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Sample records for coordination polymers based

  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. 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

  3. 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

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  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. 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.

  19. 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)

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. Two coordination polymers based on semicarbazone Schiff base and azide: synthesis, crystal structure, electrochemistry, magnetic properties and biological activity

    Czech Academy of Sciences Publication Activity Database

    Shaabani, B.; Khandar, A.A.; Dušek, Michal; Pojarová, Michaela; Mahmoudi, F.; Feher, A.; Kajňaková, M.

    2013-01-01

    Roč. 66, č. 5 (2013), s. 748-762 ISSN 0095-8972 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional support: RVO:68378271 Keywords : Schiff bases * semicarbazone * coordination polymer * structure analyses Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.224, year: 2013

  8. 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-.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. White polymer light-emitting diode based on polymer blending

    International Nuclear Information System (INIS)

    Lee, Yong Kyun; Kwon, Soon Kab; Kim, Jun Young; Park, Tae Jin; Song, Dae Ho; Kwon, Jang Hyuk; Choo, Dong Jun; Jang, Jin; Jin, Jae Kyu; You, Hong

    2006-01-01

    A series of white polymer light emitting devices have been fabricated by using a polymer blending system of polyfluorene-based blue and MEH-PPV red polymers. A device structure of ITO/PEDOT:PSS/polymer/LiF/Al was employed. The white polymer device exhibited a current efficiency of 4.33 cd/A (4,816 cd/m 2 , Q.E. = 1.9 %) and a maximum luminance of 21,430 cd/m 2 at 9.2 V. The CIE coordinates were (0.35, 0.37) at 5 V and (0.29, 0.30) at 9 V.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  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. 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

  2. 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)

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. A copper-based layered coordination polymer: synthesis, magnetic properties and electrochemical performance in supercapacitors.

    Science.gov (United States)

    Liu, Qi; Liu, Xiuxiu; Shi, Changdong; Zhang, Yanpeng; Feng, Xuejun; Cheng, Mei-Ling; Su, Seng; Gu, Jiande

    2015-11-28

    A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g(-1) at a current density of 1 A g(-1) in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles.

  11. 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...

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. White Polymer Light-Emitting Diodes Based on Exciplex Electroluminescence from Polymer Blends and a Single Polymer.

    Science.gov (United States)

    Liang, Junfei; Zhao, Sen; Jiang, Xiao-Fang; Guo, Ting; Yip, Hin-Lap; Ying, Lei; Huang, Fei; Yang, Wei; Cao, Yong

    2016-03-09

    In this Article, we designed and synthesized a series of polyfluorene derivatives, which consist of the electron-rich 4,4'-(9-alkyl-carbazole-3,6-diyl)bis(N,N-diphenylaniline) (TPA-Cz) in the side chain and the electron-deficient dibenzothiophene-5,5-dioxide (SO) unit in the main chain. The resulting copolymer PF-T25 that did not comprise the SO unit exhibited blue light-emission with the Commission Internationale de L'Eclairage coordinates of (0.16, 0.10). However, by physically blending PF-T25 with a blue light-emitting SO-based oligomer, a novel low-energy emission correlated to exciplex emerged due to the appropriate energy level alignment of TPA-Cz and the SO-based oligomers, which showed extended exciton lifetime as confirmed by time-resolved photoluminescent spectroscopy. The low-energy emission was also identified in copolymers consisting of SO unit in the main chain, which can effectively compensate for the high-energy emission to produce binary white light-emission. Polymer light-emitting diodes based on the exciplex-type single greenish-white polymer exhibit the peak luminous efficiency of 2.34 cd A(-1) and the maximum brightness of 12 410 cd m(-2), with Commission Internationale de L'Eclairage color coordinates (0.27, 0.39). The device based on such polymer showed much better electroluminescent stability than those based on blending films. These observations indicated that developing a single polymer with the generated exciplex emission can be a novel and effective molecular design strategy toward highly stable and efficient white polymer light-emitting diodes.

  20. 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.

  1. 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

  2. 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.

  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. 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.

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. A rational route to SCM materials based on a 1-D cobalt selenocyanato coordination polymer.

    Science.gov (United States)

    Boeckmann, Jan; Näther, Christian

    2011-07-07

    Thermal annealing of a discrete complex with terminal SeCN anions and monodentate coligands enforces the formation of a 1D cobalt selenocyanato coordination polymer that shows slow relaxation of the magnetization. Therefore, this approach offers a rational route to 1D materials that might show single chain magnetic behaviour. This journal is © The Royal Society of Chemistry 2011

  13. 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.

  14. Towards Acid-Tolerated Ethanol Dehydration: Chitosan-Based Mixed Matrix Membranes Containing Cyano-Bridged Coordination Polymer Nanoparticles.

    Science.gov (United States)

    Wu, C-W; Kang, Chao-Hsiang; Lin, Yi-Feng; Tung, Kuo-Lun; Deng, Yu-Heng; Ahamad, Tansir; Alshehri, Saad M; Suzuki, Norihiro; Yamauchi, Yusuke

    2016-04-01

    Prussian blue (PB) nanoparticles, one of many cyano-bridged coordination polymers, are successfully incorporated into chitosan (CS) polymer to prepare PB/CS mixed matrix membranes (MMMs). The PB nanoparticles are uniformly distributed in the MMMs without the collapse of the original PB structure. As-prepared PB/CS MMMs are used for ethanol dehydration at 25 °C in the pervaporation process. The effect of loading PB in CS matrix on pervaporation performance is carefully investigated. The PB/CS membrane with 30 wt% PB loading shows the best performance with a permeate flux of 614 g. m-2 . h-1 and a separation factor of 1472. The pervaporation using our PB/CS membranes exhibits outstanding performance in comparison with the previously reported CS-based membranes and MMMs. Furthermore, the addition of PB allows PB/CS MMMs to be tolerant of acidic environment. The present work demonstrates good pervaporation performance of PB/CS MMMs for the separation of an ethanol/water (90:10 in wt%) solution. Our new system provides an opportunity for dehydration of bioethanol in the future.

  15. 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.

  16. 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.

  17. Utilization of mixed ligands to construct diverse Ni(II)-coordination polymers based on terphenyl-2,2′,4,4′-tetracarboxylic acid and varied N-donor co-ligands

    International Nuclear Information System (INIS)

    Wang, Chao; Zhao, Jun; Xia, Liang; Wu, Xue-Qian; Wang, Jian-Fang; Dong, Wen-Wen; Wu, Ya-Pan

    2016-01-01

    Three new coordination polymers, namely, {[Ni(H 2 L)(bix)(H 2 O) 2 ]·2h 2 O} n (1), {[Ni(HL)(Hdpa)(H 2 O) 2 ]·H 2 O} n (2), {[Ni(L) 0.5 (bpp)(H 2 O)]·H 2 O} n (3) (H 4 L=terphenyl-2,2′,4,4′-tetracarboxylic acid; bix=1,4-bis(imidazol-1-ylmethyl)benzene; dpa =4,4′-dipyridylamine; bpp=1,3-bis(4-pyridyl)propane), based on rigid H 4 L ligand and different N-donor co-ligands, have been synthesized under hydrothermal conditions. Compound 1 features a 3D 4-connected 6 6 -dia-type framework with H 4 L ligand adopts a μ 2 -bridging mode with two symmetry-related carboxylate groups in μ 1 -η 1 :η 0 monodentate mode. Compound 2 displays a 1D [Ni(HL)(Hdpa)] n ribbon chains motif, in which the H 4 L ligand adopts a μ 2 -bridging mode with two carboxylate groups in μ 1 -η 1 :η 1 and μ 1 -η 1 :η 0 monodentate modes, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology, with H 4 L ligand displays a μ 4 -bridging coordination mode. The H 4 L ligand displays not only different deprotonated forms but also diverse coordination modes and conformations. The structural diversities among 1–3 have been carefully discussed, and the roles of N-donor co-ligands in the self-assembly of coordination polymers have been well documented. - Graphical abstract: Three nickel coordination polymers with different architectures based on mixed ligand system were synthesized and structurally characterized. Topology analyses indicate that 1 shows the 4-connected 6 6 -dia net, 1D ribbon chains for 2 and 3D (4,4)-connected bbf network for 3. Display Omitted - Highlights: • Three Ni-based coordination polymers with distinct features have been prepared. • Compound 1 features a 3D 4-connected 66-dia-type framework, 2 displays a 1D [Ni(HL)(Hdpa)] n ribbon chains motif, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology. • The “mixed ligand assembled” strategy is significant potential for network design.

  18. Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

    Science.gov (United States)

    Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming; Wu, Qing-Ran; Xie, Juan; Dong, Fa-Xin; Yang, Meng-Lin; Xue, Gang-Lin

    2014-04-01

    Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln2(Hpdc)2(C2O4)(H2O)4]n·2nH2O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H3pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H3pdc was decomposed into (ox)2- with Cu(II)-Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P21/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.

  19. 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

  20. 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)

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. Two new coordination polymers based on tartaric acid ligand: Syntheses, crystal structure and thermal stability

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Fei-Yan; Lan, You-Zhao, E-mail: sky37@zjnu.cn; Han, Min-Min; Feng, Yun-Long, E-mail: lyzhao@zjnu.cn [Zhejiang Normal University, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry (China)

    2016-09-15

    Two new coordination polymers [Cd{sub 3}(D-Tar){sub 3}]{sub n} (1) and [Pb(meso-Tar)]{sub n} (2) (H{sub 2}Tar = tartaric acid) have been synthesized by hydrothermal reaction and characterized by single crystal X-ray diffraction analysis and IR spectra. 1 crystallizes in the C222{sub 1} chiral space group and shows a 3D (4,4)-connected net with the (4.6.8{sup 4}){sub 4}(4.6{sup 2}.8{sup 2}.10)(4.6{sup 2}.8{sup 3})(4.6{sup 3}.8{sup 2})(4.6{sup 3}.8{sup 2}){sub 4}(4.8{sup 5}){sub 2} topology. 2 possesses a 3D (4,4)-connected net with the (4{sup 3}.6{sup 2}.8) topology. In addition, the thermogravimetric analyses (TGA) results for polymers are discussed.

  7. Utilization of mixed ligands to construct diverse Ni(II)-coordination polymers based on terphenyl-2,2′,4,4′-tetracarboxylic acid and varied N-donor co-ligands

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chao [College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Zhao, Jun, E-mail: junzhao08@126.com [College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 35002 (China); Xia, Liang [College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 35002 (China); Wu, Xue-Qian; Wang, Jian-Fang; Dong, Wen-Wen; Wu, Ya-Pan [College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China)

    2016-06-15

    Three new coordination polymers, namely, {[Ni(H_2L)(bix)(H_2O)_2]·2h_2O}{sub n} (1), {[Ni(HL)(Hdpa)(H_2O)_2]·H_2O}{sub n} (2), {[Ni(L)_0_._5(bpp)(H_2O)]·H_2O}{sub n} (3) (H{sub 4}L=terphenyl-2,2′,4,4′-tetracarboxylic acid; bix=1,4-bis(imidazol-1-ylmethyl)benzene; dpa =4,4′-dipyridylamine; bpp=1,3-bis(4-pyridyl)propane), based on rigid H{sub 4}L ligand and different N-donor co-ligands, have been synthesized under hydrothermal conditions. Compound 1 features a 3D 4-connected 6{sup 6}-dia-type framework with H{sub 4}L ligand adopts a μ{sub 2}-bridging mode with two symmetry-related carboxylate groups in μ{sub 1}-η{sup 1}:η{sup 0} monodentate mode. Compound 2 displays a 1D [Ni(HL)(Hdpa)]{sub n} ribbon chains motif, in which the H{sub 4}L ligand adopts a μ{sub 2}-bridging mode with two carboxylate groups in μ{sub 1}-η{sup 1}:η{sup 1} and μ{sub 1}-η{sup 1}:η{sup 0} monodentate modes, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology, with H{sub 4}L ligand displays a μ{sub 4}-bridging coordination mode. The H{sub 4}L ligand displays not only different deprotonated forms but also diverse coordination modes and conformations. The structural diversities among 1–3 have been carefully discussed, and the roles of N-donor co-ligands in the self-assembly of coordination polymers have been well documented. - Graphical abstract: Three nickel coordination polymers with different architectures based on mixed ligand system were synthesized and structurally characterized. Topology analyses indicate that 1 shows the 4-connected 6{sup 6}-dia net, 1D ribbon chains for 2 and 3D (4,4)-connected bbf network for 3. Display Omitted - Highlights: • Three Ni-based coordination polymers with distinct features have been prepared. • Compound 1 features a 3D 4-connected 66-dia-type framework, 2 displays a 1D [Ni(HL)(Hdpa)]{sub n} ribbon chains motif, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology. • The “mixed ligand assembled

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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)

  14. Synthesis, structural characterization and antitumor activity of a Ca(II) coordination polymer based on 4-formyl-1,3-benzenedisulfonate-2-furoic acid hydrazide ligands

    Energy Technology Data Exchange (ETDEWEB)

    Tai, Xi-Shi, E-mail: taixs@wfu.edu.cn [Weifang University, College of Chemistry and Chemical Engineering (China); Wang, Xin [Qinghai Normal University, Department of Chemistry (China)

    2017-03-15

    A new Ca(II) coordination polymer, ([CaL(H{sub 2}O){sub 4}] · (H{sub 2}O){sub 4}){sub n} (L = 4-formyl-1,3-benzenedisulfonate-2-furoic acid hydrazide) has been prepared by one-pot synthesis method. And it was characterized by elemental analysis, IR and thermal analysis. The result of X-ray single-crystal diffraction analysis shows that the Ca(II) complex molecules form one-dimensional chain structure by the bridging oxygen atoms. The anti-tumor activity of L ligand and the Ca(II) coordination polymer has also been studied.

  15. 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.

  16. 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

  17. Pressure Sensor via Optical Detection Based on a 1D Spin Transition Coordination Polymer

    Science.gov (United States)

    Jureschi, Cătălin M.; Linares, Jorge; Rotaru, Aurelian; Ritti, Marie Hélène; Parlier, Michel; Dîrtu, Marinela M.; Wolff, Mariusz; Garcia, Yann

    2015-01-01

    We have investigated the suitability of using the 1D spin crossover coordination polymer [Fe(4-(2′-hydroxyethyl)-1,2,4-triazole)3]I2·H2O, known to crossover around room temperature, as a pressure sensor via optical detection using various contact pressures up to 250 MPa. A dramatic persistent colour change is observed. The experimental data, obtained by calorimetric and Mössbauer measurements, have been used for a theoretical analysis, in the framework of the Ising-like model, of the thermal and pressure induced spin state switching. The pressure (P)-temperature (T) phase diagram calculated for this compound has been used to obtain the P-T bistability region. PMID:25621610

  18. Syntheses, structures and properties of two new coordination polymers based on D-camphoric acid and 2-phenyl-4,6-diamino-1,3,5-triazine

    Energy Technology Data Exchange (ETDEWEB)

    Lun, Huijie; Yang, Jinghe; Jin, Linyu; Cui, Sasa; Bai, Yanlong [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Zhang, Xudong [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Li, Yamin, E-mail: liyamin@henu.edu.cn [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China)

    2015-05-15

    By hydrothermal method, two new coordination polymers [Co(ca)(phdat)]{sub n} (1), [Ni(ca)(phdat).0.125H{sub 2}O]{sub n} (2) (H{sub 2}ca=D-camphoric acid, phdat=2-phenyl-4,6-diamino-1,3,5-triazine) have been achieved and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isostructural, both of which exhibit two-dimensional layered network built up from paddle-wheel Co{sub 2}(CO{sub 2}){sub 4}/Ni{sub 2}(CO{sub 2}){sub 4} SBUs by ca{sup 2−} ligand. In the existence of π…π stacking interactions between triazine rings and phenyl rings, the 3D networks are constructed with the hanging phdat filled between the neighboring layers. Furthermore, compounds 1–2 exhibit antiferromagnetic behavior and compound 2 displays a good activity for methanol oxidation. - Graphical abstract: Two new coordination compounds 1–2 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses, magnetic and electrochemical measurement. - Highlights: • This paper reports two new coordination polymers based on D-camphoric acid. • Both the compounds feather two-dimensional layered networks built up from paddle-wheel SBUs. • The magnetism and electrochemical property are investigated.

  19. 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.

  20. 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.

  1. Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

    International Nuclear Information System (INIS)

    Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen; Ma, Lu-Fang; Wang, Li-Ya

    2014-01-01

    Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H 2 O)]) n (1), ([Co(4-Nbdc)(bpp) (H 2 O)]) n (2), ([Ni(4-Nbdc)(bpp)(H 2 O)]·H 2 O) n (3), and ([Mn 2 (3-Nbdc) 2 (bib) 3 ]·2H 2 O) n (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal–carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (6 6 ) dia topology and (4 4 .6 10 .8)(4 4 .6 2 ) fsc topology, and both of them contain metal–carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)–carboxylate binuclear in 1 (J=1.27 cm −1 ) and Ni(II)–carboxylate chain in 3 (J=1.44 cm −1 ), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)–carboxylate chain in 4 (J=−0.77 cm −1 ). - Highlights: • Four novel coordination polymers were hydrothermally synthesized. • 1 is 1D quasi-trapezoidal chain and 2 is brick-wall layer both with dinuclear units. • 3 and 4 show 3D frameworks both with 1D metal–carboxylate chains. • 1 and 3 exhibit ferromagnetic coupling, while 4 shows antiferromagnetic coupling

  2. Novel Inorganic Coordination Polymers Based on Cadmium Oxalates

    Science.gov (United States)

    Prasad, P. A.; Neeraj, S.; Vaidhyanathan, R.; Natarajan, Srinivasan

    2002-06-01

    Three new cadmium oxalate coordination polymers, I-III, with extended layered structures have been synthesized in the presence of imidazole. While I was prepared by the reaction between imidazolium oxalate and Cd, II and III were synthesized from their constituents using hydrothermal methods. [Cd(C2O4)(C3N2H4)]∞ (I): monoclinic, space group P21/c (no. 14), a=8.7093(1) Å, b=9.9477(3) Å, c=8.4352 Å, β=93.796(1)°, Z=4; [Cd(C2O4)2(C3N2H4)3(H2O)]∞ (II): monoclinic, space group P21/c (no. 14), a=7.8614(2) Å, b=14.9332(3) Å, c=15.9153(4) Å β=94.587(1)°, Z=4; [Cd(C2O4)2(C3N2H4)3(H2O)]∞ (III): monoclinic, space group P21/c (no. 14), a=11.844(2) Å, b=9.066(1) Å, c=18.583(2) Å, β=103.84(2)°, Z=4. While the structure of I is made from CdO5N distorted octahedra linked with oxalate, II and III are built-up from CdO6N, CdO5N2 distorted pentagonal bi-pyramids connected to oxalate units. The framework formulas of II and III are identical and their structures closely related. In all the cases, the networking between the Cd-O/N polyhedra and oxalates give rise to layered architectures with the amine molecules pointing in a direction perpendicular to the layers (in the inter-lamellar region). The difference in the linkages between the oxalates and the Cd atoms in I-III, produces unusual Cd-O-Cd one-dimensional chains, which have been observed for the first time.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. High-performance supercapacitors of Cu-based porous coordination polymer nanowires and the derived porous CuO nanotubes.

    Science.gov (United States)

    Wu, Meng-Ke; Zhou, Jiao-Jiao; Yi, Fei-Yan; Chen, Chen; Li, Yan-Li; Li, Qin; Tao, Kai; Han, Lei

    2017-12-12

    Electrode materials for supercapacitors with one-dimensional porous nanostructures, such as nanowires and nanotubes, are very attractive for high-efficiency storage of electrochemical energy. Herein, ultralong Cu-based porous coordination polymer nanowires (copper-l-aspartic acid) were used as the electrode material for supercapacitors, for the first time. The as-prepared material exhibits a high specific capacitance of 367 F g -1 at 0.6 A g -1 and excellent cycling stability (94% retention over 1000 cycles). Moreover, porous CuO nanotubes were successfully fabricated by the thermal decomposition of this nanowire precursor. The CuO nanotube exhibits good electrochemical performance with high rate capacity (77% retention at 12.5 A g -1 ) and long-term stability (96% retention over 1000 cycles). The strategy developed here for the synthesis of porous nanowires and nanotubes can be extended to the construction of other electrode materials for more efficient energy storage.

  8. 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

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

    Energy Technology Data Exchange (ETDEWEB)

    Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen; Ma, Lu-Fang [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, Henan (China); Wang, Li-Ya, E-mail: gzliuly@126.com [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, Henan (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473061, Henan (China)

    2014-12-15

    Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H{sub 2}O)]){sub n} (1), ([Co(4-Nbdc)(bpp) (H{sub 2}O)]){sub n} (2), ([Ni(4-Nbdc)(bpp)(H{sub 2}O)]·H{sub 2}O){sub n} (3), and ([Mn{sub 2}(3-Nbdc){sub 2}(bib){sub 3}]·2H{sub 2}O){sub n} (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal–carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (6{sup 6}) dia topology and (4{sup 4}.6{sup 10}.8)(4{sup 4}.6{sup 2}) fsc topology, and both of them contain metal–carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)–carboxylate binuclear in 1 (J=1.27 cm{sup −1}) and Ni(II)–carboxylate chain in 3 (J=1.44 cm{sup −1}), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)–carboxylate chain in 4 (J=−0.77 cm{sup −1}). - Highlights: • Four novel coordination polymers were hydrothermally synthesized. • 1 is 1D quasi-trapezoidal chain and 2 is brick-wall layer both with dinuclear units. • 3 and 4 show 3D frameworks both with 1D metal–carboxylate chains. • 1 and 3 exhibit ferromagnetic coupling, while 4 shows antiferromagnetic coupling.

  14. Barium coordination polymers based on fluorinated and fluorine-free benzene-dicarboxylates: Mechanochemical synthesis and spectroscopic characterization

    Science.gov (United States)

    Al-Terkawi, Abdal-Azim; Scholz, Gudrun; Emmerling, Franziska; Kemnitz, Erhard

    2018-05-01

    A series of new Ba-based coordination polymers (CPs) were mechanochemically synthesized by milling Ba-hydroxide samples with perfluorinated and fluorine-free benzene-dicarboxylic acids, including tetrafluoroisophthalic acid (H2mBDC-F4), tetrafluorophthalic acid (H2oBDC-F4), isophthalic acid (H2mBDC) and phthalic acid (H2oBDC). The new fluorinated CPs: [Ba(mBDC-F4)·0.5H2O] (1) and [Ba(oBDC-F4)·1.5H2O] (2) are compared to their nonfluorinated counterparts: [Ba(mBDC)·2.5H2O] (3), and [Ba(oBDC)·1H2O] (4). These materials are thoroughly characterized using powder X-ray diffraction. The products obtained by milling are all hydrated but vary in their water contents. Compositions and local structures are investigated by elemental analysis, thermal analysis, MAS NMR and attenuated total reflection-infrared spectroscopy. These materials exhibit high thermal stabilities but small surface areas that remain unchanged even after thermal treatments.

  15. Weak cooperativity in selected iron(II) 1D coordination polymers

    International Nuclear Information System (INIS)

    Dîrtu, Marinela M.; Gillard, Damien; Naik, Anil D.; Rotaru, Aurelian; Garcia, Yann

    2012-01-01

    The spin crossover behaviour of a new class of Fe II coordination polymers [Fe(phtptrz) 3 ]I 2 (1), [Fe(phtptrz) 3 ](ReO 4 ) 2 •CH 3 OH (2) and [Fe(phtptrz) 3 ]TaF 7 •6H 2 O (3) based on a novel ligand 4-(3 ′ -N-phtalimido-propyl)-1,2,4-triazole (phtptrz), were investigated by temperature dependent 57 Fe Mössbauer spectroscopy and magnetic susceptibility measurements. The adverse effect of bulky substituent on 1,2,4-triazole, favorable supramolecular interactions and influence of increasing anion size on spin crossover profile is discussed. 1 and 2 show thermally induced spin conversions of gradual and incomplete nature with associated thermochromism, and transition temperatures T 1/2 ∼ 163 K and 137 K, respectively. A spin state crossover is also identified for 3.

  16. Two New Preyssler-Type Polyoxometalate-Based Coordination Polymers and Their Application in Horseradish Peroxidase Immobilization.

    Science.gov (United States)

    Du, Jing; Cao, Mei-Da; Feng, Shu-Li; Su, Fang; Sang, Xiao-Jing; Zhang, Lan-Cui; You, Wan-Sheng; Yang, Mei; Zhu, Zai-Ming

    2017-10-17

    Enzyme immobilization is of increasing importance for biocatalysis, for which good supports are critical. Herein, two new Preyssler-type polyoxometalate (POM)-based coordination polymers, namely, {[Cu(H 2 biim) 2 ][{Cu(H 2 biim) 2 (μ-H 2 O)} 2 Cu(H 2 biim)(H 2 O) 2 ]H[({Cu(H 2 biim)(H 2 O) 2 } 0.5 ) 2 ((μ-C 3 HN 2 Cl 2 ){Cu(H 2 biim)} 2 ){Z(H 2 O)P 5 W 30 O 110 }]⋅x H 2 O} n (1: Z=Na, x=9; 2: Z=Ag, x=10; H 2 biim=2,2'-biimidazole) were designed and synthesized. Compounds 1 and 2 exhibit the same skeletons, which contain multiple Cu II complex fragments and penta-supported {ZP 5 W 30 } (Z=Na, Ag) clusters. They were first employed to immobilize horseradish peroxidase (HRP). Results show that compounds 1 and 2 are good supports for HRP immobilization, and exhibit higher enzyme loading, lower loading times, and excellent reusability. The immobilized HRP (HRP/1 or HRP/2) was further applied to detect H 2 O 2 , and good sensitivity, wide linear range, low detection limit, and fast response were achieved. This work shows that POM-based hybrid materials are a new kind of promising support for enzyme immobilization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Anion-directed assembly of lanthanide coordination polymers with SMMs properties based on a dihydrazone ligand

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lina [Henan Polytechnic Univ., Jiaozuo (China). College of Chemistry and Chemical Engineering; Zhengzhou Univ. (China). College of Chemistry and Molecular Engineering; Duan, Peigao; Zhao, Dan [Henan Polytechnic Univ., Jiaozuo (China). College of Chemistry and Chemical Engineering; Liu, Yang; Sun, Jingxian [Henan Polytechnic Univ., Jiaozuo (China). College of Materials Science and Engineering; Du, Chenxia [Zhengzhou Univ. (China). College of Chemistry and Molecular Engineering

    2018-04-01

    Four new Ln(III)-based coordination polymers (CPs), [Eu(HL)Cl{sub 2}(DMF){sub 2}] . (H{sub 2}L) (1), [Dy(HL)Cl{sub 2}(DMF){sub 2}] . (H{sub 2}L) (2), [Er(HL)Cl{sub 2}(DMF)(CH{sub 3}OH)] . (DMF) (3) and [Yb(HL)Cl{sub 2}(DMF)(H{sub 2}O)] . (DMF) (4) (H{sub 2}L=2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine) have been synthesized through the reaction of Ln(III) chloride and H{sub 2}L by using the vapour diffusion method. Interestingly, Cl{sup -} as a template agent plays a vital role in the formation of the target complexes. Single-crystal X-ray diffraction studies indicate that 1 and 2 are isostructural and crystallize in triclinic space group P anti 1, while complexes 3 and 4 are isostructural and crystallize in monoclinic space group C2/c. Variable temperature magnetization measurement (χ{sub M}T-T) demonstrates possible antiferromagnetic interactions in complex 2. Alternating-current (ac) susceptibility measurement furthermore indicated frequency dependence for both the in-phase (χ{sup '}) and out-of-phase (χ'') components in 2, suggesting that there is a slow relaxation behavior of the magnetization, which is typical of single-molecule magnets (SMMs). This is the first time that Ln(III) CPs based on such a dihydrazone ligand has been reported so far.

  18. 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

  19. 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.

  20. Secondary ligand-directed assembly of Co(II) coordination polymers based on a pyridine carboxylate ligand

    International Nuclear Information System (INIS)

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni; Xu, Xiao-Wei; Feng, Yun-Long

    2014-01-01

    To investigate the influence of hydrogen bonds and secondary ligands on the structures and properties of the resulting frameworks, five new Co(II) compounds have been synthesized by the reactions of Co(II) salts and 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL) with four rationally selected dicarboxylic acid ligands. Without secondary ligand, we got one compound [CoL 2 (H 2 O) 2 ] n ·2nH 2 O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H 2 adbc), terephthalic acid (H 2 tpa), thiophene-2,5-dicarboxylic acid (H 2 tdc) and 1,4-benzenedithioacetic acid (H 2 bdtc), four 3D structures [Co 2 L 2 (adbc)] n ·nH 2 O (2), [Co 2 L 2 (tpa)] n (3), [Co 2 L 2 (tdc)] n (4), [Co 2 L 2 (bdtc)(H 2 O)] n (5) were obtained, respectively. It can be observed from the architectures of 1–5 that hydrogen bonds and secondary ligands both have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. The XRPD, TGA data of title polymers and the magnetic properties for 2 and 5 have also been investigated. - Graphical abstract: The structural differences show that the ancillary ligands have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. - Highlights: • Five new Co(II) coordination polymers have been synthesized by solvothermal reactions based on 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL). • The long-flexible ligand (HL) is a good candidate to produce interpenetrating architectures. • The secondary dicarboxylic acid ligands play important roles in the spatial connective fashions and the formation of various dimensional compounds. • The magnetism studies show that both 2 and 5 exhibit antiferromagnetic interactions

  1. 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.

  2. 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

  3. Copper coordination polymers constructed from thiazole-5-carboxylic acid: Synthesis, crystal structures, and structural transformation

    Energy Technology Data Exchange (ETDEWEB)

    Meundaeng, Natthaya; Rujiwatra, Apinpus [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Prior, Timothy J., E-mail: t.prior@hull.ac.uk [Chemistry, University of Hull, Kingston upon Hull HU6 7RX (United Kingdom)

    2017-01-15

    We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu{sup 2+} coordination polymers with different dimensionality, namely, 1D [Cu{sub 2}(5-tza){sub 2}(1,10-phenanthroline){sub 2}(NO{sub 3}){sub 2}] (1), 2D [Cu(5-tza){sub 2}(MeOH){sub 2}] (2), and 3D [Cu(5-tza){sub 2}]·H{sub 2}O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza){sub 2}]·1.5H{sub 2}O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air. - Highlights: • Rare examples of coordination polymers of thiazole-5-carboxylic acid were prepared. • Non-covalent interactions play a key role on the assembly of the complexes in solid state. • Structural transformation of a 2D framework to a 3D upon removal of methanol is observed.

  4. Weak cooperativity in selected iron(II) 1D coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Dirtu, Marinela M.; Gillard, Damien; Naik, Anil D. [Universite Catholique de Louvain, Institute of Condensed Matter and Nanosciences, MOST - Inorganic Chemistry (Belgium); Rotaru, Aurelian [' Stefan cel Mare' University, Department of Electrical Engineering and Computer Science (Romania); Garcia, Yann, E-mail: ann.garcia@uclouvain.be [Universite Catholique de Louvain, Institute of Condensed Matter and Nanosciences, MOST - Inorganic Chemistry (Belgium)

    2012-03-15

    The spin crossover behaviour of a new class of Fe{sup II} coordination polymers [Fe(phtptrz){sub 3}]I{sub 2} (1), [Fe(phtptrz){sub 3}](ReO{sub 4}){sub 2} Bullet CH{sub 3}OH (2) and [Fe(phtptrz){sub 3}]TaF{sub 7} Bullet 6H{sub 2}O (3) based on a novel ligand 4-(3{sup Prime} -N-phtalimido-propyl)-1,2,4-triazole (phtptrz), were investigated by temperature dependent {sup 57}Fe Moessbauer spectroscopy and magnetic susceptibility measurements. The adverse effect of bulky substituent on 1,2,4-triazole, favorable supramolecular interactions and influence of increasing anion size on spin crossover profile is discussed. 1 and 2 show thermally induced spin conversions of gradual and incomplete nature with associated thermochromism, and transition temperatures T{sub 1/2} {approx} 163 K and 137 K, respectively. A spin state crossover is also identified for 3.

  5. 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).

  6. White polymer light-emitting diodes based on star-shaped polymers with an orange dendritic phosphorescent core.

    Science.gov (United States)

    Zhu, Minrong; Li, Yanhu; Cao, Xiaosong; Jiang, Bei; Wu, Hongbin; Qin, Jingui; Cao, Yong; Yang, Chuluo

    2014-12-01

    A series of new star-shaped polymers with a triphenylamine-based iridium(III) dendritic complex as the orange-emitting core and poly(9,9-dihexylfluorene) (PFH) chains as the blue-emitting arms is developed towards white polymer light-emitting diodes (WPLEDs). By fine-tuning the content of the orange phosphor, partial energy transfer and charge trapping from the blue backbone to the orange core is realized to achieve white light emission. Single-layer WPLEDs with the configuration of ITO (indium-tin oxide)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer/CsF/Al exhibit a maximum current efficiency of 1.69 cd A(-1) and CIE coordinates of (0.35, 0.33), which is very close to the pure white-light point of (0.33, 0.33). To the best of our knowledge, this is the first report on star-shaped white-emitting single polymers that simultaneously consist of fluorescent and phosphorescent species. © 2014 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. 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

  9. 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

  10. Two interpenetrating Cu{sup II}/Ni{sup II}-coordinated polymers based on an unsymmetrical bifunctional N/O-tectonic: Syntheses, structures and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yong-Liang [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Department of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shang Luo University, Shang Luo 726000 (China); Wu, Ya-Pan [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Dong, Wen-Wen [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Zhou, Chun-Sheng [Department of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shang Luo University, Shang Luo 726000 (China)

    2015-03-15

    Two new interpenetrating Cu{sup II}/Ni{sup II} coordination polymers, based on a unsymmetrical bifunctional N/O-tectonic 3-(pyrid-4′-yl)-5-(4″-carbonylphenyl)-1,2,4-triazolyl (H{sub 2}pycz), ([Cu-(Hpycz){sub 2}]·2H{sub 2}O){sub n} (1) and ([Ni(Hpycz){sub 2}]·H{sub 2}O){sub n} (2), have been solvothermally synthesized and structure characterization. Single crystal X-ray analysis indicates that compound 1 shows 2-fold parallel interpenetrated 4{sup 4}-sql layers with the same handedness. The overall structure of 1 is achiral—in each layer of doubly interpenetrating nets, the two individual nets have the opposite handedness to the corresponding nets in the adjoining layers—while 2 features a rare 8-fold interpenetrating 6{sup 6}-dia network that belongs to class IIIa interpenetration. In addition, compounds 1 and 2 both show similar paramagnetic characteristic properties. - Graphical abstract: Two new Cu(II)/Ni(II) coordination polymers present 2D parallel 2-fold interpenetrated 4{sup 4}-sql layers and a rare 3D 8-fold interpenetrating 6{sup 6}-dia network. In addition, magnetic susceptibility measurements show similar paramagnetic characteristic for two complexes. - Highlights: • A new unsymmetrical bifunctional N/O-tectonic as 4-connected spacer. • A 2-fold parallel interpenetrated sql layer with the same handedness. • A rare 8-fold interpenetrating dia network (class IIIa)

  11. Syntheses, structures, and photoluminescence of lanthanide coordination polymers based on 4-oxo-1,4-dihydro-2,6-pyridinedicarboxylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Jing; Li, Lei; Peng, Jing-Wei; Qiao, Wei-Wei; Sun, Mei-Mei [College of Chemistry, Tianjin Normal University, Tianjin (China); Gu, Wen [College of Chemistry, Nankai University, Tianjin (China)

    2018-03-15

    Investigating the coordination chemistry of H{sub 2}CDA (4-oxo-1,4-dihydro-2,6-pyridinedicarboxylic acid) with rare earth salts Ln(NO{sub 3}){sub 3} under hydrothermal conditions, structure transformation phenomenon was observed. The ligand, H{sub 2}CDA charged to its position isomer, enol type structure, H{sub 3}CAM (4-hydroxypyridine-2,6-dicarboxylic acid). Six new lanthanide(III) coordination polymers with the formulas [Ln(CAM)(H{sub 2}O){sub 3}]{sub n} [Ln = La (1), Pr, (2)] and {[Ln(CAM)(H_2O)_3].H_2O}{sub n} [Ln = Nd, (3), Sm, (4), Eu, (5), Y, (6)] were synthesized and characterized. The X-ray structure analyses show two kinds of coordination structures. The complexes 1 and 2 and 3-6 are isostructural. Complexes 1 and 2 crystallize in the monoclinic C{sub 2}/c space group, whereas 3-6 crystallize in the monoclinic system with space group P2{sub 1}/n. In the two kinds of structures, H{sub 3}CAM displays two different coordination modes. The Sm{sup III} and Eu{sup III} complexes exhibit the corresponding characteristic luminescence in the visible region at an excitation of 376 nm. (copyright 2018 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Construction of Six Coordination Polymers Based on a 5,5′-(1,2-Ethynyl)bis-1,3-benzenedicarboxylic Ligand: Synthesis, Structure, Gas Sorption, and Magnetic Properties

    KAUST Repository

    Zheng, Bing; Luo, Jiahuan; Wang, Fang; Peng, Yu; Li, Guanghua; Huo, Qisheng; Liu, Yunling

    2013-01-01

    Six novel coordination polymers based on a multifunctional ligand, 5,5'-(1,2-ethynyl)bis-1,3-benzenedicarboxylic (H4EBDC), namely, |(C3H7NO)2(H2O)7(C 2H5OH)3| [Zn2(C18H 6O8)(C10H8N2) 2] (1), |(C3H7NO)3(H2O)30- (CH3CN)2|[Zn 6(C18H6O8)3(C 6H12N2O2)2

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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

  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

    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

  19. 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

  20. Fluorescent sensing of nitroaromatics by two coordination polymers having potential active sites

    Energy Technology Data Exchange (ETDEWEB)

    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); Wang, Jun, E-mail: scwangjun2011@126.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); Wu, Wei-Ping [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); Liu, Jian-Qiang [School of Pharmacy, Guangdong Medical University, Dongguan 523808 (China); Yadav, Reena [Department of Chemistry, Faculty of Science, University of Lucknow, Lucknow 226 007 (India); Kumar, Abhinav, E-mail: abhinavmarshal@gmail.com [Department of Chemistry, Faculty of Science, University of Lucknow, Lucknow 226 007 (India)

    2017-06-15

    Two new d{sup 10} based coordination polymers having formula [Cd(HL1)(L2)] (1) and [Zn(HL1)(L2)] (2) (H{sub 3}L1=5-(4-carboxyphenoxy)isophthalic acid and L2=3-(4-methyl-6-(pyridine-3-yl)pyridine-2-yl)pyridine) have been synthesized and characterized using IR, thermogravimetric analyses (TGA), photoluminescence and single-crystal X-ray diffraction techniques. The single-crystal X-ray investigation reveals that both of 1 and 2 show 2D layer architectures with square lattice topology. The photoluminescence investigation indicates that both 1 and 2 could be a prospective candidate for developing luminescence sensors for the highly sensing of nitroaromatic analytes. Furthermore, the luminescent property of 1 and 2 in different solvents analytes as well as nitrobenzene derivative have been investigated and the observed quenching in fluorescence have been corroborated by theoretical calculations. - Graphical abstract: Two new d{sup 10}-based luminescent MOFs synthesized and their sensing properties towards different nitroaromatics investigated.

  1. 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

  2. Cd (II) and holodirected lead (II) 3D-supramolecular coordination polymers based on nicotinic acid: Structure, fluorescence property and photocatalytic activity

    Science.gov (United States)

    Etaiw, Safaa El-din H.; Abd El-Aziz, Dina M.; Marie, Hassan; Ali, Elham

    2018-05-01

    Two new supramolecular coordination polymers namely {[Cd(NA)2(H2O)]}, SCP 1 and {[Pb(NA)2]}, SCP 2, (NA = nicotinate ligand) were synthesized by self-assembly method and structurally characterized by different analytical and spectroscopic methods. Single-crystal X-ray diffraction showed that SCP 1 extend in three dimensions containing bore structure where the 3D- network is constructed via interweaving zigzag chains. The Cd atom coordinates to (O4N2) atoms forming distorted-octahedral configuration. The structure of SCP 2 extend down the projection of the b-axis creating parallel zigzag 1D-chains connected by μ2-O2 atoms and H-bonds forming a holodirected lead (II) hexagonal bi-pyramid configuration. SCP 2 extend to 3D-network via coordinate and hydrogen bonds. The thermal stability, photoluminescence properties, photocatalytic activity for the degradation of methylene blue dye (MB) under UV-irradiation and sunlight irradiation were also studied.

  3. 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.

  4. Zn(II) coordination polymers with flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Li, Lin [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); Yang, Gao-Shan [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Xiong, Zhi-Qiang [Center for Analysis and Testing, Nanchang Hangkong University, Nanchang 330063 (China); Liu, Hong [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)

    2015-11-15

    Hydrothermal reactions of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) and zinc ions in the presence of N-donor ancillary ligands afford four novel coordination polymers, namely, [Zn{sub 2}(μ{sub 2}-OH)(μ{sub 4}-O){sub 0.5}(L)]·0.5H{sub 2}O (1), [Zn(L)(2,2′-bipy)(H{sub 2}O)] (2), [Zn{sub 3}(L){sub 3}(phen){sub 2}]·H{sub 2}O (3) and [Zn{sub 2}(L){sub 2}(4,4′-bipy)] (4) (2,2′-bipy=2,2′-bipyridine; 4,4′-bipy=4,4′-bipyridine; phen=1,10-phenanthroline). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complex 1 shows a 3-D clover framework consisting of [Zn{sub 4}(µ{sub 4}-O)(µ{sub 2}-OH){sub 2}]{sup 4+} clusters, and exhibits a novel (3,8)-connected topological net with the Schläfli symbol of {3·4·5}{sub 2}{3"4·4"4·5"2·6"6·7"1"0·8"2}, and contains double-stranded and two kinds of meso-helices. 2 displays a helical chain structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with meso-helix chains. 3 displays a 2-D {4"4·6"2} parallelogram structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with single-stranded helical chains. 4 shows a 2-D {4"4·6"2} square structure with left- and right-handed helical chains. Moreover, the luminescent properties of 1–4 have been investigated. - Graphical abstract: Four new Zn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent properties have been investigated. - Highlights: • Four novel Zn(II) coordination polymers with V-shaped ligand were characterized. • Complexes 1–4 show diverse intriguing helical characters. • Fluorescence properties of complexes 1–4 were investigated.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Carboxylate ligands induced structural diversity of zinc(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Hong-Jian, E-mail: hjcheng@cslg.cn; Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin, E-mail: yuanrx@cslg.edu.cn

    2015-12-15

    Solvothermal reactions of Zn(NO{sub 3}){sub 2}·6H{sub 2}O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H{sub 2}bdc), p-phenylenediacetic acid (p-H{sub 2}pda), benzophenone-4,4-dicarboxylic acid (H{sub 2}bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]{sub n} (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H_2O}{sub n} (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H_2O}{sub n} (3). Complexes 1–3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1–3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored. - Graphical abstract: Reactions of Zn(NO{sub 3}){sub 2} and 3,6-(1-imidazolyl)carbazole with 1,4-benzenedicarboxylic acid, p-phenylenediacetic acid or benzophenone-4,4-dicarboxylic acid afforded three coordination polymers with different topologies and photocatalytic activity. - Highlights: • Reactions of 1,4-H{sub 2}bdc, p-H{sub 2}pda or H{sub 2}bpda with 3,6-bmcz and Zn(II) gave three CPs. • Complex 1 is a 3D entanglement. • Complex 2 or 3 is a 3D supramolecular structure based on different 2D layers. • Complex 2 exhibited good catalytic activity of methylene blue photodegradation.

