at high energies applied to a metal/polymer multilayer can improve the adhesion of a metal layer to a polymer surface, if not sufficient. Different metal/polymer systems will be presented as well as specific applications

  15. Nanoscale zero-valent iron impregnation of covalent organic polymer grafted activated carbon for water treatment

    DEFF Research Database (Denmark)

    Mines, Paul D.; Uthuppu, Basil; Thirion, Damien

    2016-01-01

    The use of nanoscale zero valent iron (nZVI) has quickly become a leading research material for the treatment of typically hard to degrade contaminants found in groundwater. These contaminants include antibiotics, pesticides, halogenated organics, heavy metals, among others. However, the effectiv......The use of nanoscale zero valent iron (nZVI) has quickly become a leading research material for the treatment of typically hard to degrade contaminants found in groundwater. These contaminants include antibiotics, pesticides, halogenated organics, heavy metals, among others. However...... polymeric network already previously proven to stabilize nZVI and a long-standing water treatment material,1 activated carbon; we have developed an advanced material that allows for the not only the stabilization of nZVI, but also the improved degradation of various water contaminants. This was done...... by performing a series of surface modification techniques to the surface of the activated carbon, then physically grafting the covalent organic polymer to the carbon in a shell-like manner, and ultimately synthesizing nZVI in situ within the pores of both the activated carbon and the polymeric network. Not only...

  16. LDRD final report on intelligent polymers for nanodevice performance control

    Energy Technology Data Exchange (ETDEWEB)

    JAMISON,GREGORY M.; LOY,DOUGLAS A.; WHEELER,DAVID R.; SAUNDERS,RANDALL S.L; SHELNUTT,JOHN A.; CARR,MARTIN J.; SHALTOUT,RAAFAT M.

    2000-01-01

    A variety of organic and hybrid organic-inorganic polymer systems were prepared and evaluated for their bulk response to optical, thermal and chemical environmental changes. These included modeling studies of polyene-bridged metal porphyrin systems, metal-mediated oligomerization of phosphaalkynes as heteroatomic analogues to polyacetylene monomers, investigations of chemically amplified degradation of acid- and base-sensitive polymers and thermally responsive thermoplastic thermosets based on Diels-Alder cycloaddition chemistry. The latter class of materials was utilized to initiate work to develop a new technique for rapidly building a library of systems with varying depolymerization temperatures.

  17. CHAPTER 3. High-performance Organic Photovoltaic Donor Polymers

    KAUST Repository

    Wadsworth, Andrew

    2017-11-08

    The field of organic photovoltaics has advanced a great deal over the last decade, with device efficiencies now exceeding 11%. A large part of this success can be attributed to the development of donor polymer materials, from their humble beginnings as homopolymers to the highly tuned push-pull copolymer and terpolymer materials that are now being reported on a regular basis. Through the careful use of chemical modification, it has been possible to design and synthesize a wide variety of donor polymers, allowing optimization of both the optoelectronic and structural properties of the materials. In doing so, more favourable active layer blends have been achieved and therefore significant improvements in device performance have been observed. Herein we discuss how the chemical design of donor polymers for organic photovoltaics has led to the emergence of high-performance materials.

  18. CHAPTER 3. High-performance Organic Photovoltaic Donor Polymers

    KAUST Repository

    Wadsworth, Andrew; Baran, Derya; Gorman, Jeffrey; McCulloch, Iain

    2017-01-01

    The field of organic photovoltaics has advanced a great deal over the last decade, with device efficiencies now exceeding 11%. A large part of this success can be attributed to the development of donor polymer materials, from their humble beginnings as homopolymers to the highly tuned push-pull copolymer and terpolymer materials that are now being reported on a regular basis. Through the careful use of chemical modification, it has been possible to design and synthesize a wide variety of donor polymers, allowing optimization of both the optoelectronic and structural properties of the materials. In doing so, more favourable active layer blends have been achieved and therefore significant improvements in device performance have been observed. Herein we discuss how the chemical design of donor polymers for organic photovoltaics has led to the emergence of high-performance materials.

