Sample records for one-dimensional coordination polymers

  1. Two-dimensional Zn(II) and one-dimensional Co(II) coordination polymers based on benzene-1,4-dicarboxylate and pyridine ligands.

    PubMed

    Zhou, Li-Juan; Han, Chang-Bao; Wang, Yu-Ling

    2016-02-01

    Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene-1,4-dicarboxylic acid (H2BDC) and pyridine (py) with Zn(II) or Co(II) yielded two new coordination polymers, namely, poly[(μ4-benzene-1,4-dicarboxylato-κ(4)O:O':O'':O''')(pyridine-κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena-poly[aqua(μ3-benzene-1,4-dicarboxylato-κ(3)O:O':O'')bis(pyridine-κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the Zn(II) cation is five-coordinated by four carboxylate O atoms from four BDC(2-) ligands and one pyridine N atom in a distorted square-pyramidal coordination geometry. Four carboxylate groups bridge two Zn(II) ions to form centrosymmetric paddle-wheel-like Zn2(μ2-COO)4 units, which are linked by the benzene rings of the BDC(2-) ligands to generate a two-dimensional layered structure. The two-dimensional layer is extended into a three-dimensional supramolecular structure with the help of π-π stacking interactions between the aromatic rings. Compound (II) has a one-dimensional double-chain structure based on Co2(μ2-COO)2 units. The Co(II) cations are bridged by BDC(2-) ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC(2-) ligands, one water O atom and two pyridine N atoms. Interchain O-H...O hydrogen-bonding interactions link these chains to form a three-dimensional supramolecular architecture.

  2. One-dimensional Cu(II) coordination polymers containing C2h-symmetric 1,1':4',1''-terphenyl-3,3'-dicarboxylate linkers.

    PubMed

    Kim, Hyun Chul; Gu, Ja Min; Huh, Seong; Yo, Chul Hyun; Kim, Youngmee

    2015-10-01

    Two new one-dimensional Cu(II) coordination polymers (CPs) containing the C2h-symmetric terphenyl-based dicarboxylate linker 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC), namely catena-poly[[bis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(4)O,O':O'':O'''] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), and catena-poly[[aquabis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(2)O(3):O(3')] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3'-TPDC bridging ligands coordinate the Cu(II) ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).

  3. A one-dimensional zinc(II) coordination polymer with a three-dimensional supramolecular architecture incorporating 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole and adipate.

    PubMed

    Liu, Chun Li; Huang, Qiu Ying; Meng, Xiang Ru

    2016-12-01

    The synthesis of coordination polymers or metal-organic frameworks (MOFs) has attracted considerable interest owing to the interesting structures and potential applications of these compounds. It is still a challenge to predict the exact structures and compositions of the final products. A new one-dimensional coordination polymer, catena-poly[[[bis{1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κN 3 }zinc(II)]-μ-hexane-1,6-dicarboxylato-κ 4 O 1 ,O 1' :O 6 ,O 6' ] monohydrate], {[Zn(C 6 H 8 O 4 )(C 9 H 8 N 6 ) 2 ]·H 2 O} n , has been synthesized by the reaction of Zn(Ac) 2 (Ac is acetate) with 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) and adipic acid (H 2 adi) at room temperature. In the polymer, each Zn II ion exhibits an irregular octahedral ZnN 2 O 4 coordination geometry and is coordinated by two N atoms from two symmetry-related bimt ligands and four O atoms from two symmetry-related dianionic adipate ligands. Zn II ions are connected by adipate ligands into a one-dimensional chain which runs parallel to the c axis. The bimt ligands coordinate to the Zn II ions in a monodentate mode on both sides of the main chain. In the crystal, the one-dimensional chains are further connected through N-H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the title polymer exhibits fluorescence, with emissions at 334 and 350 nm in the solid state at room temperature.

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

    PubMed

    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.

  5. A one-dimensional nickel(II) coordination polymer containing 2,6-dipicolinate and dipyrido[3,2-a:2',3'-c]phenazine.

    PubMed

    Ma, Yi; Zhang, Li-Tian; Wang, Xiao-Fang; He, Yong-Ke; Han, Zheng-Bo

    2007-12-01

    A new coordination polymer, catena-poly[[(dipyrido[3,2-a:2',3'-c]phenazine-kappa(2)N,N')nickel(II)]-mu-2,6-dipicolinato-kappa(4)O(2),N,O(6):O(2')], [Ni(C7H3NO4)(C18H10N4)]n, exhibits a one-dimensional structure in which 2,6-dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one Ni(II) center, one dipyrido[3,2-a:2',3'-c]phenazine ligand and one 2,6-dipicolinate ligand. Each Ni(II) center is six-coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2-a:2',3'-c]phenazine ligand and two different 2,6-dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by pi-pi stacking interactions and weak interactions to form a three-dimensional supramolecular network.

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

    PubMed

    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.

  7. One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties

    NASA Astrophysics Data System (ADS)

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Şahin, Onur

    2016-11-01

    Two new one dimensional (1D) cyanide complexes, namely [M(4-aepy)2(H2O)2][Pt(CN)4], (4-aepy = 4-(2-aminoethyl)pyridine M = Cu(II) (1) or Zn(II) (2)), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The crystallographic analyses reveal that 1 and 2 are isomorphous and isostructural, and crystallize in the monoclinic system and C2 space group. The Pt(II) ions are coordinated by four cyanide-carbon atoms in the square-planar geometry and the [Pt(CN)4]2- ions act as a counter ion. The M(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4-aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. The crystal structures of 1 and 2 are similar each other and linked via intermolecular hydrogen bonding, Pt⋯π interactions to form 3D supramolecular network. Vibration assignments of all the observed bands are given and the spectral features also supported to the crystal structures of the complexes.

  8. Coordination chemistry of 6-thioguanine derivatives with cobalt: toward formation of electrical conductive one-dimensional coordination polymers.

    PubMed

    Amo-Ochoa, Pilar; Alexandre, Simone S; Hribesh, Samira; Galindo, Miguel A; Castillo, Oscar; Gómez-García, Carlos J; Pike, Andrew R; Soler, José M; Houlton, Andrew; Zamora, Félix; Harrington, Ross W; Clegg, William

    2013-05-06

    In this work we have synthetized and characterized by X-ray diffraction five cobalt complexes with 6-thioguanine (6-ThioGH), 6-thioguanosine (6-ThioGuoH), or 2'-deoxy-6-thioguanosine (2'-d-6-ThioGuoH) ligands. In all cases, these ligands coordinate to cobalt via N7 and S6 forming a chelate ring. However, independently of reagents ratio, 6-ThioGH provided monodimensional cobalt(II) coordination polymers, in which the 6-ThioG(-) acts as bridging ligand. However, for 2'-d-6-ThioGuoH and 6-ThioGuoH, the structure directing effect of the sugar residue gives rise to mononuclear cobalt complexes which form extensive H-bond interactions to generate 3D supramolecular networks. Furthermore, with 2'-d-6-ThioGuoH the cobalt ion remains in the divalent state, whereas with 6-ThioGuoH oxidation occurs and Co(III) is found. The electrical and magnetic properties of the coordination polymers isolated have been studied and the results discussed with the aid of DFT calculations, in the context of molecular wires.

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

    PubMed

    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.

  10. A new Pb{sup II}(ethylenediaminetetraacetate) coordination polymer with a two-dimensional layer structure

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, D., E-mail: iamzd@hpu.edu.cn; Zhang, R. H.; Li, F. F.

    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.

  11. One- and two-dimensional divalent copper coordination polymers based on kinked organodiimine and long flexible aliphatic dicarboxylate ligands

    NASA Astrophysics Data System (ADS)

    Mallika Krishnan, Subhashree; Supkowski, Ronald M.; LaDuca, Robert L.

    2008-11-01

    Hydrothermal synthesis under acidic conditions has afforded a pair of divalent copper coordination polymers containing the kinked dipodal tethering organodiimine 4,4'-dipyridylamine (dpa) and flexible long-chain aliphatic dicarboxylate ligands. The new materials were characterized by single crystal X-ray structure determination, infrared spectroscopy, and thermogravimetric analysis. [CuCl(suberate) 0.5(dpa)] ( 1) manifests 1-D ladder-like motifs aggregated into 3-D through hydrogen bonding and copper-mediated supramolecular interactions. Extension of the aliphatic chain within the dicarboxylate ligand by one methylene unit resulted in {[Cu(azelate)(dpa)(H 2O)] · 3H 2O} ( 2), a (4,4) rhomboid grid 2-D coordination polymer encapsulating acyclic water molecule trimers.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li

    2013-09-15

    Three new metal-organic coordination polymers [Co(4-bbc){sub 2}(bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H{sub 2}O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H{sub 2}pdc=3,5-pyridinedicarboxylic acid, 1,4-H{sub 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{sup II} ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3{sup 2}·4·5·6{sup 2}·7{sup 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. - graphicalmore » 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.« less

  13. Dimensional modulation and magnetic properties of triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin

    2014-04-01

    Five new metal–organic coordination polymers ([Cu{sub 3}(μ{sub 2}-OH){sub 2}(atrz){sub 2}(nph){sub 2}(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (1), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)]·2H{sub 2}O){sub n} (2), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)(H{sub 2}O)]·H{sub 2}O){sub n} (3), [Cu(dth){sub 0.5}(nph)(H{sub 2}O)]{sub n} (4) and [Cu(dth)(Hnip){sub 2}]{sub n} (5) [atrz=4-amino-1,2,4-triazole, dth=N,N'-di(4H-1,2,4-triazole)hexanamide, H{sub 2}nph=3-nitrophthalic acid, 1,2,4-H{sub 3}btc=1,2,4-benzenetricarboxylic acid and H{sub 2}nip=5-nitroisophthalic acid] were hydrothermally synthesized and structurally characterized. Polymer 1 shows a one-dimensional (1D) chain. Polymers 2 and 3 exhibit similar tetranuclear Cu{sup II}{sub 4} cluster-based three-dimensional (3D) frameworks with the same components. Polymer 4 possesses a 3D framework with a 4{sup 12}·6{sup 3}-pcu topology. Polymer 5 displays a 3D frameworkmore » with a 4{sup 4}·6{sup 10}·8-mab topology. The magnetic properties of 1–4 were investigated. - Graphical abstract: Five triazole-based copper(II) polymers modulated by polycarboxylates were synthesized. Bis-triazole-bis-amide ligand and polycarboxylates play important roles in tuning dimensionality of polymers. Magnetic properties of polymers were investigated. - Highlights: • Five triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates were obtained. • The aromatic polycarboxylates have an important influence on the dimensionality of five polymers. • The magnetic properties of four polymers were investigated.« less

  14. One-dimensional coordination polymers of whole row rare earth tris-pivalates

    NASA Astrophysics Data System (ADS)

    Tsymbarenko, Dmitry; Martynova, Irina; Grebenyuk, Dimitry; Shegolev, Vsevolod; Kuzmina, Natalia

    2018-02-01

    Fourteen 1D coordination polymers of rare earth pivalates [Ln(Piv)3]∞ (Ln = Y, La, Pr, Nd, Sm-Lu) were synthesized and characterized by powder X-ray diffraction, IR spectroscopy, TGA, and conventional elemental analysis. Crystal structures of [La(Piv)3]∞, [Yb(Piv)3]∞, [Lu(Piv)3]∞ were determined by means of single crystal X-ray analysis at 120 K, those of [Y(Piv)3]∞ and [Ho(Piv)3]∞ - from powder XRD data at 293 K. Transformation of [Ln(Piv)3]∞ structure and Piv- anions coordination mode along the whole row has been derived from powder XRD and IR spectroscopy results, and shown to crucially affect the relative location of 1D chains in the crystal structure, as well as the Ln···Ln distance within the single chain. Negative thermal expansion along 1D [Ln(Piv)3]∞ chain was revealed for Ln = Tm, Yb, Lu. Enforcement of 1D polymeric structure with the decrease of Ln ionic radius has been established from solid-state DFT calculations.

  15. Interpenetrating and non-interpenetrating 3-dimensional coordination polymer frameworks from multiple building blocks

    NASA Astrophysics Data System (ADS)

    Bradshaw, Darren; Rosseinsky, Matthew J.

    2005-12-01

    Reaction of Co(NO3)2ṡ6H2O with the multidentate ligands benzene-1,3,5-tricarboxylate (btc) and the flexible bipyridyl ligand 1,2-bis(4-pyridyl)ethane (bpe) affords the 3-dimensional coordination polymers [Co3(btc)2(bpe)3(eg)2]ṡ(guests) 1, where eg = ethylene glycol, and [Co2(Hbtc)2(bpe)2]ṡ(bpe) 2. Both phases are comprised of infinite metal-carboxylate dimer chains, linked into 2-dimensional sheets by the bpe ligands. These sheets are further linked to adjacent sheets through covalent interactions, 1, or through hydrogen-bonding interactions, 2, to yield the 3-dimensional structures. Phase 1 exhibits solvent filled 1-dimensional pores, whereas 2 is triply-interpenetrated to form a dense solid array.

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

    PubMed

    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.

  17. Photoluminescent lead(II) coordination polymers stabilised by bifunctional organoarsonate ligands

    NASA Astrophysics Data System (ADS)

    Lin, Jian-Di; Onet, Camelia I.; Schmitt, Wolfgang

    2015-04-01

    Four lead(II) coordination polymers were isolated under hydro(solvo)thermal conditions. The applied synthetic methodology takes advantage of the coordination behaviour of a new bifunctional organoarsonate ligand, 4-(1, 2, 4-triazol-4-yl)phenylarsonic acid (H2TPAA) and involves the variation of lead(II) reactants, metal/ligand mole ratios, and solvents. The constitutional composition of the four lead(II) coordination polymers can be formulated as [Pb2(TPAA)(HTPAA)(NO3)]·6H2O (1), [Pb2(TPAA)(HTPAA)2]·DMF·0.5H2O (DMF = N, N-Dimethylformamide) (2), [Pb2Cl2(TPAA)H2O] (3), and [Pb3Cl(TPAA)(HTPAA)2H2O]Cl (4). The compounds were characterized by single-crystal and powder x-ray diffraction techniques, thermogravimetric analyses, infra-red spectroscopy, and elemental analyses. Single-crystal x-ray diffraction reveals that 1 and 2 represent two-dimensional (2D) layered structures whilst 3 and 4 form three-dimensional (3D) frameworks. The structures of 1, 2, and 4 contain one-dimensional (1D) {PbII/AsO3} substructures, while 3 is composed of 2D {PbII/AsO3} arrays. Besides their interesting topologies, 1-4 all exhibit photoluminescence properties in the solid state at room temperature.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Abbasi, Alireza, E-mail: aabbasi@khayam.ut.ac.ir; Gharib, Maniya; Najafi, Mahnaz

    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 leastmore » 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.« less

  19. How the World Changes By Going from One- to Two-Dimensional Polymers in Solution.

    PubMed

    Schlüter, A Dieter; Payamyar, Payam; Öttinger, Hans Christian

    2016-10-01

    Scaling behavior of one-dimensional (1D) and two-dimensional (2D) polymers in dilute solution is discussed with the goal of stimulating experimental work by chemists, physicists, and material scientists in the emerging field of 2D polymers. The arguments are based on renormalization-group theory, which is explained for a general audience. Many ideas and methods successfully applied to 1D polymers are found not to work if one goes to 2D polymers. The role of the various states exhibiting universal behavior is turned upside down. It is expected that solubility will be a serious challenge for 2D polymers. Therefore, given the crucial importance of solutions in characterization and processing, synthetic concepts are proposed that allow the local bending rigidity and the molar mass to be tuned and the long-range interactions to be engineered, all with the goal of preventing the polymer from falling into flat or compact states. © 2016 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Syntheses, structures and properties of four Cd(II) coordination polymers induced by the pH regulator

    NASA Astrophysics Data System (ADS)

    Xu, Yun; Ding, Fang; Liu, Dong; Yang, Pei-Pei; Zhu, Li-Li

    2018-03-01

    Four new coordination polymers [Cd2(CHDC)2(APYZ)(H2O)2](H2O) (1), [Cd(HCHDC)2(APYZ) (H2O)] (2), [Cd2(CHDC)2(PYZ)(H2O)2](H2O) (3), and [Cd(HCHDC)2(PYZ)(H2O)] (4) (H2CHDC = 1,4-cyclohexanedicarboxylic acid, APYZ = 2-aminopyrazine, PYZ = pyrazine) have been synthesized under the hydrothermal conditions by changing the pH regulator and the N-containing ligands. The pH regulator impacted on the degree of deprotonation of the 1,4-cyclohexanedicarboxylic acid ligand and resulted in the formation of the two pairs of different networks. Polymers 1 and 3 crystallize in monoclinic, space group P21/c, exhibit two dimensional 63 net, which further formed three-dimensional supramolecular structure by the Csbnd H⋯O hydrogen bond interactions. While polymers 2 and 4 possess one dimensional chain structures and further link into two dimensional layered supramolecular structures by intermolecular hydrogen bonding interactions. From all three conformers of H2CHDC, e,a-cis is consistently present in the Cd coordination polymers. Furthermore, photoluminescence properties of four polymers are also investigated, the luminescent intensity of polymer 1 (or 2) with amino group in pyrazine is dramatically stronger than that of the similar structure of polymer 3 (or 4) without amino group in pyrazine, the results shown that the presence of the amino group from 2-aminopyrazine play a key role in increasing the luminescence properties.

  1. Air and moisture stable covalently-bonded tin(ii) coordination polymers.

    PubMed

    de Lima, G M; Walton, R I; Clarkson, G J; Bitzer, R S; Ardisson, J D

    2018-06-05

    Four covalently-bonded tin(ii) coordination polymers, (1)-(4), were hydrothermally prepared in aqueous alkaline media by the reactions of SnSO4 with 1,2,4,5-benzenetetracarboxylic acid (1), 1,3,5-benzenetricarboxylic acid (2), 4-hydroxypyridine-2,6-dicarboxylic acid (3), and 1,3,5-cyclohexanetricarboxylic acid (4). All products were structurally authenticated by single-crystal X-ray diffraction, and the number of different tin centres and their oxidation states were confirmed by 119Sn Mössbauer spectroscopy. In addition, the comparison between experimental and simulated X-ray powder diffraction patterns confirmed the authenticity of the samples. Our crystallographic results for (1)-(4) show that the Sn(ii) centres are tetracoordinated and exhibit distorted disphenoidal geometries, corroborating the presence of one stereochemically active lone electron pair at each metal site. Products (1) and (2) display bi-dimensional polymeric structures, (3) exhibits a one-dimensional architecture, whereas (4) shows a remarkable three-dimensional coordination network. Hirshfeld surface and supramolecular analyses for the repeating units of (1)-(4) were also performed in order to identify structurally important non-covalent interactions.

  2. Coordinate axes, location of origin, and redundancy for the one and two-dimensional discrete Fourier transform

    NASA Technical Reports Server (NTRS)

    Ioup, G. E.; Ioup, J. W.

    1985-01-01

    Appendix 4 of the Study of One- and Two-Dimensional Filtering and Deconvolution Algorithms for a Streaming Array Computer discusses coordinate axes, location of origin, and redundancy for the one- and two-dimensional Fourier transform for complex and real data.

  3. A new redox-active coordination polymer with cobalticinium dicarboxylate.

    PubMed

    Kondo, Mitsuru; Hayakawa, Yuri; Miyazawa, Makoto; Oyama, Aiko; Unoura, Kei; Kawaguchi, Hiroyuki; Naito, Tetsuyoshi; Maeda, Kenji; Uchida, Fumio

    2004-09-20

    A new two-dimensional coordination polymer with cobalticinium 1,1'-dicarboxylate (ccdc) incorporated in the framework has been prepared, the ccdc functioning as unique monoanionic dicarboxylate ligands. The compound shows a high redox activity based on the ccdc units. Copyright 2004 American Chemical Society

  4. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

    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.

  5. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

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

    2013-09-10

    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.

  6. Four one-dimensional lanthanide-phenylacetate polymers exhibiting luminescence and magnetic cooling/spin-glass behavior.

    PubMed

    Li, Zhong-Yi; Xu, Ya-Lan; Zhang, Xiang-Fei; Zhai, Bin; Zhang, Fu-Li; Zhang, Jian-Jun; Zhang, Chi; Li, Su-Zhi; Cao, Guang-Xiu

    2017-12-21

    Four isostructural lanthanide coordination polymers with a phenylacetate (PAA - ) ligand, [Ln(PAA) 3 (H 2 O)] n (Ln = Eu (1); Gd (2); Tb (3); Dy (4)), were synthesized under hydrothermal conditions. Complexes 1-4 display a one-dimensional (1D) wave chain structure bridged by the carboxylate of the PAA - ligand, which was generated via the in situ decarboxylation of phenylmalonic acid. Magnetic studies suggest the presence of ferromagnetic LnLn coupling in the 1D chain of 1-4. Meanwhile, 2 has a significant cryogenic magnetocaloric effect with the maximum -ΔS m of 26.73 at 3 K and 7 T, and 3 and 4 show interesting spin-glass behavior, which is rarely reported for Ln-containing complexes. Additionally, the solid-state photophysical properties of 1 and 3 display strong characteristic Eu 3+ and Tb 3+ photoluminescence emission in the visible region, indicating that Eu- and Tb-based luminescence are sensitized by the effective energy transfer from the ligand to the metal centers.

  7. Stepwise assembly of a semiconducting coordination polymer [Cd8S(SPh)14(DMF)(bpy)]n and its photodegradation of organic dyes.

    PubMed

    Xu, Chao; Hedin, Niklas; Shi, Hua-Tian; Xin, ZhiFeng; Zhang, Qian-Feng

    2015-04-14

    Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4'-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4'-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

    NASA Astrophysics Data System (ADS)

    Luo, Qianqian; Han, Ying; Lin, Hechun; Zhang, Yuanyuan; Duan, Chungang; Peng, Hui

    2017-03-01

    One dimensional coordination polymer Gd[(SO4)(NO3)(C2H6SO)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 SO42- ions to generate a 1-D chain, and all oxygen atoms in SO42- groups are connected to three nearest Gd atoms in μ3:η1:η1:η2 fashion. Gd, S and N from SO42- and NO3- 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 -ΔSm=28.8 J Kg-1 K-1 for ΔH=7 T.

  10. Synthesis and structures of ligand-dominated one-dimensional silver(I)–bis(pyridylmethyl)amine coordination chains

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lin, Hung-Jui; Liu, Yu-Chiao; Tseng, Yu-Jui

    2016-10-15

    Reactants slow diffusion of Ag(I) salts with 3,4′-bis(pyridylmethyl)amine (3,4′-bpma), an unsymmetric bis-pyridyl ligand equipped with a non-innocent amine backbone, afforded polymeric coordination adducts 1–5 having a general formula ([Ag(3,4′-bpma)(solv)]X){sub n} (solv = H{sub 2}O, CH{sub 3}OH, and none; X= CF{sub 3}CO{sub 2}{sup –}, BF{sub 4}{sup –}, ClO{sub 4}{sup –}, CF{sub 3}SO{sub 3}{sup –}, and SbF{sub 6}{sup –}). Single-crystal X-ray diffraction (SCXRD) analyses reveal that colorless crystals of Ag(I) coordination polymers (CPs) 1–5 have very similar one-dimensional (1D) non-flat chain structures, which are preferentially depicted as a “zipper-like” rather than a ladder-like or a double-stranded chain topologies. The 3,4′-bpma ligand inmore » these Ag(I) CPs displays a μ{sub 3}-bridging mode with a gauche–trans (1,4, and 5) and a trans–trans (2 and 3) conformations. Noteworthy, anions do not show strong influence on structural modulation of Ag(I) CPs in the solid state, but really affect CP conformations and packing fashions, indicative of a ligand-dominated assembly process for such a Ag(I)–3,4′-bpma system. Thermal stabilities and solid-state photoluminescence properties of crystalline materials 1–5 were investigated. - Graphical abstract: This work has addressed five ligand-dominated Ag(I)–3,4′-bpma polymeric adducts, which show similar one-dimensional non-flat chain structures depicting a “zipper-like” topology rather than a ladder-like or a double-stranded chain structures.« less

  11. Substituent-induced effects on dimensionality in cadmium isophthalate coordination polymers containing 3-pyridylisonicotinamide

    NASA Astrophysics Data System (ADS)

    O'Donovan, Megan E.; Wudkewych, Megan J.; LaDuca, Robert L.

    2015-08-01

    Hydrothermal treatment of cadmium nitrate, a 5-substituted isophthalic acid, and 3-pyridylisonicotinamide (3-pina) resulted in three coordination polymers whose dimensionality depended critically on the nature of the aromatic ring substituent. These three new phases were characterized by single crystal X-ray diffraction. {[Cd(hip)(3-pina)(H2O)2]·2H2O}n (1, hip = 5-hydroxyisophthalate) and {[Cd(meoip)(3-pina)(H2O)2]·H2O}n (2, meoip = 5-methoxyisophthalate) both manifest simple 1-D chain structures with pendant 3-pina ligands. [Cd(mip)(3-pina)]n (3, mip = 5-methylisophthalate) possesses [Cd(mip)]n 1-D chains featuring {Cd2(OCO)2} dimeric units, linked by tethering 3-pina ligands into a non-interpenetrated 3-D 6-connected 41263 pcu network. Luminescent behavior in all cases is attributed to intra-ligand molecular orbital transitions.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. One-dimensional mercury(II) halide coordination polymers of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine ligand: Synthesis, crystal structure, spectroscopic and DFT studies

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Saghatforoush, Lotfali, E-mail: saghatforoush@gmail.com; Khoshtarkib, Zeinab; Amani, Vahid

    2016-01-15

    Three new coordination polymers, [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl (1), Br (2)) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} (3) (bptz=3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) were synthesized. X-ray structural analysis indicated that compounds 1 and 2 are composed of one-dimensional (1D) linear chains while the compound 3 has 1D stair-stepped structure. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that compound 1 and 2 are direct band gap semiconductors; however, compound 3 is an indirect semiconductor. The linear optical properties of the compounds are also calculated by DFT method. According to the DFT calculations, the observed emission bandmore » of the compounds in solid state is due to electron transfer from an excited bptz-π* state (CBs) to the top of VBs. {sup 1}H NMR spectra of the compounds indicate that, in solution phase, the compounds don’t decompose completely. Thermal stability of the compounds is studied using TG, DTA methods. - Graphical abstract: Synthesis, crystal structure and emission spectra of [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} are presented. The electronic band structure and linear optical properties of the compounds are calculated by the DFT method. - Highlights: • Three 1D Hg(II) halide coordination polymers with bptz ligand have been prepared. • The structures of the compounds are determined by single crystal XRD. • DFT calculations show that [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) have a direct band gap. • DFT calculations show that [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} has an indirect band gap. • The compounds show an intraligand electron transfer emission band in solid state.« less

  14. Two novel two-dimensional copper(II) coordination polymers with 1-(4-aminobenzyl)-1,2,4-triazole: Synthesis, crystal structure, magnetic characterization and absorption of anion pollutants

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Wu, Xiang Xia; Guo, Jian-Hua; Huo, Jian-Zhong; Ding, Bin

    2017-01-01

    In this work a flexible multi-dentate 1-(4-aminobenzyl)-1,2,4-triazole (abtz) ligand has been employed, two novel triazole-Cu(II) coordination polymers {[Cu(abtz)2(Br)2]·(H2O)2}n (1) and {[Cu(abtz)2]·(SiF6)·(H2O)2}n (2) have been isolated under solvo-thermal conditions. 1 is a 2D neutral CuII coordination polymer while 2 is 2D cation micro-porous CuII coordination polymer with the channel dimensionalities of 11.852(1) Å × 11.852(1) Å (metal-metal distances). Variable-temperature magnetic susceptibility data of 1 and 2 have been recorded in the 2-300 K temperature range indicating weak anti-ferromagnetic interactions. Further absorption properties of anion pollutants for 2 also have been investigated. 2 presents the novel example of cationic triazole-copper(II) coordination framework for effectively capturing anion pollutants Cr2O72- in the water solutions and selectively capturing Congo Red in the methanol solutions.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tai, Xi-Shi, E-mail: taixs@wfu.edu.cn; Wang, Xin

    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.

  16. Coordination polymer gels with important environmental and biological applications.

    PubMed

    Jung, Jong Hwa; Lee, Ji Ha; Silverman, Julian R; John, George

    2013-02-07

    Coordination Polymer Gels (CPGs) constitute a subset of solid-like metal ion and bridging organic ligand structures (similar to metal-organic frameworks) that form multi-dimensional networks through a trapped solvent as a result of non-covalent interactions. While physical properties of these gels are similar to conventional high molecular weight organic polymer gels, coordination polymer gel systems are often fully reversible and can be assembled and disassembled in the presence of additional energy (heat, sonication, shaking) to give a solution of solvated gelators. Compared to gels resulting from purely organic self-assembled low molecular weight gelators, metal ions incorporated into the fibrilar networks spanning the bulk solvent can impart CPGs with added functionalities. The solid/liquid nature of the gels allows for species to migrate through the gel system and interact with metals, ligands, and the solvent. Chemosensing, catalysis, fluorescence, and drug-delivery applications are some of the many potential uses for these dynamic systems, taking advantage of the metal ion's coordination, the organic polydentate ligand's orientation and functionality, or a combination of these properties. By fine tuning these systems through metal ion and ligand selection and by directing self-assembly with external stimuli the rational synthesis of practical systems can be envisaged.

  17. Particle-in-a-box model of one-dimensional excitons in conjugated polymers

    NASA Astrophysics Data System (ADS)

    Pedersen, Thomas G.; Johansen, Per M.; Pedersen, Henrik C.

    2000-04-01

    A simple two-particle model of excitons in conjugated polymers is proposed as an alternative to usual highly computationally demanding quantum chemical methods. In the two-particle model, the exciton is described as an electron-hole pair interacting via Coulomb forces and confined to the polymer backbone by rigid walls. Furthermore, by integrating out the transverse part, the two-particle equation is reduced to one-dimensional form. It is demonstrated how essentially exact solutions are obtained in the cases of short and long conjugation length, respectively. From a linear combination of these cases an approximate solution for the general case is obtained. As an application of the model the influence of a static electric field on the electron-hole overlap integral and exciton energy is considered.

  18. Honeycomb-shaped coordination polymers based on the self-assembly of long flexible ligands and alkaline-earth ions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lian, Chen; Liu, Liu; Guo, Xu

    2016-01-15

    Two novel coordination polymers, namely, [Ca(NCP){sub 2}]{sub ∞} (I) and [Sr(NCP){sub 2}]{sub ∞} (II) were synthesized under hydrothermal conditions based on 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (HNCP) and characterized by elemental analysis, infrared spectrometry, X-ray powder diffraction and single crystal X-ray diffraction. Findings indicate that I and II are isomorphous and isostructural, containing the unit of M(NCP{sup −}){sub 4} (M=Ca(II) and Sr(II)), based on which to assemble into three-dimensional (3D) porous 4-fold interpenetration honeycomb-shaped neutral coordination polymers (CPs). Between the adjacent lamellar structures in I and II, there exist π–π interactions between the pyridine rings belonging to phenanthroline of NCP{sup −} which stabilize themore » frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability. - Graphical abstract: One-dimensional nanotubular channels with the cross dimension of 37.1959(20)×23.6141(11)Å{sup 2} in the three-dimensional honeycomb-shaped coordination network of II are observed. The topological analysis of II indicates that there exists a typical diamond framework possessing large adamantanoid cages, which containing four cyclohexane-shaped patterns in chair conformations. - Highlights: • Two isomorphous and isostructural coordination polymers based on flexible ligand and two alkaline-earth metal salts have been synthesized and characterized. • Structural analysis indicates that I and II are assembled into 3D porous honeycomb-shaped metal-organic frameworks. • Both I and II display stronger fluorescence emissions and higher thermal stability.« less

  19. Lanthanide coordination polymers: Synthesis, diverse structure and luminescence properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Song, Xue-Qin, E-mail: songxq@mail.lzjtu.cn; Lei, Yao-Kun; Wang, Xiao-Run

    2014-10-15

    The new semirigid exo-bidentate ligand incorporating furfurysalicylamide terminal groups, namely, 1,4-bis([(2′-furfurylaminoformyl)phenoxyl]methyl)-2,5-bismethylbenzene (L) was synthesized and used as building blocks for constructing lanthanide coordination polymers with luminescent properties. The series of lanthanide nitrate complexes have been characterized by elemental analysis, IR spectroscopy, and X-ray diffraction analysis. The semirigid ligand L, as a bridging ligand, reacts with lanthanide nitrates forming three distinct structure types: chiral noninterpenetrated two-dimensional (2D) honeycomblike (6,3) (hcb, Schläfli symbol 6{sup 3}, vertex symbol 6 6 6) topological network as type I, 1D zigzag chain as type II and 1D trapezoid ladder-like chain as type III. The structural diversitiesmore » indicate that lanthanide contraction effect played significant roles in the structural self-assembled process. The luminescent properties of Eu{sup III}, Tb{sup III} and Dy{sup III} complexes are discussed in detail. Due to the good match between the lowest triplet state of the ligand and the resonant energy level of the lanthanide ion, the lanthanide ions in Eu{sup III}, Tb{sup III} and Dy{sup III} complexes can be efficiently sensitized by the ligand. - Graphical abstract: We present herein six lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display diverse structures but also possess strong luminescence properties. - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit diverse structures. • The luminescent properties of Tb{sup III}, Eu{sup III} and Dy{sup III} complexes are discussed in detail.« less

  20. 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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Cui, Zhongping; Qi, Ji; Xu, Xinxin, E-mail: xuxx@mail.neu.edu.cn

    2013-09-15

    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 compositemore » 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.« less

  1. Metal aminocarboxylate coordination polymers with chain and layered structures.

    PubMed

    Dan, Meenakshi; Rao, C N R

    2005-11-18

    The synthesis and structures of metal aminocarboxylates prepared in acidic, neutral, or alkaline media have been explored with the purpose of isolating coordination polymers with linear chain and two-dimensional layered structures. Metal glycinates of the formulae [CoCl2(H2O)2(CO2CH2NH3)] (I), [MnCl2(CO2CH2NH3)2] (II), and [Cd3Cl6(CO2CH2NH3)4] (III) with one-dimensional chain structures have been obtained by the reaction of the metal salts with glycine in an acidic medium under hydro/solvothermal conditions. These chain compounds contain glycine in the zwitterionic form. 4-Aminobutyric acid transforms to a cyclic amide under such reaction conditions, and the amide forms a chain compound of the formula [CdBr2(C4H7NO)2] (IV). Glycine in the zwitterionic form also forms a two-dimensional layered compound of the formula [Mn(H2O)2(CO2CH2NH3)2]Br2 (V). 6-Aminocaproic acid under alkaline conditions forms layered compounds with metals at room temperature, the metal being coordinated both by the amino nitrogen and the carboxyl oxygen atoms. Of the two layered compounds [Cd{CO2(CH2)5NH2}2]2 H2O (VI) and [Cu{CO2(CH2)5NH2}2]2 H2O (VII), the latter has voids in which water molecules reside.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning

    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. Formore » 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.« less

  3. Water molecule-enhanced CO{sub 2} insertion in lanthanide coordination polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Luo Liushan; Huang Xiaoyuan; Wang Ning

    2009-08-15

    Two new lanthanide coordination polymers H{sub 2}N(CH{sub 3}){sub 2}.[Eu{sup III}{sub 2}(L{sub 1}){sub 3}(L{sub 2})] (1, L{sub 1}=isophthalic acid dianion, L{sub 2}=formic acid anion) and [La{sup III}(2,5-PDC)(L{sub 2})](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L{sub 2}) is not contained in the stating materials, but arises from the water molecule-enhanced CO{sub 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{sub 2} insertion resulting in the formation of formic anion and dimethylammonium cation weremore » synthesized under solvothermal conditions.« less

  4. A series of three-dimensional lanthanide coordination polymers with rutile and unprecedented rutile-related topologies.

    PubMed

    Qin, Chao; Wang, Xin-Long; Wang, En-Bo; Su, Zhong-Min

    2005-10-03

    The complexes of formulas Ln(pydc)(Hpydc) (Ln = Sm (1), Eu (2), Gd (3); H2pydc = pyridine-2,5-dicarboxylic acid) and Ln(pydc)(bc)(H2O) (Ln = Sm (4), Gd (5); Hbc = benzenecarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG analysis, and single-crystal X-ray diffraction. Compounds 1-3 are isomorphous and crystallize in the orthorhombic system, space group Pbcn. Their final three-dimensional racemic frameworks can be considered as being constructed by helix-linked scalelike sheets. Compounds 4 and 5 are isostructural and crystallize in the monoclinic system, space group P2(1)/c. pydc ligands bridge dinuclear lanthanide centers to form the three-dimensional frameworks featuring hexagonal channels along the a-axis that are occupied by one-end-coordinated bc ligands. From the topological point of view, the five three-dimensional nets are binodal with six- and three-connected nodes, the former of which exhibit a rutile-related (4.6(2))(2)(4(2).6(9).8(4)) topology that is unprecedented within coordination frames, and the latter two species display a distorted rutile (4.6(2))(2)(4(2).6(10).8(3)) topology. Furthermore, the luminescent properties of 2 were studied.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xu, Zhong-Xuan, E-mail: xuzhongxuan4201@163.com; Ma, Yu-Lu; Lv, Guo-ling

    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 enantiomericmore » 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.« less

  6. Synthesis, crystal structures and luminescent properties of two 4 d-4 f Ln-Ag heterometallic coordination polymers based on anion template

    NASA Astrophysics Data System (ADS)

    Fan, Le-Qing; Chen, Yuan; Wu, Ji-Huai; Huang, Yun-Fang

    2011-04-01

    Two new 4 d-4 f Ln-Ag heterometallic coordination polymers, {[ Ln3Ag 5(IN) 10(H 2O) 7]·4(ClO 4)·4(H 2O)} n ( Ln=Eu ( 1) and Sm ( 2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions by reactions of Ln2O 3, AgNO 3, HIN and HClO 4, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. It is proved that HClO 4 not only adjusts the pH value of the reaction mixture, but also acts as anion template. The structure determination reveals that 1 and 2 are isostructural and feature a novel two-dimensional (2D) layered hetrometallic structure constructed from one-dimensional Ln-carboxylate chains and pillared Ag(IN) 2 units. The 2D layers are further interlinked through Ag⋯Ag and Ag⋯O(ClO 4-) multiple weak interactions, which form a rare Ag-ClO 4 ribbon in lanthanide-transition metal coordination polymers, to give rise to a three-dimensional supramolecular architecture. Moreover, the luminescent properties of these two compounds have also been investigated at room temperature.

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

    PubMed

    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.

  8. Toward lanthanide containing coordination polymers and nanomaterials

    NASA Astrophysics Data System (ADS)

    Greig, Natalie E.

    The focus of this thesis is to develop lanthanide (Ln) luminescent materials through the exploration of coordination polymers and nanomaterials. Herein, dimethyl-3,4-furanedicarboxylate acid undergoes hydrolysis under hydrothermal conditions to form coordination polymers with lanthanide ions. The resulting coordination polymers exhibited luminescent properties, with quantum yields and lifetimes for the Eu- and Tb-CP of 1.14±0.31% and 0.387±0.0001 ms, and 3.33±0.82% and 0.769±0.006 ms, respectively. While the incorporation of lanthanides was not achieved in this work, progress toward the production of pure phase InP in the nanoregime has been made, using a low-cost, hydrothermal method. Though SEM and PXRD conflict, it is believed that pure InP particles with a size range of 58-81 nm were successfully synthesized.

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

    PubMed

    Huang, Jing-Kai; Li, Mengliu; Wan, Yi; Dey, Sukumar; Ostwal, Mayur; Zhang, Daliang; Yang, Chih-Wen; Su, Chun-Jen; Jeng, U-Ser; Ming, Jun; Amassian, Aram; Lai, Zhiping; Han, Yu; Li, Sean; Li, Lain-Jong

    2018-01-23

    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 Zn 2 (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 Zn 2 (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.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg{sup 2+}, Ca{sup 2+} and Ba{sup 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){sub 4}, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (4{sup 4}·6{sup 2}){sub 3}(4{sup 9}·6{sup 6}){sub 2}. The calcium compound consists of 1D infinite “Ca-O” inorganic chains connected by the deprotonated ligands to from a 3Dmore » 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

  11. Cobalt-cadmium bimetallic porphyrin coordination polymers for electrochemistry application

    NASA Astrophysics Data System (ADS)

    Wang, C. Y.; Cui, G. Y.; Ding, D.; Zhou, B.

    2018-01-01

    In this paper, we used tetra (4-carboxyphenyl) porphyrin (H2TCPP) and metal cadmium, cobalt as reactants to synthesize metal porphyrin coordination polymers that they had different metal ratio. They were expressed as Co1Cd3TCPP, Co1Cd1TCPP, Co3Cd1TCPP, respectively. The results were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and inductively coupled plasma atomic emission spectrometer (ICP). Herein, a series of metal porphyrin coordination polymers has multiple metal active centers and constructs electrochemistry sensors. In order to increase the conductivity, multi-walled carbon nanotubes (MWCNTs) can be used to modify the electrodes. The polymer/MWCNTs/GCE electrode was studied by cyclic voltammetry and chronoamperometry as sensor for sodium nitrite. The performance of Co1Cd1TCPP/MWCNTs/GCE electrode is best, the sensitivity for sodium nitrite is 350.95 mA M-1 cm-2 and the. The results indicate that metal porphyrin coordination polymers have excellent performance. It also enriches the application of metal porphyrin coordination polymer in electrochemistry sensor.

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

    PubMed

    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.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Novosibirsk State University, Novosibirsk 630090

    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.more » 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hazari, Debdoot; Jana, Swapan Kumar; Fleck, Michel

    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:more » 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.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Coordinative nanoporous polymers synthesized with hydrogen-bonded columnar liquid crystals.

    PubMed

    Ishihara, Shinsuke; Furuki, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko; Takeoka, Shinji

    2012-10-01

    In this paper, we report the development of nanoporous polymer which demonstrates the coordination property toward zinc porphyrin. A hydrogen-bonded columnar liquid crystalline precursor composed of a triphenylene template and three equivalent of the surrounding dendric amphiphile bearing a pyridyl head group and a polymerizable aliphatic chain, was covalently fixed by photopolymerization, and then the subsequent selective removal of the template successively resulted in a nanoporous polymer in which the pore wall is modified with pyridyl groups. The nanoporous polymer reflected the conformation of template, and displayed considerable coordination ability of the pyridyl groups towards zinc porphyrin. The coordinative nanoporous polymer is promising as a nano-scaled scaffold for the organization of dyes into functional supramolecular architectures.

  17. A novel one-dimensional manganese(II) coordination polymer containing both dicyanamide and pyrazinamide ligands: Synthesis, spectroscopic investigations, X-ray studies and evaluation of biological activities

    NASA Astrophysics Data System (ADS)

    Tabrizi, Leila; Chiniforoshan, Hossein; McArdle, Patrick

    2015-03-01

    A novel 1D coordination polymer {[Mn(μ1,5-dca)2(PZA)2](PZA)2}n, 1, has been synthesized and characterized by single crystal X-ray crystallography. The coordination mode of dicyanamide (dca) and pyrazinamide (PZA) ligands was inferred by IR spectroscopy. The compound 1 was evaluated for in vitro antimycobacterial and antitumor activities. It demonstrated better in vitro activity against Mycobacterium tuberculosis than pyrazinamide and its MIC value was determined. Complex 1 was also screened for its in vitro antitumor activity towards LM3 and LP07 murine cancer cell lines. In addition, the antibacterial activity of complex 1 has been tested against Gram(+) and Gram(-) bacteria and it has shown promising broad range anti-bacterial activity.

  18. Double layer zinc-UDP coordination polymers: structure and properties.

    PubMed

    Qiu, Qi-Ming; Gu, Leilei; Ma, Hongwei; Yan, Li; Liu, Minghua; Li, Hui

    2018-05-17

    A homochiral Zn-UDP coordination polymer with an alternating parallel ABAB sequence was constructed and studied by X-ray single crystal diffraction analysis. Its crystal structure shows that there are potentially open sites in the 2D layers. The activation of the sites makes the coordination polymer a fluorescent sensor for novel heterogeneous detection of amino acids.

  19. Tellurium-containing polymer micelles: competitive-ligand-regulated coordination responsive systems.

    PubMed

    Cao, Wei; Gu, Yuwei; Meineck, Myriam; Li, Tianyu; Xu, Huaping

    2014-04-02

    Nanomaterials capable of achieving tunable cargo release kinetics are of significance in a fundamental sense and various biological or medical applications. We report a competitive coordination system based on a novel tellurium-containing polymer and its ligand-regulated release manners. Tellurium was introduced to water-soluble polymers for the first time as drug delivery vehicles. The coordination chemistry between platinum and tellurium was designed to enable the load of platinum-based drugs. Through the competitive coordination of biomolecules, the drugs could be released in a controlled manner. Furthermore, the release kinetics could be modulated by the competitive ligands involved due to their different coordination ability. This tellurium-containing polymer may enrich the family of delivery systems and provide a new platform for future biomedical nanotechnologies.