  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. 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...

  14. 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.

  15. 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.

  16. 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.

  17. Synthesis, Crystal Structure, and Luminescence Properties of a New Calcium(II Coordination Polymer Based on L-Malic Acid

    Directory of Open Access Journals (Sweden)

    Duraisamy Senthil Raja

    2013-01-01

    Full Text Available A new calcium coordination polymer [Ca(HL-MA]n (H3L-MA = L-malic acid has been solvothermally synthesized. The structure of the newly synthesized complex has been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, reflectance UV-Vis & IR spectra, powder X-ray diffraction (PXRD, and thermogravimetric analysis (TGA. The single crystal structure analysis showed that the complex forms three-dimensional framework. The new Ca(II complex has displayed very high thermal stability which was inferred from TGA and PXRD results. As far as the optical property of the new complex is concerned, the complex emitted its own characteristic sensitized luminescence.

  18. Structural optimization of interpenetrated pillared-layer coordination polymers for ethylene/ethane separation.

    Science.gov (United States)

    Kishida, Keisuke; Horike, Satoshi; Watanabe, Yoshihiro; Tahara, Mina; Inubushi, Yasutaka; Kitagawa, Susumu

    2014-06-01

    With the goal of achieving effective ethylene/ethane separation, we evaluated the gas sorption properties of four pillared-layer-type porous coordination polymers with double interpenetration, [Zn2(tp)2(bpy)]n (1), [Zn2(fm)2(bpe)]n (2), [Zn2(fm)2(bpa)]n (3), and [Zn2(fm)2(bpy)]n (4) (tp = terephthalate, bpy = 4,4'-bipyridyl, fm = fumarate, bpe = 1,2-di(4-pyridyl)ethylene and bpa = 1,2-di(4-pyridyl)ethane). It was found that 4, which contains the narrowest pores of all of these compounds, exhibited ethylene-selective sorption profiles. The ethylene selectivity of 4 was estimated to be 4.6 at 298 K based on breakthrough experiments using ethylene/ethane gas mixtures. In addition, 4 exhibited a good regeneration ability compared with a conventional porous material. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

  20. 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.

  1. 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

  2. In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers.

    Science.gov (United States)

    Ghani, Milad; Frizzarin, Rejane M; Maya, Fernando; Cerdà, Víctor

    2016-07-01

    Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni-Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15-0.35μgL(-1). The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD's, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6-11.2%. Enrichment factors of 15-21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7-95.3%. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. 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

  4. 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

  5. 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.

  6. The Role of IAEA in Coordinating Research and Transferring Technology in Radiation Chemistry and Processing of Polymers

    International Nuclear Information System (INIS)

    Haji Saeid, M.

    2006-01-01

    The IAEA has been playing a significant role in fostering developments in radiation technology in general and radiation processing of polymers in particular, among its Member States (MS) and facilitate know-how/technology transfer to developing MS. The former is usually achieved through coordinated research projects (CRP) and thematic technical meetings, while the latter is mainly accomplished through Technical Cooperation (TC) projects. Coordinated research projects encourage research on, and development and practical application of, radiation technology to foster exchange of scientific and technical information. The CRP brings together typically 10 - 15 groups of participants to share and complement core competencies and work on specific areas of development needed to benefit from an emerging radiation technique and its applications. The technical cooperation (TC) programme helps Member States realize their development priorities through the application of appropriate radiation technology. TC builds national capacities through training, expert advice and delivery of equipment. The impact of the IAEA's efforts is visible by the progress noticeable in adoption of radiation technology and/or growth in the range of activities in several MS in different regions. The IAEA has implemented several coordinated research projects (CRP) recently, including one on-going project, in the field of radiation processing of polymeric materials. The CRPs facilitated the acquisition and dissemination of know-how and technology for controlling of degradation effects in radiation processing of polymers, radiation synthesis of stimuli-responsive membranes, hydrogels and absorbents for separation purposes and the use of radiation processing to prepare biomaterials for applications in medicine. A number of technical cooperation projects have been implemented in this field to strengthen the capability of developing Member States and to create awareness in the industries about the technical

  7. The role of IAEA in coordinating research and transferring technology in radiation chemistry and processing of polymers

    Energy Technology Data Exchange (ETDEWEB)

    Haji-Saeid, M. [International Atomic Energy Agency (IAEA), Wagramer Strasse 5, A-1400 Vienna (Austria)], E-mail: M.Haji-Saeid@iaea.org; Sampa, M.H.; Ramamoorthy, N. [International Atomic Energy Agency (IAEA), Wagramer Strasse 5, A-1400 Vienna (Austria); Gueven, O. [Hacettepe University, Department of Chemistry, Ankara (Turkey); Chmielewski, A.G. [Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warsaw (Poland)

    2007-12-15

    The IAEA has been playing a significant role in fostering developments in radiation technology in general and radiation processing of polymers in particular, among its Member States (MS) and facilitate know-how/technology transfer to developing MS. The former is usually achieved through coordinated research projects (CRP) and thematic technical meetings, while the latter is mainly accomplished through technical cooperation (TC) projects. Coordinated research projects encourage research on, and development and practical application of, radiation technology to foster exchange of scientific and technical information. The technical cooperation (TC) programme helps Member States to realize their development priorities through the application of appropriate radiation technology. The IAEA has implemented several coordinated research projects (CRP) recently, including one on-going project, in the field of radiation processing of polymeric materials. The CRPs facilitated the acquisition and dissemination of know-how and technology for controlling of degradation effects in radiation processing of polymers, radiation synthesis of stimuli-responsive membranes, hydrogels and absorbents for separation purposes and the use of radiation processing to prepare biomaterials for applications in medicine. The IAEA extends cooperation to well-known international conferences dealing with radiation technology to facilitate participation of talented scientists from developing MS and building collaborations. The IAEA published technical documents, covering the findings of thematic technical meetings (TM) and coordinated research projects have been an important source of valuable practical information.

  8. The role of IAEA in coordinating research and transferring technology in radiation chemistry and processing of polymers

    International Nuclear Information System (INIS)

    Haji-Saeid, M.; Sampa, M.H.; Ramamoorthy, N.; Gueven, O.; Chmielewski, A.G.

    2007-01-01

    The IAEA has been playing a significant role in fostering developments in radiation technology in general and radiation processing of polymers in particular, among its Member States (MS) and facilitate know-how/technology transfer to developing MS. The former is usually achieved through coordinated research projects (CRP) and thematic technical meetings, while the latter is mainly accomplished through technical cooperation (TC) projects. Coordinated research projects encourage research on, and development and practical application of, radiation technology to foster exchange of scientific and technical information. The technical cooperation (TC) programme helps Member States to realize their development priorities through the application of appropriate radiation technology. The IAEA has implemented several coordinated research projects (CRP) recently, including one on-going project, in the field of radiation processing of polymeric materials. The CRPs facilitated the acquisition and dissemination of know-how and technology for controlling of degradation effects in radiation processing of polymers, radiation synthesis of stimuli-responsive membranes, hydrogels and absorbents for separation purposes and the use of radiation processing to prepare biomaterials for applications in medicine. The IAEA extends cooperation to well-known international conferences dealing with radiation technology to facilitate participation of talented scientists from developing MS and building collaborations. The IAEA published technical documents, covering the findings of thematic technical meetings (TM) and coordinated research projects have been an important source of valuable practical information

  9. Cd(II)-coordination polymers based on tetracarboxylic acid and diverse bis(imidazole) ligands: Synthesis, structural diversity and photoluminescence 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); Yeşilel, Okan Zafer [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Taş, Murat [Department of Science Education, Education Faculty, Ondokuz Mayıs University, 55139 Samsun (Turkey)

    2017-01-15

    Three new Cd(II)-coordination polymers, namely, ([Cd{sub 2}(μ{sub 6}-ao{sub 2}btc)(μ-1,5-bipe){sub 2}]·2H{sub 2}O){sub n} (1), ([Cd{sub 2}(μ{sub 6}-ao{sub 2}btc)(μ-1,4-bix){sub 2}]{sub n}·2DMF) (2) and ([Cd{sub 2}(μ{sub 8}-abtc)(μ-1,4-betix)]·DMF·H{sub 2}O){sub n} (3) (ao{sub 2}btc=di-oxygenated form of 3,3′,5,5′-azobenzenetetracarboxylate, 1,5-bipe: 1,5-bis(imidazol-1yl)pentane, 1,4-bix=1,4-bis(imidazol-1ylmethyl)benzene, 1,4-betix=1,4-bis(2-ethylimidazol-1ylmethyl)benzene) were synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1–3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the rare sqc27 topology. When semi-flexible substituted bis(imidazole) linker was used, 3D framework of complex 3 was obtained with the paddlewheel Cd{sub 2}(CO{sub 2}){sub 4}-type binuclear SBU. Moreover, thermal and photoluminescence properties of the complexes were determined in detailed. - Graphical abstract: In this study, three novel Cd(II)-coordination polymers were synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1–3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the rare sqc27 topology. When semi

  10. Colorimetric assay for on-the-spot alcoholic strength sensing in spirit samples based on dual-responsive lanthanide coordination polymer particles with ratiometric fluorescence

    International Nuclear Information System (INIS)

    Deng, Jingjing; Shi, Guoyue; Zhou, Tianshu

    2016-01-01

    This study demonstrates a new strategy for colorimetric detection of alcoholic strength (AS) in spirit samples based on dual-responsive lanthanide infinite coordination polymer (Ln-ICP) particles with ratiometric fluorescence. The ICP used in this study are composed of two components: one is the supramolecular Ln-ICP network formed by the coordination between the ligand 2,2’-thiodiacetic acid (TDA) and central metal ion Eu"3"+; and the other is a fluorescent dye, i.e., coumarin 343 (C343), both as the cofactor ligand and as the sensitizer, doped into the Ln-ICP network through self-adaptive chemistry. Upon being excited at 300 nm, the red fluorescence of Ln-ICP network itself at 617 nm is highly enhanced due to the concomitant energy transfer from C343 to Eu"3"+, while the fluorescence of C343 at 495 nm is supressed. In pure ethanol solvent, the as-formed C343@Eu-TDA is well dispersed and quite stable. However, the addition of water into ethanolic dispersion of C343@Eu-TDA destructs Eu-TDA network structure, resulting in the release of C343 from ICP network into the solvent. Consequently, the fluorescence of Eu-TDA turns off and the fluorescence of C343 turns on, leading to the fluorescent color change of the dispersion from red to blue, which constitutes a new mechanism for colorimetric sensing of AS in commercial spirit samples. With the method developed here, we could clearly distinguish the AS of different spirit samples within a wide linear range from 10% vol to 100% vol directly by “naked eye” with the help of UV-lamp (365 nm). This study not only offers a new method for on-the-spot visible detection of AS, but also provides a strategy for dual-responsive sensing mode by rational designing the optical properties of the Ln-ICP network and the guest, respectively. - Highlights: • Dual responsive lanthanide coordination polymer particles C343@Eu-TDA were synthesized. • The guest molecular coumarin 343 sensitized the luminescence of Eu-TDA network

  11. Colorimetric assay for on-the-spot alcoholic strength sensing in spirit samples based on dual-responsive lanthanide coordination polymer particles with ratiometric fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Jingjing, E-mail: jjdeng@des.ecnu.edu.cn [School of Ecological and Environmental Sciences, East China Normal University, 500 Dongchuan Road, Shanghai 200241 (China); Shi, Guoyue [Department of Chemistry, East China Normal University, 500 Dongchuan Road, Shanghai 200241 (China); Zhou, Tianshu, E-mail: tszhou@des.ecnu.edu.cn [School of Ecological and Environmental Sciences, East China Normal University, 500 Dongchuan Road, Shanghai 200241 (China)

    2016-10-26

    This study demonstrates a new strategy for colorimetric detection of alcoholic strength (AS) in spirit samples based on dual-responsive lanthanide infinite coordination polymer (Ln-ICP) particles with ratiometric fluorescence. The ICP used in this study are composed of two components: one is the supramolecular Ln-ICP network formed by the coordination between the ligand 2,2’-thiodiacetic acid (TDA) and central metal ion Eu{sup 3+}; and the other is a fluorescent dye, i.e., coumarin 343 (C343), both as the cofactor ligand and as the sensitizer, doped into the Ln-ICP network through self-adaptive chemistry. Upon being excited at 300 nm, the red fluorescence of Ln-ICP network itself at 617 nm is highly enhanced due to the concomitant energy transfer from C343 to Eu{sup 3+}, while the fluorescence of C343 at 495 nm is supressed. In pure ethanol solvent, the as-formed C343@Eu-TDA is well dispersed and quite stable. However, the addition of water into ethanolic dispersion of C343@Eu-TDA destructs Eu-TDA network structure, resulting in the release of C343 from ICP network into the solvent. Consequently, the fluorescence of Eu-TDA turns off and the fluorescence of C343 turns on, leading to the fluorescent color change of the dispersion from red to blue, which constitutes a new mechanism for colorimetric sensing of AS in commercial spirit samples. With the method developed here, we could clearly distinguish the AS of different spirit samples within a wide linear range from 10% vol to 100% vol directly by “naked eye” with the help of UV-lamp (365 nm). This study not only offers a new method for on-the-spot visible detection of AS, but also provides a strategy for dual-responsive sensing mode by rational designing the optical properties of the Ln-ICP network and the guest, respectively. - Highlights: • Dual responsive lanthanide coordination polymer particles C343@Eu-TDA were synthesized. • The guest molecular coumarin 343 sensitized the luminescence of Eu

  12. 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.

  13. 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. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. 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.

  15. Lattice architecture effect on the cooperativity of spin transition coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Chiruta, Daniel [Faculty of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Ştefan cel Mare University, Suceava 720229 (Romania); GEMaC, Université de Versailles Saint-Quentin-en-Yvelines, CNRS-UVSQ (UMR 8635), 78035 Versailles Cedex (France); LISV, Université de Versailles Saint-Quentin-en-Yvelines, 78140 Velizy (France); Jureschi, Catalin-Maricel; Rotaru, Aurelian, E-mail: jorge.linares@uvsq.fr, E-mail: rotaru@eed.usv.ro [Faculty of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Ştefan cel Mare University, Suceava 720229 (Romania); Linares, Jorge, E-mail: jorge.linares@uvsq.fr, E-mail: rotaru@eed.usv.ro [GEMaC, Université de Versailles Saint-Quentin-en-Yvelines, CNRS-UVSQ (UMR 8635), 78035 Versailles Cedex (France); Garcia, Yann [Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur, 1, 1348 Louvain-la-Neuve (Belgium)

    2014-02-07

    We have investigated in the framework of the Ising-like model, by means of Monte Carlo Metropolis method with open boundary condition, the architecture effect on the cooperativity of spin transition coordination polymers. We have analyzed the influence of several physical parameters (size, pressure, and edge effects) on different lattice architectures which were in good agreement with reported experimental data. We show that the cooperativity of a spin crossover system, characterized by the same number of molecules and the same short- and long-range interaction parameters, is progressively enhanced when going from a 1D chain to a 1D ladder type lattice and to a 2D square lattice.

  16. 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

  17. Hexafluoridophosphate partial hydrolysis leading to the one-dimensional coordination polymer [{Cu(xantphos)(µ-PO2F2)}n

    OpenAIRE

    Keller, S.; Brunner, F.; Prescimone, A.; Constable, E. C.; Housecroft, C. E.

    2015-01-01

    The one-dimensional coordination polymer [{Cu(xantphos)(μ-PO2F2)}n] (xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) is reported, the first extended structure in which copper(I) centres are linked by μ-PO2F2 units.

  18. 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

  19. Three-Dimensional Cadmium(II Cyanide Coordination Polymers with Ethoxy-, Butoxy- and Hexyloxy-ethanol

    Directory of Open Access Journals (Sweden)

    Takeshi Kawasaki

    2016-08-01

    Full Text Available The three novel cadmium(II cyanide coordination polymers with alkoxyethanols, [Cd(CN2(C2H5OCH2CH2OH]n (I, [{Cd(CN2(C4H9OCH2CH2OH}3{Cd(CN2}]n (II and [{Cd(CN2(H2O2}{Cd(CN2}3·2(C6H13OCH2CH2OH]n (III, were synthesized and charcterized by structural determination. Three complexes have three-dimensional Cd(CN2 frameworks; I has distorted tridymite-like structure, and, II and III have zeolite-like structures. The cavities of Cd(CN2 frameworks of the complexes are occupied by the alkoxyethanol molecules. In I and II, hydroxyl oxygen atoms of alkoxyethanol molecules coordinate to the Cd(II ions, and the Cd(II ions exhibit slightly distort trigonal-bipyramidal coordination geometry. In II, there is also tetrahedral Cd(II ion which is coordinated by only the four cyanides. The hydroxyl oxygen atoms of alkoxyethanol connects etheric oxygen atoms of the neighboring alkoxyethanol by hydrogen bond in I and II. In III, hexyloxyethanol molecules do not coordinate to the Cd(II ions, and two water molecules coordnate to the octahedral Cd(II ions. The framework in III contains octahedral Cd(II and tetrahedral Cd(II in a 1:3 ratio. The Cd(CN2 framework structures depended on the difference of alkyl chain for alkoxyethanol molecules.

  20. Synthesis, crystal structure and catalytic effect on thermal decomposition of RDX and AP: An energetic coordination polymer [Pb{sub 2}(C{sub 5}H{sub 3}N{sub 5}O{sub 5}){sub 2}(NMP)·NMP]{sub n}

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jin-jian [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Yancheng Teachers College, Yancheng 224002 (China); Liu, Zu-Liang, E-mail: liuzl@mail.njust.edu.cn [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Cheng, Jian [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Yancheng Teachers College, Yancheng 224002 (China); Fang, Dong, E-mail: fangdong106@163.com [Yancheng Teachers College, Yancheng 224002 (China)

    2013-04-15

    An energetic lead(II) coordination polymer based on the ligand ANPyO has been synthesized and its crystal structure has been got. The polymer was characterized by FT-IR spectroscopy, elemental analysis, DSC and TG-DTG technologies. Thermal analysis shows that there are one endothermic process and two exothermic decomposition stages in the temperature range of 50–600 °C with final residues 57.09%. The non-isothermal kinetic has also been studied on the main exothermic decomposition using the Kissinger's and Ozawa–Doyle's methods, the apparent activation energy is calculated as 195.2 KJ/mol. Furthermore, DSC measurements show that the polymer has significant catalytic effect on the thermal decomposition of ammonium perchlorate. - Graphical abstract: An energetic lead(II) coordination polymer of ANPyO has been synthesized, structurally characterized and properties tested. Highlights: ► We have synthesized and characterized an energetic lead(II) coordination polymer. ► We have measured its molecular structure and thermal decomposition. ► It has significant catalytic effect on thermal decomposition of AP.

  1. 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.

  2. A two-dimensional Zn coordination polymer with a three-dimensional supramolecular architecture

    Directory of Open Access Journals (Sweden)

    Fuhong Liu

    2017-10-01

    Full Text Available The title compound, poly[bis{μ2-4,4′-bis[(1,2,4-triazol-1-ylmethyl]biphenyl-κ2N4:N4′}bis(nitrato-κOzinc(II], [Zn(NO32(C18H16N62]n, is a two-dimensional zinc coordination polymer constructed from 4,4′-bis[(1H-1,2,4-triazol-1-ylmethyl]-1,1′-biphenyl units. It was synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The ZnII cation is located on an inversion centre and is coordinated by two O atoms from two symmetry-related nitrate groups and four N atoms from four symmetry-related 4,4′-bis[(1H-1,2,4-triazol-1-ylmethyl]-1,1′-biphenyl ligands, forming a distorted octahedral {ZnN4O2} coordination geometry. The linear 4,4′-bis[(1H-1,2,4-triazol-1-ylmethyl]-1,1′-biphenyl ligand links two ZnII cations, generating two-dimensional layers parallel to the crystallographic (132 plane. The parallel layers are connected by C—H...O, C—H...N, C—H...π and π–π stacking interactions, resulting in a three-dimensional supramolecular architecture.

  3. (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.

  4. 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.

  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. Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

    Science.gov (United States)

    Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

    2017-07-01

    Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

  7. Syntheses, structures and luminescence for zinc coordination polymers based on a multifunctional 4′-(3-carboxyphenyl)- 3,2′:6′,3″-terpyridine ligand

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Yue; Yang, Meng-Lin; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN; Xu, Bing; Wang, Xiaofang; Xue, Ganglin

    2016-07-15

    Six new coordination polymers, [ZnLCl]{sub n}(1), [ZnL{sub 2}]{sub n}·2nH{sub 2}O (2), [Zn{sub 2}L(o-bdc)(OH)]{sub n}·0.5nH{sub 2}O (3), [Zn{sub 2}L(m-bdc)(OH)]{sub n}·nH{sub 2}O (4), [Zn{sub 2}L{sub 2}(p-bdc) (H{sub 2}O){sub 2}]{sub n}·nH{sub 2}O (5), [Zn{sub 2}L(1,2,4-btc)(H{sub 2}O)]{sub n}(6), (HL=4′-(3-carboxyphenyl)- 3,2′:6′,3″-terpyridine, H{sub 2}(o-bdc)= benzene-1,2-dicarboxylic acid, H{sub 2}(m-bdc)= benzene-1,3-dicarboxylic acid, H{sub 2}(p-bdc)= benzene-1,4-dicarboxylic acid, H{sub 3}(1,2,4-btc)= benzene-1,2,4-tricarboxylic acid) have been synthesized under the hydrothermal conditions. Compound 1 displays a 3-connected 2D network structure with point symbol of {8"2.10}. Compound 2 exhibits 1D infinite loop chain structure. Compound 3 possesses a (3,8)-connected 3D framework composed of tetranuclear units with point symbol of {4"3}{sub 2}{4"6.6"1"8.8"4}. Compound 4 features a typical 2D hcb network based on tetranuclear zinc(II) units with point symbol of {4"4.6"2}. Compound 5 presents a classical two-fold penetration sql network with point symbol of {6"3}. Compound 6 can be seen as a (3,3,6)-connected 3D net with point symbol of {4"2.6"4.8"9}{4"2.6}{6"3}. The thermal stability and luminescent properties of compounds 1–6 in the solid state are discussed in detail. - Graphical abstract: Six new Zn(II) coordination polymers based on multicarboxylate and terpyridyl derivative ligands have synthesized under the hydrothermal conditions and the thermal stability and luminescence are discussed. Display Omitted.

  8. 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.

  9. Syntheses, structures and selective dye adsorption of five formic-based coordination polymers prepared by in-situ hydrolysis of N, N′-dimethylformamide

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei; Zhang, Xia; Wang, Mei [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100 (China); Jin, Fan [Max Planck Institute for Terrestrial Microbiology & LOEWE Center for Synthetic Microbiology (SYNMIKRO), Marburg 35043 (Germany); Fan, Yu-hua [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100 (China)

    2017-04-15

    Five functional coordination polymers (formic-based CPs) namely: ([Cu{sub 2}(CHOO){sub 3}(bibp){sub 2}]·CHOO){sub n} (1), ([Co{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O)n (2), ([Ni{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O){sub n} (3) [Co(CHOO){sub 2}(bbibp)]{sub n} (4) and [Zn(CHOO){sub 2}(bbibp)]{sub n} (5) (bibp=4,4′-bis(imidazolyl)biphenyl, bbibp=4,4′-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N′-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1–3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member between the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C–H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.

  10. Selective high capacity adsorption of Congo red, luminescence and antibacterial assessment of two new cadmium(II) coordination polymers

    Science.gov (United States)

    Beheshti, Azizolla; Nozarian, Kimia; Ghamari, Narges; Mayer, Peter; Motamedi, Hossein

    2018-02-01

    Coordination polymers [CdCl(NCS)L]n (1) and {[Cd2I4(L)2]·H2O·DMF}n (2) (where L = 1, 1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione)) were synthesized and structurally characterized. Compounds 1 and 2 both possess a tetrahedral arrangement with CdS2NCl and CdS2I2 cores, respectively. In these structures, the flexible thione ligands adopt a μ- bridging coordination mode to form 1D chains along the b-axis. The 1D chains are join together by C-H--Cl hydrogen bonds (in 1) and water molecules (in 2) to create a 2D supramolecular framework with an ABAB…packing mode. Remarkably, compounds 1 and 2 in particular polymer 1 exhibit excellent capacity to adsorb Congo red (CR) with high selectivity. The experimental data demonstrate that the mechanism of sorption process can be described by the Elovich and pseudo second order kinetic models for 1 and 2, respectively. Furthermore, the possible mechanism of CR absorption was investigated by UV-Vis and solid state fluorescence spectra for the title polymers. In addition, the antibacterial assessment of these compounds have also been studied.

  11. A series of Zn/Cd coordination polymers constructed from 1,4-naphthalenedicarboxylate and N-donor ligands: Syntheses, structures and luminescence sensing of Cr{sup 3+} in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Dong-Cheng [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou 515063 (China); Fan, Yan; Si, Chang-Dai; Wu, Ya-Jun; Dong, Xiu-Yan; Yang, Yun-Xia; Yao, Xiao-Qiang [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Liu, Jia-Cheng, E-mail: jcliu8@nwnu.edu.cn [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China)

    2016-09-15

    A novel series of Zn/Cd coordination polymers based on H{sub 3}L, namely, [Zn{sub 2}(HL){sub 2}(bipy){sub 2}(H{sub 2}O){sub 6}]{sub n} (1), [Zn(HL)(phen)]{sub n} (2), [Cd{sub 3}L{sub 2}(bbi){sub 3}]{sub n} (3), [Zn{sub 3}L{sub 2}(bbi){sub 3}]{sub n} (4) [(H{sub 3}L =4-[(1-carboxynaphthalen-2-yl)oxy]phthalic acid, bipy =4,4′-bipyridine, phen =1,10-phenanthroline, bbi =1,1′-(1,4-butanediyl)bis(imidazole] have been successfully synthesized by solvothermal reaction. Compound 1 possesses two diverse 1D chains constructed by different bipy coligands, which were further connected to form a 3D supramolecular architecture by hydrogen bonding interactions. Compound 2 possesses a complicated 1D chain based on secondary building unit (SBU) with binuclear Zn cluster. Compounds 3 and 4 exhibit similar 2D→3D framework, which can be rationalized as (3,4,4)-connected 3D net with a Schläfli symbol of (6{sup 3}.8.10{sup 2}){sub 2}(6{sup 3}){sub 2}(6{sup 4}.8.10). In particular, compound 3 exhibited a high sensitivity for Cr{sup 3+} in aqueous solutions, which suggest that compound 3 is a promising luminescent probe for selectively sensing Cr{sup 3+}. - Graphical abstract: A series of novel Zn/Cd coordination polymers have been successfully synthesized by solvothermal reaction. The unique 3D Cd{sup 2+} polymer containing bbi as second ligand demonstrates high sensitivity for detection of toxic Cr{sup 3+} in aqueous solutions. Display Omitted - Highlights: • π-conjugated semirigid tricarboxylate ligands with naphthalene rings(H{sub 3}L) were rationally designed. • Four Zn/Cd coordination polymers based on H{sub 3}L have been successfully synthesized by solvothermal reaction. • Compound 3 is a promising luminescent probe for selectively sensing Cr{sup 3+} with high sensitivity in aqueous solutions.

  12. Three coordination polymers constructed from 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid: Synthesis, crystal structure and properties

    Science.gov (United States)

    Zhai, Dandan; Sun, Wujuan; Fan, Fei; Liao, Xuzhao; Chen, Sanping; Yang, Xuwu

    2017-04-01

    Three new coordination polymers, namely, {[Co2(TPA)(μ3-O)3]·0.5DMA}n (1), {[Co(H2TPA)(bibp)(H2O)3]·H2O}n (2) and {[Cd3(TPA)2(phen)4]·4H2O}n (3), (H3TPA = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid, bibp = 4,4'-bis(imidazolyl)biphenyl, phen = 1,10-phenanthroline and DMA = N,N-dimethylacetamide), have been synthesized under solvothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. Polymer 1 exhibits a three-dimensional (3D) structure constructed from 5-connected secondary building units (SBUs) [Co3(μ3-O)] and 3-connected H3TPA ligands. Polymer 2 has a 1D zigzag polymer chain connected by H3TPA and bibp ligands. Polymer 3 features an unusual 3D framework with a (3,4,2)-connected {4; 6;8}{4; 62;83} topology. Moreover, the thermal stabilities of 1-3 and photoluminescence properties of 3 have been investigated. Magnetic susceptibility measurements indicate that polymers 1-2 display antiferromagnetic exchange properties.

  13. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

    KAUST Repository

    Chen, Xia; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

    2012-01-01

    Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

  14. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

    KAUST Repository

    Chen, Xia

    2012-05-02

    Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

  15. 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

  16. 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.

  17. Syntheses and Characterization of New Nickel Coordination Polymers with 4,4’-Dipyridylsulfide. Dynamic Rearrangements of One-Dimensional Chains Responding to External Stimuli: Temperature Variation and Guest Releases/Re-Inclusions

    Directory of Open Access Journals (Sweden)

    Hiroyuki Kawaguchi

    2010-08-01

    Full Text Available Crystal structures and dynamic rearrangements of one-dimensional coordination polymers with 4,4'-dipyridylsulfide (dps have been studied. Reaction of Ni(NO32·6H2O with dps in EtOH yielded [Ni(dps2(NO32]·EtOH (1, which had channels filled with guest EtOH molecules among the four Ni(dps2 chains. This coordination polymer reversibly transformed the channel structure responding to temperature variations. Immersion of 1 in m-xylene released guest EtOH molecules to yield a guest-free coordination polymer [Ni(dps2(NO32] (2a, which was also obtained by treatment of Ni(NO32·6H2O with dps in MeOH. On the other hand, removal of the guest molecules from 1 upon heating at 130 °C under reduced pressure produced a guest-free coordination polymer [Ni(dps2(NO32] (2b. Although the 2a and 2b guest-free coordination polymers have the same formula, they showed differences in the assembled structures of the one-dimensional chains. Exposure of 2b to EtOH vapor reproduced 1, while 2a did not convert to 1 in a similar reaction. Reaction of Ni(NO32·6H2O with dps in acetone provided [Ni(dps(NO32(H2O]·Me2CO (4 with no channel structure. When MeOH or acetone was used as a reaction solvent, the [Ni(dps2(NO32]·(guest molecule type coordination polymer ,which was observed in 1, was not formed. Nevertheless, the reaction of Ni(NO32·6H2O with dps in MeOH/acetone mixed solution produced [Ni(dps2(NO32]·0.5(MeOH·acetone (5, which has an isostructural Ni-dps framework to 1.

  18. 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.

  19. 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.

  20. 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.

  1. A two-dimensional Zn coordination polymer with a three-dimensional supra-molecular architecture.

    Science.gov (United States)

    Liu, Fuhong; Ding, Yan; Li, Qiuyu; Zhang, Liping

    2017-10-01

    The title compound, poly[bis-{μ 2 -4,4'-bis-[(1,2,4-triazol-1-yl)meth-yl]biphenyl-κ 2 N 4 : N 4' }bis-(nitrato-κ O )zinc(II)], [Zn(NO 3 ) 2 (C 18 H 16 N 6 ) 2 ] n , is a two-dimensional zinc coordination polymer constructed from 4,4'-bis-[(1 H -1,2,4-triazol-1-yl)meth-yl]-1,1'-biphenyl units. It was synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Zn II cation is located on an inversion centre and is coordinated by two O atoms from two symmetry-related nitrate groups and four N atoms from four symmetry-related 4,4'-bis-[(1 H -1,2,4-triazol-1-yl)meth-yl]-1,1'-biphenyl ligands, forming a distorted octa-hedral {ZnN 4 O 2 } coordination geometry. The linear 4,4'-bis-[(1 H -1,2,4-triazol-1-yl)meth-yl]-1,1'-biphenyl ligand links two Zn II cations, generating two-dimensional layers parallel to the crystallographic (132) plane. The parallel layers are connected by C-H⋯O, C-H⋯N, C-H⋯π and π-π stacking inter-actions, resulting in a three-dimensional supra-molecular architecture.

  2. N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Zhi-Hang [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Han, Min-Le [College of Chemistry and Chemical Engineering, Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471022 (China); Wu, Ya-Pan; Dong, Wen-Wen [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Lu, Jack Y., E-mail: lu@uhcl.edu [Department of Chemistry, University of Houstons-Clear Lake, Houston, TX 77058 (United States)

    2016-10-15

    Two new Co(II) coordination polymers(CPs), namely [Co{sub 2}(bpe){sub 2}(Hbppc)]{sub n} (1) and [Co{sub 3}(μ{sub 3}-OH)(bppc)(bpm)(H{sub 2}O)]·3H{sub 2}O (2) (H{sub 5}bppc=biphenyl-2,4,6,3′,5′-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co{sub 3}(μ{sub 3}-OH)]{sup 5+} units with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system. - Graphical abstract: Two new Co(II) coordination polymers with bi- and trinuclear units have been obtained. 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology and antiferromagnetic interactions between the adjacent Co(II) ions, while 2 is a binodal (5,7)-connected 3D network with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology and a ferromagnetic system. - Highlights: • Two Co(II) coordination polymers with different multimetallic clusters as building units. • A (4,6)-connected fsc net and a (5,7)-connected 3D network. • A antiferromagnetic coupling for 1 and A ferromagnetic coupling for 2.

  3. 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

  4. Synthesis of metalloporphyrin-based conjugated microporous polymer spheres directed by bipyridine-type ligands.

    Science.gov (United States)

    Ji, Guipeng; Yang, Zhenzhen; Zhao, Yanfei; Zhang, Hongye; Yu, Bo; Xu, Jilei; Xu, Huanjun; Liu, Zhimin

    2015-04-30

    Zinc porphyrin (TP-Zn)-based conjugated microporous polymer (Zn-CMP) spheres were obtained via Sonagashira-Hagihara cross coupling reactions between 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin-Zn(II) and brominated monomers directed by bidentate bipyridine (BP)-type ligands for the first time, and the sphere diameters could be adjusted from 320 to 740 nm. The coordination between BP and TP-Zn was proved to be the key to forming spheres.

  5. Synthesis, Structural Characterization and Catalytic Activity of A Cu(II Coordination Polymer Constructed from 1,4-Phenylenediacetic Acid and 2,2’-Bipyridine

    Directory of Open Access Journals (Sweden)

    Wang Li-Hua

    2017-04-01

    Full Text Available In order to study the catalytic activity of Cu(II coordination polymer material, a novel 1D chained Cu(II coordination polymer material, [CuL(bipy(H2O5]n (A1 (H2L = 1,4-phenylenediacetic acid, bipy = 2,2’-bipyridine, has been prepared by the reaction of 1,4-phenylenediacetic acid, 2,2’-bipyridine, Cu(CH3COO2·H2O and NaOH. The composition of A1 was determined by elemental analysis, IR spectra and single crystal X-ray diffraction. The results of characterization show that each Cu(II atom adopts six-coordination and forms a distorted octahedral configuration. The catalytic activity and reusability of A1 catalyst for A3 coupling reaction of benzaldehyde, piperidine, and phenylacetylene have been investigated. And the results show that the Cu(II complex catalyst has good catalytic activity with a maximum yield of 54.3% and stability. Copyright © 2017 BCREC GROUP. All rights reserved Received: 21st October 2016; Revised: 17th November 2016; Accepted: 22nd November 2016 How to Cite: Li-Hua, W., Lei, L., Xin, W. (2017. Synthesis, Structural Characterization and Catalytic Activity of A Cu(II Coordination Polymer Constructed from 1,4-Phenylenediacetic Acid and 2,2’-Bipyridine. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 113-118 (doi:10.9767/bcrec.12.1.735.113-118 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.735.113-118

  6. Construction, Structural Diversity and Properties of Five Coordination Polymers Based on 5-Nitroisophthalate and Bis(imidazole) Linkers

    Science.gov (United States)

    Arıcı, Mürsel

    2018-06-01

    Five coordination polymers, namely, [Cd(μ3-5-nip)(μ-obix)]n (1), [Co(μ3-5-nip)(μ-obix)]n (2), [Zn(μ-5-nip)(μ-obix)]n (3 and 4) and [Cd(μ-5-nip)(μ-bisobix)]n (5) (5-nip: 5-nitroisophthalate, obix: 1,2-bis(imidazol-1ylmethyl)benzene, bisobix: 1,2-bis(2-isopropylimidazol-1ylmethyl)benzene) were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). X-ray results showed that the complexes displayed structural diversity depending on metal ions and conformations of bis(imidazole) linkers. Complexes 1 and 2 were 1D structures and obix ligand displayed cis-conformation. Complexes 3 and 4 exhibited 2D and 3D structures with same components depending on obix conformation. In complex 5, 3D+3D→3D interpenetrated structure was obtained with dia topology when bisobix having sterically hindered groups on imidazole rings was used. Moreover, thermal, photoluminescence and optical properties of the complexes were also investigated.

  7. Synthesis and photoluminescence properties of novel Schiff base type polymer-rare earth complexes containing furfural-based bidentate Schiff base ligands

    Science.gov (United States)

    Gao, Baojiao; Zhang, Dandan; Li, Yanbin

    2018-03-01

    Luminescent polymer-rare earth complexes are an important class of photoluminescence and electroluminescence materials. Via molecular design, two furfural-based bidentate Schiff base ligands, furfural-aniline (FA) type ligand and furfural-cyclohexylamine (FC) type ligand, were bonded on the side chains of polysulfone (PSF), respectively, forming two functionalized macromolecules, PSF-FA and PSF-FC. And then through respective coordination reactions of the two functionalized macromolecules with Eu(Ⅲ) ion and Tb(Ⅲ) ion, novel luminescent binary and ternary (with 1,10-phenanthroline as the second ligand) polymer-rare earth complexes were synthesized. For these complexes, on basis of the characterization of their chemical structures, they photoluminescence properties were main researched, and the relationship between their luminescent properties and structures was explored. The experimental results show that the complexes coming from PSF-FA and Eu(Ⅲ) ion including binary and ternary complexes emit strong red luminescence, indicating that the bonded bidentate Schiff base ligand FA can sensitize the fluorescence emission of Eu(III) ion. While the complexes coming from PSF-FC and Tb(Ⅲ) ion produce green luminescence, displaying that the bonded bidentate Schiff base ligand FC can sensitize the fluorescence emission of Tb(Ⅲ) ion. The fluorescence emission intensities of the ternary complexes were stronger than that of binary complexes, reflecting the important effect of the second ligand. The fluorescence emission of the solid film of complexes is much stronger than that of the solutions of complexes. Besides, by comparison, it is found that the furfural (as a heteroaromatic compound)-based Schiff base type polymer-rare earth complexes have stronger fluorescence emission and higher energy transfer efficiency than salicylaldehyde (as a common aromatic compound)-based Schiff base type polymer-rare earth complexes.

  8. Gas Sensors Based on Electrodeposited Polymers

    Directory of Open Access Journals (Sweden)

    Boris Lakard

    2015-07-01

    Full Text Available Electrochemically deposited polymers, also called “synthetic metals”, have emerged as potential candidates for chemical sensing due to their interesting and tunable chemical, electrical, and structural properties. In particular, most of these polymers (including polypyrrole, polyaniline, polythiophene and their derivatives can be used as the sensitive layer of conductimetric gas sensors because of their conducting properties. An important advantage of polymer-based gas sensors is their efficiency at room temperature. This characteristic is interesting since most of the commercially-available sensors, usually based on metal oxides, work at high temperatures (300–400 °C. Consequently, polymer-based gas sensors are playing a growing role in the improvement of public health and environment control because they can lead to gas sensors operating with rapid detection, high sensitivity, small size, and specificity in atmospheric conditions. In this review, the recent advances in electrodeposited polymer-based gas sensors are summarized and discussed. It is shown that the sensing characteristics of electrodeposited polymers can be improved by chemical functionalization, nanostructuration, or mixing with other functional materials to form composites or hybrid materials.

  9. Indaceno-Based Conjugated Polymers for Polymer Solar Cells.

    Science.gov (United States)

    Yin, Yuli; Zhang, Yong; Zhao, Liancheng

    2018-01-04

    Polymer solar cells have received considerable attention due to the advantages of low material cost, tunable band gaps, ultralight weight, and high flexible properties, and they have been a promising organic photovoltaic technology for alternative non-renewable fossil fuels for the past decade. Inspired by these merits, numerous state-of-the-art organic photovoltaic materials have been constructed. Among them, indaceno-based polymer materials have made an impact in obtaining an impressive power conversion efficiency of more than 11%, which shows the momentous potential of this class of materials for commercial applications. In this review, recent progress of indaceno-based organic polymer solar cells are reviewed, and the structure-property device performance correlations of the reported materials are highlighted. Then, common regularities of these successful cases are collected, and encouraging viewpoints on the further development of more exciting indaceno-based organic photovoltaic materials are provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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.

  11. 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

  12. Synthesis and structural characterization of a calcium coordination ...

    Indian Academy of Sciences (India)

    Synthesis and structural characterization of a calcium coordination polymer based on a μ3-bridging. tetradentate binding mode of glycine. SUBRAMANIAN NATARAJAN*a, BIKSHANDARKOIL R. SRINIVASANb , J. KALYANA SUNDARa, K. RAVIKUMARc , R.V. KRISHNAKUMARd , J. SURESHe,. aSchool of Physics, ...

  13. [New polymer-drug systems based on natural and synthetic polymers].

    Science.gov (United States)

    Racoviţă, Stefania; Vasiliu, Silvia; Foia, Liliana

    2010-01-01

    The great versatility of polymers makes them very useful in the biomedical and pharmaceutical fields. The combination of natural and synthetic polymers leads to new materials with tailored functional properties. The aim of this work consists in the preparation of new drug delivery system based on chitosan (natural polymer) and polybetaines (synthetic polymers), by a simple process, well known in the literature as complex coacervation methods. Also, the adsorption and release studies of two antibiotics as well as the preservation of their bactericidal capacities were performed.