  19. Structural diversification and photocatalytic properties of three Cd(II) coordination polymers decorated with different auxiliary ligands

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Wen-Yu; Zhuang, Guo-Yong; Huang, Zuo-Long; Cheng, Hong-Jian; Zhou, Li; Ma, Man-Hong; Wang, Hao; Tang, Xiao-Yan, E-mail: xytang@cslg.edu.cn; Ma, Yun-Sheng; Yuan, Rong-Xin, E-mail: yuanrx@cslg.edu.cn

    2016-03-15

    Three cadmium coordination polymers, [Cd(bismip)]{sub n} (1), {[Cd(bismip)(phen)]·H_2O}{sub n} (2) and {[Cd_2(bismip)_2(4,4′-bipy)]·2H_2O}{sub n} (3) (H{sub 2}bismip=5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid, phen=1,10-phenanthroline, 4,4′-bipy=4,4′-bipyridine) have been prepared under solvothermal conditions. In 1, the [Cd{sub 4}(bismip){sub 3}] units are jointed by bismip ligands to afford a three-dimensional (3D) architecture. Complex 2 exhibits a 3D supramolecular framework based on the interconnection of 1D chains through hydrogen bonding interactions and π-π packing interactions. 3 is a two-fold interpenetrating 3D architecture with a (4·8{sup 2})(4{sup 2}·8{sup 4}) Schläfli symbol in which 2D layers are interlinked by 4,4′-bipy ligands. The diverse structures of compounds 1–3 indicate that the auxiliary ligands have significant effects on the final structures. The photoluminescent properties and photocatalytic properties of these coordination polymers in the solid state were also investigated. Remarkably, 3 shows the wide gap semiconductor nature and exhibit excellent photocatalytic performance. - Graphical abstract: Three cadmium coordination polymers with different architectures based on 5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid have been prepared. Their photoluminescent properties were also investigated. - Highlights: • Three new Cd(II) Cps were synthesized based on H{sub 2}bismip. • Compounds 1 and 3 show 3D networks and 2 exhibits a 1D chain. • Compoud 3 exhibits good catalytic activity of methylene blue photodegradation.

  20. Characterization of interfaces between metals and organic thin films by electron and ion spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Schmid, Martin

    2012-01-18

    In this thesis, interfaces between metals and organic thin films have been characterized with photoelectron and ion-scattering spectroscopies. Two different classes of metal/organic interfaces were examined in detail. First, interfaces which can be mainly characterized by relatively weak coordinative interactions between substrate and adsorbate. Second, interfaces which are mostly determined, or even created, by chemical reactions between different adsorbates or between adsorbates and substrate. Typical examples from the first class are metalated tetrapyrrole monolayers on Ag(111) and Au(111) single-crystal substrates. In this study, a focus was set to the interaction between iron and cobalt tetrapyrroles with Ag(111) or Au(111) substrates. A detailed examination of the corresponding photoelectron spectra revealed that the adsorbatesubstrate interaction is associated with a charge transfer from the metallic substrate to the Fe(II) or Co(II) ions within the tetrapyrrole units. The examination of cobalt(II) phthalocyanine monolayers further led to the conclusion that the magnetic moment, as present in unperturbed CoPc molecules, is efficiently quenched by the contact to the Ag(111) surface and the associated charge transfer. Similar investigations on Au(111) substrates gave evidence for possible adsorption site effects, further complicating the adsorbate/substrate interaction. Furthermore the formation of two-dimensional structures of poly(p-phenylene-terephthalamide) (PPTA, trademark Kevlar) on Ag(111) was closely examined. The Ag(111) surface does not only provide the geometrical boundary for the formation of the 2D covalent structures, but, moreover, actively participates in the reaction; after the adsorption of TPC molecules, a scission of the C-Cl bond, in particular at temperatures above 120 K, was evident. The resulting radical fragments appear stable and can act as reaction partners for