  20. Nanometrization of Lanthanide-Based Coordination Polymers.

    PubMed

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Multivalent Ion Transport in Polymers via Metal-Ligand Coordination

    NASA Astrophysics Data System (ADS)

    Sanoja, Gabriel; Schauser, Nicole; Evans, Christopher; Majumdar, Shubhaditya; Segalman, Rachel

    Elucidating design rules for multivalent ion conducting polymers is critical for developing novel high-performance materials for electrochemical devices. Herein, we molecularly engineer multivalent ion conducting polymers based on metal-ligand interactions and illustrate that both segmental dynamics and ion coordination kinetics are essential for ion transport through polymers. We present a novel statistical copolymer, poly(ethylene oxide-stat-imidazole glycidyl ether) (i.e., PEO-stat-PIGE), that synergistically combines the structural hierarchy of PEO with the Lewis basicity of tethered imidazole ligands (xIGE = 0.17) required to coordinate a series of transition metal salts containing bis(trifluoromethylsulfonyl)imide anions. Complexes of PEO-stat-PIGE with salts exhibit a nanostructure in which ion-enriched regions alternate with ion-deficient regions, and an ionic conductivity above 10-5 S/cm. Novel normalization schemes that account for ion solvation kinetics are presented to attain a universal scaling relationship for multivalent ion transport in polymers via metal-ligand coordination. AFOSR MURI program under FA9550-12-1.

  2. Developing multifunctional nanoparticles in a 1-D coordination polymer of Cd(II)

    NASA Astrophysics Data System (ADS)

    Agarwal, Rashmi A.; Gupta, Neeraj K.

    2017-11-01

    A simple synthesis for the integration of different nanoparticles (NPs) including Ag, Au, Pd, Cr and mixed (Cu/Fe), has been demonstrated within the nanopores of a non-activated one dimensional porous coordination polymer (PCP) of Cd(II) due to its high flexible structure. There are two different mechanisms (acid formation (HCl/HNO3) and redox activity of the framework) elucidated by electron paramagnetic resonance (EPR). Presence of -NO2 groups of the ligand act as anchoring sites for metal ions of metal precursors leading to NPs growth within the PCP explained by FTIR. High resolution transmission electron microscopy (HRTEM) images provided insight of the chemical and physical characteristics of the NPs within the framework. Ag/AgO NPs exhibit excellent antibacterial properties at extremely low concentrations. The polymer shows potential for sequestration and reduction of hexavalent Cr (highly toxic) to elemental, trivalent and tetravalent Cr (non toxic). This framework is also an excellent template for fabrication and dry storage of nanoparticles synthesized by mixed metal precursors. Ferromagnetic properties have been shown by Ag and Au NPs integrated frameworks while Cu/Fe@Cd-PCP behaves as a paramagnet material at room temperature.

  3. Fabrication routes for one-dimensional nanostructures via block copolymers

    NASA Astrophysics Data System (ADS)

    Tharmavaram, Maithri; Rawtani, Deepak; Pandey, Gaurav

    2017-05-01

    Nanotechnology is the field which deals with fabrication of materials with dimensions in the nanometer range by manipulating atoms and molecules. Various synthesis routes exist for the one, two and three dimensional nanostructures. Recent advancements in nanotechnology have enabled the usage of block copolymers for the synthesis of such nanostructures. Block copolymers are versatile polymers with unique properties and come in many types and shapes. Their properties are highly dependent on the blocks of the copolymers, thus allowing easy tunability of its properties. This review briefly focusses on the use of block copolymers for synthesizing one-dimensional nanostructures especially nanowires, nanorods, nanoribbons and nanofibers. Template based, lithographic, and solution based approaches are common approaches in the synthesis of nanowires, nanorods, nanoribbons, and nanofibers. Synthesis of metal, metal oxides, metal oxalates, polymer, and graphene one dimensional nanostructures using block copolymers have been discussed as well.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Amorphous-amorphous transition in a porous coordination polymer.

    PubMed

    Ohtsu, Hiroyoshi; Bennett, Thomas D; Kojima, Tatsuhiro; Keen, David A; Niwa, Yasuhiro; Kawano, Masaki

    2017-07-04

    The amorphous state plays a key role in porous coordination polymer and metal-organic framework phase transitions. We investigate a crystalline-to-amorphous-to-amorphous-to-crystalline (CAAC) phase transition in a Zn based coordination polymer, by X-ray absorption fine structure (XAFS) and X-ray pair distribution function (PDF) analysis. We show that the system shows two distinct amorphous phases upon heating. The first involves a reversible transition to a desolvated form of the original network, followed by an irreversible transition to an intermediate phase which has elongated Zn-I bonds.

  6. Diorganotin-based coordination polymers derived from sulfonate/phosphonate/phosphonocarboxylate ligands.

    PubMed

    Shankar, Ravi; Jain, Archana; Kociok-Köhn, Gabriele; Molloy, Kieran C

    2011-02-21

    The reactions of diorganotin precursors [R(2)Sn(OR(1))(OSO(2)R(1))](n) [R = R(1) = Me (1); R = Me, R(1) = Et (2)] with an equimolar amount of t-butylphosphonic acid (RT, 8-10 h) in methanol result in the formation of identical products, of composition [(Me(2)Sn)(3)(O(3)PBu(t))(2)(O(2)P(OH)Bu(t))(2)](n) (3). On the other hand, a similar reaction of 2, when carried out in dichloromethane, affords [(Me(2)Sn)(3)(O(3)PBu(t))(2)(OSO(2)Et)(2)·MeOH](n) (4). A plausible mechanism implicating the role of solvent in the formation of these compounds has been put forward. In addition, the synthesis of [(Me(2)Sn)(3)(O(3)PCH(2)CH(2)COOMe)(2)(OSO(2)Me)(2)](n) (5) and [R(2)Sn(O(2)P(OH)CH(2)CH(2)COOMe)(OSO(2)R(1))](n) [R = Et, R(1) = Me (6); R = (n)Bu, R(1) = Et (7)] has been achieved by reacting 1 and related diorganotin(alkoxy)alkanesulfonates with 3-phosphonopropionic acid in methanol. The formation of a methylpropionate functionality on the phosphorus center in these structural frameworks results from in situ esterification of the carboxylic group. X-ray crystallographic studies of 1-7 are presented. The structures of 1 and 2 represent one-dimensional (1D) coordination polymers composed of alternate [Sn-O](2) and [Sn-O-S-O](2) cyclic rings formed by μ(2)-alkoxo and sulfonate ligands, respectively. For 3-5 and 7, variable bonding modes of phosphonate and/or sulfonate ligands afford the construction of two- and three-dimensional self-assemblies that are comprised of trinuclear tin entities with an Sn(3)P(2)O(6) core as well as [Sn-O-P-O](2) and/or [Sn-O-S-O](2) rings. The formation of a 1D coordination polymer in 6 is unique in terms of repeating eight-membered cyclic rings containing Sn, O, P, and S heteroatoms. The contribution from hydrogen-bonding interactions is also found to be significant in these structures.

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

    NASA Astrophysics Data System (ADS)

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-01

    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)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]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)]3[Re(CN)7]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)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

  8. Redox and catalysis 'all-in-one' infinite coordination polymer for electrochemical immunosensor of tumor markers.

    PubMed

    Zhang, Bing; Liu, Bingqian; Chen, Guonan; Tang, Dianping

    2015-02-15

    Prostate-specific antigen (PSA), as a glycoprotein enzyme encoded in humans by the KLK3 gene, is one of the most important biomarkers for the diagnosis and prognosis of prostate cancer. Herein, a new electrochemical immunosensor for sensitive determination of PSA was designed by using redox and catalysis 'all-in-one' infinite coordination polymer (PtNP@ICP) as signal tag on the polyamidoamine dendrimers modified electrode interface. To construct such 'all-in-one' PtNP@ICP nanostructures, the coordination polymerization was fully carried between metal ions and polydentate bridging ligands, and the PtNP was encapsulated into the ICP in the process of polymerization. The prepared PtNP@ICP nanocatalyst was characterized by transmission electron microscope (TEM), energy dispersive X-ray spectrometry (EDX), ultraviolet and visible (UV-vis) spectrophotometry and Fourier transform infrared spectroscope (FTIR). And the synthesized PtNP@ICP was utilized as signal tag for the label of PSA. With a sandwich-type immunoassay format, the conjugated signal tag on the transducer increased with the increasing PSA concentration in the sample thus enhancing the signal of the electrochemical immunosensor due to the catalytic reduction toward H2O2 of the enveloped PtNP. Under optimal conditions, the current was proportional to the logarithm of PSA concentration ranging from 0.001 to 60 ng/mL. The detection limit (LOD) was 0.3 pg/mL at 3 sB. The immunosensor displayed an acceptable reproducibility, stability and selectivity. In addition, the methodology was evaluated with human serum specimens receiving good correlation with results from commercialized enzyme-linked immunosorbent assay (ELISA) method. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Hydrothermal synthesis of zinc(II)-phosphonate coordination polymers with different dimensionality (0D, 2D, 3D) and dimensionality change in the solid phase (0D→3D) induced by temperature

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Fernández-Zapico, Eva; Montejo-Bernardo, Jose; Fernández-González, Alfonso

    2015-05-15

    Three new zinc(II) coordination polymers, [Zn(HO{sub 3}PCH{sub 2}CH{sub 2}COO)(C{sub 12}H{sub 8}N{sub 2})(H{sub 2}O)] (1), [Zn{sub 3}(O{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(C{sub 12}H{sub 8}N{sub 2})](H{sub 2}O){sub 3.40} (2) and [Zn{sub 5}(HO{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(O{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(C{sub 12}H{sub 8}N{sub 2}){sub 4}](H{sub 2}O){sub 0.32} (3), with different structural dimensionality (0D, 2D and 3D, respectively) have been prepared by hydrothermal synthesis, and their structures were determined by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system (P2{sub 1}/c) forming discrete dimeric units bonded through H-bonds, while compounds 2 and 3 crystallize in the triclinic (P−1) and the monoclinic (C2/c) systems, respectively.more » Compound 3, showing three different coordination numbers (4, 5 and 6) for the zinc atoms, has also been obtained by thermal treatment of 1 (probed by high-temperature XRPD experiments). The crystalline features of these compounds, related to the coordination environments for the zinc atoms in each structure, provoke the increase of the relative fluorescence for 2 and 3, compared to the free phenanthroline. Thermal analysis (TG and DSC) and XPS studies have been also carried out for all compounds. - Graphical abstract: Three new coordination compounds of zinc with 2-carboxyethylphosphonic acid (H{sub 2}PPA) and phenanthroline have been obtained by hydrothermal synthesis. The crystalline structure depends on the different coordination environments of the zinc atoms (see two comparative Zn{sub 6}-moieties). The influence of the different coordination modes of H{sub 2}PPA with the central atom in all structures have been studied, being found new coordination modes for this ligand. Several compounds show a significant increase in relative fluorescence with respect to the free phenanthroline. - Highlights: • Compounds have been obtained modifying the reaction time and the rate

  10. Studies on the relation between the size and dispersion of metallic silver nanoparticles and morphologies of initial silver(I) coordination polymer precursor

    NASA Astrophysics Data System (ADS)

    Moradi, Zhaleh; Akhbari, Kamran; Phuruangrat, Anukorn; Costantino, Ferdinando

    2017-04-01

    Micro and nano-structures of [Ag2(μ2-dcpa)2]n (1), [Hdcpa = 2,4-dichlorophenoxyacetic acid] which is a one-dimensional coordination polymer with corrugated tape chains, were synthesized as the bulk sample (1B), by sonochemical process (1S) and from mechanochemical reaction (1M). These three samples have been used as new precursors for fabricating silver nanoparticles via direct calcination at 300 °C and also thermal decomposition in oleic acid (OA) as a surfactant at 180 °C. In the presence of OA less agglomerated nanostructures were formed. It seems that the size, dispersion, morphology and agglomeration of initial precursor have direct influence on size, dispersion, morphology and agglomeration of metallic silver. This coordination polymer with various micro and nano morphologies were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Thermal stability of these samples were studied and compared with each other, too.

  11. (1-Butyl-4-methyl-pyridinium)[Cu(SCN)2]: a coordination polymer and ionic liquid.

    PubMed

    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.

  12. A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Jin-Hua; Tang, Gui-Mei, E-mail: meiguit@163.com; Qin, Ting-Xiao

    2014-11-15

    Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11more » nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one-dimensional

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen Jianshan; Sheng Tianlu; Hu Shengmin

    2012-08-15

    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{sub 2}O){sub 2}]{sub n} (3), [Cu(cbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O)]{sub n} (4) (cbop=(S)-N-(4-cyanobenzoic)-5-oxoproline, 4,4 Prime -bipy=4,4 Prime -bipyridine), {l_brace}[Cu(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}4H{sub 2}O{r_brace}{sub n} (5) (nbop=(S)-N-(4-nitrobenzoic)-5-oxoproline), {l_brace}[Cd(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}2H{sub 2}O{r_brace}{sub n} (6), and [Ni(nbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O){sub 2}]{sub 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-dimensionalmore » 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 Prime -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: Black-Right-Pointing-Pointer Two new chiral aminocarboxylate derivates were firstly synthesized. Black-Right-Pointing-Pointer Five new homochiral metal organic complexes were obtained hydrothermally based on these ligands. Black-Right-Pointing-Pointer Intramolecular amidation was taken place on the aminocarboxylate derivates during the formation of these complexes. Black-Right-Pointing-Pointer In

  14. Structure and electrical properties of a one-dimensional polymeric silver thiosaccharinate complex with argentophilic interactions.

    PubMed

    Dennehy, Mariana; Amo-Ochoa, Pilar; Freire, Eleonora; Suárez, Sebastián; Halac, Emilia; Baggio, Ricardo

    2018-02-01

    Among the potential applications of coordination polymers, electrical conductivity ranks high in technological interest. We report the synthesis, crystal structure and spectroscopic analysis of an Ag I -thiosaccharinate one-dimensional coordination polymer {systematic name: catena-poly[[[aquatetrakis(μ 3 -1,1-dioxo-1,2-benzisothiazole-3-thiolato-κ 3 N:S 3 :S 3 )tetrasilver(I)]-μ 2 -4,4'-(propane-1,3-diyl)dipyridine-κ 2 N:N'] dimethyl sulfoxide hemisolvate]}, {[Ag 4 (C 7 H 4 NO 2 S 2 ) 4 (C 13 H 14 N 2 )(H 2 O)]·0.5C 2 H 6 OS} n , with the 4,4'-(propane-1,3-diyl)dipyridine ligand acting as a spacer. A relevant feature of the structure is the presence of an unusually short Ag...Ag distance of 2.8306 (9) Å, well within the range of argentophilic interactions, confirmed experimentally as such by a Raman study on the low-frequency spectrum, and corroborated theoretically by an Atoms in Molecules (AIM) analysis of the calculated electron density. Electrical conductivity measurements show that this complex can act as a semiconductor with moderate conductivity.

  15. Luminescent zinc and cadmium complexes incorporating 1,3,5-benzenetricarboxylate and a protonated kinked organodiimine: From a hydrogen-bonded layer motif to thermally robust two-dimensional coordination polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Braverman, Maxwell A.; Supkowski, Ronald M.; LaDuca, Robert L.

    2007-06-15

    Hydrothermal treatment of zinc chloride, 1,3,5-benzenetricarboxylic acid (H{sub 3}BTC), and 4,4'-dipyridylamine (dpa) afforded two different complexes depending on reaction conditions, which were characterized by single-crystal X-ray diffraction, infrared spectroscopy, and elemental analysis. Under acidic conditions, a discrete neutral molecular species with formulation [Zn(HBTC){sub 2}(Hdpa){sub 2}] (1) was isolated, which aggregates into two-dimensional hydrogen-bonded layers. Under more basic conditions, the two-dimensional layered coordination polymer [Zn(BTC)(Hdpa)] (2) is obtained, which manifests covalent linkage of [Zn(BTC)(Hdpa)] serpentine chain motifs into 3-connected undulating 4.8{sup 2} topology 2-D layers. Both 1 and 2 possess tetrahedral coordination at Zn. Use of cadmium nitrate in the synthesismore » resulted in [Cd(BTC)(H{sub 2}O)(Hdpa)] (3), which displays a similar layer topology as 2 but with significant adjustments imparted by octahedral coordination at Cd. In all cases, supramolecular hydrogen bonding promoted by Hdpa ligands provide an important assistive structure-directing role. All materials display blue luminescence upon excitation with ultraviolet light, ascribed to intraligand transitions. Crystallographic data: 1: monoclinic, C2/c, a=25.389(6) A, b=9.811(2) A, c=17.309(4) A, and {beta}=128.957(3){sup o}, 2: monoclinic, P2{sub 1}/c, a=13.212(17)c, b=17.15(2) A, c=7.506(10) A, and {beta}=93.71(2){sup o}, and 3: monoclinic, C2/c, a=14.241(6) A, b=15.218(6) A, c=17.976(7) A, and {beta}=109.330(6){sup o}. - Graphical abstract: Hydrothermal synthesis has afforded a family of luminescent complexes based on divalent d {sup 10} cations with 1,3,5-benzenetricarboxylate (BTC) and 4,4'-dipyridylamine (dpa) ligands. [Zn(HBTC){sub 2}(Hdpa){sub 2}] (1) is a discrete neutral molecular species. [Zn(BTC)(Hdpa)] (2, pictured) and [Cd(BTC)(H{sub 2}O)(Hdpa)] (3) are 2-D coordination polymers with different morphologies depending on coordination

  16. Influence of biphenyl spacer appended to the flexible phosphonate arms in modulating the dimensionality of the coordination polymers: Synthesis, structural chemistry and magnetic properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tripuramallu, Bharat Kumar; Das, Samar K., E-mail: skdsc@uohyd.ernet.in

    2013-01-15

    Two new compounds [Co (2,2 Prime -bipy) (H{sub 2}dbp)]{sub n} (1) and [Ni (2,2 Prime -bipy){sub 2}(H{sub 2}dbp)(H{sub 2}O)]{center_dot}H{sub 2}O (2) based on the flexible ligand 4,4 Prime -dimethylenebiphenyldiphosphonic acid (H{sub 4}dbp) with 2,2 Prime -bipyridine as secondary ligand have been synthesized under hydrothermal conditions. Both the compounds are well characterized by routine elemental analysis, IR, electronic spectroscopies, thermogravimetric analysis and finally by single crystal X-ray diffraction analysis. Compound 1 is a 1D extended coordination polymer and 2 is a discrete molecular compound. A comparative study between the geometries of H{sub 4}dbp ligand (in compounds 1 and 2, present study)more » and p-xylylenediphosphonic acid (H{sub 4}pxp) ligand (in previously reported compounds [Cu(2,2 Prime -bipy)(H{sub 2}pxp)]{center_dot}nH{sub 2}O (1A) and Ni(2,2 Prime -bipy){sub 2}H{sub 4}pxp]{sub n}[H{sub 2}pxp]{sub n} (2A), see text) demonstrate the effect of the twisting in the benzene rings in changing higher dimensional H{sub x}pxp (x refers to number of protonated hydroxyl groups) compounds to lower dimensional H{sub x}dbp compounds. The eight membered Co-dimer rings formed in compound 1 represents the simple and isolated Co-dimer, exhibiting weak antiferromagnetic exchange between metal centers through OPO bridges. - Graphical abstract: Two new compounds based on the dimethylenebiphenyldiphosphonic acid have been synthesized. The effect of twisting of benzene rings in the biphenyl spacer containing multidentate ligands alters dimensionality of final compounds. Highlights: Black-Right-Pointing-Pointer Cobalt containing coordination polymer and a nickel discrete compound have been synthesized. Black-Right-Pointing-Pointer Flexible ligand 4,4'-dimethylenebiphenyldiphosphonic acid has been employed. Black-Right-Pointing-Pointer Co(II) and Ni(II) ions are square pyramidal and octahedral respectively. Black-Right-Pointing-Pointer The effect of the

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

    PubMed

    Wang, Cheng; Yang, Li; Chang, Guanjun

    2018-03-01

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

  18. 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.

    PubMed

    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.

  19. [2D correlation spectral study of a coordination polymer [Eu(PCPOA)3 (H2O)]n].

    PubMed

    Sun, Rui-qing; Zhang, Han-hui; Cao, Yan-ning; Chen, Yi-ping; Yang, Qi-yu; Wang, Zhi-yang

    2007-05-01

    A novel two dimensional coordination polymer [Eu(PCPOA)3 (H2O)], was synthesized under hydrothermal condition. Based on the determination of the structure, the 2D correlation FTIR spectra with the perturbation of magnetism and the 2D correlation fluorescence spectra with the perturbation of temperature were investigated. The energy bonds were calculated using CASTEP Program of Material studio. The Europium ions are nine-coordinated and the ligands adopted two different modes to connect the Eu3+ ions to 2D layer structure. The study of the 2D-FTIR reveals that the carboxylates coordinate with the center ions not only as monodentate, but also as bidentate chelate. The 2D fluorescence spectra indicates that the transition of (5)D0-->(7)F2 is influenced intensively by the perturbation of temperature.

  20. Metal-coordination: Using one of nature’s tricks to control soft material mechanics

    PubMed Central

    Holten-Andersen, Niels; Jaishankar, Aditya; Harrington, Matthew; Fullenkamp, Dominic E.; DiMarco, Genevieve; He, Lihong; McKinley, Gareth H.; Messersmith, Phillip B.; Lee, Ka Yee C.

    2015-01-01

    Growing evidence supports a critical role of dynamic metal-coordination crosslinking in soft biological material properties such as self-healing and underwater adhesion1. Using bio-inspired metal-coordinating polymers, initial efforts to mimic these properties have shown promise2. Here we demonstrate how bio-inspired aqueous polymer network mechanics can be easily controlled via metal-coordination crosslink dynamics; metal ion-based crosslink stability control allows aqueous polymer network relaxation times to be finely tuned over several orders of magnitude. In addition to further biological material insights, our demonstration of this compositional scaling mechanism should provide inspiration for new polymer material property-control designs. PMID:26413297

  1. Metal-Organic Framework-Polymer Composite as a Highly Efficient Sorbent for Sulfonamide Adsorption and Desorption: Effect of Coordinatively Unsaturated Metal Site and Topology.

    PubMed

    Shih, Yung-Han; Wang, Kuen-Yun; Singco, Brenda; Lin, Chia-Her; Huang, Hsi-Ya

    2016-11-08

    In this study, we first demonstrated the effect of two types of metal-organic framework-polymer (MOF-polymer) monoliths on in-tube solid-phase microextraction (IT-SPME) of sulfonamides. Sulfonamides were successfully adsorbed onto MIL-101(Cr)-polymer but were difficult to elute due to these sulfonamides could interact via Lewis acid-base interaction with the presence of Cr(III) coordinatively unsaturated metal sites (CUS). Moreover, the cage-type topology of MIL-101(Cr) that could produce multiple pathways thus complicates the desorption of the test analytes from the sorbent. Contrastingly, MIL-53(Al)-polymer provided weaker Al(III) CUS, and its one-dimensional channel pore structure could provide an unhindered pathway for sulfonamides transfer during elution. After optimizing the IT-SPME condition such as MOF content, pH of sample matrix, column length, extraction flow rate, and elution volume, the calculated extraction recovery of sulfonamides in MIL-53(Al)-polymer as analyzed by microemulsion electrokinetic chromatography (MEEKC) were in the range of 40%-90% with relative standard deviations (RSDs) below 5% and a reusability of at least 30 times.

  2. Syntheses, structures and characterization of isomorphous CoII and NiII coordination polymers based on 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole and benzene-1,4-dicarboxylate.

    PubMed

    Huang, Qiu Ying; Zhao, Yang; Meng, Xiang Ru

    2017-08-01

    Careful choice of the organic ligands is one of the most important parameters in the rational design and synthesis of coordination polymers. Aromatic polycarboxylates have been widely used in the preparation of metal-organic polymers since they can utilize various coordination modes to form diverse structures and can act as hydrogen-bond acceptors and donors in the assembly of supramolecular structures. Nitrogen-heterocyclic organic compounds have also been used extensively as ligands for the construction of polymers with interesting structures. In the polymers catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN 3 }cobalt(II)]-μ 2 -benzene-1,4-dicarboxylato-κ 2 O 1 :O 4 ] dihydrate], {[Co(C 8 H 4 O 4 )(C 12 H 11 N 4 ) 2 (H 2 O) 2 ]·2H 2 O} n , (I), and catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN 3 }nickel(II)]-μ 2 -benzene-1,4-dicarboxylato-κ 2 O 1 :O 4 ] dihydrate], {[Ni(C 8 H 4 O 4 )(C 12 H 11 N 4 ) 2 (H 2 O) 2 ]·2H 2 O} n , (II), the Co II or Ni II ion lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry, coordinated by two N atoms from two imidazole rings and four O atoms from two monodentate carboxylate groups and two water molecules. The dicarboxylate ligands bridge metal ions forming a polymeric chain. The 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole ligands coordinate to the Co II or Ni II centres in monodentate modes through an imidazole N atom and are pendant on opposite sides of the main chain. The two structures are isomorphous. In the crystal, the one-dimensional chains are further connected through O-H...O, O-H...N and N-H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviours and fluorescence properties of both polymers have been investigated.

  3. EXAFS study of some coordination polymers of copper

    NASA Astrophysics Data System (ADS)

    Deshpande, A. P.

    1995-02-01

    The EXAFS spectra for (1) azelaic acid bis phenyl hydrazide, (2) azelaic acid bis 2,4 dinitro phenyl hydrazide and (3) sebacic acid bis phenyl hydrazide coordination polymers of copper were obtained using the EXAFS facility of the Daresbury Laboratory. The EXAFS analysis revealed that copper is surrounded by four nitrogen and two oxygen atoms in the first coordination shell, while the second coordination shell consists of two carbon atoms. This information suggests the octahedral geometry for the repeating units of polymeric complexes, in contrast to the square planar geometry previously proposed.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. A two-dimensional bilayered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating 1,2-bis(pyridin-4-yl)ethene and 2,2'-(diazenediyl)dibenzoic acid.

    PubMed

    Liu, Lei-Lei; Zhou, Yan; Li, Ping; Tian, Jiang-Ya

    2014-02-01

    In poly[[μ2-1,2-bis(pyridin-4-yl)ethene-κ(2)N:N'][μ2-2,2'-(diazenediyl)dibenzoato-κ(3)O,O':O'']cadmium(II)], [Cd(C14H8N2O4)(C12H10N2)]n, the asymmetric unit contains one Cd(II) cation, one 2,2'-(diazenediyl)dibenzoate anion (denoted L(2-)) and one 1,2-bis(pyridin-4-yl)ethene ligand (denoted bpe). Each Cd(II) centre is six-coordinated by four O atoms of bridging/chelating carboxylate groups from three L(2-) ligands and by two N atoms from two bpe ligands, forming a distorted octahedron. The Cd(II) cations are bridged by L(2-) and bpe ligands to give a two-dimensional (4,4) layer. The layers are interlinked through bridging carboxylate O atoms from L(2-) ligands, generating a two-dimensional bilayered structure with a 3(6)4(13)6(2) topology. The bilayered structures are further extended to form a three-dimensional supramolecular architecture via a combination of hydrogen-bonding and aromatic stacking interactions.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN

    2014-04-01

    Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln{sub 2}(Hpdc){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 4}]{sub n}·2nH{sub 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{sub 3}pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H{sub 3}pdc was decomposed into (ox){sup 2−} with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2{sub 1}/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groupsmore » 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{sub 3}pdc was decomposed into (ox){sup 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Arıcı, Mürsel; Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr; Keskin, Seda

    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 complexmore » 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.« less

  8. Silver(I) coordination polymers assembled from flexible cyclotriphosphazene ligand: structures, topologies and investigation of the counteranion effects.

    PubMed

    Davarcı, Derya; Gür, Rüştü; Beşli, Serap; Şenkuytu, Elif; Zorlu, Yunus

    2016-06-01

    The reactions of a flexible ligand hexakis(3-pyridyloxy)cyclotriphosphazene (HPCP) with a variety of silver(I) salts (AgX; X = NO3(-), PF6(-), ClO4(-), CH3PhSO3(-), BF4(-) and CF3SO3(-)) afforded six silver(I) coordination polymers, namely {[Ag2(HPCP)]·(NO3)2·H2O}n (1), {[Ag2(HPCP)(CH3CN)]·(PF6)2}n (2), {[Ag2(HPCP)(CH3CN)]·(ClO4)2}n (3), [Ag3(HPCP)(CH3PhSO3)3]n (4), [Ag2(HPCP)(CH3CN)(BF4)2]n (5) and {[Ag(HPCP)]·(CF3SO3)}n (6). All of the isolated crystalline compounds were structurally determined by X-ray crystallography. Changing the counteranions in the reactions, which were conducted under similar conditions of M/L ratio (1:1), temperature and solvent, resulted in structures with different types of topologies. In complexes (1)-(6), the ligand HPCP shows different coordination modes with Ag(I) ions giving two-dimensional layered structures and three-dimensional frameworks with different topologies. Complex (1) displays a new three-dimensional framework adopting a (3,3,6)-connected 3-nodal net with point symbol {4.6(2)}2{4(2).6(10).8(3)}. Complexes (2) and (3) are isomorphous and have a two-dimensional layered structure showing the same 3,6L60 topology with point symbol {4.2(6)}2{4(8).6(6).8}. Complex (4) is a two-dimensional structure incorporating short Ag...Ag argentophilic interactions and has a uninodal 4-connected sql/Shubnikov tetragonal plane net with {4(4).6(2)} topology. Complex (5) exhibits a novel three-dimensional framework and more suprisingly contains twofold interpenetrated honeycomb-like networks, in which the single net has a trinodal (2,3,5)-connected 3-nodal net with point symbol {6(3).8(6).12}{6(3)}{8}. Complex (6) crystallizes in a trigonal crystal system with the space group R\\bar 3 and possesses a three-dimensional polymeric structure showing a binodal (4,6)-connected fsh net with the point symbol (4(3).6(3))2.(4(6).6(6).8(3)). The effect of the counteranions on the formation of coordination polymers is discussed in this study.

  9. Zinc(II) and Cadmium(II) coordination polymers constructed from phenylenediacetate ligands

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sezer, Güneş Günay; Department of Chemistry, Eskişehir Osmangazi University, Eskişehir; Yeşilel, Okan Zafer

    ABSTRACT: A series of new coordination polymers {[Zn(μ-opda)(μ-bpa)]·2H_2O}{sub n} (1), [Zn(μ{sub 3}-ppda)(μ-bpa)]{sub n} (2), [Cd(μ{sub 3}-ppda)(μ-bpa)]{sub n} (3), [Cd(μ{sub 3}-mpda)(μ-bpa)]{sub n} (4) and [Cd(μ{sub 3}-mpda)(μ-bipy)]{sub n} (5), (o/m/ppda=1,2/1,3/1,4-phenylenediacetate, bpa=1,2-bi(4-pyridyl)ethane, bipy=4,4′-bipyridine) were synthesized. Their structures were characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. Furthermore, the effect of metal sources (zinc acetate and zinc oxide) and acidity of the solution on the structure of the coordination polymers was discussed for complexes 1 and 5, respectively. The single-crystal X-ray crystallographic studies revealed that complexes 1, 3, 4 and 5 are uninodal (4)-connected 2D frameworks and display sql topology withmore » the point symbol of (4{sup 4}.6{sup 2}). Complex 2 is 3D coordination polymer and exhibits pcu topology with the point symbol of (4{sup 12}.6{sup 3}). In addition, the luminescent properties and thermal behavior of all complexes were also investigated. - Graphical abstract: Scheme 1. Topologies of Coordination Polymers Reported in This Paper.« less

  10. Coordination-supported organic polymers: mesoporous inorganic–organic materials with preferred stability

    DOE PAGES

    Chen, Dong; Zhang, Pengfei; Fang, Qianrong; ...

    2018-01-01

    A simple and versatile strategy is developed for the synthesis of coordination-supported organic polymers(COPs) via coordination between Al 3+ and 5-amino-8-hydroxyquinoline together with organic imine- or imide-based polycondensation.

  11. Coordination-supported organic polymers: mesoporous inorganic–organic materials with preferred stability

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Dong; Zhang, Pengfei; Fang, Qianrong

    A simple and versatile strategy is developed for the synthesis of coordination-supported organic polymers(COPs) via coordination between Al 3+ and 5-amino-8-hydroxyquinoline together with organic imine- or imide-based polycondensation.

  12. Mixing of immiscible polymers using nanoporous coordination templates

    NASA Astrophysics Data System (ADS)

    Uemura, Takashi; Kaseda, Tetsuya; Sasaki, Yotaro; Inukai, Munehiro; Toriyama, Takaaki; Takahara, Atsushi; Jinnai, Hiroshi; Kitagawa, Susumu

    2015-07-01

    The establishment of methodologies for the mixing of immiscible substances is highly desirable to facilitate the development of fundamental science and materials technology. Herein we describe a new protocol for the compatibilization of immiscible polymers at the molecular level using porous coordination polymers (PCPs) as removable templates. In this process, the typical immiscible polymer pair of polystyrene (PSt) and poly(methyl methacrylate) (PMMA) was prepared via the successive homopolymerizations of their monomers in a PCP to distribute the polymers inside the PCP particles. Subsequent dissolution of the PCP frameworks in a chelator solution affords a PSt/PMMA blend that is homogeneous in the range of several nanometers. Due to the unusual compatibilization, the thermal properties of the polymer blend are remarkably improved compared with the conventional solvent-cast blend. This method is also applicable to the compatibilization of PSt and polyacrylonitrile, which have very different solubility parameters.

  13. Syntheses, structures and luminescent properties of a series of 3D lanthanide coordination polymers with tripodal semirigid ligand

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Qin Junsheng; Department of Applied Chemistry, Jilin Institute of Chemical Technology, Jilin 132022; Du Dongying

    2011-02-15

    Reactions of the tripodal bridging ligand 5-(4-carboxy-phenoxy)-isophthalic acid (abbreviated as H{sub 3}cpia) with lanthanide salts lead to the formation of a family of different coordination polymers, that is, [Ln(cpia)(H{sub 2}O){sub 2}]{sub n}.nH{sub 2}O (Ln=Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Dy (7), Er (8), Tm (9) and Y (10)) in the presence of formic acid or diethylamine, which are characterized by elemental analysis, IR spectrum, thermogravimetric analysis (TGA), XRPD spectrum and single-crystal X-ray diffraction. Compounds 1-10 are isostructural and exhibit three-dimensional microporous frameworks. Furthermore, the photoluminescent properties of 4, 5 and 7 have been studiedmore » in detail. -- Graphical abstract: Reactions of the tripodal bridging ligand (H{sub 3}cpia) with lanthanide ions lead to the formation of a series of coordination polymers in the presence of formic acid or diethylamine. Display Omitted Research Highlights: {yields} Ten new lanthanides-based coordination polymers (1-10) have been synthesized. {yields} 1-10 exhibit 3D (4,8)-connected fluorite topology networks with 1D channel parallel to the b-axis. {yields} Compounds 4, 5 and 7 exhibit characteristic luminescence of Sm{sup 3+}, Eu{sup 3+} and Dy{sup 3+} ions, respectively.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Feng, Xun; Liu, Lang; College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022

    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 casemore » 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    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 ismore » 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.« less

  16. Two-dimensional correlation spectroscopy in polymer study

    PubMed Central

    Park, Yeonju; Noda, Isao; Jung, Young Mee

    2015-01-01

    This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation. The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted. PMID:25815286

  17. Investigating the geometrical preferences of a flexible benzimidazolone-based linker in the synthesis of coordination polymers

    PubMed Central

    Jones, Corey L.; Marsden, Elizabeth A.; Nevin, Adam C.; Kariuki, Benson M.; Bhadbhade, Mohan M.; Martin, Adam D.

    2017-01-01

    A series of new group 2 coordination polymers, MgL ={MgL(H2O)(DMF)0.75}∞, CaL = {CaL(DMF)2}∞, SrL = {SrL(H2O)0.5}∞ and BaL = {BaL(H2O)0.5}∞, were synthesized using a flexible benzimidazolone diacetic acid linker (H2L) in which the two carboxylic acid binding sites are connected to a planar core via {–CH2–} spacers that can freely rotate in solution. In a ‘curiosity-led' diversion from group 2 metals, the first row transition metal salts Mn2+, Cu2+ and Zn2+ were also reacted with L to yield crystals of MnL = {MnL(DMF)(H2O)3.33}∞, Cu3L2 = {Cu3L2(DMF)2(CHO2)2}∞ and ZnL = {ZnL(DMF)}∞. Crystal structures were obtained for all seven materials. All structures form as two-dimensional sheets and contain six-coordinate centres, with the exception of ZnL, which displays tetrahedrally coordinated metal centres, and Cu3L2, which contains square planar coordinated metal centres and Cu paddle-wheels. In each structure, the linker adopts one of two distinct conformations, with the carboxylate groups either cis or trans with respect to the planar core. All materials were also characterized by powder X-ray diffraction and thermogravimetric analysis. PMID:29308246

  18. A new 1D manganese(II) coordination polymer with end-to-end azide bridge and isonicotinoylhydrazone Schiff base ligand: Crystal structure, Hirshfeld surface, NBO and thermal analyses

    NASA Astrophysics Data System (ADS)

    Khani, S.; Montazerozohori, M.; Masoudiasl, A.; White, J. M.

    2018-02-01

    A new manganese (II) coordination polymer, [MnL2 (μ-1,3-N3)2]n, with co-ligands including azide anion and Schiff base based on isonicotinoylhydrazone has been synthesized and characterized. The crystal structure determination shows that the azide ligand acts as end-to-end (EE) bridging ligand and generates a one-dimensional coordination polymer. In this compound, each manganes (II) metal center is hexa-coordinated by four azide nitrogens and two pyridinic nitrogens for the formation of octahedral geometry. The analysis of crystal packing indicates that the 1D chain of [MnL2 (μ-1,3-N3)2]n, is stabilized as a 3D supramolecular network by intra- and inter-chain intermolecular interactions of X-H···Y (X = N and C, Y = O and N). Hirshfeld surface analysis and 2D fingerprint plots have been used for a more detailed investigation of intermolecular interactions. Also, natural bond orbital (NBO) analysis was performed to get information about atomic charge distributions, hybridizations and the strength of interactions. Finally, thermal analysis of compound showed its complete decomposition during three thermal steps.

  19. Structural diversification and photocatalytic properties of three Cd(II) coordination polymers decorated with different auxiliary ligands

    NASA Astrophysics Data System (ADS)

    Yin, Wen-Yu; Zhuang, Guo-Yong; Huang, Zuo-Long; Cheng, Hong-Jian; Zhou, Li; Ma, Man-Hong; Wang, Hao; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin

    2016-03-01

    Three cadmium coordination polymers, [Cd(bismip)]n (1), {[Cd(bismip)(phen)]·H2O}n (2) and {[Cd2(bismip)2(4,4‧-bipy)]·2H2O}n (3) (H2bismip=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 [Cd4(bismip)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 (4·82)(42·84) 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.

  20. Rare earth niobate coordination polymers

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. One-dimensional ferromagnetic array compound [Co3(SBA)2(OH)2(H2O)2]n, (SBA = 4-sulfobenzoate)

    NASA Astrophysics Data System (ADS)

    Honda, Zentaro; Nomoto, Naoyuki; Fujihara, Takashi; Hagiwara, Masayuki; Kida, Takanori; Sawada, Yuya; Fukuda, Takeshi; Kamata, Norihiko

    2018-06-01

    We report on the syntheses, crystal structure, and magnetic properties of the transition metal coordination polymer [Co3(SBA)2(OH)2(H2O)2]n, (SBA = 4-sulfobenzoate) in which CoO6 octahedra are linked through their edges, forming one-dimensional (1D) Co(II) arrays running along the crystal a-axis. These arrays are further perpendicularly bridged by SBA ligand to construct a three-dimensional framework. Its magnetic properties have been investigated, and ferromagnetic interactions within the arrays have been found. From heat capacity measurements, we have found that this compound exhibits a three-dimensional ferromagnetic phase transition at TC = 1.54 K, and the specific heat just above TC shows a Schottky anomaly which originates from an energy gap caused by uniaxial magnetic anisotropy. These results suggest that [Co3(SBA)2(OH)2(H2O)2]n consists of weakly coupled 1D ferromagnetic Ising arrays.

  3. Sonochemical synthesis and structural characterization of a new nanostructured Co(II) supramolecular coordination polymer with Lewis base sites as a new catalyst for Knoevenagel condensation.

    PubMed

    Joharian, Monika; Abedi, Sedigheh; Morsali, Ali

    2017-11-01

    A new Co(II) mixed-ligand coordination supramolecular polymer with composition [Co 2 (ppda)(4-bpdh) 2 (NO 3 ) 2 ] n (1) (where, ppda=p-phenylenediacrylic acid, 4-bpdh=2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) was synthesized using solvothermal, mechanochemical and sonochemical methods. Compound 1 and the new nanostructure have been characterized by single-crystal X-ray, infrared spectroscopy (IR), powder X-ray diffraction (PXRD) analysis and scanning electron microscopy (SEM). The thermal stability of compound 1 was also studied by thermal gravimetric analysis (TGA). The surface area of these compounds was determined by BET. The single-crystal X-ray data shows a new interesting two-dimensional coordination polymer (CP). In addition, the effect of various sonication concentrations of initial reagents, power of ultrasound irradiation and also the time on the size and morphology of nano-structured coordination polymer 1 were evaluated. Moreover, it has been demonstrated that the nanostructure of the CP1 can be used as a catalyst in Knoevenagel condensation reaction. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Dimensional coordinate measurements: application in characterizing cervical spine motion

    NASA Astrophysics Data System (ADS)

    Zheng, Weilong; Li, Linan; Wang, Shibin; Wang, Zhiyong; Shi, Nianke; Xue, Yuan

    2014-06-01

    Cervical spine as a complicated part in the human body, the form of its movement is diverse. The movements of the segments of vertebrae are three-dimensional, and it is reflected in the changes of the angle between two joint and the displacement in different directions. Under normal conditions, cervical can flex, extend, lateral flex and rotate. For there is no relative motion between measuring marks fixed on one segment of cervical vertebra, the cervical vertebrae with three marked points can be seen as a body. Body's motion in space can be decomposed into translational movement and rotational movement around a base point .This study concerns the calculation of dimensional coordinate of the marked points pasted to the human body's cervical spine by an optical method. Afterward, these measures will allow the calculation of motion parameters for every spine segment. For this study, we choose a three-dimensional measurement method based on binocular stereo vision. The object with marked points is placed in front of the CCD camera. Through each shot, we will get there two parallax images taken from different cameras. According to the principle of binocular vision we can be realized three-dimensional measurements. Cameras are erected parallelly. This paper describes the layout of experimental system and a mathematical model to get the coordinates.

  5. Coordination polymer-derived nano-sized zinc ferrite with excellent performance in nitro-explosive detection.

    PubMed

    Singha, Debal Kanti; Mahata, Partha

    2017-08-29

    Herein, a mixed metal coordination polymer, {(H 2 pip)[Zn 1/3 Fe 2/3 (pydc-2,5) 2 (H 2 O)]·2H 2 O} 1 {where H 2 pip = piperazinediium and pydc-2,5 = pyridine-2,5-dicarboxylate}, was successfully synthesized using a hydrothermal technique. To confirm the structure and phase purity of 1, single crystals of an isomorphous pure Fe compound, {(H 2 pip)[Fe(pydc-2,5) 2 (H 2 O)]·2H 2 O} 1a, were synthesized based on similar synthetic conditions. Single crystal X-ray data of 1a confirmed the one-dimensional anionic metal-organic coordination polymer hydrogen bonded with protonated piprazine (piperazinediium) and lattice water molecules. The phase purity of 1 and 1a were confirmed via powder X-ray diffraction. Compound 1 was systematically characterized using IR, TGA, SEM, and EDX elemental mapping analysis. Compound 1 was used as a single source precursor for the preparation of nano-sized ZnFe 2 O 4 via thermal decomposition. The as-obtained ZnFe 2 O 4 was fully characterized using PXRD, SEM, TEM, and EDX elemental mapping analysis. It was found that ZnFe 2 O 4 was formed in its pure form with particle size in the nano-dimension. The aqueous dispersion of nano-sized ZnFe 2 O 4 exhibits a strong emission at 402 nm upon excitation at 310 nm. This emissive property was employed for luminescence-based detection of nitroaromatic explosives in an aqueous medium through luminescence quenching for the first time. Importantly, selective detections have been observed for phenolic nitroaromatics based on differential luminescence quenching behaviour along with a detection limit of 57 ppb for 2,4,6-trinitrophenol (TNP) in water.

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

    PubMed

    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.