  14. 2D water layer enclathrated between Mn(II)-Ni(CN)4 coordination frameworks

    International Nuclear Information System (INIS)

    Ray, Ambarish; Bhowmick, Indrani; Sheldrick, William S.; Jana, Atish Dipankar; Ali, Mahammed

    2009-01-01

    A [Ni(CN) 4 ] 2- based two-dimensional Mn(II) coordination polymer {Mn(H 2 O) 2 [NiCN] 4 .4H 2 O}, in which the coordination layers are stacked on top of each other sandwiching 2D water layer of boat-shaped hexagonal water clusters has been synthesized. The complex exhibits high thermal decomposition temperature and reversible water absorption, which were clearly demonstrated by thermal and PXRD studies on the parent and rehydrated complex after dehydration. - Abstract: A coordination polymer, {Mn(H 2 O) 2 [NiCN] 4 .4H 2 O} n , showed that the coordination layers are stacked on top of each other sandwiching 2D ice layer of boat-shaped hexagonal water clusters . Display Omitted

  15. Hydrothermal synthesis and crystal structure of a europium(III) coordination polymer with 5-sulfoisophthalate trivalent anions and free 4, 4'-bipyridine molecules

    International Nuclear Information System (INIS)

    Lin Humao; Qing Caixiao; Qian Miao; Ping Xiaohong

    2005-01-01

    A novel europium(III) coordination polymer [Eu(Sip)(H 2 O) 5 ] n · nH 2 O · 1.5 n(Bipy) (I) (Sip is 5-sulfoisophthalate trivalent anion and Bipy is 4,4'-bipyridine) is hydrothermally synthesized and determined by the single crystal X-ray diffraction method. Polymer I crystallizes in the monoclinic system, space group C2/c with a = 30.7515(6), b = 10.9577(2), c = 17.5545(4) A, β = 112.040(1) deg, Z = 4. In I, each Eu 3+ ion is coordinated by four oxygen atoms from two carboxylate groups of two different Sip anions and five oxygen atoms from five coordinated water molecules to complete a deformed mono-cap square antiprism. Moreover, each Sip anion acts as a tetradentate ligand to connect two adjacent Eu 3+ ions through its two chelating carboxylate groups, resulting in one-dimensional linear chains. In addition, fifteen different kinds of hydrogen-bonding interactions link the chains, lattice water molecules, and free Bipy molecules to engender a complicated hydrogen-bonding network [ru

  16. Syntheses, structures and luminescence properties of lanthanide coordination polymers with helical character

    International Nuclear Information System (INIS)

    Zhou Ruisha; Cui Xiaobing; Song Jiangfeng; Xu Xiaoyu; Xu Jiqing; Wang Tiegang

    2008-01-01

    A series of lanthanide coordination polymers, (Him) n [Ln(ip) 2 (H 2 O)] n [Ln=La(1), Pr(2), Nd(3) and Dy(4), H 2 ip=isophthalic acid, im=imidazole] and [Y 2 (ip) 3 (H 2 O) 2 ] n .nH 2 O (5), have been synthesized and characterized by elemental analyses, infrared (IR), ultraviolet-visible-near infrared (UV-Vis-NIR) and single-crystal X-ray diffraction analyses. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 features a 2-D network making of two different kinds of quadruple-helical chains. Compounds 2 and 3 present the characteristic emissions of Pr(III) and Nd(III) ions in NIR region, respectively. Compound 4 shows sensitized luminescence of Dy(III) ions in visible region. - Graphical abstract: A series of lanthanide coodination polymers, (Him) n [Ln(ip) 2 (H 2 O)] n [Ln=La(1), Pr(2), Nd(3) and Dy(4)] and [Y 2 (ip) 3 (H 2 O) 2 ] n .nH 2 O (5), have been reported. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 displays a 2-D network making of two kinds of quadruple-helical chains. Display Omitted

  17. Bio-Based Polymers with Potential for Biodegradability

    Directory of Open Access Journals (Sweden)

    Thomas F. Garrison

    2016-07-01

    Full Text Available A variety of renewable starting materials, such as sugars and polysaccharides, vegetable oils, lignin, pine resin derivatives, and proteins, have so far been investigated for the preparation of bio-based polymers. Among the various sources of bio-based feedstock, vegetable oils are one of the most widely used starting materials in the polymer industry due to their easy availability, low toxicity, and relative low cost. Another bio-based plastic of great interest is poly(lactic acid (PLA, widely used in multiple commercial applications nowadays. There is an intrinsic expectation that bio-based polymers are also biodegradable, but in reality there is no guarantee that polymers prepared from biorenewable feedstock exhibit significant or relevant biodegradability. Biodegradability studies are therefore crucial in order to assess the long-term environmental impact of such materials. This review presents a brief overview of the different classes of bio-based polymers, with a strong focus on vegetable oil-derived resins and PLA. An entire section is dedicated to a discussion of the literature addressing the biodegradability of bio-based polymers.

  18. 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).

  19. Radiation Synthesis of Superabsorbent Polymers Based on Natural Polymers

    International Nuclear Information System (INIS)

    Sen, Murat; Hayrabolulu, Hande

    2010-01-01

    The objectives of proposed research contract were first synthesize superabsorbent polymers based on natural polymers to be used as disposable diapers and soil conditioning materials in agriculture, horticulture and other super adsorbent using industries. We have planned to use the natural polymers; locust beam gum, tara gum, guar gum and sodium alginate on the preparation of natural superabsorbent polymers(SAP). The aqueous solution of natural polymers and their blends with trace amount of monomer and cross-linking agents will be irradiated in paste like conditions by gamma rays for the preparation of cross-linked superabsorbent systems. The water absorption and deswellling capacity of prepared super adsorbents and retention capacity, absorbency under load, suction power, swelling pressure and pet-rewet properties will be determined. Use of these materials instead of synthetic super absorbents will be examined by comparing the performance of finished products. The experimental studies achieved in the second year of project mainly on the effect of radiation on the chemistry of sodium alginate polymers in different irradiation conditions and structure-property relationship particularly with respect to radiation induced changes on the molecular weight of natural polymers and preliminary studies on the synthesis of natural-synthetic hydride super adsorbent polymers were given in details

  20. Diversity of coordination modes in the polymers based on 3,3',4,4'-biphenylcarboxylate ligand

    International Nuclear Information System (INIS)

    Du Xiaodi; Xiao Hongping; Zhou Xinhui; Wu Tao; You Xiaozeng

    2010-01-01

    Four new compounds [Ni 2 (4,4'-bpy)(3,4-bptc)(H 2 O) 4 ] n (1), [Ni(4,4'-bpy)(3,4-H 2 bptc)(H 2 O) 3 ] n (2), [Mn 2 (2,2'-bpy) 4 (3,4-H 2 bptc) 2 ] (3) and {[Mn(1,10-phen) 2 (3,4-H 2 bptc)].4H 2 O} n (4) (3,4-H 4 bptc=3,3',4,4'-biphenyltetracarboxylic acid, 4,4'-bpy=4,4'-bipyridine, 2,2'-bpy=2,2'-bipyridine, 1, 10-phen=1, 10-phenanthroline), have been prepared and structurally characterized. In all compounds, the derivative ligands of 3,4-H 4 bptc (3,4-bptc 4- and 3,4-H 2 bptc 2- ) exhibit different coordination modes and lead to the formation of various architectures. Compounds 1 and 2 display the three-dimensional (3D) framework: 1 shows a 3,4-connected topological network with (8 3 )(8 5 .10) topology symbol based on the coordination bonds while in 2, the hydrogen-bonding interactions are observed to connect the 1D linear chain generating a final 3D framework. 3 exhibits the 2D layer constructed from the hydrogen-bonding interactions between the dinuclear manganese units. Complex 4 shows the double layers motif through connecting the 1D zigzag chains with hydrogen-bonded rings. The thermal stability of 1-4 and magnetic property of 1 were also reported. - Graphical abstract: Four coordination compounds exhibiting four coordination modes of the 3,3',4,4'-biphenylcarboxylate ligand, with three of new in this system, are obtained showing diversified architectures.

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

    Science.gov (United States)

    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(H2O)]n·2n(H2O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H2sfpip)(ox)(H2O)4]n·2n(H2O) (Ln=Nd (8) Sm (9)), [H2ox=oxalic acid, H3sfpip=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 H3sfpip resulted in two types of structures. Compounds 1-7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox2- 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.

  2. Polymer based tunneling sensor

    Science.gov (United States)

    Cui, Tianhong (Inventor); Wang, Jing (Inventor); Zhao, Yongjun (Inventor)

    2006-01-01

    A process for fabricating a polymer based circuit by the following steps. A mold of a design is formed through a lithography process. The design is transferred to a polymer substrate through a hot embossing process. A metal layer is then deposited over at least part of said design and at least one electrical lead is connected to said metal layer.

  3. Catalytic nanocrystalline coordination polymers as an efficient peroxidase mimic for labeling and optical immunoassays

    International Nuclear Information System (INIS)

    Čunderlová, Veronika; Hlaváček, Antonín; Horňáková, Veronika; Peterek, Miroslav; Němeček, Daniel; Skládal, Petr; Hampl, Aleš; Eyer, Luděk

    2016-01-01

    We report that nanocrystalline Prussian blue of the type Fe 4 [Fe(CN) 6 ] 3 is a powerful peroxidase mimic for use in labeling of biomolecules. The cubic nanocrystals typically have a diameter of 15 nm and are capable of catalyzing the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine in the presence of H 2 O 2 to form an intensively colored product with an absorption maximum at 662 nm. The determined pseudo turnover number is ∼20,000 s −1 which is the highest value reported for nanoparticles of a size comparable to common proteins. We also present a method for the biotinylation of the surface of these nanocrystals, and show their use in competitive bioaffinity based assays of biotin and human serum albumin. The limits of detection are 0.35 and 0.27 μg mL −1 , respectively. The results prove the applicability of coordination polymers for signal amplification and also their compatibility with the format of enzyme linked immunosorbent assays. (author)

  4. Synthesis, Crystal Structure, and Electroconducting Properties of a 1D Mixed-Valence Cu(I–Cu(II Coordination Polymer with a Dicyclohexyl Dithiocarbamate Ligand

    Directory of Open Access Journals (Sweden)

    Kenji Nakatani

    2015-04-01

    Full Text Available A new mixed-valence Cu(I–Cu(II 1D coordination polymer, [CuI4CuIIBr4(Cy2dtc2]n, with an infinite chain structure is synthesized by the reaction of Cu(Cy2dtc2 (Cy2dtc− = dicyclohexyl dithiocarbamate, C13H22NS2 with CuBr·S(CH32. The as-synthesized polymer consists of mononuclear copper(II units of CuII(Cy2dtc2 and tetranuclear copper(I cluster units, CuI4Br4. In the cluster unit, all the CuI ions have distorted trigonal pyramidal coordination geometries, and the CuI–CuI or CuI–CuII distances between the nearest copper ions are shorter than the sum of van der Waals radii for Cu–Cu.

  5. Multi-scale optical metrology for the quality control of polymer microfluidic systems

    DEFF Research Database (Denmark)

    Tosello, Guido; Marinello, Francesco; Hansen, Hans Nørgaard

    2009-01-01

    Micro injection moulding is a replication technology enabling large scale production of polymer-based micro products. To this respect, optical measuring technologies were selected to perform the quality control of a polymer micro-component: an optical coordinate measuring machine (CMM) and a white...

  6. Polyphosphazine-based polymer materials

    Science.gov (United States)

    Fox, Robert V.; Avci, Recep; Groenewold, Gary S.

    2010-05-25

    Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

  7. A 1D coordination polymer of UF{sub 5} with HCN as a ligand

    Energy Technology Data Exchange (ETDEWEB)

    Scheibe, Benjamin; Rudel, Stefan S.; Buchner, Magnus R.; Kraus, Florian [Fachbereich Chemie, Philipps-Universitaet Marburg (Germany); Karttunen, Antti J. [Department of Chemistry, Aalto University (Finland)

    2017-01-05

    β-Uranium(V) fluoride was reacted with liquid anhydrous hydrogen cyanide to obtain a 1D coordination polymer with the composition {sup 1}{sub ∞}[UF{sub 5}(HCN){sub 2}], {sup 1}{sub ∞}[UF{sub 4/1}F{sub 2/2}-(HCN){sub 2/1}], revealed by single-crystal X-ray structure determination. The reaction system was furthermore studied by means of vibrational and NMR spectroscopy, as well as by quantum chemical calculations. The compound presents the first described polymeric HCN Lewis adduct and the first HCN adduct of a uranium fluoride. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Structural study on the gas adsorption phenomena in porous coordination polymers by synchrotron powder diffraction method

    International Nuclear Information System (INIS)

    Kubota, Yoshiki

    2017-01-01

    In situ synchrotron powder diffraction measurement of gas adsorption and crystal structure analysis for porous coordination polymers (PCPs) were performed. From the obtained accurate crystal structure in both atomic and charge density levels, not only the position and orientation of adsorbed gas molecules but also the interaction between the adsorbed gas molecule and host framework were found. The information enables us to understand the mechanism of gas adsorption phenomena and functions of PCPs. It will give us the guiding principles for the novel functional materials design. (author)

  9. High-Performance All-Polymer Solar Cells Achieved by Fused Perylenediimide-Based Conjugated Polymer Acceptors.

    Science.gov (United States)

    Yin, Yuli; Yang, Jing; Guo, Fengyun; Zhou, Erjun; Zhao, Liancheng; Zhang, Yong

    2018-05-09

    We report three n-type polymeric electron acceptors (PFPDI-TT, PFPDI-T, and PFPDI-Se) based on the fused perylene diimide (FPDI) and thieno[3,2- b]thiophene, thiophene, or selenophene units for all-polymer solar cells (all-PSCs). These FPDI-based polymer acceptors exhibit strong absorption between 350 and 650 nm with wide optical bandgap of 1.86-1.91 eV, showing good absorption compensation with the narrow bandgap polymer donor. The lowest unoccupied molecular orbital (LUMO) energy levels were located at around -4.11 eV, which are comparable with those of the fullerene derivatives and other small molecular electron acceptors. The conventional all-PSCs based on the three polymer acceptors and PTB7-Th as polymer donor gave remarkable power conversion efficiencies (PCEs) of >6%, and the PFPDI-Se-based all-PSC achieved the highest PCE of 6.58% with a short-circuit current density ( J sc ) of 13.96 mA/cm 2 , an open-circuit voltage ( V oc ) of 0.76 V, and a fill factor (FF) of 62.0%. More interestingly, our results indicate that the photovoltaic performances of the FPDI-based polymer acceptors are mainly determined by the FPDI unit with a small effect from the comonomers, which is quite different from the others reported rylenediimide-based polymer acceptors. This intriguing phenomenon is speculated as the huge geometry configuration of the FPDI unit, which minimizes the effect of the comonomer. These results highlight a promising future for the application of the FPDI-based polymer acceptors in the highly efficient all-PSCs.

  10. Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Ran, Xing-Rui [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Wang, Ning [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Long, Yi [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Yue, Shan-Tang, E-mail: yuesht@scnu.edu.cn [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou (China); Liu, Ying-Liang [College of Science, South China Agricultural University, Guangzhou 510642 (China)

    2015-05-15

    By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.

  11. 40 CFR 721.10036 - Acetaldehyde based polymer (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acetaldehyde based polymer (generic... Specific Chemical Substances § 721.10036 Acetaldehyde based polymer (generic). (a) Chemical substance and... based polymer (PMN P-02-406) is subject to reporting under this section for the significant new uses...

  12. 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...

  13. 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.

  14. 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.

  15. Syntheses, crystal structures, and properties of four coordination polymers based on mixed multi-N donor and polycarboxylate ligands

    Science.gov (United States)

    Chen, Shui-Sheng; Guo, Xing-Zhe; Zhao, Yue; Li, Wei-Dong

    2018-02-01

    Four new coordination polymers [Ni2(HL1)2(L1)3(BTC)2]·6H2O (1), [Ni2(L1)3(HBTC)2]·4H2O (2), [Cd2(L2)(BTC)(H2O)3]·2H2O (3) and [Cd2(HL2)(BTCA)] (4) were synthesized by reactions of nickel(II)/ cadmium(II) salts with rigid ligands of 1,4-di(1H-imidazol-4-yl)benzene (L1), 1,3-di(1-imidazolyl)-5-(4H-tetrazol-5-yl)benzene (HL2) and polycarboxylic acids of 1,3,5-benzenetricarboxylic acid (H3BTC), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), respectively. The structures of the complexes were determined by single crystal X-ray diffraction analysis. The complex 1 is one-dimensional (1D) chain while 2 is a (4, 4)-connected two-dimensional (2D) layered structure with 2D → 2D parallel interpenetration. Complex 3 is a rare tetranodal (3,4)-connected three-dimensional (3D) CrVTiSc architecture with Point (Schläfli) symbol of (4·82)(4·84·10)(42·82·102)(83), and compound 4 has the 2D network with (4,4) topology based on the [Cd2(COO)4] SBUs. The weak interactions such as hydrogen bonds and π···π stacking contribute to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. The UV-vis absorption spectra of 1 - 4 are discussed. Moreover, the photo luminescent properties of 3 and 4 and gas sorption property of 2 have been investigated.

  16. 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.

  17. Segment-based Eyring-Wilson viscosity model for polymer solutions

    International Nuclear Information System (INIS)

    Sadeghi, Rahmat

    2005-01-01

    A theory-based model is presented for correlating viscosity of polymer solutions and is based on the segment-based Eyring mixture viscosity model as well as the segment-based Wilson model for describing deviations from ideality. The model has been applied to several polymer solutions and the results show that it is reliable both for correlation and prediction of the viscosity of polymer solutions at different molar masses and temperature of the polymer

  18. Microbial conversion of biomass into bio-based polymers.

    Science.gov (United States)

    Kawaguchi, Hideo; Ogino, Chiaki; Kondo, Akihiko

    2017-12-01

    The worldwide market for plastics is rapidly growing, and plastics polymers are typically produced from petroleum-based chemicals. The overdependence on petroleum-based chemicals for polymer production raises economic and environmental sustainability concerns. Recent progress in metabolic engineering has expanded fermentation products from existing aliphatic acids or alcohols to include aromatic compounds. This diversity provides an opportunity to expand the development and industrial uses of high-performance bio-based polymers. However, most of the biomonomers are produced from edible sugars or starches that compete directly with food and feed uses. The present review focuses on recent progress in the microbial conversion of biomass into bio-based polymers, in which fermentative products from renewable feedstocks serve as biomonomers for the synthesis of bio-based polymers. In particular, the production of biomonomers from inedible lignocellulosic feedstocks by metabolically engineered microorganisms and the synthesis of bio-based engineered plastics from the biological resources are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Nanocomposites Based on Biodegradable Polymers

    Directory of Open Access Journals (Sweden)

    Ilaria Armentano

    2018-05-01

    Full Text Available In the present review paper, our main results on nanocomposites based on biodegradable polymers (on a time scale from 2010 to 2018 are reported. We mainly focused our attention on commercial biodegradable polymers, which we mixed with different nanofillers and/or additives with the final aim of developing new materials with tunable specific properties. A wide list of nanofillers have been considered according to their shape, properties, and functionalization routes, and the results have been discussed looking at their roles on the basis of different adopted processing routes (solvent-based or melt-mixing processes. Two main application fields of nanocomposite based on biodegradable polymers have been considered: the specific interaction with stem cells in the regenerative medicine applications or as antimicrobial materials and the active role of selected nanofillers in food packaging applications have been critically revised, with the main aim of providing an overview of the authors’ contribution to the state of the art in the field of biodegradable polymeric nanocomposites.

  20. 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)

  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. A coordination polymer of CdII with benzene-1,3-dicarboxylate and 1,4-bis[1-(2-pyridylmethylbenzimidazol-2-yl]butane

    Directory of Open Access Journals (Sweden)

    Wei-Ping Zhang

    2009-11-01

    Full Text Available The title CdII coordination polymer, catena-poly[[{1,4-bis[1-(2-pyridylmethylbenzimidazol-2-yl]butane}cadmium(II]-μ-benzene-1,3-dicarboxylato], [Cd(C8H4O4(C30H28N6]n, was obtained by reaction of CdCO3, benzene-1,3-dicarboxylic acid (H2btc and 1,4-bis[1-(2-pyridylmethylbenzimidazol-2-yl]butane (L. The CdII cation is six-coordinated by an N2O4-donor set. L acts as a bidentate ligand and btc anions link CdII centers into a chain propagating parallel to [010].

  3. 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.

  4. 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.

  5. [Cu.sub.2./sub.(μ-Me.sub.2./sub.N-ba).sub.2./sub.bn)I].sub.n./sub., 1D coordination polymer of copper(I) iodide: synthesis, characterization, and crystal structure

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Jafari, K.; Bahramian, B.; Fejfarová, Karla; Dušek, Michal

    2013-01-01

    Roč. 144, č. 11 (2013), s. 1621-1626 ISSN 0026-9247 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional research plan: CEZ:AV0Z10100521 Keywords : coordination polymer * Schiff base * copper * x-ray diffraction * structure analysis Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.347, year: 2013

  6. 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

  7. 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

  8. 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.

  9. Three PbII coordination polymers based on 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid: Syntheses, crystal structures, and fluorescent properties

    International Nuclear Information System (INIS)

    Yu, Xiao-Yang; Xin, Rui; Gao, Wei-Ping; Wang, Na; Zhang, Xiao; Yang, Yan-Yan; Qu, Xiao-Shu

    2013-01-01

    Three lead coordination polymers, [PbCl(C 10 H 6 N 3 O 4 )(H 2 O)·H 2 O] n (1), [Pb(C 10 H 6 N 3 O 4 ) 2 (H 2 O)] n (2) and [Pb 3 (C 10 H 5 N 3 O 4 ) 3 ] n (3) (C 10 H 7 N 3 O 4 =2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. In 1, Cl anions connected neighboring wave-like 2D layers, which are constructed with left- and right-handed helical chains, into a 3D network structure with a (6 3 )(6 5 ·8) topology. In 2, Pb cations are linked into a 3D 6 6 network with left- and right-handed helixes by μ 2 -bridging C 10 H 6 N 3 O 4 − ligands. In 3, C 10 H 5 N 3 O 4 2− ligands link Pb 6 O 12 clusters into a 3D (4 12 ·6 3 ) network. Their fluorescent properties were also investigated. - Graphical abstract: Three 3D lead compounds based on 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid have been hydrothermally synthesized. Four new coordination modes of the organic ligand are first reported. Display Omitted - Highlights: • Three new Pb(II) complexes have been synthesized and characterized. • Left- and right-handed helical chains can be found in the 3D networks of 1 and 2. • Pb 6 O 12 clusters are connected into (4 12 ·6 3 ) network in 3

  10. Polymer and small molecule based hybrid light source

    Science.gov (United States)

    Choong, Vi-En; Choulis, Stelios; Krummacher, Benjamin Claus; Mathai, Mathew; So, Franky

    2010-03-16

    An organic electroluminescent device, includes: a substrate; a hole-injecting electrode (anode) coated over the substrate; a hole injection layer coated over the anode; a hole transporting layer coated over the hole injection layer; a polymer based light emitting layer, coated over the hole transporting layer; a small molecule based light emitting layer, thermally evaporated over the polymer based light emitting layer; and an electron-injecting electrode (cathode) deposited over the electroluminescent polymer layer.

  11. Recent Advances in Edible Polymer Based Hydrogels as a Sustainable Alternative to Conventional Polymers.

    Science.gov (United States)

    Ali, Akbar; Ahmed, Shakeel

    2018-06-26

    The over increasing demand of eco-friendly materials to counter various problems, such as environmental issues, economics, sustainability, biodegradability, and biocompatibility, open up new fields of research highly focusing on nature-based products. Edible polymer based materials mainly consisting of polysaccharides, proteins, and lipids could be a prospective contender to handle such problems. Hydrogels based on edible polymer offer many valuable properties compared to their synthetic counterparts. Edible polymers can contribute to the reduction of environmental contamination, advance recyclability, provide sustainability, and thereby increase its applicability along with providing environmentally benign products. This review is highly emphasizing on toward the development of hydrogels from edible polymer, their classification, properties, chemical modification, and their potential applications. The application of edible polymer hydrogels covers many areas including the food industry, agricultural applications, drug delivery to tissue engineering in the biomedical field and provide more safe and attractive products in the pharmaceutical, agricultural, and environmental fields, etc.

  12. An electroactive conducting polymer actuator based on NBR/RTIL solid polymer electrolyte

    Science.gov (United States)

    Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

    2007-04-01

    This paper reports the fabrication of a dry-type conducting polymer actuator using nitrile rubber (NBR) as the base material in a solid polymer electrolyte. The conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique. Room-temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X (where X = BF4-, PF6-, (CF3SO2)2N-), were absorbed into the composite film. The compatibility between the ionic liquids and the NBR polymer was confirmed by DMA. The effect of the anion size of the ionic liquids on the displacement of the actuator was examined. The displacement increased with increasing anion size of the ionic liquids. The cyclic voltammetry responses and the redox switching dynamics of the actuators were examined in different ionic liquids.

  13. A one-dimensional ladder-like coordination polymer: poly[[hexa-aqua-bis(μ-5-nitro-benzene-1,3-dicarboxyl-ato-κO,O',O'')(μ-oxalato-κO,O':O'',O''')diyttrium(III)] trihydrate].

    Science.gov (United States)

    Fu, Zhong; Lin, Ying; Zhou, Yun-You; Zhang, Hong-Tao

    2007-12-06

    In the crystal structure of the title one-dimensional coordination polymer, [Y(2)(C(8)H(3)NO(6))(2)(C(2)O(4))(H(2)O)(6)]·3H(2)O, each Y(III) ion is bridged to its neighbours by two 5-nitro-benzene-1,3-dicarboxyl-ate (nbdc) dianions and one oxalate dianion (located on an inversion centre) to form a ladder-like polymeric structure. The two carboxylate groups of nbdc assume different modes of coordination, one is chelating whereas the other is monodentate. Three water mol-ecules coordinate to the Y(III) ion to complete an eight-coordinate distorted dodecahedral geometry. The ladder-like polymers are assembled together by hydrogen bonding and π-π stacking [centrio-centriod distance = 3.819 (9) Å] in the crystal structure.

  14. 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.

  15. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min, E-mail: xiejm391@sohu.com

    2014-11-15

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (La-TTTA) and [Nd(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La{sup 3+} and Nd{sup 3+}) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H{sub 3}TTTA). La-TTTA and Nd-TTTA are isostructural and both show three dimensional structures. La-TTTA and Nd-TTTA show good recognition of amine molecules via quenching the luminescent intensities in amines emulsions. They can also recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions with the quenching the peak around 361 nm when the compounds immersed in ionic solutions. The two compounds act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde and derivatives in high yields shortly due to the strong Lewis acidity and the possible open sites of the lanthanide ions. - Graphical abstract: We have synthesized two isostructural 3D compounds based on H{sub 3}TTTA. They are chemical sensor of amine solvents and cations. They have higher yields and TOFs to catalyze cyanosilylation reactions. - Highlights: • The compounds show recognition of amine molecules via quenching luminescent intensities. • The compounds recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields.

  16. Three coordination polymers based on a star-like geometry 4, 4', 4'' -nitrilotribenzoic acid ligand and their framework dependent luminescent properties

    Science.gov (United States)

    Hu, Zhiyong; Zhao, Meng; Su, Jian; Xu, Shasha; Hu, Lei; Liu, Hui; Zhang, Qiong; Zhang, Jun; Wu, Jieying; Tian, Yupeng

    2018-02-01

    Three novel coordination polymers, [Zn(μ2-HTCA)(Phen)]n (1), {[Cd(μ3-HTCA)(Phen)]·2H2O}n (2), [Mn(μ2-HTCA)(Phen)(H2O)]n (3) were prepared by hydrothermal synthesis from the 4, 4', 4''-nitrilotribenzoicacid (H3TCA) and 1, 10-phenanthroline monohydrate (Phen) with different transition metal salts, which were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray diffraction and thermogravimetric analysis. The photophysical properties of the complexes were investigated by solid-state diffuse reflectance spectra, photoluminescent properties, lifetime and quantum yield. For these complexes, it was found that the band gaps follow the order: 3 < 2 < 1 < 2.80 eV, fluorescence intensity order: 1 > H3TCA > 2 > 3; quantum yield order: H3TCA > 1 > 2 > 3; while the lifetime order: 1 > 2 > H3TCA > 3.

  17. 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.

  18. A primer on polymer nomenclature: Structure-based, sourced-based and trade names

    Science.gov (United States)

    Polymer nomenclature is important because it is part of the language of polymer science and is needed for polymer identification, reference, and documentation. A primer on polymer nomenclature is provided herein for people new to the field or for instructional use. Both structure-based and source-...

  19. 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.

  20. Extrudable polymer-polymer composites based on ultra-high molecular weight polyethylene

    Science.gov (United States)

    Panin, S. V.; Kornienko, L. A.; Alexenko, V. O.; Buslovich, D. G.; Dontsov, Yu. V.

    2017-12-01

    Mechanical and tribotechnical characteristics of polymer-polymeric composites of UHMWPE are studied with the aim of developing extrudable, wear-resistant, self-lubricant polymer mixtures for Additive Manufacturing (AM). The motivation of the study is their further application as feedstocks for 3D printing. Blends of UHMWPE with graft- and block copolymers of low-density polyethylene (HDPE-g-VTMS, HDPE-g-SMA, HDPE-b-EVA), polypropylene (PP), block copolymers of polypropylene and polyamide with linear low density polyethylene (PP-b-LLDPE, PA-b-LLDPE), as well as cross-linked polyethylene (PEX-b), are examined. The choice of compatible polymer components for an ultra- high molecular weight matrix for increasing processability (extrudability) is motivated by the search for commercially available and efficient additives aimed at developing wear-resistant extrudable polymer composites for additive manufacturing. The extrudability, mechanical properties and wear resistance of UHMWPE-based polymer-polymeric composites under sliding friction with different velocities and loads are studied.

  1. Performance limitations of polymer electrolytes based on ethylene oxide polymers

    International Nuclear Information System (INIS)

    Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger

    1999-01-01

    Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles

  2. Two novel penetrating coordination polymers based on flexible S-containing dicarboxylate acid with sensing properties towards Fe3+ and Cr2O72- ions

    Science.gov (United States)

    Chen, Zhiwei; Mi, Xiuna; Wang, Suna; Lu, Jing; Li, Yunwu; Li, Dacheng; Dou, Jianmin

    2018-05-01

    Two new coordination polymers (CPs), namely, {[Zn(L)(bpp)]·DMF}n (1) and {[Zn(L)(bpe)]·DMF}n (2) (L = 2,2'-[benzene-1,3-diylbis(methanediylsulfanediyl)]dibenzoic acid, bpp= 1,3-bis(4-pyridyl)propane, bpe = 1,2-Bis(4-pyridyl)ethylene, DMF = N,N-Dimethylformamide), have been solvothermally synthesized and fully characterized. Complex 1 displays a 2D→2D three-fold"false" interpenetrating structure while complex 2 possesses a novel 3-D 4-connected structure with fascinating self-penetrating moieties. The luminescence studies reveal that these complexes exhibited excellent selectivity for Fe3+ and Cr2O72- ions in DMF. The sensing mechanism was investigated through PXRD, XPS , EDS mapping measurements, and discussed in details.

  3. Integrated circuits based on conjugated polymer monolayer.

    Science.gov (United States)

    Li, Mengmeng; Mangalore, Deepthi Kamath; Zhao, Jingbo; Carpenter, Joshua H; Yan, Hongping; Ade, Harald; Yan, He; Müllen, Klaus; Blom, Paul W M; Pisula, Wojciech; de Leeuw, Dago M; Asadi, Kamal

    2018-01-31

    It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm 2  V -1  s -1 . The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Real logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.

  4. Diverse assemblies of the (4,4) grid layers exemplified in Zn(II)/Co(II) coordination polymers with dual linear ligands

    International Nuclear Information System (INIS)

    Liu, Guang-Zhen; Li, Xiao-Dong; Xin, Ling-Yun; Li, Xiao-Ling; Wang, Li-Ya

    2013-01-01

    Diverse (4,4) grid layers are exemplified in five two-dimensional coordination polymers with dual µ 2 -bridged ligands, namely, ([Zn(cbaa)(bpp)]·H 2 O) n (1), [Zn 2 (cbaa) 2 (bpy)] n (2), [Co 2 (cbaa) 2 (bpp) 2 ] n (3), [Co(cbaa)(bpp)] n (4), and [Co(bdaa)(bpp)(H 2 O) 2 ] n (5) (H 2 cbaa=4-carboxybenzeneacetic acid, bpp=1,3-di(4-pyridyl)propane, bpy=4,4′-bipyridyl, and H 2 bdaa=1,4-benzenediacrylic acid). For 1, two (4,4) grid layers with [ZnN 2 O 2 ] tetrahedron as the node are held together by lattice water forming a H-bonding bilayer. Individual (4,4) grid layer in 2 is based on (Zn 2 (OCO) 4 ) paddlewheel unit as the node. Two (4,4) grid layers with (Co 2 O(OCO) 2 ) dimer as the node are covalently interconnected by organic ligands affording a thick bilayer of 3 with new framework topology. The different entanglements between two coincident (4,4) grid layers with [CoN 2 O 4 ] octahedron as the node leads to two 2D→2D interpenetrated structures for 4 and 5. Furthermore, fluorescent properties of 1 and 2 as well as magnetic properties of 3 are investigated. - Graphical abstract: Diverse assemblies of the (4,4) grid layers with different network nodes forms five coordination polymers that are well characterized by IR, TGA, element analysis, fluorescent and magnetic measurement. - Highlights: • Diverse assemblies of the (4,4) grid layers with different structural units as the nodes. • A new topology type with the uninodal 6-connected net of (4 12 .5 2 .6) is found. • Intense fluorescence emissions with a rare blue-shift of 55 nm compared to free carboxylate ligand

  5. DFT studies for three Cu(II) coordination polymers: Geometrical and electronic structures, g factors and UV-visible spectra

    Science.gov (United States)

    Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Wu, Li-Na; Zhang, Li-Juan

    2018-05-01

    This work presents a systematic density functional theory (DFT) study for geometrical and electronic structures, g factors and UV-vis spectra of three Cu(II) coordination polymers (CPs) [Cu(XL)(NO3)2]n (1), {[Cu(XL)(4,4‧-bpy)(NO3)2]•CH3CN}n (2) and {[Cu(XL)3](NO3)2·3.5H2O}n (3) based on the ligand N,N‧-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide bi(1,2,4-triazole) (XL) with the linker triazole coordinated with copper to construct the CPs. For three CPs with distinct ligands, the optimized molecular structures with PBE0 hybrid functional and the 6-311g basis set agree well with the corresponding XRD data. Meanwhile, the electronic properties are also analyzed for all the systems. The calculated g factors are found sensitive to the (Hartree-Fock) HF character due to the significant hybridization between copper and ligand orbitals. The calculated UV-visible spectra reveal that the main electronic transitions for CP 1 contain d-d and CT transitions, while those for CPs 2 and 3 largely belong to CT ones. The present CPs seem difficult to adsorb small molecules, e.g., CP 1 with H2O and NO2 exhibit unfavorable adsorption and deformation structures near the Cu2+ site.

  6. Functional Two-Dimensional Coordination Polymeric Layer as a Charge Barrier in Li–S Batteries

    KAUST Repository

    Huang, Jing-Kai

    2018-01-04

    Ultrathin two-dimensional (2D) polymeric layers are capable of separating gases and molecules based on the reported size exclusion mechanism. What is equally important but missing today is an exploration of the 2D layers with charge functionality, which enables applications using the charge exclusion principle. This work demonstrates a simple and scalable method of synthesizing a free-standing 2D coordination polymer Zn2(benzimidazolate)2(OH)2 at the air–water interface. The hydroxyl (−OH) groups are stoichiometrically coordinated and implement electrostatic charges in the 2D structures, providing powerful functionality as a charge barrier. Electrochemical performance of the Li–S battery shows that the Zn2(benzimidazolate)2(OH)2 coordination polymer layers efficiently mitigate the polysulfide shuttling effects and largely enhance the battery capacity and cycle performance. The synthesis of the proposed coordination polymeric layers is simple, scalable, cost saving, and promising for practical use in batteries.

  7. Ultrasonic synthesis of two new zinc(II) bipyridine coordination polymers: New precursors for preparation of zinc(II) oxide nano-particles.

    Science.gov (United States)

    Fard, Mohammad Jaafar Soltanian; Hayati, Payam; Firoozadeh, Azita; Janczak, Jan

    2017-03-01

    Nanoparticles of two zinc(II) coordination polymers (CPs), [Zn(μ-4,4'-bipy)Cl 2 ] n (1) and [Zn(μ-4,4'-bipy)Br 2 ] n (2) L=bpy=4,4'-bipyridine ligand, have 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 compounds 1 and 2 imply that the Zn +2 ions are four coordinated. Topological analysis shows that 1D coordination networks of 1 and 2 can be classified as underlying nets of topological types 2C1. Nanoparticles of zinc(II) oxide have been prepared by calcination of two different zinc (II) CPs at 450°C that were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and IR spectroscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Radiation synthesis and modification of polymers for biomedical applications. Final results of a co-ordinated research project. 1996-2000

    CERN Document Server

    2002-01-01

    Radiation techniques are being used for synthesis of hydrogels, functional polymers, interpenetrating systems, chemical modification of surfaces, immobilization of bioactive materials, synthesis of functional micro- and nanospheres and processing of naturally derived biomaterials. Potential medical applications of these biomaterials include implants, topical dressings, treatment devices and drug delivery systems. Biotechnological applications include diagnostic assays, separation and purification systems, immobilized enzyme and cell bioprocesses and cell culture surfaces. The main objective of the CRP on The use of Radiation Processing to Prepare Biomaterials for Application in Medicine was to co-ordinate the research carried out in the participating countries, to ensure that different research programmes complement each other and the information exchange is available to all. Furthermore, the objective was to expand the use of ionizing radiation in two major areas: synthesis of polymers and gels for medical a...

  9. Development and characterization of rosin-based polymer and its application as a cream base.

    Science.gov (United States)

    Dhanorkar, V T; Gawande, R S; Gogte, B B; Dorle, A K

    2002-01-01

    The literature contains many references to the wide range of uses of rosin-based polymers, but little has appeared in the area of rosin-based polymers used as cream bases. Various rosin polymers based on glycerol, sorbitol, and pentaerythritol were prepared and screened for efficacy as cream bases. Among these polymers, polymer 2 (glycerol-based) is reported in the present study as it produced creams with a better stability and release profile as compared to other creams. The creams were formulated employing polymer 2 (P2) and Tween 60 as surfactants. The stability of the prepared creams, as well as the diclofenac diethylammonium release pattern, was investigated using particle size analysis, conductivity, relative dielectric constant, spreadability, and irritation potential measurement, and was compared with that of creams containing Tween 60 (RT) prepared in the laboratory. The release of the drug, diclofenac diethylammonium, was measured after eight hours and compared with a standard cream (RT) and a marketed cream (RM).

  10. Atomistic simulation of graphene-based polymer nanocomposites

    International Nuclear Information System (INIS)

    Rissanou, Anastassia N.; Bačová, Petra; Harmandaris, Vagelis

    2016-01-01

    Polymer/graphene nanostructured systems are hybrid materials which have attracted great attention the last years both for scientific and technological reasons. In the present work atomistic Molecular Dynamics simulations are performed for the study of graphene-based polymer nanocomposites composed of pristine, hydrogenated and carboxylated graphene sheets dispersed in polar (PEO) and nonpolar (PE) short polymer matrices (i.e., matrices containing chains of low molecular weight). Our focus is twofold; the one is the study of the structural and dynamical properties of short polymer chains and the way that they are affected by functionalized graphene sheets while the other is the effect of the polymer matrices on the behavior of graphene sheets.

  11. A role based coordination model in agent systems

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ya-ying; YOU Jin-yuan

    2005-01-01

    Coordination technology addresses the construction of open, flexible systems from active and independent software agents in concurrent and distributed systems. In most open distributed applications, multiple agents need interaction and communication to achieve their overall goal. Coordination technologies for the Internet typically are concerned with enabling interaction among agents and helping them cooperate with each other.At the same time, access control should also be considered to constrain interaction to make it harmless. Access control should be regarded as the security counterpart of coordination. At present, the combination of coordination and access control remains an open problem. Thus, we propose a role based coordination model with policy enforcement in agent application systems. In this model, coordination is combined with access control so as to fully characterize the interactions in agent systems. A set of agents interacting with each other for a common global system task constitutes a coordination group. Role based access control is applied in this model to prevent unauthorized accesses. Coordination policy is enforced in a distributed manner so that the model can be applied to the open distributed systems such as Intemet. An Internet online auction system is presented as a case study to illustrate the proposed coordination model and finally the performance analysis of the model is introduced.

  12. 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

  13. On-surface synthesis of covalent coordination polymers on micrometer scale

    Institute of Scientific and Technical Information of China (English)

    Mathieu Koudia; Elena Nardi; Olivier Siri; Mathieu Abel

    2017-01-01

    On-surface synthesis under ultrahigh vacuum provides a promising strategy to control matter at the atomic level,with important implications for the design of new two-dimensional materials having remarkable electronic,magnetic,or catalytic properties.This strategy must address the problem of limited extension of the domains due to the irreversible nature of covalent bonds,which prevents the ripening of defects.We show here that extended materials can be produced by a controlled co-deposition process.In particular,co-deposition of quinoid zwitterion molecules with iron atoms on a Ag(111) surface held at 570 K allows the formation of micrometer-sized domains based on covalent coordination bonds.This work opens up the construction of micrometer-scale single-layer covalent coordination materials under vacuum conditions.

  14. Exploring the role of peptides in polymer-based gene delivery.

    Science.gov (United States)

    Sun, Yanping; Yang, Zhen; Wang, Chunxi; Yang, Tianzhi; Cai, Cuifang; Zhao, Xiaoyun; Yang, Li; Ding, Pingtian

    2017-09-15

    Polymers are widely studied as non-viral gene vectors because of their strong DNA binding ability, capacity to carry large payload, flexibility of chemical modifications, low immunogenicity, and facile processes for manufacturing. However, high cytotoxicity and low transfection efficiency substantially restrict their application in clinical trials. Incorporating functional peptides is a promising approach to address these issues. Peptides demonstrate various functions in polymer-based gene delivery systems, such as targeting to specific cells, breaching membrane barriers, facilitating DNA condensation and release, and lowering cytotoxicity. In this review, we systematically summarize the role of peptides in polymer-based gene delivery, and elaborate how to rationally design polymer-peptide based gene delivery vectors. Polymers are widely studied as non-viral gene vectors, but suffer from high cytotoxicity and low transfection efficiency. Incorporating short, bioactive peptides into polymer-based gene delivery systems can address this issue. Peptides demonstrate various functions in polymer-based gene delivery systems, such as targeting to specific cells, breaching membrane barriers, facilitating DNA condensation and release, and lowering cytotoxicity. In this review, we highlight the peptides' roles in polymer-based gene delivery, and elaborate how to utilize various functional peptides to enhance the transfection efficiency of polymers. The optimized peptide-polymer vectors should be able to alter their structures and functions according to biological microenvironments and utilize inherent intracellular pathways of cells, and consequently overcome the barriers during gene delivery to enhance transfection efficiency. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  15. 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...

  16. A one-dimensional ladder-like coordination polymer: poly[[hexaaquabis(μ-5-nitrobenzene-1,3-dicarboxylato-κ3O,O′,O′′(μ-oxalato-κ4O,O′:O′′,O′′′diyttrium(III] trihydrate

    Directory of Open Access Journals (Sweden)

    Zhong Fu

    2008-01-01

    Full Text Available In the crystal structure of the title one-dimensional coordination polymer, [Y2(C8H3NO62(C2O4(H2O6]·3H2O, each YIII ion is bridged to its neighbours by two 5-nitrobenzene-1,3-dicarboxylate (nbdc dianions and one oxalate dianion (located on an inversion centre to form a ladder-like polymeric structure. The two carboxylate groups of nbdc assume different modes of coordination, one is chelating whereas the other is monodentate. Three water molecules coordinate to the YIII ion to complete an eight-coordinate distorted dodecahedral geometry. The ladder-like polymers are assembled together by hydrogen bonding and π–π stacking [centrio–centriod distance = 3.819 (9 Å] in the crystal structure.

  17. 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

  18. Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jinfang, E-mail: zjf260@jiangnan.edu.cn [China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Wang, Chao [China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Wang, Yinlin; Chen, Weitao [China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang 212013 (China); Cifuentes, Marie P.; Humphrey, Mark G. [Research School of Chemistry, Australian National University, Canberra ACT 0200 (Australia); Zhang, Chi, E-mail: chizhang@jiangnan.edu.cn [China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China)

    2015-11-15

    The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}{sub n} (1), {[Pr_4N][WS_4Cu_4(CN)_3]}{sub n} (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}{sub n} (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}{sub n} (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}{sub n} (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS{sub 4}Cu{sub 3}]{sup +} and single CN{sup −} bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS{sub 4}Cu{sub 4}]{sup 2+} and single CN{sup −} bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS{sub 3}Cu{sub 3}]{sup +} linked by single CN{sup −} bridges, but containing the different cations [Pr{sub 4}N]{sup +} and [Bu{sub 4}N]{sup +}, respectively. 5 is constructed from nest-shaped clusters [MoOS{sub 3}Cu{sub 3}]{sup +} and single CN{sup −} bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN{sup −} bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr{sub 4}N]{sup +} vs. [Bu{sub 4}N]{sup +}) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic

  19. Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

    International Nuclear Information System (INIS)

    Zhang, Jinfang; Wang, Chao; Wang, Yinlin; Chen, Weitao; Cifuentes, Marie P.; Humphrey, Mark G.; Zhang, Chi

    2015-01-01

    The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}_n (1), {[Pr_4N][WS_4Cu_4(CN)_3]}_n (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}_n (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}_n (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}_n (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS_4Cu_3]"+ and single CN"− bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS_4Cu_4]"2"+ and single CN"− bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS_3Cu_3]"+ linked by single CN"− bridges, but containing the different cations [Pr_4N]"+ and [Bu_4N]"+, respectively. 5 is constructed from nest-shaped clusters [MoOS_3Cu_3]"+ and single CN"− bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN"− bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr_4N]"+ vs. [Bu_4N]"+) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2

  20. Markovian description of unbiased polymer translocation

    International Nuclear Information System (INIS)

    Mondaini, Felipe; Moriconi, L.

    2012-01-01

    We perform, with the help of cloud computing resources, extensive Langevin simulations which provide compelling evidence in favor of a general Markovian framework for unbiased three-dimensional polymer translocation. Our statistical analysis consists of careful evaluations of (i) two-point correlation functions of the translocation coordinate and (ii) the empirical probabilities of complete polymer translocation (taken as a function of the initial number of monomers on a given side of the membrane). We find good agreement with predictions derived from the Markov chain approach recently addressed in the literature by the present authors. -- Highlights: ► We investigate unbiased polymer translocation through membrane pores. ► Large statistical ensembles have been produced with the help of cloud computing resources. ► We evaluate the two-point correlation function of the translocation coordinate. ► We evaluate empirical probabilities for complete polymer translocation. ► Unbiased polymer translocation is described as a Markov stochastic process.

  1. Markovian description of unbiased polymer translocation

    Energy Technology Data Exchange (ETDEWEB)

    Mondaini, Felipe [Instituto de Física, Universidade Federal do Rio de Janeiro, C.P. 68528, 21945-970 Rio de Janeiro, RJ (Brazil); Centro Federal de Educação Tecnológica Celso Suckow da Fonseca, UnED Angra dos Reis, Angra dos Reis, 23953-030, RJ (Brazil); Moriconi, L., E-mail: moriconi@if.ufrj.br [Instituto de Física, Universidade Federal do Rio de Janeiro, C.P. 68528, 21945-970 Rio de Janeiro, RJ (Brazil)

    2012-10-01

    We perform, with the help of cloud computing resources, extensive Langevin simulations which provide compelling evidence in favor of a general Markovian framework for unbiased three-dimensional polymer translocation. Our statistical analysis consists of careful evaluations of (i) two-point correlation functions of the translocation coordinate and (ii) the empirical probabilities of complete polymer translocation (taken as a function of the initial number of monomers on a given side of the membrane). We find good agreement with predictions derived from the Markov chain approach recently addressed in the literature by the present authors. -- Highlights: ► We investigate unbiased polymer translocation through membrane pores. ► Large statistical ensembles have been produced with the help of cloud computing resources. ► We evaluate the two-point correlation function of the translocation coordinate. ► We evaluate empirical probabilities for complete polymer translocation. ► Unbiased polymer translocation is described as a Markov stochastic process.

  2. Self-Assembly of 1D/2D Hybrid Nanostructures Consisting of a Cd(II Coordination Polymer and NiAl-Layered Double Hydroxides

    Directory of Open Access Journals (Sweden)

    Gonzalo Abellán

    2015-12-01

    Full Text Available The preparation and characterization of a novel hybrid material based on the combination of a 2D-layered double hydroxide (LDH nanosheets and a 1D-coordination polymer (1D-CP has been achieved through a simple mixture of suspensions of both building blocks via an exfoliation/restacking approach. The hybrid material has been thoroughly characterized demonstrating that the 1D-CP moieties are intercalated as well as adsorbed on the surface of the LDH, giving rise to a layered assembly with the coexistence of the functionalities of their initial constituents. This hybrid represents the first example of the assembly of 1D/2D nanomaterials combining LDH with CP and opens the door for a plethora of different functional hybrid systems.

  3. Development of controlled drug release systems based on thiolated polymers.

    Science.gov (United States)

    Bernkop-Schnürch, A; Scholler, S; Biebel, R G

    2000-05-03

    The purpose of the present study was to generate mucoadhesive matrix-tablets based on thiolated polymers. Mediated by a carbodiimide, L-cysteine was thereby covalently linked to polycarbophil (PCP) and sodium carboxymethylcellulose (CMC). The resulting thiolated polymers displayed 100+/-8 and 1280+/-84 micromol thiol groups per gram, respectively (means+/-S.D.; n=6-8). In aqueous solutions these modified polymers were capable of forming inter- and/or intramolecular disulfide bonds. The velocity of this process augmented with increase of the polymer- and decrease of the proton-concentration. The oxidation proceeded more rapidly within thiolated PCP than within thiolated CMC. Due to the formation of disulfide bonds within thiol-containing polymers, the stability of matrix-tablets based on such polymers could be strongly improved. Whereas tablets based on the corresponding unmodified polymer disintegrated within 2 h, the swollen carrier matrix of thiolated CMC and PCP remained stable for 6.2 h (mean, n=4) and more than 48 h, respectively. Release studies of the model drug rifampicin demonstrated that a controlled release can be provided by thiolated polymer tablets. The combination of high stability, controlled drug release and mucoadhesive properties renders matrix-tablets based on thiolated polymers useful as novel drug delivery systems.

  4. Study on the Antimicrobial Properties of Citrate-Based Biodegradable Polymers

    Directory of Open Access Journals (Sweden)

    Lee-Chun eSu

    2014-07-01

    Full Text Available Citrate-based polymers possess unique advantages for various biomedical applications since citric acid is a natural metabolism product, which is biocompatible and antimicrobial. In polymer synthesis, citric acid also provides multiple functional groups to control the crosslinking of polymers and active binding sites for further conjugation of biomolecules. Our group recently developed a number of citrate-based polymers for various biomedical applications by taking advantage of their controllable chemical, mechanical, and biological characteristics. In this study, various citric acid derived biodegradable polymers were synthesized and investigated for their physicochemical and antimicrobial properties. Results indicate that citric acid derived polymers reduced bacterial proliferation to different degrees based on their chemical composition. Among the studied polymers, poly(octamethylene citrate (POC showed approximately 70-80% suppression to microbe proliferation, owing to its relatively higher ratio of citric acid contents. Crosslinked urethane-doped polyester elastomers (CUPEs and biodegradable photoluminescent polymers (BPLPs also exhibited significant bacteria reduction of ~20% and ~50% for Staphylococcus aureus and Escherichia coli, respectively. Thus, the intrinsic antibacterial properties in citrate-based polymers enable them to inhibit bacteria growth without incorporation of antibiotics, silver nanoparticles, and other traditional bacteria-killing agents suggesting that they are unique beneficial materials for wound dressing, tissue engineering, and other potential medical applications where antimicrobial property is desired.

  5. Linear polarizers based on oriented polymer blends

    NARCIS (Netherlands)

    Jagt, H.J.B.; Dirix, Y.J.L.; Hikmet, R.A.M.; Bastiaansen, C.W.M.

    1998-01-01

    Linear sheet polarizers based on the anisotropic scattering of light by drawn polymer blends are introduced here. The proper selection of materials and processing conditions for the production of large-area, flexible films of phase-segregated polymer blends suitable for polarization applications are

  6. Precision moulding of polymer micro components

    DEFF Research Database (Denmark)

    Tosello, Guido

    2008-01-01

    The present research work contains a study concerning polymer micro components manufacturing by means of the micro injection moulding (µIM) process. The overall process chain was considered and investigated during the project, including part design and simulation, tooling, process analysis, part...... optimization, quality control, multi-material solutions. A series of experimental investigations were carried out on the influence of the main µIM process factors on the polymer melt flow within micro cavities. These investigations were conducted on a conventional injection moulding machine adapted...... to the production of micro polymer components, as well as on a micro injection moulding machine. A new approach based on coordinate optical measurement of flow markers was developed during the project for the characterization of the melt flow. In-line pressure measurements were also performed to characterize...

  7. 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.

  8. Solid-Phase Extraction of Hemoglobin from Human Whole Blood with a Coordination-Polymer-Derived Composite Material Based on ZnO and Mesoporous Carbon.

    Science.gov (United States)

    Jia, Yuan; Xu, Xinxin; Ou, Jinzhao; Liu, Xiaoxia

    2017-11-13

    A composite material, ZnO@MC, has been synthesized successfully by calcination using a one-dimensional zinc-based coordination polymer as the precursor. In ZnO@MC, ZnO particles with a size of about 5-8 nm are dispersed evenly in a mesoporous carbon matrix. Adsorption experiments at pH 6.8 with 2 mg ZnO@MC as adsorbent illustrated an adsorption efficiency of 92.3 % in 5 mL hemoglobin (Hb) solution with a concentration of 100 mg L -1 . In contrast, the adsorption of bovine serum albumin can almost be ignored under the same conditions. The selectivity originates from a strong Zn II -histidine interaction between ZnO@MC and hemoglobin. The adsorption behavior of hemoglobin on ZnO@MC fits the Temkin model perfectly with a capacity as high as 11646 mg g -1 . The hemoglobin adsorbed on the composite material can be eluted easily with sodium dodecyl sulfate stripping reagent with an extraction efficiency of 87.7 %. Circular dichroism spectra and protein activity studies suggest the structure and biological activity of hemoglobin is the same before and after the adsorption/desorption experiment. Finally, the ZnO@MC composite material was employed to extract hemoglobin from human whole blood without any pretreatment, and gave a very satisfactory result. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electrospun PVdF-based fibrous polymer electrolytes for lithium ion polymer batteries

    International Nuclear Information System (INIS)

    Kim, Jeong Rae; Choi, Sung Won; Jo, Seong Mu; Lee, Wha Seop; Kim, Byung Chul

    2004-01-01

    This paper discusses the preparation of microporous fibrous membranes from PVdF solutions with different polymer contents, using the electrospinning technique. Electrospun PVdF-based fibrous membranes with average fiber diameters (AFD's) of 0.45-1.38 μm have an apparent porosity and a mean pore size (MPS) of 80-89% and 1.1-4.3 μm, respectively. They exhibited a high uptake of the electrolyte solution (320-350%) and a high ionic conductivity of above 1 x 10 -3 s/cm at room temperature. Their ionic conductivity increased with the decrease in the AFD of the fibrous membrane due to its high electrolyte uptake. The interaction between the electrolyte molecules and the PVdF with a high crystalline content may have had a minor effect on the lithium ion transfer in the fibrous polymer electrolyte, unlike in a nanoporous gel polymer electrolyte. The fibrous polymer electrolyte that contained a 1 M LiPF 6 -EC/DMC/DEC (1/1/1 by weight) solution showed a high electrochemical stability of above 5.0 V, which increased with the decrease in the AFD The interfacial resistance (R i ) between the polymer electrolyte and the lithium electrode slightly increased with the storage time, compared with the higher increase in the interfacial resistance of other gel polymer electrolytes. The prototype cell (MCMB/PVdF-based fibrous electrolyte/LiCoO 2 ) showed a very stable charge-discharge behavior with a slight capacity loss under constant current and voltage conditions at the C/2-rate of 20 and 60 deg. C

  10. Properties and applications of polymer nanocomposites clay and carbon based polymer nanocomposites

    CERN Document Server

    Prasad Sahoo, Bibhu

    2017-01-01

    The aim of the present edited book is to furnish scientific information about manufacturing, properties, and application of clay and carbon based polymer nanocomposites. It can be used as handbook for undergraduate and post graduate courses (for example material science and engineering, polymer science and engineering, rubber technology, manufacturing engineering, etc.) as well as as reference book for research fellows and professionals. Polymer nanocomposites have received outstanding importance in the present decade because of their broad range of high-performance applications in various areas of engineering and technology due to their special material properties. A great interest is dedicated to nanofiller based polymeric materials, which exhibit excellent enhancement in macroscopic material properties (mechanical, thermal, dynamic mechanical, electrical and many more) at very low filler contents and can therefore be used for the development of next-generation composite materials.

  11. EFFICIENT POLYMER PHOTOVOLTAIC DEVICES BASED ON POLYMER D-A BLENDS

    Institute of Scientific and Technical Information of China (English)

    Xian-yu Deng; Li-ping Zheng; Yue-qi Mo; Gang Yu; Wei Yang; Wen-hua Weng; Yong Cao

    2001-01-01

    Recent work demonstrated that efficient solar-energy conversion could be achieved in polymer photovoltaic cells (PVCs) based on interpenetrating bi-continuous networks[1,2]. In this paper we present a comprehensive study on improving energy conversion efficiencies of PVCs based on composite films of MEHPPV and fullerene derivatives. Carrier collection efficiency of ca. 30% el/ph and energy conversion efficiency of 3.9% were achieved at 500 nm. At reverse bias of 15 V, the photosensitivity reached 0.8 A/W, corresponding to a quantum efficiency over 100% el/ph. These results suggest that high efficiency photoelectric conversion can be achieved in polymer devices with M-P-M structure. These devices are promising for practical applications such as plastic solar cells and plastic photodetectors.

  12. Mössbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy){sub 2}[Pd(CN){sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Kitazawa, Takafumi, E-mail: kitazawa@chem.sci.toho-u.ac.jp; Sekiya, Madoka; Kawasaki, Takeshi; Takahashi, Masashi [Toho University, Department of Chemistry, Faculty of Science (Japan)

    2016-12-15

    {sup 57}Fe Mössbauer spectroscopic results on the alternatively prepared spin crossover coordination polymer Fe(3-Clpy){sub 2}Pd(CN){sub 4} sample I agree with those of SQUID data. Mössbauer specrum at RT shows two diffrent doublets which correspond to the HS1(inner doublet) and HS2(outer doublet). The intensity of the HS1 doublet decreases on cooling to 78 K at the expense of a new one featuring the LS singlet. Almost 100 % of HS1 change to LS singlet due to iron(II) ions coordinated by four N atoms of cyano groups and two N atoms of 3-Clpy ligand in the sample I. The SQUID data of the sample I prepared by a new direct contact method are different from those of the already reported Fe(3-Clpy){sub 2}Pd(CN){sub 4} sample. The differences of the SQUID data are associated with particle size effects in molecule spin crossover samples.

  13. 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.

  14. Radiation detectors based by polymer materials

    International Nuclear Information System (INIS)

    Cherestes, Margareta; Cherestes, Codrut; Constantinescu, Livia

    2004-01-01

    Scintillation counters make use of the property of certain chemical compounds to emit short light pulses after excitation produced by the passage of charged particles or photons of high energy. These flashes of light are detected by a photomultiplier tube that converts the photons into a voltage pulse. The light emitted from the detector also can be collected, focussed and dispersed by a CCD detector. The study of the evolution of the light emission and of the radiation damage under irradiation is a primary topic in the development of radiation hard polymer based scintillator. Polymer scintillator thin films are used in monitoring radiation beam intensities and simultaneous counting of different radiations. Radiation detectors have characteristics which depend on: the type of radiation, the energy of radiation, and the material of the detector. Three types of polymer thin films were studied: a polyvinyltoluene based scintillator, fluorinated polyimide and PMMA. (authors)

  15. Ontology-based composition and matching for dynamic service coordination

    OpenAIRE

    Pahl, Claus; Gacitua-Decar, Veronica; Wang, MingXue; Yapa Bandara, Kosala

    2011-01-01

    Service engineering needs to address integration problems allowing services to collaborate and coordinate. The need to address dynamic automated changes - caused by on-demand environments and changing requirements - can be addressed through service coordination based on ontology-based composition and matching techniques. Our solution to composition and matching utilises a service coordination space that acts as a passive infrastructure for collaboration. We discuss the information models an...

  16. Rectangular coordination polymer nanoplates: large-scale, rapid synthesis and their application as a fluorescent sensing platform for DNA detection.

    Directory of Open Access Journals (Sweden)

    Yingwei Zhang

    Full Text Available In this paper, we report on the large-scale, rapid synthesis of uniform rectangular coordination polymer nanoplates (RCPNs assembled from Cu(II and 4,4'-bipyridine for the first time. We further demonstrate that such RCPNs can be used as a very effective fluorescent sensing platform for multiple DNA detection with a detection limit as low as 30 pM and a high selectivity down to single-base mismatch. The DNA detection is accomplished by the following two steps: (1 RCPN binds dye-labeled single-stranded DNA (ssDNA probe, which brings dye and RCPN into close proximity, leading to fluorescence quenching; (2 Specific hybridization of the probe with its target generates a double-stranded DNA (dsDNA which detaches from RCPN, leading to fluorescence recovery. It suggests that this sensing system can well discriminate complementary and mismatched DNA sequences. The exact mechanism of fluorescence quenching involved is elucidated experimentally and its use in a human blood serum system is also demonstrated successfully.

  17. Toward flexible polymer and paper-based energy storage devices

    Energy Technology Data Exchange (ETDEWEB)

    Nyholm, Leif [Department of Materials Chemistry, The Aangstroem Laboratory, Uppsala University, Box 538, SE-751 21 Uppsala (Sweden); Nystroem, Gustav; Mihranyan, Albert; Stroemme, Maria [Nanotechnology and Functional Materials, Department of Engineering Sciences, The Aangstroem Laboratory, Uppsala University, Box 534, SE-751 21 Uppsala (Sweden)

    2011-09-01

    All-polymer and paper-based energy storage devices have significant inherent advantages in comparison with many currently employed batteries and supercapacitors regarding environmental friendliness, flexibility, cost and versatility. The research within this field is currently undergoing an exciting development as new polymers, composites and paper-based devices are being developed. In this report, we review recent progress concerning the development of flexible energy storage devices based on electronically conducting polymers and cellulose containing composites with particular emphasis on paper-based batteries and supercapacitors. We discuss recent progress in the development of the most commonly used electronically conducting polymers used in flexible device prototypes, the advantages and disadvantages of this type of energy storage devices, as well as the two main approaches used in the manufacturing of paper-based charge storage devices. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. 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.

  19. Construction of Six Coordination Polymers Based on a 5,5′-(1,2-Ethynyl)bis-1,3-benzenedicarboxylic Ligand: Synthesis, Structure, Gas Sorption, and Magnetic Properties

    KAUST Repository

    Zheng, Bing

    2013-03-06

    Six novel coordination polymers based on a multifunctional ligand, 5,5\\'-(1,2-ethynyl)bis-1,3-benzenedicarboxylic (H4EBDC), namely, |(C3H7NO)2(H2O)7(C 2H5OH)3| [Zn2(C18H 6O8)(C10H8N2) 2] (1), |(C3H7NO)3(H2O)30- (CH3CN)2|[Zn 6(C18H6O8)3(C 6H12N2O2)2] (2), |(C 3H7NO)2- (H2O)2(H 3O)2|[Cd3(C18H6O 8)2] (3), |(C3H7NO)|[Mn- (C 18H8O8)(C3H7NO) 2] (4), |(C3H7NO)2(H2O)(C 2H7N)3| [Mn6(C18H 7O8)4(H2O)8] (5), and [Mn2(C18H6O8)(C3H 7NO)2] (6), have been constructed under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. In these compounds, the ligand, H4EBDC, exhibits different coordination modes and conformations, constructing various architectures by bridging a variety of metal ions or polynuclear clusters. Compound 1 forms a three-dimensional (3D) FSC network constructed from two-dimensional (2D) layer motifs joined by EBDC4- and 4,4\\'-bipyridine bridges. Compound 2 possesses an NbO topology by linking Zn2(CO2)4 units with the ligand, coordinated amine molecules fill the pores, while compound 3 exhibits a 3D FLU network with Cd2+ as the cation and features an infinite framework built from tricadmium clusters. Compound 4 is based on PtS net, constructed of 4-connected rectangular H4EBDC units with tetrahedral monometallic Mn(CO2)4 nodes. Compound 5 is composed of 2D layers with (3,6)-connected KGD topology, and compound 6 consists of a 3D PtS-X network, built by bridging a metal chain with the ligand. The structures of these compounds have been discussed together with their corresponding properties, such as gas storage, separation, and magnetic properties. © 2013 American Chemical Society.

  20. EFRC: Polymer-Based Materials for Harvesting Solar Energy (stimulus)"

    Energy Technology Data Exchange (ETDEWEB)

    Russell, Thomas P. [Univ. of Massachusetts, Amherst, MA (United States)

    2016-12-08

    The University of Massachusetts Amherst is proposing an Energy Frontier Research Center (EFRC) on Polymer-Based Materials for Harvesting Solar Energy that will integrate the widely complementary experimental and theoretical expertise of 23 faculty at UMass-Amherst Departments with researchers from the University of Massachusetts Lowell, University of Pittsburgh, the Pennsylvania State University and Konarka Technologies, Inc. Collaborative efforts with researchers at the Oak Ridge National Laboratory, the University of Bayreuth, Seoul National University and Tohoku University will complement and expand the experimental efforts in the EFRC. Our primary research aim of this EFRC is the development of hybrid polymer-based devices with efficiencies more than twice the current organic-based devices, by combining expertise in the design and synthesis of photoactive polymers, the control and guidance of polymer-based assemblies, leadership in nanostructured polymeric materials, and the theory and modeling of non-equilibrium structures. A primary goal of this EFRC is to improve the collection and conversion efficiency of a broader spectral range of solar energy using the directed self-assembly of polymer-based materials so as to optimize the design and fabrication of inexpensive devices.

  1. 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.

  2. synthesis and optical properties of self-assembled coordination ...

    African Journals Online (AJOL)

    The coordination chemistry of the phenylmalonic acid and 4-1H- amino- 1,2,4- triazole with Zn(II) ions has been investigated. The coordination polymer was synthesized by slow evaporation method and characterized by FT-infrared spectroscopy, ultraviolet-visible measurements, scanning electron microscopy, Electron ...

  3. Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

    Science.gov (United States)

    Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

    2016-01-11

    The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Diverse assemblies of the (4,4) grid layers exemplified in Zn(II)/Co(II) coordination polymers with dual linear ligands

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Guang-Zhen; Li, Xiao-Dong; Xin, Ling-Yun; Li, Xiao-Ling [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, Henan 471022 (China); Wang, Li-Ya, E-mail: wlya@lynu.edu.cn [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, Henan 471022 (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang, Henan 473061 (China)

    2013-07-15

    Diverse (4,4) grid layers are exemplified in five two-dimensional coordination polymers with dual µ{sub 2}-bridged ligands, namely, ([Zn(cbaa)(bpp)]·H{sub 2}O){sub n} (1), [Zn{sub 2}(cbaa){sub 2}(bpy)]{sub n} (2), [Co{sub 2}(cbaa){sub 2}(bpp){sub 2}]{sub n} (3), [Co(cbaa)(bpp)]{sub n} (4), and [Co(bdaa)(bpp)(H{sub 2}O){sub 2}]{sub n} (5) (H{sub 2}cbaa=4-carboxybenzeneacetic acid, bpp=1,3-di(4-pyridyl)propane, bpy=4,4′-bipyridyl, and H{sub 2}bdaa=1,4-benzenediacrylic acid). For 1, two (4,4) grid layers with [ZnN{sub 2}O{sub 2}] tetrahedron as the node are held together by lattice water forming a H-bonding bilayer. Individual (4,4) grid layer in 2 is based on (Zn{sub 2}(OCO){sub 4}) paddlewheel unit as the node. Two (4,4) grid layers with (Co{sub 2}O(OCO){sub 2}) dimer as the node are covalently interconnected by organic ligands affording a thick bilayer of 3 with new framework topology. The different entanglements between two coincident (4,4) grid layers with [CoN{sub 2}O{sub 4}] octahedron as the node leads to two 2D→2D interpenetrated structures for 4 and 5. Furthermore, fluorescent properties of 1 and 2 as well as magnetic properties of 3 are investigated. - Graphical abstract: Diverse assemblies of the (4,4) grid layers with different network nodes forms five coordination polymers that are well characterized by IR, TGA, element analysis, fluorescent and magnetic measurement. - Highlights: • Diverse assemblies of the (4,4) grid layers with different structural units as the nodes. • A new topology type with the uninodal 6-connected net of (4{sup 12}.5{sup 2}.6) is found. • Intense fluorescence emissions with a rare blue-shift of 55 nm compared to free carboxylate ligand.

  5. Synthesis and Characterization of Chlorinated Bisphenol-Based Polymers and Polycarbodiimides as Inherently Fire-Safe Polymers

    National Research Council Canada - National Science Library

    Stewart, Jennifer

    2000-01-01

    .... The first class, 1,1-dichloro-2,2-(4-hydroxyphenyl)ethylidene (bisphenol C) based polymers, were found to be among the most fire- resistant polymers with peak heat release capacities as low as 20 J/g-K...

  6. Field-Induced Single-Ion Magnet Behaviour in Two New Cobalt(II Coordination Polymers with 2,4,6-Tris(4-pyridyl-1,3,5-triazine

    Directory of Open Access Journals (Sweden)

    Dong Shao

    2017-12-01

    Full Text Available We herein reported the syntheses, crystal structures, and magnetic properties of a two-dimensional coordination polymer {[CoII(TPT2/3(H2O4][CH3COO]2·(H2O4}n (1 and a chain compound {[CoII(TPT2(CHOO2(H2O2]}n (2 based on the 2,4,6-Tris(4-pyridyl-1,3,5-triazine (TPT ligand. Structure analyses showed that complex 1 had a cationic hexagonal framework structure, while 2 was a neutral zig-zag chain structure with different distorted octahedral coordination environments. Magnetic measurements revealed that both complexes exhibit large easy-plane magnetic anisotropy with the zero-field splitting parameter D = 47.7 and 62.1 cm−1 for 1 and 2, respectively. This magnetic anisotropy leads to the field-induced slow magnetic relaxation behaviour. However, their magnetic dynamics are quite different; while complex 1 experienced a dominating thermally activated Orbach relaxation at the whole measured temperature region, 2 exhibited multiple relaxation pathways involving direct, Raman, and quantum tunneling (QTM processes at low temperatures and Orbach relaxation at high temperatures. The present complexes enlarge the family of framework-based single-ion magnets (SIMs and highlight the significance of the structural dimensionality to the final magnetic properties.

  7. 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

  8. 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.

  9. Micro practices of coordination based on complex adaptive systems: user needs and strategies for coordinating public health in Denmark.

    Science.gov (United States)

    Terkildsen, Morten Deleuran; Wittrup, Inge; Burau, Viola

    2015-01-01

    Many highly formalised approaches to coordination poorly fit public health and recent studies call for coordination based on complex adaptive systems. Our contribution is two-fold. Empirically, we focus on public health, and theoretically we build on the patient perspective and treat coordination as a process of contingent, two-level negotiations of user needs. The paper draws on the concept of user needs-based coordination and sees coordination as a process, whereby needs emerging from the life world of the user are made amenable to the health system through negotiations. The analysis is based on an explorative case study of a health promotion initiative in Denmark. It adopts an anthropological qualitative approach and uses a range of qualitative data. The analysis identifies four strategies of coordination: the coordinator focusing on the individual user or on relations with other professionals; and the manager coaching the coordinator or providing structural support. Crucially, the coordination strategies by management remain weak as they do not directly relate to specific user needs. In process of bottom-up negotiations user needs become blurred and this is especially a challenge for management. The study therefore calls for an increased focus on the level nature of negotiations to bridge the gap that currently weakens coordination strategies by management.

  10. Practical applications of the geographic coordinate data base in Arkansas

    Science.gov (United States)

    Mickie Warwick; Don C. Bragg

    2005-01-01

    Though not intended for these applications, the General Land Office (GLO) survey notes are a primary source of historical, ecological, and cultural information, making it imperative that their spatial coordinates be as reliable as possible. The Geographic Coordinate Data Base (GCDB) is a statistically-based coordinate fitting program that uses the GLO notes and other...

  11. 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.

  12. Monomers, dimers, and trimers of [Au(CN2]− in a Ba(diaza-18-crown-62+ coordination polymer

    Directory of Open Access Journals (Sweden)

    2009-03-01

    Full Text Available The structure of the title compound, poly[triaquatetra-μ-cyanido-tetracyanidobis(1,4,10,13-tetraoxa-7,16-diazacyclooctadecanedibarium(IItetragold(I], [Au4Ba2(CN8(C12H26N2O42(H2O3]n, displays O—H...N hydrogen bonding between water molecules and cyano ligands and an unusual pattern of aurophilic interactions that yields a monomer, dimer, and trimer of [Au(CN2]− within the same crystal structure. In two of the five Au positions, the atom resides on a center of inversion. The overall arrangement is that of a coordination polymer assisted by aurophilic and hydrogen-bonded interactions.

  13. 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.

  14. Pyridine-Based Conjugated Polymers: Photophysical Properties and Light- Emitting Diodes

    National Research Council Canada - National Science Library

    Epstein, A

    1997-01-01

    We study the photophysical properties of the pyridine-based polymers poly (p-pyridyl vinylene) (PPyV) and poly (p-pyridine) (PPy). The primary photoexcitations in the pyridine-based polymers are singlet excitons...

  15. Micro practices of coordination based on complex adaptive systems: user needs and strategies for coordinating public health in Denmark

    Directory of Open Access Journals (Sweden)

    Morten Deleuran Terkildsen

    2015-09-01

    Full Text Available Introduction: Many highly formalised approaches to coordination poorly fit public health and recent studies call for coordination based on complex adaptive systems. Our contribution is two-fold. Empirically, we focus on public health, and theoretically we build on the patient perspective and treat coordination as a process of contingent, two-level negotiations of user needs.Theory and Methods: The paper draws on the concept of user needs-based coordination and sees coordination as a process, whereby needs emerging from the life world of the user are made amenable to the health system through negotiations. The analysis is based on an explorative case study of a health promotion initiative in Denmark. It adopts an anthropological qualitative approach and uses a range of qualitative data.Results: The analysis identifies four strategies of coordination: the coordinator focusing on the individual user or on relations with other professionals; and the manager coaching the coordinator or providing structural support. Crucially, the coordination strategies by management remain weak as they do not directly relate to specific user needs.Discussion: In process of bottom-up negotiations user needs become blurred and this is especially a challenge for management. The study therefore calls for an increased focus on the level nature of negotiations to bridge the gap that currently weakens coordination strategies by management.

  16. Appraisal of the coordinator-based transplant organizational model.

    Science.gov (United States)

    Filipponi, F; De Simone, P; Mosca, F

    2005-01-01

    In 1999, the Italian Parliament passed a law aimed at setting the standards of practice and quality in organ, tissue and cell donation, and transplantation. For the first time in the history of Italian transplantation, a coordinator-based model reproducing some of the basic principles of the Spanish system was officially enacted by the Parliament, bringing to an end years of lacking regulation. What differentiates those coordinator-based systems adopted in Southern Europe from Northern European national and multinational transplant organizations is the functional integration of donor and transplant care activities enacted by national governments. The Italian model of transplant health care consists of four levels of transplant coordination: local, regional, interregional, and national. The latter is represented by Centro Nazionale Trapianti (CNT; the Italian National Center for Transplantation). CNT objectives consist of ensuring equitable access to donation and transplant care for all citizens according to the principles of the Italian National Health System. In achieving these goals, CNT acts in cooperation with three interregional transplant agencies: the Nord Italia Transplant program, the Associazione InterRegionale Trapianti, and the Organizzazione Centro Sud Trapianti. Whereas local and interregional coordinators are at the front line of all donation and transplant activities, regional and national coordinators function to monitor, direct, and plan donation and transplant health care activities. Based on the increase in donation and transplant activities recently achieved in those countries that have adopted a governmental coordinator-based transplant care model, we believe that such a system is appropriate to serve patients' interests according to the principles of subsidiary and equity. However, it should further be improved by expansion of the governance model throughout Europe, through implementation of current standards of care, and by adopting the

  17. Design, synthesis, and characterization of 0-D, 1-D, and 2-D Zinc–Adeninate coordination assemblies

    Energy Technology Data Exchange (ETDEWEB)

    An, Ji Hyun [Dept. of Chemistry Education, Seoul National University, Seoul (Korea, Republic of); Geib, Steven J. [Dept. of Chemistry, University of Pittsburgh, Pittsburgh (United States); Kim, Myung Gil [Dept. of Chemistry, Chungang University, Seoul (Korea, Republic of)

    2015-08-15

    In this study, we demonstrate the synthesis and characterization of zinc– adeninate coordination polymers with 0-D, 1-D, and 2-D structures. We describe methods for controlling the structure of these materials by applying different synthetic conditions and discuss their structural relationships. 0-D, 1-D, and 2-D zinc–adeninate coordination polymers with the same metal–adeninate coordination mode were synthesized and characterized. By controlling the temperature, a material with 0-D macrocycle or 1-D chain coordination polymer was prepared. A replacement of pyridine with bipyridine formed 2-D sheet structure by connecting 1-D chains with each other. They exhibited an interesting relationship between synthetic methods and structures. Further study of metal–adeninate coordination chemistry will render a precise control of the structure in synthesis and will open a new venue to new materials with fascinating properties.

  18. 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...

  19. Thermo- and piezochromic properties of [Fe(hyptrz)]A{sub 2}·H{sub 2}O spin crossover 1D coordination polymer: Towards spin crossover based temperature and pressure sensors

    Energy Technology Data Exchange (ETDEWEB)

    Jureschi, Catalin-Maricel [Department of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Stefan cel Mare University, University Street 13, Suceava 720229 (Romania); LISV, UVSQ, 78035 Versailles Cedex (France); Rusu, Ionela [Department of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Stefan cel Mare University, University Street 13, Suceava 720229 (Romania); Codjovi, Epiphane [Groupe d’Etude de la Matière Condensée (GEMaC), CNRS-UMR 8635, UVSQ, 78035 Versailles Cedex (France); Linares, Jorge, E-mail: jorge.linares@uvsq.fr [Groupe d’Etude de la Matière Condensée (GEMaC), CNRS-UMR 8635, UVSQ, 78035 Versailles Cedex (France); Garcia, Yann [Institute of Condensed Matter and Nanosciences, Molecules, Solids, Reactivity (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium); Rotaru, Aurelian, E-mail: rotaru@eed.usv.ro [Department of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Stefan cel Mare University, University Street 13, Suceava 720229 (Romania)

    2014-09-15

    We have used reflectance measurements to investigate the effect of a hydrostatic pressure on the molecular 1D spin crossover coordination polymer [Fe(hyptrz)]A{sub 2}·H{sub 2}O (hyptrz=4-(3′-hydroxypropyl)-1,2,4-triazole and A=4-chloro-benzenesulfonate) Rev. Sci. Instrum. 80 (2009) 123901. Both thermal and pressure hysteresis have been recorded at different pressures and temperatures, respectively, in order to obtain valuable information about the optimal conditions of their use as wireless temperature and pressure sensors. The experimental analysis has been completed with a theoretical study and potential applications in terms of temperature and pressure wireless detection are discussed.

  20. 1D Cu(II) coordination polymer derived from 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzenesulfonate chelator and pyrazine spacer

    Science.gov (United States)

    Mahmudov, Kamran T.; Haukka, Matti; Sutradhar, Manas; Mizar, Archana; Kopylovich, Maximilian N.; Pombeiro, Armando J. L.

    2013-02-01

    Reaction of 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzenesulfonic acid (H2L) with copper(II) nitrate hydrate in the presence of pyrazine (pz) in methanol affords the coordination polymer [Cu2(μ-L)2(H2O)2(μ-pz)]n (1), where the bidentate pz molecule links two Cu(II) centres of two different dimeric units, giving rise to a one-dimensional chain. The dimeric unit [Cu2(μ-L)2(H2O)2] consists of two distorted octahedral Cu(II) centres connected via oxygen atoms of the sulfo group of the bridging L2- ligand. The extensive hydrogen bonding between the coordinated water and pz molecules leads to the formation of a supramolecular 3D associate. Compound 1 has been characterized by elemental analysis, ESI-MS, IR spectroscopy and single-crystal X-ray diffraction analysis.

  1. Perturbing Tandem Energy Transfer in Luminescent Heterobinuclear Lanthanide Coordination Polymer Nanoparticles Enables Real-Time Monitoring of Release of the Anthrax Biomarker from Bacterial Spores.

    Science.gov (United States)

    Gao, Nan; Zhang, Yunfang; Huang, Pengcheng; Xiang, Zhehao; Wu, Fang-Ying; Mao, Lanqun

    2018-06-05

    Lanthanide-based luminescent sensors have been widely used for the detection of the anthrax biomarker dipicolinic acid (DPA). However, mainly based on DPA sensitization to the lanthanide core, most of them failed to realize robust detection of DPA in bacterial spores. We proposed a new strategy for reliable detection of DPA by perturbing a tandem energy transfer in heterobinuclear lanthanide coordination polymer nanoparticles simply constructed by two kinds of lanthanide ions, Tb 3+ and Eu 3+ , and guanosine 5'-monophosphate. This smart luminescent probe was demonstrated to exhibit highly sensitive and selective visual luminescence color change upon exposure to DPA, enabling accurate detection of DPA in complex biosystems such as bacterial spores. DPA release from bacterial spores on physiological germination was also successfully monitored in real time by confocal imaging. This probe is thus expected to be a powerful tool for efficient detection of bacterial spores in responding to anthrax threats.

  2. Role of water in the dynamic disproportionation of Zn-based TCNQ(F4) coordination polymers (TCNQ = tetracyanoquinodimethane).

    Science.gov (United States)

    Nafady, Ayman; Le, Thanh Hai; Vo, Nguyen; Haworth, Naomi L; Bond, Alan M; Martin, Lisandra L

    2014-02-17

    Intriguingly, coordination polymers containing TCNQ(2–) and TCNQF4(2–) (TCNQ = 7,7,8,8-tetracyanoquinodimethane, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, both designated as TCNQ(F4)(2–)) may be generated from reaction of metal ions with TCNQ(F4)•–. An explanation is now provided in terms of a solvent-dependent dynamic disproportionation reaction. A systematic study of reactions associated with TCNQ(F4) and electrochemically generated TCNQ(F4)MeCN•– and TCNQ(F4)MeCN(2–) revealed that disproportionation of TCNQ(F4)MeCN•– radical anions in acetonitrile containing a low concentration of water is facilitated by the presence of ZnMeCN(2+). Thus, while the disproportionation reaction 2TCNQ(F4)MeCN•– TCNQ(F4)MeCN + TCNQ(F4)MeCN(2–) is thermodynamically very unfavorable in this medium (Keq ≈ 9 × 10(–10); TCNQF4), the preferential precipitation of ZnTCNQ(F4)(s) drives the reaction: ZnMeCN(2+) + 2 TCNQ(F4)MeCN•– ZnTCNQ(F4)(s) + TCNQ(F4)MeCN. The concomitant formation of soluble TCNQ(F4)MeCN and insoluble ZnTCNQ(F4)(s) and the loss of TCNQ(F4)MeCN•– were verified by UV–visible and infrared spectroscopy and steady-state voltammetry. Importantly, the reverse reaction of comproportionation rather than disproportionation becomes the favored process in the presence of ≥3% (v/v) water, due to the increased solubility of solid ZnTCNQ(F4)(s). Thus, in this “wet” environment, ZnMeCN(2+) and TCNQ(F4)MeCN•– are produced from a mixture of ZnTCNQ(F4)(s) and TCNQ(F4)MeCN and with the addition of water provides a medium for synthesis of [Zn(TCNQ(F4))2(H2O)2]. An important conclusion from this work is that the redox level of TCNQ(F4)-based materials, synthesized from a mixture of metal cations and TCNQ(F4)•–, is controlled by a solvent-dependent disproportionation/comproportionation reaction that may be tuned to favor formation of solids containing the monoanion radical, the dianion, or even a mixture of both.

  3. Synthesis and characterization of the mixed ligand coordination polymer CPO-5

    International Nuclear Information System (INIS)

    Kongshaug, K.O.; FjellvAg, Helmer

    2003-01-01

    The synthesis and crystal structures of a novel coordination polymer and its high-temperature variant are described. The as-synthesized material (CPO-5-as), of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate)·3H 2 O, crystallizes in the triclinic space group P-1 (No. 2) with a=11.0197(2), b=14.2975(3), c=7.6586(1) A, α=95.9760(9) deg. , β=108.026(1) deg. , γ=91.373(1) deg. and V=1139.16(4) A 3 . CPO-5-as is composed of tetrahedral zinc centers that are connected by the organic linkers to give five independent, interpenetrating diamond networks. In the structure, there is additional space for channels that are filled with three water molecules. These water molecules can be removed, leading to an anhydrous variant at 130 o C. CPO-5-130, of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate), crystallizes in the triclinic space group P-1 (No. 2) with a=11.1844(6), b=14.0497(7), c=7.7198(3) A, α=96.917(2) deg. , β=109.527(2) deg. , γ=89.115(3) deg. and V=1134.6(1) A 3 . The structure of the five interpenetrating networks is virtually unchanged after the dehydration resulting in CPO-5-130 being a porous structure with an estimated free volume of 19.8%

  4. Photo- and thermochromic and adsorption properties of porous coordination polymers based on bipyridinium carboxylate ligands.