  7. Metal coordination polymer derived mesoporous Co3O4 nanorods with uniform TiO2 coating as advanced anodes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Geng, Hongbo; Ang, Huixiang; Ding, Xianguang; Tan, Huiteng; Guo, Guile; Qu, Genlong; Yang, Yonggang; Zheng, Junwei; Yan, Qingyu; Gu, Hongwei

    2016-01-01

    In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural stability during cycling.In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural

  8. Mixed ligand coordination polymers with flexible bis-imidazole linker and angular sulfonyldibenzoate: Crystal structure, photoluminescence and photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Bisht, Kamal Kumar; Rachuri, Yadagiri; Parmar, Bhavesh; Suresh, Eringathodi

    2014-05-01

    Four ternary coordination polymers (CPs) namely, {[Ni(SDB)(BITMB)(H2O)]·H2O}n (CP1), {[Cd(SDB)(BITMB) (H2O)]·(THF)(H2O)}n (CP2), {[Zn2(SDB)2(BITMB)]·(THF)2}n (CP3) and {[Co2(SDB)2(BITMB)]·(Dioxane)3}n (CP4) composed of angular dicarboxylate SDB (4,4'-sulfonyldibenzoate) and N-donor BITMB (1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethyl benzene) have been synthesized by solvothermal reactions and characterized by single crystal X-ray diffraction and other physico-chemical techniques. CP1 possesses one-dimensional ribbon type metal-organic motifs glued together by H-bonds and π⋯π interactions, whereas CP2-CP4, exhibit non-interpenetrated sql networks supported by weak supramolecular interactions. Structural diversity of these CPs can be attributed to the coordination geometry adopted by the metal nodes, versatile coordination modes of SDB and conformational flexibility of BITMB. Solid state luminescence properties of CP1-CP4 were explored. Photocatalytic performance of all CPs for the decomposition of metanil yellow by dilute hydrogen peroxide in the presence of visible light was also investigated. 25-83% dye removal from aqueous solutions in the presence of CP1-CP4 was observed.

  9. Controlled Interactions between Two Dimensional Layered Inorganic Nanosheets and Polymers

    DTIC Science & Technology

    2016-06-15

    with end-functionalized polymers . First, an end-functionalized polymer with conjugated end-molecule, pyrene, is successfully employed to boron... polymers . First, an end-functionalized polymer with conjugated end-molecule, pyrenes, is successfully employed to boron nitride nanosheets (BNNS), and...AFRL-AFOSR-JP-TR-2016-0071 Controlled Interactions between Two Dimensional Layered Inorganic Nanosheets and Polymers Cheolmin Park YONSEI UNIVERSITY

  10. Self-consistent field theory of tethered polymers: one dimensional, three dimensional, strong stretching theories and the effects of excluded-volume-only interactions.

    PubMed

    Suo, Tongchuan; Whitmore, Mark D

    2014-11-28

    We examine end-tethered polymers in good solvents, using one- and three-dimensional self-consistent field theory, and strong stretching theories. We also discuss different tethering scenarios, namely, mobile tethers, fixed but random ones, and fixed but ordered ones, and the effects and important limitations of including only binary interactions (excluded volume terms). We find that there is a "mushroom" regime in which the layer thickness is independent of the tethering density, σ, for systems with ordered tethers, but we argue that there is no such plateau for mobile or disordered anchors, nor is there one in the 1D theory. In the other limit of brushes, all approaches predict that the layer thickness scales linearly with N. However, the σ(1/3) scaling is a result of keeping only excluded volume interactions: when the full potential is included, the dependence is faster and more complicated than σ(1/3). In fact, there does not appear to be any regime in which the layer thickness scales in the combination Nσ(1/3). We also compare the results for two different solvents with each other, and with earlier Θ solvent results.

  11. Rare Earth coordination polymers with zeolite topology constructed from 4-connected building units.

    PubMed

    Guo, Xiaodan; Zhu, Guangshan; Li, Zhongyue; Chen, Yan; Li, Xiaotian; Qiu, Shilun

    2006-05-15

    A series of rare earth coordination polymers, M(BTC)(DMF)(DMSO) (M = Tb (1), Ho (2), Er (3), Yb (4), Y (5)), with zeolite ABW topology have been synthesized under mild conditions. They exhibit the same three-dimensional (3D) architecture and crystallize in monoclinic symmetry space group P2(1)/n. Their structures are built up from inorganic and organic 4-connected building units, whose vertex symbols are 4.4.6.6.6.8. The building units link to each other to generate approximate 5 x 8 angstroms2 channels along the [100] direction. The luminescent and magnetic properties of these compounds are investigated, and the results reveal that they could be anticipated to be potential antiferromagnetic and fluorescent materials.

  12. Structure and topology of three-dimensional hydrocarbon polymers.

    PubMed

    Kondrin, Mikhail V; Lebed, Yulia B; Brazhkin, Vadim V

    2016-08-01

    A new family of three-dimensional hydrocarbon polymers which are more energetically favorable than benzene is proposed. Although structurally these polymers are closely related to well known diamond and lonsdaleite carbon structures, using topological arguments we demonstrate that they have no known structural analogs. Topological considerations also give some indication of possible methods of synthesis. Taking into account their exceptional optical, structural and mechanical properties these polymers might have interesting applications.

  13. Rare earth niobate coordination polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Muniz, Collin N.; Patel, Hiral; Fast, Dylan B.

    Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. In this paper we described the synthesis of a heterometallic rare-earth coordination compound ((CH 3) 2SO) 3(RE)NbO(C 2O 4) 3 ((CH 3) 2SO) = dimethylsulfoxide, DMSO, (C 2O 2 = 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 themore » 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. Finally, 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.« less

  14. Rare earth niobate coordination polymers

    DOE PAGES

    Muniz, Collin N.; Patel, Hiral; Fast, Dylan B.; ...

    2018-01-03

    Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. In this paper we described the synthesis of a heterometallic rare-earth coordination compound ((CH 3) 2SO) 3(RE)NbO(C 2O 4) 3 ((CH 3) 2SO) = dimethylsulfoxide, DMSO, (C 2O 2 = 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 themore » 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. Finally, 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.« less

  15. Group 10 Metal Benzene-1,2-dithiolate Derivatives in the Synthesis of Coordination Polymers Containing Potassium Countercations.

    PubMed

    Castillo, Oscar; Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martín, Avelino; Martínez, José I; Zamora, Félix

    2017-10-02

    The use of theoretical calculations has allowed us to predict the coordination behavior of dithiolene [M(SC 6 H 4 S) 2 ] 2- (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K 2 (μ-H 2 O) 2 ][Ni(SC 6 H 4 S) 2 ]} n and {[K 2 (μ-H 2 O) 2 (thf)] 2 [K 2 (μ-H 2 O) 2 (thf) 2 ][Pd 3 (SC 6 H 4 S) 6 ]} n by one-pot reactions of the corresponding d 10 metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on σ,π interactions between potassium atoms and [M(SC 6 H 4 S) 2 ] 2- (M = Ni, Pd) entities. In contrast, only σ interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K 2 (μ-thf) 2 ][Pt(SC 6 H 4 S) 2 ]} n .

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

    PubMed

    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.

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

    DOEpatents

    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.

  18. Design and its limitations in the construction of bi- and poly-nuclear coordination complexes and coordination polymers (aka MOFs): a personal view.

    PubMed

    Robson, R

    2008-10-14

    This article, presented from a personal point of view, is concerned with the design of ligands intended to give specifically either binuclear or tetranuclear metal complexes or coordination polymers. No attempt is made to provide a comprehensive coverage of these topics, the focus being mainly upon results from our laboratory. Some emphasis is placed upon aspects of the historical development of the deliberate construction of coordination polymers (aka MOFs)--materials promising useful applications, the study of which continues to expand exponentially. Some of our recent research is described in which the carbonate ion and the tetracyanoquinodimethane dianion are used as bridging ligands to generate targeted coordination polymers. It is intended that Dalton Perspectives be easily comprehensible to non-specialists in the field; an average second year university chemistry student should be easily able to understand the present contribution.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lytvynenko, Anton S.; Kiskin, Mikhail A., E-mail: mkiskin@igic.ras.ru; Dorofeeva, Victoria N.

    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 Lmore » 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni

    2014-07-01

    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{sub 2}(H{sub 2}O){sub 2}]{sub n}·2nH{sub 2}O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H{sub 2}adbc), terephthalic acid (H{sub 2}tpa), thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) and 1,4-benzenedithioacetic acid (H{sub 2}bdtc), four 3D structures [Co{sub 2}L{sub 2}(adbc)]{sub n}·nH{sub 2}O (2), [Co{sub 2}L{sub 2}(tpa)]{sub n}more » (3), [Co{sub 2}L{sub 2}(tdc)]{sub n} (4), [Co{sub 2}L{sub 2}(bdtc)(H{sub 2}O)]{sub 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.« less

  1. Two-dimensional dynamics of elasto-inertial turbulence and its role in polymer drag reduction

    NASA Astrophysics Data System (ADS)

    Sid, S.; Terrapon, V. E.; Dubief, Y.

    2018-02-01

    The goal of the present study is threefold: (i) to demonstrate the two-dimensional nature of the elasto-inertial instability in elasto-inertial turbulence (EIT), (ii) to identify the role of the bidimensional instability in three-dimensional EIT flows, and (iii) to establish the role of the small elastic scales in the mechanism of self-sustained EIT. Direct numerical simulations of viscoelastic fluid flows are performed in both two- and three-dimensional straight periodic channels using the Peterlin finitely extensible nonlinear elastic model (FENE-P). The Reynolds number is set to Reτ=85 , which is subcritical for two-dimensional flows but beyond the transition for three-dimensional ones. The polymer properties selected correspond to those of typical dilute polymer solutions, and two moderate Weissenberg numbers, Wiτ=40 ,100 , are considered. The simulation results show that sustained turbulence can be observed in two-dimensional subcritical flows, confirming the existence of a bidimensional elasto-inertial instability. The same type of instability is also observed in three-dimensional simulations where both Newtonian and elasto-inertial turbulent structures coexist. Depending on the Wi number, one type of structure can dominate and drive the flow. For large Wi values, the elasto-inertial instability tends to prevail over the Newtonian turbulence. This statement is supported by (i) the absence of typical Newtonian near-wall vortices and (ii) strong similarities between two- and three-dimensional flows when considering larger Wi numbers. The role of small elastic scales is investigated by introducing global artificial diffusion (GAD) in the hyperbolic transport equation for polymers. The aim is to measure how the flow reacts when the smallest elastic scales are progressively filtered out. The study results show that the introduction of large polymer diffusion in the system strongly damps a significant part of the elastic scales that are necessary to feed

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Meundaeng, Natthaya; Rujiwatra, Apinpus; Prior, Timothy J., E-mail: t.prior@hull.ac.uk

    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 2more » 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.« less

  3. Co-assembly of Zn(SPh){sub 2} and organic linkers into helical and zig-zag polymer chains

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu Yi; Yu Lingmin; Loo, Say Chye Joachim

    2012-07-15

    Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (EG=ethylene glycol) (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized under solvothermal conditions at 150 Degree-Sign C or room temperature by the co-assembly of Zn(SPh){sub 2} and organic linkers such as 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPyTA) and 1,3-bis(trans-4-pyridylvinyl)benzene (BPyVB). X-ray crystallography study reveals that both polymers 1 and 2 crystallize in space group P2{sub 1}/c of the monoclinic system. The solid-state UV-vis absorption spectra show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up tomore » 110 Degree-Sign C and 210 Degree-Sign C. - Graphical abstract: Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized. Solid-state UV-vis absorptions show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up to 110 Degree-Sign C and 210 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Two novel one-dimensional coordination polymers have been synthesized. Black-Right-Pointing-Pointer TPyTA results in helical structures in 1 while BPyVB leads to zig-zag chains in 2. Black-Right-Pointing-Pointer Solid-state UV-vis absorption spectra and TGA analysis of the title polymers were studied.« less

  4. Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics

    PubMed Central

    Grindy, Scott C.; Learsch, Robert; Mozhdehi, Davoud; Cheng, Jing; Barrett, Devin G.; Guan, Zhibin; Messersmith, Phillip B.; Holten-Andersen, Niels

    2015-01-01

    In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design1. Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the relative concentration of two types of metal-ligand crosslinks, we demonstrate control over the material’s mechanical hierarchy of energy-dissipating modes under dynamic mechanical loading, and therefore the ability to engineer a priori the viscoelastic properties of these materials by controlling the types of crosslinks rather than by modifying the polymer itself. This strategy to decouple material mechanics from structure may inform the design of soft materials for use in complex mechanical environments. PMID:26322715

  5. Fluorescent nanoscale zinc(II)-carboxylate coordination polymers for explosive sensing.

    PubMed

    Zhang, Chengyi; Che, Yanke; Zhang, Zengxing; Yang, Xiaomei; Zang, Ling

    2011-02-28

    Fluorescent nanoscale coordination polymers with cubic morphology and long range ordered structure were fabricated and exhibited efficient sensing for both nitroaromatic explosive and nitromethane due to large surface area to volume ratio and strong binding affinity to explosive molecules.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lun, Huijie; Yang, Jinghe; Jin, Linyu

    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 antiferromagneticmore » 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.« less

  7. 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid as linker for Co(II)/Ni(II)/Cu(II) coordination polymers: Synthesis, structures and properties

    NASA Astrophysics Data System (ADS)

    Wang, Duo-Zhi; Wang, Xin-Fang; Du, Jia-Qiang; Dong, Jun-Liang; Xie, Fei

    2018-02-01

    We report the synthesis and characterization of five transition metal coordination polymers (CPs) based on M(II) (M: Co, Ni and Cu), 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid (H2L) ligand. They are formulated as {[Co2(HL)2(H2O)3(SO4)]·H2O}n (1), {[Co2(HL)2(H2O)2]·SiF6}n (2), {[Ni2(HL)2(H2O)3(SO4)]·2H2O}n (3), {[Ni2(HL)2(H2O)4]·H2O·SiF6}n (4), {[Cu2(HL)2(H2O)2]·SiF6}n (5). The complexes 1-5 structure were characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Complexes 1-5 are two-dimensional (2D) network type coordination polymers that 1-3, 5 crystallize in monoclinic system within the centrosymmetric space group P2(1)/c, and 4 in triclinic system P-1 space group, they show the same coordination modes (κ1-κ1)-(κ1)-(κ1)-μ3 in coordination polymers. Complexes 1 and 3 expand to three-dimensional framework by means of hydrogen bond interactions, and can be rationalized to be three-connected {63} topological network, while 2, 4, 5 exhibit the topological network with a four-connected {44·62} topological sql network. The luminescent properties (for complexes 1, 2) and UV diffuse reflectance (for complexes 1-5) in the solid state at room temperature were also investigated and discussed. Complexes 1-5 act as effective heterogeneous catalysts, under mild conditions, for the homocoupling reaction of 4-substituted aryl iodides bearing electron-donating groups (-CH3, -OCH3).

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Qin, Ling, E-mail: qinling@hfut.edu.cn; Jiangsu Engineering Technology Research Center of Environmental Cleaning Materials; State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093

    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 polymersmore » 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.« less

  9. Second order symmetry-preserving conservative Lagrangian scheme for compressible Euler equations in two-dimensional cylindrical coordinates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Cheng, Juan, E-mail: cheng_juan@iapcm.ac.cn; Shu, Chi-Wang, E-mail: shu@dam.brown.edu

    In applications such as astrophysics and inertial confinement fusion, there are many three-dimensional cylindrical-symmetric multi-material problems which are usually simulated by Lagrangian schemes in the two-dimensional cylindrical coordinates. For this type of simulation, a critical issue for the schemes is to keep spherical symmetry in the cylindrical coordinate system if the original physical problem has this symmetry. In the past decades, several Lagrangian schemes with such symmetry property have been developed, but all of them are only first order accurate. In this paper, we develop a second order cell-centered Lagrangian scheme for solving compressible Euler equations in cylindrical coordinates, basedmore » on the control volume discretizations, which is designed to have uniformly second order accuracy and capability to preserve one-dimensional spherical symmetry in a two-dimensional cylindrical geometry when computed on an equal-angle-zoned initial grid. The scheme maintains several good properties such as conservation for mass, momentum and total energy, and the geometric conservation law. Several two-dimensional numerical examples in cylindrical coordinates are presented to demonstrate the good performance of the scheme in terms of accuracy, symmetry, non-oscillation and robustness. The advantage of higher order accuracy is demonstrated in these examples.« less

  10. Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis.

    PubMed

    Zhang, Pengfei; Yang, Shize; Chisholm, Matthew F; Jiang, Xueguang; Huang, Caili; Dai, Sheng

    2017-07-26

    The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognized as a barrier hampering their practical applications. Here, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100 °C, 24 h) and air (up to 390 °C) is presented. The bifunctional 1-vinylimidazole (VIm) with a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches through a coordination process at room temperature, followed by a radical polymerization. We refer to this material as coordination-supported imidazolate networks (CINs). Interestingly, CINs are composed of rich mesopores from 2-15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. In particular, the stable CINs illustrate a high turnover frequency (TOF) of 779 h -1 in the catalytic oxidation of phenol with H 2 O as the green solvent. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis

    DOE PAGES

    Zhang, Pengfei; Yang, Shize; Chisholm, Matthew F.; ...

    2017-05-29

    The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognised as a barrier hampering their practical applications. Herein, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100°C, 24 h) and air (up to 390°C) is presented. The bifunctional 1-vinylimidazole (VIm) with both a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches via a coordination process at room temperature, followed by a radical polymerization. Here we callmore » this material Coordination-supported Imidazolate Networks (CINs). Interestingly, CINs are composed of rich mesopores from 2 to 15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. Especially, the stable CINs illustrate a high turnover frequency (TOF) of 779 h -1 in the catalytic oxidation of phenol with H 2O as the green solvent.« less

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

    PubMed

    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.

  13. Synthesis, structure, and luminescence property of a series of Ag–Ln coordination polymers with the N-heterocyclic carboxylato ligand

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jin, Jing, E-mail: jinjing_crystal@126.com; Chen, Chong; Gao, Yan

    Six Ln–Ag coordination polymers {[LnAg_2(IN)_4(H_2O)_5]·NO_3·2H_2O}{sub n} (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg_2(IN)_4(H_2O)_2]·NO_3·H_2O}{sub n} (3), [LnAg(pdc){sub 2}]{sub n} (Ln=Eu(4) and Pr (5), H{sub 2}pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc){sub 2}(H{sub 2}O){sub 4}]{sub n} (6) (H{sub 2}bidc=benzimidazole-5,6-dicarboxylic acid) have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV–vis-NIR absorption spectra, fluorescence spectra and thermogravimetric analysis. Structural analyses reveal that the six polymers exhibit 0D (polymer (1)), 1D (polymer (2)), 2D (polymers (3) and (5)) and 3D (polymers (4) and (6)) infinite structures, respectively. Polymers (1)–(6) exhibit the Ln(III) characteristic emission in the near-infrared (NIR) region or inmore » the visible region. Especially, the NIR emission bands of polymers 1, 5 and 6 evidently present shift or splitting due to formation of the Ln–Ag coordination polymers. This can be attributed to the tune of inner levels in Ln–Ag system caused by the interact and influence between the 4d orbital of the Ag(I) ion and the 4f orbital of the Ln(III) ion, which can be confirmed by the UV–vis-NIR absorption spectra of the polymers. In addition, the distortion of coordination geometry as well as difference of the coordination number around the Ag(I) ion affect the structure framework. - Graphical abstract: Six Ag–Ln coordination polymers have been hydrothermally synthesized and characterized. The photoluminescence properties were studied. The distortion of coordination geometry of Ag(I) ion affect structure framework. Introduction of Ag(I) cause wonderful changes to the NIR emission of Ln(III) ions. - Highlights: • Six Ln–Ag polymers have been synthesized and characterized. • The distortion of coordination geometry of Ag(I) ion affect structure framework. • Introduction of Ag(I) cause wonderful changes to

  14. Isostructural 1D coordination polymers of Zn(II), Cd(II) and Cu(II) with phenylpropynoic acid and DABCO as organic linkers

    NASA Astrophysics Data System (ADS)

    Saravanakumar, Rajendran; Varghese, Babu; Sankararaman, Sethuraman

    2014-11-01

    Using phenylpropynoic acid (PPA) and 1,4-diazabicyclo[2.2.2]octane (DABCO) as organic spacers, isostructural coordination polymers of Zn(II), Cd(II) and Cu(II) were synthesized by solvothermal method and structurally characterized using single crystal XRD, powder XRD, 13C CP-MAS NMR spectroscopy. Single crystal XRD data revealed four PPA units coordinating with two metal ions forming a paddle wheel secondary building unit (SBU). The paddle wheel units are connected through coordination of DABCO nitrogen to the metal centers from the axial positions leading to the formation of the 1D coordination polymers along the c axis. Intermolecular π stacking and Csbnd H…π interactions between the adjacent polymer chains convert the 1D coordination polymer into an interesting 3D network with the Csbnd H…π bonds running along the crystallographic a and b axes. Thermal and nitrogen adsorption studies of these coordination polymers are reported.

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

    PubMed

    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

  16. Coordination polymers of 5-substituted isophthalic acid

    DOE PAGES

    McCormick, Laura J.; Morris, Samuel A.; Slawin, Alexandra M. Z.; ...

    2015-12-10

    In this work, the synthesis and characterisation of five coordination polymers - Ni 2(mip) 2 (H 2O) 8 ·2H 2O (1), Zn 6(mip) 5(OH) 2(H 2O) 4 ·7.4H 2O (2), Zn 6(mip) 5(OH) 2(H 2O) 2 ·4H 2O (3), Mn(HMeOip) 2 (4), and Mn 3(tbip) 2(Htbip) 2(EtOH) 2 (5) - are reported. Preliminary nitric oxide release data on compounds 2 and 3 are also given.

  17. Nanoscale coordination polymers exhibiting luminescence properties and NMR relaxivity

    NASA Astrophysics Data System (ADS)

    Chelebaeva, Elena; Larionova, Joulia; Guari, Yannick; Ferreira, Rute A. S.; Carlos, Luis D.; Trifonov, Alexander A.; Kalaivani, Thangavel; Lascialfari, Alessandro; Guérin, Christian; Molvinger, Karine; Datas, Lucien; Maynadier, Marie; Gary-Bobo, Magali; Garcia, Marcel

    2011-03-01

    This article presents the first example of ultra-small (3-4 nm) magneto-luminescent cyano-bridged coordination polymer nanoparticles Ln0.333+Gdx3+/[Mo(CN)8]3- (Ln = Eu (x = 0.34), Tb (x = 0.35)) enwrapped by a natural biocompatible polymer chitosan. The aqueous colloidal solutions of these nanoparticles present a luminescence characteristic of the corresponding lanthanides (5D0 --> 7F0-4 (Eu3+) or the 5D4 --> 7F6-2 (Tb3+)) under UV excitation and a green luminescence of the chitosan shell under excitation in the visible region. Magnetic Resonance Imaging (MRI) efficiency, i.e. the nuclear relaxivity, measurements performed for Ln0.333+Gdx3+/[Mo(CN)8]3- nanoparticles show r1p and r2p relaxivities slightly higher than or comparable to the ones of the commercial paramagnetic compounds Gd-DTPA® or Omniscan® indicating that our samples may potentially be considered as a positive contrast agent for MRI. The in vitro studies performed on these nanoparticles show that they maybe internalized into human cancer and normal cells and well detected by fluorescence at the single cell level. They present high stability even at low pH and lack of cytotoxicity both in human cancer and normal cells.This article presents the first example of ultra-small (3-4 nm) magneto-luminescent cyano-bridged coordination polymer nanoparticles Ln0.333+Gdx3+/[Mo(CN)8]3- (Ln = Eu (x = 0.34), Tb (x = 0.35)) enwrapped by a natural biocompatible polymer chitosan. The aqueous colloidal solutions of these nanoparticles present a luminescence characteristic of the corresponding lanthanides (5D0 --> 7F0-4 (Eu3+) or the 5D4 --> 7F6-2 (Tb3+)) under UV excitation and a green luminescence of the chitosan shell under excitation in the visible region. Magnetic Resonance Imaging (MRI) efficiency, i.e. the nuclear relaxivity, measurements performed for Ln0.333+Gdx3+/[Mo(CN)8]3- nanoparticles show r1p and r2p relaxivities slightly higher than or comparable to the ones of the commercial paramagnetic compounds Gd

  18. One-Dimensional Brownian Motion of Charged Nanoparticles along Microtubules: A Model System for Weak Binding Interactions

    PubMed Central

    Minoura, Itsushi; Katayama, Eisaku; Sekimoto, Ken; Muto, Etsuko

    2010-01-01

    Abstract Various proteins are known to exhibit one-dimensional Brownian motion along charged rodlike polymers, such as microtubules (MTs), actin, and DNA. The electrostatic interaction between the proteins and the rodlike polymers appears to be crucial for one-dimensional Brownian motion, although the underlying mechanism has not been fully clarified. We examined the interactions of positively-charged nanoparticles composed of polyacrylamide gels with MTs. These hydrophilic nanoparticles bound to MTs and displayed one-dimensional Brownian motion in a charge-dependent manner, which indicates that nonspecific electrostatic interaction is sufficient for one-dimensional Brownian motion. The diffusion coefficient decreased exponentially with an increasing particle charge (with the exponent being 0.10 kBT per charge), whereas the duration of the interaction increased exponentially (exponent of 0.22 kBT per charge). These results can be explained semiquantitatively if one assumes that a particle repeats a cycle of binding to and movement along an MT until it finally dissociates from the MT. During the movement, a particle is still electrostatically constrained in the potential valley surrounding the MT. This entire process can be described by a three-state model analogous to the Michaelis-Menten scheme, in which the two parameters of the equilibrium constant between binding and movement, and the rate of dissociation from the MT, are derived as a function of the particle charge density. This study highlights the possibility that the weak binding interactions between proteins and rodlike polymers, e.g., MTs, are mediated by a similar, nonspecific charge-dependent mechanism. PMID:20409479

  19. One-dimensional Brownian motion of charged nanoparticles along microtubules: a model system for weak binding interactions.

    PubMed

    Minoura, Itsushi; Katayama, Eisaku; Sekimoto, Ken; Muto, Etsuko

    2010-04-21

    Various proteins are known to exhibit one-dimensional Brownian motion along charged rodlike polymers, such as microtubules (MTs), actin, and DNA. The electrostatic interaction between the proteins and the rodlike polymers appears to be crucial for one-dimensional Brownian motion, although the underlying mechanism has not been fully clarified. We examined the interactions of positively-charged nanoparticles composed of polyacrylamide gels with MTs. These hydrophilic nanoparticles bound to MTs and displayed one-dimensional Brownian motion in a charge-dependent manner, which indicates that nonspecific electrostatic interaction is sufficient for one-dimensional Brownian motion. The diffusion coefficient decreased exponentially with an increasing particle charge (with the exponent being 0.10 kBT per charge), whereas the duration of the interaction increased exponentially (exponent of 0.22 kBT per charge). These results can be explained semiquantitatively if one assumes that a particle repeats a cycle of binding to and movement along an MT until it finally dissociates from the MT. During the movement, a particle is still electrostatically constrained in the potential valley surrounding the MT. This entire process can be described by a three-state model analogous to the Michaelis-Menten scheme, in which the two parameters of the equilibrium constant between binding and movement, and the rate of dissociation from the MT, are derived as a function of the particle charge density. This study highlights the possibility that the weak binding interactions between proteins and rodlike polymers, e.g., MTs, are mediated by a similar, nonspecific charge-dependent mechanism. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  20. Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir; Nozarian, Kimia; Babadi, Susan Soleymani

    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, themore » 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

  1. Highly luminescent and triboluminescent coordination polymers assembled from lanthanide β-diketonates and aromatic bidentate O-donor ligands.

    PubMed

    Eliseeva, Svetlana V; Pleshkov, Dmitry N; Lyssenko, Konstantin A; Lepnev, Leonid S; Bünzli, Jean-Claude G; Kuzmina, Natalia P

    2010-10-18

    The reaction of hydrated lanthanide hexafluoroacetylacetonates, [Ln(hfa)(3)(H(2)O)(2)], with 1,4-disubstituted benzenes afforded a new series of one-dimensional coordination polymers [Ln(hfa)(3)(Q)](∞), where Ln = Eu, Gd, Tb, and Lu and Q = 1,4-diacetylbenzene (acbz), 1,4-diacetoxybenzene (acetbz), or 1,4-dimethyltherephtalate (dmtph). X-ray single crystal analyses reveal [Ln(hfa)(3)(acbz)](∞) (Ln = Eu, Gd, Tb) consisting of zigzag polymeric chains with Ln-Ln-Ln angles equal to 128°, while the arrays are more linear in [Eu(hfa)(3)(acetbz)](∞) and [Eu(hfa)(3)(dmtph)](∞), with Ln-Ln-Ln angles of 165° and 180°, respectively. In all structures, Ln(III) ions are 8-coordinate and lie in distorted square-antiprismatic environments. The coordination polymers are thermally stable up to 180-210 °C under a nitrogen atmosphere. Their volatility has been tested in vacuum sublimation experiments at 200-250 °C and 10(-2) Torr: the metal-organic frameworks with acetbz and dmtph can be quantitatively sublimed, while [Ln(hfa)(3)(acbz)](∞) undergoes thermal decomposition. The triplet state energies of the ancillary ligands, 21,600 (acetbz), 22,840 (acbz), and 24,500 (dmtph) cm(-1), lie in an ideal range for sensitizing the luminescence of Eu(III) and/or Tb(III). As a result, all of the [Ln(hfa)(3)(Q)](∞) polymers display bright red or green luminescence due to the characteristic (5)D(0) → (7)F(J) (J = 0-4) or (5)D(4) → (7)F(J) (J = 6-0) transitions, respectively. Absolute quantum yields reach 51(Eu) and 56(Tb) % for the frameworks built from dmtph. Thin films of [Eu(hfa)(3)(Q)](∞) with 100-170 nm thickness can be obtained by thermal evaporation (P < 3 × 10(-5) Torr, 200-250 °C). They are stable over a long period of time, and their photophysical parameters are similar to those of the bulk samples so that their use as active materials in luminescent devices can be envisaged. Mixtures of [Ln(hfa)(3)(dmpth)](∞) with Ln = Eu and Tb yield color

  2. Metal coordination polymer derived mesoporous Co3O4 nanorods with uniform TiO2 coating as advanced anodes for lithium ion batteries.

    PubMed

    Geng, Hongbo; Ang, Huixiang; Ding, Xianguang; Tan, Huiteng; Guo, Guile; Qu, Genlong; Yang, Yonggang; Zheng, Junwei; Yan, Qingyu; Gu, Hongwei

    2016-02-07

    In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g(-1), good cycling stability (around 803 mA h g(-1) at a current density of 200 mA g(-1) after 100 cycles), and stable rate performance (around 520 mA h g(-1) at a current density of 1000 mA g(-1)). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural stability during cycling.

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

    NASA Astrophysics Data System (ADS)

    Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei; Zhang, Xia; Wang, Mei; Jin, Fan; Fan, Yu-hua

    2017-04-01

    Five functional coordination polymers (formic-based CPs) namely: {[Cu2(CHOO)3(bibp)2]·CHOO}n (1), {[Co2(CHOO)3(bibp)2]·NO3·H2O}n (2), {[Ni2(CHOO)3(bibp)2]·NO3·H2O}n (3) [Co(CHOO)2(bbibp)]n (4) and [Zn(CHOO)2(bbibp)]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.

  4. Synthesis, structure, luminescence and photocatalytic properties of an uranyl-2,5-pyridinedicarboxylate coordination polymer

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Si, Zhen-Xiu; Xu, Wei, E-mail: xuwei@nbu.edu.cn; Zheng, Yue-Qing, E-mail: yqzhengmc@163.com

    2016-07-15

    An uranium coordination polymer, namely [(UO{sub 2}(pydc)(H{sub 2}O)]·H{sub 2}O (1) (H{sub 2}pydc=2,5-pyridinedicarboxylic acid), has been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 1D chain coordination polymer, in which UO{sub 2}{sup 2+} ions are bridged by 2,5-pyridinedicarboxylate ligands and the chains are connected into a 3D supramolecular network by O–H···O hydrogen bond interactions and π–π stacking interactions. The photocatalytic properties of 1 for degradation of methylene blue (MB), Rhodamine B (RhB) and methyl orange (MO) under Hg-lamp irradiation have been performed, and the amount of the catalyst as wellmore » as Hg-lamp irradiation with different power on the photodegradation efficiency of MB have been investigated. Elemental analyses, infrared spectroscopy, TG-DTA analyses and luminescence properties were also discussed. - Graphical abstract: Complex 1 exhibits 1D chain coordination polymer in which UO{sub 2}{sup 2+} ions are bridged by 2,5-pyridinedicarboxylate ligand. Photoluminescence studies reveal that complex 1 exhibits characteristic emissions of uranyl centers. The compound is selective to degraded dye and displays good photocatalytic activities for the degradation of MB under Hg-lamp. Display Omitted - Highlights: • Complex 1 exhibits 1D chain coordination polymer. • Complex 1 could degrade methylene blue and Rhodamine B under Hg-lamp irradiation. • Luminescent property of 1 has been studied.« less

  5. Metal Coordination Stoichiometry Controlled Formation of Linear and Hyperbranched Supramolecular Polymers.

    PubMed

    Lin, Cuiling; Xu, Luonan; Huang, Libo; Chen, Jia; Liu, Yuanyuan; Ma, Yifan; Ye, Feixiang; Qiu, Huayu; He, Tian; Yin, Shouchun

    2016-09-01

    Controlling the topologies of polymers is a hot topic in polymer chemistry because the physical and/or chemical properties of polymers are determined (at least partially) by their topologies. This study exploits the host-guest interactions between dibenzo-24-crown-8 and secondary ammonium salts and metal coordination interactions between 2,6-bis(benzimidazolyl)-pyridine units with metal ions (Zn(II) and/or Eu(III) ) as orthogonal non-covalent interactions to prepare supramolecular polymers. By changing the ratios of the metal ion additives (Zn(NO3 )2 and Eu(NO3 )3 ) linkers to join the host-guest dimeric complex, the linear supramolecular polymers (100 mol% Zn(NO3 )2 per ligand) and hyperbranched supramolecular polymers (97 mol% Zn(NO3 )2 and 3 mol% Eu(NO3 )3 per ligand) are separately and successfully constructed. This approach not only expands topological control over polymeric systems, but also paves the way for the functionalization of smart and adaptive materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Tuning zinc coordination architectures by benzenedicarboxylate position isomers and bis(triazole)

    NASA Astrophysics Data System (ADS)

    Peng, Yan-fen; Li, Ke; Zhao, Shan; Han, Shan-shan; Li, Bao-long; Li, Hai-Yan

    2015-08-01

    Three position isomers 1,2-, 1,3-, 1,4-benzenedicarboxylate and 1,4-bis(1,2,4-triazol-4-yl)benzene were used to assembly zinc(II) coordination polymers {[Zn2(btx)0.5(1,2-bdc)2(H2O)]·H2O}n (1), {[Zn(btx)(1,3-bdc)]·2H2O·(DMF)}n (2) and {[Zn(btx)(1,4-bdc)]·3H2O}n (3). 1 is a (3,4,4,4)-connected two-dimensional network with point symbol (42·6)(44·62)(43·62·8)(42·6·103). 2 shows a two-dimensional (4,4) network. 3 exhibits a 5-fold interpenetrated three-dimensional diamondoid network. The structural versatility shows that the structures of coordination polymers can be tuned by the position isomers ligands. The luminescence and thermal stability were investigated.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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 PdX2 and KPtCl4 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.

  10. Novel Three-Dimensional Interphase Characterisation of Polymer Nanocomposites Using Nanoscaled Topography.

    PubMed

    Mousa, Mohanad; Dong, Yu

    2018-06-19

    Mechanical properties of polymer nanocomposites depend primarily on nanointerphases as transitional zones between nanoparticles and surrounding matrices. Due to the difficulty in the quantitative characterisation of nanointerphases, previous literatures generally deemed such interphases as one-dimensional uniform zones around nanoparticles by assumption for analytical or theoretical modelling. We hereby have demonstrated for the first time direct three-dimensional topography and physical measurement of nanophase mechanical properties between nanodimeter bamboo charcoals (NBCs) and poly (vinyl alcohol) (PVA) in polymer nanocomposites. Topographical features, nanomechanical properties and dimensions of nanointerphases were systematically determined via peak force quantitative nanomechanical tapping mode (PFQNM). Significantly different mechanical properties of nanointerphases were revealed as opposed to those of individual NBCs and PVA matrices. Non-uniform irregular three-dimensional structures and shapes of nanointerphases are manifested around individual NBCs, which can be greatly influenced by nanoparticle size and roughness, and nanoparticle dispersion and distribution. Elastic moduli of nanointerphases were experimentally determined in range from 25.32 ±3.4 to 66.3±3.2 GPa. Additionally, it is clearly shown that the interphase modulus strongly depends on interphase surface area SAInterphase and interphase volume VInterphase. Different NBC distribution patterns from fully to partially embedded nanoparticles are proven to yield a remarkable reduction in elastic moduli of nanointerphases. © 2018 IOP Publishing Ltd.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping

    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)more » 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.« less

  12. Morphology design of porous coordination polymer crystals by coordination modulation.

    PubMed

    Umemura, Ayako; Diring, Stéphane; Furukawa, Shuhei; Uehara, Hiromitsu; Tsuruoka, Takaaki; Kitagawa, Susumu

    2011-10-05

    The design of crystal morphology, or exposed crystal facets, has enabled the development (e.g., catalytic activities, material attributes, and oriented film formation) of porous coordination polymers (PCPs) without changing material compositions. However, because crystal growth mechanisms are not fully understood, control of crystal morphology still remains challenging. Herein, we report the morphology design of [Cu(3)(btc)(2)](n) (btc = benzene-1,3,5-tricarboxylate) by the coordination modulation method (modulator = n-dodecanoic acid or lauric acid). A morphological transition (octahedron-cuboctahedron-cube) in the [Cu(3)(btc)(2)](n) crystal was observed with an increase in concentration of the modulator. By suitably defining a coarse-grained standard unit of [Cu(3)(btc)(2)](n) as its cuboctahedron main pore and determining its attachment energy on crystal surfaces, Monte Carlo coarse-grain modeling revealed the population and orientation of carboxylates and elucidated an important role of the modulator in determining the <100>- and <111>-growth throughout the crystal growth process. This comprehension, in fact, successfully led to designed crystal morphologies with oriented growth on bare substrates. Because selective crystal orientations on the bare substrates were governed by crystal morphology, this contribution also casts a new light on the unexplored issue of the significance of morphology design of PCPs.

  13. One-dimensional nanomaterials for energy storage

    NASA Astrophysics Data System (ADS)

    Chen, Cheng; Fan, Yuqi; Gu, Jianhang; Wu, Liming; Passerini, Stefano; Mai, Liqiang

    2018-03-01

    The search for higher energy density, safer, and longer cycling-life energy storage systems is progressing quickly. One-dimensional (1D) nanomaterials have a large length-to-diameter ratio, resulting in their unique electrical, mechanical, magnetic and chemical properties, and have wide applications as electrode materials in different systems. This article reviews the latest hot topics in applying 1D nanomaterials, covering both their synthesis and their applications. 1D nanomaterials can be grouped into the categories: carbon, silicon, metal oxides, and conducting polymers, and we structure our discussion accordingly. Then, we survey the unique properties and application of 1D nanomaterials in batteries and supercapacitors, and provide comments on the progress and advantages of those systems, paving the way for a better understanding of employing 1D nanomaterials for energy storage.

  14. One-Dimensionality and Whiteness

    ERIC Educational Resources Information Center

    Calderon, Dolores

    2006-01-01

    This article is a theoretical discussion that links Marcuse's concept of one-dimensional society and the Great Refusal with critical race theory in order to achieve a more robust interrogation of whiteness. The author argues that in the context of the United States, the one-dimensionality that Marcuse condemns in "One-Dimensional Man" is best…

  15. Novel 3D bismuth-based coordination polymers: Synthesis, structure, and second harmonic generation properties

    NASA Astrophysics Data System (ADS)

    Wibowo, Arief C.; Smith, Mark D.; Yeon, Jeongho; Halasyamani, P. Shiv; zur Loye, Hans-Conrad

    2012-11-01

    Two new 3D bismuth containing coordination polymers are reported along with their single crystal structures and SHG properties. Compound 1: Bi2O2(pydc) (pydc=pyridine-2, 5-dicarboxylate), crystallizes in the monoclinic, polar space group, P21 (a=9.6479(9) Å, b=4.2349(4) Å, c=11.9615(11) Å, β=109.587(1)°), which contains Bi2O2 chains that are connected into a 3D structure via the pydc ligands. Compound 2: Bi4Na4(1R3S-cam)8(EtOH)3.1(H2O)3.4 (1R3S cam=1R3S-camphoric acid) crystallizes in the monoclinic, polar space group, P21 (a=19.0855(7) Å, b=13.7706(5) Å, c=19.2429(7) Å, β=90.701(1)°) and is a true 3D coordination polymer. These are two example of SHG compounds prepared using unsymmetric ligands (compound 1) or chiral ligands (compound 2), together with metals that often exhibit stereochemically-active lone pairs, such as Bi3+, a synthetic approach that resulted in polar, non-centrosymmetric, 3D metal-organic coordination polymer.

  16. Functional Parallel Factor Analysis for Functions of One- and Two-dimensional Arguments.

    PubMed

    Choi, Ji Yeh; Hwang, Heungsun; Timmerman, Marieke E

    2018-03-01

    Parallel factor analysis (PARAFAC) is a useful multivariate method for decomposing three-way data that consist of three different types of entities simultaneously. This method estimates trilinear components, each of which is a low-dimensional representation of a set of entities, often called a mode, to explain the maximum variance of the data. Functional PARAFAC permits the entities in different modes to be smooth functions or curves, varying over a continuum, rather than a collection of unconnected responses. The existing functional PARAFAC methods handle functions of a one-dimensional argument (e.g., time) only. In this paper, we propose a new extension of functional PARAFAC for handling three-way data whose responses are sequenced along both a two-dimensional domain (e.g., a plane with x- and y-axis coordinates) and a one-dimensional argument. Technically, the proposed method combines PARAFAC with basis function expansion approximations, using a set of piecewise quadratic finite element basis functions for estimating two-dimensional smooth functions and a set of one-dimensional basis functions for estimating one-dimensional smooth functions. In a simulation study, the proposed method appeared to outperform the conventional PARAFAC. We apply the method to EEG data to demonstrate its empirical usefulness.

  17. Shell-crossing in quasi-one-dimensional flow

    NASA Astrophysics Data System (ADS)

    Rampf, Cornelius; Frisch, Uriel

    2017-10-01

    Blow-up of solutions for the cosmological fluid equations, often dubbed shell-crossing or orbit crossing, denotes the breakdown of the single-stream regime of the cold-dark-matter fluid. At this instant, the velocity becomes multi-valued and the density singular. Shell-crossing is well understood in one dimension (1D), but not in higher dimensions. This paper is about quasi-one-dimensional (Q1D) flow that depends on all three coordinates but differs only slightly from a strictly 1D flow, thereby allowing a perturbative treatment of shell-crossing using the Euler-Poisson equations written in Lagrangian coordinates. The signature of shell-crossing is then just the vanishing of the Jacobian of the Lagrangian map, a regular perturbation problem. In essence, the problem of the first shell-crossing, which is highly singular in Eulerian coordinates, has been desingularized by switching to Lagrangian coordinates, and can then be handled by perturbation theory. Here, all-order recursion relations are obtained for the time-Taylor coefficients of the displacement field, and it is shown that the Taylor series has an infinite radius of convergence. This allows the determination of the time and location of the first shell-crossing, which is generically shown to be taking place earlier than for the unperturbed 1D flow. The time variable used for these statements is not the cosmic time t but the linear growth time τ ˜ t2/3. For simplicity, calculations are restricted to an Einstein-de Sitter universe in the Newtonian approximation, and tailored initial data are used. However it is straightforward to relax these limitations, if needed.

  18. A coordination polymer with unusual structural features from imidazolylbutyric acid and titanium isopropoxide.

    PubMed

    Czakler, Matthias; Puchberger, Michael; Artner, Christine; Schubert, Ulrich

    The coordination polymer [Ti(O i Pr) 3 (OOCCH 2 CH 2 CH 2 C 3 N 2 H 3 )] n was prepared from 4-(imidazol-1-yl)butyric acid and titanium isopropoxide. The structure of the compound is remarkable, as the carboxylate group is coordinated in a chelating manner and no dimerization of the Ti(O i Pr) 3 groups through OR bridges was observed.

  19. Orbitals, Occupation Numbers, and Band Structure of Short One-Dimensional Cadmium Telluride Polymers.

    PubMed

    Valentine, Andrew J S; Talapin, Dmitri V; Mazziotti, David A

    2017-04-27

    Recent work found that soldering CdTe quantum dots together with a molecular CdTe polymer yielded field-effect transistors with much greater electron mobility than quantum dots alone. We present a computational study of the CdTe polymer using the active-space variational two-electron reduced density matrix (2-RDM) method. While analogous complete active-space self-consistent field (CASSCF) methods scale exponentially with the number of active orbitals, the active-space variational 2-RDM method exhibits polynomial scaling. A CASSCF calculation using the (48o,64e) active space studied in this paper requires 10 24 determinants and is therefore intractable, while the variational 2-RDM method in the same active space requires only 2.1 × 10 7 variables. Natural orbitals, natural-orbital occupations, charge gaps, and Mulliken charges are reported as a function of polymer length. The polymer, we find, is strongly correlated, despite possessing a simple sp 3 -hybridized bonding scheme. Calculations reveal the formation of a nearly saturated valence band as the polymer grows and a charge gap that decreases sharply with polymer length.

  20. Solvothermal synthesis and structural characterization of a three-dimensional metal organic polymer [NaZn(1,2,4-BTC)] (1,2,4-BTC=1,2,4-benzenetricarboxylate)

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Shi, Zhan; Li, Guanghua; Fan, Yong; Fu, Wensheng; Feng, Shouhua

    2004-01-01

    A new three-dimensional metal-organic polymer, [NaZn(1,2,4-BTC)] (where 1,2,4-BTC=1,2,4-benzenetricarboxylate), has been prepared under solvothermal conditions and characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2 1/ c, with cell parameters: a=9.7706(4) Å, b=12.3549(5) Å, c=6.8897(3) Å, β=91.640(2)°, V=831.35(6) Å 3 and Z=4. In the three-dimensional structure of the compound, each Zn atom is five-coordinated in distorted trigonal bipyramidal geometry, while the sixfold coordination of Na corresponds to a slightly distorted triangular prism. The organic ligand, 1,2,4-BTC, shows a novel and unprecedented coordination mode: 11 bonds to 10 metals with each carboxylate function exhibiting different linkages. It remains stable when desolvated and when heated up to 410 °C.

  1. Studies of the structural and magnetic properties of an unsymmetrical ligand 1,2,4-benzenetricarboxylic acid based chiral 3-D trinickel coordination polymer as an alkali base-influenced hydrothermal reaction product

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Peng, Yi-Ru; Chien, Po-Hsiu; Chung, Huey-Ting

    2014-04-01

    The reaction of 1,2,4-benzenetricarboxylic acid (H{sub 3}btc), as a ligand, under pH-controlled hydrothermal conditions with nickel salts leads to the formation of a coordination polymer of (CsNi{sub 3}(OH)(H{sub 2}O){sub 3}[C{sub 6}H{sub 3}(CO{sub 2}){sub 3}]{sub 2}·3H{sub 2}O){sub n} (1). The subunit of compound 1 contains a hydroxide- and carboxylate-bridged trinickel clusters that are linked by an unsymmetrical organic carboxylate spacer to form a chiral three-dimensional anionic framework, in which cesium cations and guest water molecules are located in one-dimensional channels. The presence of a hydroxide ion serves both as a deprotonation agent and a cation source during the hydrothermal reaction, thusmore » permitting the extent of deprotonation of the unsymmetrical ligand H{sub 3}btc to be controlled, which is essential for the successful formation of compound 1. The magnetic properties of compound 1 were analyzed. Both dc and ac magnetic susceptibility as well as reduced magnetization measurements confirmed the spin-frustration nature of 1. - Graphical abstract: A chiral three-dimension MOF compound and its magnetic properties are described. - Highlights: • A new chiral three-dimension coordination polymer were made. • An un-symmetric bridging ligand was used. • Alkali metal ion Cs{sup +} was incorporated in the structure. • Magnetic properties were studied.« less

  2. Hypersonic three-dimensional nonequilibrium boundary-layer equations in generalized curvilinear coordinates

    NASA Technical Reports Server (NTRS)

    Lee, Jong-Hun

    1993-01-01

    The basic governing equations for the second-order three-dimensional hypersonic thermal and chemical nonequilibrium boundary layer are derived by means of an order-of-magnitude analysis. A two-temperature concept is implemented into the system of boundary-layer equations by simplifying the rather complicated general three-temperature thermal gas model. The equations are written in a surface-oriented non-orthogonal curvilinear coordinate system, where two curvilinear coordinates are non-orthogonial and a third coordinate is normal to the surface. The equations are described with minimum use of tensor expressions arising from the coordinate transformation, to avoid unnecessary confusion for readers. The set of equations obtained will be suitable for the development of a three-dimensional nonequilibrium boundary-layer code. Such a code could be used to determine economically the aerodynamic/aerothermodynamic loads to the surfaces of hypersonic vehicles with general configurations. In addition, the basic equations for three-dimensional stagnation flow, of which solution is required as an initial value for space-marching integration of the boundary-layer equations, are given along with the boundary conditions, the boundary-layer parameters, and the inner-outer layer matching procedure. Expressions for the chemical reaction rates and the thermodynamic and transport properties in the thermal nonequilibrium environment are explicitly given.

  3. Porous coordination polymers as novel sorption materials for heat transformation processes.

    PubMed

    Janiak, Christoph; Henninger, Stefan K

    2013-01-01

    Porous coordination polymers (PCPs)/metal-organic frameworks (MOFs) are inorganic-organic hybrid materials with a permanent three-dimensional porous metal-ligand network. PCPs or MOFs are inorganic-organic analogs of zeolites in terms of porosity and reversible guest exchange properties. Microporous water-stable PCPs with high water uptake capacity are gaining attention for low temperature heat transformation applications in thermally driven adsorption chillers (TDCs) or adsorption heat pumps (AHPs). TDCs or AHPs are an alternative to traditional air conditioners or heat pumps operating on electricity or fossil fuels. By using solar or waste heat as the operating energy TDCs or AHPs can significantly help to minimize primary energy consumption and greenhouse gas emissions generated by industrial or domestic heating and cooling processes. TDCs and AHPs are based on the evaporation and consecutive adsorption of coolant liquids, preferably water, under specific conditions. The process is driven and controlled by the microporosity and hydrophilicity of the employed sorption material. Here we summarize the current investigations, developments and possibilities of PCPs/MOFs for use in low-temperature heat transformation applications as alternative materials for the traditional inorganic porous substances like silica gel, aluminophosphates or zeolites.

  4. Commensurate Superstructure of the {Cu(NO3)(H2O)}(HTae)(Bpy) Coordination Polymer: An Example of 2D Hydrogen-Bonding Networks as Magnetic Exchange Pathway.

    PubMed

    Fernández de Luis, Roberto; Larrea, Edurne S; Orive, Joseba; Lezama, Luis; Arriortua, María I

    2016-11-21

    The average and commensurate superstructures of the one-dimensional coordination polymer {Cu(NO 3 )(H 2 O)}(HTae)(Bpy) (H 2 Tae = 1,1,2,2-tetraacetylethane, Bpy = 4,4'-bipyridine) were determined by single-crystal X-ray diffraction, and the possible symmetry relations between the space group of the average structure and the superstructure were checked. The crystal structure consists in parallel and oblique {Cu(HTae)(Bpy)} zigzag metal-organic chains stacked along the [100] crystallographic direction. The origin of the fivefold c axis in the commensurate superstructure is ascribed to a commensurate modulation of the coordination environment of the copper atoms. The commensurately ordered nitrate groups and coordinated water molecules establish a two-dimensional hydrogen-bonding network. Moreover, the crystal structure shows a commensurate to incommensurate transition at room temperature. The release of the coordination water molecules destabilizes the crystal framework, and the compound shows an irreversible structure transformation above 100 °C. Despite the loss of crystallinity, the spectroscopic studies indicate that the main building blocks of the crystal framework are retained after the transformation. The hydrogen-bonding network not only plays a crucial role stabilizing the crystal structure but also is an important pathway for magnetic exchange transmission. In fact, the magnetic susceptibility curves indicate that after the loss of coordinated water molecules, and hence the collapse of the hydrogen-bonding network, the weak anti-ferromagnetic coupling observed in the initial compound is broken. The electron paramagnetic resonance spectra are the consequence of the average signals from Cu(II) with different orientations, indicating that the magnetic coupling is effective between them. In fact, X- and Q-band data are reflecting different situations; the X-band spectra show the characteristics of an exchange g-tensor, while the Q-band signals are coming from

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

    PubMed

    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.

  6. Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol

    PubMed Central

    Troyano, Javier; Perles, Josefina; Amo-Ochoa, Pilar; Martínez, Jose Ignacio; Concepción Gimeno, Maria; Fernández-Moreira, Vanesa; Zamora, Félix; Delgado, Salomé

    2016-01-01

    Solvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3X(HT)2]n (X= Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room temperature and low temperature (110 K), showing a general shortening in Cu-S, Cu-X and Cu···Cu bond distances at low temperatures. 1 and 2 are isostructural consisting of layers in which the halogen ligands act as μ3-bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4-mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, while upon cooling at 77 K 1 and 2 show stronger yellow as well as 3 displays stronger green emission. DFT calculations have been used to rationalise these observations. These results suggest a high potential for this novel and promising stimuli-responsive materials. PMID:27809369

  7. Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol.

    PubMed

    Troyano, Javier; Perles, Josefina; Amo-Ochoa, Pilar; Martínez, Jose Ignacio; Concepción Gimeno, Maria; Fernández-Moreira, Vanesa; Zamora, Félix; Delgado, Salomé

    2016-12-12

    Solvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu 3 X(HT) 2 ] n (X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu-S, Cu-X and Cu-Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ 3 -bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ 4 -mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materials. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Design and Synthesis of a Biocompatible 1D Coordination Polymer as Anti-Breast Cancer Drug Carrier, 5-Fu: In Vitro and in Vivo Studies.

    PubMed

    Rezaei, Mahsa; Abbasi, Alireza; Dinarvand, Rassoul; Jeddi-Tehrani, Mahmood; Janczak, Jan

    2018-05-17

    Designable coordination polymers with suitable chemical diversities and biocompatible structures have been proposed as a promising class of vehicles for drug delivery systems. Here, we hydrothermally synthesized a novel one-dimensional (1D) coordination polymer, [Zn(H 2 O) 6 K 2 (H 2 BTC) 2 (H 2 O) 4 ](H 2 BTC) 2 ·2H 2 O, where H 3 BTC = benzene-1,3,5-tricarboxylic acid (trimesic acid), cp.1. As the hydrogen bonds stabilized 1D chains in three dimensions, the cp.1 could be a good candidate for delivering small-molecule chemotherapeutics such as 5-fluorouracil (5-Fu). The synthesized cp.1 showed a remarkable 5-Fu loading of 66% with encapsulation efficiency of 98% and almost complete release process. The 5-Fu-loaded cp.1 displayed a time-dependent cytotoxicity effect against breast cancer cell lines MCF-7 and 4T1. The cellular uptake of cp.1 particles was investigated via confocal laser scanning microscopy using fluorescein isothiocyanate and LysoTracker Red staining. Furthermore, the in vivo antitumor impact of 5-Fu-loaded cp.1 was studied on 4T1 breast cancer BALB/c mice model. The intratumor treatment of 5-Fu-loaded cp.1 demonstrated beneficial antitumor efficacy by postponing tumor growth. These results suggest that the 5-Fu-loaded cp.1 microparticles with a great locoregional delivery can be efficient anticancer drug carriers for further clinical treatments.

  9. Hand-Ground Nanoscale ZnII -Based Coordination Polymers Derived from NSAIDs: Cell Migration Inhibition of Human Breast Cancer Cells.

    PubMed

    Paul, Mithun; Sarkar, Koushik; Deb, Jolly; Dastidar, Parthasarathi

    2017-04-27

    Increased levels of intracellular prostaglandin E 2 (PGE 2 ) have been linked with the unregulated cancer cell migration that often leads to metastasis. Non-steroidal anti-inflammatory drugs (NSAIDs) are known inhibitors of cyclooxygenase (COX) enzymes, which are responsible for the increased PGE 2 concentration in inflamed as well as cancer cells. Here, we demonstrate that NSAID-derived Zn II -based coordination polymers are able to inhibit cell migration of human breast cancer cells. Various NSAIDs were anchored to a series of 1D Zn II coordination polymers through carboxylate-Zn coordination, and these structures were fully characterized by single-crystal X-ray diffraction. Hand grinding in a pestle and mortar resulted in the first reported example of nanoscale coordination polymers that were suitable for biological studies. Two such hand-ground nanoscale coordination polymers NCP1 a and NCP2 a, which contained naproxen (a well-studied NSAID), were successfully internalized by the human breast cancer cells MDA-MB-231, as was evident from cellular imaging by using a fluorescence microscope. They were able to kill the cancer cells (MTT assay) more efficiently than the corresponding mother drug naproxen, and most importantly, they significantly inhibited cancer cell migration thereby displaying anticancer activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhuang Guilin, E-mail: glzhuang@zjut.edu.cn; Chen Wulin; Zheng Jun

    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-Signmore » 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN

    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 themore » 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.« less

  12. Different water clusters dependent on long-chain dicarboxylates in two Ag(I) coordination polymers: Synthesis, structure and thermal stability

    NASA Astrophysics Data System (ADS)

    Sun, Di; Liu, Fu-Jing; Hao, Hong-Jun; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-10-01

    Two mixed-ligand Ag(I) coordination polymers (CPs), [Ag 2(bipy) 2(sub)·5H 2O] n ( 1), [Ag 2(bipy) 2(aze)·3H 2O] n ( 2), (bipy = 4,4'-bipyridine, H 2sub = suberic acid, H 2aze = azelaic acid) have been synthesized and structurally characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis, and single crystal X-ray diffraction. Both 1 and 2 are two-dimensional (2D) sheets based on infinite [Ag(bipy)] n double chain incorporating Ag⋯Ag interactions. Interestingly, two different water clusters are encapsulated in the voids between the sheets of 1 and 2. For 1, one water decamer (H 2O) 10 based on a cyclic water tetramer was hydrogen-bonded with the host 2D sheet. While, one water hexamer (H 2O) 6 also based on a cyclic water tetramer was observed in 2. Comparing the experimental results, it is comprehensible that the dicarboxylates play a crucial role in the formation of the different water clusters. Moreover, the thermal stabilities of them were also discussed.

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

    NASA Astrophysics Data System (ADS)

    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. Three-dimensionally ordered array of air bubbles in a polymer film

    NASA Technical Reports Server (NTRS)

    Srinivasarao, M.; Collings, D.; Philips, A.; Patel, S.; Brown, C. S. (Principal Investigator)

    2001-01-01

    We report the formation of a three-dimensionally ordered array of air bubbles of monodisperse pore size in a polymer film through a templating mechanism based on thermocapillary convection. Dilute solutions of a simple, coil-like polymer in a volatile solvent are cast on a glass slide in the presence of moist air flowing across the surface. Evaporative cooling and the generation of an ordered array of breath figures leads to the formation of multilayers of hexagonally packed water droplets that are preserved in the final, solid polymer film as spherical air bubbles. The dimensions of these bubbles can be controlled simply by changing the velocity of the airflow across the surface. When these three-dimensionally ordered macroporous materials have pore dimensions comparable to the wavelength of visible light, they are of interest as photonic band gaps and optical stop-bands.

  15. A statistical formulation of one-dimensional electron fluid turbulence

    NASA Technical Reports Server (NTRS)

    Fyfe, D.; Montgomery, D.

    1977-01-01

    A one-dimensional electron fluid model is investigated using the mathematical methods of modern fluid turbulence theory. Non-dissipative equilibrium canonical distributions are determined in a phase space whose co-ordinates are the real and imaginary parts of the Fourier coefficients for the field variables. Spectral densities are calculated, yielding a wavenumber electric field energy spectrum proportional to k to the negative second power for large wavenumbers. The equations of motion are numerically integrated and the resulting spectra are found to compare well with the theoretical predictions.

  16. Survival condition for low-frequency quasi-one-dimensional breathers in a two-dimensional strongly anisotropic crystal

    NASA Astrophysics Data System (ADS)

    Savin, A. V.; Zubova, E. A.; Manevitch, L. I.

    2005-06-01

    We investigate a two-dimensional (2D) strongly anisotropic crystal (2D SAC) on substrate: 2D system of coupled linear chains of particles with strong intrachain and weak interchain interactions, each chain being subjected to the sine background potential. Nonlinear dynamics of one of these chains when the rest of them are fixed is reduced to the well known Frenkel-Kontorova (FK) model. Depending on strengh of the substrate, the 2D SAC models a variety of physical systems: polymer crystals with identical chains having light side groups, an array of inductively coupled long Josephson junctions, anisotropic crystals having light and heavy sublattices. Continuum limit of the FK model, the sine-Gordon (sG) equation, allows two types of soliton solutions: topological solitons and breathers. It is known that the quasi-one-dimensional topological solitons can propagate also in a chain of 2D system of coupled chains and even in a helix chain in a three-dimensional model of polymer crystal. In contrast to this, numerical simulation shows that the long-living breathers inherent to the FK model do not exist in the 2D SAC with weak background potential. The effect changes scenario of kink-antikink collision with small relative velocity: at weak background potential the collision always results only in intensive phonon radiation while kink-antikink recombination in the FK model results in long-living low-frequency sG breather creation. We found the survival condition for breathers in the 2D SAC on substrate depending on breather frequency and strength of the background potential. The survival condition bears no relation to resonances between breather frequency and frequencies of phonon band—contrary to the case of the FK model.

  17. Self-interacting polymer chains terminally anchored to adsorbing surfaces of three-dimensional fractal lattices

    NASA Astrophysics Data System (ADS)

    Živić, I.; Elezović-Hadžić, S.; Milošević, S.

    2018-01-01

    We have studied the adsorption problem of self-attracting linear polymers, modeled by self-avoiding walks (SAWs), situated on three-dimensional fractal structures, exemplified by 3d Sierpinski gasket (SG) family of fractals as containers of a poor solvent. Members of SG family are enumerated by an integer b (b ≥ 2), and it is assumed that one side of each SG fractal is an impenetrable adsorbing surface. We calculate the critical exponents γ1 ,γ11, and γs, which are related to the numbers of all possible SAWs with one, both, and no ends anchored to the adsorbing boundary, respectively. By applying the exact renormalization group (RG) method (for the first three members of the SG fractal family, b = 2 , 3, and 4), we have obtained specific values of these exponents, for θ-chain and globular polymer phase. We discuss their mutual relations and relations with corresponding values pertinent to extended polymer chain phase.

  18. From 1D Polymers to 2D Polymers: Preparation of Free-Standing Single-Monomer-Thick Two-Dimensional Conjugated Polymers in Water.

    PubMed

    Zhang, Na; Wang, Taisheng; Wu, Xing; Jiang, Chen; Zhang, Taiming; Jin, Bangkun; Ji, Hengxing; Bai, Wei; Bai, Ruke

    2017-07-25

    Recently, investigation on two-dimensional (2D) organic polymers has made great progress, and conjugated 2D polymers already play a dynamic role in both academic and practical applications. However, a convenient, noninterfacial approach to obtain single-layer 2D polymers in solution, especially in aqueous media, remains challenging. Herein, we present a facile, highly efficient, and versatile "1D to 2D" strategy for preparation of free-standing single-monomer-thick conjugated 2D polymers in water without any aid. The 2D structure was achieved by taking advantage of the side-by-side self-assembly of a rigid amphiphilic 1D polymer and following topochemical photopolymerization in water. The spontaneous formation of single-layer polymer sheets was driven by synergetic association of the hydrophobic interactions, π-π stacking interactions, and electrostatic repulsion. Both the supramolecular sheets and the covalent sheets were confirmed by spectroscopic analyses and electron microscope techniques. Moreover, in comparison of the supramolecular 2D polymer, the covalent 2D polymer sheets exhibited not only higher mechanical strength but also higher conductivity, which can be ascribed to the conjugated network within the covalent 2D polymer sheets.

  19. Two novel zinc(II) coordination polymers constructed from in situ amidation ligands

    NASA Astrophysics Data System (ADS)

    Yu, Xiao-Yang; Fu, Yao; Fu, Jian-Tao; Xu, Jia-Ning; Luo, Ya-Nan; Yang, Yan-Yan; Qu, Xiao-Shu; Zhang, Jing; Lu, Shu-Lai

    2018-04-01

    Two novel coordination compounds, [Zn(Hbimh) (H2O)]·H2O (1) and [Zn(Hbimh)]·(4,4ʹ-bpy)0.5 (2) (H3bimh = benzimidazole-5,6-hydrazide, 4,4ʹ-bpy = 4,4ʹ-bipyridine), have been prepared from the hydrothermal in situ amidation cyclization reactions of H3bimdc (H3bimdc = benzimidazole-5,6-dicarboxylic acid) and hydrazine hydrate (N2H4·H2O). Compound 1 exhibits a one-dimensional (1D) hexagon channel structure. Compound 2 is a three-dimensional (3D) framework structure, with 4,4ʹ-bpy fill the channels. We also obtained the ligand H3bimh. The compounds were characterized by IR, PXRD, TGA and elemental analysis. The fluorescence properties in the solid state at room temperature were also investigated.

  20. Dynamic Coordination of Eu-Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli.

    PubMed

    Weng, Gengsheng; Thanneeru, Srinivas; He, Jie

    2018-03-01

    New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light-emitting materials. A new design of Eu-containing polymer hydrogels showing fast self-healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu-iminodiacetate (IDA) coordination in a hydrophilic poly(N,N-dimethylacrylamide) matrix. Dynamic metal-ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self-healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol-gel transition through the reversible formation and dissociation of Eu-IDA complexes upon various stimuli. It is demonstrated that Eu-containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei

    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 betweenmore » 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen

    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 groupsmore » 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.« less

  3. Two-dimensional homogeneous isotropic fluid turbulence with polymer additives

    NASA Astrophysics Data System (ADS)

    Gupta, Anupam; Perlekar, Prasad; Pandit, Rahul

    2015-03-01

    We carry out an extensive and high-resolution direct numerical simulation of homogeneous, isotropic turbulence in two-dimensional fluid films with air-drag-induced friction and with polymer additives. Our study reveals that the polymers (a) reduce the total fluid energy, enstrophy, and palinstrophy; (b) modify the fluid energy spectrum in both inverse- and forward-cascade régimes; (c) reduce small-scale intermittency; (d) suppress regions of high vorticity and strain rate; and (e) stretch in strain-dominated regions. We compare our results with earlier experimental studies and propose new experiments.

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

    PubMed

    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.

  5. Mechanism of polymer drag reduction using a low-dimensional model.

    PubMed

    Roy, Anshuman; Morozov, Alexander; van Saarloos, Wim; Larson, Ronald G

    2006-12-08

    Using a retarded-motion expansion to describe the polymer stress, we derive a low-dimensional model to understand the effects of polymer elasticity on the self-sustaining process that maintains the coherent wavy streamwise vortical structures underlying wall-bounded turbulence. Our analysis shows that at small Weissenberg numbers, Wi, elasticity enhances the coherent structures. At higher Wi, however, polymer stresses suppress the streamwise vortices (rolls) by calming down the instability of the streaks that regenerates the rolls. We show that this behavior can be attributed to the nonmonotonic dependence of the biaxial extensional viscosity on Wi, and identify it as the key rheological property controlling drag reduction.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Wenjie; Li, Guoting; Lv, Lulu

    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{submore » 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    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 2more » 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.« less

  8. Coordination Polymer: Synthesis, Spectral Characterization and Thermal Behaviour of Starch-Urea Based Biodegradable Polymer and Its Polymer Metal Complexes

    PubMed Central

    Malik, Ashraf; Parveen, Shadma; Ahamad, Tansir; Alshehri, Saad M.; Singh, Prabal Kumar; Nishat, Nahid

    2010-01-01

    A starch-urea-based biodegradable coordination polymer modified by transition metal Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) was prepared by polycondensation of starch and urea. All the synthesized polymeric compounds were characterized by Fourier transform-infrared spectroscopy (FT-IR), 1H-NMR spectroscopy, 13C-NMR spectroscopy, UV-visible spectra, magnetic moment measurements, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). The results of electronic spectra and magnetic moment measurements indicate that Mn(II), Co(II), and Ni(II) complexes show octahedral geometry, while Cu(II) and Zn(II) complexes show square planar and tetrahedral geometry, respectively. The thermogravimetric analysis revealed that all the polymeric metal complexes are more thermally stable than the parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM standards of biodegradable polymers by CO2 evolution method. PMID:20414461

  9. Coordination Polymer of M(II)-Pyrazinamide (M = Co, Cd) with Double End-to-End Thiocyanate Bridge

    NASA Astrophysics Data System (ADS)

    Ponco Prananto, Yuniar

    2018-01-01

    Pyrazinamide (pza, C4N2H3-CONH2) is a good ligand for coordination polymer. Their transition metal complexes are known to have antibacterial activities, magnetic properties, etc. Coordination polymers of M(II)-pyrazinamide with thiocyanate (M = Co (a), Cd (b)), prepared using bench-top layering technique with M(II):pza:SCN ratio of 1:2:2, is successfully crystallised at room temperature. Single crystal XRD was used to determine the crystal structure. Infrared and melting point determination were also performed. Crystal structure of both complexes, solved in Triclinic P-1, show that each octahedral metal centre is connected to two adjacent metal centres by double end-to-end thiocyanate bridge forming a 1D polymeric structure with M···M distances of 5.524 Å (in a) and 5.887 Å (in b). Two monodentate pyrazinamide ligands occupy the rest of the coordination sites on the metal centre in a trans relationship. Only in complex a, one lattice pyrazinamide molecule is involved in the asymmetric unit. Crystal packing of both a and b are also displaying non-covalent networks as a result of hydrogen-bonding involving the pyrazine ring, amide and carbonyl groups between adjacent chains and π···π interactions (only occurred in a). In addition, the observed melting points of both a and b are relatively close to each other (around 180°C), and ATR-IR spectra support the presence of the bridging thiocyanate and terminal pyrazinamide.

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

    NASA Astrophysics Data System (ADS)

    Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian; Long, Yi; Yue, Shan-Tang; Liu, Ying-Liang

    2015-05-01

    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, {[LnIIIAgI(na)(ina)(ox)]·2(H2O)}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.

  11. Polymers functionalized with bronsted acid groups

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Van Humbeck, Jeffrey; Long, Jeffrey R.; McDonald, Thomas M.

    Porous aromatic framework polymers functionalized with Bronsted acid moieties are prepared by polymerization of a three-dimensional organic aryl or heteroaryl monomer and its copolymerization with a second aryl or heteroaryl monomer functionalized with one or more Bronsted acid moiety. The polymers are characterized by a stable three-dimensional structure, which, in exemplary embodiments, includes interpenetrating subunits within one or more domain of the bulk polymer structure. The polymers are of use in methods of adsorbing ammonia and amines and in devices and systems configured for this purpose.

  12. One-dimensional cuts through multidimensional potential-energy surfaces by tunable x rays

    NASA Astrophysics Data System (ADS)

    Eckert, Sebastian; da Cruz, Vinícius Vaz; Gel'mukhanov, Faris; Ertan, Emelie; Ignatova, Nina; Polyutov, Sergey; Couto, Rafael C.; Fondell, Mattis; Dantz, Marcus; Kennedy, Brian; Schmitt, Thorsten; Pietzsch, Annette; Odelius, Michael; Föhlisch, Alexander

    2018-05-01

    The concept of the potential-energy surface (PES) and directional reaction coordinates is the backbone of our description of chemical reaction mechanisms. Although the eigenenergies of the nuclear Hamiltonian uniquely link a PES to its spectrum, this information is in general experimentally inaccessible in large polyatomic systems. This is due to (near) degenerate rovibrational levels across the parameter space of all degrees of freedom, which effectively forms a pseudospectrum given by the centers of gravity of groups of close-lying vibrational levels. We show here that resonant inelastic x-ray scattering (RIXS) constitutes an ideal probe for revealing one-dimensional cuts through the ground-state PES of molecular systems, even far away from the equilibrium geometry, where the independent-mode picture is broken. We strictly link the center of gravity of close-lying vibrational peaks in RIXS to a pseudospectrum which is shown to coincide with the eigenvalues of an effective one-dimensional Hamiltonian along the propagation coordinate of the core-excited wave packet. This concept, combined with directional and site selectivity of the core-excited states, allows us to experimentally extract cuts through the ground-state PES along three complementary directions for the showcase H2O molecule.

  13. Absolute judgment for one- and two-dimensional stimuli embedded in Gaussian noise

    NASA Technical Reports Server (NTRS)

    Kvalseth, T. O.

    1977-01-01

    This study examines the effect on human performance of adding Gaussian noise or disturbance to the stimuli in absolute judgment tasks involving both one- and two-dimensional stimuli. For each selected stimulus value (both an X-value and a Y-value were generated in the two-dimensional case), 10 values (or 10 pairs of values in the two-dimensional case) were generated from a zero-mean Gaussian variate, added to the selected stimulus value and then served as the coordinate values for the 10 points that were displayed sequentially on a CRT. The results show that human performance, in terms of the information transmitted and rms error as functions of stimulus uncertainty, was significantly reduced as the noise variance increased.

  14. Tunable emission in lanthanide coordination polymer gels based on a rationally designed blue emissive gelator.

    PubMed

    Sutar, Papri; Suresh, Venkata M; Maji, Tapas Kumar

    2015-06-18

    Rational design and synthesis of a new low molecular weight gelator (LMWG) having 9,10-diphenylanthracene core and terminal terpyridine is reported. Tb(III) and Eu(III) ion coordination to a LMWG results in green and pink emissive coordination polymer gels, respectively, with coiled nanofiber morphology. Further, control over stoichiometry of LMWG:Tb(III):Eu(III) leads to yellow and white light emitting bimetallic gels.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hu, Bin; School of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang, 330063; Geng, Jiao

    2014-07-01

    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{sup 1}) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 2}), has been synthesized and characterized. They are used as μ{sub 2}-bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L{sup 1})(NO{sub 3})]{sub n} (1) and [Ag(L{sup 2})(NO{sub 3})]{sub 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{sup 1} and L{sup 2})more » 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{sup 4} and 2.17×10{sup 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{sup 1} and L{sup 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{sup 1}) and L{sup 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{sub 2}-bridging ligands to prepare a pair of silver

  16. Microfabrication and Test of a Three-Dimensional Polymer Hydro-focusing Unit for Flow Cytometry Applications

    NASA Technical Reports Server (NTRS)

    Yang, Ren; Feeback, Daniel L.; Wang, Wan-Jun

    2005-01-01

    This paper details a novel three-dimensional (3D) hydro-focusing micro cell sorter for micro flow cytometry applications. The unit was microfabricated by means of SU-8 3D lithography. The 3D microstructure for coaxial sheathing was designed, microfabricated, and tested. Three-dimensional hydrofocusing capability was demonstrated with an experiment to sort labeled tanned sheep erythrocytes (red blood cells). This polymer hydro-focusing microstructure is easily microfabricated and integrated with other polymer microfluidic structures. Keywords: SU-8, three-dimensional hydro-focusing, microfluidic, microchannel, cytometer

  17. Two-dimensional Ising model on random lattices with constant coordination number

    NASA Astrophysics Data System (ADS)

    Schrauth, Manuel; Richter, Julian A. J.; Portela, Jefferson S. E.

    2018-02-01

    We study the two-dimensional Ising model on networks with quenched topological (connectivity) disorder. In particular, we construct random lattices of constant coordination number and perform large-scale Monte Carlo simulations in order to obtain critical exponents using finite-size scaling relations. We find disorder-dependent effective critical exponents, similar to diluted models, showing thus no clear universal behavior. Considering the very recent results for the two-dimensional Ising model on proximity graphs and the coordination number correlation analysis suggested by Barghathi and Vojta [Phys. Rev. Lett. 113, 120602 (2014), 10.1103/PhysRevLett.113.120602], our results indicate that the planarity and connectedness of the lattice play an important role on deciding whether the phase transition is stable against quenched topological disorder.

  18. Syntheses and structural characterization of Co(II) and Cd(II) coordination polymers with 1,4-bis(imidazolyl)butane ligand

    NASA Astrophysics Data System (ADS)

    Lalegani, Arash; Khalaj, Mehdi; Sedaghat, Sajjad; Łyczko, Krzysztof; Lipkowski, Janusz

    2017-11-01

    Two new coordination polymers, {[Co(bib)3](PF6)2}n (1) and [Cd (bib) Cl2]n (2), were prepared at room temperature by the reaction of appropriate salts of cobalt (II) and cadmium (II) with the flexible linker ligands 1,4-bis(imidazolyl) butane (bib). The compounds were characterized by elemental analyses, IR spectroscopy and single crystal X-ray diffraction. In the polymeric structure of 1, the Co(II) ion lies on an inversion centre and adopts the CoN6 octahedral geometry, while in the structure of 2, the Cd(II) ions adopt the CdN2Cl4 pseudo-octahedral geometry. In compound 1, six bib ligands are coordinated to one central cobalt (II) to form an open 3D 2-fold interpenetrating framework of the α-polonium (pcu) type topology, while in compound 2 two bib ligands are coordinated to one central cadmium (II) to form 2D network structure.

  19. Systematic design and research on a series of cadmium coordination polymers assembled due to tetracarboxylate ligands

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lü, Lei; Mu, Bao; Li, Chang-Xia

    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 4more » 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

  20. Painleve-gullstrand-type Coordinates for the Five-dimensional Myers-Perry Black Hole

    NASA Technical Reports Server (NTRS)

    Finch, Tehani Kahi

    2013-01-01

    The Painleve-Gullstrand coordinates provide a convenient framework for presenting the Schwarzschild geometry because of their flat constant-time hypersurfaces, and the fact that they are free of coordinate singularities outside r=0. Generalizations of Painlev´e-Gullstrand coordinates suitable for the Kerr geometry have been presented by Doran and Nat´ario. These coordinate systems feature a time coordinate identical to the proper time of zero-angular-momentum observers that are dropped from infinity. Here, the methods of Doran and Nat´ario are extended to the five-dimensional rotating black hole found by Myers and Perry. The result is a new formulation of the Myers-Perry metric. The properties and physical significance of these new coordinates are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Four new coordination polymers {[Ni(4-Nbdc)(bpa)(H2O)]}n (1), {[Co(4-Nbdc)(bpp) (H2O)]}n (2), {[Ni(4-Nbdc)(bpp)(H2O)]·H2O}n (3), and {[Mn2(3-Nbdc)2(bib)3]·2H2O}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 (66) dia topology and (44.610.8)(44.62) 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).

  2. A coordination polymer based magnetic adsorbent material for hemoglobin isolation from human whole blood, highly selective and recoverable

    NASA Astrophysics Data System (ADS)

    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.

  3. Hydrothermal Synthesis, Crystal Structure and Electrochemical Behavior of 2d Hybrid Coordination Polymer

    NASA Astrophysics Data System (ADS)

    Fan, Weiqiang; Zhu, Lin; Shi, Weidong; Chen, Fuxiao; Bai, Hongye; Song, Shuyan; Yan, Yongsheng

    2013-04-01

    A novel metal-organic coordination polymer [Cu(phen)(L)0.5(H2O)]n (H4L = (N,N‧-5,5‧-bis(isophthalic acid)-p-xylylenediamine, and phen = 1,10-phenanthroline) has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, and single-crystal X-ray diffraction. The crystallographic data show that the title compound crystallizes in monoclinic space group P21/n with a = 10.682(2), b = 15.682(3), c = 11.909(2) Å, β = 91.39(3)°, V = 1994.3(7) Å3, C24H17CuN3O5, Mr = 490.95, Dc = 1.635 g/cm3, F(000) = 1004, Z = 4, μ(MoKα) = 1.141 mm-1, the final R = 0.0418 and wR = 0.0983 for 3578 observed reflections (I > 2σ(I)). The structural analyses reveal that the title compound exhibits shows a 2D layer structure, which are further linked by hydrogen bonding interactions to form a three-dimensional supramolecular network. In addition, the thermal stability and electrochemical behavior of title compound has been studied. CCDC: 900413.

  4. Multi-particle three-dimensional coordinate estimation in real-time optical manipulation

    NASA Astrophysics Data System (ADS)

    Dam, J. S.; Perch-Nielsen, I.; Palima, D.; Gluckstad, J.

    2009-11-01

    We have previously shown how stereoscopic images can be obtained in our three-dimensional optical micromanipulation system [J. S. Dam et al, Opt. Express 16, 7244 (2008)]. Here, we present an extension and application of this principle to automatically gather the three-dimensional coordinates for all trapped particles with high tracking range and high reliability without requiring user calibration. Through deconvolving of the red, green, and blue colour planes to correct for bleeding between colour planes, we show that we can extend the system to also utilize green illumination, in addition to the blue and red. Applying the green colour as on-axis illumination yields redundant information for enhanced error correction, which is used to verify the gathered data, resulting in reliable coordinates as well as producing visually attractive images.

  5. Photophysical studies of europium coordination polymers based on a tetracarboxylate ligand.

    PubMed

    Gai, Yan-Li; Jiang, Fei-Long; Chen, Lian; Bu, Yang; Su, Kong-Zhao; Al-Thabaiti, Shaeel A; Hong, Mao-Chun

    2013-07-01

    Reaction of europium sulfate octahydrate with p-terphenyl-3,3″,5,5″-tetracarboxylic acid (H4ptptc) in a mixed solvent system has afforded three new coordination polymers formulated as {[Eu(ptptc)0.75(H2O)2]·0.5DMF·1.5H2O}n (1), {[Me2H2N]2 [Eu2(ptptc)2(H2O)(DMF)]·1.5DMF·7H2O}n (2), and {[Eu(Hptptc)(H2O)4]·0.5DMF·H2O}n (3). Complex 1 exhibits a three-dimensional (3D) metal-organic framework based on {Eu2(μ2-COO)2(COO)4}n chains, complex 2 shows a 3D metal-organic framework constructed by [Eu2(μ2-COO)2(COO)6](2-) dimetallic subunits, and complex 3 features a 2D layer architecture assembling to 3D framework through π···π interactions. All complexes exhibit the characteristic red luminescence of Eu(III) ion. The triplet state of ligand H4ptptc matches well with the emission level of Eu(III) ion, which allows the preparation of new optical materials with enhanced luminescence properties. The luminescence properties of these complexes are further studied in terms of their emission quantum yields, emission lifetimes, and the radiative/nonradiative rates.

  6. Syntheses, structures and photoelectric properties of a series of Cd(II)/Zn(II) coordination polymers and coordination supramolecules

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jin Jing; Han Xiao; Meng Qin

    2013-01-15

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz){sub 2}(H{sub 2}O)]{sub n} (1), [Cd1Cd2(btec)(H{sub 2}O){sub 6}]{sub n} (2), [Cd(3,4-pdc) (H{sub 2}O)]{sub n} (3), [Zn(2,5-pdc)(H{sub 2}O){sub 4}]{center_dot}2H{sub 2}O (4) and {l_brace} [Zn(2,5-pdc)(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O{r_brace} {sub n} (5) (H{sub 2}bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H{sub 4}btec=1,2,4,5-benzenetetracarboxylic acid, H{sub 2}pdc=pyridine-dicarboxylic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, surface photovoltage spectroscopy, XRD, TG analysis, IR and UV-vis spectra and elemental analysis. Structural analyses show that complexes 1-3 are 1D, 2D and 3D Cd(II) coordination polymers, respectively. Complex 4 is a mononuclear Zn(II) complex. Complex 5 is a 3D Zn(II) coordination polymer. The surface photoelectric properties of complexesmore » were investigated by SPS. The results indicate that all complexes exhibit photoelectric responses in the range of 300-600 nm, which reveals that they all possess certain photoelectric conversion properties. By the comparative analyses, it can be found that the species and coordination micro-environment of central metal ion, the species and property of ligands affect the intensity and scope of photoelectric response. - Graphical abstract: Five Cd(II)/Zn(II) complexes have been hydrothermally synthesized and characterized. The photoelectric properties were studied with SPS. The species and coordination micro-environment of central metal ion, the species and property of ligands all affect the photoelectric responses. Highlights: Black-Right-Pointing-Pointer Five Cd/Zn complexes have been synthesized and characterized. Black-Right-Pointing-Pointer The SPS results indicate they possess obvious photoelectric conversion property. Black-Right-Pointing-Pointer The species and coordination environment of central metal ion affect SPS. Black-Right-Pointing-Pointer The species and property of ligands

  7. Three-dimensional patterning in polymer optical waveguides using focused ion beam milling

    NASA Astrophysics Data System (ADS)

    Kruse, Kevin; Burrell, Derek; Middlebrook, Christopher

    2016-07-01

    Waveguide (WG) photonic-bridge taper modules are designed for symmetric planar coupling between silicon WGs and single-mode fibers (SMFs) to minimize photonic chip and packaging footprint requirements with improving broadband functionality. Micromachined fabrication and evaluation of polymer WG tapers utilizing high-resolution focused ion beam (FIB) milling is performed and presented. Polymer etch rates utilizing the FIB and optimal methods for milling polymer tapers are identified for three-dimensional patterning. Polymer WG tapers with low sidewall roughness are manufactured utilizing FIB milling and optically tested for fabrication loss. FIB platforms utilize a focused beam of ions (Ga+) to etch submicron patterns into substrates. Fabricating low-loss polymer WG taper prototypes with the FIB before moving on to mass-production techniques provides theoretical understanding of the polymer taper and its feasibility for connectorization devices between silicon WGs and SMFs.

  8. Highly efficient temperature-dependent chiral separation with a nucleotide-based coordination polymer.

    PubMed

    Bruno, Rosaria; Marino, Nadia; Bartella, Lucia; Di Donna, Leonardo; De Munno, Giovanni; Pardo, Emilio; Armentano, Donatella

    2018-06-05

    We report a new chiral coordination polymer, prepared from the cytidine 5'-monophosphate (CMP) nucleotide, capable of separating efficiently (enantiomeric excess of ca. 100%) racemic mixtures of l- and d-Asp in a temperature-dependent manner. The crystal structure of the host-guest adsorbate, with the d-Asp guest molecules loaded within its channels, could be solved allowing a direct visualization of the chiral recognition process.

  9. Coordination Polymers of 5-Alkoxy Isophthalic Acids

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    McCormick, Laura J.; Morris, Samuel A.; Slawin, Alexandra M. Z.

    The topology of coordination polymers containing 5-alkoxy isophthalic acids and first row transition metals was found to be dependent on the combination of solvent system used and length of the alkyl chain. Four different framework types were thus identified: Phase A, M 6(ROip) 5(OH) 2(H 2O) 4·xH 2O (M = Co and R = Et, Pr, or nBu, or M = Zn and R = Et); Phase B,M 2(ROip) 2(H 2O) (M = Co or Zn and R = Et, Pr, nBu, or iBu, or M = Mn and R = nBu or iBu); Phase C, Zn 3(EtOip) 2(OH) 2;more » and Phase D, Zn 2(EtOip) 2(H 2O) 3. Preliminary screening of the NO storage and release capabilities of the Co-containing materials is also reported.« less

  10. Coordination Polymers of 5-Alkoxy Isophthalic Acids

    DOE PAGES

    McCormick, Laura J.; Morris, Samuel A.; Slawin, Alexandra M. Z.; ...

    2016-08-23

    The topology of coordination polymers containing 5-alkoxy isophthalic acids and first row transition metals was found to be dependent on the combination of solvent system used and length of the alkyl chain. Four different framework types were thus identified: Phase A, M 6(ROip) 5(OH) 2(H 2O) 4·xH 2O (M = Co and R = Et, Pr, or nBu, or M = Zn and R = Et); Phase B,M 2(ROip) 2(H 2O) (M = Co or Zn and R = Et, Pr, nBu, or iBu, or M = Mn and R = nBu or iBu); Phase C, Zn 3(EtOip) 2(OH) 2;more » and Phase D, Zn 2(EtOip) 2(H 2O) 3. Preliminary screening of the NO storage and release capabilities of the Co-containing materials is also reported.« less

  11. Facile synthesis of novel two- and three-dimensional coordination polymers containing dialkyltin phosphonate-based tri/tetra-nuclear clusters with appended sulfonate groups.

    PubMed

    Shankar, Ravi; Jain, Archana; Singh, Atul Pratap; Kociok-Köhn, Gabriele; Molloy, Kieran C

    2009-04-20

    The coordination-driven self-assemblies of mixed-ligand dialkyltin derivatives, [(Et(2)Sn)(4) (O(2)P(OH)Me)(2)(O(3)PMe)(2)(OSO(2)Et)(2) x 2 H(2)O](n) 1, [(Et(2)Sn)(3)(O(3)PMe)(2)(OSO(2)Me)(2) x CHCl(3)](n) 2, and [(Me(2)Sn)(3)(O(3)PBu(t))(2)(OSO(2)Me)(2) x 2 CHCl(3)](n) 3 have been achieved by reacting the tin precursors, [R(2)Sn(OR(1))(OSO(2)R(1))](n) (R = Et, R(1) = Et (1a), Me (2a); R = Me, R(1) = Me (3a)) with an equimolar amount of methylphosphonic/t-butylphosphonic acid under mild conditions (rt, 8 h, CH(2)Cl(2)). These have been characterized by IR and multinuclear ((1)H, (13)C, (31)P, and (119)Sn) NMR spectroscopy as well as single crystal X-ray diffraction. The asymmetric unit of 1 is composed of a tetranuclear, Sn(4)(mu(2)-PO(2))(2)(mu(3)-PO(3))(2) core bearing an appended ethanesulfonate group on each terminal tin (Sn2) atom and two P(OH)...O hydrogen bonded water molecules. The ladder-like structural motif thus formed is extended into one-dimensional polymeric chains by virtue of bridging bidentate mode of the sulfonate groups. These chains are linked by O-H...O(S) hydrogen bonds involving H(2)O molecules and oxygen atoms of the sulfonate groups. The asymmetric units of 2 and 3 are composed of trinuclear tin clusters with a Sn(3)(mu(3)-PO(3))(2) core and two dangling methanesulfonate groups which are covalently bonded to the tin centers. The construction of three-dimensional self-assemblies is effected by variable bonding modes (mu(2), mu(3) in 2; mu(2) in 3) of the methanesulfonate groups. Both the structural motifs possess five- and six-coordinated tin atoms and form rectangular channels which are occupied by CHCl(3) molecules.