    Science.gov (United States)

    Toma, Oksana; Mercier, Nicolas; Allain, Magali; Kassiba, Abdel Adi; Bellat, Jean-Pierre; Weber, Guy; Bezverkhyy, Igor

    2015-09-21

    The zwitterionic bipyridinium carboxylate ligand 1-(4-carboxyphenyl)-4,4'-bipyridinium (hpc1) in the presence of 1,4-benzenedicarboxylate anions (BDC(2-)) and Zn(2+) ions affords three porous coordination polymers (PCPs): [Zn5(hpc1)2(BDC)4(HCO2)2]·2DMF·EtOH·H2O (1), [Zn3(hpc1)(BDC)2(HCO2)(OH)(H2O)]·DMF·EtOH·H2O (2), and [Zn10(hpc1)4(BDC)7(HCO2)2(OH)4(EtOH)2]·3DMF·3H2O (3), with the formate anions resulting from the in situ decomposition of dimethylformamide (DMF) solvent molecules. 1 and 3 are photo- and thermochromic, turning dark green as a result of the formation of bipyridinium radicals, as shown by electron paramagnetic resonance measurements. Particularly, crystals of 3 are very photosensitive, giving an eye-detectable color change upon exposure to the light of the microscope in air within 1-2 min. A very nice and interesting feature is the regular discoloration of crystals from the "edge" to the "core" upon exposition to O2 (reoxidation of organic radicals) due to the diffusion of O2 inside the pores, with this discoloration being slower in an oxygen-poor atmosphere. The formation of organic radicals is explained by an electron transfer from the oxygen atoms of the carboxylate groups to pyridinium cycles. In the structure of 3', [Zn10(hpc1)4(BDC)7(OH)6(H2O)2], resulting from the heating of sample 3 (desolvation and loss of CO molecules due to the decomposition of formate anions), no suitable donor-acceptor interaction is present, and as a consequence, this compound does not exhibit any chromic properties. The presence of permanent porosity in desolvated 1, 2, and 3' is confirmed by methanol adsorption at 25 °C with the adsorbed amount reaching 5 wt % for 1, 10 wt % for 3', and 13 wt % for 2. The incomplete desorption of methanol at 25 °C under vacuum points to strong host-guest interactions.

  5. Preparation and mechanical property of polymer-based biomaterials

    International Nuclear Information System (INIS)

    Zhang, P; Chen, G; Zheng, X F

    2010-01-01

    The porous polymer-based biomaterial has been synthesized from PLGA, dioxane and tricalcium phosphate (TCP) by low-temperature deposition process. The deformation behaviours and fracture mechanism of polymer-based biomaterials were investigated using the compression test and the finite element (FE) simulation. The results show that the stress-strain curve of compression process includes linear elastic stage I, platform stage II and densification stage III, and the fracture mechanism can be considered as brittle fracture.

  6. 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.

  7. based gel polymer electrolytes

    Indian Academy of Sciences (India)

    (PVdF) as a host polymer, lithium perchlorate (LiClO4), lithium triflate ... TG/DTA studies showed the thermal stability of the polymer electrolytes. .... are observed while comparing pure XRD spectra with .... batteries as its operating temperature is normally in the .... chain ion movements and the conductivity of the polymer.

  8. Radiation synthesis and modification of polymers for biomedical applications. Final results of a co-ordinated research project. 1996-2000

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2002-12-01

    Radiation techniques are being used for synthesis of hydrogels, functional polymers, interpenetrating systems, chemical modification of surfaces, immobilization of bioactive materials, synthesis of functional micro- and nanospheres and processing of naturally derived biomaterials. Potential medical applications of these biomaterials include implants, topical dressings, treatment devices and drug delivery systems. Biotechnological applications include diagnostic assays, separation and purification systems, immobilized enzyme and cell bioprocesses and cell culture surfaces. The main objective of the CRP on The use of Radiation Processing to Prepare Biomaterials for Application in Medicine was to co-ordinate the research carried out in the participating countries, to ensure that different research programmes complement each other and the information exchange is available to all. Furthermore, the objective was to expand the use of ionizing radiation in two major areas: synthesis of polymers and gels for medical and biotechnological applications, and modification of surfaces to achieve a specific functionality and/or to immobilize bioactive materials. This publication contains 10 reports of participants; each of the reports has been indexed separately.

  9. Radiation synthesis and modification of polymers for biomedical applications. Final results of a co-ordinated research project. 1996-2000

    International Nuclear Information System (INIS)

    2002-12-01

    Radiation techniques are being used for synthesis of hydrogels, functional polymers, interpenetrating systems, chemical modification of surfaces, immobilization of bioactive materials, synthesis of functional micro- and nanospheres and processing of naturally derived biomaterials. Potential medical applications of these biomaterials include implants, topical dressings, treatment devices and drug delivery systems. Biotechnological applications include diagnostic assays, separation and purification systems, immobilized enzyme and cell bioprocesses and cell culture surfaces. The main objective of the CRP on The use of Radiation Processing to Prepare Biomaterials for Application in Medicine was to co-ordinate the research carried out in the participating countries, to ensure that different research programmes complement each other and the information exchange is available to all. Furthermore, the objective was to expand the use of ionizing radiation in two major areas: synthesis of polymers and gels for medical and biotechnological applications, and modification of surfaces to achieve a specific functionality and/or to immobilize bioactive materials. This publication contains 10 reports of participants; each of the reports has been indexed separately

  10. Synthesis and characterization of new coordination polymer with l-proline amino acid ligand, new precursor for preparation of pure phase lead(II) oxide nanoparticles via thermal decomposition

    Czech Academy of Sciences Publication Activity Database

    Varzdar, S.; Hashemi, L.; Morsali, A.; Dušek, Michal

    2017-01-01

    Roč. 14, č. 11 (2017), s. 2255-2261 ISSN 1735-207X Institutional support: RVO:68378271 Keywords : coordination polymer * nanoparticle * lead(II) oxide * proline amino acid Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.407, year: 2016

  11. Polymer-based oral rehydration solution for treating acute watery diarrhoea

    Science.gov (United States)

    Gregorio, Germana V; Gonzales, Maria Liza M; Dans, Leonila F; Martinez, Elizabeth G

    2016-01-01

    Background Acute diarrhoea is one of the main causes of morbidity and mortality among children in low-income countries. Glucose-based oral rehydration solution (ORS) helps replace fluid and prevent further dehydration from acute diarrhoea. Since 2004, the World Health Organization (WHO) has recommended the osmolarity of less than 270 mOsm/L (ORS ≤ 270) versus greater than 310 mOsm/L formulation (ORS ≥ 310). Polymer-based ORS (for example, prepared using rice or wheat) slowly releases glucose and may be superior to glucose-based ORS. Objectives To compare polymer-based oral rehydration solution (polymer-based ORS) with glucose-based oral rehydration solution (glucose-based ORS) for treating acute watery diarrhoea. Search methods We searched the following sources up to 5 September 2016: the Cochrane Infectious Diseases Group (CIDG) Specialized Register, the Cochrane Central Register of Controlled Trials (CENTRAL) (the Cochrane Library 2016, Issue 9), MEDLINE (1966 to 5 September 2016), EMBASE (1974 to 5 September 2016), LILACS (1982 to 5 September 2016), and mRCT (2007 to 5 September 2016). We also contacted researchers, organizations, and pharmaceutical companies, and searched reference lists. Selection criteria We included randomized controlled trials (RCTs) of people with acute watery diarrhoea (cholera and non-cholera associated) that compared polymer-based and glucose-based ORS (with identical electrolyte contents). Data collection and analysis Two review authors independently assessed the search results and risk of bias, and extracted data. In multiple-treatment arms with two or more treatment groups, we combined outcomes as appropriate and compared collectively with the control group. Main results Thirty-five trials that included 4284 participants met the inclusion criteria: 28 trials exclusively included children, five included adults, and two included both adults and children. Polymer-based ORS versus glucose-based ORS (osmolarity ≤ 270) Eight trials

  12. Team Scaffolds: How Minimal Team Structures Enable Role-based Coordination

    OpenAIRE

    Valentine, Melissa A

    2013-01-01

    In this dissertation, I integrate research on role-based coordination with concepts adapted from the team effectiveness literature to theorize how minimal team structures support effective coordination when people do not work together regularly. I argue that role-based coordination among relative strangers can be interpersonally challenging and propose that team scaffolds (minimal team structures that bound groups of roles rather than groups of individuals) may provide occupants with a tempor...

  13. 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.

  14. Plastic scintillators based on polymers with eliminated excimer forming

    Energy Technology Data Exchange (ETDEWEB)

    Adadurov, A.F., E-mail: adadurov@isma.kharkov.u [Institute for Scintillating Materials NAN of Ukraine, 60 Lenin Ave, 61001 Kharkov (Ukraine); Yelyseev, D.A.; Titskaya, V.D.; Lebedev, V.N.; Zhmurin, P.N. [Institute for Scintillating Materials NAN of Ukraine, 60 Lenin Ave, 61001 Kharkov (Ukraine)

    2011-05-15

    Plastic scintillators (PS) were made based on benzyl methacrylate and methyl-methacrylate P(BzMA + MMA) copolymer in which the excimer forming rate is by two order lesser than that in polystyrene-based polymer matrix. Studying of these PS light yield demonstrates the importance of migration processes comparing to excimer formation. It is found that to obtain PS with high scintillation efficiency it is necessary to use the polymer base (matrix) in which excimer forming is eliminated but the migration process along the chromophores is maximally favored. To explain the accelerated energy transfer between phenyl chromophores it is proposed to use a mechanism of exchange of that virtual excitons that can propagate along a one-dimensional back-bone of polymer molecule. Clearing the details of mechanism of interaction between chromophores of polymer molecules which is responsible for accelerated radiationless energy transfer enable will determine in future the way of effective plastic scintillators designing.

  15. New Ag(I)-iminophosphorane coordination polymers as efficient catalysts precursors for the MW-assisted Meyer-Schuster rearrangement of propargylic alcohols in water.

    Science.gov (United States)

    García-Álvarez, Joaquín; Díez, Josefina; Vidal, Cristian; Vicent, Cristian

    2013-06-03

    Treatment of the N-thiophosphorylated iminophosphorane ligands (PTA)═NP(═S)(OR)2 [PTA = 1,3,5-triaza-7-phosphaadamantane, 3a and 3b] and (DAPTA)═NP(═S)(OR)2 [DAPTA = 3,7-diacetyl-1,3,7-triaza-5-bicyclo[3.3.1]nonane, 4a and 4b] with an equimolecular amount of AgSbF6 leads to high-yield formation of the new one-dimensional coordination polymers [Ag{μ(2)-N,S-(PTA)═NP(═S)(OR)2}]x[SbF6]x (5a and 5b) and [Ag{μ(2)-O,S-(DAPTA)═NP(═S)(OR)2}]x[SbF6]x (6a and 6b), respectively. These new (iminophosphorane)silver(I) coordination polymers are efficient catalyst precursors for the Meyer-Schuster isomerization of both terminal and internal alkynols. Reactions proceeded in water, under aerobic conditions and using microwave irradiation as heating source, to afford the corresponding α,β-unsaturated carbonyl compounds in excellent yields, without the addition of any cocatalyst. Remarkably, it should be noted that this catalytic system can be recycled up to 10 consecutive runs (1st cycle 45 min, 99%; 10th cycle 6 h, 97%). ESI-MS analysis of 5a in water has been carried out providing valuable insight into the monomeric active species responsible for catalytic activity in water.

  16. Injection Molding and Mechanical Properties of Bio-Based Polymer Nanocomposites

    Directory of Open Access Journals (Sweden)

    Maria Chiara Mistretta

    2018-04-01

    Full Text Available The use of biodegradable/bio-based polymers is of great importance in addressing several issues related to environmental protection, public health, and new, stricter legislation. Yet some applications require improved properties (such as barrier or mechanical properties, suggesting the use of nanosized fillers in order to obtain bio-based polymer nanocomposites. In this work, bionanocomposites based on two different biodegradable polymers (coming from the Bioflex and MaterBi families and two different nanosized fillers (organo-modified clay and hydrophobic-coated precipitated calcium carbonate were prepared and compared with traditional nanocomposites with high-density polyethylene (HDPE as matrix. In particular, the injection molding processability, as well as the mechanical and rheological properties of the so-obtained bionanocomposites were investigated. It was found that the processability of the two biodegradable polymers and the related nanocomposites can be compared to that of the HDPE-based systems and that, in general, the bio-based systems can be taken into account as suitable alternatives.

  17. Synthesis and Characterization of Novel Copper(II 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability

    Directory of Open Access Journals (Sweden)

    Kayoko Kasai

    2011-11-01

    Full Text Available Two-dimensional (2D grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyltetrafluorobenzene (bpf with Cu(NO32 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf2(NO32]·(biphenyl2}n (1, {[Cu(bpf2(NO32]·(m-C6H4(OMe22}n (2, {[Cu(bpf2(NO32]·PhtBu}n (3 and {[Cu(bpf2(NO3(H2O]NO3·(bpf0.5}n (4 were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3− anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds.

  18. 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.

  19. Radiation processing of natural polymers: The IAEA contribution

    Science.gov (United States)

    Haji-Saeid, Mohammad; Safrany, Agnes; Sampa, Maria Helena de O.; Ramamoorthy, Natesan

    2010-03-01

    Radiation processing offers a clean and additive-free method for preparation of value-added novel materials based on renewable, non-toxic, and biodegradable natural polymers. Crosslinked natural polymers can be used as hydrogel wound dressings, face cleaning cosmetic masks, adsorbents of toxins, and non-bedsore mats; while low molecular weight products show antibiotic, antioxidant, and plant-growth promoting properties. Recognizing the potential benefits that radiation technology can offer for processing of natural polymers into useful products, the IAEA implemented a coordinated research project (CRP) on "Development of Radiation-processed products of Natural Polymers for application in Agriculture, Healthcare, Industry and Environment". This CRP was launched at the end of 2007 with participation of 16 MS to help connecting radiation technology and end-users to derive enhanced benefits from these new value-added products of radiation-processed natural materials. In this paper the results of activities in participating MS related to this work will be presented.

  20. Radiation processing of natural polymers: The IAEA contribution

    International Nuclear Information System (INIS)

    Haji-Saeid, Mohammad; Safrany, Agnes; Sampa, Maria Helena de O.; Ramamoorthy, Natesan

    2010-01-01

    Radiation processing offers a clean and additive-free method for preparation of value-added novel materials based on renewable, non-toxic, and biodegradable natural polymers. Crosslinked natural polymers can be used as hydrogel wound dressings, face cleaning cosmetic masks, adsorbents of toxins, and non-bedsore mats; while low molecular weight products show antibiotic, antioxidant, and plant-growth promoting properties. Recognizing the potential benefits that radiation technology can offer for processing of natural polymers into useful products, the IAEA implemented a coordinated research project (CRP) on 'Development of Radiation-processed products of Natural Polymers for application in Agriculture, Healthcare, Industry and Environment'. This CRP was launched at the end of 2007 with participation of 16 MS to help connecting radiation technology and end-users to derive enhanced benefits from these new value-added products of radiation-processed natural materials. In this paper the results of activities in participating MS related to this work will be presented.

  1. Development of buccal drug delivery systems based on a thiolated polymer.

    Science.gov (United States)

    Langoth, Nina; Kalbe, Jochen; Bernkop-Schnürch, Andreas

    2003-02-18

    The purpose of the present study was to investigate the benefit of thiolated polymers (thiomers) for the development of buccal drug delivery systems. L-Cysteine was thereby covalently attached to polycarbophil (PCP) mediated by a carbodiimide. The resulting conjugate displayed 140.5+/-8.4 microM thiol groups per gram polymer. Disintegration studies were carried out with tablets based on unmodified polymer and conjugated polymer, respectively. Due to the formation of disulfide bonds within the thiolated polymer, the stability of matrix-tablets based on this polymer was strongly improved. Additionally tensile studies were carried out, which were in good correlation with further results obtained by mucoadhesion studies, using the rotating cylinder method. These results showed that tablets based on thiolated PCP remained attached on freshly excised porcine mucosa 1.8 times longer than the corresponding control. Moreover, the enzyme inhibitory properties of polymers were evaluated as well. Thiolated PCP increased the stability of the synthetic substrate for aminopeptidase N-leu-p-nitroanilide (N-leu-pNA) and the model drug leucin-enkephalin (leu-enkephalin) against enzymatic degradation on buccal mucosa. Due to the use of thiolated polymers also a controlled drug release for leu-enkephalin was guaranteed over a time period for more than 24 h. Results of the present studies suggest that thiolated polymers represent a very useful tool for buccal delivery of peptide drugs.

  2. Chemical microsensors based on polymer fiber composites

    Science.gov (United States)

    Kessick, Royal F.; Levit, Natalia; Tepper, Gary C.

    2005-05-01

    There is an urgent need for new chemical sensors for defense and security applications. In particular, sensors are required that can provide higher sensitivity and faster response in the field than existing baseline technologies. We have been developing a new solid-state chemical sensor technology based on microscale polymer composite fiber arrays. The fibers consist of an insulating polymer doped with conducting particles and are electrospun directly onto the surface of an interdigitated microelectrode. The concentration of the conducting particles within the fiber is controlled and is near the percolation threshold. Thus, the electrical resistance of the polymer fiber composite is very sensitive to volumetric changes produced in the polymer by vapor absorption. Preliminary results are presented on the fabrication and testing of the new microsensor. The objective is to take advantage of the very high surface to volume ratio, low thermal mass and linear geometry of the composite fibers to produce sensors exhibiting an extremely high vapor sensitivity and rapid response. The simplicity and low cost of a resistance-based chemical microsensor makes this sensing approach an attractive alternative to devices requiring RF electronics or time-of-flight analysis. Potential applications of this technology include battlespace awareness, homeland security, environmental surveillance, medical diagnostics and food process monitoring.

  3. Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

    KAUST Repository

    Pinnau, Ingo

    2015-02-05

    Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymers, a method of using triptycene-based ladder polymers, a structure incorporating triptycene-based ladder polymers, a method of gas separation, and the like.

  4. Electrostatic polymer-based microdeformable mirror for adaptive optics

    Science.gov (United States)

    Zamkotsian, Frederic; Conedera, Veronique; Granier, Hugues; Liotard, Arnaud; Lanzoni, Patrick; Salvagnac, Ludovic; Fabre, Norbert; Camon, Henri

    2007-02-01

    Future adaptive optics (AO) systems require deformable mirrors with very challenging parameters, up to 250 000 actuators and inter-actuator spacing around 500 μm. MOEMS-based devices are promising for the development of a complete generation of new deformable mirrors. Our micro-deformable mirror (MDM) is based on an array of electrostatic actuators with attachments to a continuous mirror on top. The originality of our approach lies in the elaboration of layers made of polymer materials. Mirror layers and active actuators have been demonstrated. Based on the design of this actuator and our polymer process, realization of a complete polymer-MDM has been done using two process flows: the first involves exclusively polymer materials while the second uses SU8 polymer for structural layers and SiO II and sol-gel for sacrificial layers. The latest shows a better capability in order to produce completely released structures. The electrostatic force provides a non-linear actuation, while AO systems are based on linear matrices operations. Then, we have developed a dedicated 14-bit electronics in order to "linearize" the actuation, using a calibration and a sixth-order polynomial fitting strategy. The response is nearly perfect over our 3×3 MDM prototype with a standard deviation of 3.5 nm; the influence function of the central actuator has been measured. First evaluation on the cross non-linarities has also been studied on OKO mirror and a simple look-up table is sufficient for determining the location of each actuator whatever the locations of the neighbor actuators. Electrostatic MDM are particularly well suited for open-loop AO applications.

  5. N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

    Science.gov (United States)

    Zhou, Zhi-Hang; Han, Min-Le; Wu, Ya-Pan; Dong, Wen-Wen; Li, Dong-Sheng; Lu, Jack Y.

    2016-10-01

    Two new Co(II) coordination polymers(CPs), namely [Co2(bpe)2(Hbppc)]n (1) and [Co3(μ3-OH)(bppc)(bpm)(H2O)]·3H2O (2) (H5bppc=biphenyl-2,4,6,3‧,5‧-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (44·610·8)(44·62) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co3(μ3-OH)]5+ units with unusual (3.46.52.6)(32.46.57.65.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system.

  6. Coordination Analysis Using Global Structural Constraints and Alignment-based Local Features

    Science.gov (United States)

    Hara, Kazuo; Shimbo, Masashi; Matsumoto, Yuji

    We propose a hybrid approach to coordinate structure analysis that combines a simple grammar to ensure consistent global structure of coordinations in a sentence, and features based on sequence alignment to capture local symmetry of conjuncts. The weight of the alignment-based features, which in turn determines the score of coordinate structures, is optimized by perceptron training on a given corpus. A bottom-up chart parsing algorithm efficiently finds the best scoring structure, taking both nested or non-overlapping flat coordinations into account. We demonstrate that our approach outperforms existing parsers in coordination scope detection on the Genia corpus.

  7. Coordinate based random effect size meta-analysis of neuroimaging studies.

    Science.gov (United States)

    Tench, C R; Tanasescu, Radu; Constantinescu, C S; Auer, D P; Cottam, W J

    2017-06-01

    Low power in neuroimaging studies can make them difficult to interpret, and Coordinate based meta-analysis (CBMA) may go some way to mitigating this issue. CBMA has been used in many analyses to detect where published functional MRI or voxel-based morphometry studies testing similar hypotheses report significant summary results (coordinates) consistently. Only the reported coordinates and possibly t statistics are analysed, and statistical significance of clusters is determined by coordinate density. Here a method of performing coordinate based random effect size meta-analysis and meta-regression is introduced. The algorithm (ClusterZ) analyses both coordinates and reported t statistic or Z score, standardised by the number of subjects. Statistical significance is determined not by coordinate density, but by a random effects meta-analyses of reported effects performed cluster-wise using standard statistical methods and taking account of censoring inherent in the published summary results. Type 1 error control is achieved using the false cluster discovery rate (FCDR), which is based on the false discovery rate. This controls both the family wise error rate under the null hypothesis that coordinates are randomly drawn from a standard stereotaxic space, and the proportion of significant clusters that are expected under the null. Such control is necessary to avoid propagating and even amplifying the very issues motivating the meta-analysis in the first place. ClusterZ is demonstrated on both numerically simulated data and on real data from reports of grey matter loss in multiple sclerosis (MS) and syndromes suggestive of MS, and of painful stimulus in healthy controls. The software implementation is available to download and use freely. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. Moving beyond mass-based parameters for conductivity analysis of sulfonated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Seung [Los Alamos National Laboratory; Pivovar, Bryan [NREL

    2009-01-01

    Proton conductivity of polymer electrolytes is critical for fuel cells and has therefore been studied in significant detail. The conductivity of sulfonated polymers has been linked to material characteristics in order to elucidate trends. Mass based measurements based on water uptake and ion exchange capacity are two of the most common material characteristics used to make comparisons between polymer electrolytes, but have significant limitations when correlated to proton conductivity. These limitations arise in part because different polymers can have significantly different densities and conduction happens over length scales more appropriately represented by volume measurements rather than mass. Herein, we establish and review volume related parameters that can be used to compare proton conductivity of different polymer electrolytes. Morphological effects on proton conductivity are also considered. Finally, the impact of these phenomena on designing next generation sulfonated polymers for polymer electrolyte membrane fuel cells is discussed.

  9. Study of a thiophene-based polymer for optoelectronic applications

    International Nuclear Information System (INIS)

    Cheylan, S.; Fraleoni-Morgera, A.; Puigdollers, J.; Voz, C.; Setti, L.; Alcubilla, R.; Badenes, G.; Costa-Bizzarri, P.; Lanzi, M.

    2006-01-01

    A thiophene-based conjugated polymer bearing a cyano group (-CN) as a side chain substituent was successfully synthesized. The polymer evidences an excellent film ability from various organic solvents as well as an enhanced photoluminescence. The polymer has been characterized optically (Fourier Transformed Infrared spectroscopy, absorption and photoluminescence) in solution and in film, while X-ray diffraction measurements (XRD) of thin films were performed to investigate its bulk morphological features. From the absorption edge of the spectrum of a thin polymer film, the optical band gap of the polymer is estimated to be 2.0 eV, which corresponds to orange emission. Furthermore, a single layer light emitting diode (LED) was fabricated. The device produced bright stable electroluminescence at room temperature. All of the results indicate that this polymer is a promising emissive material for application in polymeric LEDs

  10. Reversible and Topotactic Solvent Removal in a Magnetic Ni(NCS)2 Coordination Polymer.

    Science.gov (United States)

    Suckert, Stefan; Rams, Michał; Rams, Marek M; Näther, Christian

    2017-07-17

    Reaction of Ni(NCS) 2 with 4-(Boc-amino)pyridine in acetonitrile leads to the formation of a new coordination polymer with the composition Ni(NCS) 2 (4-(Boc-amino)pyridine) 2 ·MeCN (1-MeCN). In the crystal structure the Ni(II) cations are linked by the anionic ligands into chains that are further connected into layers by intermolecular N-H···O hydrogen bonding. These layers are stacked and channels are formed, in which acetonitrile molecules are located. Solvent removal leads to the ansolvate 1, which shows microporosity as proven by sorption measurements. Single crystal X-ray investigations reveal that the solvent removal leads to a change in symmetry from primitive to C-centered, which is reversible and which proceeds via a topotactic reaction leaving the network intact. The magnetic properties of 1-MeCN and 1 are governed by the ferromagnetic exchange between spins of Ni(II) forming chains. The susceptibility and specific heat for such a quantum Heisenberg chain of S = 1 spins with zero-field splitting are calculated using the DMRG method and compared with the experimental results.

  11. Two three-dimensional coordination polymers of lead(II) with iminodiacetate and naphthalene-dicarboxylate anions: Synthesis, characterization and luminescence behavior

    Energy Technology Data Exchange (ETDEWEB)

    Hazari, Debdoot; Jana, Swapan Kumar [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721 102, West Bengal (India); Fleck, Michel [Institute of Mineralogy and Crystallography, University of Vienna, Geozentrum, Althanstr. 9, A-1090 Vienna (Austria); Zangrando, Ennio [Department of Chemical and Pharmaceutical Sciences, University of Trieste, 34127 Trieste (Italy); Dalai, Sudipta, E-mail: sudipta@mail.vidyasagar.ac.in [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721 102, West Bengal (India)

    2014-11-15

    Two lead(II) compounds [Pb{sub 3}(idiac){sub 3}(phen){sub 2}(H{sub 2}O)]·2(H{sub 2}O) (1) and [Pb(ndc)]{sub n} (2), where H{sub 2}idiac=iminodiacetic acid, phen=1,10-phenanthroline and H{sub 2}ndc=naphthalene-2,6-dicarboxylic acid, have been synthesized and structurally characterized. Single crystal X-ray diffraction analysis showed that compound 1 is a discrete trinuclear complex (of two-fold symmetry) which evolves to a supramolecular 3D network via π–π interactions, while in compound 2 the naphthalene dicarboxylate anion act as a linker to form a three dimensional architecture, where the anion adopts a bis-(bidentate bridging) coordination mode connecting four Pb(II) centers. The photoluminescence property of the two complexes has been studied. - graphical abstract: Two new topologically different 1D coordination polymers formed by Pb{sub 4} clusters have been synthesized and characterized by x-ray analysis. The luminescence and thermal properties have been studied. - Highlights: • 1 is a trinuclear complex of Pb(II) growing to 3D network via weak interactions. • In 1, layers of (4,4) rhomboidal topology are identified. • In 2, the ndc anion adopts interesting bis-(bidentate bridging) coordination. • In 2, network is reinforced by C–H…π-ring interactions between the ndc rings.

  12. Synthesis, crystal structures, and luminescent properties of Cd(II) coordination polymers assembled from semi-rigid multi-dentate N-containing ligand

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Gang; Shao, Kui-Zhan; Chen, Lei; Liu, Xin-Xin [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Su, Zhong-Min, E-mail: zmsu@nenu.edu.cn [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Ma, Jian-Fang [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China)

    2012-12-15

    Three new polymers, [Cd(L){sub 2}(H{sub 2}O){sub 2}]{sub n} (1), [Cd{sub 3}(L){sub 2}({mu}{sub 3}-OH){sub 2}({mu}{sub 2}-Cl){sub 2}(H{sub 2}O){sub 2}]{sub n} (2), {l_brace}[Cd{sub 2}(L){sub 2}(nic){sub 2}(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O{r_brace}{sub n} (3) (HL=5-(4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)-1H-tetrazole, Hnic=nicotinic acid) have been prepared and structurally characterized. Compounds 1 and 2 display 2D monomolecular layers built by the inter-linking single helical chains and L{sup -} ligands connecting chain-like [Cd({mu}{sub 3}-OH)({mu}{sub 2}-Cl)]{sub n} secondary building units, respectively. Compound 3 is constructed from the mixed ligands and possesses a (3,4)-connected framework with (4{center_dot}8{sup 2})(4{center_dot}8{sup 2}{center_dot}10{sup 3}) topology. Moreover, the fluorescent properties of HL ligand and compounds 1-3 are also been investigated. - Graphical abstract: Three new coordination polymers based on the semi-rigid multidentate N-donor ligand have been successfully synthesized by hydrothermal reaction. Complexes 1 and 2 exhibit the 2D layers formed by inter-linking single helices and L{sup -} anions bridging 1D chain-like SBUs, respectively. Complex 3 is buit by L{sup -} and assistant nic{sup -} ligands connecting metal centers and possesses a (3,4)-connected framework with (4 Multiplication-Sign 8{sup 2})(4 Multiplication-Sign 8{sup 2} Multiplication-Sign 10{sup 3}) topology. Moreover, these complexes display fluorescent properties indicating that they may have potential applications as optical materials. Highlights: Black-Right-Pointing-Pointer Three Cd-compounds were prepared from semi-rigid HL ligand with different N-containing groups. Black-Right-Pointing-Pointer They exhibit diverse structures from 2D monomolecular layer to 3D covalent framework. Black-Right-Pointing-Pointer The HL ligands displayed various coordination modes under different reaction conditions. Black-Right-Pointing-Pointer These compounds exhibit

  13. Molecular design toward highly efficient photovoltaic polymers based on two-dimensional conjugated benzodithiophene.

    Science.gov (United States)

    Ye, Long; Zhang, Shaoqing; Huo, Lijun; Zhang, Maojie; Hou, Jianhui

    2014-05-20

    As researchers continue to develop new organic materials for solar cells, benzo[1,2-b:4,5-b']dithiophene (BDT)-based polymers have come to the fore. To improve the photovoltaic properties of BDT-based polymers, researchers have developed and applied various strategies leading to the successful molecular design of highly efficient photovoltaic polymers. Novel polymer materials composed of two-dimensional conjugated BDT (2D-conjugated BDT) have boosted the power conversion efficiency of polymer solar cells (PSCs) to levels that exceed 9%. In this Account, we summarize recent progress related to the design and synthesis of 2D-conjugated BDT-based polymers and discuss their applications in highly efficient photovoltaic devices. We introduce the basic considerations for the construction of 2D-conjugated BDT-based polymers and systematic molecular design guidelines. For example, simply modifying an alkoxyl-substituted BDT to form an alkylthienyl-substituted BDT can improve the polymer hole mobilities substantially with little effect on their molecular energy level. Secondly, the addition of a variety of chemical moieties to the polymer can produce a 2D-conjugated BDT unit with more functions. For example, the introduction of a conjugated side chain with electron deficient groups (such as para-alkyl-phenyl, meta-alkoxyl-phenyl, and 2-alkyl-3-fluoro-thienyl) allowed us to modulate the molecular energy levels of 2D-conjugated BDT-based polymers. Through the rational design of BDT analogues such as dithienobenzodithiophene (DTBDT) or the insertion of larger π bridges, we can tune the backbone conformations of these polymers and modulate their photovoltaic properties. We also discuss the influence of 2D-conjugated BDT on polymer morphology and the blends of these polymers with phenyl-C61 (or C71)-butyric acid methyl ester (PCBM). Finally, we summarize the various applications of the 2D-conjugated BDT-based polymers in highly efficient PSC devices. Overall, this Account

  14. Seven 3d-4f coordination polymers of macrocyclic oxamide with polycarboxylates: Syntheses, crystal structures and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Xin, Na [College of Chemistry, Tianjin Normal University, Tianjin 300387 (China); Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education (China); Tianjin Key Laboratory of Structure and Performance for Functional Molecules (China); Sun, Ya-Qiu, E-mail: hxxysyq@mail.tjnu.edu.cn [College of Chemistry, Tianjin Normal University, Tianjin 300387 (China); Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education (China); Tianjin Key Laboratory of Structure and Performance for Functional Molecules (China); Zheng, Yan-Feng; Xu, Yan-Yan; Gao, Dong-Zhao; Zhang, Guo-Ying [College of Chemistry, Tianjin Normal University, Tianjin 300387 (China); Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education (China); Tianjin Key Laboratory of Structure and Performance for Functional Molecules (China)

    2016-11-15

    Seven new 3d–4f heterometallic coordination polymers, [Ln(CuL){sub 2}(Hbtca)(btca)(H{sub 2}O)]·2H{sub 2}O (Ln = Tb{sup III}1, Pr{sup III}2, Sm{sup III}3, Eu{sup III}4, Yb{sup III}5), [Nd(NiL)(nip)(Rnip)]·0·25H{sub 2}O·0.25CH{sub 3}OH (R= 0.6CH{sub 3}, 0.4H) 6 and [Nd{sub 2}(NiL)(nip){sub 3}(H{sub 2}O)]·2H{sub 2}O 7(CuL or NiL, H{sub 2}L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1, 4, 8, 12-tetraazacyclo-pentadeca-7, 13-dien; H{sub 2}btca = benzotriazole-5-carboxylic acid; H{sub 2}nip = 5-nitroisophthalic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1–5 exhibit a double-strand meso-helical chain structures formed by [Ln{sup III}Cu{sup II}{sub 2}] units via the oxamide and benzotriazole-5-carboxylate bridges, while complex 6 exhibits a four-strand meso-helical chain formed by NdNi unit via the oxamide and 5-nitroisophthalate bridges. Complex 7 consists of a 2D layer framework formed by four-strand meso-helical chain via the nip{sup 2−} bridges. Moreover, the magnetic properties of them were investigated, and the best-fit analysis of χ{sub M}T versus T show that the anisotropic contribution of Ln(III) ions (arising from the spin-orbit coupling or the crystal field perturbation) dominates (weak exchange limit) in these complexes(for 3, λ = 214.6 cm{sup −1}, zj’ = −0.33 cm{sup −1}, g{sub av} = 1.94; for 5, Δ = 6.98 cm{sup −1}, zj’ = 1.53 cm{sup −1}, g{sub av} = 1.85). - Graphical-abstract: Seven novel oxamido-bridged 3d-4f heterometallic coordination polymers with benzotriazole-5-carboxylate or 5-nitroisophthalate co-ligands under solvothermal reaction conditions. Polymers 1–7 hold 1D or 2D framework structure, viz., double-strand meso-helical chain of 1–5, four-strand meso-helical chain of 6, and 2D net of 7 consisting of four-strand meso-helical chain. Moreover, the temperature dependences of magnetic susceptibilities of compounds 1–7 were also studied.

  15. 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.

  16. Comparison of Flexural Strength of Different CAD/CAM PMMA-Based Polymers.

    Science.gov (United States)

    Alp, Gülce; Murat, Sema; Yilmaz, Burak

    2018-01-28

    To compare the flexural strength of different computer-aided design/computer-aided manufacturing (CAD/CAM) poly(methyl methacrylate)-based (PMMA) polymers and conventional interim resin materials after thermocycling. Rectangular-shaped specimens (n = 15, for each material) (25 × 2 × 2 mm 3 ) were fabricated from 3 CAD/CAM PMMA-based polymers (Telio CAD [T]; M-PM-Disc [M]; Polident-PMMA [P]), 1 bis-acrylate composite resin (Protemp 4 [PT]), and 1 conventional PMMA (ArtConcept Artegral Dentine [C]) according to ISO 10477:2004 Standards (Dentistry-Polymer-Based Crown and Bridge Materials). The specimens were subjected to 10,000 thermocycles (5 to 55°C). Three-point flexural strength of the specimens was tested in a universal testing machine at a 1.0 mm/min crosshead speed, and the flexural strength data (σ) were calculated (MPa). The flexural strength values were statistically analyzed using 1-way ANOVA, and Tukey HSD post-hoc test for multiple comparisons (α = 0.05). Flexural strength values ranged between 66.1 ± 13.1 and 131.9 ± 19.8 MPa. There were significant differences among the flexural strengths of tested materials, except for between T and P CAD/CAM PMMA-based polymers (p > 0.05). CAD/CAM PMMA-based polymer M had the highest flexural strength and conventional PMMA had the lowest (p CAD/CAM PMMA-based T and P polymers had significantly higher flexural strength than the bis-acrylate composite resin (p CAD/CAM PMMA-based M (p CAD/CAM PMMA-based polymers was greater than the flexural strength of bis-acrylate composite resin, which had a greater flexural strength compared to conventional PMMA resin. © 2018 by the American College of Prosthodontists.

  17. Formulation of caesium based and caesium containing geo-polymers

    Energy Technology Data Exchange (ETDEWEB)

    Berger, S.; Joussot-Dubien, C.; Frizon, F. [CEA Valrho, Dir. de l' Energie Nucleaire, DEN, Decontamination and Conditioning Department, DEN/DTCD/SPDE/L2ED, 30 - Marcoule (France)

    2009-10-15

    Cement encapsulation is widely used as a low- and intermediate level radioactive waste immobilisation process. Among these wastes, caesium ions are poorly immobilised by Portland cement based materials. This work consists of an experimental investigation into the ability of geo-polymers to effectively encapsulate this chemical species and to determine the impact of caesium incorporation on the geo-polymer properties. Geo-polymers were synthesised with several compositions based on the activation of metakaolin with an alkali hydroxide solution containing caesium. The setting time, mineralogy, porosity and mechanical properties of the samples were examined for one month. Leach tests were conducted during the same period to determine the immobilisation efficiency. The results depend to a large extent on the composition of the activation solution in terms of soluble silica content and alkali used. These parameters determine both the degree of condensation and the geo-polymer composition. (authors)

  18. Formulation of caesium based and caesium containing geo-polymers

    International Nuclear Information System (INIS)

    Berger, S.; Joussot-Dubien, C.; Frizon, F.

    2009-01-01

    Cement encapsulation is widely used as a low- and intermediate level radioactive waste immobilisation process. Among these wastes, caesium ions are poorly immobilised by Portland cement based materials. This work consists of an experimental investigation into the ability of geo-polymers to effectively encapsulate this chemical species and to determine the impact of caesium incorporation on the geo-polymer properties. Geo-polymers were synthesised with several compositions based on the activation of metakaolin with an alkali hydroxide solution containing caesium. The setting time, mineralogy, porosity and mechanical properties of the samples were examined for one month. Leach tests were conducted during the same period to determine the immobilisation efficiency. The results depend to a large extent on the composition of the activation solution in terms of soluble silica content and alkali used. These parameters determine both the degree of condensation and the geo-polymer composition. (authors)

  19. Preparation and characterization of high performance Schiff-base liquid crystal diepoxide polymer

    International Nuclear Information System (INIS)

    Liu Huan; Fu Zien; Xu Kai; Cai Hualun; Liu Xin; Chen Mingcai

    2012-01-01

    Graphical abstract: The specific effects of highly conjugated Schiff-base moiety on thermal properties of the Schiff-base epoxy polymer were proposed first by us. From the point of view of structure-properties relationship, it can be considered that owing to the presence of the Schiff-base group, the high performance liquid crystal diepoxide polymer displayed improved thermal stability. Highlights: ► In this work, we first proposed that specific effects of highly conjugated Schiff-base moiety on thermal properties of the Schiff-base epoxy polymer. ► As one aim of this study, the thermal and thermal-oxidative stabilities of the thermosets were studied by TGA under nitrogen and under air. ► The second aim of this study was to further understand the thermal degradation mechanism. ► For thermal degradation mechanism of this polymer under nitrogen, TG-IR was used to investigate volatile components, and SEM/EDS was used to explore morphologies and chemical components of the residual char. ► From the point of view of structure-properties relationship, it can be considered that owing to the presence of the Schiff-base group, the high performance liquid crystal diepoxide polymer displayed the improved thermal stability. - Abstract: A novel Schiff-base liquid crystal diepoxide polymer was prepared via a thermal copolymerization of a Schiff-base epoxy monomer (PBMBA) with a diamine co-monomer (MDA). We first proposed that specific effects of highly conjugated Schiff-base moiety on thermal properties of the Schiff-base epoxy polymer (PBMBA/MDA). Thermal degradation behavior of the polymer was characterized using thermogravimetric analysis (TGA) under nitrogen and under air, respectively. Thermogravimetric data obtained from TGA under nitrogen and under air reveal that PBMBA/MDA exhibits higher thermal stability compared with bisphenol-A type epoxy polymer (DGEBA/MDA) and other mesogene-containing epoxy polymer. It is worth pointing out that the outstanding residual

  20. Syntheses, structures and properties of three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers based on 2,2'-dipyridyl-5,5'-dicarboxylate ligands.

    Science.gov (United States)

    Zhao, Junwei; Cheng, Yamin; Shang, Sensen; Zhang, Fang; Chen, Li; Chen, Lijuan

    2013-12-01

    Three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers [Ln(III)Cu2(I)(Hbpdc)4] · Cl · xH2O [Ln(III) = La(III), x = 8 (1); Ln(III) = Pr(III), x=9 (2); Ln(III) = Eu(III), x = 8 (3)] (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid) have been prepared under hydrothermal conditions and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. X-ray diffraction indicates that the isomorphic 1-3 display the two-dimensional sheet structure constructed from [Cu(I)(Hbpdc)2](-) fragments through Ln(3+) connectors. Moreover, the solid-state photoluminescence measurements of 3 indicate that the Eu(III) ions, Hbpdc(-) ligands and Cu(I) cations make contributions to its luminescent properties simultaneously. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. 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.

  2. Fabrication of polymer-alloy based on polytetrafluoroethylene by radiation-crosslinking

    International Nuclear Information System (INIS)

    Oshima, A.; Asano, S.; Hyunga, T.; Ichizuri, S.; Washio, M.