  12. Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide

    PubMed Central

    Tran, Phong D.; Tran, Thu V.; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

    2017-01-01

    Molybdenum sulfides are very attractive noble-metal free electrocatalysts for the hydrogen evolution reaction (HER) from water. Atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx) which displays significantly higher HER activity compared to its crystalline counterpart. Here we show that HER–active a-MoSx, prepared either as nanoparticles or as films, is a molecular–based coordination polymer consisting of discrete [Mo3S13]2– building blocks. Of the three terminal disulfide (S22–) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimisation of this HER electrocatalyst as an alternative to platinum. PMID:26974410

  13. Linking 1D Transition-Metal Coordination Polymers and Different Inorganic Boron Oxides To Construct a Series of 3D Inorganic-Organic Hybrid Borates.

    PubMed

    Zhi, Shao-Chen; Wang, Yue-Lin; Sun, Li; Cheng, Jian-Wen; Yang, Guo-Yu

    2018-02-05

    Three inorganic-organic hybrid borates, M(1,4-dab)[B 5 O 7 (OH) 3 ] [M = Zn (1), Cd (2), 1,4-dab = 1,4-diaminobutane)] and Co(1,3-dap)[B 4 O 7 ] (3, 1,3-dap = 1,3-diaminopropane), which integrated characteristics of 1D coordination polymers and 1D/3D inorganic boron oxides have been obtained under solvothermal conditions. Compounds 1 and 2 are isostructural and crystallize in a centrosymmetric space group P2 1 /c; the 3D achiral structures of 1 and 2 consist of the nonhelical Zn/Cd-1,4-dap coordination polymers and 1D B-O chains. Compound 3 crystallizes in a chiral space group P4 3 2 1 2; the helical Co-1,3-dap coordination polymer chains are entrained within a 3D B-O network and finally form the chiral framework. Compounds 1-3 represent good examples of using coordination polymers to construct mixed-motif inorganic-organic hybrid borates. Compounds 1 and 2 display blue luminescence when excited with UV light.

  14. Anisotropic compressibility of the coordination polymer emim[Mn(btc)].

    PubMed

    Madsen, Solveig R; Moggach, Stephen A; Overgaard, Jacob; Brummerstedt Iversen, Bo

    2016-06-01

    The effect of pressure on the crystal structure of a coordination polymer, emim[Mn(II)(btc)] (emim = 1-ethyl,3-methyl imidazolium cation, btc = 1,3,5-benzene-tricarboxylate), was investigated with single-crystal X-ray diffraction. At 4.3 GPa the unit-cell volume had decreased by 14% compared with ambient conditions. The unit-cell contraction is highly anisotropic, with the a- and b-axes decreasing by 5.5 and 9.5%, respectively, and the c-axis compressing a mere 0.25% up to 1.7 GPa followed by a 0.2% expansion between 1.7 and 4.3 GPa. The 0.2% increase in length of the c-axis in this interval happens above the quasi-hydrostatic limit of the pressure-transmitting medium and therefore it might be a consequence of strain gradients. Under ambient conditions, two MnO6 units are connected by two carboxylate ligands to form dimeric units. On increasing pressure, a non-bonded O atom from a bridging carboxylate group approaches the Mn atom, with the Mn-O distance decreasing from 2.866 (1) Å at 0.3 GPa to 2.482 (6) Å at 4.3 GPa, increasing the coordination environment of the Mn ion from six- to seven-coordinated.

  15. 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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

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

    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)]{sub 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)]{sub 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 ofmore » 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)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)]{sub 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.« less

  16. Highly Sensitive Detection of UV Radiation Using a Uranium Coordination Polymer.

    PubMed

    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.

  17. Microfabrication and Test of a Three-Dimensional Polymer Hydro-focusing Unit for Flow Cytometry Applications

    NASA Technical Reports Server (NTRS)

    Yang, Ren; Feeback, Daniel L.; Wang, Wanjun

    2004-01-01

    This paper details a novel three-dimensional (3D) hydro-focusing micro cell sorter for micro flow cytometry applications. The unit was microfabricated by means of SU-8 3D lithography. The 3D microstructure for coaxial sheathing was designed, microfabricated, and tested. Three-dimensional hydro-focusing capability was demonstrated with an experiment to sort labeled tanned sheep erythrocytes (red blood cells). This polymer hydro-focusing microstructure is easily microfabricated and integrated with other polymer microfluidic structures.

  18. Microfabrication and Test of a Three-Dimensional Polymer Hydro-Focusing Unit for Flow Cytometry Applications

    NASA Technical Reports Server (NTRS)

    Yang, Ren; Feedback, Daniel L.; Wang, Wanjun

    2004-01-01

    This paper details a novel three-dimensional (3D) hydro-focusing micro cell sorter for micro flow cytometry applications. The unit was micro-fabricated by means of SU-8 3D lithography. The 3D microstructure for coaxial sheathing was designed, micro-fabricated, and tested. Three-dimensional hydrofocusing capability was demonstrated with an experiment to sort labeled tanned sheep erythrocytes (red blood cells). This polymer hydro-focusing microstructure is easily micro-fabricated and integrated with other polymer microfluidic structures.

  19. Facile synthesis of 2D Zn(II) coordination polymer and its crystal structure, selective removal of methylene blue and molecular simulations

    NASA Astrophysics Data System (ADS)

    Sezer, Güneş Günay; Yeşilel, Okan Zafer; Şahin, Onur; Arslanoğlu, Hasan; Erucar, İlknur

    2017-09-01

    A new coordination polymer {[Zn(μ3-ppda)(H2O)(μ-bpa)Zn(μ-ppda)(μ-bpa)]·4H2O}n (1) (ppda = 1,4-phenylenediacetate, bpa = 1,2-bis(4-pyridyl)ethane) has been synthesized by microwave-assisted reaction and characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffractions. The asymmetric unit of 1 consists of two Zn(II) ions, two bpa ligands, two ppda ligands, one coordinated and four non-coordinated water molecules. In 1, ppda2- anions are linked the adjacent Zn(II) centers to generate 1D double-stranded chains. These chains are connected into 2D sheets by the bridging bpa ligands. Atomically detailed modeling was performed to compute single and binary component adsorption isotherms of H2, CO2, CH4 and N2 in complex 1. Results showed that 1 exhibits a high adsorption selectivity towards CO2 due to its high affinity for CO2. Results of this study will be helpful to guide the microwave-assisted reaction of coordination polymers to design promising adsorbents for gas storage and gas separation applications. The luminescent property of 1 and the selective removal of dyes in 1 have been also discussed. Results showed that 1 can be a potential candidate for luminescence applications and can selectively adsorb methylene blue (MB) dye molecules.

  20. Exciton size and binding energy limitations in one-dimensional organic materials

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kraner, S., E-mail: stefan.kraner@iapp.de; Koerner, C.; Leo, K.

    2015-12-28

    In current organic photovoltaic devices, the loss in energy caused by the charge transfer step necessary for exciton dissociation leads to a low open circuit voltage, being one of the main reasons for rather low power conversion efficiencies. A possible approach to avoid these losses is to tune the exciton binding energy to a value of the order of thermal energy, which would lead to free charges upon absorption of a photon, and therefore increase the power conversion efficiency towards the Shockley-Queisser limit. We determine the size of the excitons for different organic molecules and polymers by time dependent densitymore » functional theory calculations. For optically relevant transitions, the exciton size saturates around 0.7 nm for one-dimensional molecules with a size longer than about 4 nm. For the ladder-type polymer poly(benzimidazobenzophenanthroline), we obtain an exciton binding energy of about 0.3 eV, serving as a lower limit of the exciton binding energy for the organic materials investigated. Furthermore, we show that charge transfer transitions increase the exciton size and thus identify possible routes towards a further decrease of the exciton binding energy.« less

  1. Exciton size and binding energy limitations in one-dimensional organic materials.

    PubMed

    Kraner, S; Scholz, R; Plasser, F; Koerner, C; Leo, K

    2015-12-28

    In current organic photovoltaic devices, the loss in energy caused by the charge transfer step necessary for exciton dissociation leads to a low open circuit voltage, being one of the main reasons for rather low power conversion efficiencies. A possible approach to avoid these losses is to tune the exciton binding energy to a value of the order of thermal energy, which would lead to free charges upon absorption of a photon, and therefore increase the power conversion efficiency towards the Shockley-Queisser limit. We determine the size of the excitons for different organic molecules and polymers by time dependent density functional theory calculations. For optically relevant transitions, the exciton size saturates around 0.7 nm for one-dimensional molecules with a size longer than about 4 nm. For the ladder-type polymer poly(benzimidazobenzophenanthroline), we obtain an exciton binding energy of about 0.3 eV, serving as a lower limit of the exciton binding energy for the organic materials investigated. Furthermore, we show that charge transfer transitions increase the exciton size and thus identify possible routes towards a further decrease of the exciton binding energy.

  2. One-Dimensional Fokker-Planck Equation with Quadratically Nonlinear Quasilocal Drift

    NASA Astrophysics Data System (ADS)

    Shapovalov, A. V.

    2018-04-01

    The Fokker-Planck equation in one-dimensional spacetime with quadratically nonlinear nonlocal drift in the quasilocal approximation is reduced with the help of scaling of the coordinates and time to a partial differential equation with a third derivative in the spatial variable. Determining equations for the symmetries of the reduced equation are derived and the Lie symmetries are found. A group invariant solution having the form of a traveling wave is found. Within the framework of Adomian's iterative method, the first iterations of an approximate solution of the Cauchy problem are obtained. Two illustrative examples of exact solutions are found.

  3. Outgassing and dimensional changes of polymer matrix composites in space

    NASA Technical Reports Server (NTRS)

    Tennyson, R. C.; Matthews, R.

    1993-01-01

    A thermal-vacuum outgassing model and test protocol for predicting outgassing times and dimensional changes for polymer matrix composites is described. Experimental results derived from a 'control' sample are used to provide the basis for analytical predictions to compare with the outgassing response of Long Duration Exposure Facility (LDEF) flight samples.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Approximating high-dimensional dynamics by barycentric coordinates with linear programming.

    PubMed

    Hirata, Yoshito; Shiro, Masanori; Takahashi, Nozomu; Aihara, Kazuyuki; Suzuki, Hideyuki; Mas, Paloma

    2015-01-01

    The increasing development of novel methods and techniques facilitates the measurement of high-dimensional time series but challenges our ability for accurate modeling and predictions. The use of a general mathematical model requires the inclusion of many parameters, which are difficult to be fitted for relatively short high-dimensional time series observed. Here, we propose a novel method to accurately model a high-dimensional time series. Our method extends the barycentric coordinates to high-dimensional phase space by employing linear programming, and allowing the approximation errors explicitly. The extension helps to produce free-running time-series predictions that preserve typical topological, dynamical, and/or geometric characteristics of the underlying attractors more accurately than the radial basis function model that is widely used. The method can be broadly applied, from helping to improve weather forecasting, to creating electronic instruments that sound more natural, and to comprehensively understanding complex biological data.

  6. A two-dimensional DNA lattice implanted polymer solar cell.

    PubMed

    Lee, Keun Woo; Kim, Kyung Min; Lee, Junwye; Amin, Rashid; Kim, Byeonghoon; Park, Sung Kye; Lee, Seok Kiu; Park, Sung Ha; Kim, Hyun Jae

    2011-09-16

    A double crossover tile based artificial two-dimensional (2D) DNA lattice was fabricated and the dry-wet method was introduced to recover an original DNA lattice structure in order to deposit DNA lattices safely on the organic layer without damaging the layer. The DNA lattice was then employed as an electron blocking layer in a polymer solar cell causing an increase of about 10% up to 160% in the power conversion efficiency. Consequently, the resulting solar cell which had an artificial 2D DNA blocking layer showed a significant enhancement in power conversion efficiency compared to conventional polymer solar cells. It should be clear that the artificial DNA nanostructure holds unique physical properties that are extremely attractive for various energy-related and photonic applications.

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

    PubMed

    Perez, Emilie; Andre, Marie-Laure; Navarro Amador, Ricardo; Hyvrard, François; Borrini, Julien; Carboni, Michaël; Meyer, Daniel

    2016-11-05

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Photodeposition Method For Fabricating A Three-Dimensional, Patterned Polymer Microstructure

    DOEpatents

    Walt, David R.; Healey, Brian G.

    2001-03-13

    The present invention is a photodeposition methodology for fabricating a three-dimensional patterned polymer microstructure. A variety of polymeric structures can be fabricated on solid substrates using unitary fiber optic arrays for light delivery. The methodology allows micrometer-scale photopatterning for the fabricated structures using masks substantially larger than the desired dimensions of the microstructure.

  9. Ordered quasi-two-dimensional structure of nanoparticles in semiflexible ring polymer brushes under compression

    NASA Astrophysics Data System (ADS)

    Hua, Yunfeng; Deng, Zhenyu; Jiang, Yangwei; Zhang, Linxi

    2017-06-01

    Molecular dynamics simulations of a coarse-grained bead-spring model of ring polymer brushes under compression are presented. Flexible polymer brushes are always disordered during compression, whereas semiflexible polymer brushes tend to be ordered under sufficiently strong compression. Further, the polymer monomer density of the semiflexible polymer brush is very high near the brush surface, inducing a peak value of the free energy near the surface. Therefore, when nanoparticles are compressed in semiflexible ring polymer brushes, they tend to exhibit a closely packed single-layer structure between the brush surface and the impenetrable wall, and a quasi-two-dimensional ordered structure near the brush surface is formed under strong compression. These findings provide a new approach to designing responsive applications.

  10. Coordination Polymers Derived from Non-Steroidal Anti-Inflammatory Drugs for Cell Imaging and Drug Delivery.

    PubMed

    Paul, Mithun; Dastidar, Parthasarathi

    2016-01-18

    A new series of Mn(II) coordination polymers, namely, [{Mn(L)(H2 O)2 }⋅2 Nap]∞ (CP1), [{Mn(L)(Ibu)2 (H2 O)2 }]∞ (CP2), [{Mn(L)(Flr)2 (H2 O)2 }]∞ (CP3), [{Mn(L)(Ind)2 (H2 O)2 }⋅H2 O]∞ (CP4), [{Mn2 (L)2 (μ-Flu)4 (H2 O)}⋅L]∞ (CP5), [{Mn2 (L)2 (μ-Tol)4 (H2 O)2 }]∞ (CP6) and [{Mn2 (L)2 (μ-Mef)4 (H2 O)2 }]∞ (CP7) (Nap=naproxen, Ibu=ibuprofen, Flr=flurbiprofen, Ind=indometacin, Flu=flufenamic acid, Tol=tolfenamic acid and Mef=mefenamic acid) derived from various non-steroidal anti-inflammatory drugs (NSAIDs) and the organic linker 1,2-bis(4-pyridyl)ethylene (L) have been synthesized with the aim of being used for cell imaging and drug delivery. Single-crystal X-ray diffraction (SXRD) studies revealed that the NSAID molecules were part of the coordination polymeric network either through coordination to the metal center (in the majority of the cases) or through hydrogen bonding. Remarkably, all the Mn(II) coordination polymers were found to be soluble in DMSO, thereby making them particularly suitable for the desired biological applications. Two of the coordination polymers (namely, CP1 and CP3) reported herein, were found to be photoluminescent both in the solid as well as in the solution state. Subsequent experiments (namely, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), and PGE2 (prostaglandin E2 ) assays) established their biocompatibility and anti-inflammatory response. In vitro studies by using a macrophage cell line (i.e., RAW 264.7) revealed that both CP1 and CP3 were excellent cell imaging agents. Finally, biodegradability studies under simulated physiological conditions in phosphate-buffered saline (PBS) at pH 7.6 showed that slow and sustained release of the corresponding NSAID was indeed possible from both CP1 and CP3. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Approximating high-dimensional dynamics by barycentric coordinates with linear programming

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hirata, Yoshito, E-mail: yoshito@sat.t.u-tokyo.ac.jp; Aihara, Kazuyuki; Suzuki, Hideyuki

    The increasing development of novel methods and techniques facilitates the measurement of high-dimensional time series but challenges our ability for accurate modeling and predictions. The use of a general mathematical model requires the inclusion of many parameters, which are difficult to be fitted for relatively short high-dimensional time series observed. Here, we propose a novel method to accurately model a high-dimensional time series. Our method extends the barycentric coordinates to high-dimensional phase space by employing linear programming, and allowing the approximation errors explicitly. The extension helps to produce free-running time-series predictions that preserve typical topological, dynamical, and/or geometric characteristics ofmore » the underlying attractors more accurately than the radial basis function model that is widely used. The method can be broadly applied, from helping to improve weather forecasting, to creating electronic instruments that sound more natural, and to comprehensively understanding complex biological data.« less

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

    PubMed

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

    2016-12-20

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

  13. Novel polymer-free iridescent lamellar hydrogel for two-dimensional confined growth of ultrathin gold membranes

    NASA Astrophysics Data System (ADS)

    Niu, Jian; Wang, Dong; Qin, Haili; Xiong, Xiong; Tan, Pengli; Li, Youyong; Liu, Rui; Lu, Xuxing; Wu, Jian; Zhang, Ting; Ni, Weihai; Jin, Jian

    2014-02-01

    Hydrogels are generally thought to be formed by nano- to micrometre-scale fibres or polymer chains, either physically branched or entangled with each other to trap water. Although there are also anisotropic hydrogels with apparently ordered structures, they are essentially polymer fibre/discrete polymer chains-based network without exception. Here we present a type of polymer-free anisotropic lamellar hydrogels composed of 100-nm-thick water layers sandwiched by two bilayer membranes of a self-assembled nonionic surfactant, hexadecylglyceryl maleate. The hydrogels appear iridescent as a result of Bragg’s reflection of visible light from the periodic lamellar plane. The particular lamellar hydrogel with extremely wide water spacing was used as a soft two-dimensional template to synthesize single-crystalline nanosheets in the confined two-dimensional space. As a consequence, flexible, ultrathin and large area single-crystalline gold membranes with atomically flat surface were produced in the hydrogel. The optical and electrical properties were detected on a single gold membrane.

  14. Coordination Polymer Gels with Modular Nanomorphologies, Tunable Emissions, and Stimuli-Responsive Behavior Based on an Amphiphilic Tripodal Gelator.

    PubMed

    Sutar, Papri; Maji, Tapas Kumar

    2017-08-21

    The recent upsurge in research on coordination polymer gels (CPGs) stems from their synthetic modularity, nanoscale processability, and versatile functionalities. Here we report self-assembly of an amphiphilic, tripodal low-molecular weight gelator (L) that consists of 4,4',4-[1,3,5-phenyl-tri(methoxy)]-tris-benzene core and 2,2':6',2″-terpyridyl termini, with different metal ions toward the formation of CPGs that show controllable nanomorphologies, tunable emission, and stimuli-responsive behaviors. L can also act as a selective chemosensor for Zn II with very low limit of detection (0.18 ppm) in aqueous medium. Coordination-driven self-assembly of L with Zn II in H 2 O/MeOH solvent mixture results in a coordination polymer hydrogel (ZnL) that exhibits sheet like morphology and charge-transfer emission. On the other hand, coordination of L with Tb III and Eu III in CHCl 3 /tetrahydrofuran solvent mixture results in green- and red-emissive CPGs, respectively, with nanotubular morphology. Moreover, precise stoichiometric control of L/Eu III /Tb III ratio leads to the formation of bimetallic CPGs that show emissions over a broad spectral range, including white-light-emission. We also explore the multistimuli responsive properties of the white-light-emitting CPG by exploiting the dynamics of Ln III -tpy coordination.

  15. Flexible porous coordination polymer of Ni(II) for developing nanoparticles through acid formation and redox activity of the framework

    NASA Astrophysics Data System (ADS)

    Agarwal, Rashmi A.

    2017-10-01

    Immobilization of the nanoparticles (NPs) in a two dimensional porous coordination polymer (PCP) is currently an emerging field for a number of applications. But still it is a great challenge to fabricate any specified metal NPs in a single network. Herein the synthesis of Au, Pd, Mn, Fe, Cu, Zn, Mg, Li, Fe/Cu, Zn/Mg etc, NPs in a highly flexible PCP of Ni(II); {[Ni3(TBIB)2(BTC)2(H2O)6]·5C2H5OH·9H2O}n [TBIB = 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene, H3BTC = 1,3,5-benzenetricarboxylic acid] have been reported. This universal host is able to grow mixed metal NPs from mixed metal precursors. Monodentate carboxylate groups of BTC linker act as anchoring sites for the metal ions of the metal precursors. This is the main driving force to grow NPs within the cavities along with the high flexibility of this polymer at room temperature. Mechanism involves acid formation followed by redox reaction to synthesize metal NPs explained by EPR and FTIR. Paramagnetic properties have been shown by as-synthesized Fe NPs integrated framework at room temperature under applied magnetic field up to 17,500 Oe.

  16. Low-dimensional quantum magnetism in Cu (NCS) 2: A molecular framework material

    NASA Astrophysics Data System (ADS)

    Cliffe, Matthew J.; Lee, Jeongjae; Paddison, Joseph A. M.; Schott, Sam; Mukherjee, Paromita; Gaultois, Michael W.; Manuel, Pascal; Sirringhaus, Henning; Dutton, Siân E.; Grey, Clare P.

    2018-04-01

    Low-dimensional magnetic materials with spin-1/2 moments can host a range of exotic magnetic phenomena due to the intrinsic importance of quantum fluctuations to their behavior. Here, we report the structure, magnetic structure, and magnetic properties of copper ii thiocyanate, Cu(NCS ) 2, a one-dimensional coordination polymer which displays low-dimensional quantum magnetism. Magnetic susceptibility, electron paramagnetic resonance spectroscopy, 13C magic-angle spinning nuclear magnetic resonance spectroscopy, and density functional theory investigations indicate that Cu(NCS ) 2 behaves as a two-dimensional array of weakly coupled antiferromagnetic spin chains [J2=133 (1 ) K , α =J1/J2=0.08 ] . Powder neutron-diffraction measurements confirm that Cu(NCS ) 2 orders as a commensurate antiferromagnet below TN=12 K , with a strongly reduced ordered moment (0.3 μB ) due to quantum fluctuations.

  17. Three-dimensional radiation dosimetry using polymer gel and solid radiochromic polymer: From basics to clinical applications

    PubMed Central

    Watanabe, Yoichi; Warmington, Leighton; Gopishankar, N

    2017-01-01

    Accurate dose measurement tools are needed to evaluate the radiation dose delivered to patients by using modern and sophisticated radiation therapy techniques. However, the adequate tools which enable us to directly measure the dose distributions in three-dimensional (3D) space are not commonly available. One such 3D dose measurement device is the polymer-based dosimeter, which changes the material property in response to radiation. These are available in the gel form as polymer gel dosimeter (PGD) and ferrous gel dosimeter (FGD) and in the solid form as solid plastic dosimeter (SPD). Those are made of a continuous uniform medium which polymerizes upon irradiation. Hence, the intrinsic spatial resolution of those dosimeters is very high, and it is only limited by the method by which one converts the dose information recorded by the medium to the absorbed dose. The current standard methods of the dose quantification are magnetic resonance imaging, optical computed tomography, and X-ray computed tomography. In particular, magnetic resonance imaging is well established as a method for obtaining clinically relevant dosimetric data by PGD and FGD. Despite the likely possibility of doing 3D dosimetry by PGD, FGD or SPD, the tools are still lacking wider usages for clinical applications. In this review article, we summarize the current status of PGD, FGD, and SPD and discuss the issue faced by these for wider acceptance in radiation oncology clinic and propose some directions for future development. PMID:28396725

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

    NASA Astrophysics Data System (ADS)

    Li, Wenjie; Li, Guoting; Lv, Lulu; Zhao, Hong; Wu, Benlai

    2015-05-01

    Four metal-5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic)2(H2O)2]n (1), [Ni(Brnic)2]n (2), [Ni(Brnic)(bpy)(H2O)2]n·n(Brnic)·4.5nH2O (3), and [Co2(Brnic)3(bpy)2(OH)]n·nH2O (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 [Ni2(Brnic)4] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni2(Brnic)2] and trigons [Co2(Brnic)3(OH)], 63-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 [Ni2(Brnic)4] and trigon [Co2(Brnic)3(OH)] cores, respectively.

  19. Zinc coordination polymers containing substituted isophthalate ligands and fragments from in situ hydrolysis of 4-pyridylisonicotinamide

    NASA Astrophysics Data System (ADS)

    O'Donovan, Megan E.; LaDuca, Robert L.

    2015-03-01

    Hydrothermal treatment of zinc nitrate, a 5-substituted isophthalic acid, and 4-pyridylisonicotinamide (4-pina) resulted in crystalline coordination polymers that incorporated different fragments formed by in situ hydrolysis of the 4-pina precursor. These materials were characterized by single crystal X-ray diffraction. In the case of {[4-ampyrH]2[Zn(hip)2]·H2O}n (1, 4-ampyrH = 4-aminopyridinium, hip = 5-hydroxyisophthalate), anionic [Zn(hip)2]n2n- (4,4) grid layers co-crystallize with protonated 4-ampyr cations. Using 5-nitroisophthalic acid (H2nip), [Zn7(isonic)4(OH)6(nip)2]n (2, isonic = isonicotinate) was formed. This material manifests [Zn7(OH)6]n cationic inorganic chain motifs linked by isonic and nip ligands into a non-interpenetrated 3-D coordination polymer network with pcu topology. Luminescent behavior is attributed to intra-ligand molecular orbital transitions.

  20. Two-fold interpenetrating btc based cobaltous coordination polymer: A promising catalyst for solvent free oxidation of 1-hexene

    NASA Astrophysics Data System (ADS)

    Bora, Sanchay J.; Paul, Rima; Nandi, Mithun; Bhattacharyya, Pradip K.

    2017-12-01

    This work describes the synthesis of a new 2-D coordination polymer (CP), [Co3(btc)2(dmp)8]n (btc = 1,3,5-benzenetricarboxylate and dmp = 3,5-dimethylpyrazole) and its catalytic activity towards the oxidation reaction of 1-hexene to form oxygenated compounds under solvent free condition. Structural analysis reveals that Co(II) cations in this polymeric compound are linked by btc3- anions with alternate tetrahedral/octahedral coordination forming a two-fold interpenetrated 3-connected hcb underlying net. Electronic spectrum of the cobaltous polymer has been calculated using TDDFT/B3LYP method for making the appropriate assignments of electronic transitions. Catalytic results show good conversions of the starting material to oxygenated products with high selectivities for 1,2-epoxyhexane and 1-hexanal.

  1. A threefold interpenetrated two-dimensional zinc(II) supramolecular architecture based on 3-nitrobenzoic acid and 4,4'-bipyridine.

    PubMed

    Tang, Long; Wang, Ji-Jiang; Fu, Feng; Wang, Sheng-Wen; Liu, Qi-Rui

    2016-02-01

    With regard to crystal engineering, building block or modular assembly methodologies have shown great success in the design and construction of metal-organic coordination polymers. The critical factor for the construction of coordination polymers is the rational choice of the organic building blocks and the metal centre. The reaction of Zn(OAc)2·2H2O (OAc is acetate) with 3-nitrobenzoic acid (HNBA) and 4,4'-bipyridine (4,4'-bipy) under hydrothermal conditions produced a two-dimensional zinc(II) supramolecular architecture, catena-poly[[bis(3-nitrobenzoato-κ(2)O,O')zinc(II)]-μ-4,4'-bipyridine-κ(2)N:N'], [Zn(C7H4NO4)2(C10H8N2)]n or [Zn(NBA)2(4,4'-bipy)]n, which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction analysis. The Zn(II) ions are connected by the 4,4'-bipy ligands to form a one-dimensional zigzag chain and the chains are decorated with anionic NBA ligands which interact further through aromatic π-π stacking interactions, expanding the structure into a threefold interpenetrated two-dimensional supramolecular architecture. The solid-state fluorescence analysis indicates a slight blue shift compared with pure 4,4'-bipyridine and HNBA.

  2. Hydrothermal synthesis and structural characterization of a novel three-dimensional supramolecular framework constructed by zinc salt and pyridine-2,5-dicarboxylate

    NASA Astrophysics Data System (ADS)

    Wang, Xinlong; Qin, Chao; Wang, Enbo; Hu, Changwen; Xu, Lin

    2004-07-01

    A novel metal-organic coordination polymer, [Zn(PDB)(H 2O) 2] 4 n (H 2PDB=pyridine-2,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. Colorless crystals crystallized in the triclinic system, space group P-1, a=7.0562(14) Å, b=7.38526(15) Å, c=18.4611(4) Å, α=90.01(3)°, β=96.98(3)°, γ=115.67(3)°, V=859.1(3) Å 3, Z=1 and R=0.0334. The structure of the compound exhibits a novel three-dimensional supramolecular network, mainly based on multipoint hydrogen bonds originated from within and outside of a large 24-membered ring. Interestingly, the three-dimensional network consists of one-dimensional parallelogrammic channels in which coordinated water molecules point into the channel wall.

  3. Algorithm for transforming the coordinates of lunar objects while changing from various coordinate systems into the selenocentric one

    NASA Astrophysics Data System (ADS)

    Mazurova, Elena; Mikhaylov, Aleksandr

    2013-04-01

    The selenocentric network of objects setting the coordinate system on the Moon, with the origin coinciding with the mass centre and axes directed along the inertia axes can become one of basic elements of the coordinate-time support for lunar navigation with use of cartographic materials and control objects. A powerful array of highly-precise and multiparameter information obtained by modern space vehicles allows one to establish Lunar Reference Frames (LRF) of an essentially another accuracy. Here, a special role is played by the results of scanning the lunar surface by the Lunar Reconnaissance Orbiter(LRO) American mission. The coordinates of points calculated only from the results of laser scanning have high enough accuracy of position definition with respect to each other, but it is possible to check up the real accuracy of spatial tie and improve the coordinates only by a network of points whose coordinates are computed both from laser scanning and other methods too, for example, by terrestrial laser location, space photogrammetry methods, and so on. The paper presents the algorithm for transforming selenocentric coordinate systems and the accuracy estimation of changing from one lunar coordinate system to another one. Keywords: selenocentric coordinate system, coordinate-time support.

  4. One-dimensional Gromov minimal filling problem

    NASA Astrophysics Data System (ADS)

    Ivanov, Alexandr O.; Tuzhilin, Alexey A.

    2012-05-01

    The paper is devoted to a new branch in the theory of one-dimensional variational problems with branching extremals, the investigation of one-dimensional minimal fillings introduced by the authors. On the one hand, this problem is a one-dimensional version of a generalization of Gromov's minimal fillings problem to the case of stratified manifolds. On the other hand, this problem is interesting in itself and also can be considered as a generalization of another classical problem, the Steiner problem on the construction of a shortest network connecting a given set of terminals. Besides the statement of the problem, we discuss several properties of the minimal fillings and state several conjectures. Bibliography: 38 titles.

  5. The Extraction of One-Dimensional Flow Properties from Multi-Dimensional Data Sets

    NASA Technical Reports Server (NTRS)

    Baurle, Robert A.; Gaffney, Richard L., Jr.

    2007-01-01

    The engineering design and analysis of air-breathing propulsion systems relies heavily on zero- or one-dimensional properties (e.g. thrust, total pressure recovery, mixing and combustion efficiency, etc.) for figures of merit. The extraction of these parameters from experimental data sets and/or multi-dimensional computational data sets is therefore an important aspect of the design process. A variety of methods exist for extracting performance measures from multi-dimensional data sets. Some of the information contained in the multi-dimensional flow is inevitably lost when any one-dimensionalization technique is applied. Hence, the unique assumptions associated with a given approach may result in one-dimensional properties that are significantly different than those extracted using alternative approaches. The purpose of this effort is to examine some of the more popular methods used for the extraction of performance measures from multi-dimensional data sets, reveal the strengths and weaknesses of each approach, and highlight various numerical issues that result when mapping data from a multi-dimensional space to a space of one dimension.

  6. Multielectron-Transfer-based Rechargeable Energy Storage of Two-Dimensional Coordination Frameworks with Non-Innocent Ligands.

    PubMed

    Wada, Keisuke; Sakaushi, Ken; Sasaki, Sono; Nishihara, Hiroshi

    2018-04-19

    The metallically conductive bis(diimino)nickel framework (NiDI), an emerging class of metal-organic framework (MOF) analogues consisting of two-dimensional (2D) coordination networks, was found to have an energy storage principle that uses both cation and anion insertion. This principle gives high energy led by a multielectron transfer reaction: Its specific capacity is one of the highest among MOF-based cathode materials in rechargeable energy storage devices, with stable cycling performance up to 300 cycles. This mechanism was studied by a wide spectrum of electrochemical techniques combined with density-functional calculations. This work shows that a rationally designed material system of conductive 2D coordination networks can be promising electrode materials for many types of energy devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Universality class of the two-dimensional polymer collapse transition

    NASA Astrophysics Data System (ADS)

    Nahum, Adam

    2016-05-01

    The nature of the θ point for a polymer in two dimensions has long been debated, with a variety of candidates put forward for the critical exponents. This includes those derived by Duplantier and Saleur for an exactly solvable model. We use a representation of the problem via the CPN -1σ model in the limit N →1 to determine the stability of this critical point. First we prove that the Duplantier-Saleur (DS) critical exponents are robust, so long as the polymer does not cross itself: They can arise in a generic lattice model and do not require fine-tuning. This resolves a longstanding theoretical question. We also address an apparent paradox: Two different lattice models, apparently both in the DS universality class, show different numbers of relevant perturbations, apparently leading to contradictory conclusions about the stability of the DS exponents. We explain this in terms of subtle differences between the two models, one of which is fine-tuned (and not strictly in the DS universality class). Next we allow the polymer to cross itself, as appropriate, e.g., to the quasi-two-dimensional case. This introduces an additional independent relevant perturbation, so we do not expect the DS exponents to apply. The exponents in the case with crossings will be those of the generic tricritical O (n ) model at n =0 and different from the case without crossings. We also discuss interesting features of the operator content of the CPN -1 model. Simple geometrical arguments show that two operators in this field theory, with very different symmetry properties, have the same scaling dimension for any value of N (or, equivalently, any value of the loop fugacity). Also we argue that for any value of N the CPN -1 model has a marginal odd-parity operator that is related to the winding angle.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Feng, Xun; Liu, Jing; College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022

    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 inmore » 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.« less

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

    PubMed

    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.

  10. Effect of hydrogen peroxide on the three-dimensional polymer network in composites.

    PubMed

    Durner, Jürgen; Stojanovic, Marija; Urcan, Ebru; Spahl, Werner; Haertel, Ursula; Hickel, Reinhard; Reichl, Franx-Xaver

    2011-06-01

    Less data are available about the effects of hydrogen peroxide on the three-dimensional polymer network of polymerized composites. Therefore the study was performed to test the effects of hydrogen peroxide on the three-dimensional polymer network in composites. Polymerized specimens from Tetric Flow®, Tetric Ceram® and Filtek™ Supreme XT were bleached with Opalescence® PF 15% for 5h or PF 35% for 0.5h, respectively, and then stored in methanol for 1d and 7d. Controls were unbleached specimens. The eluates were analyzed by gas chromatography/mass spectrometry. More methacrylic acid (MAA), bisphenol-A (BPA), ethoxylated bisphenol-A-dimethacrylate (BisEMA), hydroquinone monomethyl ether (HQME), 1,10-decanediol dimethacrylate (DDDMA) and/or triethylene glycol dimethacrylate (TEGDMA) were eluted from bleached specimens compared with non bleached controls (1d). The highest DDDMA amount of 419.8 μmol/l was found in the eluates after 7d in Tetric Flow® specimens treated with PF 15. The highest HQME amount of 159.6 μmol/l was found in eluates from Tetric Ceram® specimens treated with PF after 7d. The highest TEGDMA amount of 178.7 μmol/l was found in eluates from Filtek™ Supreme XT specimens treated with PF 35 after 7d. Bleaching with hydrogen peroxide has an effect on the three-dimensional polymer network in polymerized composites leading to an increase in the release of unpolymerized monomers, additives and unspecific oxidative products. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  11. Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

    NASA Astrophysics Data System (ADS)

    Steiner, Christian; Gebhardt, Julian; Ammon, Maximilian; Yang, Zechao; Heidenreich, Alexander; Hammer, Natalie; Görling, Andreas; Kivala, Milan; Maier, Sabine

    2017-03-01

    The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free two-dimensional (2D) covalent networks remains a challenge, which makes it difficult to unveil their electronic structure. Here we report on the hierarchical on-surface synthesis of nearly defect-free 2D covalent architectures with carbonyl-functionalized pores on Au(111), which is investigated by low-temperature scanning tunnelling microscopy in combination with density functional theory calculations. The carbonyl-bridged triphenylamine precursors form six-membered macrocycles and one-dimensional (1D) chains as intermediates in an Ullmann-type coupling reaction that are subsequently interlinked to 2D networks. The electronic band gap is narrowed when going from the monomer to 1D and 2D surface-confined π-conjugated organic polymers comprising the same building block. The significant drop of the electronic gap from the monomer to the polymer confirms an efficient conjugation along the triphenylamine units within the nanostructures.

  12. Heterobimetallic thiocyanato-bridged coordination polymers based on [Hg(SCN){sub 4}]{sup 2-}: Synthesis, crystal structure, magnetic properties and ESR studies

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jian Fangfang; Xiao Hailian; Liu Faqian

    2006-12-15

    Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN){sub 4}Ni(Im){sub 3}] {sub {infinity}} 1, [Hg(SCN){sub 4}Mn(Im){sub 2}] {sub {infinity}} 2, and [Hg(SCN){sub 4}Cu(Me-Im){sub 2} Hg(SCN){sub 4}Cu(Me-Im){sub 4}] {sub {infinity}} 3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by means of elemental analysis, ESR, and single-crystal X-ray. X-ray diffraction analysis reveals that these three complexes all form 3D network structure, and their structures all contain a thiocyanato-bridged Hg...Hg chain (M=Mn, Ni, Cu) in which the metal and mercury centers exhibit different coordination environments. In complex 1, the [Hg(SCN){sub 4}]{sup 2-} anion connects three [Ni(Im){sub 3}]{sup 2+} using three SCN ligands giving risemore » to a 3D structure, and in complex 2, four SCN ligands bridge [Hg(SCN){sub 4}]{sup 2-} and [Mn(Im){sub 2}]{sup 2+} to form a 3D structure. The structure of 3 contains two copper atoms with distinct coordination environment; one is coordinated by four N-methyl-imidazole ligands and two axially elongated SCN groups, and another by four SCN groups (two elongated) and two N-methyl-imidazole ligands. The magnetic property of complex 1 has been investigated. The spin state structure in hetermetallic NiHgNi systems of complex 1 is irregular. The ESR spectra results of complex 3 demonstrate Cu{sup 2+} ion lie on octahedral environment. -- Graphical abstract: Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN){sub 4}Ni(Im){sub 3}] {sub {infinity}} 1, [Hg(SCN){sub 4}Mn(Im){sub 2}] {sub {infinity}} 2, and [Hg(SCN){sub 4}Cu(Me-Im){sub 2} Hg(SCN){sub 4}Cu(Me-Im){sub 4}] {sub {infinity}} 3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by single-crystal X-ray. All coordination polymers possess 3-D structures, and consist of organic base neutral ligands (imidazole and N-methyl-imidazole) and SCN{sup -1} anions. Their structural difference

  13. A triple helical calcium-based coordination polymer with strong blue fluorescent emission

    NASA Astrophysics Data System (ADS)

    Yu, Liang-Cai; Chen, Zhen-Feng; Liang, Hong; Zhou, Chun-Shan; Li, Yan

    2005-08-01

    A hydrothermal reaction of 1,3-dicyanobenzene and Ca(OH)2 yielded a triple helical calcium-based coordination polymer of the formula, C20H25Ca2.50O18.50 (1). The 1,3-benzenecarboxylate anion, found in the final product was generated in situ during the synthesis by the hydrolysis of 1,3-dicyanobenzene. X-ray diffraction study shows that the complex 1 crystallizes in the monoclinic system, C2/c space group, a=15.5701(5), b=21.4445(7), c=17.1601(6) Å, β=111.7400(7)°, V=5322.1(3) Å3, Z=8, Dc=1.651 Mg/m3. The calcium atoms show differences in the coordination environments. Complex 1 emits strong blue fluorescent light (λem(max)=419 nm) when it is excited by UV light (λex(max)=316 nm) in the solid state at room temperature.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vallejos, Javier; Brito, Iván, E-mail: ivanbritob@yahoo.com; Cárdenas, Alejandro

    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 differencesmore » 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.« less

  15. Packaging consideration of two-dimensional polymer-based photonic crystals for laser beam steering

    NASA Astrophysics Data System (ADS)

    Dou, Xinyuan; Chen, Xiaonan; Chen, Maggie Yihong; Wang, Alan Xiaolong; Jiang, Wei; Chen, Ray T.

    2009-02-01

    In this paper, we report the theoretical study of polymer-based photonic crystals for laser beam steering which is based on the superprism effect as well as the experiment fabrication of the two dimensional photonic crystals for the laser beam steering. Superprism effect, the principle for beam steering, was separately studied in details through EFC (Equifrequency Contour) analysis. Polymer based photonic crystals were fabricated through double exposure holographic interference method using SU8-2007. The experiment results were also reported.

  16. One-Dimensional Quantum Walks with One Defect

    NASA Astrophysics Data System (ADS)

    Cantero, M. J.; Grünbaum, F. A.; Moral, L.; Velázquez, L.

    The CGMV method allows for the general discussion of localization properties for the states of a one-dimensional quantum walk, both in the case of the integers and in the case of the nonnegative integers. Using this method we classify, according to such localization properties, all the quantum walks with one defect at the origin, providing explicit expressions for the asymptotic return probabilities to the origin.

  17. One-step preparation of antimicrobial silver nanoparticles in polymer matrix

    NASA Astrophysics Data System (ADS)

    Lyutakov, O.; Kalachyova, Y.; Solovyev, A.; Vytykacova, S.; Svanda, J.; Siegel, J.; Ulbrich, P.; Svorcik, V.

    2015-03-01

    Simple one-step procedure for in situ preparation of silver nanoparticles (AgNPs) in the polymer thin films is described. Nanoparticles (NPs) were prepared by reaction of N-methyl pyrrolidone with silver salt in semi-dry polymer film and characterized by transmission electron microscopy, XPS, and UV-Vis spectroscopy techniques. Direct synthesis of NPs in polymer has several advantages; even though it avoids time-consuming NPs mixing with polymer matrix, uniform silver distribution in polymethylmethacrylate (PMMA) films is achieved without necessity of additional stabilization. The influence of the silver concentration, reaction temperature and time on reaction conversion rate, and the size and size-distribution of the AgNPs was investigated. Polymer films doped with AgNPs were tested for their antibacterial activity on Gram-negative bacteria. Antimicrobial properties of AgNPs/PMMA films were found to be depended on NPs concentration, their size and distribution. Proposed one-step synthesis of functional polymer containing AgNPs is environmentally friendly, experimentally simple and extremely quick. It opens up new possibilities in development of antimicrobial coatings with medical and sanitation applications.

  18. Assembly of 4-, 6- and 8-connected Cd(II) pseudo-polymorphic coordination polymers: Synthesis, solvent-dependent structural variation and properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Zhao-Hao; Xue, Li-Ping, E-mail: lpxue@163.com; Miao, Shao-Bin

    2016-08-15

    The reaction of Cd(NO{sub 3}){sub 2}·4H{sub 2}O, 2,5-thiophenedicarboxylic acid (H{sub 2}tdc) and 1,2-bis(imidazol-1′-yl)methane (bimm) by modulating solvent systems yielded three highly connected pseudo-polymorphic coordination polymers based on different dinuclear [Cd{sub 2}(CO{sub 2}){sub 2}] subunits bridged by carboxylate groups. Single crystal structural analyses reveal structural variation from 4-connected 2D sql layer, 6-connected 2-fold interpenetrated 3D pcu to 8-connected 3D bcu-type network in compounds 1–3. The structural dissimilarity in the structures dependent on the coordination environments of Cd(II) ions and linking modes of mixed ligand influenced by different solvent systems during the synthesis process. Moreover, thermogravimetric and photoluminescence behaviors of 1–3 weremore » also investigated for the first time, and all the complexes emit blue luminescence in the solid state. - Graphical abstract: Key Topic. Different solvent systems modulated three Cd(II) pseudo-polymorphic coordination polymers based on thiophene-2,5-dicarboxylate and 1,2-bis(imidazol-1′-yl)methane mixed ligands. Display Omitted - Highlights: • Three solvent-dependent Cd(II) pseudo-polymorphic coordination polymers have been synthesized. • Structural variation from 4-connected 2D layer, 6-connected 2-fold interpenetrated 3D net to 8-connected 3D net. • All complexes emit blue luminescence.« less

  19. 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}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Jin-jian; Yancheng Teachers College, Yancheng 224002; Liu, Zu-Liang, E-mail: liuzl@mail.njust.edu.cn

    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 decompositionmore » 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.« less

  20. A computer code for three-dimensional incompressible flows using nonorthogonal body-fitted coordinate systems

    NASA Technical Reports Server (NTRS)

    Chen, Y. S.