    2003-01-01

    Perfluoropolymer such as polytetrafluoroethylene (PTFE), tetrafluoroethylene co-perfluoroalkylvinylether (PFA) and tetrafluoroethylene-co-hexafluoropropylene (FFP) have been classified to be a typical polymer of radiation-induced degradation. However, we confirmed that the crosslinking of PTFE, PFA and FEP proceed by irradiation under selective condition where oxygen-free and high temperature above the melting temperature of them. In this study, fabrication of polymer-alloy based on PTFE has been demonstrated by radiation-crosslinking techniques. The polymer alloy, which was PTFE fine powder contained with other polymeric materials, was obtained by electron beams irradiation under oxygen-free atmosphere. Characterization of polymer-alloy based on PTFE has been studied by various measurements such as solid state 19F- and 13C-NMR spectroscopy, thermal analysis (DSC, TGA)

  3. Hydrothermal synthesis and characteristics of 3-D hydrated bismuth oxalate coordination polymers with open-channel structure

    International Nuclear Information System (INIS)

    Chen Xinxiang; Cao Yanning; Zhang Hanhui; Chen Yiping; Chen Xuehuan; Chai Xiaochuan

    2008-01-01

    Two new 3-D porous bismuth coordination polymers, (C 5 NH 6 ) 2 [Bi 2 (H 2 O) 2 (C 2 O 4 ) 4 ].2H 2 O 1 and (NH 4 )[Bi(C 2 O 4 ) 2 ].3H 2 O 2, have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic symmetry, P2 1 /c space group with a=10.378(2) A, b=17.285(3) A, c=16.563(5) A, α=90 deg., β=119.66(2) deg., γ=90 deg., V=2581.8(10) A 3 , Z=4, R 1 =0.0355 and wR 2 =0.0658 for unique 4713 reflections I >2σ(I). Compound 2 crystallizes in the tetragonal symmetry, I4 1 /amd space group with a=11.7026(17) A, b=11.7026(17) A, c=9.2233(18) A, α=90 deg., β=90 deg., γ=90 deg., V=1263.1(4) A 3 , Z=32, R 1 =0.0208 and wR 2 =0.0518 for unique 359 reflections I> 2σ(I). Compounds 1 and 2 are 3-D open-framework structures with a 6 6 uniform net, which consist of honeycomb-like layers connected to each other by oxalate units. While different guest molecules fill in their cavities of honeycomb-like layers, study of ultrasonic treatment on 2 indicates the replacement of NH 4 + by K + on potassium ion exchange. Thermogravimetric analysis indicates that the open-channel frameworks are thermally stable up to 200 deg. C, and other characterizations are also described by elemental analysis, IR and ultraviolet-visible diffuse reflectionintegral spectrum (UV-Vis DRIS). - Graphical abstract: Two novel 3-D extended porous coordination polymers have been synthesized by hydrothermal method. Both compounds are 3-D open-framework structures with a 6 6 uniform net, which consist of honeycomb-like layers connected to each other by oxalate units. While different guest molecules fill in their cavities of honeycomb-like layers. Study of ultrasonic treatment on 2 indicates the replacement of NH 4 + by K + on potassium ion exchange

  4. Electrochemical Sensor Based on Rh(III) Ion-Imprinted Polymer as a New Modifying Agent for Rhodium Determination.

    Science.gov (United States)

    Bai, Huiping; Xiong, Caiyun; Wang, Chunqiong; Liu, Peng; Dong, Su; Cao, Qiue

    2018-05-01

    A rhodium (III) ion carbon paste electrode (CPE) based on an ion imprinted polymer (IIP) as a new modifying agent has been prepared and studied. Rh(III) ion imprinted polymer was synthesized by copolymerization of acrylamide-Rh(III) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Acrylamide acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. The ion imprinted carbon paste electrode (IIP-CPE) was prepared by mixing rhodium IIP-nanoparticles and graphite powder in n-eicosane as an adhesive and then embedding them in a Teflon tube. Amperometric i-t curve method was applied as the determination technique. Several parameters, including the functional monomer, molar ratio of template, monomer and cross-linking agent, the amounts of IIP, the applied potential, the buffer solution and pH have been studied. According to the results, IIP-CPE showed a considerably higher response in comparison with the electrode embedded with non-imprinted polymer (NIP), indicating the formation of suitable recognition sites in the IIP structure during the polymerization stage. The introduced electrode showed a linear range of 1.00×10-8~3.0×10-5 mol·L-1 and detection limit of 6.0 nmol L-1 (S/N = 3). The IIP-CPE was successfully applied for the trace rhodium determination in catalyst and plant samples with RSD of less than 3.3% (n = 5) and recoveries in the range of 95.5~102.5%.

  5. Vehicle coordinated transportation dispatching model base on multiple crisis locations

    Science.gov (United States)

    Tian, Ran; Li, Shanwei; Yang, Guoying

    2018-05-01

    Many disastrous events are often caused after unconventional emergencies occur, and the requirements of disasters are often different. It is difficult for a single emergency resource center to satisfy such requirements at the same time. Therefore, how to coordinate the emergency resources stored by multiple emergency resource centers to various disaster sites requires the coordinated transportation of emergency vehicles. In this paper, according to the problem of emergency logistics coordination scheduling, based on the related constraints of emergency logistics transportation, an emergency resource scheduling model based on multiple disasters is established.

  6. Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

    International Nuclear Information System (INIS)

    Hu, Bin; Geng, Jiao; Zhang, Lie; Huang, Wei

    2014-01-01

    A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L 1 ) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L 2 ), has been synthesized and characterized. They are used as μ 2 -bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L 1 )(NO 3 )] n (1) and [Ag(L 2 )(NO 3 )] n (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L 1 and L 2 ) and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10 4 and 2.17×10 3 times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L 1 and L 2 are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L 1 ) and L 2 are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ 2 -bridging ligands to prepare a pair of silver(I) polymeric isomers. • Significant enhancement of solid-state conductivity is observed

  7. Laser welding of polymers, compatibility and mechanical properties

    DEFF Research Database (Denmark)

    Nielsen, Steen Erik; Strange, Marianne; Kristensen, Jens Klæstrup

    2013-01-01

    for research and development. This paper presents some research results related to laser welding of various polymer materials, including weld compatibility investigations related to the joining of different polymers. Theory for bonding mechanisms, strength development, mechanical properties testing and other......Laser welding of polymers is today a commonly used industrial technology. It has shown obvious advantages compared to e.g. adhesive bonding in terms of higher productivity, better quality and easiness for automation. The ongoing development of lasers tailored for polymer welding in coordination...

  8. Low Humidity Characteristics of Polymer-Based Capacitive Humidity Sensors

    OpenAIRE

    Majewski Jacek

    2017-01-01

    Polymer-based capacitive humidity sensors emerged around 40 years ago; nevertheless, they currently constitute large part of sensors’ market within a range of medium (climatic and industrial) humidity 20−80%RH due to their linearity, stability and cost-effectiveness. However, for low humidity values (0−20%RH) that type of sensor exhibits increasingly nonlinear characteristics with decreasing of humidity values. This paper presents the results of some experimental trials of CMOS polymer-based ...

  9. 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.

  10. Thermally activated 3D to 2D structural transformation of [Ni2(en)2(H2O)6(pyr)]·4H2O flexible coordination polymer

    International Nuclear Information System (INIS)

    Begović, Nebojša N.; Blagojević, Vladimir A.; Ostojić, Sanja B.; Radulović, Aleksandra M.; Poleti, Dejan; Minić, Dragica M.

    2015-01-01

    Thermally activated 3D to 2D structural transformation of the binuclear [Ni 2 (en) 2 (H 2 O) 6 (pyr)]·4H 2 O complex was investigated using a combination of theoretical and experimental methods. Step-wise thermal degradation (dehydration followed by release of ethylene diamine) results in two layered flexible coordination polymer structures. Dehydration process around 365 K results in a conjugated 2D structure with weak interlayer connectivity. It was shown to be a reversible 3D to 2D framework transformation by a guest molecule, and rehydration of the dehydration product occurs at room temperature in saturated water vapor. Rehydrated complex exhibits lower dehydration temperature, due to decreased average crystalline size, with higher surface area resulting in easier release and diffusion of water during dehydration. Thermal degradation of dehydration around 570 K, results in loss of ethylene diamine, producing a related 2D layered polymer structure, without interconnectivity between individual polymer layers. - Highlights: • Reversible 3D to 2D framework topochemical transformation on dehydration around 365 K. • Resulting polymer exhibits 2D layered structure with weak interlayer connectivity. • Dehydration is fully reversible in saturated water vapor at room temperature. • Further degradation around 570 K yields 2D polymer without interlayer connectivity. • 2D polymer exhibits conjugated electronic system

  11. Optimization of mechanical performance of oxidative nano-particle electrode nitrile butadiene rubber conducting polymer actuator.

    Science.gov (United States)

    Kim, Baek-Chul; Park, S J; Cho, M S; Lee, Y; Nam, J D; Choi, H R; Koo, J C

    2009-12-01

    Present work delivers a systematical evaluation of actuation efficiency of a nano-particle electrode conducting polymer actuator fabricated based on Nitrile Butadiene Rubber (NBR). Attempts are made for maximizing mechanical functionality of the nano-particle electrode conducting polymer actuator that can be driven in the air. As the conducting polymer polypyrrole of the actuator is to be fabricated through a chemical oxidation polymerization process that may impose certain limitations on both electrical and mechanical functionality of the actuator, a coordinated study for optimization process of the actuator is necessary for maximizing its performance. In this article actuation behaviors of the nano-particle electrode polypyrrole conducting polymer is studied and an optimization process for the mechanical performance maximization is performed.

  12. 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

  13. Polymer containing functional end groups is base for new polymers

    Science.gov (United States)

    Hirshfield, S. M.

    1971-01-01

    Butadiene is polymerized with lithium-p-lithiophenoxide to produce linear polymer containing oxy-lithium group at one end and active carbon-lithium group at other end. Living polymers represent new approach to preparation of difunctional polymers in which structural features, molecular weight, type and number of end groups are controlled.

  14. Alkyl group dependence on structure and magnetic properties in layered cobalt coordination polymers containing substituted glutarate ligands and 4,4'-bipyridine

    International Nuclear Information System (INIS)

    Nettleman, Joseph H.; Supkowski, Ronald M.; LaDuca, Robert L.

    2010-01-01

    Five two-dimensional divalent cobalt coordination polymers containing 4,4'-bipyridine (bpy) and substituted or unsubstituted glutarate ligands have been prepared hydrothermally and structurally characterized by single-crystal X-ray diffraction. [Co(mg)(bpy)] n (1, mg=3-methylglutarate) forms a (4,4) rhomboid grid structure based on the connection of {Co 2 (CO 2 ) 2 } dimeric units. Using the more sterically encumbered ligands 3,3-dimethylglutarate (dmg) and 3-ethyl, 3-methylglutarate (emg) generated {[Co(dmg)(bpy)(H 2 O)].2H 2 O} n (2) and {[Co(emg)(bpy)(H 2 O)].H 2 O} n (3), respectively. These complexes manifest {Co(CO 2 )} n chains linked into 2-D by aliphatic dicarboxylate and bpy ligands. The 'tied-back' substituted glutarate ligand 1,1-cyclopentanediacetate (cda) afforded [Co(cda)(bpy)] n (4), and the unsubstituted glutarate (glu) generated [Co(glu)(bpy)] n (5), both of which exhibit a topology similar to that of 1. The magnetic properties of complexes 1-4 were analyzed successfully with a recently developed phenomenological chain model accounting for both magnetic coupling (J) and zero-field splitting effects (D), even though 1 and 4 contain isolated, discrete {Co 2 (CO 2 ) 2 } dimers. The D parameter in this series varied between 21.8(8) and 48.0(9) cm -1 . However weak antiferromagnetic coupling was observed in 1 (J=-2.43(4) cm -1 ) and 4 (J=-0.89(2) cm -1 ), while weak ferromagnetic coupling appears to be operative in both 2 (J=0.324(5) cm -1 ) and 3 (J=0.24(1) cm -1 ). - Five two-dimensional divalent cobalt coordination polymers containing 4,4'-bipyridine (bpy) and substituted or unsubstituted glutarate ligands have been prepared and structurally characterized by single-crystal X-ray diffraction. Three contain dimeric {Co 2 (CO 2 ) 2 } units, while two manifest {Co(CO 2 )} n chains, depending on the steric bulk of the substituent. The magnetic properties of the complexes were analyzed successfully with a recently developed phenomenological chain model

  15. Asymmetric Alkyl Side-Chain Engineering of Naphthalene Diimide-Based n-Type Polymers for Efficient All-Polymer Solar Cells.

    Science.gov (United States)

    Jia, Tao; Li, Zhenye; Ying, Lei; Jia, Jianchao; Fan, Baobing; Zhong, Wenkai; Pan, Feilong; He, Penghui; Chen, Junwu; Huang, Fei; Cao, Yong

    2018-02-13

    The design and synthesis of three n-type conjugated polymers based on a naphthalene diimide-thiophene skeleton are presented. The control polymer, PNDI-2HD, has two identical 2-hexyldecyl side chains, and the other polymers have different alkyl side chains; PNDI-EHDT has a 2-ethylhexyl and a 2-decyltetradecyl side chain, and PNDI-BOOD has a 2-butyloctyl and a 2-octyldodecyl side chain. These copolymers with different alkyl side chains exhibit higher melting and crystallization temperatures, and stronger aggregation in solution, than the control copolymer PNDI-2HD that has the same side chain. Polymer solar cells based on the electron-donating copolymer PTB7-Th and these novel copolymers exhibit nearly the same open-circuit voltage of 0.77 V. Devices based on the copolymer PNDI-BOOD with different side chains have a power-conversion efficiency of up to 6.89%, which is much higher than the 4.30% obtained with the symmetric PNDI-2HD. This improvement can be attributed to the improved charge-carrier mobility and the formation of favorable film morphology. These observations suggest that the molecular design strategy of incorporating different side chains can provide a new and promising approach to developing n-type conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Magnetoelectric polymer-based composites fundamentals and applications

    CERN Document Server

    Martins, Pedro

    2017-01-01

    The first book on this topic provides a comprehensive and well-structured overview of the fundamentals, synthesis and emerging applications of magnetoelectric polymer materials. Following an introduction to the basic aspects of polymer based magnetoelectric materials and recent developments, subsequent chapters discuss the various types as well as their synthesis and characterization. There then follows a review of the latest applications, such as memories, sensors and actuators. The book concludes with a look at future technological advances. An essential reference for entrants to the field as well as for experienced researchers.

  17. Polymer-based surface plasmon resonance biochip: construction and experimental aspects

    Directory of Open Access Journals (Sweden)

    Cleumar da Silva Moreira

    Full Text Available Abstract Introduction: Surface plasmon resonance biosensors are high sensitive analytical instruments that normally employ glass materials at the optical substrate layer. However, the use of polymer-based substrates is increasing in the last years due to favorable features, like: disposability, ease to construction and low-cost design. Review Recently, a polymer-based SPR biochip was proposed by using monochromatic and polychromatic input sources. Its construction and experimental considerations are detailed here. Experimental considerations and results, aspects from performance characteristics (resonance parameters, sensitivity and full width at half maximum – FWHM – calculations are presented for hydrophilic and hydrophobic solutions. It is included also a brief description of the state of the art of polymer-based SPR biosensors.

  18. Graphene-based polymer nanocomposites

    NARCIS (Netherlands)

    Tkalya, E.

    2012-01-01

    The main reason for the rapid development of polymer composite materials is that the traditional "pure" polymers have largely played out its performance capabilities whereas technology requires materials with new properties and advances. There are a number of advantages polymeric composites have

  19. Highly Sensitive Polymer-based Cantilever-sensors for DNA Detection

    DEFF Research Database (Denmark)

    Gomez, Montserrat; Nordström, Maria; Alvarez, M.

    2005-01-01

    We present a technology for the fabrication of cantilever arrays aimed to develop an integrated biosensor microsystem. The fabrication process is based on spin coating of the photosensitive polymer and near-ultraviolet exposure. Arrays of up to 33 microcantilevers are fabricated in the novel...... polymer material SU-8. The low Young's modulus of the polymer, 40 times lower than that of silicon, enables to improve the sensitivity of the sensor device for target detection. The mechanical properties of SU-8 cantilevers, such as spring constant, resonant frequency and quality factor are characterized...

  20. Performance of Lithium Polymer Cells with Polyacrylonitrile based Electrolyte

    DEFF Research Database (Denmark)

    Perera, Kumudu; Dissanayake, M.A.K.L.; Skaarup, Steen

    2006-01-01

    The performance of lithium polymer cells fabricated with Polyacrylonitrile (PAN) based electrolytes was studied using cycling voltammetry and continuous charge discharge cycling. The electrolytes consisted of PAN, ethylene carbonate (EC), propylene carbonate (PC) and lithium...... trifluoromethanesulfonate (LiCF3SO3 – LiTF). The polymer electrode material was polypyrrole (PPy) doped with dodecyl benzene sulfonate (DBS). The cells were of the form, Li / PAN : EC : PC : LiCF3SO3 / PPy : DBS. Polymer electrodes of three different thicknesses were studied using cycling at different scan rates. All cells...

  1. 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.

  2. S-Layer Based Bio-Imprinting - Synthetic S-Layer Polymers

    Science.gov (United States)

    2015-07-09

    AFRL-OSR-VA-TR-2015-0161 S-Layer Based Bio- Imprinting - Synthetic S-Layer Polymers Dietmar Pum ZENTRUM FUER NANOBIOTECHNOLOGIE Final Report 07/09...COVERED (From - To)      01-06-2012 to 31-05-2015 4.  TITLE AND SUBTITLE S-Layer Based Bio- Imprinting - Synthetic S-Layer Polymers 5a.  CONTRACT...technology for the fabrication of nano patterned thin film imprints by using functional S-layer protein arrays as templates. The unique feature of

  3. A detailed study on the interaction of a novel water-soluble glycine bridged zinc(II) Schiff base coordination polymer with BSA: synthesis, crystal structure, molecular docking and cytotoxicity effect against A549, Jurkat and Raji cell lines

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Golchin, M.; Eigner, Václav; Dušek, Michal; Amirghofran, Z.

    2017-01-01

    Roč. 465, Aug (2017), s. 50-60 ISSN 0020-1693 R&D Projects: GA MŠk LO1603; GA ČR(CZ) GA14-03276S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : water-soluble * coordination polymer * BSA * docking study * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.002, year: 2016

  4. Detection of low-concentration ammonia using differential laser-induced fluorescence on vapochromic coordination polymers

    Science.gov (United States)

    Yin, Dawei; Chapman, Glenn H.; Stevens, David; Gray, Bonnie; Leznoff, Daniel

    2018-02-01

    The detection of ammonia in parts per millions range has been challenging in sensors research, and is of great importance for industrial applications. In previous literature, Vapochromic Coordination Polymers (VCP) were developed to achieve luminescence upon a targeted gas exposures. We investigate a specific VCP, Zn[Au(CN)2]2,as an ammonia sensing material. Upon high concentration ammonia exposure, the fluorescent peak under near-UV stimulation undergoes a spectral shift from 460nm to 520nm, while the intensity increases by 3 4X. However, at ammonia concentrations portable spectrometer (Photon Control SPM-002), and processed the data by separating the spectrum into two regions; (A) from 425 nm to 460 nm and (B) from 460nm to 500nm. Next, the integrated emissions under both regions were computed, and the value of shorter wavelength region (A) was subtracted from the longer wavelength one (B). When exposed to ammonia, region (A) reduces overall intensity while region (B) increases, resulting a signal starting from negative value and gradually increases to positive values, enabling the detection of 5ppm ammonia in less than 30 seconds gas exposure.

  5. A two-dimensional bismuth coordination polymer with tartaric acid: synthesis, characterization and thermal decomposition to Bi.sub.2./sub.O.sub.3./sub. nanoparticles

    Czech Academy of Sciences Publication Activity Database

    Ahadiat, G.; Tabatabaee, M.; Gholivand, K.; Zare, K.; Dušek, Michal; Kučeráková, Monika

    2017-01-01

    Roč. 16, č. 1 (2017), s. 7-16 ISSN 1024-1221 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : bismuth coordination polymer * tartrate ligand * thermal decomposition * alpha-Bi 2 O 3 nanoparticles Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 0.565, year: 2016

  6. Colorimetric and Fluorescent Dual Mode Sensing of Alcoholic Strength in Spirit Samples with Stimuli-Responsive Infinite Coordination Polymers.

    Science.gov (United States)

    Deng, Jingjing; Ma, Wenjie; Yu, Ping; Mao, Lanqun

    2015-07-07

    This study demonstrates a new strategy for colorimetric and fluorescent dual mode sensing of alcoholic strength (AS) in spirit samples based on stimuli-responsive infinite coordination polymers (ICPs). The ICP supramolecular network is prepared with 1,4-bis(imidazol-1-ylmethyl)benzene (bix) as the ligand and Zn(2+) as the central metal ion in ethanol, in which rhodamine B (RhB) is encapsulated through self-adaptive chemistry. In pure ethanol solvent, the as-formed RhB/Zn(bix) is well dispersed and quite stable. However, the addition of water into the ethanol dispersion of RhB/Zn(bix) destroys Zn(bix) network structure, resulting in the release of RhB from ICP into the solvent. As a consequence, the solvent displays the color of released RhB and, at the meantime, turns on the fluorescence of RhB, which constitutes a new mechanism for colorimetric and fluorescent dual mode sensing of AS in commercial spirit samples. With the method developed here, we could distinguish the AS of different commercial spirit samples by the naked eye within a wide linear range from 20 to 100% vol and by monitoring the increase of fluorescent intensity of the released RhB. This study not only offers a new method for on-spot visible detection of AS in commercial spirit samples, but also provides a strategy for designing dual mode sensing mechanisms for different analytical purposes based on novel stimuli-responsive materials.

  7. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

    Energy Technology Data Exchange (ETDEWEB)

    Ylikantola, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Linnanto, J., E-mail: juha.m.linnanto@gmail.com [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); University of Tartu, Institute of Physics, Riia 142, EE-51014 Tartu (Estonia); Knuutinen, J.; Oravilahti, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Toivakka, M. [Åbo Akademi University, Laboratory of Paper Coating and Converting and Center for Functional Materials, FI-20500 Turku/Åbo (Finland)

    2013-07-01

    The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree–Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree–Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

  8. 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.

  9. 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.

  10. National Coordination Office for Space-Based PNT

    Science.gov (United States)

    Shaw, M. E.

    2008-12-01

    In December 2004, President Bush issued the US Policy on space-based positioning, navigation, and timing (PNT), providing guidance on the management of the Global Positioning System (GPS) and other space- based PNT systems. The policy established the National Executive Committee (EXCOM) to advise and coordinate federal agencies on matters related to space-based PNT. Chaired jointly by the deputy secretaries of defense and transportation, the EXCOM includes equivalent level officials from the Departments of State, the Interior, Agriculture, Commerce, and Homeland Security, the Joint Chiefs of Staff, and the National Aeronautics and Space Administration (NASA). A National Coordination Office (NCO) supports the EXCOM through an interagency staff. Since establishing the EXCOM and NCO in 2005, the organizations have quickly grown in influence and effectiveness, leading or managing many interagency initiatives including the development of a Five-Year National Space-Based PNT Plan, the Space-Based PNT Interference Detection and Mitigation (IDM) Plan, and other strategic documents. The NCO has also facilitated interagency coordination on numerous policy issues and on external communications intended to spread a consistent, positive US message about space-based PNT. Role of the NCO - The purpose of the EXCOM is to provide top-level guidance to US agencies regarding space-based PNT infrastructure. The president established it at the deputy secretary level to ensure its strategic recommendations effect real change in agency budgets. Recognizing such high-level officials could only meet every few months, the president directed the EXCOM to establish an NCO to carry out its day-to-day business, including overseeing the implementation of EXCOM action items across the member agencies. These range from the resolution of funding issues to the assessment of strategic policy options. They also include the completion of specific tasks and documents requested by the EXCOM co

  11. Halloysite-based dopamine-imprinted polymer for selective protein capture.

    Science.gov (United States)

    Zhu, Xiaohong; Li, Hui; Liu, Hui; Peng, Wei; Zhong, Shian; Wang, Yan

    2016-06-01

    We describe a facile, general, and highly efficient approach to obtain polydopamine-coated molecularly imprinted polymer based on halloysite nanotubes for bovine serum albumin. The method combined surface molecular imprinting and one-step immobilized template technique. Hierarchically structured polymer was prepared in physiological conditions adopting dopamine as functional monomer. A thin layer of polydopamine can be coated on the surface of amino-modified halloysite nanotubes by self-polymerization, and the thickness of the imprinted shells can be controlled by the mass ratio of matrix and dopamine. The polymer was characterized by Fourier transform infrared spectrometry, transmission electron microscopy, and thermogravimetric analysis. The prepared material showed high binding capacity (45.4 mg/g) and specific recognition behavior toward the template protein. In addition, stability and regeneration analyses indicated that the imprinted polymer exhibited excellent reusability (relative standard deviation < 9% for batch-to-batch evaluation). Therefore, the developed polymer is effective for protein recognition and separation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Phenothiazine based polymers for energy and data storage application

    Energy Technology Data Exchange (ETDEWEB)

    Golriz, Seyed Ahmad Ali

    2013-03-15

    charge and discharge cycles. In addition to applications in batteries the bistability of phenothiazine polymers for high density data storage purposes was studied. Using the conductive mode of scanning force microscopy (SFM), nano-scaled patterning of spin-coated polymer films induced by electrochemical oxidation was successfully demonstrated. The scanning probe experiments revealed differences in the conductive states of written patterns before and after oxidation with no significant change in topography. Remarkably, the patterns were stable with respect to the storage time as well as mechanical wear. Finally, new synthetic approaches towards mechanically nanowear stable and redox active surfaces were established. Via grafting from methods based on Atom Transfer Radical Polymerization (ATRP), redox active polymer brushes with phenothiazine moieties were prepared and characterized by SFM and X-ray techniques. In particular, a synthetic route based on polymer brush structures with activated ester functionality appeared as a very promising and versatile fabrication method. The activated ester brushes were used for attachment of phenothiazine moieties in a successive step. By using crosslinkable diamine moieties, polymer brushes with redox functionalities and with increased surface wear resistance were successfully synthesized. In summary, this work offers deep insights into the electronic properties of polymers with phenothiazine redox active moieties. Furthermore, the applicability of phenothiazine polymers for electronic devices was explored and improved from synthetic polymer chemistry point of view.

  13. Kinetics and mechanism of thermal degradation of pentose- and hexose-based carbohydrate polymers.

    Science.gov (United States)

    Akbar, Jamshed; Iqbal, Mohammad S; Massey, Shazma; Masih, Rashid

    2012-10-15

    This work aims at study of thermal degradation kinetics and mechanism of pentose- and hexose-based carbohydrate polymers isolated from Plantago ovata (PO), Salvia aegyptiaca (SA) and Ocimum basilicum (OB). The analysis was performed by isoconversional method. The materials exhibited mainly two-stage degradation. The weight loss at ambient-115°C characterized by low activation energy corresponds to loss of moisture. The kinetic triplets consisting of E, A and g(α) model of the materials were determined. The major degradation stage represents a loss of high boiling volatile components. This stage is exothermic in nature. Above 340°C complete degradation takes place leaving a residue of 10-15%. The master plots of g(α) function clearly differentiated the degradation mechanism of hexose-based OB and SA polymers and pentose-based PO polymer. The pentose-based carbohydrate polymer showed D(4) type and the hexose-based polymers showed A(4) type degradation mechanism. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Asphaltenes-based polymer nano-composites

    Science.gov (United States)

    Bowen, III, Daniel E

    2013-12-17

    Inventive composite materials are provided. The composite is preferably a nano-composite, and comprises an asphaltene, or a mixture of asphaltenes, blended with a polymer. The polymer can be any polymer in need of altered properties, including those selected from the group consisting of epoxies, acrylics, urethanes, silicones, cyanoacrylates, vulcanized rubber, phenol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, imides, esters, cyanate esters, allyl resins.

  15. Evaluation of polymer based third order nonlinear integrated optics devices

    NARCIS (Netherlands)

    Driessen, A.; Hoekstra, Hugo; Blom, F.C.; Horst, F.; Horst, F.; Krijnen, Gijsbertus J.M.; van Schoot, J.B.P.; van Schoot, J.B.P.; Lambeck, Paul; Popma, T.J.A.; Diemeer, Mart

    Nonlinear polymers are promising materials for high speed active integrated optics devices. In this paper we evaluate the perspectives polymer based nonlinear optical devices can offer. Special attention is directed to the materials aspects. In our experimental work we applied mainly Akzo Nobel DANS

  16. New polysaccharide-based polymer electrolytes; Nouveaux electrolytes polymeres a base de polysaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Velasquez-Morales, P.; Le Nest, J.F.; Gandini, A. [Ecole Francaise de Papeterie et des Industries Graphique, 38 - Saint Martin d`Heres (France)

    1996-12-31

    Polysaccharides like cellulose and chitosan are known for their filmic properties. This paper concerns the synthesis and the study of chitosan-based polymer electrolytes. A preliminary work concerns the study of glucosamine reactivity. The poly-condensation of chitosan ethers (obtained by reaction with ethylene oxide or propylene oxide) with bifunctional and monofunctional oligo-ethers leads to the formation of thin lattices (10 {mu}m) having excellent mechanical properties. The presence of grafted polyether chains along the polysaccharide skeleton allows to modify the vitreous transition temperature and the molecular disorder of the system. Two type of polymer electrolytes have been synthesized: electrolytes carrying a dissolved alkaline metal salt and ionomers. The analysis of their thermal, dynamical mechanical, nuclear magnetic relaxation, electrical, and electrochemical properties shows that this new class of polymer electrolytes has the same performances as ethylene poly-oxide based amorphous lattices plus the advantage of having good filmic properties. Abstract only. (J.S.)

  17. New polysaccharide-based polymer electrolytes; Nouveaux electrolytes polymeres a base de polysaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Velasquez-Morales, P; Le Nest, J F; Gandini, A [Ecole Francaise de Papeterie et des Industries Graphique, 38 - Saint Martin d` Heres (France)

    1997-12-31

    Polysaccharides like cellulose and chitosan are known for their filmic properties. This paper concerns the synthesis and the study of chitosan-based polymer electrolytes. A preliminary work concerns the study of glucosamine reactivity. The poly-condensation of chitosan ethers (obtained by reaction with ethylene oxide or propylene oxide) with bifunctional and monofunctional oligo-ethers leads to the formation of thin lattices (10 {mu}m) having excellent mechanical properties. The presence of grafted polyether chains along the polysaccharide skeleton allows to modify the vitreous transition temperature and the molecular disorder of the system. Two type of polymer electrolytes have been synthesized: electrolytes carrying a dissolved alkaline metal salt and ionomers. The analysis of their thermal, dynamical mechanical, nuclear magnetic relaxation, electrical, and electrochemical properties shows that this new class of polymer electrolytes has the same performances as ethylene poly-oxide based amorphous lattices plus the advantage of having good filmic properties. Abstract only. (J.S.)

  18. Coordinated control of micro-grid based on distributed moving horizon control.

    Science.gov (United States)

    Ma, Miaomiao; Shao, Liyang; Liu, Xiangjie

    2018-05-01

    This paper proposed the distributed moving horizon coordinated control scheme for the power balance and economic dispatch problems of micro-grid based on distributed generation. We design the power coordinated controller for each subsystem via moving horizon control by minimizing a suitable objective function. The objective function of distributed moving horizon coordinated controller is chosen based on the principle that wind power subsystem has the priority to generate electricity while photovoltaic power generation coordinates with wind power subsystem and the battery is only activated to meet the load demand when necessary. The simulation results illustrate that the proposed distributed moving horizon coordinated controller can allocate the output power of two generation subsystems reasonably under varying environment conditions, which not only can satisfy the load demand but also limit excessive fluctuations of output power to protect the power generation equipment. Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.

  19. Effect- and Performance-Based Auditory Feedback on Interpersonal Coordination

    Directory of Open Access Journals (Sweden)

    Tong-Hun Hwang

    2018-03-01

    Full Text Available When two individuals interact in a collaborative task, such as carrying a sofa or a table, usually spatiotemporal coordination of individual motor behavior will emerge. In many cases, interpersonal coordination can arise independently of verbal communication, based on the observation of the partners' movements and/or the object's movements. In this study, we investigate how social coupling between two individuals can emerge in a collaborative task under different modes of perceptual information. A visual reference condition was compared with three different conditions with new types of additional auditory feedback provided in real time: effect-based auditory feedback, performance-based auditory feedback, and combined effect/performance-based auditory feedback. We have developed a new paradigm in which the actions of both participants continuously result in a seamlessly merged effect on an object simulated by a tablet computer application. Here, participants should temporally synchronize their movements with a 90° phase difference and precisely adjust the finger dynamics in order to keep the object (a ball accurately rotating on a given circular trajectory on the tablet. Results demonstrate that interpersonal coordination in a joint task can be altered by different kinds of additional auditory information in various ways.

  20. Crystal structure of a mixed-ligand terbium(III coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

    Directory of Open Access Journals (Sweden)

    Chainok Kittipong

    2016-01-01

    Full Text Available The title compound, poly[(μ3-formato(μ4-oxalatoterbium(III], [Tb(CHO2(C2O4]n, is a three-dimensional coordination polymer, and is isotypic with the LaIII, CeIII and SmIII analogues. The asymmetric unit contains one TbIII ion, one formate anion (CHO2− and half of an oxalate anion (C2O42−, the latter being completed by application of inversion symmetry. The TbIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C2O42− ligands, two carboxylate oxygen atoms from another two C2O42− ligands and three oxygen atoms from three CHO2− ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19 to 2.478 (3 Å and 64.53 (6 to 144.49 (4°, respectively. The CHO2− and C2O42− anions adopt μ3-bridging and μ4-chelating-bridging coordination modes, respectively, linking adjacent TbIII ions into a three-dimensional 12-connected fcu topology with point symbol (324.436.56. The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

  1. A quantum generalization of intrinsic reaction coordinate using path integral centroid coordinates

    International Nuclear Information System (INIS)

    Shiga, Motoyuki; Fujisaki, Hiroshi

    2012-01-01

    We propose a generalization of the intrinsic reaction coordinate (IRC) for quantum many-body systems described in terms of the mass-weighted ring polymer centroids in the imaginary-time path integral theory. This novel kind of reaction coordinate, which may be called the ''centroid IRC,'' corresponds to the minimum free energy path connecting reactant and product states with a least amount of reversible work applied to the center of masses of the quantum nuclei, i.e., the centroids. We provide a numerical procedure to obtain the centroid IRC based on first principles by combining ab initio path integral simulation with the string method. This approach is applied to NH 3 molecule and N 2 H 5 - ion as well as their deuterated isotopomers to study the importance of nuclear quantum effects in the intramolecular and intermolecular proton transfer reactions. We find that, in the intramolecular proton transfer (inversion) of NH 3 , the free energy barrier for the centroid variables decreases with an amount of about 20% compared to the classical one at the room temperature. In the intermolecular proton transfer of N 2 H 5 - , the centroid IRC is largely deviated from the ''classical'' IRC, and the free energy barrier is reduced by the quantum effects even more drastically.

  2. Characterization of Novel Castor Oil-Based Polyurethane Polymer Electrolytes

    Directory of Open Access Journals (Sweden)

    Salmiah Ibrahim

    2015-04-01

    Full Text Available Castor oil-based polyurethane as a renewable resource polymer has been synthesized for application as a host in polymer electrolyte for electrochemical devices. The polyurethane was added with LiI and NaI in different wt% to form a film of polymer electrolytes. The films were characterized by using attenuated total reflectance-Fourier transform infrared spectroscopy, dynamic mechanical analysis, electrochemical impedance spectroscopy, linear sweep voltammetry and transference number measurement. The highest conductivity of 1.42 × 10−6 S cm−1 was achieved with the addition of 30 wt% LiI and 4.28 × 10−7 S·cm−1 upon addition of 30 wt% NaI at room temperature. The temperature dependence conductivity plot indicated that both systems obeyed Arrhenius law. The activation energy for the PU-LiI and PU-NaI systems were 0.13 and 0.22 eV. Glass transition temperature of the synthesized polyurethane decreased from −15.8 °C to ~ −26 to −28 °C upon salts addition. These characterizations exhibited the castor oil-based polyurethane polymer electrolytes have potential to be used as alternative membrane for electrochemical devices.

  3. Libraries for spectrum identification: Method of normalized coordinates versus linear correlation

    International Nuclear Information System (INIS)

    Ferrero, A.; Lucena, P.; Herrera, R.G.; Dona, A.; Fernandez-Reyes, R.; Laserna, J.J.

    2008-01-01

    In this work it is proposed that an easy solution based directly on linear algebra in order to obtain the relation between a spectrum and a spectrum base. This solution is based on the algebraic determination of an unknown spectrum coordinates with respect to a spectral library base. The identification capacity comparison between this algebraic method and the linear correlation method has been shown using experimental spectra of polymers. Unlike the linear correlation (where the presence of impurities may decrease the discrimination capacity), this method allows to detect quantitatively the existence of a mixture of several substances in a sample and, consequently, to beer in mind impurities for improving the identification

  4. Fiber-optical accelerometers based on polymer optical fiber Bragg gratings

    DEFF Research Database (Denmark)

    Yuan, Scott Wu; Stefani, Alessio; Bang, Ole

    2010-01-01

    Fiber-optical accelerometers based on polymer optical fiber Bragg gratings (FBGs) are reported. We have written 3mm FBGs for 1550nm operation, characterized their temperature and strain response, and tested their performance in a prototype accelerometer.......Fiber-optical accelerometers based on polymer optical fiber Bragg gratings (FBGs) are reported. We have written 3mm FBGs for 1550nm operation, characterized their temperature and strain response, and tested their performance in a prototype accelerometer....

  5. Porous coordination polymer with flexibility imparted by coordinatively changeable lithium ions on the pore surface.

    Science.gov (United States)

    Xie, Lin-Hua; Lin, Jian-Bin; Liu, Xiao-Min; Wang, Yu; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming

    2010-02-01

    Solvothermal reactions of equimolar zinc acetate, lithium acetate, and 1,3,5-benzenetricarboxylic acid (H(3)btc) in different mixed solvents yielded isostructural three-dimensional frameworks [LiZn(btc)(cG)].lG [cG and lG denote coordinated and lattice guests, respectively; cG = (nmp)(0.5)(H(2)O)(0.5), lG = (EtOH)(0.5) (1a); cG = H(2)O, lG = EtOH (1b); nmp = N-methyl-2-pyrrolidone] with one-dimensional channels occupied by guest molecules and solvent-coordinated, extrusive Li(+) ions. Thermogravimetry analyses and powder X-ray diffraction measurements revealed that both 1a and 1b can lose all lattice and coordinated guests to form a desolvated phase [LiZn(btc)] (MCF-27, 1) and almost retains the original framework structure. Gas adsorption measurements on 1 confirmed its permanent porosity but suggested a structural transformation from 1a/1b to 1. It is noteworthy that only 1a can undergo a single-crystal to single-crystal (SCSC) transformation into 1 upon desolvation. The crystal structure of 1 revealed that the Li(+) ions were retracted into the channel walls via complementary coordination to the carboxylate oxygen atoms in the framework rather than being exposed on the pore surface. Single-crystal X-ray diffraction analyses were also performed for N(2)- and CO(2)-loaded samples of 1, revealing that the framework remained unchanged when the gases were adsorbed. Although the gas molecules could not be modeled, the residue electrons inside the channels demonstrated that the retracted Li(+) ions still behave as the primary interacting site for CO(2) molecules. Nevertheless, solvent molecules such as H(2)O can readily compete with the framework oxygen atom to retrieve the extrusive Li(+) ions, accompanying the reverse structural transformation, i.e., from 1 to 1a/1b.

  6. 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.

  7. Supramolecular materials based on hydrogen-bonded polymers

    NARCIS (Netherlands)

    ten Brinke, Gerrit; Ruokolainen, Janne; Ikkala, Olli; Binder, W

    2007-01-01

    Combining supramolecular principles with block copolymer self-assembly offers unique possibilities to create materials with responsive and/or tunable properties. The present chapter focuses on supramolecular materials based on hydrogen bonding and (block co-) polymers. Several cases will be

  8. BCB polymer based row-column addressed CMUT

    DEFF Research Database (Denmark)

    Havreland, Andreas Spandet; Ommen, Martin Lind; Silvestre, Chantal

    2017-01-01

    This paper presents an inexpensive, low temperature and rapid fabrication method for capacitive micromachined ultrasonic transducers (CMUT). The fabrication utilizes the bonding and dielectric properties of the photosensitive polymer Benzocyclobutene (BCB). A BCB based row-column addressed CMUT w...

  9. 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.

  10. Iodide-conducting polymer electrolytes based on poly-ethylene glycol and MgI2: Synthesis and structural characterization

    International Nuclear Information System (INIS)

    Vittadello, Michele; Waxman, David I.; Sideris, Paul J.; Gan Zhehong; Vezzù, Keti; Negro, Enrico; Safari, Ahmad; Greenbaum, Steve G.; Di Noto, Vito

    2011-01-01

    A major obstacle for a viable technological development of dye sensitized solar cells (DSSCs) is still the synthesis of a high performance iodide-conducting polymer electrolyte. Here we present a series of eight electrolytic complexes with formula PEG1000/(MgI 2 ) x (I 2 ) y (0.0038 ≤ x ≤ 0.5801, 0 ≤ y ≤ 0.0636). The synthesis involves the preparation of a disordered form of MgI 2 by a metallorganic route, which enables us to dissolve high amounts of salt in the chosen polymer host. The thermal analysis of the resulting polymer electrolytes was performed using modulated differential scanning calorimetry measurements. Vibrational studies were carried out using medium FT-IR, far FT-IR and FT-Raman. The variation of the CO and OH stretching modes in the medium infrared, as a function of the mole-to-mole ratio n Mg /n O , was investigated by Gaussian decomposition to provide insight into the polymer–polymer and salt–polymer interactions in these materials. The FT-Raman spectra confirmed and complemented the vibrational assignment. The conductivity study of these systems was performed by electrical spectroscopy in the frequency interval 10 mHz–10 MHz. The direct current conductivity (σ DC ) profiles versus the reciprocal temperature exhibited a Vögel-Tamman-Fülcher (VTF) behavior. The best σ DC at 50 °C was 5 × 10 −5 S cm −1 . The overall results indicate the presence of bivalent, monovalent and neutral species, Mg 2+ , [MgI] + and MgI 2 , respectively, which participate in the conduction process. These results are consistent with what was previously observed in PEG400-based systems doped with δ-MgCl 2 . The presence of at least one Mg site containing a distribution in parameters was observed using 25 Mg solid state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The site has been assigned to a Mg complex involving the coordination by oxygen atoms of the polymer backbone.

  11. Conducting Polymer Based Nanobiosensors

    Directory of Open Access Journals (Sweden)

    Chul Soon Park

    2016-06-01

    Full Text Available In recent years, conducting polymer (CP nanomaterials have been used in a variety of fields, such as in energy, environmental, and biomedical applications, owing to their outstanding chemical and physical properties compared to conventional metal materials. In particular, nanobiosensors based on CP nanomaterials exhibit excellent performance sensing target molecules. The performance of CP nanobiosensors varies based on their size, shape, conductivity, and morphology, among other characteristics. Therefore, in this review, we provide an overview of the techniques commonly used to fabricate novel CP nanomaterials and their biosensor applications, including aptasensors, field-effect transistor (FET biosensors, human sense mimicking biosensors, and immunoassays. We also discuss prospects for state-of-the-art nanobiosensors using CP nanomaterials by focusing on strategies to overcome the current limitations.

  12. Micelle-like nanoassemblies based on polymer-drug conjugates as an emerging platform for drug delivery.

    Science.gov (United States)

    Liu, Zhihong; Wang, Yutao; Zhang, Na

    2012-07-01

    During the past decades, polymer-drug conjugates are one of the hottest topics in novel drug development fields. Amphiphilic polymer-drug conjugates in aqueous solution could form micelles or micelle-like nanoassemblies. Compared with polymer-drug conjugates and the micelles into which drugs are physically entrapped, micelles or micelle-like nanoassemblies based on polymer-drug conjugates bring several additional advantages, including increased drug-loading capacity, enhanced intracellular uptake, reduced systemic toxicity, and improved therapeutic efficacy. This review focuses on recent progress achieved in the research field of micelles or micelle-like nanoassemblies based on polymer-drug conjugates. Firstly, properties of polymers, drugs, and linkers which could be used to build polymer-drug conjugate micelles or micelle-like nanoassemblies are summarized. Then, the characterization methods are described. Finally, the drug-targeting mechanisms are discussed. Micelles or micelle-like nanoassemblies based on polymer-drug conjugates as an emerging platform have the potential to achieve medical treatments with enhanced therapeutic effect. The application of micelles or micelle-like nanoassemblies based on polymer-drug conjugates may give new life to old active compounds abandoned due to their low solubility problems. For clinical application, there is a need to further optimize the properties of the polymer, drug, and linker.

  13. 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.

  14. Projections for the Production of Bulk Volume Bio-Based Polymers in Europe and Environmental Implications

    NARCIS (Netherlands)

    Patel, M.K.; Crank, M.

    2007-01-01

    In this paper we provide an overview of the most important emerging groups of bio-based polymers for bulk volume applications and we discuss market projections for these types of bio-based polymers in the EU, thereby distinguishing between three scenarios. Bio-based polymers are projected to reach a

  15. Building-up novel coordination polymer with Zn(II) porphyrin dimer ...

    Indian Academy of Sciences (India)

    mer with porphyrin dimer. Solution structures of the complexes along with binding studies in solution between ... porphyrin polymers by self-assembly is fascinating ..... ture determination. ..... J K M 2000 In The Porphyrin Handbook Kadish K M,.

  16. Ibuprofen-loaded microspheres based on a co-polymer of Eudragit ...

    African Journals Online (AJOL)

    The objective of this study was to encapsulate ibuprofen in microspheres based on a co-polymer of Eudragit® RS100 and RL100 with a view to achieving a controlled release of the incorporated drug. The microparticles were prepared by an o/o emulsion-solvent evaporation method using varying polymer ratios and ...

  17. 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

  18. A Fluorescent Thermometer Based on a Pyrene-Labeled Thermoresponsive Polymer

    Directory of Open Access Journals (Sweden)

    Ulrich S. Schubert

    2010-08-01

    Full Text Available Thermoresponsive polymers that undergo a solubility transition by variation of the temperature are important materials for the development of ‘smart’ materials. In this contribution we exploit the solubility phase transition of poly(methoxy diethylene glycol methacrylate, which is accompanied by a transition from hydrophilic to hydrophobic, for the development of a fluorescent thermometer. To translate the polymer phase transition into a fluorescent response, the polymer was functionalized with pyrene resulting in a change of the emission based on the microenvironment. This approach led to a soluble polymeric fluorescent thermometer with a temperature range from 11 °C to 21 °C. The polymer phase transition that occurs during sensing is studied in detail by dynamic light scattering.

  19. Comparison of selenophene and thienothiophene incorporation into pentacyclic lactam-based conjugated polymers for organic solar cells

    KAUST Repository

    Kroon, Renee; Melianas, Armantas; Zhuang, Wenliu; Bergqvist, Jonas; Diaz De Zerio Mendaza, Amaia; Steckler, Timothy T.; Yu, Liyang; Bradley, Siobhan J.; Musumeci, Chiara; Gedefaw, Desta; Nann, Thomas; Amassian, Aram; Mü ller, Christian; Inganä s, Olle; Andersson, Mats R.

    2015-01-01

    In this work, we compare the effect of incorporating selenophene versus thienothiophene spacers into pentacyclic lactam-based conjugated polymers for organic solar cells. The two cyclic lactam-based copolymers were obtained via a new synthetic method for the lactam moiety. Selenophene incorporation results in a broader and red-shifted optical absorption while retaining a deep highest occupied molecular orbital level, whereas thienothienophene incorporation results in a blue-shifted optical absorption. Additionally, grazing-incidence wide angle X-ray scattering data indicates edge- and face-on solid state order for the selenophene-based polymer as compared to the thienothiophene-based polymer, which orders predominantly edge-on with respect to the substrate. In polymer:PCBM bulk heterojunction solar cells both materials show a similar open-circuit voltage of ∼0.80-0.84 V, however the selenophene-based polymer displays a higher fill factor of ∼0.70 vs. ∼0.65. This is due to the partial face-on backbone orientation of the selenophene-based polymer, leading to a higher hole mobility, as confirmed by single-carrier diode measurements, and a concomitantly higher fill factor. Combined with improved spectral coverage of the selenophene-based polymer, as confirmed by quantum efficiency experiments, it offers a larger short-circuit current density of ∼12 mA cm. Despite the relatively low molecular weight of both materials, a very robust power conversion efficiency ∼7% is achieved for the selenophene-based polymer, while the thienothiophene-based polymer demonstrates only a moderate maximum PCE of ∼5.5%. Hence, the favorable effects of selenophene incorporation on the photovoltaic performance of pentacyclic lactam-based conjugated polymers are clearly demonstrated.

  20. Comparison of selenophene and thienothiophene incorporation into pentacyclic lactam-based conjugated polymers for organic solar cells

    KAUST Repository

    Kroon, Renee

    2015-09-08

    In this work, we compare the effect of incorporating selenophene versus thienothiophene spacers into pentacyclic lactam-based conjugated polymers for organic solar cells. The two cyclic lactam-based copolymers were obtained via a new synthetic method for the lactam moiety. Selenophene incorporation results in a broader and red-shifted optical absorption while retaining a deep highest occupied molecular orbital level, whereas thienothienophene incorporation results in a blue-shifted optical absorption. Additionally, grazing-incidence wide angle X-ray scattering data indicates edge- and face-on solid state order for the selenophene-based polymer as compared to the thienothiophene-based polymer, which orders predominantly edge-on with respect to the substrate. In polymer:PCBM bulk heterojunction solar cells both materials show a similar open-circuit voltage of ∼0.80-0.84 V, however the selenophene-based polymer displays a higher fill factor of ∼0.70 vs. ∼0.65. This is due to the partial face-on backbone orientation of the selenophene-based polymer, leading to a higher hole mobility, as confirmed by single-carrier diode measurements, and a concomitantly higher fill factor. Combined with improved spectral coverage of the selenophene-based polymer, as confirmed by quantum efficiency experiments, it offers a larger short-circuit current density of ∼12 mA cm. Despite the relatively low molecular weight of both materials, a very robust power conversion efficiency ∼7% is achieved for the selenophene-based polymer, while the thienothiophene-based polymer demonstrates only a moderate maximum PCE of ∼5.5%. Hence, the favorable effects of selenophene incorporation on the photovoltaic performance of pentacyclic lactam-based conjugated polymers are clearly demonstrated.

  1. Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

    KAUST Repository

    Pinnau, Ingo; Ghanem, Bader; Swaidan, Raja

    2015-01-01

    Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymers, a method of using

  2. Synthesis and characterization of triglyceride based thermosetting polymers

    Science.gov (United States)

    Can, Erde

    2005-07-01

    Plant oils, which are found in abundance in all parts of the world and are easily replenished annually, have the potential to replace petroleum as a chemical feedstock for making polymers. Within the past few years, there has been growing interest to use triglycerides as the basic constituent of thermosetting polymers with the necessary rigidity, strength and glass transition temperatures required for engineering applications. Plant oils are not polymerizable in their natural form, however various functional groups that can polymerize can easily be attached to the triglyceride structure making them ideal cross-linking monomers for thermosetting liquid molding resins. Through this research project a number of thermosetting liquid molding resins based on soybean and castor oil, which is a specialty oil with hydroxyls on its fatty acids, have been developed. The triglyceride based monomers were prepared via the malination of the alcoholysis products of soybean and castor oil with various polyols, such as pentaerythritol, glycerol, and Bisphenol A propoxylate. The malinated glycerides were then cured in the presence of a reactive diluent, such as styrene, to form rigid glassy materials with a wide range of properties. In addition to maleate half-esters, methacrylates were also introduced to the glyceride structure via methacrylation of the soybean oil glycerolysis product with methacrylic anhydride. This product, which contains methacrylic acid as by-product, and its blends with styrene also gave rigid materials when cured. The triglyceride based monomers were characterized via conventional spectroscopic techniques. Time resolved FTIR analysis was used to determine the curing kinetics and the final conversions of polymerization of the malinated glyceride-styrene blends. Dynamic Mechanical Analysis (DMA) was used to determine the thermomechanical behavior of these polymers and other mechanical properties were determined via standard mechanical tests. The use of lignin

  3. Stimulus-responsive hydrogels based on associative polymers

    DEFF Research Database (Denmark)

    Hietala, Sami; Hvilsted, Søren; Jankova Atanasova, Katja

    2008-01-01

    An important group of water soluble polymers are associative ones in which hydrophobic parts of the polymer molecules interact, self-assemble and enhance the viscosity of aqueous solutions even at low polymer concentrations. For many applications it would be beneficial to be able to combine the a......, in press. 3. S. Hietala, P. Mononen, S. Strandman, P. Jarvi, M. Torkkeli, K. Jankova, S. Hvilsted, H. Tenhu Polymer, 48 (2007) 4087-4096........ The resulting hydrogels were studied with respect to the polymer concentration, temperature and ionic strength.3 REFERENCES 1. Nuopponen M.; Kalliomaki K.; Laukkanen A.; Hietala S.; Tenhu H. 1. Polym. Sci. Polym. Chern. 2008, 46, 38-46. 2. Hietala S.; Nuopponen M.; Kalliomaki K.; Tenhu H. Macromolecules...

  4. Polymer Nanoparticle-Based Chemotherapy for Spinal Malignancies

    Directory of Open Access Journals (Sweden)

    Hongyun Ma

    2016-01-01

    Full Text Available Malignant spinal tumors, categorized into primary and metastatic ones, are one of the most serious diseases due to their high morbidity and mortality rates. Common primary spinal tumors include chordoma, chondrosarcoma, osteosarcoma, Ewing’s sarcoma, and multiple myeloma. Spinal malignancies are not only locally invasive and destructive to adjacent structures, such as bone, neural, and vascular structures, but also disruptive to distant organs (e.g., lung. Current treatments for spinal malignancies, including wide resection, radiotherapy, and chemotherapy, have made significant progress like improving patients’ quality of life. Among them, chemotherapy plays an important role, but its potential for clinical application is limited by severe side effects and drug resistance. To ameliorate the current situation, various polymer nanoparticles have been developed as promising excipients to facilitate the effective treatment of spinal malignancies by utilizing their potent advantages, for example, targeting, stimuli response, and synergetic effect. This review overviews the development of polymer nanoparticles for antineoplastic delivery in the treatment of spinal malignancies and discusses future prospects of polymer nanoparticle-based treatment methods.

  5. Synthesis, structure and magnetic properties of cobalt(II) and copper(II) coordination polymers assembled by phthalate and 4-methylimidazole

    International Nuclear Information System (INIS)

    Baca, S.G.; Malinovskii, S.T.; Franz, Patrick; Ambrus, Christina; Stoeckli-Evans, Helen; Gerbeleu, Nicolae; Decurtins, Silvio

    2004-01-01

    New coordination polymers [M(Pht)(4-MeIm) 2 (H 2 O)] n (M=Co (1), Cu (2); Pht 2- =dianion of o-phthalic acid; 4-MeIm=4-methylimidazole) have been synthesized and characterized by IR spectroscopy, X-ray crystallography, thermogravimetric analysis and magnetic measurements. The crystal structures of 1 and 2 are isostructural and consist of [M(4-MeIm) 2 (H 2 O)] building units linked in infinite 1D helical chains by 1,6-bridging phthalate ions which also act as chelating ligands through two O atoms from one carboxylate group in the case of 1. In complex 1, each Co(II) atom adopts a distorted octahedral N 2 O 4 geometry being coordinated by two N atoms from two 4-MeIm, three O atoms of two phthalate residues and one O atom of a water molecule, whereas the square-pyramidal N 2 O 3 coordination of the Cu(II) atom in 2 includes two N atoms of N-containing ligands, two O atoms of two carboxylate groups from different Pht, and a water molecule. An additional strong O-H↑··O hydrogen bond between a carboxylate group of the phthalate ligand and a coordinated water molecule join the 1D helical chains to form a 2D network in both compounds. The thermal dependences of the magnetic susceptibilities of the polymeric helical Co(II) chain compound 1 were simulated within the temperature range 20-300 K as a single ion case, whereas for the Cu(II) compound 2, the simulations between 25 and 300 K, were made for a linear chain using the Bonner-Fisher approximation. Modelling the experimental data of compound 1 with MAGPACK resulted in: g=2.6, vertical bar D vertical bar=62 cm -1 . Calculations using the Bonner-Fisher approximation gave the following result for compound 2: g=2.18, J=-0.4 cm -1

  6. COORDINATE-BASED META-ANALYTIC SEARCH FOR THE SPM NEUROIMAGING PIPELINE

    DEFF Research Database (Denmark)

    Wilkowski, Bartlomiej; Szewczyk, Marcin; Rasmussen, Peter Mondrup

    2009-01-01

    . BredeQuery offers a direct link from SPM5 to the Brede Database coordinate-based search engine. BredeQuery is able to ‘grab’ brain location coordinates from the SPM windows and enter them as a query for the Brede Database. Moreover, results of the query can be displayed in an SPM window and/or exported...

  7. A Coordinate-Based Proof of the Scallop Theorem

    OpenAIRE

    Ishimoto, Kenta; Yamada, Michio

    2012-01-01

    We reconsider fluid dynamics for a self-propulsive swimmer in Stokes flow. With an exact definition of deformation of a swimmer, a coordinate-based proof is first given to Purcell's scallop theorem including the body rotation.

  8. Graphene-Based Polymer Nanocomposites

    Science.gov (United States)

    2015-03-31

    polymerize in-situ around the fillers or even graft to them [71], thus it overcomes the problem of dramatically increased viscosity of the polymer...filler dispersion, increased polymer viscosity during processing and filler damage due to thermal degradation or strong shear forces [3, 82]. At...123, 124]. Figure 1.12 (a) SEM image of the fracture surface of GO/PVA nanocomposite film [85]. (b) TEM image of a clay reinforced Nylon-6

  9. 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.

  10. Brush Polymer of Donor-Accepter Dyads via Adduct Formation between Lewis Base Polymer Donor and All Carbon Lewis Acid Acceptor

    Directory of Open Access Journals (Sweden)

    Yang Wang

    2017-09-01

    Full Text Available A synthetic method that taps into the facile Lewis base (LB→Lewis acid (LA adduct forming reaction between the semiconducting polymeric LB and all carbon LA C60 for the construction of covalently linked donor-acceptor dyads and brush polymer of dyads is reported. The polymeric LB is built on poly(3-hexylthiophene (P3HT macromers containing either an alkyl or vinyl imidazolium end group that can be readily converted into the N-heterocyclic carbene (NHC LB site, while the brush polymer architecture is conveniently constructed via radical polymerization of the macromer P3HT with the vinyl imidazolium chain end. Simply mixing of such donor polymeric LB with C60 rapidly creates linked P3HT-C60 dyads and brush polymer of dyads in which C60 is covalently linked to the NHC junction connecting the vinyl polymer main chain and the brush P3HT side chains. Thermal behaviors, electronic absorption and emission properties of the resulting P3HT-C60 dyads and brush polymer of dyads have been investigated. The results show that a change of the topology of the P3HT-C60 dyad from linear to brush architecture enhances the crystallinity and Tm of the P3HT domain and, along with other findings, they indicate that the brush polymer architecture of donor-acceptor domains provides a promising approach to improve performances of polymer-based solar cells.

  11. Synthesis, structural characterization and photoluminescent properties of 2D multilayer Cu+ coordination polymers via Csbnd H⋯π and π⋯π interactions

    Science.gov (United States)

    Huang, Ting-Hong; Zhu, Sheng-Lan; Xiong, Xian-Lian; Li, Jia-Dong; Yang, Hu; Huang, Xin; Huang, Xue-Ren; Zhang, Kunming

    2017-09-01

    Two Cu(I) coordination polymers, {[Cu(pmbb)0.5(4,4'-bipy)0.5(PPh3)](BF4) (H2O)2}n (1) and {[Cu(pmbb)0.5(bpe)0.5(PPh3)](BF4)(DMF)}n (2) (pmbb = N, N'-bis(pyridin-2-ylmethylene)biphenyl -4,4'-diamine, 4,4'-bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene), PPh3 = triphenyl phosphine), have been synthesized and characterized by IR, 1H NMR, 13C NMR, 31P NMR, 19F NMR, 11B-NMR, TG and X-ray crystal structure analysis. The structural analysis shows that complexes 1 and 2 contain diverse and interesting 2D supramolecular networks based on inter-chain interactions. Complex 1 displays a 1D zig-zag chain and a 1D+1D→2D supramolecular network formed by intermolecular Csbnd H···π interaction. For 2, each 1D zig-zag chain interacts with neighboring ones via intermolecular Csbnd H···π and π···π stacking interactions, leading to the formation of a 2D-stacking network. Furthermore, solid-state UV-Vis absorption spectra of complexes 1 and 2 indicate the existence of MLCT absorption. Complexes 1 and 2 show efficient luminescent emission peaks at 435 and 452 nm assigned to MLCT excited states, and the emission decay lifetimes are 20.82 μs for 1 and 20.72 μs for 2, displaying strong room-temperature solid-state photoluminescence. Moreover, thermogravimetric analysis shows that the heat stability of polymers is 1>2.

  12. The determination of acid-base properties of polymer surfaces by XPS: Present status and future prospects

    International Nuclear Information System (INIS)

    Chehimi, M.M.; Delamar, M.; Shahidzadeh-Ahmadi, N.; Arefi-Khonsari, F.; Amouroux, J.; Watts, J.F.

    1996-01-01

    The use of the molecular probe technique in conjunction with X-ray photoelectron spectroscopy (XPS) for the assessment of acid-base properties of polymer surfaces is reviewed. The method is based on the determination of the concentration and chemical shifts of Lewis acids (bases) sorbed in polymers of basic (acidic) character. In the case of chloroform (Lewis acid) sorbed in polymers of Lewis basic character, C12p binding energy is linearly correlated with ΔH AB , the heat of acid-base complex formation chloroform-polymer. This relationship has been used to determine the acid-base properties of poly(phenylene oxide), a homopolymer, and ammonia plasma-treated polypropylene. This work shows that XPS can now indeed be used to quantitatively assess the acid-base properties of modified polymer surfaces and perhaps be extended to map acid-base properties of polymer surfaces at the micron or submicron scale. copyright 1996 American Institute of Physics

  13. 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

  14. 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

  15. Molecular Motion in Polymers: Mechanical Behavior of Polymers Near the Glass-Rubber Transition Temperature.

    Science.gov (United States)

    Sperling, L. H.

    1982-01-01

    The temperature at which the onset of coordinated segmental motion begins is called the glass-rubber transition temperature (Tg). Natural rubber at room temperature is a good example of a material above its Tg. Describes an experiment examining the response of a typical polymer to temperature variations above and below Tg. (Author/JN)

  16. Position Accuracy of Implant Analogs on 3D Printed Polymer versus Conventional Dental Stone Casts Measured Using a Coordinate Measuring Machine.

    Science.gov (United States)

    Revilla-León, Marta; Gonzalez-Martín, Óscar; Pérez López, Javier; Sánchez-Rubio, José Luis; Özcan, Mutlu

    2017-11-17

    To compare the accuracy of implant analog positions on complete edentulous maxillary casts made of either dental stone or additive manufactured polymers using a coordinate measuring machine (CMM). A completely edentulous maxillary model of a patient with 7 implant analogs was obtained. From this model, two types of casts were duplicated, namely conventional dental stone (CDS) using a custom tray impression technique after splinting (N = 5) and polymer cast using additive manufacturing based on the STL file generated. Polymer casts (N = 20; n = 5 per group) were fabricated using 4 different additive manufacturing technologies (multijet printing-MJP1, direct light processing-DLP, stereolithography-SLA, multijet printing-MJP2). CMM was used to measure the correct position of each implant, and distortion was calculated for each system at x-, y-, and z-axes. Measurements were repeated 3 times per specimen in each axis yielding a total of 546 measurements. Data were analyzed using ANOVA, Sheffé tests, and Bonferroni correction (α = 0.05). Compared to CMM, the mean distortion (μm) ranged from 22.7 to 74.9, 23.4 to 49.1, and 11.0 to 85.8 in the x-, y-, and z-axes, respectively. CDS method (x-axis: 37.1; z-axis: 27.62) showed a significant difference compared to DLP on the x-axis (22.7) (p = 0.037) and to MJP1 on the z-axis (11.0) (p = 0.003). Regardless of the cast system, x-axes showed more distortion (42.6) compared to y- (34.6) and z-axes (35.97). Among additive manufacturing technologies, MJP2 presented the highest (64.3 ± 83.6), and MJP1 (21.57 ± 16.3) and DLP (27.07 ± 20.23) the lowest distortion, which was not significantly different from CDS (32.3 ± 22.73) (p > 0.05). For the fabrication of the definitive casts for implant prostheses, one of the multijet printing systems and direct light processing additive manufacturing technologies showed similar results to conventional dental stone. Conventional dental stone casts could be accurately duplicated using some

  17. Modification of polylactide bioplastic using hyperbranched polymer based nanostructures

    Science.gov (United States)

    Bhardwaj, Rahul

    Polylactide (PLA) is the most well known renewable resource based biodegradable polymer. The inherent brittleness and poor processability of PLA pose considerable technical challenges and limit its range of commercial applications. The broad objective of this research was to investigate novel pathways for polylactide modification to enhance its mechanical and rheological properties. The focus of this work was to tailor the architecture of a dendritic hyperbranched polymer (HBP) and study its influence on the mechanical and rheological properties of PLA bioplastic. The hyperbranched polymers under consideration are biodegradable aliphatic hydroxyl-functional hyperbranched polyesters having nanoscale dimensions, unique physical properties and high peripheral functionalities. This work relates to identifying a new and industrially relevant research methodology to develop PLA based nanoblends having outstanding stiffness-toughness balance. In this approach, a hydroxyl functional hyperbranched polymer was crosslinked in-situ with a polyanhydride (PA) in the PLA matrix during melt processing, leading to the generation of new nanoscale hyperbranched polymer based domains in the PLA matrix. Transmission electron microscopy and atomic force microscopy revealed the "sea-island" morphology of PLA-crosslinked HBP blends. The domain size of a large portion of the crosslinked HBP particles in PLA matrix was less than 100 nm. The presence of crosslinked hyperbranched polymers exhibited more than 500% and 800% improvement in the tensile toughness and elongation at break values of PLA, respectively, with a minimal sacrifice of tensile strength and modulus as compared to unmodified PLA. The toughening mechanism of PLA in the presence of crosslinked HBP particles was comprised of shear yielding and crazing. The volume fraction of crosslinked HBP particles and matrix ligament thickness (inter-particle distance) were found to be the critical parameters for the toughening of PLA. The

  18. Functional Hybrid Biomaterials based on Peptide-Polymer Conjugates for Nanomedicine

    Science.gov (United States)

    Shu, Jessica Yo

    The focus of this dissertation is the design, synthesis and characterization of hybrid functional biomaterials based on peptide-polymer conjugates for nanomedicine. Generating synthetic materials with properties comparable to or superior than those found in nature has been a "holy grail" for the materials community. Man-made materials are still rather simplistic when compared to the chemical and structural complexity of a cell. Peptide-polymer conjugates have the potential to combine the advantages of the biological and synthetic worlds---that is they can combine the precise chemical structure and diverse functionality of biomolecules with the stability and processibility of synthetic polymers. As a new family of soft matter, they may lead to materials with novel properties that have yet to be realized with either of the components alone. In order for peptide-polymer conjugates to reach their full potential as useful materials, the structure and function of the peptide should be maintained upon polymer conjugation. The success in achieving desirable, functional assemblies relies on fundamentally understanding the interactions between each building block and delicately balancing and manipulating these interactions to achieve targeted assemblies without interfering with designed structures and functionalities. Such fundamental studies of peptide-polymer interactions were investigated as the nature of the polymer (hydrophilic vs. hydrophobic) and the site of its conjugation (end-conjugation vs. side-conjugation) were varied. The fundamental knowledge gained was then applied to the design of amphiphiles that self-assemble to form stable functional micelles. The micelles exhibited exceptional monodispersity and long-term stability, which is atypical of self-assembled systems. Thus such micelles based on amphiphilic peptide-polymer conjugates may meet many current demands in nanomedicine, in particular for drug delivery of hydrophobic anti-cancer therapeutics. Lastly

  19. Synthesis, structure, and electrochemistry and magnetic properties of a novel 1D homochiral MnIII(5-Brsalen) coordination polymer with left-handed helical character

    Science.gov (United States)

    Dong, Dapeng; Yu, Naisen; Zhao, Haiyan; Liu, Dedi; Liu, Jia; Li, Zhenghua; Liu, Dongping

    2016-01-01

    A novel homochiral manganese (III) Mn(5-Brsalen) coordination polymer with left-handed helical character by spontaneous resolution on crystallization by using Mn(5-Brsalen) and 4,4-bipyridine, [MnIII(5-Brsalen)(4,4-bipy)]·ClO4·CH3OH (1) (4,4-bipy = 4,4-bipyridine) has been synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analysis and infrared spectroscopy. In compound 1, each manganese(III) anion is six-coordinate octahedral being bonded to four atoms of 5-Brsalen ligand in an equatorial plane and two nitrogen atoms from a 4,4-bipyridine ligand in axial positions. The structure of compound 1 can be described a supramolecular 2D-like structure which was formed by the intermolecular π-stacking interactions between the neighboring chains of the aromatic rings of 4,4-bipyridine and 5-Brsalen molecules. UV-vis absorption spectrum, electrochemistry and magnetic properties of the compound 1 have also been studied.

  20. Polycyanurates and Polycarbonates Based on Eugenol: Alternatives to Thermosetting and Thermoplastic Polymers Based on Bisphenol A

    Science.gov (United States)

    2014-08-14

    to 5a. CONTRACT NUMBER In-House Thermosetting and Thermoplastic Polymers based on Bisphenol A 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6...Francisco, CA, 14 August 2014. PA#14389 14. ABSTRACT Polycyanurate thermosetting networks, polycarbonate thermoplastics, and homogenous polycarbonate...ON EUGENOL: ALTERNATIVES TO THERMOSETTING AND THERMOPLASTIC POLYMES BASED ON BISPHENOL A 14 August 2014 Andrew J. Guenthner1, Benjamin G. Harvey2

  1. Polymer-based platform for microfluidic systems

    Science.gov (United States)

    Benett, William [Livermore, CA; Krulevitch, Peter [Pleasanton, CA; Maghribi, Mariam [Livermore, CA; Hamilton, Julie [Tracy, CA; Rose, Klint [Boston, MA; Wang, Amy W [Oakland, CA

    2009-10-13

    A method of forming a polymer-based microfluidic system platform using network building blocks selected from a set of interconnectable network building blocks, such as wire, pins, blocks, and interconnects. The selected building blocks are interconnectably assembled and fixedly positioned in precise positions in a mold cavity of a mold frame to construct a three-dimensional model construction of a microfluidic flow path network preferably having meso-scale dimensions. A hardenable liquid, such as poly (dimethylsiloxane) is then introduced into the mold cavity and hardened to form a platform structure as well as to mold the microfluidic flow path network having channels, reservoirs and ports. Pre-fabricated elbows, T's and other joints are used to interconnect various building block elements together. After hardening the liquid the building blocks are removed from the platform structure to make available the channels, cavities and ports within the platform structure. Microdevices may be embedded within the cast polymer-based platform, or bonded to the platform structure subsequent to molding, to create an integrated microfluidic system. In this manner, the new microfluidic platform is versatile and capable of quickly generating prototype systems, and could easily be adapted to a manufacturing setting.

  2. Unconventional, amphiphilic polymers based on chiral polyethylene oxide derivatives I. Synthesis and Characterization.

    NARCIS (Netherlands)

    Janssen, H.M.; Peeters, E.; Zundert, van M.F.; Genderen, van M.H.P.; Meijer, E.W.

    1997-01-01

    The first representatives of a new class of synthetic, amphiphilic polymers based on poly(ethylene oxide) are introduced. These polymers are constituted in a similar way to that for coiled-coil-forming peptides: the polymers possess a regular repeat of apolar (A) residues in a polar (P) sequence of

  3. Two-coordinate scintillation hodoscope based on hodoscopical photomultipliers

    International Nuclear Information System (INIS)

    Vishnevskij, N.K.; Ronzhin, A.I.; Semenov, V.K.; Khachaturov, B.A.

    1982-01-01

    The results of investigations of scintillation hodoscope on the basis of hodoscopic photomultipliers (HPM) for simultaneous measuring two coordinates (x and y) of a particle. The hodoscope consists of scintillation electrodes bent at the angle of 135 deg C and made an angle of 90 deg with each other. For measuring X-coordinate the half part of the photocathode is used, the second part is used for measuring Y-coordinate. HPM provides for simultaneous measuring two coordinates of a particle in the working region of 90 mm at using the photocathode with 180 mm long working region along the photocathode. The discrete separation of neighbouring positions in relation to the photocathode is possible at the minimum size of scintillation electrode being equil to >= 2 mm. For suppression of multiparticle background at the information output from the hodoscope as well as for simultaneous observation at the amplitude analyser of spectra of reference signals or X and Y profiles a fast processor cicuit has been developed. High detecting efficiency (about 90%) and low background level have been observed at the processor operation where the presence only of one signal in each of X- or Y projections is required. The two-coordinate hodoscope based on HPM due to its compactness and mobility may be used for expedient and precision beam guidance onto a target, its position control, shape and dimensions directly in the region of a polarized target location

  4. Lignin-based monomers: Utilization in high-performance polymers and the effects of their structures on polymer properties

    Science.gov (United States)

    Stanzione, Joseph F., III

    With the uncertainty of petroleum reserves and future crude oil prices, lignocellulosic biomass is becoming an increasingly valuable resource for the sustainable development of fuels, chemicals, and materials, including vinyl ester resins (VERs). Petroleum-based VERs are used to produce polymer composites for a wide variety of commercial applications. Although possessing relatively high moduli, strengths, and glass transition temperatures, commercial VERs typically contain high concentrations of a reactive diluent, such as styrene. However, these reactive diluents are often considered hazardous air pollutants (HAPs), volatile organic compounds (VOCs), and anticipated carcinogens. Moreover, bisphenol-A, which has gained considerable attention due to potential associated health-related issues, is utilized as a precursor in the synthesis of VERs. A green chemistry and engineering approach in the development of new VERs and renewable reactive diluents that are based on lignin is presented in this dissertation. Lignin, which is currently an abundant, renewable waste product of the paper and pulping industry, is primarily burned as a low value fuel. However, lignin has the potential to be a low cost feedstock in future lignocellulosic biorefineries that could yield highly valuable aromatic chemicals (lignin model compounds, LMCs) when strategically depolymerized. The incorporation of aromaticity in a resin's chemical structure is known to improve overall polymer composite performance and the high aromatic content found in lignin is ideal for novel resin development. Highlighted in this dissertation are three projects: (1) the synthesis and characterization of a lignin-based bio-oil resin/reactive diluent, (2) the use of functionalized LMCs as styrene replacements in VERs, and (3) the synthesis and characterization of a vanillin-based resin. Through the use of traditional and new polymer theory coupled with spectroscopic, thermal, and mechanical techniques, structure

  5. New NIR Absorbing DPP-based Polymer for Thick Organic Solar Cells

    KAUST Repository

    Oklem, Gulce

    2018-02-05

    infrared region (NIR) for better photon harvesting in organic solar cells. It has been shown that copolymers compromising diketopyrrolopyrrole based acceptors and simple donors (thiophene or furan) achieve absorption maximum around 800 nm. In this study, the selenophene based donor units coupled with diketopyrrolopyrrole acceptor unit based polymer (PFDPPSe) was synthesized with an absorption maximum at 830 nm and absorption onset of 930 nm. The optimized organic solar cells with PFDDPSe: PC71BM active layer blends of 210 nm showed maximum PCE of 6.16 % (ave. 6.02 %) via solvent additive engineering with inverted device structure. Charge transport, recombination loss mechanism, and morphology are systematically studied. These results demonstrate that highly efficient NIR polymer can be achieved by the introduction of selenophene and a suitable solvent additive process suitable for NIR organic solar cells. PFDPPSe is also one of the rare examples of a polymer with a PCE over 6% that does not contain any thiophene-based unit in its backbone.

  6. Hydrothermal synthesis of Bismuth(III) coordination polymer and its transformation to nano α-Bi{sub 2}O{sub 3} for photocatalytic degradation

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Ya-Jing; Zheng, Yue-Qing, E-mail: zhengnbu@163.com; Zhu, Hong-Lin; Wang, Jin-Jian

    2016-07-15

    A new Bi(III) coordination polymer Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O (H{sub 2}pdc=pyridine-2,6-dicarboxylic acid) was synthesized by hydrothermal method. Solid state thermal decomposition of this complex under 500 °C for 1 h led to the foliated Bi{sub 2}O{sub 3} nanoparticles, which were then characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Comparative study on their photocatalytic activity toward the degradation of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) in polluted water was explored, and the mechanism of these photocatalytic degradation was discussed. These results provided some interesting insights into their photocatalytic applications. - Graphical abstract: We regard Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O with 1D chain structures as the precursor, then calcinate the complex to prepare nano-powder α-Bi{sub 2}O{sub 3}. The photochemical experiment indicates that Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O can be used as an efficient photocatalyst for the degradation of RhB and MB. Interestingly, nano α-Bi{sub 2}O{sub 3} shows higher activity than the commercial Bi{sub 2}O{sub 3} for the degradation of RhB, MB or MO. Display Omitted - Highlights: • A novel dinuclear Bi(III) coordination polymer is hydrothermally synthesized. • Calcinating the precursor Bi-CP will result in the nano Bi{sub 2}O{sub 3} with foliated morphology. • Nano Bi{sub 2}O{sub 3} shows higher activity than the commercial Bi{sub 2}O{sub 3} for the degradation of dyes.

  7. The potential of organic polymer-based hydrogen storage materials.

    Science.gov (United States)

    Budd, Peter M; Butler, Anna; Selbie, James; Mahmood, Khalid; McKeown, Neil B; Ghanem, Bader; Msayib, Kadhum; Book, David; Walton, Allan

    2007-04-21

    The challenge of storing hydrogen at high volumetric and gravimetric density for automotive applications has prompted investigations into the potential of cryo-adsorption on the internal surface area of microporous organic polymers. A range of Polymers of Intrinsic Microporosity (PIMs) has been studied, the best PIM to date (a network-PIM incorporating a triptycene subunit) taking up 2.7% H(2) by mass at 10 bar/77 K. HyperCrosslinked Polymers (HCPs) also show promising performance as H(2) storage materials, particularly at pressures >10 bar. The N(2) and H(2) adsorption behaviour at 77 K of six PIMs and a HCP are compared. Surface areas based on Langmuir plots of H(2) adsorption at high pressure are shown to provide a useful guide to hydrogen capacity, but Langmuir plots based on low pressure data underestimate the potential H(2) uptake. The micropore distribution influences the form of the H(2) isotherm, a higher concentration of ultramicropores (pore size <0.7 nm) being associated with enhanced low pressure adsorption.

  8. Investigation of ITO free transparent conducting polymer based electrode

    Science.gov (United States)

    Sharma, Vikas; Sapna, Sachdev, Kanupriya

    2016-05-01

    The last few decades have seen a significant improvement in organic semiconductor technology related to solar cell, light emitting diode and display panels. The material and structure of the transparent electrode is one of the major concerns for superior performance of devices such as OPV, OLED, touch screen and LCD display. Commonly used ITO is now restricted due to scarcity of indium, its poor mechanical properties and rigidity, and mismatch of energy levels with the active layer. Nowadays DMD (dielectric-metal-dielectric) structure is one of the prominent candidates as alternatives to ITO based electrode. We have used solution based spin coated polymer layer as the dielectric layer with silver thin film embedded in between to make a polymer-metal-polymer (PMP) structure for TCE applications. The PMP structure shows low resistivity (2.3 x 10-4Ω-cm), high carrier concentration (2.9 x 1021 cm-3) and moderate transparency. The multilayer PMP structure is characterized with XRD, AFM and Hall measurement to prove its suitability for opto-electronic device applications.

  9. Investigation of ITO free transparent conducting polymer based electrode

    International Nuclear Information System (INIS)

    Sharma, Vikas; Sapna,; Sachdev, Kanupriya

    2016-01-01

    The last few decades have seen a significant improvement in organic semiconductor technology related to solar cell, light emitting diode and display panels. The material and structure of the transparent electrode is one of the major concerns for superior performance of devices such as OPV, OLED, touch screen and LCD display. Commonly used ITO is now restricted due to scarcity of indium, its poor mechanical properties and rigidity, and mismatch of energy levels with the active layer. Nowadays DMD (dielectric-metal-dielectric) structure is one of the prominent candidates as alternatives to ITO based electrode. We have used solution based spin coated polymer layer as the dielectric layer with silver thin film embedded in between to make a polymer-metal-polymer (PMP) structure for TCE applications. The PMP structure shows low resistivity (2.3 x 10"−"4Ω-cm), high carrier concentration (2.9 x 10"2"1 cm"−"3) and moderate transparency. The multilayer PMP structure is characterized with XRD, AFM and Hall measurement to prove its suitability for opto-electronic device applications.

  10. Investigation of ITO free transparent conducting polymer based electrode

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Vikas; Sapna,; Sachdev, Kanupriya [Department of Physics, Malaviya National Institute of Technology Jaipur, JLN Marg, Jaipur-India-302017 (India)

    2016-05-23

    The last few decades have seen a significant improvement in organic semiconductor technology related to solar cell, light emitting diode and display panels. The material and structure of the transparent electrode is one of the major concerns for superior performance of devices such as OPV, OLED, touch screen and LCD display. Commonly used ITO is now restricted due to scarcity of indium, its poor mechanical properties and rigidity, and mismatch of energy levels with the active layer. Nowadays DMD (dielectric-metal-dielectric) structure is one of the prominent candidates as alternatives to ITO based electrode. We have used solution based spin coated polymer layer as the dielectric layer with silver thin film embedded in between to make a polymer-metal-polymer (PMP) structure for TCE applications. The PMP structure shows low resistivity (2.3 x 10{sup −4}Ω-cm), high carrier concentration (2.9 x 10{sup 21} cm{sup −3}) and moderate transparency. The multilayer PMP structure is characterized with XRD, AFM and Hall measurement to prove its suitability for opto-electronic device applications.

  11. All-polymer photonic sensing platform based on whispering-gallery mode microgoblet lasers

    OpenAIRE

    Wienhold, T.; Kraemmer, S.; Wondimu, S.F.; Siegle, T.; Bog, U.; Weinzierl, U.; Schmidt, S.; Becker, H.; Kalt, H.; Mappes, T.; Koeber, S.; Koos, C.

    2015-01-01

    We present an all-polymer photonic sensing platform based on whispering-gallery mode microgoblet lasers integrated into a microfluidic chip. The chip is entirely made from polymers, enabling the use of the devices as low-cost disposables. The microgoblet cavities feature quality factors exceeding 105 and are fabricated from poly(methyl methacrylate) (PMMA) using spin-coating, mask-based optical lithography, wet chemical etching, and thermal reflow. In contrast to silica-based microtoroid reso...

  12. Coordinated SLNR based Precoding in Large-Scale Heterogeneous Networks

    KAUST Repository

    Boukhedimi, Ikram

    2017-03-06

    This work focuses on the downlink of large-scale two-tier heterogeneous networks composed of a macro-cell overlaid by micro-cell networks. Our interest is on the design of coordinated beamforming techniques that allow to mitigate the inter-cell interference. Particularly, we consider the case in which the coordinating base stations (BSs) have imperfect knowledge of the channel state information. Under this setting, we propose a regularized SLNR based precoding design in which the regularization factor is used to allow better resilience with respect to the channel estimation errors. Based on tools from random matrix theory, we provide an analytical analysis of the SINR and SLNR performances. These results are then exploited to propose a proper setting of the regularization factor. Simulation results are finally provided in order to validate our findings and to confirm the performance of the proposed precoding scheme.

  13. Coordinated SLNR based Precoding in Large-Scale Heterogeneous Networks

    KAUST Repository

    Boukhedimi, Ikram; Kammoun, Abla; Alouini, Mohamed-Slim

    2017-01-01

    This work focuses on the downlink of large-scale two-tier heterogeneous networks composed of a macro-cell overlaid by micro-cell networks. Our interest is on the design of coordinated beamforming techniques that allow to mitigate the inter-cell interference. Particularly, we consider the case in which the coordinating base stations (BSs) have imperfect knowledge of the channel state information. Under this setting, we propose a regularized SLNR based precoding design in which the regularization factor is used to allow better resilience with respect to the channel estimation errors. Based on tools from random matrix theory, we provide an analytical analysis of the SINR and SLNR performances. These results are then exploited to propose a proper setting of the regularization factor. Simulation results are finally provided in order to validate our findings and to confirm the performance of the proposed precoding scheme.

  14. Polymer-mediated formation of polyoxomolybdate nanomaterials

    Science.gov (United States)

    Wan, Quan

    A polymer-mediated synthetic pathway to a polyoxomolybdate nanomaterial is investigated in this work. Block copolymers or homopolymers containing poly(ethylene oxide) (PEO) are mixed with a MoO2(OH)(OOH) aqueous solution to form a golden gel or viscous solution. As revealed by synchrotron X-ray scattering measurements, electron microscopy, and other characterization techniques, the final dark blue polyoxomolybdate product is a highly ordered simple cubic network similar to certain zeolite structure but with a much larger lattice constant of ˜5.2 nm. The average size of the cube-like single crystals is close to 1 mum. Based on its relatively low density (˜2.2 g/cm3), the nanomaterial can be highly porous if the amount of the residual polymer can be substantially reduced. The valence of molybdenum is ˜5.7 based on cerimetric titration, representing the mixed-valence nature of the polyoxomolybdate structure. The self-assembled structures (if any) of the polymer gel do not have any correlation with the final polyoxomolybdate nanostructure, excluding the possible role of polymers being a structure-directing template. On the other hand, the PEO polymer stabilizes the precursor molybdenum compound through coordination between its ether oxygen atoms and molybdenum atoms, and reduces the molybdenum (VI) precursor compound with its hydroxyl group being a reducing agent. The rare simple cubic ordering necessitates the existence of special affinities among the polyoxomolybdate nanosphere units resulted from the reduction reaction. Our mechanism study shows that the acidified condition is necessary for the synthesis of the mixed-valence polyoxomolybdate clusters, while H2O2 content modulates the rate of the reduction reaction. The polymer degradation is evidenced by the observation of a huge viscosity change, and is likely through a hydrolysis process catalyzed by molybdenum compounds. Cube-like polyoxomolybdate nanocrystals with size of ˜40 nm are obtained by means of

  15. Chiral and achiral helical coordination polymers of zinc and ...

    Indian Academy of Sciences (India)

    rality depends on formation of cis coordination geom- etry around the ..... lographic Data Centre via www.ccdc.cam.ac.uk/data_ .... 324; (b) Han L and Hong M 2005 Inorg. Chem. Com ... Kang Y, Chen S, Wang F, Zhang J and Bu X 2011 Chem.

  16. Synthesis and characterization of thiolated polymers based on polyhydroxyethylakrylate and 3-mercaptopropylmethoxysilane

    Directory of Open Access Journals (Sweden)

    G. Irmukhametova

    2012-03-01

    Full Text Available In the presented paper thiolated polymer based on nonionic polyhydroxyethylmethacrylate (PHEMA and 3-mercaptopropyltrimethoxysilane (MPTS was obtained and characterized. Results of Raman-spectroscopy and Elman’s assay showed the presence of thiol groups in the modified polymer.