    1986-01-01

    In this report, a numerical method for solving the equations of motion of three-dimensional incompressible flows in nonorthogonal body-fitted coordinate (BFC) systems has been developed. The equations of motion are transformed to a generalized curvilinear coordinate system from which the transformed equations are discretized using finite difference approximations in the transformed domain. The hybrid scheme is used to approximate the convection terms in the governing equations. Solutions of the finite difference equations are obtained iteratively by using a pressure-velocity correction algorithm (SIMPLE-C). Numerical examples of two- and three-dimensional, laminar and turbulent flow problems are employed to evaluate the accuracy and efficiency of the present computer code. The user's guide and computer program listing of the present code are also included.

  1. Comparison between iteration schemes for three-dimensional coordinate-transformed saturated-unsaturated flow model

    NASA Astrophysics Data System (ADS)

    An, Hyunuk; Ichikawa, Yutaka; Tachikawa, Yasuto; Shiiba, Michiharu

    2012-11-01

    SummaryThree different iteration methods for a three-dimensional coordinate-transformed saturated-unsaturated flow model are compared in this study. The Picard and Newton iteration methods are the common approaches for solving Richards' equation. The Picard method is simple to implement and cost-efficient (on an individual iteration basis). However it converges slower than the Newton method. On the other hand, although the Newton method converges faster, it is more complex to implement and consumes more CPU resources per iteration than the Picard method. The comparison of the two methods in finite-element model (FEM) for saturated-unsaturated flow has been well evaluated in previous studies. However, two iteration methods might exhibit different behavior in the coordinate-transformed finite-difference model (FDM). In addition, the Newton-Krylov method could be a suitable alternative for the coordinate-transformed FDM because it requires the evaluation of a 19-point stencil matrix. The formation of a 19-point stencil is quite a complex and laborious procedure. Instead, the Newton-Krylov method calculates the matrix-vector product, which can be easily approximated by calculating the differences of the original nonlinear function. In this respect, the Newton-Krylov method might be the most appropriate iteration method for coordinate-transformed FDM. However, this method involves the additional cost of taking an approximation at each Krylov iteration in the Newton-Krylov method. In this paper, we evaluated the efficiency and robustness of three iteration methods—the Picard, Newton, and Newton-Krylov methods—for simulating saturated-unsaturated flow through porous media using a three-dimensional coordinate-transformed FDM.

  2. Self-assembly of coordination polymers of Pr(III), Nd(III), Tb(III), Dy(III) and Ho(III) with 5-hydroxyisophthalic acid and adipic acid: Syntheses, structures, porosity, luminescence and magnetic properties

    NASA Astrophysics Data System (ADS)

    Kariem, Mukaddus; Yawer, Mohd; Kumar, Manesh; Nawaz Sheikh, Haq; Sood, Puneet; Kolekar, Sanjay S.

    2017-11-01

    Five novel coordination polymers (CPs) with the formula [Ln (hip) (adip)0.5(H2O)2]n. nH2O [Ln = Pr (1), Nd (2), Tb (3), Dy (4) and Ho (5)] were synthesized by self-organization of lanthanide salts with rigid [5-hydroxyisophthalic acid (H2hip)] and flexible [adipic acid (H2adip)] linkers under solvothermal condition. X-ray diffraction revealed data that all five CPs 1-5 are isostructural and crystallizes in monoclinic C2/c space group. Coordination polymers 1-5 exhibit 1D linear ladder shaped extension with the linkage of lanthanide carboxylate chains having the backbone of H2hip and H2adip ligands. The 1D linear ladder chains get transformed into three dimensional (3D) supramolecular network via non-covalent interactions (π-π and H - bonding). The porosity study showed that 20.34 mL of N2 gets adsorbed per 1.0 g of sample at 1 atm pressure. The CP 3 (Tb) and 4 (Dy) emit strong ligand sensitized characteristic f-f luminescence emission. The CPs 3 and 4 exhibit weak ferromagnetic interactions at lower temperatures.

  3. C-H...Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu{sup I}Cu{sup II} coordination polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shi Ling; Yang Ping; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510631

    Two mixed-valence Cu{sup I}Cu{sup II} coordination polymers [Cu{sup I}Cu{sup II}(qdiol)ClL]{sub n} (qdiol{sup 2-}=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl{sub 2}, 1,4-dihydro-2,3-quinoxalinedione and L under the solvothermal condition. 1 and 2 are similar in composition, but differ remarkably in structure. The coordination modes of Cu{sup II}, qdiol{sup 2-} and L are identical in both complexes. But the Cu{sup I} ions are two- and three-coordinated, and the Cl{sup -} ions are terminal and bridging, in 1 and 2, respectively, which are relevant to the significantly different C-H...Cl hydrogen bonding pattern of bpy and phen. The temperaturemore » variable magnetic susceptibilities show that 1 is paramagnetic and 2 is weakly antiferromagnetic. The complex impedance spectroscopic studies indicate that both 1 and 2 are semiconductors and 2 is more conducting. - Graphical Abstract: Subtly different C-H...Cl bonding nature leads to diverse coordination modes and supramolecular networks, as well as physical properties of two Cu{sup I}Cu{sup II} coordination polymers with similar compositions. Highlights: > Two new Cu(I)-Cu(II) mixed-valence coordination polymers are obtained. > Environments of Cu(I) and Cl are different caused by C-H...Cl H-bonding. > Supramolecular networks are hence diverse. > Magnetic and semiconducting properties are influenced by the structures.« less

  4. A generalized orthogonal coordinate system for describing families of axisymmetric and two-dimensional bodies

    NASA Technical Reports Server (NTRS)

    Gnoffo, P. A.

    1977-01-01

    A generalized curvilinear orthogonal coordinate system is presented which can be used for approximating various axisymmetric and two-dimensional body shapes of interest to aerodynamicists. Such body shapes include spheres, ellipses, spherically capped cones, flat-faced cylinders with rounded corners, circular disks, and planetary probe vehicles. A set of transformation equations is also developed whereby a uniform velocity field approaching a body at any angle of attack can be resolved in the transformed coordinate system. The Navier-Stokes equations are written in terms of a generalized orthogonal coordinate system to show the resultant complexity of the governing equations.

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

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

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

  6. Oscillatory Dynamics of One-Dimensional Homogeneous Granular Chains

    NASA Astrophysics Data System (ADS)

    Starosvetsky, Yuli; Jayaprakash, K. R.; Hasan, Md. Arif; Vakakis, Alexander F.

    The acoustics of the homogeneous granular chains has been studied extensively both numerically and experimentally in the references cited in the previous chapters. This chapter focuses on the oscillatory behavior of finite dimensional homogeneous granular chains. It is well known that normal vibration modes are the building blocks of the vibrations of linear systems due to the applicability of the principle of superposition. One the other hand, nonlinear theory is deprived of such a general superposition principle (although special cases of nonlinear superpositions do exist), but nonlinear normal modes ‒ NNMs still play an important role in the forced and resonance dynamics of these systems. In their basic definition [1], NNMs were defined as time-periodic nonlinear oscillations of discrete or continuous dynamical systems where all coordinates (degrees-of-freedom) oscillate in-unison with the same frequency; further extensions of this definition have been considered to account for NNMs of systems with internal resonances [2]...

  7. The Art of Extracting One-Dimensional Flow Properties from Multi-Dimensional Data Sets

    NASA Technical Reports Server (NTRS)

    Baurle, R. A.; Gaffney, R. L.

    2007-01-01

    The engineering design and analysis of air-breathing propulsion systems relies heavily on zero- or one-dimensional properties (e:g: thrust, total pressure recovery, mixing and combustion efficiency, etc.) for figures of merit. The extraction of these parameters from experimental data sets and/or multi-dimensional computational data sets is therefore an important aspect of the design process. A variety of methods exist for extracting performance measures from multi-dimensional data sets. Some of the information contained in the multi-dimensional flow is inevitably lost when any one-dimensionalization technique is applied. Hence, the unique assumptions associated with a given approach may result in one-dimensional properties that are significantly different than those extracted using alternative approaches. The purpose of this effort is to examine some of the more popular methods used for the extraction of performance measures from multi-dimensional data sets, reveal the strengths and weaknesses of each approach, and highlight various numerical issues that result when mapping data from a multi-dimensional space to a space of one dimension.

  8. On the cross-field diffusion of ions in one- and two-dimensional hybrid simulations of collisionless shocks

    NASA Technical Reports Server (NTRS)

    Giacalone, Joe

    1994-01-01

    It can be demonstrated analytically that under certain geometries used in numerical simulations of collisionless shocks in which there is at least one ignorable spatial coordinate, the transport of particles across the magnetic field is essentially zero. This notion is tested using one- and two-dimensional hybrid simulations (kinetic ions/fluid electrons). We find, as the theorem predicts, the particles treated kinetically are tied to the same field line on which they start.

  9. 1D helical cadmium coordination polymers containing hydrazide ligand: The role of solvent and molar ratio

    NASA Astrophysics Data System (ADS)

    Notash, Behrouz

    2018-03-01

    Three new cadmium coordination polymers, [Cd(L)(NO3)2CH3OH]n, 1, {[Cd(L)2(NO3)]NO3}n, 2 and {[Cd(L)2(NO3)]NO3.H2O}n3, which L is nicotinohydrazide have been synthesized and characterized by spectroscopic methods as well as single crystal X-ray diffraction. Compounds 1-3 have been synthesized by changing solvent and metal-to-ligand ratio. X-ray crystallography showed that compounds 1-3 have different 1D helical structural motif. Semi-flexible nature of L ligand causes to syn-syn conformation which leading to form 1D helical chains coordination polymers. Compounds 2 and 3 were synthesized under the same reaction conditions with similar molar ratio, but using different solvent system. These compounds are pseudopolymorph which differs in the presence or absence of water molecule in their crystal packing. Hirshfeld surface analysis of the structures 1-3 have been performed and find the percent of participation of intermolecular interactions in the crystal packing of compounds.

  10. Three-dimensionally modulated anisotropic structure for diffractive optical elements created by one-step three-beam polarization holographic photoalignment

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kawai, Kotaro, E-mail: s135016@stn.nagaokaut.ac.jp; Sakamoto, Moritsugu; Noda, Kohei

    2016-03-28

    A diffractive optical element with a three-dimensional liquid crystal (LC) alignment structure for advanced control of polarized beams was fabricated by a highly efficient one-step photoalignment method. This study is of great significance because different two-dimensional continuous and complex alignment patterns can be produced on two alignment films by simultaneously irradiating an empty glass cell composed of two unaligned photocrosslinkable polymer LC films with three-beam polarized interference beam. The polarization azimuth, ellipticity, and rotation direction of the diffracted beams from the resultant LC grating widely varied depending on the two-dimensional diffracted position and the polarization states of the incident beams.more » These polarization diffraction properties are well explained by theoretical analysis based on Jones calculus.« less

  11. Novel octanuclear copper(I) metallomacrocycles and their transformation into hexanuclear 2-dimensional grids of copper(i) coordination polymers containing cyclodiphosphazanes, [(micro-NtBuP)2(NC4H8X)2] (X = NMe, O).

    PubMed

    Suresh, D; Balakrishna, Maravanji S; Mague, Joel T

    2008-07-07

    Novel octanuclear copper(I) macrocyclic complexes and hexanuclear 2-dimensional grid-like polymers containing [P(micro-NR)](2) scaffold in which the anionic moieties are trapped inside the cationic macrocyclic cavities are reported.

  12. Two-dimensional correlation spectroscopic studies on coordination between organic ligands and Ni2 + ions

    NASA Astrophysics Data System (ADS)

    Bao, Ya-nan; Zeng, Yi-wei; Guo, Ran; Ablikim, Mesude; Shi, Hai-fang; Yang, Li-min; Yang, Zhan-lan; Xu, Yi-zhuang; Noda, Isao; Wu, Jin-guang

    2018-05-01

    3A2g → 3T1g(P) transition band of Ni2 + is used to probe the coordination of Ni2 +. Two-dimensional asynchronous spectra (2DCOS) are generated using the Double Asynchronous Orthogonal Sample Design (DAOSD), Asynchronous Spectrum with Auxiliary Peaks (ASAP) and Two-Trace Two-Dimensional (2T2D) approaches. Cross peaks relevant to the 3A2g → 3T1g(P) transition band of Ni2 + are utilized to probe coordination between Ni2 + and various ligands. We studied the spectral behavior of the 3A2g → 3T1g(P) transition band when Ni2 + is coordinated with ethylenediaminetetraacetic acid disodium salt (EDTA). The pattern of cross peaks in 2D asynchronous spectrum demonstrates that coordination brings about significant blue shift of the band. In addition, the absorptivity of the band increases remarkably. The interaction between Ni2 + and galactitol is also investigated. Although no clearly observable change is found on the 3A2g → 3T1g(P) transition band when galactitol is introduced, the appearance of cross peak in 2D asynchronous spectrum demonstrates that coordination indeed occurs between Ni2 + and galactitol. Furthermore, the pattern of cross peak indicates that peak position, bandwidth and absorptivity of the 3A2g → 3T1g(P) transition band of Ni(galactitol)x2 + is considerably different from those of Ni(H2O)62 +. Thus, 2DCOS is helpful to reveal subtle spectral variation, which might be helpful in shedding light on the physical-chemical nature of coordination.

  13. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

    NASA Astrophysics Data System (ADS)

    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

    2015-05-01

    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 21 helical chains. While the Nd(III) ions are bridged through μ2-HIDC2- 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.

  14. 2-and 1-D coordination polymers of Dy(III) and Ho(III) with near infrared and visible luminescence by efficient charge-transfer antenna ligand

    NASA Astrophysics Data System (ADS)

    Oylumluoglu, Gorkem; Coban, Mustafa Burak; Kocak, Cagdas; Aygun, Muhittin; Kara, Hulya

    2017-10-01

    Two new lanthanide-based coordination complexes, [Dy(2-stp).2(H2O)]n (1) and {[Ho(2-stp).3(H2O)]·(H2O)}n (2) [2-stp = 2-sulfoterephthalic acid] were synthesized by hydrothermal reaction and characterized by elemental analysis, UV, IR, single crystal X-ray diffraction and solid state photoluminescence. DyIII and HoIII atoms are eight-coordinated and adopt a distorted square-antiprismatic geometry in complexes 1 and 2, respectively. In compound 1, Dy atoms are coordinated by four bridging 2-stp ligands forming two-dimensional (2D) layer, while Ho atoms by three bridging 2-stp ligands creating one dimensional (1D) double chains in 2. In addition, complexes 1 and 2 display in the solid state and at room temperature an intense yellow emission, respectively; this photoluminescence is achieved by an indirect process (antenna effect). The excellent luminescent performances make these complexes very good candidates for potential luminescence materials.

  15. Visible and NIR photoluminescence properties of a series of novel lanthanide-organic coordination polymers based on hydroxyquinoline-carboxylate ligands.

    PubMed

    Gai, Yan-Li; Xiong, Ke-Cai; Chen, Lian; Bu, Yang; Li, Xing-Jun; Jiang, Fei-Long; Hong, Mao-Chun

    2012-12-17

    A series of novel two-dimensional (2D) lanthanide coordination polymers with 4-hydroxyquinoline-2-carboxylate (H(2)hqc) ligands, [Ln(Hhqc)(3)(H(2)O)](n)·3nH(2)O (Ln = Eu (1), Tb (2), Sm (3), Nd (4), and Gd (5)) and [Ln(Hhqc)(ox)(H(2)O)(2)](n) (Ln = Eu (6), Tb (7), Sm (8), Tm (9), Dy (10), Nd (11), Yb (12), and Gd (13); H(2)ox = oxalic acid), have been synthesized under hydrothermal conditions. Complexes 1-5 are isomorphous, which can be described as a two-dimensional (2D) hxl/Shubnikov network based on Ln(2)(CO(2))(4) paddle-wheel units, and the isomorphous complexes 6-13 feature a 2D decker layer architecture constructed by Ln-ox infinite chains cross-linked alternatively by bridging Hhqc(-) ligands. The room-temperature photoluminescence spectra of complexes Eu(III) (1 and 6), Tb(III) (2 and 7), and Sm(III) (3 and 8) exhibit strong characteristic emissions in the visible region, whereas Nd(III) (4 and 11) and Yb(III) (12) complexes display NIR luminescence upon irradiation at the ligand band. Moreover, the triplet state of H(2)hqc matches well with the emission level of Eu(III), Tb(III), and Sm(III) ions, which allows the preparation of new optical materials with enhanced luminescence properties.

  16. Three-Dimensional (3D) Printing of Polymer-Metal Hybrid Materials by Fused Deposition Modeling.

    PubMed

    Fafenrot, Susanna; Grimmelsmann, Nils; Wortmann, Martin; Ehrmann, Andrea

    2017-10-19

    Fused deposition modeling (FDM) is a three-dimensional (3D) printing technology that is usually performed with polymers that are molten in a printer nozzle and placed line by line on the printing bed or the previous layer, respectively. Nowadays, hybrid materials combining polymers with functional materials are also commercially available. Especially combinations of polymers with metal particles result in printed objects with interesting optical and mechanical properties. The mechanical properties of objects printed with two of these metal-polymer blends were compared to common poly (lactide acid) (PLA) printed objects. Tensile tests and bending tests show that hybrid materials mostly containing bronze have significantly reduced mechanical properties. Tensile strengths of the 3D-printed objects were unexpectedly nearly identical with those of the original filaments, indicating sufficient quality of the printing process. Our investigations show that while FDM printing allows for producing objects with mechanical properties similar to the original materials, metal-polymer blends cannot be used for the rapid manufacturing of objects necessitating mechanical strength.

  17. Two-dimensional beam profiles and one-dimensional projections

    NASA Astrophysics Data System (ADS)

    Findlay, D. J. S.; Jones, B.; Adams, D. J.

    2018-05-01

    One-dimensional projections of improved two-dimensional representations of transverse profiles of particle beams are proposed for fitting to data from harp-type monitors measuring beam profiles on particle accelerators. Composite distributions, with tails smoothly matched on to a central (inverted) parabola, are shown to give noticeably better fits than single gaussian and single parabolic distributions to data from harp-type beam profile monitors all along the proton beam transport lines to the two target stations on the ISIS Spallation Neutron Source. Some implications for inferring beam current densities on the beam axis are noted.

  18. Fully automated measuring setup for tactile coordinate measuring machine for three dimensional measurement of freeform eyeglass frames

    NASA Astrophysics Data System (ADS)

    Rückwardt, M.; Göpfert, A.; Correns, M.; Schellhorn, M.; Linß, G.

    2010-07-01

    Coordinate measuring machines are high precession all-rounder in three dimensional measuring. Therefore the versatility of parameters and expandability of additionally hardware is very comprehensive. Consequently you need much expert knowledge of the user and mostly a lot of advanced information about the measuring object. In this paper a coordinate measuring machine and a specialized measuring machine are compared at the example of the measuring of eyeglass frames. For this case of three dimensional measuring challenges the main focus is divided into metrological and economical aspects. At first there is shown a fully automated method for tactile measuring of this abstract form. At second there is shown a comparison of the metrological characteristics of a coordinate measuring machine and a tracer for eyeglass frames. The result is in favour to the coordinate measuring machine. It was not surprising in these aspects. At last there is shown a comparison of the machine in front of the economical aspects.

  19. Two Dimensional Polymer That Generates Nitric Oxide.

    DOEpatents

    McDonald, William F.; Koren, Amy B.

    2005-10-04

    A polymeric composition that generates nitric oxide and a process for rendering the surface of a substrate nonthrombogenic by applying a coating of the polymeric composition to the substrate are disclosed. The composition comprises: (1) a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, and (ii) a crosslinking agent containing functional groups capable of reacting with the amino groups; and (2) a plurality of nitric oxide generating functional groups associated with the crosslinked chemical combination. Once exposed to a physiological environment, the coating generates nitric oxide thereby inhibiting platelet aggregation. In one embodiment, the nitric oxide generating functional groups are provided by a nitrated compound (e.g., nitrocellulose) imbedded in the polymeric composition. In another embodiment, the nitric oxide generating functional groups comprise N2O2- groups covalently bonded to amino groups on the polymer.

  20. Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications.

    PubMed

    Miao, Shida; Zhu, Wei; Castro, Nathan J; Leng, Jinsong; Zhang, Lijie Grace

    2016-10-01

    The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term "4D printing" refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from -8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at -18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and development of

  1. Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications

    PubMed Central

    Miao, Shida; Zhu, Wei; Castro, Nathan J.; Leng, Jinsong

    2016-01-01

    The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term “4D printing” refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from −8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at −18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and

  2. Semiflexible macromolecules in quasi-one-dimensional confinement: Discrete versus continuous bond angles.

    PubMed

    Huang, Aiqun; Hsu, Hsiao-Ping; Bhattacharya, Aniket; Binder, Kurt

    2015-12-28

    The conformations of semiflexible polymers in two dimensions confined in a strip of width D are studied by computer simulations, investigating two different models for the mechanism by which chain stiffness is realized. One model (studied by molecular dynamics) is a bead-spring model in the continuum, where stiffness is controlled by a bond angle potential allowing for arbitrary bond angles. The other model (studied by Monte Carlo) is a self-avoiding walk chain on the square lattice, where only discrete bond angles (0° and ±90°) are possible, and the bond angle potential then controls the density of kinks along the chain contour. The first model is a crude description of DNA-like biopolymers, while the second model (roughly) describes synthetic polymers like alkane chains. It is first demonstrated that in the bulk the crossover from rods to self-avoiding walks for both models is very similar, when one studies average chain linear dimensions, transverse fluctuations, etc., despite their differences in local conformations. However, in quasi-one-dimensional confinement two significant differences between both models occur: (i) The persistence length (extracted from the average cosine of the bond angle) gets renormalized for the lattice model when D gets less than the bulk persistence length, while in the continuum model it stays unchanged. (ii) The monomer density near the repulsive walls for semiflexible polymers is compatible with a power law predicted for the Kratky-Porod model in the case of the bead-spring model, while for the lattice case it tends to a nonzero constant across the strip. However, for the density of chain ends, such a constant behavior seems to occur for both models, unlike the power law observed for flexible polymers. In the regime where the bulk persistence length ℓp is comparable to D, hairpin conformations are detected, and the chain linear dimensions are discussed in terms of a crossover from the Daoud/De Gennes "string of blobs

  3. Hydrothermal synthesis, crystal structure, and catalytic potential of a one-dimensional molybdenum oxide/bipyridinedicarboxylate hybrid.

    PubMed

    Amarante, Tatiana R; Neves, Patrícia; Valente, Anabela A; Paz, Filipe A Almeida; Fitch, Andrew N; Pillinger, Martyn; Gonçalves, Isabel S

    2013-04-15

    The reaction of MoO3, 2,2'-bipyridine-5,5-dicarboxylic acid (H2bpdc), water, and dimethylformamide in the mole ratio 1:1:1730:130 at 150 °C for 3 days in a rotating Teflon-lined digestion bomb leads to the isolation of the molybdenum oxide/bipyridinedicarboxylate hybrid material (DMA)[MoO3(Hbpdc)]·nH2O (1) (DMA = dimethylammonium). Compound 1 was characterized by scanning electron microscopy, FT-IR and (13)C{(1)H} CP MAS NMR spectroscopies, and elemental and thermogravimetric analyses. The solid state structure of 1 was solved and refined through Rietveld analysis of high resolution synchrotron X-ray powder diffraction data in conjunction with information derived from the above techniques. The material, crystallizing in the noncentrosymmetric monoclinic space group Pc, is composed of an anionic one-dimensional organic-inorganic hybrid polymer, ∞(1)[MoO3(Hbpdc)](-), formed by corner-sharing distorted {MoO4N2} octahedra, which cocrystallizes with charge-balancing DMA(+) cations and one water molecule per metal center. In the crystal structure of 1, the close packing of individual anionic polymers, DMA(+) cations, and water molecules is mediated by a series of supramolecular contacts, namely strong (O-H···O, N(+)-H···O(-)) and weak (C-H···O) hydrogen bonding interactions, and π-π contacts involving adjacent coordinated Hbpdc(-) ligands. The catalytic potential of 1 was investigated in the epoxidation reactions of the bioderived olefins methyl oleate (Ole) and DL-limonene (Lim) using tert-butylhydroperoxide (TBHP) as the oxygen donor and 1,2-dichloroethane (DCE) or (trifluoromethyl)benzene (BTF) as cosolvent, at 55 or 75 °C. Under these conditions, 1 acts as a source of active soluble species, leading to epoxide yields of up to 98% for methyl 9,10-epoxystearate (BTF, 75 °C, 100% conversion of Ole) and 89% for 1,2-epoxy-p-menth-8-ene (DCE, 55 °C, 95% conversion of Lim). Catalytic systems employing the ionic liquid 1-butyl-3-methylimidazolium bis

  4. Photonic polymer-blend structures and method for making

    DOEpatents

    Barnes, Michael D.

    2004-06-29

    The present invention comprises the formation of photonic polymer-blend structures having tunable optical and mechanical properties. The photonic polymer-blend structures comprise monomer units of spherical microparticles of a polymer-blend material wherein the spherical microparticles have surfaces partially merged with one another in a robust inter-particle bond having a tunable inter-particle separation or bond length sequentially attached in a desired and programmable architecture. The photonic polymer-blend structures of the present invention can be linked by several hundred individual particles sequentially linked to form complex three-dimensional structures or highly ordered two-dimensional arrays of 3D columns with 2D spacing.

  5. A 3D Polymer Based Printed Two-Dimensional Laser Scanner

    NASA Astrophysics Data System (ADS)

    Oyman, H. A.; Gokdel, Y. D.; Ferhanoglu, O.; Yalcinkaya, A. D.

    2016-10-01

    A two-dimensional (2D) polymer based scanning mirror with magnetic actuation is developed for imaging applications. Proposed device consists of a circular suspension holding a rectangular mirror and can generate a 2D scan pattern. Three dimensional (3D) printing technology which is used for implementation of the device, offers added flexibility in controlling the cross-sectional profile as well as the stress distribution compared to the traditional planar process technologies. The mirror device is developed to meet a portable, miniaturized confocal microscope application in mind, delivering 4.5 and 4.8 degrees of optical scan angles at 111 and 267 Hz, respectively. As a result of this mechanical performance, the resulting microscope incorporating the mirror is estimated to accomplish a field of view (FOV) of 350 µm × 350 µm.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Cadmium-1,4-cyclohexanedicarboxylato coordination polymers bearing different di-alkyl-2,2'-bipyridines: syntheses, crystal structures and photoluminescence studies.

    PubMed

    Rosales-Vázquez, Luis D; Sánchez-Mendieta, Víctor; Dorazco-González, Alejandro; Martínez-Otero, Diego; García-Orozco, Iván; Morales-Luckie, Raúl A; Jaramillo-Garcia, Jonathan; Téllez-López, Antonio

    2017-09-26

    Four coordination polymers have been synthesized using self-assembly solution reactions under ambient conditions, reacting Cd(ii) ions with 1,4-cyclohexanedicarboxylic acid in the presence of different 2,2'-bipyridine co-ligands: {[Cd(H 2 O)(e,a-cis-1,4-chdc)(2,2'-bpy)]·H 2 O} n (1); [Cd 2 (H 2 O) 2 (e,a-cis-1,4-chdc) 2 (4,4'-dmb) 2 ] n (2); {[Cd(e,a-cis-1,4-chdc)(5,5'-dmb)]·H 2 O·CH 3 OH} n (3) and {[Cd(e,e-trans-1,4-chdc)(4,4'-dtbb)]·CH 3 OH} n (4), where 1,4-chdc = 1,4-cyclohexanedicarboxylato, 2,2'-bpy = 2,2'-bipyridine, 4,4'-dmb = 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dmb = 5,5'-dimethyl-2,2'-bipyridine and 4,4'-dtbb = 4,4'-di-tert-butyl-2,2'-bipyridine. Crystallographic studies show that compound 1 has a 1D structure propagating along the crystallographic b-axis; the Cd ion in 1 is six-coordinated with a distorted-octahedral coordination sphere. Compound 2 has two crystallographic different Cd ions and both are six-coordinated with a distorted-octahedral coordination sphere. Compound 3 exhibits a seven-coordinated Cd ion having a distinctive distorted-monocapped trigonal prismatic geometry. In compound 4, the Cd ion is also seven-coordinated in a distorted monocapped octahedral geometry. Compounds 2, 3 and 4 possess rhombic-shaped dinuclear units (Cd 2 O 2 ) as nodes to generate larger cycles made up of four dinuclear units, a Cd 4 motif, bridged by four 1,4-chdc ligands, accomplishing, thus, 2D structures. Remarkably, in compound 4 the 1,4-chdc ligand conformation changes to the equatorial, equatorial trans, unlike the other compounds where the bridging ligand conformation is the more typical equatorial, axial cis. The solid state luminescence properties of 1-4 were investigated; polymers 3 and 4 exhibited a strong blue emission (λ em = 410-414 nm) compared to 1 and 2; structure-related photoluminescence is attributed to the degree of hydration of the compounds. Furthermore, Cd-polymer 3 suspended in acetone allows the fluorescence selective sensing of

  9. One-shot exogenous interventions increase subsequent coordination in Denmark, Spain and Ghana

    PubMed Central

    Thorsen, Bo Jellesmark

    2017-01-01

    Everyday, we are bombarded with periodic, exogenous appeals and instructions on how to behave. How do these appeals and instructions affect subsequent coordination? Using experimental methods, we investigate how a one-time exogenous instruction affects subsequent coordination among individuals in a lab. Participants play a minimum effort game repeated 5 times under fixed matching with a one-time behavioral instruction in either the first or second round. Since coordination behavior may vary across countries, we run experiments in Denmark, Spain and Ghana, and map cross-country rankings in coordination with known national measures of fractualization, uncertainty avoidance and long-term orientation. Our results show that exogenous interventions increase subsequent coordination, with earlier interventions yielding better coordination than later interventions. We also find that cross-country rankings in coordination map with published national measures of fractualization, uncertainty avoidance, and long-term orientation. PMID:29145411

  10. One-shot exogenous interventions increase subsequent coordination in Denmark, Spain and Ghana.

    PubMed

    Abatayo, Anna Lou; Thorsen, Bo Jellesmark

    2017-01-01

    Everyday, we are bombarded with periodic, exogenous appeals and instructions on how to behave. How do these appeals and instructions affect subsequent coordination? Using experimental methods, we investigate how a one-time exogenous instruction affects subsequent coordination among individuals in a lab. Participants play a minimum effort game repeated 5 times under fixed matching with a one-time behavioral instruction in either the first or second round. Since coordination behavior may vary across countries, we run experiments in Denmark, Spain and Ghana, and map cross-country rankings in coordination with known national measures of fractualization, uncertainty avoidance and long-term orientation. Our results show that exogenous interventions increase subsequent coordination, with earlier interventions yielding better coordination than later interventions. We also find that cross-country rankings in coordination map with published national measures of fractualization, uncertainty avoidance, and long-term orientation.

  11. The Nature of Bonding in Bulk Tellurium Composed of One-Dimensional Helical Chains.

    PubMed

    Yi, Seho; Zhu, Zhili; Cai, Xiaolin; Jia, Yu; Cho, Jun-Hyung

    2018-05-07

    Bulk tellurium (Te) is composed of one-dimensional (1D) helical chains which have been considered to be coupled by van der Waals (vdW) interactions. However, on the basis of first-principles density functional theory calculations, we here propose a different bonding nature between neighboring chains: i.e., helical chains made of normal covalent bonds are connected together by coordinate covalent bonds. It is revealed that the lone pairs of electrons of Te atoms participate in forming coordinate covalent bonds between neighboring chains, where each Te atom behaves as both an electron donor to neighboring chains and an electron acceptor from neighboring chains. This ligand-metal-like bonding nature in bulk Te results in the same order of bulk moduli along the directions parallel and perpendicular to the chains, contrasting with the large anisotropy of bulk moduli in vdW crystals. We further find that the electron effective masses parallel and perpendicular to the chains are almost the same as each other, consistent with the observed nearly isotropic electrical resistivity. It is thus demonstrated that the normal/coordinate covalent bonds parallel/perpendicular to the chains in bulk Te lead to a minor anisotropy in structural and transport properties.

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

    NASA Astrophysics Data System (ADS)

    Zhuang, Gui-lin; Chen, Wu-lin; Zheng, Jun; Yu, Hui-you; Wang, Jian-guo

    2012-08-01

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H3SIDA) and Ln(NO3)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 Gd3+ ions for anti-anti and syn-anti carboxylate bridges are -1.0×10-3 and -5.0×10-3 cm-1, respectively, which reveals weak antiferromagnetic interaction in 4.

  13. Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.

    PubMed

    Vitórica-Yrezábal, Iñigo J; Libri, Stefano; Loader, Jason R; Mínguez Espallargas, Guillermo; Hippler, Michael; Fletcher, Ashleigh J; Thompson, Stephen P; Warren, John E; Musumeci, Daniele; Ward, Michael D; Brammer, Lee

    2015-06-08

    Despite an absence of conventional porosity, the 1D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 ] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 (ROH)2 ] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10(-5) (MeOH), 9.5(3)×10(-6) (EtOH), 6.14(5)×10(-5) (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH→1→2, in which 2 is the 2D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)2 ] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-A(LT) , 1-A(HT) , 1-B(LT) and 1-B(HT) ; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH→1→2 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-A(HT) show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Functional Supramolecular Polymers*

    PubMed Central

    Aida, T.; Meijer, E.W.; Stupp, S.I.

    2012-01-01

    Supramolecular polymers can be random and entangled coils with the mechanical properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramolecular polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among molecular subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramolecular assemblies of the cell cytoskeleton, and possess useful biological and electronic functions. PMID:22344437

  15. A luminescent zinc(ii) coordination polymer with unusual (3,4,4)-coordinated self-catenated 3D network for selective detection of nitroaromatics and ferric and chromate ions: a versatile luminescent sensor.

    PubMed

    Zhang, Ya-Qian; Blatov, Vladislav A; Zheng, Tian-Rui; Yang, Chang-Hao; Qian, Lin-Lu; Li, Ke; Li, Bao-Long; Wu, Bing

    2018-05-01

    A zinc(ii) coordination polymer {[Zn3(mtrb)3(btc)2]·3H2O}n (1) was synthesized and characterized (mtrb = 1,3-bis(1,2,4-triazole-4-ylmethyl)benzene, btc = 1,3,5-benzenetricarboxylate). The polymer 1 shows an unusual (3,4,4)-coordinated self-catenated 3D network with the point symbol of {63}2{62·82·102}{64·82}2. The polymer 1 is the first luminescent sensor for the detection of 2-amino-4-nitrophenol (ANP). The polymer 1 is also a good luminescence sensor for detection of TNP, 2,4-DNP, 4-NP, ANP and 2-NP in MeOH, particularly for TNP. The order of detection efficiency is TNP > 2,4-DNP > 4-NP > ANP > 2-NP. The polymer 1 also exhibits high sensitivity and selectivity as a luminescence sensor for the detection of Fe3+, Cr2O72- and CrO42- in aqueous solution. Our experiments showed that the presence of interfering ions had no significant effect on the sensing of Fe3+, Cr2O72- or CrO42- ions. The detection limits for TNP, ANP, Fe3+, Cr2O72- and CrO42- are 0.22 μM, 4.12 μM, 1.78 μM, 2.83 μM, and 4.52 μM, respectively. The luminescence sensor is stable and can be recycled for detection at least five times. The possible quenching mechanisms are discussed. The polymer 1 is also an effective photocatalyst for degradation of methylene blue (MB) under visible or UV light irradiation.

  16. Two new coordination polymers with flexible alicyclic carboxylate and bipyridyl co-ligands bearing trinuclear [Ni3(COO)6] SBUs: Synthesis, crystal structures, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Zhu, Xian-Dong; Li, Yong; Gao, Jian-Gang; Wang, Fen-Hua; Li, Qing-Hai; Yang, Hong-Xun; Chen, Lei

    2017-02-01

    Two new coordination polymers generally formulated as [Ni3(Hchda)2(chda)2(bpy)2(H2O)2]n (1) and [Ni3(Hchda)2(chda)2(bpp)2(H2O)2]n (2) [H2chda = 1,1'-cyclohexanediacetic acid, bpy = 4,4'-bipyridine and bpp = 1,3-bis(4-pyridyl)propane], have been successfully assembled through mixed-ligands synthetic strategy with flexible alicyclic carboxylate and bipyridyl ligands. There structures feature trinuclear nickel secondary building units connected via the bridging bipyridyl spacers to form two-dimensional (4,4) grid layer. The nature of the different N-donor auxiliary ligands leads to the discrepancy in supramolecular structure of the two compounds. Magnetic studies indicate the ferromagnetic intra-complex magnetic interaction in the molecule for 1 and 2.

  17. Trace Detection of Metalloporphyrin-Based Coordination Polymer Particles via Modified Surface-Enhanced Raman Scattering Assisted by Surface Metallization.

    PubMed

    Sun, Yu; Caravella, Alessio

    2016-01-01

    This study proposed a facile method to detect metalloporphyrin-based coordination polymer particles (Z-CPPs) in aqueous solution by modified surface-enhanced Raman scattering (SERS). The SERS-active particles are photodeposited on the surface of Z-CPPs, offering an enhanced Raman signal for the trace detection of Z-CPPs.

  18. Benchtop fabrication of three-dimensional reconfigurable microfluidic devices from paper-polymer composite.

    PubMed

    Han, Yu Long; Wang, Wenqi; Hu, Jie; Huang, Guoyou; Wang, Shuqi; Lee, Won Gu; Lu, Tian Jian; Xu, Feng

    2013-12-21

    We presented a benchtop technique that can fabricate reconfigurable, three-dimensional (3D) microfluidic devices made from a soft paper-polymer composite. This fabrication approach can produce microchannels at a minimal width of 100 μm and can be used to prototype 3D microfluidic devices by simple bending and stretching. The entire fabrication process can be finished in 2 hours on a laboratory bench without the need for special equipment involved in lithography. Various functional microfluidic devices (e.g., droplet generator and reconfigurable electronic circuit) were prepared using this paper-polymer hybrid microfluidic system. The developed method can be applied in a wide range of standard applications and emerging technologies such as liquid-phase electronics.

  19. One-dimensional zinc oxide nanomaterials synthesis and photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Weintraub, Benjamin A.

    As humanly engineered materials systems approach the atomic scale, top-down manufacturing approaches breakdown and following nature's example, bottom-up or self-assembly methods have the potential to emerge as the dominant paradigm. Synthesis of one-dimensional nanomaterials takes advantage of such self-assembly manufacturing techniques, but until now most efforts have relied on high temperature vapor phase schemes which are limited in scalability and compatibility with organic materials. The solution-phase approach is an attractive low temperature alternative to overcome these shortcomings. To this end, this thesis is a study of the rationale solution-phase synthesis of ZnO nanowires and applications in photovoltaics. The following thesis goals have been achieved: rationale synthesis of a single ZnO nanowire on a polymer substrate without seeding, design of a wafer-scale technique to control ZnO nanowire array density using layer-by-layer polymers, determination of optimal nanowire field emitter density to maximize the field enhancement factor, design of bridged nanowires across metal electrodes to order to circumvent post-synthesis manipulation steps, electrical characterization of bridged nanowires, rationale solution-phase synthesis of long ZnO nanowires on optical fibers, fabrication of ZnO nanowire dye-sensitized solar cells on optical fibers, electrical and optical characterization of solar cell devices, comparison studies of 2-D versus 3-D nanowire dye-sensitized solar cell devices, and achievement of 6-fold solar cell power conversion efficiency enhancement using a 3-D approach. The thesis results have implications in nanomanufacturing scale-up and next generation photovoltaics.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

    The spin crossover behaviour of a new class of FeII coordination polymers [Fe(phtptrz)3]I2 ( 1), [Fe(phtptrz)3](ReO4)2•CH3OH ( 2) and [Fe(phtptrz)3]TaF7•6H2O ( 3) based on a novel ligand 4-(3' -N-phtalimido-propyl)-1,2,4-triazole (phtptrz), were investigated by temperature dependent 57Fe 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 T1/2 ~ 163 K and 137 K, respectively. A spin state crossover is also identified for 3.

  1. One-dimensional magnetic nanocomposites with attapulgites as templates: Growth, formation mechanism and magnetic alignment

    NASA Astrophysics Data System (ADS)

    Fu, Meng; Li, Xiangming; Jiang, Rui; Zhang, Zepeng

    2018-05-01

    Magnetic nanocomposite composed of attapulgite and Fe3O4 was synthesized by a simple and facile co-precipitation method. Its structure and morphology was verified using X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. Although the difficulty of forming uniform Fe3O4 on the attapulgite surface was discussed in detail in this study, one-dimensional magnetic nanorod with attapulgites as core and Fe3O4 as uniform shell was implemented for the first time using a cationic polymer surfactant, polyethylenimine. Polyethylenimine concentration, Fe3+/Fe2+ concentration and temperature were controlled to investigate the morphological evolutions of this nanocomposite. It was found that a uniform shell could be available with thickness tuning from 10 nm to 40 nm when Fe3+ concentration ranged from 0.01 mol/L to 0.03 mol/L meanwhile the polyethylenimine concentration was kept at 0.2 mg/mL and the temperature was kept at 60-80 °C. Finally, a possible mechanism for the formation of the Fe3O4 shell was suggested. The polyethylenimine on the surface of the attapulgites first adsorbed Fe3+/Fe2+ and then released under the action of alkali. It acted as a linker for the Fe3O4 nanoparticles nucleation in situ. The synthesized one-dimensional nanocomposites exhibit the superparamagnetism and fast response to an external magnetic field. The alignment of attapulgite-Fe3O4 one-dimensional nanocomposite along the external magnetic field was demonstrated. It provides promising candidates for building blocks and functional devices, which are low cost, non-toxic and eco-friendly, and opens the door for the application of attapulgite as one-dimensional nanomaterials.

  2. Anisotropic elasticity of quasi-one-component polymer nanocomposites.

    PubMed

    Voudouris, Panayiotis; Choi, Jihoon; Gomopoulos, Nikos; Sainidou, Rebecca; Dong, Hongchen; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Fytas, George

    2011-07-26

    The in-plane and out-of-plane elastic properties of thin films of "quasi-one-component" particle-brush-based nanocomposites are compared to those of "classical" binary particle-polymer nanocomposite systems with near identical overall composition using Brillouin light scattering. Whereas phonon propagation is found to be independent of the propagation direction for the binary particle/polymer blend systems, a pronounced splitting of the phonon propagation velocity along the in-plane and out-of-plane film direction is observed for particle-brush systems. The anisotropic elastic properties of quasi-one-component particle-brush systems are interpreted as a consequence of substrate-induced order formation into layer-type structures and the associated breaking of the symmetry of the film. The results highlight new opportunities to engineer quasi-one-component nanocomposites with advanced control of structural and physical property characteristics based on the assembly of particle-brush materials.

  3. The structures and luminescence properties of lanthanide (Ln = Sm, Eu and Tb) metal-organic coordination polymers based on 5-(2-hydroxyethoxy)isophthalate ligand

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Zhang, Yu-Jie; Qin, Jie; Chen, Yong; Zhao, Ying

    2015-03-01

    Three unreported isomorphous Ln-containing metal-organic coordination polymeric complexes {LnL(HL)ṡ(H2O)2}n (Ln = Sm (1), Eu (2) and Tb (3), CCDC 971815-971817) were synthesized based on 5-(2-hydroxyethoxy) isophthalic acid (H2L) under hydrothermal conditions. The obtained coordination polymers were characterized by IR, elemental analysis, thermal analysis and X-ray diffraction In solid state, these polymers featured 3-D supramolecular structures constructed by 2-D sheets through H-bonds. Investigation of photoluminescence properties of H2L and 1-3 showed all of them exhibited intense fluorescent emissions in the solid state at room temperature.

  4. Three-Dimensional (3D) Printing of Polymer-Metal Hybrid Materials by Fused Deposition Modeling

    PubMed Central

    Fafenrot, Susanna; Grimmelsmann, Nils; Wortmann, Martin

    2017-01-01

    Fused deposition modeling (FDM) is a three-dimensional (3D) printing technology that is usually performed with polymers that are molten in a printer nozzle and placed line by line on the printing bed or the previous layer, respectively. Nowadays, hybrid materials combining polymers with functional materials are also commercially available. Especially combinations of polymers with metal particles result in printed objects with interesting optical and mechanical properties. The mechanical properties of objects printed with two of these metal-polymer blends were compared to common poly (lactide acid) (PLA) printed objects. Tensile tests and bending tests show that hybrid materials mostly containing bronze have significantly reduced mechanical properties. Tensile strengths of the 3D-printed objects were unexpectedly nearly identical with those of the original filaments, indicating sufficient quality of the printing process. Our investigations show that while FDM printing allows for producing objects with mechanical properties similar to the original materials, metal-polymer blends cannot be used for the rapid manufacturing of objects necessitating mechanical strength. PMID:29048347

  5. Unique Proton Transportation Pathway in a Robust Inorganic Coordination Polymer Leading to Intrinsically High and Sustainable Anhydrous Proton Conductivity.

    PubMed

    Gui, Daxiang; Dai, Xing; Tao, Zetian; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Shu, Jie; Chen, Lanhua; Wang, Yanlong; Zhang, Tiantian; Xie, Jian; Zou, Lin; Xia, Yuanhua; Zhang, Jujia; Zhang, Jin; Zhao, Ling; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

    2018-05-16

    Although comprehensive progress has been made in the area of coordination polymer (CP)/metal-organic framework (MOF)-based proton-conducting materials over the past decade, searching for a CP/MOF with stable, intrinsic, high anhydrous proton conductivity that can be directly used as a practical electrolyte in an intermediate-temperature proton-exchange membrane fuel cell assembly for durable power generation remains a substantial challenge. Here, we introduce a new proton-conducting CP, (NH 4 ) 3 [Zr(H 2/3 PO 4 ) 3 ] (ZrP), which consists of one-dimensional zirconium phosphate anionic chains and fully ordered charge-balancing NH 4 + cations. X-ray crystallography, neutron powder diffraction, and variable-temperature solid-state NMR spectroscopy suggest that protons are disordered within an inherent hydrogen-bonded infinite chain of acid-base pairs (N-H···O-P), leading to a stable anhydrous proton conductivity of 1.45 × 10 -3 S·cm -1 at 180 °C, one of the highest values among reported intermediate-temperature proton-conducting materials. First-principles and quantum molecular dynamics simulations were used to directly visualize the unique proton transport pathway involving very efficient proton exchange between NH 4 + and phosphate pairs, which is distinct from the common guest encapsulation/dehydration/superprotonic transition mechanisms. ZrP as the electrolyte was further assembled into a H 2 /O 2 fuel cell, which showed a record-high electrical power density of 12 mW·cm -2 at 180 °C among reported cells assembled from crystalline solid electrolytes, as well as a direct methanol fuel cell for the first time to demonstrate real applications. These cells were tested for over 15 h without notable power loss.

  6. Synthesis, structures and fluorescent properties of two novel lanthanide [Ln = Ce(III), Pr(III)] coordination polymers based on 1,3-benzenedicarboxylate and 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ligands

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Ni, Liang; yao, Jia

    2012-09-01

    Two structurally diverse coordination polymers [Ce2(m-BDC)2(m-HBDC)2(MOPIP)2·3/2H2O]n (1) and [Pr2(m-BDC)3(MOPIP)2·H2O]n(2) have been synthesized by hydrothermal reaction of lanthanide chloride with mixed ligands benzene-1,3-dicarboxylic acid and 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (MOPIP). The crystal structures of the complexes are zipper-like chains of octacoordinate Ln3+ ions, in which Ln3+ ions are bridged in different coordination modes by m-BDC2+ and decorated by MOPIP ligands. These chains are further assembled into three-dimensional supramolecular framework by π⋯π stacking and hydrogen bonding interactions. The fluorescent property and thermal stability were also investigated. Additionally, Natural bond orbital (NBO) analysis of complex 2 shows a weak covalent interaction between the coordinated atoms and Pr3+ ions.

  7. Computer Simulation of Spatial Arrangement and Connectivity of Particles in Three-Dimensional Microstructure: Application to Model Electrical Conductivity of Polymer Matrix Composite

    NASA Technical Reports Server (NTRS)

    Louis, P.; Gokhale, A. M.

    1996-01-01

    Computer simulation is a powerful tool for analyzing the geometry of three-dimensional microstructure. A computer simulation model is developed to represent the three-dimensional microstructure of a two-phase particulate composite where particles may be in contact with one another but do not overlap significantly. The model is used to quantify the "connectedness" of the particulate phase of a polymer matrix composite containing hollow carbon particles in a dielectric polymer resin matrix. The simulations are utilized to estimate the morphological percolation volume fraction for electrical conduction, and the effective volume fraction of the particles that actually take part in the electrical conduction. The calculated values of the effective volume fraction are used as an input for a self-consistent physical model for electrical conductivity. The predicted values of electrical conductivity are in very good agreement with the corresponding experimental data on a series of specimens having different particulate volume fraction.

  8. Porous, Hyper-cross-linked, Three-Dimensional Polymer as Stable, High Rate Capability Electrode for Lithium-Ion Battery.

    PubMed

    Mukherjee, Debdyuti; Gowda Y K, Guruprasada; Makri Nimbegondi Kotresh, Harish; Sampath, S

    2017-06-14

    Organic materials containing active carbonyl groups have attracted considerable attention as electrodes in Li-ion batteries due to their reversible redox activity, ability to retain capacity, and, in addition, their ecofriendly nature. Introduction of porosity will help accommodate as well as store small ions and molecules reversibly. In the present work, we introduce a mesoporous triptycene-related, rigid network polymer with high specific surface area as an electrode material for rechargeable Li-ion battery. The designed polymer with a three-dimensional (3D), rigid porous network allows free movement of ions/electrolyte as well as helps in interacting with the active anhydride moieties (containing two carbonyl groups). Considerable intake of Li + ions giving rise to very high specific capacity of 1100 mA h g -1 at a discharge current of 50 mA g -1 and ∼120 mA h g -1 at a high discharge current of 3 A g -1 are observed with excellent cyclability up to 1000 cycles. This remarkable rate capability, which is one of the highest among the reported organic porous polymers to date, makes the triptycene-related rigid 3D network a very good choice for Li-ion batteries and opens up a new method to design polymer-based electrode materials for metal-ion battery technology.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Lin; Liu, Chong-Bo, E-mail: cbliu@nchu.edu.cn; Yang, Gao-Shan

    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}, andmore » 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.« less

  10. Effective characterization of polymer residues on two-dimensional materials by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Park, Ji-Hoon; Choi, Soo Ho; Chae, Won Uk; Stephen, Boandoh; Park, Hyeon Ki; Yang, Woochul; Kim, Soo Min; Lee, Joo Song; Kim, Ki Kang

    2015-12-01

    Large-area two-dimensional (2D) materials grown by chemical vapor deposition need to be transferred onto a target substrate for real applications. Poly(methyl methacrylate) as a supporting layer is widely used during the transfer process and removed after finishing it. However, it is a challenge to diminish the polymer layer completely. It is necessary to readily characterize the polymer residues on 2D materials to facilitate the removal process. Here, we report a method that characterizes the polymer residues on 2D materials by tracking the presence of G-band of amorphous carbons (a-Cs) in the Raman spectrum after forming carbonized a-Cs through thermal annealing. The 13C-graphene is employed to separate the Raman signal G-band between 12C-a-Cs and 13C-graphene in the Raman spectrum. The residence of the polymer residues is clearly confirmed by the different Raman signals of two different isotopes (12C and 13C) due to differences in mass. Our effective method recognizes that while the polymer residue is not easily removed on graphene, those on hexagonal boron nitride and molybdenum disulfide are almost diminished under optimum thermal annealing conditions. Our method will not only contribute to the development of a new transfer process, but also help to achieve a clean surface of 2D materials.

  11. Glassy dynamics of polymethylphenylsiloxane in one- and two-dimensional nanometric confinement—A comparison

    NASA Astrophysics Data System (ADS)

    Kipnusu, Wycliffe K.; Elsayed, Mohamed; Krause-Rehberg, Reinhard; Kremer, Friedrich

    2017-05-01

    Glassy dynamics of polymethylphenylsiloxane (PMPS) is studied by broadband dielectric spectroscopy in one-dimensional (1D) and two-dimensional (2D) nanometric confinement; the former is realized in thin polymer layers having thicknesses down to 5 nm, and the latter in unidirectional (thickness 50 μm) nanopores with diameters varying between 4 and 8 nm. Based on the dielectric measurements carried out in a broad spectral range at widely varying temperatures, glassy dynamics is analyzed in detail in 1D and in 2D confinements with the following results: (i) the segmental dynamics (dynamic glass transition) of PMPS in 1D confinement down to thicknesses of 5 nm is identical to the bulk in the mean relaxation rate and the width of the relaxation time distribution function; (ii) additionally a well separated surface induced relaxation is observed, being assigned to adsorption and desorption processes of polymer segments with the solid interface; (iii) in 2D confinement with native inner pore walls, the segmental dynamics shows a confinement effect, i.e., the smaller the pores are, the faster the segmental dynamics; on silanization, this dependence on the pore diameter vanishes, but the mean relaxation rate is still faster than in 1D confinement; (iv) in a 2D confinement, a pronounced surface induced relaxation process is found, the strength of which increases with the decreasing pore diameter; it can be fully removed by silanization of the inner pore walls; (v) the surface induced relaxation depends on its spectral position only negligibly on the pore diameter; (vi) comparing 1D and 2D confinements, the segmental dynamics in the latter is by about two orders of magnitude faster. All these findings can be comprehended by considering the density of the polymer; in 1D it is assumed to be the same as in the bulk, hence the dynamic glass transition is not altered; in 2D it is reduced due to a frustration of packaging resulting in a higher free volume, as proven by ortho

  12. Nanoscale coordination polymers for anticancer drug delivery

    NASA Astrophysics Data System (ADS)

    Phillips, Rachel Huxford

    This dissertation reports the synthesis and characterization of nanoscale coordination polymers (NCPs) for anticancer drug delivery. Nanoparticles have been explored in order to address the limitations of small molecule chemotherapeutics. NCPs have been investigated as drug delivery vehicles as they can exhibit the same beneficial properties as the bulk metal-organic frameworks as well as interesting characteristics that are unique to nanomaterials. Gd-MTX (MTX = methotrexate) NCPs with a MTX loading of 71.6 wt% were synthesized and stabilized by encapsulation within a lipid bilayer containing anisamide (AA), a small molecule that targets sigma receptors which are overexpressed in many cancer tissues. Functionalization with AA allows for targeted delivery and controlled release to cancer cells, as shown by enhanced efficacy against leukemia cells. The NCPs were doped with Ru(bpy)32+ (bpy = 2,2'-bipyridine), and this formulation was utilized as an optical imaging agent by confocal microscopy. NCPs containing the chemotherapeutic pemetrexed (PMX) were synthesized using different binding metals. Zr-based materials could not be stabilized by encapsulation with a lipid bilayer, and Gd-based materials showed that PMX had degraded during synthesis. However, Hf-based NCPs containing 19.7 wt% PMX were stabilized by a lipid coating and showed in vitro efficacy against non-small cell lung cancer (NSCLC) cell lines. Enhanced efficacy was observed for formulations containing AA. Additionally, NCP formulations containing the cisplatin prodrug disuccinatocisplatin were prepared; one of these formulations could be stabilized by encapsulation within a lipid layer. Coating with a lipid layer doped with AA rendered this formulation an active targeting agent. The resulting formulation proved more potent than free cisplatin in NSCLC cell lines. Improved NCP uptake was demonstrated by confocal microscopy and competitive binding assays. Finally, a Pt(IV) oxaliplatin prodrug was

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

    PubMed

    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.

  14. Lift, Drag, and Pressure Distribution Effects Accompanying Drag-Reducing Polymer Injection on Two-Dimensional Hydrofoil

    DTIC Science & Technology

    1975-10-01

    associated with drag- reducing polymers since Wu’s discovery of pump effects in 1969(16) Some of the research has involved tests on propellers finite span...AD-A022 433 LIFT, DRAG, AND PRESSURE DISTRIBUTION EFFECTS ACCOMPANYING DRAG- REDUCING POLYMER INJECTION ON TWO-DIMENSIONAL HYDROFOIL Daniel H. Fruman...et al Hydronautits, IncorponAted "Prepared f’or: Office of Naval Research October 197’ .!. S.IIE KA NTO CmaY - t 093103 A pprove!- for p~thic relpsa

  15. Molecular weaving via surface-templated epitaxy of crystalline coordination networks.

    PubMed Central

    Wang, Zhengbang; Błaszczyk, Alfred; Fuhr, Olaf; Heissler, Stefan; Wöll, Christof; Mayor, Marcel

    2017-01-01

    One of the dream reactions in polymer chemistry is the bottom-up, self-assembled synthesis of polymer fabrics, with interwoven, one-dimensional fibres of monomolecular thickness forming planar pieces of textiles. We have made a major step towards realizing this goal by assembling sophisticated, quadritopic linkers into surface-mounted metal-organic frameworks. By sandwiching these quadritopic linkers between sacrificial metal-organic framework thin films, we obtained multi-heteroepitaxial, crystalline systems. In a next step, Glaser–Hay coupling of triple bonds in the quadritopic linkers yields linear, interwoven polymer chains. X-ray diffraction studies revealed that this topochemical reaction leaves the MOF backbone completely intact. After removing the metal ions, the textile sheets can be transferred onto different supports and imaged using scanning electron microscopy and atomic-force microscopy. The individual polymer strands forming the two-dimensional textiles have lengths on the order of 200 nm, as evidenced by atomic-force microscopy images recorded from the disassembled textiles. PMID:28198388

  16. Molecular weaving via surface-templated epitaxy of crystalline coordination networks.

    NASA Astrophysics Data System (ADS)

    Wang, Zhengbang; Błaszczyk, Alfred; Fuhr, Olaf; Heissler, Stefan; Wöll, Christof; Mayor, Marcel

    2017-02-01

    One of the dream reactions in polymer chemistry is the bottom-up, self-assembled synthesis of polymer fabrics, with interwoven, one-dimensional fibres of monomolecular thickness forming planar pieces of textiles. We have made a major step towards realizing this goal by assembling sophisticated, quadritopic linkers into surface-mounted metal-organic frameworks. By sandwiching these quadritopic linkers between sacrificial metal-organic framework thin films, we obtained multi-heteroepitaxial, crystalline systems. In a next step, Glaser-Hay coupling of triple bonds in the quadritopic linkers yields linear, interwoven polymer chains. X-ray diffraction studies revealed that this topochemical reaction leaves the MOF backbone completely intact. After removing the metal ions, the textile sheets can be transferred onto different supports and imaged using scanning electron microscopy and atomic-force microscopy. The individual polymer strands forming the two-dimensional textiles have lengths on the order of 200 nm, as evidenced by atomic-force microscopy images recorded from the disassembled textiles.

  17. From particle condensation to polymer aggregation

    NASA Astrophysics Data System (ADS)

    Janke, Wolfhard; Zierenberg, Johannes

    2018-01-01

    We draw an analogy between droplet formation in dilute particle and polymer systems. Our arguments are based on finite-size scaling results from studies of a two-dimensional lattice gas to three-dimensional bead-spring polymers. To set the results in perspective, we compare with in part rigorous theoretical scaling laws for canonical condensation in a supersaturated gas at fixed temperature, and derive corresponding scaling predictions for an undercooled gas at fixed density. The latter allows one to efficiently employ parallel multicanonical simulations and to reach previously not accessible scaling regimes. While the asymptotic scaling can not be observed for the comparably small polymer system sizes, they demonstrate an intermediate scaling regime also observable for particle condensation. Altogether, our extensive results from computer simulations provide clear evidence for the close analogy between particle condensation and polymer aggregation in dilute systems.

  18. A two-dimensional silver(I) coordination polymer constructed from 4-aminophenylarsonate and triphenylphosphane: poly[[(μ₃-4-aminophenylarsonato-κ³N:O:O)(triphenylphosphane-κP)silver(I)] monohydrate].

    PubMed

    Xiao, Zu-Ping; Wen, Meng; Wang, Chun-Ya; Huang, Xi-He

    2015-04-01

    The title compound, {[Ag(C6H7AsNO3)(C18H15P)]·H2O}n, has been synthesized from the reaction of 4-aminophenylarsonic acid with silver nitrate, in aqueous ammonia, with the addition of triphenylphosphane (PPh3). The Ag(I) centre is four-coordinated by one amino N atom, one PPh3 P atom and two arsonate O atoms, forming a severely distorted [AgNPO2] tetrahedron. Two Ag(I)-centred tetrahedra are held together to produce a dinuclear [Ag2O2N2P2] unit by sharing an O-O edge. 4-Aminophenylarsonate (Hapa(-)) adopts a μ3-κ(3)N:O:O-tridentate coordination mode connecting two dinuclear units, resulting in a neutral [Ag(Hapa)(PPh3)]n layer lying parallel to the (101̄) plane. The PPh3 ligands are suspended on both sides of the [Ag(Hapa)(PPh3)]n layer, displaying up and down orientations. There is an R2(2)(8) hydrogen-bonded dimer involving two arsonate groups from two Hapa(-) ligands related by a centre of inversion. Additionally, there are hydrogen-bonding interactions involving the solvent water molecules and the arsonate and amine groups of the Hapa(-) ligands, and weak π-π stacking interactions within the [Ag(Hapa)(PPh3)]n layer. These two-dimensional layers are further assembled by weak van der Waals interactions to form the final architecture.

  19. Rapid Stencil Mask Fabrication Enabled One-Step Polymer-Free Graphene Patterning and Direct Transfer for Flexible Graphene Devices

    PubMed Central

    Yong, Keong; Ashraf, Ali; Kang, Pilgyu; Nam, SungWoo

    2016-01-01

    We report a one-step polymer-free approach to patterning graphene using a stencil mask and oxygen plasma reactive-ion etching, with a subsequent polymer-free direct transfer for flexible graphene devices. Our stencil mask is fabricated via a subtractive, laser cutting manufacturing technique, followed by lamination of stencil mask onto graphene grown on Cu foil for patterning. Subsequently, micro-sized graphene features of various shapes are patterned via reactive-ion etching. The integrity of our graphene after patterning is confirmed by Raman spectroscopy. We further demonstrate the rapid prototyping capability of a stretchable, crumpled graphene strain sensor and patterned graphene condensation channels for potential applications in sensing and heat transfer, respectively. We further demonstrate that the polymer-free approach for both patterning and transfer to flexible substrates allows the realization of cleaner graphene features as confirmed by water contact angle measurements. We believe that our new method promotes rapid, facile fabrication of cleaner graphene devices, and can be extended to other two dimensional materials in the future. PMID:27118249

  20. Solvothermal synthesis and structure of coordination polymers of Nd(III) and Dy(III) with rigid isophthalic acid derivatives and flexible adipic acid

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

    Two new coordination polymers (CPs) with the formula [Nd(hip)(adip) 0.5(H2O)2]n.nH2O (1) and [Dy(aip)(adip)0.5(H2O)2]n.nH2O (2) were synthesized by self-assembly of lanthanide salts with rigid [5-hydroxyisophthalic acid (H2hip)], [5-aminoisophthalic acid (H2aip)] and flexible [adipic acid (H2adip)] linkers under solvothermal conditions. The CPs 1 &2 crystallize in monoclinic C2/c space group. Both the CPs have 1D linear ladder shaped extension with the linkages having the backbone of hip2-, aip2- and adip2- ligands. The 1D linear ladder chains generate three dimensional (3D) supramolecular frameworks via significant π-π and hydrogen bonding interactions. The CP 2 (Dy) emit strong ligand sensitized characteristic f-f luminescence emission. The CP 2 also exhibit weak ferromagnetic interactions at low temperatures.

  1. Large exchange anisotropy in quasi-one-dimensional spin-1/2 fluoride antiferromagnets with a d (z2)1 ground state

    NASA Astrophysics Data System (ADS)

    Kurzydłowski, D.; Grochala, W.

    2017-10-01

    Hybrid density functional calculations are performed for a variety of systems containing d9 ions (C u2 + and A g2 + ) and exhibiting quasi-one-dimensional magnetic properties. In particular, we study fluorides containing these ions in a rarely encountered compressed octahedral coordination that forces the unpaired electron into the local d (z2) orbital. We predict that such systems should exhibit exchange anisotropies surpassing that of S r2Cu O3 , one of the best realizations of a one-dimensional system known to date. In particular, we predict that the interchain coupling in the A g2 + -containing [AgF ] [B F4 ] system should be nearly four orders of magnitude smaller than the intrachain interaction. Our results indicate that quasi-one-dimensional spin-1/2 systems containing chains with spin sites in the d (z2)1 local ground state could constitute a versatile model for testing modern theories of quantum many-body physics in the solid state.

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

    PubMed

    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

  3. Carbon dioxide separation with a two-dimensional polymer membrane.

    PubMed

    Schrier, Joshua

    2012-07-25

    Carbon dioxide gas separation is important for many environmental and energy applications. Molecular dynamics simulations are used to characterize a two-dimensional hydrocarbon polymer, PG-ES1, that uses a combination of surface adsorption and narrow pores to separate carbon dioxide from nitrogen, oxygen, and methane gases. The CO2 permeance is 3 × 10(5) gas permeation units (GPU). The CO2/N2 selectivity is 60, and the CO2/CH4 selectivity exceeds 500. The combination of high CO2 permeance and selectivity surpasses all known materials, enabling low-cost postcombustion CO2 capture, utilization of landfill gas, and horticulture applications.

  4. One-Dimensional Czedli-Type Islands

    ERIC Educational Resources Information Center

    Horvath, Eszter K.; Mader, Attila; Tepavcevic, Andreja

    2011-01-01

    The notion of an island has surfaced in recent algebra and coding theory research. Discrete versions provide interesting combinatorial problems. This paper presents the one-dimensional case with finitely many heights, a topic convenient for student research.

  5. Construction of (CuX)2n cluster-containing (X = Br, I; n = 1, 2) coordination polymers assembled by dithioethers ArS(CH2)(m)SAr (Ar = Ph, p-Tol; m = 3, 5): effect of the spacer length, aryl group, and metal-to-ligand ratio on the dimensionality, cluster nuclearity, and the luminescence properties of the metal-organic frameworks.

    PubMed

    Knorr, Michael; Guyon, Fabrice; Khatyr, Abderrahim; Strohmann, Carsten; Allain, Magali; Aly, Shawkat M; Lapprand, Antony; Fortin, Daniel; Harvey, Pierre D

    2012-09-17

    Reaction of CuI with bis(phenylthio)propane in a 1:1 ratio yields the two-dimensional coordination polymer [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (1). The 2D-sheet structure of 1 is built up by dimeric Cu(2)I(2) units, which are connected via four bridging 1,3-bis(phenylthio)propane ligands. In contrast, treatment of 2 equiv of CuI with 1,3-bis(phenylthio)propane in MeCN solution affords in a self-assembly reaction the strongly luminescent metal-organic 2D-coordination polymer [Cu(4)I(4){μ-PhS(CH(2))(3)Ph}(2)](n) (2), in which cubane-like Cu(4)(μ(3)-I)(4) cluster units are linked by the dithioether ligands. The crystallographically characterized one-dimensional (1D) compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (3) is obtained using CuBr. The outcome of the reaction of PhS(CH(2))(5)SPh with CuI also depends of the metal-to-ligand ratio employed. Mixing CuI and the dithioether in a 2:1 ratio results in formation of [Cu(4)I(4){μ-PhS(CH(2))(5)Ph}(2)](n) (4) in which cubane-like Cu(4)(μ(3)-I)(4) clusters are linked by the bridging dithioether ligand giving rise to a 1D necklace structure. A ribbon-like 1D-polymer with composition [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (5), incorporating rhomboid Cu(2)I(2) units, is produced upon treatment of CuI with 1,5-bis(phenylthio)pentane in a 1:1 ratio. Reaction of CuBr with PhS(CH(2))(5)SPh produces the isomorphous 1D-compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (6). Strongly luminescent [Cu(4)I(4){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (7) is obtained after mixing 1,5-bis(p-tolylthio)pentane with CuI in a 1:2 ratio, and the 2D-polymer [{Cu(μ(2)-I)(2)Cu}(2){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (8) results from reaction in a 1:1 metal-to-ligand ratio. Under the same reaction conditions, 1D-polymeric [{Cu(μ(2)-Br)(2)Cu}{μ-p-TolS(CH(2))(5)STol-p}(2)](n) (9) is formed using CuBr. This study reveals that the structure of the self-assembly process between CuX and ArS(CH(2))(m)SAr ligands is

  6. 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.

    PubMed

    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

  7. Crystal structure and magnetic properties of a unique 3D coordination polymer constructed from flexible aliphatic tricarballylic acid ligands featuring linear trimeric Manganese(II)-based, metal carboxylate chains

    NASA Astrophysics Data System (ADS)

    Zou, Hua-Hong; Zhang, Shu-Hua; Zeng, Ming-Hua; Zhou, Yan-Ling; Liang, Hong

    2008-08-01

    A novel linear trimeric-based, Mn(II)-carboxylate chain well separated by long-linking flexible aliphatic tricarballylic acid ligands in a 3D coordination polymer [Mn 3(C 6H 5O 6) 2(H 2O) 4] n ( 1, C 6H 5O 6dbnd CH (COO -)(CH 2COO -) 2, TCA) exhibits low-dimensional antiferromagnetic order at 3.0 K. Such magnetic behavior is arises from the alternate Antiferro-Antiferro-Antiferro' ( J1J1J2) repeating interactions sequence, based on the nature of the binding modes of Mn(II)-carboxylate chain and the effect of interchains arrangement of 1. The reported carboxylate-bridged metal chain systems display a new structurally authenticated example of linear homometallic spin arranged antiferromagnet among metal carboxylates.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. A 3D porous indium(III) coordination polymer involving in-situ ligand synthesis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Han Zhengbo, E-mail: ceshzb@lnu.edu.c; Song Yongjuan; Ji Jianwei

    2009-11-15

    The hydrothermal reaction of In{sup 3+} and 1,2,4-benzenetricarboxylic acid with the presence of piperazine leads to the generation of a novel 3D porous coordination polymer, [H{sub 3}O][In{sub 2}(btc)(bdc)(OH){sub 2}].5.5H{sub 2}O (1), (btc=1,2,4-benzenetricarboxylate, bdc=1,4-benzenedicarboxylate). Compound 1 crystallizes in orthorhombic space group Pbca with a=16.216(7) A, b=13.437(6) A, c=31.277(14) A, and Z=8. It is interesting to find that the in-situ decarboxylation reaction of 1,2,4-benzenetricarboxylate (btc) partially transformed into 1,4-benzenedicarboxylate (bdc) occurs. The 16 indium(III) centers were linked by four btc, four bdc and two mu{sub 2}-OH ligands to form a box-girder. The adjacent box-girders are further connected by the bdc and btcmore » ligands to generate a novel porous metal-organic framework containing nanotubular open channel with a cross-section of approximately 11.5x11.3 A{sup 2}. The micropores are occupied by lattice water molecules, and the solvent-accessible volume of the unit cell was estimated to be 3658.6 A{sup 3}, which is approximately 53.7% of the unit-cell volume (6815.4 A{sup 3}). - Graphical Abstract: The hydrothermal reaction of In{sup 3+} and 1,2,4-benzenetricarboxylic acid with the presence of piperazine leads to the generation of a novel 3D porous coordination polymer, [H{sub 3}O][In{sub 2}(btc)(bdc)(OH){sub 2}].5.5H{sub 2}O, (btc=1,2,4-benzenetricarboxylate, bdc=1,4-benzenedicarboxylate).« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lu, Xin-Xin; Luo, Yu-Hui; Lu, Chen

    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 bacteriamore » 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.« less

  11. Comparison of two-dimensional and quasi-one-dimensional scramjet models by the example of VAG experiment

    NASA Astrophysics Data System (ADS)

    Seleznev, R. K.

    2017-02-01

    In the paper two-dimensional and quasi-one dimensional models for scramjet combustion chamber are described. Comparison of the results of calculations for the two-dimensional and quasi-one dimensional code by the example of VAG experiment are presented.

  12. Multi-perspective views of students’ difficulties with one-dimensional vector and two-dimensional vector

    NASA Astrophysics Data System (ADS)

    Fauzi, Ahmad; Ratna Kawuri, Kunthi; Pratiwi, Retno

    2017-01-01

    Researchers of students’ conceptual change usually collects data from written tests and interviews. Moreover, reports of conceptual change often simply refer to changes in concepts, such as on a test, without any identification of the learning processes that have taken place. Research has shown that students have difficulties with vectors in university introductory physics courses and high school physics courses. In this study, we intended to explore students’ understanding of one-dimensional and two-dimensional vector in multi perspective views. In this research, we explore students’ understanding through test perspective and interviews perspective. Our research study adopted the mixed-methodology design. The participants of this research were sixty students of third semester of physics education department. The data of this research were collected by testand interviews. In this study, we divided the students’ understanding of one-dimensional vector and two-dimensional vector in two categories, namely vector skills of the addition of one-dimensionaland two-dimensional vector and the relation between vector skills and conceptual understanding. From the investigation, only 44% of students provided correct answer for vector skills of the addition of one-dimensional and two-dimensional vector and only 27% students provided correct answer for the relation between vector skills and conceptual understanding.

  13. Fast Three-Dimensional Method of Modeling Atomic Oxygen Undercutting of Protected Polymers

    NASA Technical Reports Server (NTRS)

    Snyder, Aaron; Banks, Bruce A.

    2002-01-01

    A method is presented to model atomic oxygen erosion of protected polymers in low Earth orbit (LEO). Undercutting of protected polymers by atomic oxygen occurs in LEO due to the presence of scratch, crack or pin-window defects in the protective coatings. As a means of providing a better understanding of undercutting processes, a fast method of modeling atomic-oxygen undercutting of protected polymers has been developed. Current simulation methods often rely on computationally expensive ray-tracing procedures to track the surface-to-surface movement of individual "atoms." The method introduced in this paper replaces slow individual particle approaches by substituting a model that utilizes both a geometric configuration-factor technique, which governs the diffuse transport of atoms between surfaces, and an efficient telescoping series algorithm, which rapidly integrates the cumulative effects stemming from the numerous atomic oxygen events occurring at the surfaces of an undercut cavity. This new method facilitates the systematic study of three-dimensional undercutting by allowing rapid simulations to be made over a wide range of erosion parameters.

  14. Hybrid materials based on novel 2D lanthanide coordination polymers covalently bonded to amine-modified SBA-15 and MCM-41: assembly, characterization, structural features, thermal and luminescence properties.

    PubMed

    Wang, Jun; Dou, Wei; Kirillov, Alexander M; Liu, Weisheng; Xu, Cailing; Fang, Ran; Yang, Lizi

    2016-11-22

    Three novel 2D coordination polymers [Tb 2 (μ 4 -L) 2 (μ-HL)(μ-HCOO)(DEF)] n (Tb-L), [Eu(μ 4 -L)(L)(H 2 O) 2 ] n (Eu-L), and [Nd(μ 4 -L)(L)(H 2 O) 2 ] n (Nd-L) were assembled from the corresponding lanthanide(iii) nitrates and 5 methoxy-(4-benzaldehyde)-1,3-benzenedicarboxylic acid (H 2 L) as a main multifunctional building block bearing carboxylate and aldehyde functional groups, using H 2 O/DEF {DEF = N,N-diethylformamide} as a reaction medium. The obtained coordination polymers were isolated as stable microcrystalline solids and fully characterized by elemental analysis, FT-IR spectroscopy, TGA, BET, PXRD, and single-crystal X-ray diffraction methods. Their structures feature intricate 2D metal-organic networks, which were topologically classified as underlying layers with the 4,6L26 (for Tb-L) or sql (for Eu-L and Nd-L) topologies. Besides, a novel series of mesoporous hybrid materials wherein the Tb-L, Eu-L, or Nd-L coordination polymers are covalently grafted into the amine-functionalized SBA-15-NH 2 or MCM-41-NH 2 matrices (via the formation of Schiff-base groups) was also synthesized and fully characterized. These hybrid materials show high thermal and photoluminescence stability, as well as remarkable chemical resistance to boiling water, and acidic or alkaline medium. Luminescent properties of the parent coordination polymers and derived hybrid materials are investigated in detail, showing that the latter combine the luminescent characteristics (intense green or red emissions and excellent stability) of lanthanide coordination polymers and structural features of ordered mesoporous silica molecular sieves. Moreover, light emitting devices were assembled, by coating the hybrid materials onto the surface of UV-LED bulbs, and showed excellent light emitting properties.

  15. Heterobimetallic thiocyanato-bridged coordination polymers based on [Hg(SCN) 4] 2-: Synthesis, crystal structure, magnetic properties and ESR studies

    NASA Astrophysics Data System (ADS)

    Jian, Fang-Fang; Xiao, Hai-Lian; Liu, Fa Qian

    2006-12-01

    Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN) 4Ni(Im) 3] ∞1, [Hg(SCN) 4Mn(Im) 2] ∞2, and [Hg(SCN) 4Cu(Me-Im) 2 Hg(SCN) 4Cu(Me-Im) 4] ∞3, (Im=imidazole, Me-Im= N-methyl-imidazole), have been synthesized and characterized by means of elemental analysis, ESR, and single-crystal X-ray. X-ray diffraction analysis reveals that these three complexes all form 3D network structure, and their structures all contain a thiocyanato-bridged Hg⋯M⋯Hg chain ( M=Mn, Ni, Cu) in which the metal and mercury centers exhibit different coordination environments. In complex 1, the [Hg(SCN) 4] 2- anion connects three [Ni(Im) 3] 2+ using three SCN ligands giving rise to a 3D structure, and in complex 2, four SCN ligands bridge [Hg(SCN) 4] 2- and [Mn(Im) 2] 2+ to form a 3D structure. The structure of 3 contains two copper atoms with distinct coordination environment; one is coordinated by four N-methyl-imidazole ligands and two axially elongated SCN groups, and another by four SCN groups (two elongated) and two N-methyl-imidazole ligands. The magnetic property of complex 1 has been investigated. The spin state structure in hetermetallic NiHgNi systems of complex 1 is irregular. The ESR spectra results of complex 3 demonstrate Cu 2+ ion lie on octahedral environment.

  16. Constitutive Modeling of Nanotube/Polymer Composites with Various Nanotube Orientations

    NASA Technical Reports Server (NTRS)

    Odegard, Gregory M.; Gates, Thomas S.

    2002-01-01

    In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT) with various orientations with respect to the bulk material coordinates. A nanotube, the local polymer adjacent to the nanotube, and the nanotube/polymer interface have been modeled as an equivalent-continuum fiber by using an equivalent-continuum modeling method. The equivalent-continuum fiber accounts for the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composite. As an example, the proposed approach is used for the constitutive modeling of a SWNT/LaRC-SI (with a PmPV interface) composite system, with aligned nanotubes, three-dimensionally randomly oriented nanotubes, and nanotubes oriented with varying degrees of axisymmetry. It is shown that the Young s modulus is highly dependent on the SWNT orientation distribution.

  17. One-dimensional turbulence modeling for cylindrical and spherical flows: model formulation and application

    NASA Astrophysics Data System (ADS)

    Lignell, David O.; Lansinger, Victoria B.; Medina, Juan; Klein, Marten; Kerstein, Alan R.; Schmidt, Heiko; Fistler, Marco; Oevermann, Michael

    2018-06-01

    The one-dimensional turbulence (ODT) model resolves a full range of time and length scales and is computationally efficient. ODT has been applied to a wide range of complex multi-scale flows, such as turbulent combustion. Previous ODT comparisons to experimental data have focused mainly on planar flows. Applications to cylindrical flows, such as round jets, have been based on rough analogies, e.g., by exploiting the fortuitous consistency of the similarity scalings of temporally developing planar jets and spatially developing round jets. To obtain a more systematic treatment, a new formulation of the ODT model in cylindrical and spherical coordinates is presented here. The model is written in terms of a geometric factor so that planar, cylindrical, and spherical configurations are represented in the same way. Temporal and spatial versions of the model are presented. A Lagrangian finite-volume implementation is used with a dynamically adaptive mesh. The adaptive mesh facilitates the implementation of cylindrical and spherical versions of the triplet map, which is used to model turbulent advection (eddy events) in the one-dimensional flow coordinate. In cylindrical and spherical coordinates, geometric stretching of the three triplet map images occurs due to the radial dependence of volume, with the stretching being strongest near the centerline. Two triplet map variants, TMA and TMB, are presented. In TMA, the three map images have the same volume, but different radial segment lengths. In TMB, the three map images have the same radial segment lengths, but different segment volumes. Cylindrical results are presented for temporal pipe flow, a spatial nonreacting jet, and a spatial nonreacting jet flame. These results compare very well to direct numerical simulation for the pipe flow, and to experimental data for the jets. The nonreacting jet treatment overpredicts velocity fluctuations near the centerline, due to the geometric stretching of the triplet maps and its

  18. Mapping two-dimensional polar active fluids to two-dimensional soap and one-dimensional sandblasting.

    PubMed

    Chen, Leiming; Lee, Chiu Fan; Toner, John

    2016-07-25

    Active fluids and growing interfaces are two well-studied but very different non-equilibrium systems. Each exhibits non-equilibrium behaviour distinct from that of their equilibrium counterparts. Here we demonstrate a surprising connection between these two: the ordered phase of incompressible polar active fluids in two spatial dimensions without momentum conservation, and growing one-dimensional interfaces (that is, the 1+1-dimensional Kardar-Parisi-Zhang equation), in fact belong to the same universality class. This universality class also includes two equilibrium systems: two-dimensional smectic liquid crystals, and a peculiar kind of constrained two-dimensional ferromagnet. We use these connections to show that two-dimensional incompressible flocks are robust against fluctuations, and exhibit universal long-ranged, anisotropic spatio-temporal correlations of those fluctuations. We also thereby determine the exact values of the anisotropy exponent ζ and the roughness exponents χx,y that characterize these correlations.

  19. Mapping two-dimensional polar active fluids to two-dimensional soap and one-dimensional sandblasting

    NASA Astrophysics Data System (ADS)

    Chen, Leiming; Lee, Chiu Fan; Toner, John

    2016-07-01

    Active fluids and growing interfaces are two well-studied but very different non-equilibrium systems. Each exhibits non-equilibrium behaviour distinct from that of their equilibrium counterparts. Here we demonstrate a surprising connection between these two: the ordered phase of incompressible polar active fluids in two spatial dimensions without momentum conservation, and growing one-dimensional interfaces (that is, the 1+1-dimensional Kardar-Parisi-Zhang equation), in fact belong to the same universality class. This universality class also includes two equilibrium systems: two-dimensional smectic liquid crystals, and a peculiar kind of constrained two-dimensional ferromagnet. We use these connections to show that two-dimensional incompressible flocks are robust against fluctuations, and exhibit universal long-ranged, anisotropic spatio-temporal correlations of those fluctuations. We also thereby determine the exact values of the anisotropy exponent ζ and the roughness exponents χx,y that characterize these correlations.

  20. Design and fabrication of one-dimensional and two- dimensional photonic bandgap devices

    NASA Astrophysics Data System (ADS)

    Lim, Kuo-Yi

    1999-10-01

    One-dimensional and two-dimensional photonic bandgap devices have been designed and fabricated using III-V compound semiconductors. The one-dimensional photonic bandgap devices consist of monorail and air-bridge waveguide microcavities, while the two-dimensional photonic bandgap devices consist of light-emitting devices with enhanced extraction efficiency. Fabrication techniques such as gas source molecular beam epitaxy, direct-write electron-beam lithography, reactive ion etching and thermal oxidation of AlxGa1- xAs have been employed. The III-V thermal oxide, in particular, is used as an index confinement material, as a sacrificial material for micromechanical fabrication of the air-bridge microcavity, and in the realization of a wide-bandwidth distributed Bragg reflector. The one-dimensional photonic bandgap waveguide microcavities have been designed to operate in the wavelength regimes of 4.5 m m and 1.55 m m. The devices designed to operate in the 1.55 m m wavelength regime have been optically characterized. The transmission spectra exhibit resonances at around 1.55 m m and cavity quality factors (Q's) ranging from 136 to 334. The resonant modal volume is calculated to be about 0.056 m m3. Tunability in the resonance wavelengths has also been demonstrated by changing the size of the defect in the one-dimensional photonic crystal. The two-dimensional photonic bandgap light-emitting device consists of a In0.51Ga0.49P/In0.2Ga0.8As/In 0.51Ga0.49P quantum well emitting at 980nm with a triangular photonic lattice of holes in the top cladding layer of the quantum well. The photonic crystal prohibits the propagation of guided modes in the semiconductor, thus enhancing the extraction of light vertical to the light-emitting device. A wide-bandwidth GaAs/AlxOy distributed Bragg reflector mirror under the quantum well structure further enhances the extraction of light from the devices. The extraction efficiency of the two-dimensional photonic bandgap light-emitting device

  1. One-dimensional, two-dimensional, and three-dimensional photonic crystals fabricated with interferometric techniques on ultrafine-grain silver halide emulsions

    NASA Astrophysics Data System (ADS)

    Ulibarrena, Manuel; Carretero, Luis; Acebal, Pablo; Madrigal, Roque; Blaya, Salvador; Fimia, Antonio

    2004-09-01

    Holographic techniques have been used for manufacturing multiple band one-dimensional, two-dimensional, and three-dimensional photonic crystals with different configurations, by multiplexing reflection and transmission setups on a single layer of holographic material. The recording material used for storage is an ultra fine grain silver halide emulsion, with an average grain size around 20 nm. The results are a set of photonic crystals with the one-dimensional, two-dimensional, and three-dimensional index modulation structure consisting of silver halide particles embedded in the gelatin layer of the emulsion. The characterisation of the fabricated photonic crystals by measuring their transmission band structures has been done and compared with theoretical calculations.

  2. A two-dimensional ZnII coordination polymer constructed from benzene-1,2,3-tricarboxylic acid and N,N'-bis[(pyridin-4-yl)methylidene]hydrazine.

    PubMed

    Wang, Xiangfei; Yang, Fang; Tang, Meng; Yuan, Limin; Liu, Wenlong

    2015-07-01

    The hydrothermal synthesis of the novel complex poly[aqua(μ4-benzene-1,2,3-tricarboxylato)[μ2-4,4'-(hydrazine-1,2-diylidenedimethanylylidene)dipyridine](μ3-hydroxido)dizinc(II)], [Zn(C9H3O6)(OH)(C12H10N4)(H2O)]n, is described. The benzene-1,2,3-tricarboxylate ligand connects neighbouring Zn4(OH)2 secondary building units (SBUs) producing an infinite one-dimensional chain. Adjacent one-dimensional chains are connected by the N,N'-bis[(pyridin-4-yl)methylidene]hydrazine ligand, forming a two-dimensional layered structure. Adjacent layers are stacked to generate a three-dimensional supramolecular architecture via O-H...O hydrogen-bond interactions. The thermal stability of this complex is described and the complex also appears to have potential for application as a luminescent material.

  3. Laser one-dimensional range profile and the laser two-dimensional range profile of cylinders

    NASA Astrophysics Data System (ADS)

    Gong, Yanjun; Wang, Mingjun; Gong, Lei

    2015-10-01

    Laser one-dimensional range profile, that is scattering power from pulse laser scattering of target, is a radar imaging technology. The laser two-dimensional range profile is two-dimensional scattering imaging of pulse laser of target. Laser one-dimensional range profile and laser two-dimensional range profile are called laser range profile(LRP). The laser range profile can reflect the characteristics of the target shape and surface material. These techniques were motivated by applications of laser radar to target discrimination in ballistic missile defense. The radar equation of pulse laser is given in this paper. This paper demonstrates the analytical model of laser range profile of cylinder based on the radar equation of the pulse laser. Simulations results of laser one-dimensional range profiles of some cylinders are given. Laser range profiles of cylinder, whose surface material with diffuse lambertian reflectance, is given in this paper. Laser range profiles of different pulse width of cylinder are given in this paper. The influences of geometric parameters, pulse width, attitude on the range profiles are analyzed.

  4. Three-Dimensional Microphase Separation and Synergistic Permeability in Stacked Lipid–Polymer Hybrid Membranes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kang, Minjee; Lee, Byeongdu; Leal, Cecilia

    Here, we present new structures of soft-material thin films that augment the functionality of substrate-mediated delivery systems. A hybrid material composed of phospholipids and block copolymers adopts a multilayered membrane structure supported on a solid surface. The hybrid films comprise intentional intramembrane heterogeneities that register across multilayers. These stacked domains convey unprecedented enhancement and control of permeability of solutes across micrometer-thick films. Using grazing incidence X-ray scattering, phase contrast atomic force microscopy, and confocal microscopy, we observed that in each lamella, lipid and polymers partition unevenly within the membrane plane segregating into lipid- or polymer-rich domains. Interestingly, we found evidencemore » that like-domains align in registry across multilayers, thereby making phase separation three-dimensional. Phase boundaries exist over extended length scales to compensate the height mismatch between lipid and polymer molecules. We show that microphase separation in hybrid films can be exploited to augment the capability of drug-eluting substrates. Lipid–polymer hybrid films loaded with paclitaxel show synergistic permeability of drug compared to single-component counterparts. We present a thorough structural study of stacked lipid–polymer hybrid membranes and propose that the presence of registered domains and domain boundaries impart enhanced drug release functionality. This work offers new perspectives in designing thin films for controlled delivery applications« less

  5. Three-Dimensional Microphase Separation and Synergistic Permeability in Stacked Lipid–Polymer Hybrid Membranes

    DOE PAGES

    Kang, Minjee; Lee, Byeongdu; Leal, Cecilia

    2017-10-20

    Here, we present new structures of soft-material thin films that augment the functionality of substrate-mediated delivery systems. A hybrid material composed of phospholipids and block copolymers adopts a multilayered membrane structure supported on a solid surface. The hybrid films comprise intentional intramembrane heterogeneities that register across multilayers. These stacked domains convey unprecedented enhancement and control of permeability of solutes across micrometer-thick films. Using grazing incidence X-ray scattering, phase contrast atomic force microscopy, and confocal microscopy, we observed that in each lamella, lipid and polymers partition unevenly within the membrane plane segregating into lipid- or polymer-rich domains. Interestingly, we found evidencemore » that like-domains align in registry across multilayers, thereby making phase separation three-dimensional. Phase boundaries exist over extended length scales to compensate the height mismatch between lipid and polymer molecules. We show that microphase separation in hybrid films can be exploited to augment the capability of drug-eluting substrates. Lipid–polymer hybrid films loaded with paclitaxel show synergistic permeability of drug compared to single-component counterparts. We present a thorough structural study of stacked lipid–polymer hybrid membranes and propose that the presence of registered domains and domain boundaries impart enhanced drug release functionality. This work offers new perspectives in designing thin films for controlled delivery applications« less

  6. Effects of extensional rates on characteristic scales of two-dimensional turbulence in polymer solutions

    NASA Astrophysics Data System (ADS)

    Hidema, R.