  17. Relation between exciplex formation and photovoltaic properties of PPV polymer-based blends

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Chunhong; Neher, Dieter [Institute of Physics, University of Potsdam, Am Neuen Palais 10, 14469 Potsdam (Germany); Kietzke, Thomas [Institute of Physics, University of Potsdam, Am Neuen Palais 10, 14469 Potsdam (Germany); Institute of Materials Research and Engineering (IMRE), Research Link 3, 117602 Singapore (Singapore); Kumke, Michael [Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Street 24-25, 14476 Golm (Germany); Hoerhold, Hans-Heinrich [Institute of Organic Chemistry and Macromolecular Chemistry, University of Jena, Humboldtstr. 10, 07743 Jena (Germany)

    2007-03-06

    As a new record for pure polymer-blend solar cells, an energy conversion efficiency (ECE) of 1.7% was recently achieved for M3EH-PPV:CN-ether-PPV (Poly[oxa-1,4-phenylene-1,2-(1-cyano)-ethylene-2,5-dioctyloxy-1,4-phenylene-1,2- (2-cyano)-ethylene-1,4-phenylene]) based devices [T. Kietzke, H.-H. Hoerhold, D. Neher, Chem. Mater. 17 (2005) 6532]. Even though that photoluminescence experiments indicated that 95% of the photogenerated excitions were dissociated in the blend, the external quantum efficiency reached only 31%. Thus more than 2/3 of the dissociated excitons were lost for the energy conversion. In order to identify the processes which limit the photovoltaic efficiency of polymer-blend solar cells, studies on the steady state and time-resolved photoluminescence of the individual polymer and polymer blend were performed. In the polymer-blend layer, we observed a considerable long-wavelength emission due to exciplex formation. The exciplex emission can be reduced by thermal annealing. At the same time the IPCE of the blend-based device increased, indicating a more efficient generation of free-charge carriers. These findings lead to the conclusion that charge-carrier recombination via exciplex formation constitutes one of the loss channels which limits the efficiency of polymer solar cells. (author)

  18. Post-modification by γ-radiation of VDF-based polymers: Electrochemical capacitor membrane application

    International Nuclear Information System (INIS)

    Dumas, L.

    2012-01-01

    This work deals with the modification of VDF-based polymer induced by γ-radiation as the polymer may be used in electrochemical super-capacitors. The main objective was to limit the swelling of the fluorinated matrix with a given electrolyte while a good wetting of the polymer by the liquid was also required. As the main basic process involved in polymer radiolysis is the formation of radicals, a part of the work was dedicated to the study of such species by using Electron Spin Resonance spectroscopy. A simulation model of ESR spectra was established in order to identify and quantify each radical species. The effect of several parameters such as radiation dose, annealing time or the nature of polymer matrix on the concentration of each species where investigated. A relation with the evolution of the crosslink density of the network formed during the radiolysis was proposed. In addition, one of the key steps of this work was to study the radiation crosslinking ability of VDF-based polymers and find a way to increase the crosslink density. This was achieved by incorporating, prior to the radiation process, a radiation sensitive cross linker: TAIC. Finally, a new strategy based on the modification of surface properties of PVDF was investigated. It consists in the radiation grafting of penta-fluor-styrene onto PVDF surface followed by the chemo-selective functionalization of the grafted segments. As a conclusion, the different approaches used in this thesis allowed us to understand the radiolysis of VDF-based polymers and take advantage of the elementary process involved in this type of chemistry, to build up robust and promising strategies for tuning properties. (author)

  19. Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries

    International Nuclear Information System (INIS)

    Sterby, Mia; Emanuelsson, Rikard; Huang, Xiao; Gogoll, Adolf; Strømme, Maria; Sjödin, Martin

    2017-01-01

    Lithium-ion technologies show great promise to meet the demands that the transition towards renewable energy sources and the electrification of the transport sector put forward. However, concerns regarding lithium-ion batteries, including limited material resources, high energy consumption during production, and flammable electrolytes, necessitate research on alternative technologies for electrochemical energy storage. Organic materials derived from abundant building blocks and with tunable properties, together with water based electrolytes, could provide safe, inexpensive and sustainable alternatives. In this study, two conducting redox polymers based on poly(3,4-ethylenedioxythiophene) (PEDOT) and a hydroquinone pendant group have been synthesized and characterized in an acidic aqueous electrolyte. The polymers were characterized with regards to kinetics, pH dependence, and mass changes during oxidation and reduction, as well as their conductance. Both polymers show redox matching, i.e. the quinone redox reaction occurs within the potential region where the polymer is conducting, and fast redox conversion that involves proton cycling during pendant group redox conversion. These properties make the presented materials promising candidates as electrode materials for water based all-organic batteries.

  20. Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Manh Thuong; Wang, Zheming; Rod, Kenton A.; Childers, Matthew I.; Fernandez, Carlos A.; Koech, Phillip K.; Bennett, Wendy D.; Rousseau, Roger J.; Glezakou, Vassiliki-Alexandra

    2018-01-09

    Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized towards defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement/polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG spectroscopy.

  1. Polymer electronics

    CERN Document Server

    Hsin-Fei, Meng

    2013-01-01

    Polymer semiconductor is the only semiconductor that can be processed in solution. Electronics made by these flexible materials have many advantages such as large-area solution process, low cost, and high performance. Researchers and companies are increasingly dedicating time and money in polymer electronics. This book focuses on the fundamental materials and device physics of polymer electronics. It describes polymer light-emitting diodes, polymer field-effect transistors, organic vertical transistors, polymer solar cells, and many applications based on polymer electronics. The book also disc

  2. 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.

  3. Novel silicone-based polymer containing active methylene designed for the removal of indoor formaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Song, E-mail: niusong84@163.com; Yan, Hongxia, E-mail: hongxiayan@nwpu.edu.cn

    2015-04-28

    Highlights: • A novel silicone-based polymer with active methylene was explored. • Surface tension of liquid paints could be lowered using the polymer. • The polymer was easy to migrate toward the air-coating interface. • Free HCHO could effectively be removed using the polymer. • A lights on HCHO reduction without complicated preparation procedure was shielded. - Abstract: Indoor air pollution is caused inevitably due to complicated home decoration, in which formaldehyde is one of the most typical pollutants. It will be a convenient, economical and effective strategy to remove indoor formaldehyde if imparting a feature of formaldehyde removal to decorative coatings. We have successfully explored a novel silicone-based polymer containing active methylene used as a formaldehyde absorbent in coatings via a straightforward transesterification process using inexpensive and easily available chemicals. The polymer has been characterized by {sup 13}C NMR, FTIR, GC and GPC. Formaldehyde removal capacity of the coating films containing different contents of the polymer has been investigated. The results indicated that coatings incorporating 4 wt% of the polymer could make the coating films exhibit significant improvement on formaldehyde removal including purificatory performance (>85%) and durability of purificatory effect (>60%), compared to those consisting of absorbents without any silicon, and improve yellowing resistance performance, while other properties, such as gloss, adhesion, pencil hardness, flexibility and impact resistance, were kept almost unaffected. The chemical absorption process of the silicone-based polymer filled in interior decorative coatings is demonstrated as a promising technology to purify indoor formaldehyde and thus can reduce the harm to individuals.

  4. Design of Polymer Wavelength Splitter 1310 nm/1550 nm Based on Multimode Interferences

    Directory of Open Access Journals (Sweden)

    V. Prajzler

    2010-12-01

    Full Text Available We report about design of 1x2 1310/1550 nm optical wavelength division multiplexer based on polymer waveguides. The polymer splitter was designed by using RSoft software based on beam propagation method. Epoxy novolak resin polymer was used as core waveguides layer, silicon substrate with silica layer was used as buffer layer and polymethylmethacrylate was used as protection cover layer. The simulation shows that the output energy for the fundamental mode is 67.1 % for 1310 nm and 67.8 % for 1550 nm wavelength.

  5. Two-dimensional coordination polymer matrix for solid-phase extraction of pesticide residues from plant Cordia salicifolia.

    Science.gov (United States)

    de Carvalho, Pedro Henrique Viana; Barreto, Alysson Santos; Rodrigues, Marcelo O; Prata, Vanessa de Menezes; Alves, Péricles Barreto; de Mesquita, Maria Eliane; Alves, Severino; Navickiene, Sandro

    2009-06-01

    The 2D coordination polymer (infinity[Gd(DPA)(HDPA)]) was tested for extraction of acephate, chlorpropham, pirimicarb, bifenthrin, tetradifon, and phosalone from the medicinal plant Cordia salicifolia, whose extracts are commercialized in Brazil as diuretic, appetite suppressant, and weight loss products, using GC/MS, SIM. Considering that there are no Brazilian regulations concerning maximum permissible pesticide residue concentrations in medicinal herbs, recovery experiments were carried out (seven replicates), at two arbitrary fortification levels (0.5 and 1.0 mg/kg), resulting in recoveries in range of 20 to 107.7% and SDRSDs were between 5.6 and 29.1% for infinity[Gd(DPA)(HDPA)] sorbent. Detection and quantification limits for herb ranged from 0.10 to 0.15 mg/kg and from 0.15 to 0.25 mg/kg, respectively, for the different pesticides studied. The developed method is linear over the range assayed, 0.5-10.0 microg/mL, with correlation coefficients ranging from 0.9975 to 0.9986 for all pesticides. Comparison between infinity[Gd(DPA)(HDPA)] sorbent and conventional sorbent (neutral alumina) showed similar performance of infinity[Gd(DPA)(HDPA)] polymeric sorbent for three (bifenthrin, tetradifon, and phosalone) out of six pesticides tested.

  6. Mixed Cu(i)/Au(i) coordination polymers as reversible turn-on vapoluminescent sensors for volatile thioethers.

    Science.gov (United States)

    Varju, Bryton R; Ovens, Jeffrey S; Leznoff, Daniel B

    2017-06-13

    Vapour-phase thioethers play an important role in a wide number of fields, including plant biology, chemical weapon disposal, and brewing but few sensor materials are known. The emissive coordination polymer Cu 1/2 Au 1/2 CN does not react with vapour phase dimethyl sulphide (DMS) or diethyl sulphide (DES) despite the independent synthesis of emissive [Cu 1/2 Au 1/2 CN] 2 (DMS) and [Cu 1/2 Au 1/2 CN] 2 (DES) from their constituent components in solution. However, the doped Cu 2/3 Au 1/3 CN rapidly reacts in the solid state with both of these vapour phase thioethers reversibly, with a change in emission from 380/560 nm to 460 nm (DMS) or 420 nm (DES), illustrating that doping the inactive parent Cu 1/2 Au 1/2 CN with Cu(i) generates an active sensor material. This response can be thermally cycled with little to no loss in functionality. [Cu 1/2 Au 1/2 CN] 2 (DMS), [Cu 2/3 Au 1/3 CN] 2 (DMS), and [Cu 2/3 Au 1/3 CN] 2 (DES) were structurally characterized as 3-D network structures supported by aurophilic interactions.

  7. Three coordination compounds based on benzene tetracarboxylate ...

    Indian Academy of Sciences (India)

    YUNLONG WU

    nescence, considerable attention has been focused on the construction of coordination .... measurements were performed on ground powder samples at .... Figure 2. (a) Coordination environment of Co1 ion in compound 2. (b) Coordination.

  8. Correlation of Disorder and Charge Transport in a Range of Indacenodithiophene-Based Semiconducting Polymers

    KAUST Repository

    Nikolka, Mark

    2017-12-13

    Over the past 25 years, various design motifs have emerged for the development of organic semiconductors for demanding applications in flexible organic light emitting diode display backplanes or even printed organic logic. Due to their large area uniformity paired with high charge carrier mobilities, conjugated polymers have attracted increasing attention in this respect. However, the performances delivered by current generation conjugated polymers still fall short of many industrial requirements demanding devices with ideal transistor characteristics and higher mobilities. The discovery of conjugated polymers with low energetic disorder, such as the indacenodithiophene-based polymer indacenodithiophene-co-benzothiadiazole, represent an exciting opportunity to breach this chasm if these materials can be further optimized while maintaining their low disorder. Here, it is shown how both the charge transport properties as well as the energetic disorder are affected by tuning the molecular structure of a large range of indacenodithiophene-based semiconducting polymer derivatives. This study allows to understand better the interplay between molecular design and structure of the polymer backbone and the degree of energetic disorder that governs the charge transport properties in thin polymer films.

  9. Surface decontamination studies using polyvinyl acetate based strippable polymer

    International Nuclear Information System (INIS)

    Rao, S.V.S.; Lal, K.B.

    2004-01-01

    Polyvinyl acetate based strippable polymer has been developed for surface decontamination. Stainless steel, mild steel, polyvinyl chloride and rubber have been selected as candidate materials for the radioactive decontamination studies. The ease of strippability and homogeneity of the polymer coating has been studied using infrared spectrophotometer. Decontamination of used radioactive respirator has been carried out and the peels obtained have been subjected to leaching and incineration studies. The infrared spectrophotometric studies also have been conducted to study the interaction between polyvinyl acetate and ions, like cesium, strontium and cobalt. (author)

  10. Thermally activated 3D to 2D structural transformation of [Ni{sub 2}(en){sub 2}(H{sub 2}O){sub 6}(pyr)]·4H{sub 2}O flexible coordination polymer

    Energy Technology Data Exchange (ETDEWEB)

    Begović, Nebojša N. [Faculty of Physical Chemistry, University of Belgrade (Serbia); Institute of General and Physical Chemistry, Belgrade (Serbia); Blagojević, Vladimir A. [Faculty of Physical Chemistry, University of Belgrade (Serbia); Ostojić, Sanja B.; Radulović, Aleksandra M. [Institute of General and Physical Chemistry, Belgrade (Serbia); Poleti, Dejan [Faculty of Technology and Metallurgy, University of Belgrade (Serbia); Minić, Dragica M., E-mail: dminic@ffh.bg.ac.rs [Faculty of Physical Chemistry, University of Belgrade (Serbia); Department of Biomedical Sciences, State University of Novi Pazar (Serbia)

    2015-01-15

    Thermally activated 3D to 2D structural transformation of the binuclear [Ni{sub 2}(en){sub 2}(H{sub 2}O){sub 6}(pyr)]·4H{sub 2}O complex was investigated using a combination of theoretical and experimental methods. Step-wise thermal degradation (dehydration followed by release of ethylene diamine) results in two layered flexible coordination polymer structures. Dehydration process around 365 K results in a conjugated 2D structure with weak interlayer connectivity. It was shown to be a reversible 3D to 2D framework transformation by a guest molecule, and rehydration of the dehydration product occurs at room temperature in saturated water vapor. Rehydrated complex exhibits lower dehydration temperature, due to decreased average crystalline size, with higher surface area resulting in easier release and diffusion of water during dehydration. Thermal degradation of dehydration around 570 K, results in loss of ethylene diamine, producing a related 2D layered polymer structure, without interconnectivity between individual polymer layers. - Highlights: • Reversible 3D to 2D framework topochemical transformation on dehydration around 365 K. • Resulting polymer exhibits 2D layered structure with weak interlayer connectivity. • Dehydration is fully reversible in saturated water vapor at room temperature. • Further degradation around 570 K yields 2D polymer without interlayer connectivity. • 2D polymer exhibits conjugated electronic system.

  11. 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.

  12. Current state and future prospect on polyacrylic scid based superabsorbent polymer. Polyacrylic sankei kokyusuisei polymer no genjo to kongo no tenkai

    Energy Technology Data Exchange (ETDEWEB)

    Shimomura, T.; Kobayashi, H. (Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka (Japan))

    1991-10-01

    A polymer that absorbs water vigorously and swells is called a superabsorbent polymer (SAP). This peculiar character has developed diverse applications including paper diapers, and its production showed a rapid growth to more than 200,000 tons (worldwide) in the past decade. This paper introduces the development and applications for polyacrylic acid-based SAP, a representative SAP. The research began in the U.S.A. in about the year 1976. For its characteristics suitable for paper diapers and cost advantages, the acrylate-based SAP has become accounting for the most at the present. The polymer is manufactured by polymerzation crosslinking of acrylic acid or sodium acrylate to produce polyacrylate crosslinked bodies. The polymer swells to 100 to 1000 times in deionized water, and turns into a hydrogel. Unlike a sponge, the swelled gel will not ooze out water even if pressed. However, its absorption performance decreases extremely in electrolytic aqueous solution, which is a problem for the future development. 17 refs., 5 figs., 7 tabs.

  13. Graphene-based polymer nanocomposites in electronics

    CERN Document Server

    Sadasivuni, Kishor Kumar; Kim, Jaehwan

    2015-01-01

    This book covers graphene reinforced polymers, which are useful in electronic applications, including electrically conductive thermoplastics composites, thermosets and elastomers. It systematically introduces the reader to fundamental aspects and leads over to actual applications, such as sensor fabrication, electromagnetic interference shielding, optoelectronics, superconductivity, or memory chips. The book also describes dielectric and thermal behaviour of graphene polymer composites - properties which are essential to consider for the fabrication and production of these new electronic materials. The contributions in this book critically discuss the actual questions in the development and applications of graphene polymer composites. It will thus appeal to chemists, physicists, materials scientists as well as nano technologists, who are interested in the properties of graphene polymer composites.

  14. Highly sensitive polymer-based cantilever-sensors for DNA detection

    International Nuclear Information System (INIS)

    Calleja, M.; Nordstroem, M.; Alvarez, M.; Tamayo, J.; Lechuga, L.M.; Boisen, A.

    2005-01-01

    We present a technology for the fabrication of cantilever arrays aimed to develop an integrated biosensor microsystem. The fabrication process is based on spin coating of the photosensitive polymer and near-ultraviolet exposure. Arrays of up to 33 microcantilevers are fabricated in the novel polymer material SU-8. The low Young's modulus of the polymer, 40 times lower than that of silicon, enables to improve the sensitivity of the sensor device for target detection. The mechanical properties of SU-8 cantilevers, such as spring constant, resonant frequency and quality factor are characterized as a function of the dimensions and the medium. The devices have been tested for measurement of the adsorption of single stranded DNA and subsequent interstitial adsorption of lateral spacer molecules. We demonstrate that sensitivity is enhanced by a factor of six compared to that of commercial silicon nitride cantilevers

  15. High-photovoltage all-polymer solar cells based on a diketopyrrolopyrrole-isoindigo acceptor polymer

    NARCIS (Netherlands)

    Li, Z.; Xu, X.; Zhang, W.; Genene, Z.; Mammo, W.; Yartsev, A.; Andersson, M.R.; Janssen, R.A.J.; Wang, E.

    2017-01-01

    In this work, we synthesized and characterized two new n-type polymers PTDPP-PyDPP and PIID-PyDPP. The former polymer is composed of pyridine-flanked diketopyrrolopyrrole (PyDPP) and thiophene-flanked diketopyrrolopyrrole (TDPP). The latter polymer consists of PyDPP and isoindigo (IID). PIID-PyDPP

  16. Machine learning-based screening of complex molecules for polymer solar cells

    Science.gov (United States)

    Jørgensen, Peter Bjørn; Mesta, Murat; Shil, Suranjan; García Lastra, Juan Maria; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer; Schmidt, Mikkel N.

    2018-06-01

    Polymer solar cells admit numerous potential advantages including low energy payback time and scalable high-speed manufacturing, but the power conversion efficiency is currently lower than for their inorganic counterparts. In a Phenyl-C_61-Butyric-Acid-Methyl-Ester (PCBM)-based blended polymer solar cell, the optical gap of the polymer and the energetic alignment of the lowest unoccupied molecular orbital (LUMO) of the polymer and the PCBM are crucial for the device efficiency. Searching for new and better materials for polymer solar cells is a computationally costly affair using density functional theory (DFT) calculations. In this work, we propose a screening procedure using a simple string representation for a promising class of donor-acceptor polymers in conjunction with a grammar variational autoencoder. The model is trained on a dataset of 3989 monomers obtained from DFT calculations and is able to predict LUMO and the lowest optical transition energy for unseen molecules with mean absolute errors of 43 and 74 meV, respectively, without knowledge of the atomic positions. We demonstrate the merit of the model for generating new molecules with the desired LUMO and optical gap energies which increases the chance of finding suitable polymers by more than a factor of five in comparison to the randomised search used in gathering the training set.

  17. Process modeling of conductivity in nanocomposites based on reticulated polymers and carbon nanotubes

    International Nuclear Information System (INIS)

    Dolgoshej, V.B.; Korskanov, V.V.; Karpova, I.L.; Bardash, L.V.

    2012-01-01

    The dependences of electric conductivities of thermosetting polymer nanocomposites based on epoxy polymer and polycyanurate filled by carbon nanotubes were investigated. Low values of percolation threshold at volume fraction of carbon nanotubes from 0.001 to 0.002 were observed for all samples.Absolute values of the percolation threshold are in good agreement with the results of mathematical modeling. It is established that electrical properties of thermosetting polymer nanocomposites can be characterized in the frame of the same theoretical model despite difference in polymers properties

  18. based anion exchange membrane for alkaline polymer electrolyte

    Indian Academy of Sciences (India)

    Administrator

    Abstract. Hydroxyl ion (OH–) conducting anion exchange membranes based on modified poly (phenylene oxide) are fabricated for their application in alkaline polymer electrolyte fuel cells (APEFCs). In the present study, chloromethylation of poly(phenylene oxide) (PPO) is performed by aryl substitution rather than benzyl.

  19. A Multi-agent Supply Chain Information Coordination Mode Based on Cloud Computing

    OpenAIRE

    Wuxue Jiang; Jing Zhang; Junhuai Li

    2013-01-01

     In order to improve the high efficiency and security of supply chain information coordination under cloud computing environment, this paper proposes a supply chain information coordination mode based on cloud computing. This mode has two basic statuses which are online status and offline status. At the online status, cloud computing center is responsible for coordinating the whole supply chain information. At the offline status, information exchange can be realized among different nodes by u...

  20. Effect of the polymer emission on the electroluminescence characteristics of n-ZnO nanorods/p-polymer hybrid light emitting diode

    Science.gov (United States)

    Zaman, S.; Zainelabdin, A.; Amin, G.; Nur, O.; Willander, M.

    2011-09-01

    Hybrid light emitting diodes (LEDs) based on zinc oxide (ZnO) nanorods and polymers (single and blended) were fabricated and characterized. The ZnO nanorods were grown by the chemical bath deposition method at 50°C. Three different LEDs, with blue emitting, orange-red emitting or their blended polymer together with ZnO nanorods, were fabricated and studied. The current-voltage characteristics show good diode behavior with an ideality factor in the range of 2.1 to 2.27 for all three devices. The electroluminescence spectrum (EL) of the blended device has an emission range from 450 nm to 750 nm, due to the intermixing of the blue emission generated by poly(9,9-dioctylfluorene) denoted as PFO with orange-red emission produced by poly(2-methoxy-5(20-ethyl-hexyloxy)-1,4-phenylenevinylene) 1,4-phenylenevinylene) symbolized as MEH PPV combined with the deep-band emission (DBE) of the ZnO nanorods, i.e. it covers the whole visible region and is manifested as white light. The CIE color coordinates showed bluish, orange-red and white emission from the PFO, MEH PPV and blended LEDs with ZnO nanorods, respectively. These results indicate that the choice of the polymer with proper concentration is critical to the emitted color in ZnO nanorods/p-organic polymer LEDs and careful design should be considered to obtain intrinsic white light sources.

  1. Thermally rearranged (TR) bismaleimide-based network polymers for gas separation membranes.

    Science.gov (United States)

    Do, Yu Seong; Lee, Won Hee; Seong, Jong Geun; Kim, Ju Sung; Wang, Ho Hyun; Doherty, Cara M; Hill, Anita J; Lee, Young Moo

    2016-11-15

    Highly permeable, thermally rearranged polymer membranes based on bismaleimide derivatives that exhibit excellent CO 2 permeability up to 5440 Barrer with a high BET surface area (1130 m 2 g -1 ) are reported for the first time. In addition, the membranes can be easily used to form semi-interpenetrating networks with other polymers endowing them with superior gas transport properties.

  2. Polymer solar cells with novel fullerene-based acceptor

    International Nuclear Information System (INIS)

    Riedel, I.; Martin, N.; Giacalone, F.; Segura, J.L.; Chirvase, D.; Parisi, J.; Dyakonov, V.

    2004-01-01

    Alternative acceptor materials are possible candidates to improve the optical absorption and/or the open circuit voltage of polymer-fullerene solar cells. We studied a novel fullerene-type acceptor, DPM-12, for application in polymer-fullerene bulk heterojunction photovoltaic devices. Though DPM-12 has the identical redox potentials as methanofullerene PCBM, surprisingly high open circuit voltages in the range V OC =0.95 V were measured for OC 1 C 10 -PPV:DPM-12-based samples. The potential for photovoltaic application was studied by means of photovoltaic characterization of solar cells including current-voltage measurements and external quantum yield spectroscopy. Further studies were carried out by profiling the solar cell parameters vs. temperature and white light intensity

  3. Polymer based drug delivery systems for mycobacterial infections.

    Science.gov (United States)

    Pandey, Rajesh; Khuller, G K

    2004-07-01

    In the last decade, polymer based technologies have found wide biomedical applications. Polymers, whether synthetic (e.g. polylactide-co-glycolide or PLG) or natural (e.g. alginate, chitosan etc.), have the property of encapsulating a diverse range of molecules of biological interest and bear distinct therapeutic advantages such as controlled release of drugs, protection against the premature degradation of drugs and reduction in drug toxicity. These are important considerations in the long-duration treatment of chronic infectious diseases such as tuberculosis in which patient non-compliance is the major obstacle to successful chemotherapy. Antitubercular drugs, singly or in combination, have been encapsulated in polymers to provide controlled drug release and the system also offers the flexibility of selecting various routes of administration such as oral, subcutaneous and aerosol. The present review highlights the approaches towards the preparation of polymeric antitubercular drug delivery systems, emphasizing how the route of administration may influence drug bioavailability as well as the chemotherapeutic efficacy. In addition, the pros and cons of the various delivery systems are also discussed.

  4. Multiagent System-Based Distributed Coordinated Control for Radial DC Microgrid Considering Transmission Time Delays

    DEFF Research Database (Denmark)

    Dou, Chun-Xia; Yue, Dong; Guerrero, Josep M.

    2017-01-01

    This paper focuses on a multi-agent based distributed coordinated control for radial DC microgrid considering trans-mission time delays. Firstly, a two-level multi-agent system is constructed, where local control is formulated based on local states and executed by means of the first-level agent......, and dis-tributed coordinated control law is formulated based on wide-area information and executed by means of the secondary- level agent in order to improve the voltage control performances. Afterwards, the research mainly focuses on designing the local controller and the distributed coordinated...

  5. Efficient Naphthalenediimide-Based Hole Semiconducting Polymer with Vinylene Linkers between Donor and Acceptor Units

    KAUST Repository

    Zhang, Lei

    2016-11-04

    We demonstrate a new method to reverse the polarity and charge transport behavior of naphthalenediimide (NDI)-based copolymers by inserting a vinylene linker between the donor and acceptor units. The vinylene linkers minimize the intrinsic steric congestion between the NDI and thiophene moieties to prompt backbone planarity. The polymers with vinylene linkers exhibit electron n-channel transport characteristics under vacuum, similar to the benchmark polymer, P(NDI2OD-T2). To our surprise, when the polymers are measured in air, the dominant carrier type switches from n- to p-type and yield hole mobilities up to 0.45 cm(2) s(-1) with hole to electron mobility ratio of three (mu(h)/mu(e), similar to 3), which indicates that the hole density in the active layer can be significantly increased by exposure to air. This increase is consistent with the intrinsic more delocalized nature of the highest occupied molecular orbital of the charged vinylene polymer, as estimated by density functional theory (DFT) calculations, which facilitates hole transport within the polymer chains. This is the first demonstration of an efficient NDI-based hole semiconducting polymer, which will enable new developments in all-polymer solar cells, complementary circuits, and dopable polymers for use in thermoelectrics.

  6. Efficient Naphthalenediimide-Based Hole Semiconducting Polymer with Vinylene Linkers between Donor and Acceptor Units

    KAUST Repository

    Zhang, Lei; Rose, Bradley Daniel; Liu, Yao; Nahid, Masrur M.; Gann, Eliot; Ly, Jack; Zhao, Wei; Rosa, Stephen J.; Russell, Thomas P.; Facchetti, Antonio; McNei, Christopher R.; Bredas, Jean-Luc; Briseno, Alejandro L.

    2016-01-01

    We demonstrate a new method to reverse the polarity and charge transport behavior of naphthalenediimide (NDI)-based copolymers by inserting a vinylene linker between the donor and acceptor units. The vinylene linkers minimize the intrinsic steric congestion between the NDI and thiophene moieties to prompt backbone planarity. The polymers with vinylene linkers exhibit electron n-channel transport characteristics under vacuum, similar to the benchmark polymer, P(NDI2OD-T2). To our surprise, when the polymers are measured in air, the dominant carrier type switches from n- to p-type and yield hole mobilities up to 0.45 cm(2) s(-1) with hole to electron mobility ratio of three (mu(h)/mu(e), similar to 3), which indicates that the hole density in the active layer can be significantly increased by exposure to air. This increase is consistent with the intrinsic more delocalized nature of the highest occupied molecular orbital of the charged vinylene polymer, as estimated by density functional theory (DFT) calculations, which facilitates hole transport within the polymer chains. This is the first demonstration of an efficient NDI-based hole semiconducting polymer, which will enable new developments in all-polymer solar cells, complementary circuits, and dopable polymers for use in thermoelectrics.

  7. Conducting polymer nanocomposite-based supercapacitors

    OpenAIRE

    Liew, Soon Yee; Walsh, Darren A.; Chen, George Z.

    2016-01-01

    The use of nanocomposites of electronically-conducting polymers for supercapacitors has increased significantly over the past years, due to their high capacitances and abilities to withstand many charge-discharge cycles. We have recently been investigating the use of nanocomposites of electronically-conducting polymers containing conducting and non-conducting nanomaterials such as carbon nanotubes and cellulose nanocrystals, for use in supercapacitors. In this contribution, we provide a summa...

  8. Poisson Coordinates.

    Science.gov (United States)

    Li, Xian-Ying; Hu, Shi-Min

    2013-02-01

    Harmonic functions are the critical points of a Dirichlet energy functional, the linear projections of conformal maps. They play an important role in computer graphics, particularly for gradient-domain image processing and shape-preserving geometric computation. We propose Poisson coordinates, a novel transfinite interpolation scheme based on the Poisson integral formula, as a rapid way to estimate a harmonic function on a certain domain with desired boundary values. Poisson coordinates are an extension of the Mean Value coordinates (MVCs) which inherit their linear precision, smoothness, and kernel positivity. We give explicit formulas for Poisson coordinates in both continuous and 2D discrete forms. Superior to MVCs, Poisson coordinates are proved to be pseudoharmonic (i.e., they reproduce harmonic functions on n-dimensional balls). Our experimental results show that Poisson coordinates have lower Dirichlet energies than MVCs on a number of typical 2D domains (particularly convex domains). As well as presenting a formula, our approach provides useful insights for further studies on coordinates-based interpolation and fast estimation of harmonic functions.

  9. Photoluminescent Copper(I) Complex Based on 3-(2-(Cyclohexylthio) ethoxy)pyridine: Synthesis, Structure, and Physical Properties

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyunjin; Kwon, Eunjin; Kang, Gihaeng; Kim, Jieun; Kim, Tae Ho [Gyeongsang National University, Jinju (Korea, Republic of)

    2016-07-15

    In recent years, the Cu(I) complexes, with d 10 electronic configuration, have been attracting interest due to their diverse structures and photophysical properties. A copper(I) coordination polymer 1 based on a sulfur-containing pyridyl ligand L was synthesized and identified by X-ray crystallography. Photophysical and thermal properties of 1 have been investigated. More Cu(I) coordination polymers based on mixed donor ligands are under investigation in order to discover factors governing luminescence wavelength, such as Cu[BOND]Cu distances, intermolecular interactions, structures of ligands, and so on.

  10. Naphthalene Diimide Based n-Type Conjugated Polymers as Efficient Cathode Interfacial Materials for Polymer and Perovskite Solar Cells.

    Science.gov (United States)

    Jia, Tao; Sun, Chen; Xu, Rongguo; Chen, Zhiming; Yin, Qingwu; Jin, Yaocheng; Yip, Hin-Lap; Huang, Fei; Cao, Yong

    2017-10-18

    A series of naphthalene diimide (NDI) based n-type conjugated polymers with amino-functionalized side groups and backbones were synthesized and used as cathode interlayers (CILs) in polymer and perovskite solar cells. Because of controllable amine side groups, all the resulting polymers exhibited distinct electronic properties such as oxidation potential of side chains, charge carrier mobilities, self-doping behaviors, and interfacial dipoles. The influences of the chemical variation of amine groups on the cathode interfacial effects were further investigated in both polymer and perovskite solar cells. We found that the decreased electron-donating property and enhanced steric hindrance of amine side groups substantially weaken the capacities of altering the work function of the cathode and trap passivation of the perovskite film, which induced ineffective interfacial modifications and declining device performance. Moreover, with further improvement of the backbone design through the incorporation of a rigid acetylene spacer, the resulting polymers substantially exhibited an enhanced electron-transporting property. Upon use as CILs, high power conversion efficiencies (PCEs) of 10.1% and 15.2% were, respectively, achieved in polymer and perovskite solar cells. Importantly, these newly developed n-type polymers were allowed to be processed over a broad thickness range of CILs in photovoltaic devices, and a prominent PCE of over 8% for polymer solar cells and 13.5% for perovskite solar cells can be achieved with the thick interlayers over 100 nm, which is beneficial for roll-to-roll coating processes. Our findings contribute toward a better understanding of the structure-performance relationship between CIL material design and solar cell performance, and provide important insights and guidelines for the design of high-performance n-type CIL materials for organic and perovskite optoelectronic devices.

  11. Application of polyacrylonitrile-based polymer electrolytes in rechargeable lithium batteries

    DEFF Research Database (Denmark)

    Perera, K.S.; Dissanayake, M.A.K.L.; Skaarup, Steen

    2008-01-01

    Polyacrylonitrile (PAN)-based polymer electrolytes have obtained considerable attention due to their fascinating characteristics such as appreciable ionic conductivity at ambient temperatures and mechanical stability. This study is based on the system PAN-ethylene carbonate (EC)-propylene carbona...

  12. Photochemical stability and photovoltaic performance of low-band gap polymers based on dithiophene with different bridging atoms

    DEFF Research Database (Denmark)

    Helgesen, Martin; Sørensen, Thomas J.; Manceau, Matthieu

    2011-01-01

    New low-band gap polymers based on dithienylbenzothiadiazole (DBT) and dithiophene with different bridging atoms have been synthesized and explored in a comparative study on the photochemical stability and photovoltaic performance. Two differently modified DBT units were exploited, namely 5,6- bis......(tetradecyloxy)-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DBT1) and 4,7-bis(4-dodecylthiophen-2-yl)benzo[c][1,2,5]thiadiazole (DBT2). In thin films the polymers had optical band gaps in the range of 1.51-1.70 eV where the DBT2 based polymers are red shifted 61-81 nm compared to the DBT1 based polymers...... indicating greater interchain packing when the side chains are situated on the thienyl groups compared to on the benzothiadiazole unit. The best photovoltaic devices based on blends of polymer and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) were prepared with polymers based on the DBT1 unit giving...

  13. Agent-Based Coordination Model for Designing Transportation Applications

    OpenAIRE

    BADEIG, F; BALBO, F; SCEMAMA, G; ZARGAYOUNA, M

    2008-01-01

    This paper presents an environment-centered approach to design multi-agent solutions to transportation problems. Based on the Property-based Coordination Principle (PbC), the objective of our approach is to solve three recurrent issues in the design of these solutions: the knowledge problem, the space-time dimension and the dynamics of the real environment. To demonstrate the benefits of our approach, two completely different applications, a demand-responsive transportation system and a simul...

  14. 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.

  15. Performance enhancement of quantum dot-sensitized solar cells based on polymer nano-composite catalyst

    International Nuclear Information System (INIS)

    Seo, Hyunwoong; Gopi, Chandu V.V.M.; Kim, Hee-Je; Itagaki, Naho; Koga, Kazunori; Shiratani, Masaharu

    2017-01-01

    Highlights: •We studied polymer nano-composite containing TiO 2 nano-particles as a catalyst. •Polymer nano-composite was applied for quantum dot-sensitized solar cells. •Polymer nano-composite catalyst was considerably improved with TiO 2 nano-particles. •Polymer nano-composite showed higher photovoltaic performance than conventional Au. -- Abstract: Polymer nano-composite composed of poly(3,4-ethylenedioxythiophene):poly (styrenesulfonate) and TiO 2 nano-particles was deposited on fluorine-doped tin oxide substrate and applied as an alternative to Au counter electrode of quantum dot-sensitized solar cell (QDSC). It became surface-richer with the increase in nano-particle amount so that catalytic reaction was increased by widened catalytic interface. Electrochemical impedance spectroscopy and cyclic voltammetry clearly demonstrated the enhancement of polymer nano-composite counter electrode. A QDSC based on polymer nano-composite counter electrode showed 0.56 V of V OC , 12.24 mA cm −2 of J SC , 0.57 of FF, and 3.87% of efficiency and this photovoltaic performance was higher than that of QDSC based on Au counter electrode (3.75%).

  16. Synthesis of [Fe(Leq(Lax]n coordination polymer nanoparticles using blockcopolymer micelles

    Directory of Open Access Journals (Sweden)

    Christoph Göbel

    2017-06-01

    Full Text Available Spin-crossover compounds are a class of materials that can change their spin state from high spin (HS to low spin (LS by external stimuli such as light, pressure or temperature. Applications demand compounds with defined properties concerning the size and switchability that are maintained when the compound is integrated into composite materials. Here, we report the synthesis of [Fe(Leq(Lax]n coordination polymer (CP nanoparticles using self-assembled polystyrene-block-poly(4-vinylpyridine (PS-b-P4VP block copolymer (BCP micelles as template. Variation of the solvent (THF and toluene and the rigidity of the axial ligand Lax (Lax = 1,2-di(pyridin-4-ylethane (bpea, trans-1,2-di(pyridin-4-ylethene (bpee, and 1,2-di(pyridin-4-ylethyne (bpey; Leq = 1,2-phenylenebis(iminomethylidyne-bis(2,4-pentanedionato(2− allowed the determination of the preconditions for the selective formation of nanoparticles. A low solubility of the CP in the used solvent and a high stability of the Fe–L bond with regard to ligand exchange are necessary for the formation of composite nanoparticles where the BCP micelle is filled with the CP, as in the case of the [FeLeq(bpey]n@BCP. Otherwise, in the case of more flexible ligands or ligands that lead to high spin complexes, the formation of microcrystals next to the CP–BCP nanoparticles is observed above a certain concentration of [Fe(Leq(Lax]n. The core of the nanoparticles is about 45 nm in diameter due to the templating effect of the BCP micelle, independent of the used iron complex and [Fe(Leq(Lax]n concentration. The spin-crossover properties of the composite material are similar to those of the bulk for FeLeq(bpea]n@BCP while pronounced differences are observed in the case of [FeLeq(bpey]n@BCP nanoparticles.

  17. New polymer lithium secondary batteries based on ORMOCER (R) electrolytes-inorganic-organic polymers

    DEFF Research Database (Denmark)

    Popall, M.; Buestrich, R.; Semrau, G.

    2001-01-01

    Based on new plasticized inorganic-organic polymer electrolytes CM. Popall, M. Andrei, J. Kappel, J. Kron, K. Olma, B. Olsowski,'ORMOCERs as Inorganic-organic Electrolytes for New Solid State Lithium Batteries and Supercapacitors', Electrochim. Acta 43 (1998) 1155] new flexible foil-batteries...... electrolyte, typical for polymer electrolytes. Cycling tests (more than 900 cycles) proved that the unplasticized electrolyte can act as binder in composite cathodes of lithium secondary batteries [2]. Charge/discharge cycles of complete batteries like (Cu/active carbon/ORMOCER(R)/LiCoO2/Al) with an ORMOCER......(R) as separator electrolyte were measured. The voltage drop of these batteries is very similar to cells with standard liquid electrolytes and the efficiency is close to 100%. Cycling the batteries with a current density of 0.25 mA cm(-2) between the voltage limits of 3.1 and 4.1 V results in a charge...

  18. Highly sensitive polymer-based cantilever-sensors for DNA detection

    Energy Technology Data Exchange (ETDEWEB)

    Calleja, M. [Biosensors Group, Nacional Center of Microelectronics (CNM-CSIC), Isaac Newton 8, Tres Cantos, E-28760 Madrid (Spain) and Mikroelektronics Centret, Technical University of Denmark, 345E, DK-2800, Lyngby (Denmark)]. E-mail: mcalleja@imm.cnm.csic.es; Nordstroem, M. [Mikroelektronics Centret, Technical University of Denmark, 345E, DK-2800, Lyngby (Denmark); Alvarez, M. [Biosensors Group, Nacional Center of Microelectronics (CNM-CSIC), Isaac Newton 8, Tres Cantos, E-28760 Madrid (Spain); Tamayo, J. [Biosensors Group, Nacional Center of Microelectronics (CNM-CSIC), Isaac Newton 8, Tres Cantos, E-28760 Madrid (Spain); Lechuga, L.M. [Biosensors Group, Nacional Center of Microelectronics (CNM-CSIC), Isaac Newton 8, Tres Cantos, E-28760 Madrid (Spain); Boisen, A. [Mikroelektronics Centret, Technical University of Denmark, 345E, DK-2800, Lyngby (Denmark)

    2005-11-15

    We present a technology for the fabrication of cantilever arrays aimed to develop an integrated biosensor microsystem. The fabrication process is based on spin coating of the photosensitive polymer and near-ultraviolet exposure. Arrays of up to 33 microcantilevers are fabricated in the novel polymer material SU-8. The low Young's modulus of the polymer, 40 times lower than that of silicon, enables to improve the sensitivity of the sensor device for target detection. The mechanical properties of SU-8 cantilevers, such as spring constant, resonant frequency and quality factor are characterized as a function of the dimensions and the medium. The devices have been tested for measurement of the adsorption of single stranded DNA and subsequent interstitial adsorption of lateral spacer molecules. We demonstrate that sensitivity is enhanced by a factor of six compared to that of commercial silicon nitride cantilevers.

  19. A one-dimensional ladder-like coordination polymer: poly[[hexa­aqua­bis(μ-5-nitro­benzene-1,3-dicarboxyl­ato-κ3 O,O′,O′′)(μ-oxalato-κ4 O,O′:O′′,O′′′)diyttrium(III)] trihydrate

    OpenAIRE

    Fu, Zhong; Lin, Ying; Zhou, Yun-You; Zhang, Hong-Tao

    2007-01-01

    In the crystal structure of the title one-dimensional coordination polymer, [Y2(C8H3NO6)2(C2O4)(H2O)6]·3H2O, each YIII ion is bridged to its neighbours by two 5-nitrobenzene-1,3-dicarboxylate (nbdc) dianions and one oxalate dianion (located on an inversion centre) to form a ladder-like polymeric structure. The two carboxylate groups of nbdc assume different modes of coordination, one is chelating whereas the other is monodentate. Three water molecules coordinate to the YIII ion to comple...

  20. 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