    2014-08-01

    In order to study the effects of extensional viscosities on turbulent drag reduction, experimental studies using two-dimensional turbulence have been made. Anisotropic structures and variations of energy transfer induced by polymers are considered. Polyethyleneoxide and hydroxypropyl cellulose having different flexibility, which is due to different characteristics of extensional viscosity, are added to 2D turbulence. Variations of the turbulence were visualized by interference patterns of 2D flow, and were analysed by an image processing. The effects of polymers on turbulence in the streamwise and normal directions were also analysed by 2D Fourier transform. In addition, characteristic scales in 2D turbulence were analysed by wavelet transform.

  7. Ameba-like diffusion in two-dimensional polymer melts: how critical exponents determine the structural relaxation

    NASA Astrophysics Data System (ADS)

    Kreer, Torsten; Meyer, Hendrik; Baschnagel, Joerg

    2008-03-01

    By means of numerical investigations we demonstrate that the structural relaxation of linear polymers in two dimensional (space-filling) melts is characterized by ameba-like diffusion, where the chains relax via frictional dissipation at their interfacial contact lines. The perimeter length of the contact line determines a new length scale, which does not exist in three dimensions. We show how this length scale follows from the critical exponents, which hence characterize not only the static but also the dynamic properties of the melt. Our data is in agreement with recent theoretical predictions, concerning the time-dependence of single-monomer mean-square displacements and the scaling of concomitant relaxation times with the degree of polymerization. For the latter we demonstrate a density crossover-scaling as an additional test for ameba-like relaxation. We compare our results to the conceptually different Rouse model, which predicts numerically close exponents. Our data can clearly rule out the classical picture as the relevant relaxation mechanism in two-dimensional polymer melts.

  8. Topical Review: Polymer gel dosimetry

    PubMed Central

    Baldock, C; De Deene, Y; Doran, S; Ibbott, G; Jirasek, A; Lepage, M; McAuley, K B; Oldham, M; Schreiner, L J

    2010-01-01

    Polymer gel dosimeters are fabricated from radiation sensitive chemicals which, upon irradiation, polymerize as a function of the absorbed radiation dose. These gel dosimeters, with the capacity to uniquely record the radiation dose distribution in three-dimensions (3D), have specific advantages when compared to one-dimensional dosimeters, such as ion chambers, and two-dimensional dosimeters, such as film. These advantages are particularly significant in dosimetry situations where steep dose gradients exist such as in intensity-modulated radiation therapy (IMRT) and stereotactic radiosurgery. Polymer gel dosimeters also have specific advantages for brachytherapy dosimetry. Potential dosimetry applications include those for low-energy x-rays, high-linear energy transfer (LET) and proton therapy, radionuclide and boron capture neutron therapy dosimetries. These 3D dosimeters are radiologically soft-tissue equivalent with properties that may be modified depending on the application. The 3D radiation dose distribution in polymer gel dosimeters may be imaged using magnetic resonance imaging (MRI), optical-computerized tomography (optical-CT), x-ray CT or ultrasound. The fundamental science underpinning polymer gel dosimetry is reviewed along with the various evaluation techniques. Clinical dosimetry applications of polymer gel dosimetry are also presented. PMID:20150687

  9. Communication: Coordinate-dependent diffusivity from single molecule trajectories

    NASA Astrophysics Data System (ADS)

    Berezhkovskii, Alexander M.; Makarov, Dmitrii E.

    2017-11-01

    Single-molecule observations of biomolecular folding are commonly interpreted using the model of one-dimensional diffusion along a reaction coordinate, with a coordinate-independent diffusion coefficient. Recent analysis, however, suggests that more general models are required to account for single-molecule measurements performed with high temporal resolution. Here, we consider one such generalization: a model where the diffusion coefficient can be an arbitrary function of the reaction coordinate. Assuming Brownian dynamics along this coordinate, we derive an exact expression for the coordinate-dependent diffusivity in terms of the splitting probability within an arbitrarily chosen interval and the mean transition path time between the interval boundaries. This formula can be used to estimate the effective diffusion coefficient along a reaction coordinate directly from single-molecule trajectories.

  10. Durable polymer-aerogel based superhydrophobic coatings, a composite material

    DOEpatents

    Kissel, David J; Brinker, Charles Jeffrey

    2014-03-04

    Provided are polymer-aerogel composite coatings, devices and articles including polymer-aerogel composite coatings, and methods for preparing the polymer-aerogel composite. The exemplary article can include a surface, wherein the surface includes at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140.degree. and a contact angle hysteresis of less than about 1.degree.. The polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.

  11. Durable polymer-aerogel based superhydrophobic coatings: a composite material

    DOEpatents

    Kissel, David J.; Brinker, Charles Jeffrey

    2016-02-02

    Provided are polymer-aerogel composite coatings, devices and articles including polymer-aerogel composite coatings, and methods for preparing the polymer-aerogel composite. The exemplary article can include a surface, wherein the surface includes at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140.degree. and a contact angle hysteresis of less than about 1.degree.. The polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.

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

    PubMed

    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.

  13. Extending the lanthanide-terephthalate system: Isolation of an unprecedented Tb(III)-based coordination polymer with high potential porosity and luminescence properties

    NASA Astrophysics Data System (ADS)

    Le Natur, François; Calvez, Guillaume; Freslon, Stéphane; Daiguebonne, Carole; Bernot, Kevin; Guillou, Olivier

    2015-04-01

    A novel coordination polymer with chemical formula {[Tb(bdc)1.5(H2O)]ṡ(DMF)(H2O)}∞ (1) has been synthesized by reaction between 1,4-benzene-dicarboxylic acid (H2bdc) and di-cationic hexanuclear entity [Tb6O(OH)8(NO3)6(H2O)12]2+ in an ethylene glycol (EG)/N,N-dimethylformamide (DMF) mixture. This compound has been obtained as single crystals by slow evaporation in air at room temperature. If the hexanuclear entity is destroyed during the reaction, the coordination polymer that is obtained is original and presents promising potential micro-porosity and luminescent properties. It crystallizes in the monoclinic system, space group C12/c1 (No. 15) with the cell parameters a = 23.7540(1) Å, b = 10.5390(4) Å, c = 19.7580(3) Å, β = 125.8100(1)° and Z = 8.

  14. Solitons in a one-dimensional Wigner crystal

    DOE PAGES

    Pustilnik, M.; Matveev, K. A.

    2015-04-16

    In one-dimensional quantum systems with strong long-range repulsion particles arrange in a quasi-periodic chain, the Wigner crystal. Here, we demonstrate that besides the familiar phonons, such one-dimensional Wigner crystal supports an additional mode of elementary excitations, which can be identified with solitons in the classical limit. Furthermore, we compute the corresponding excitation spectrum and argue that the solitons have a parametrically small decay rate at low energies. Finally, we discuss implications of our results for the behavior of the dynamic structure factor.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. One-dimensional velocity model of the Middle Kura Depresion from local earthquakes data of Azerbaijan

    NASA Astrophysics Data System (ADS)

    Yetirmishli, G. C.; Kazimova, S. E.; Kazimov, I. E.

    2011-09-01

    We present the method for determining the velocity model of the Earth's crust and the parameters of earthquakes in the Middle Kura Depression from the data of network telemetry in Azerbaijan. Application of this method allowed us to recalculate the main parameters of the hypocenters of the earthquake, to compute the corrections to the arrival times of P and S waves at the observation station, and to significantly improve the accuracy in determining the coordinates of the earthquakes. The model was constructed using the VELEST program, which calculates one-dimensional minimal velocity models from the travel times of seismic waves.

  17. Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

    PubMed

    Díaz-Gallifa, Pau; Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2014-06-16

    Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges.

  18. Synthesis, crystal structure, and luminescent properties of two coordination polymers based on 1,4-phenylenediacetic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Meili; Ren, Yixia; Ma, Zhenzhen; Qiao, Lei

    2017-06-01

    Two coordination polymers, [Zn(pda)(bib)]n (1) and [Cd(pda)0.5(bib)Cl]n (2)]. (H2pda = 1,4-phenylenediacetic acid, bib = 1,2-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(II)/Cd(II) salts with two flexible ligands pda and bib under hydrothermal conditions. Their structures have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD) analysis. Due to the coordination geometry around the metal ions and the diverse coordination modes of the flexible ligands, the obtained complex show diverse structures. In the structure of 1, a pair of bib ligands connect two Zn(II) atoms give rise a 22-membered ring, which is further extended by pda ligands in bidentate coordination mode leading a ring-containing 2D layer. In 2, bib ligands join [Cd2Cl2]2+ dimmers generate 1D polymeric ribbon, the pda ligands further extend such ribbon forming a 2D layer network containing rectangular windows, which discovers the effect of the central metal ions on the formation of metal-organic frameworks. In additional, luminescent properties of two complexes have also been studied, they could be potential fluorescence materials.

  19. Bio-Inspired Metal-Coordination Dynamics: A Unique Tool for Engineering Soft Matter Mechanics

    NASA Astrophysics Data System (ADS)

    Holten-Andersen, Niels

    Growing evidence supports a critical role of metal-coordination in soft biological material properties such as self-healing, underwater adhesion and autonomous wound plugging. Using bio-inspired metal-binding polymers, initial efforts to mimic these properties with metal-coordination crosslinked polymer materials have shown promise. In addition, with polymer network mechanics strongly coupled to coordinate crosslink dynamics material properties can be easily tuned from visco-elastic fluids to solids. Given their exploitation in desirable material applications in Nature, bio-inspired metal-coordinate complex crosslinking provides an opportunity to further advance synthetic polymer materials design. Early lessons from this pursuit are presented.

  20. Syntheses, structures and luminescent properties of two novel Zn (II) coordination polymers

    NASA Astrophysics Data System (ADS)

    Huang, Ya-Ru; Gao, Ling-Ling; Wang, Xiao-Qing; Fan, Li-Ming; Hu, Tuo-Ping

    2018-02-01

    Two new coordination polymers, namely [Zn(TZMB)]n (1) and {[Zn(TZMB)](H2TZMB)]·(C2H5OH)0.5(H2O)2.5}n (2), (H2TZMB = 4,4‧-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analysis, elemental analysis (EA), IR spectrum analysis (IR), powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Single X-ray diffraction analysis reveals that complex 1 is a 3D 3,6-connected net with the point symbol of (6110.84)(63)2 and complex 2 is a 2D 3-connected net with the point symbol of (63). Furthermore, luminescent properties of complexes 1 and 2 were also investigated in detail.

  1. Three-Dimensional Conformation of Folded Polymers in Single Crystals

    NASA Astrophysics Data System (ADS)

    Hong, You-lee; Yuan, Shichen; Li, Zhen; Ke, Yutian; Nozaki, Koji; Miyoshi, Toshikazu

    2015-10-01

    The chain-folding mechanism and structure of semicrystalline polymers have long been controversial. Solid-state NMR was applied to determine the chain trajectory of 13C CH3 -labeled isotactic poly(1-butene) (i PB 1 ) in form III chiral single crystals blended with nonlabeled i PB 1 crystallized in dilute solutions under low supercooling. An advanced 13C - 13C double-quantum NMR technique probing the spatial proximity pattern of labeled 13C nuclei revealed that the chains adopt a three-dimensional (3D) conformation in single crystals. The determined results indicate a two-step crystallization process of (i) cluster formation via self-folding in the precrystallization stage and (ii) deposition of the nanoclusters as a building block at the growth front in single crystals.

  2. Report of the Polymer Core Course Committee: Inclusion of Polymer Topics into Undergraduate Inorganic Chemistry Courses.

    ERIC Educational Resources Information Center

    Miller, Norman E.; And Others

    1984-01-01

    Suggests polymer topics for study in inorganic chemistry courses. Commercial materials (including list of inorganic compounds utilized in polymer industry), anchored metal catalysis, polymers modified or formed by coordination, polysiloxanes, phosphazene or phosphonitrilic halide polymers, and hetergeneous polymerization catalysts are considered.…

  3. Exploring load, velocity, and surface disorder dependence of friction with one-dimensional and two-dimensional models.

    PubMed

    Dagdeviren, Omur E

    2018-08-03

    The effect of surface disorder, load, and velocity on friction between a single asperity contact and a model surface is explored with one-dimensional and two-dimensional Prandtl-Tomlinson (PT) models. We show that there are fundamental physical differences between the predictions of one-dimensional and two-dimensional models. The one-dimensional model estimates a monotonic increase in friction and energy dissipation with load, velocity, and surface disorder. However, a two-dimensional PT model, which is expected to approximate a tip-sample system more realistically, reveals a non-monotonic trend, i.e. friction is inert to surface disorder and roughness in wearless friction regime. The two-dimensional model discloses that the surface disorder starts to dominate the friction and energy dissipation when the tip and the sample interact predominantly deep into the repulsive regime. Our numerical calculations address that tracking the minimum energy path and the slip-stick motion are two competing effects that determine the load, velocity, and surface disorder dependence of friction. In the two-dimensional model, the single asperity can follow the minimum energy path in wearless regime; however, with increasing load and sliding velocity, the slip-stick movement dominates the dynamic motion and results in an increase in friction by impeding tracing the minimum energy path. Contrary to the two-dimensional model, when the one-dimensional PT model is employed, the single asperity cannot escape to the minimum energy minimum due to constraint motion and reveals only a trivial dependence of friction on load, velocity, and surface disorder. Our computational analyses clarify the physical differences between the predictions of the one-dimensional and two-dimensional models and open new avenues for disordered surfaces for low energy dissipation applications in wearless friction regime.

  4. High-accuracy optical extensometer based on coordinate transform in two-dimensional digital image correlation

    NASA Astrophysics Data System (ADS)

    Lv, Zeqian; Xu, Xiaohai; Yan, Tianhao; Cai, Yulong; Su, Yong; Zhang, Qingchuan

    2018-01-01

    In the measurement of plate specimens, traditional two-dimensional (2D) digital image correlation (DIC) is challenged by two aspects: (1) the slant optical axis (misalignment of the optical camera axis and the object surface) and (2) out-of-plane motions (including translations and rotations) of the specimens. There are measurement errors in the results measured by 2D DIC, especially when the out-of-plane motions are big enough. To solve this problem, a novel compensation method has been proposed to correct the unsatisfactory results. The proposed compensation method consists of three main parts: 1) a pre-calibration step is used to determine the intrinsic parameters and lens distortions; 2) a compensation panel (a rigid panel with several markers located at known positions) is mounted to the specimen to track the specimen's motion so that the relative coordinate transformation between the compensation panel and the 2D DIC setup can be calculated using the coordinate transform algorithm; 3) three-dimensional world coordinates of measuring points on the specimen can be reconstructed via the coordinate transform algorithm and used to calculate deformations. Simulations have been carried out to validate the proposed compensation method. Results come out that when the extensometer length is 400 pixels, the strain accuracy reaches 10 με no matter out-of-plane translations (less than 1/200 of the object distance) nor out-of-plane rotations (rotation angle less than 5°) occur. The proposed compensation method leads to good results even when the out-of-plane translation reaches several percents of the object distance or the out-of-plane rotation angle reaches tens of degrees. The proposed compensation method has been applied in tensile experiments to obtain high-accuracy results as well.

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

    PubMed

    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.

  6. Synthesis and characterization of multifunctional coordination polymer of the type [CuxNi1-x(dedb)·2H2O]n

    NASA Astrophysics Data System (ADS)

    Singh, Deepshikha; Kushwaha, Anita; Banerjee, A.; Prasad, R. L.

    2015-07-01

    New series of multifunctional homometallic and heterobimetallic coordination polymers of the type [CuxNi1-x(dedb)·2H2O]n {where dedb = dianion of 2,5-dichloro-3,6-bis(ethylamino)-1,4-benzoquinone (1); x = 1, (2); 0 (3); 0.5 (4); 0.25 (5); 0.125 (6); 0.0625 (7) and n = degree of polymerization} have been synthesized and characterized by Powder X-ray diffraction, IR, UV-visible and ESR spectroscopic techniques. Variable temperature susceptibility measurement indicates presence of strong ferromagnetic interaction. The effects of copper doping on thermal, magnetic and conducting properties of these polymers have been investigated in this communication. A rare co-existence of ferromagnetism as well as electrical conductivity has been observed in these polymers.

  7. One-way mode transmission in one-dimensional phononic crystal plates

    NASA Astrophysics Data System (ADS)

    Zhu, Xuefeng; Zou, Xinye; Liang, Bin; Cheng, Jianchun

    2010-12-01

    We investigate theoretically the band structures of one-dimensional phononic crystal (PC) plates with both antisymmetric and symmetric structures, and show how unidirectional transmission behavior can be obtained for either antisymmetric waves (A modes) or symmetric waves (S modes) by exploiting mode conversion and selection in the linear plate systems. The theoretical approach is illustrated for one PC plate example where unidirectional transmission behavior is obtained in certain frequency bands. Employing harmonic frequency analysis, we numerically demonstrate the one-way mode transmission for the PC plate with finite superlattice by calculating the steady-state displacement fields under A modes source (or S modes source) in forward and backward direction, respectively. The results show that the incident waves from A modes source (or S modes source) are transformed into S modes waves (or A modes waves) after passing through the superlattice in the forward direction and the Lamb wave rejections in the backward direction are striking with a power extinction ratio of more than 1000. The present structure can be easily extended to two-dimensional PC plate and efficiently encourage practical studies of experimental realization which is believed to have much significance for one-way Lamb wave mode transmission.

  8. Gram-scale synthesis of coordination polymer nanodots with renal clearance properties for cancer theranostic applications

    NASA Astrophysics Data System (ADS)

    Liu, Fuyao; He, Xiuxia; Chen, Hongda; Zhang, Junping; Zhang, Huimao; Wang, Zhenxin

    2015-08-01

    An ultrasmall hydrodynamic diameter is a critical factor for the renal clearance of nanoparticles from the body within a reasonable timescale. However, the integration of diagnostic and therapeutic components into a single ultrasmall nanoparticle remains challenging. In this study, pH-activated nanodots (termed Fe-CPNDs) composed of coordination polymers were synthesized via a simple and scalable method based on coordination reactions among Fe3+, gallic acid and poly(vinylpyrrolidone) at ambient conditions. The Fe-CPNDs exhibited ultrasmall (5.3 nm) hydrodynamic diameters and electrically neutral surfaces. The Fe-CPNDs also exhibited pH-activatable magnetic resonance imaging contrast and outstanding photothermal performance. The features of Fe-CPNDs greatly increased the tumour-imaging sensitivity and facilitated renal clearance after injection in animal models in vivo. Magnetic resonance imaging-guided photothermal therapy using Fe-CPNDs completely suppressed tumour growth. These findings demonstrate that Fe-CPNDs constitute a new class of renal clearable nanomedicine for photothermal therapy and molecular imaging.

  9. Viscous Dissipation in One-Dimensional Quantum Liquids

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Matveev, K. A.; Pustilnik, M.

    We develop a theory of viscous dissipation in one-dimensional single-component quantum liquids at low temperatures. Such liquids are characterized by a single viscosity coefficient, the bulk viscosity. We show that for a generic interaction between the constituent particles this viscosity diverges in the zerotemperature limit. In the special case of integrable models, the viscosity is infinite at any temperature, which can be interpreted as a breakdown of the hydrodynamic description. In conclusion, our consideration is applicable to all single-component Galilean- invariant one-dimensional quantum liquids, regardless of the statistics of the constituent particles and the interaction strength.

  10. Viscous Dissipation in One-Dimensional Quantum Liquids

    DOE PAGES

    Matveev, K. A.; Pustilnik, M.

    2017-07-20

    We develop a theory of viscous dissipation in one-dimensional single-component quantum liquids at low temperatures. Such liquids are characterized by a single viscosity coefficient, the bulk viscosity. We show that for a generic interaction between the constituent particles this viscosity diverges in the zerotemperature limit. In the special case of integrable models, the viscosity is infinite at any temperature, which can be interpreted as a breakdown of the hydrodynamic description. In conclusion, our consideration is applicable to all single-component Galilean- invariant one-dimensional quantum liquids, regardless of the statistics of the constituent particles and the interaction strength.

  11. A series of silver(I) coordination polymers with saccarinate and flexible aliphatic diamines

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr; Karamahmut, Bingül; Semerci, Fatih

    A series of Ag(I) complexes with aliphatic diamines having a different chain length (NH{sub 2}-(CH{sub 2}){sub n}-NH{sub 2}, n=4–9), with the formulas, [Ag(μ-sac)(μ-db){sub 0.5}]{sub n} (1), ([Ag{sub 4}(sac){sub 4}(μ-dp){sub 2}]·4H{sub 2}O){sub n} (2){sub ,} ([Ag{sub 2}(sac){sub 2}(μ-dz)]·2H{sub 2}O){sub n} (3), ([Ag{sub 2}(sac){sub 2}(μ-dh)]·H{sub 2}O){sub n} (4), ([Ag{sub 2}(sac){sub 2}(μ-do)]·H{sub 2}O){sub n} (5a), [Ag{sub 2}(sac){sub 2}(μ-do){sub 2}] (5b) and [Ag{sub 4}(sac){sub 4}(μ-dn){sub 2}]·2H{sub 2}O (6), where sac=saccharinate, db=1,4-diaminobutane, dp=1,5-diaminopentane, dz=1,6-diaminohexane, dh=1,7-diaminoheptane, do=1,8-diaminooctane and dn=1,9-diaminononane, were synthesized and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction analysis. In 1, the sac ligand bridges adjacent Ag(I) ions through the nitrogen andmore » carbonyl oxygen atoms to form eight-membered bimetallic rings with the Ag···Ag distance being 3.897 Å, which are linked by db ligands to give a 1D zigzag chain. The complexes 2–5a consist of a one-dimensional (1D) linear cationic chains and discrete mononuclear anions. The discreet complex units are further connected by ligand unsupported argentophilic interactions. In 6, the dn ligands bridge adjacent silver centers to form 24-membered macrometallacyclic rings, which are further connected to the anionic [Ag(sac){sub 2}]{sup -} units by argentophilic Ag1···Ag2 interactions to form a tetranuclear structure. The adjacent dinuclear units are further linked together through ligand-unsupported argentophilic Ag···Ag (3.207(1) Å) interactions, generating a one-dimensional linear chain. The most striking feature of complexes is the presence of the rare intermolecular C-H···Ag interactions. In 5b, the do ligand bridges two Ag(I) ions to form a dinuclear with a 22-membered macrometallacyclic ring. Furthermore, biological activities, luminescence properties and thermal

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

    PubMed

    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.

  13. Room temperature rubbing for few-layer two-dimensional thin flakes directly on flexible polymer substrates

    PubMed Central

    Yu, Yan; Jiang, Shenglin; Zhou, Wenli; Miao, Xiangshui; Zeng, Yike; Zhang, Guangzu; Liu, Sisi

    2013-01-01

    The functional layers of few-layer two-dimensional (2-D) thin flakes on flexible polymers for stretchable applications have attracted much interest. However, most fabrication methods are “indirect” processes that require transfer steps. Moreover, previously reported “transfer-free” methods are only suitable for graphene and not for other few-layer 2-D thin flakes. Here, a friction based room temperature rubbing method is proposed for fabricating different types of few-layer 2-D thin flakes (graphene, hexagonal boron nitride (h-BN), molybdenum disulphide (MoS2), and tungsten disulphide (WS2)) on flexible polymer substrates. Commercial 2-D raw materials (graphite, h-BN, MoS2, and WS2) that contain thousands of atom layers were used. After several minutes, different types of few-layer 2-D thin flakes were fabricated directly on the flexible polymer substrates by rubbing procedures at room temperature and without any transfer step. These few-layer 2-D thin flakes strongly adhere to the flexible polymer substrates. This strong adhesion is beneficial for future applications. PMID:24045289

  14. Cu(II) coordination polymers constructed by tetrafluoroterephthalic acid and varied imidazole-containing ligands: Syntheses, structures and properties

    NASA Astrophysics Data System (ADS)

    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

  15. Fundamental Study on One-Dimensional-Array Medical Ultrasound Probe with Piezoelectric Polycrystalline Film by Hydrothermal Method: Experimental Fabrication of One-Dimensional-Array Ultrasound Probe

    NASA Astrophysics Data System (ADS)

    Endo, Akito; Kawashima, Norimichi; Takeuchi, Shinichi; Ishikawa, Mutsuo; Kurosawa, Minoru Kuribayashi

    2007-07-01

    We deposited a lead zirconate titanete (PZT) polycrystalline film on a titanium substrate by the hydrothermal method and fabricated a transducer using the PZT film for use as an ultrasound probe. A 10 MHz miniature one-dimensional-array medical ultrasound probe containing the PZT film was developed. After sputtering titanium on the surface of a hydroxyapatite substrate, the titanium film on the substrate was etched by the photolithography to form a one-dimensional titanium film electrode array. We could thus fabricate a miniature one-dimensional-array ultrasound probe by the hydrothermal method. Transmitted ultrasound pulses from a 10 MHz commercial ultrasound probe were received by the newly fabricated one-dimensional-array ultrasound probe. The fabrication process of the probe and the results of experiments on receiving waveforms were reported in this paper.

  16. Chemical anchoring of organic conducting polymers to semiconducting surfaces

    DOEpatents

    Frank, A.J.; Honda, K.

    1984-01-01

    According to the present invention, an improved method of coating electrodes with conductive polymer films and/or preselected catalysts is provided. The charge conductive polymer is covalently or coordinatively attached to the electrode surface to strengthen the adhesion characteristics of the polymer to the electrode surface or to improve charge conductive properties between the conductive polymer and the electrode surface. Covalent or coordinative attachment is achieved by a number of alternative methods including covalently or coordinatively attaching the desired monomer to the electrode by means of a suitable coupling reagent and, thereafter, electrochemically polymerizing the monomer in situ.

  17. Chemical anchoring of organic conducting polymers to semiconducting surfaces

    DOEpatents

    Frank, Arthur J.; Honda, Kenji

    1984-01-01

    According to the present invention, an improved method of coating electrodes with conductive polymer films and/or preselected catalysts is provided. The charge-conductive polymer is covalently or coordinatively attached to the electrode surface to strengthen the adhesion characteristics of the polymer to the electrode surface or to improve charge-conductive properties between the conductive polymer and the electrode surface. Covalent or coordinative attachment is achieved by a number of alternative methods including covalently or coordinatively attaching the desired monomer to the electrode by means of a suitable coupling reagent and, thereafter, electrochemically polymerizing the monomer in situ.

  18. Two-dimensional electron beam charging model for polymer films

    NASA Technical Reports Server (NTRS)

    Reeves, R. D.; Balmain, K. G.

    1981-01-01

    A two-dimensional model is developed to describe the charging of strips of thin polymer films above a grounded substrate exposed to a uniform mono-energetic electron beam. The study is motivated by the observed anomalous behavior of geosynchronous satellites, which has been attributed to differential charging of the satellite surfaces exposed to magnetospheric electrons. Surface and bulk electric fields are calcuated at steady state in order to identify regions of high electrical stress, with emphasis on behavior near the material's edge. The model is used to study the effects of some of the experimental parameters, notably beam energy, beam angle of incidence, beam current density, material thickness and material width. Also examined are the consequences of a central gap in the material and a discontinuity in the material thickness.

  19. Particle paths and phase plane for time-dependent similarity solutions of the one-dimensional Vlasov-Maxwell equations

    NASA Technical Reports Server (NTRS)

    Roberts, Dana Aaron; Abraham-Shrauner, Barbara

    1987-01-01

    The phase trajectories of particles in a plasma described by the one-dimensional Vlasov-Maxwell equations are determined qualitatively, analyzing exact general similarity solutions for the cases of temporally damped and growing (sinusoidal or localized) electric fields. The results of numerical integration in both untransformed and Lie-group point-transformed coordinates are presented in extensive graphs and characterized in detail. The implications of the present analysis for the stability of BGK equilibria are explored, and the existence of nonlinear solutions arbitrarily close to and significantly different from the BGK solutions is demonstrated.

  20. Synthesis, crystal structure and valence tautomerism of a 4,4‧-bipyridine-bridged one-dimensional chiral cobalt complex

    NASA Astrophysics Data System (ADS)

    Cheng, Wei-Qin; Li, Guo-Ling; Zhang, Ran; Ni, Zhong-Hai; Wang, Wen-Feng; Sato, Osamu

    2015-05-01

    A linear-chain cobalt coordination polymer, [Co(2,3-LH2)2(4,4‧-bipy)]ṡ2H2Oṡ4,4‧-bipy]n (1) (2,3-LH2 = 2,3-tetrahydroxy-9,10-dimethyl-9,10-dihydro- 9,10-ethanoanthracene, 4,4‧-bipy = 4,4‧-bipyridine), has been synthesized and structurally characterized. Single-crystal X-ray analysis reveals that complex 1 is a chiral polymer assemblied from achiral components. The complex 1 crystallizes in the chiral space group P3221 and the central Co ion has a slightly distorted octahedral coordination environment. The temperature dependence of magnetic susceptibility indicates that the complex 1 undergoes valence tautomeric interconversion between low-spin ls-[CoIII(2,3-LH2Cat)(2,3-LH2SQ)] and high-spin hs-[CoII(2,3-LH2SQ)2] (2,3-LH2Cat = 2,3-LH2catecholate, 2,3-LH2SQ = 2,3-LH2semiquinone).

  1. Quantum solution for the one-dimensional Coulomb problem

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nunez-Yepez, H. N.; Salas-Brito, A. L.; Solis, Didier A.

    2011-06-15

    The one-dimensional hydrogen atom has been a much studied system with a wide range of applications. Since the pioneering work of Loudon [R. Loudon, Am. J. Phys. 27, 649 (1959).], a number of different features related to the nature of the eigenfunctions have been found. However, many of the claims made throughout the years in this regard are not correct--such as the existence of only odd eigenstates or of an infinite binding-energy ground state. We explicitly show that the one-dimensional hydrogen atom does not admit a ground state of infinite binding energy and that the one-dimensional Coulomb potential is notmore » its own supersymmetric partner. Furthermore, we argue that at the root of many such false claims lies the omission of a superselection rule that effectively separates the right side from the left side of the singularity of the Coulomb potential.« less

  2. Fabrication of multilayered conductive polymer structures via selective visible light photopolymerization

    NASA Astrophysics Data System (ADS)

    Cullen, Andrew T.; Price, Aaron D.

    2017-04-01

    Electropolymerization of pyrrole is commonly employed to fabricate intrinsically conductive polymer films that exhibit desirable electromechanical properties. Due to their monolithic nature, electroactive polypyrrole films produced via this process are typically limited to simple linear or bending actuation modes, which has hindered their application in complex actuation tasks. This initiative aims to develop the specialized fabrication methods and polymer formulations required to realize three-dimensional conductive polymer structures capable of more elaborate actuation modes. Our group has previously reported the application of the digital light processing additive manufacturing process for the fabrication of three-dimensional conductive polymer structures using ultraviolet radiation. In this investigation, we further expand upon this initial work and present an improved polymer formulation designed for digital light processing additive manufacturing using visible light. This technology enables the design of novel electroactive polymer sensors and actuators with enhanced capabilities and brings us one step closer to realizing more advanced electroactive polymer enabled devices.

  3. Thermal conductivity in one-dimensional nonlinear systems

    NASA Astrophysics Data System (ADS)

    Politi, Antonio; Giardinà, Cristian; Livi, Roberto; Vassalli, Massimo

    2000-03-01

    Thermal conducitivity of one-dimensional nonlinear systems typically diverges in the thermodynamic limit, whenever the momentum is conserved (i.e. in the absence of interactions with an external substrate). Evidence comes from detailed studies of Fermi-Pasta-Ulam and diatomic Toda chains. Here, we discuss the first example of a one-dimensional system obeying Fourier law : a chain of coupled rotators. Numerical estimates of the thermal conductivity obtained by simulating a chain in contact with two thermal baths at different temperatures are found to be consistent with those ones based on linear response theory. The dynamics of the Fourier modes provides direct evidence of energy diffusion. The finiteness of the conductivity is traced back to the occurrence of phase-jumps. Our conclusions are confirmed by the analysis of two variants of the rotator model.

  4. Heat transfer of phase-change materials in two-dimensional cylindrical coordinates

    NASA Technical Reports Server (NTRS)

    Labdon, M. B.; Guceri, S. I.

    1981-01-01

    Two-dimensional phase-change problem is numerically solved in cylindrical coordinates (r and z) by utilizing two Taylor series expansions for the temperature distributions in the neighborhood of the interface location. These two expansions form two polynomials in r and z directions. For the regions sufficiently away from the interface the temperature field equations are numerically solved in the usual way and the results are coupled with the polynomials. The main advantages of this efficient approach include ability to accept arbitrarily time dependent boundary conditions of all types and arbitrarily specified initial temperature distributions. A modified approach using a single Taylor series expansion in two variables is also suggested.

  5. Two-Dimensional Polymer Synthesized via Solid-State Polymerization for High-Performance Supercapacitors.

    PubMed

    Liu, Wei; Ulaganathan, Mani; Abdelwahab, Ibrahim; Luo, Xin; Chen, Zhongxin; Rong Tan, Sherman Jun; Wang, Xiaowei; Liu, Yanpeng; Geng, Dechao; Bao, Yang; Chen, Jianyi; Loh, Kian Ping

    2018-01-23

    Two-dimensional (2-D) polymer has properties that are attractive for energy storage applications because of its combination of heteroatoms, porosities and layered structure, which provides redox chemistry and ion diffusion routes through the 2-D planes and 1-D channels. Here, conjugated aromatic polymers (CAPs) were synthesized in quantitative yield via solid-state polymerization of phenazine-based precursor crystals. By choosing flat molecules (2-TBTBP and 3-TBQP) with different positions of bromine substituents on a phenazine-derived scaffold, C-C cross coupling was induced following thermal debromination. CAP-2 is polymerized from monomers that have been prepacked into layered structure (3-TBQP). It can be mechanically exfoliated into micrometer-sized ultrathin sheets that show sharp Raman peaks which reflect conformational ordering. CAP-2 has a dominant pore size of ∼0.8 nm; when applied as an asymmetric supercapacitor, it delivers a specific capacitance of 233 F g -1 at a current density of 1.0 A g -1 , and shows outstanding cycle performance.

  6. Three-dimensional transformation optics for arbitrary coordinate systems: transforming conductive materials and boundaries.

    PubMed

    Kazemzadeh, Mohammad-Rahim; Alighanbari, Abbas

    2018-04-16

    A three-dimensional transformation optics method, leading to homogeneous materials, applicable to any non-Cartesian coordinate systems or waveguides/objects of arbitrary cross-sections is presented. Both the conductive boundary and internal material of the desired device is determined by the proposed formulation. The method is applicable to a wide range of waveguide, radiation, and cloaking problems, and is demonstrated for circular waveguide couplers and an external cloak. An advantage of the present method is that the material properties are simplified by appropriately selecting the conductive boundaries. For instance, a right-angle circular waveguide bend is presented which uses only one homogenous material. Also, transformation of conductive materials and boundaries are studied. The conditions in which the transformed boundaries remain conductive are discussed. In addition, it is demonstrated that negative infinite conductivity can be replaced with positive conductivity, without affecting the field outside the conductive boundary. It is also observed that a negative finite conductivity can be replaced with a positive one, by accepting some small errors. The general mathematical procedure and formulation for calculating the parametric surface equations of the conductive peripheries are presented.

  7. Limit Properties of One Dimensional Periodic Hopping Model

    NASA Astrophysics Data System (ADS)

    Zhang, Yun-xin

    2010-02-01

    One dimensional periodic hopping model is useful to understand the motion of microscopic particles in thermal noise environment. In this research, by formal calculation and based on detailed balance, the explicit expressions of the limits of mean velocity and diffusion constant of this model as the number of internal mechanochemical sates tend to infinity are obtained. These results will be helpful to understand the limit of the one dimensional hopping model. At the same time, the work can be used to get more useful results in continuous form from the corresponding ones obtained by discrete models.

  8. One-Dimensional Harmonic Model for Biomolecules

    PubMed Central

    Krizan, John E.

    1973-01-01

    Following in spirit a paper by Rosen, we propose a one-dimensional harmonic model for biomolecules. Energy bands with gaps of the order of semi-conductor gaps are found. The method is discussed for general symmetric and periodic potential functions. PMID:4709518

  9. Holographic three-dimensional telepresence using large-area photorefractive polymer.

    PubMed

    Blanche, P-A; Bablumian, A; Voorakaranam, R; Christenson, C; Lin, W; Gu, T; Flores, D; Wang, P; Hsieh, W-Y; Kathaperumal, M; Rachwal, B; Siddiqui, O; Thomas, J; Norwood, R A; Yamamoto, M; Peyghambarian, N

    2010-11-04

    Holography is a technique that is used to display objects or scenes in three dimensions. Such three-dimensional (3D) images, or holograms, can be seen with the unassisted eye and are very similar to how humans see the actual environment surrounding them. The concept of 3D telepresence, a real-time dynamic hologram depicting a scene occurring in a different location, has attracted considerable public interest since it was depicted in the original Star Wars film in 1977. However, the lack of sufficient computational power to produce realistic computer-generated holograms and the absence of large-area and dynamically updatable holographic recording media have prevented realization of the concept. Here we use a holographic stereographic technique and a photorefractive polymer material as the recording medium to demonstrate a holographic display that can refresh images every two seconds. A 50 Hz nanosecond pulsed laser is used to write the holographic pixels. Multicoloured holographic 3D images are produced by using angular multiplexing, and the full parallax display employs spatial multiplexing. 3D telepresence is demonstrated by taking multiple images from one location and transmitting the information via Ethernet to another location where the hologram is printed with the quasi-real-time dynamic 3D display. Further improvements could bring applications in telemedicine, prototyping, advertising, updatable 3D maps and entertainment.

  10. Synthesis of one-dimensional metal-containing insulated molecular wire with versatile properties directed toward molecular electronics materials.

    PubMed

    Masai, Hiroshi; Terao, Jun; Seki, Shu; Nakashima, Shigeto; Kiguchi, Manabu; Okoshi, Kento; Fujihara, Tetsuaki; Tsuji, Yasushi

    2014-02-05

    We report, herein, the design, synthesis, and properties of new materials directed toward molecular electronics. A transition metal-containing insulated molecular wire was synthesized through the coordination polymerization of a Ru(II) porphyrin with an insulated bridging ligand of well-defined structure. The wire displayed not only high linearity and rigidity, but also high intramolecular charge mobility. Owing to the unique properties of the coordination bond, the interconversion between the monomer and polymer states was realized under a carbon monoxide atmosphere or UV irradiation. The results demonstrated a high potential of the metal-containing insulated molecular wire for applications in molecular electronics.

  11. Application of a novel red-emitting cationic iridium(III) coordination polymer in warm white light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Chen, Mingxian; Sun, Riyong; Ye, Yanchun; Tang, Huaijun; Dong, Xueyan; Yan, Jialun; Wang, Kaimin; Zhou, Qiang; Wang, Zhengliang

    2018-02-01

    A novel red-emitting cationic iridium(III) coordination polymer using 2-(9-(2-ethylhexyl)-9H-carbazol-3-yl)benzo[d]thiazole as main ligands, 4,4‧-bipyridine as bridging auxiliary ligands and Clˉ as anions was synthesized. It had high thermal stability with a thermal decomposition temperature (Td) of 345 °C and low thermal quenching with an activation energy (Ea) of 0.2760 eV, with the temperature increasing from 20 °C to 100 °C, its photoluminescent intensity decreased to 76.7%. It can be efficiently excited by blue light of GaN chips, the cold white light of GaN-based LEDs using only Y3Al5O12:Ce3+ (YAG:Ce, 7.0 wt% in silicone) as phosphors can become warmer when it was blended in. When blending concentrations were 0.1 wt% and 0.2 wt%, the cold white light became neutral white light, the correlated color temperature (CCT) decreased from 6157 K to 5240 K, then to 4043 K, the color rendering index (CRI) changed from 72.7 to 81.3, then to 78.6, the luminous efficiency (ηL) changed from 134.1 lm·w-1 to 61.9 lm·w-1, then to 46.3 lm·w-1, the Commission Internationale de L'Eclairage (CIE) chromaticity coordinates changed from (0.32, 0.33) to (0.34, 0.33), then to (0.38, 0.36). At 0.3 wt%, the light became warm white light, the corresponding CCT was 3475 K, CRI was 75.6, ηL was 36.9 lm·w-1, and CIE value was (0.41, 0.40). The results suggest the coordination polymer is a promising red-emitting phosphor candidate for neutral and warm white LEDs, especially for warm white LEDs.

  12. New method to access hyperbranched polymers with uniform structure via one-pot polymerization of inimer in microemulsion.

    PubMed

    Min, Ke; Gao, Haifeng

    2012-09-26

    A facile approach is presented for successful synthesis of hyperbranched polymers with high molecular weight and uniform structure by a one-pot polymerization of an inimer in a microemulsion. The segregated space in the microemulsion confined the inimer polymerization and particularly the polymer-polymer reaction within discrete nanoparticles. At the end of polymerization, each nanoparticle contained one hyperbranched polymer that had thousands of inimer units and low polydispersity. The hyperbranched polymers were used as multifunctional macroinitiators for synthesis of "hyper-star" polymers. When a degradable inimer was applied, the hyper-stars showed fast degradation into linear polymer chains with low molecular weight.

  13. An investigation of one- versus two-dimensional semiclassical transition state theory for H atom abstraction and exchange reactions.

    PubMed

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2016-02-28

    We investigate which terms in Reduced-Dimensionality Semiclassical Transition State Theory (RD SCTST) contribute most significantly in rate constant calculations of hydrogen extraction and exchange reactions of hydrocarbons. We also investigate the importance of deep tunneling corrections to the theory. In addition, we introduce a novel formulation of the theory in Jacobi coordinates. For the reactions of H atoms with methane, ethane, and cyclopropane, we find that a one-dimensional (1-D) version of the theory without deep tunneling corrections compares well with 2-D SCTST results and accurate quantum scattering results. For the "heavy-light-heavy" H atom exchange reaction between CH3 and CH4, deep tunneling corrections are needed to yield 1-D results that compare well with 2-D results. The finding that accurate rate constants can be obtained from derivatives of the potential along only one dimension further validates RD SCTST as a computationally efficient yet accurate rate constant theory.

  14. THREED: A computer program for three dimensional transformation of coordinates. [in lunar photo triangulation mapping

    NASA Technical Reports Server (NTRS)

    Wong, K. W.

    1974-01-01

    Program THREED was developed for the purpose of a research study on the treatment of control data in lunar phototriangulation. THREED is the code name of a computer program for performing absolute orientation by the method of three-dimensional projective transformation. It has the capability of performing complete error analysis on the computed transformation parameters as well as the transformed coordinates.

  15. Nanopatterning of Surfaces with Monometallic and Heterobimetallic 1D Coordination Polymers: A Molecular Tectonics Approach at the Solid/Liquid Interface.

    PubMed

    El Garah, Mohamed; Marets, Nicolas; Mauro, Matteo; Aliprandi, Alessandro; Bonacchi, Sara; De Cola, Luisa; Ciesielski, Artur; Bulach, Véronique; Hosseini, Mir Wais; Samorì, Paolo

    2015-07-08

    The self-assembly of multiple molecular components into complex supramolecular architectures is ubiquitous in nature and constitutes one of the most powerful strategies to fabricate multifunctional nanomaterials making use of the bottom-up approach. When spatial confinement in two dimensions on a solid substrate is employed, this approach can be exploited to generate periodically ordered structures from suitably designed molecular tectons. In this study we demonstrate that physisorbed directional periodic arrays of monometallic or heterobimetallic coordination polymers can be generated on a highly oriented pyrolitic graphite surface by combinations of a suitably designed directional organic tecton or metallatecton based on a porphyrin or nickel(II) metalloporphyrin backbone bearing both a pyridyl unit and a terpyridyl unit acting as coordinating sites for CoCl2. The periodic architectures were visualized at the solid/liquid interface with a submolecular resolution by scanning tunneling microscopy and corroborated by combined density functional and time-dependent density functional theory calculations. The capacity to nanopattern the surface for the first time with two distinct metallic centers exhibiting different electronic and optical properties is a key step toward the bottom-up construction of robust multicomponent and, thus, multifunctional molecular nanostructures and nanodevices.

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

    PubMed

    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.

  17. An innovative method for coordinate measuring machine one-dimensional self-calibration with simplified experimental process.

    PubMed

    Fang, Cheng; Butler, David Lee

    2013-05-01

    In this paper, an innovative method for CMM (Coordinate Measuring Machine) self-calibration is proposed. In contrast to conventional CMM calibration that relies heavily on a high precision reference standard such as a laser interferometer, the proposed calibration method is based on a low-cost artefact which is fabricated with commercially available precision ball bearings. By optimizing the mathematical model and rearranging the data sampling positions, the experimental process and data analysis can be simplified. In mathematical expression, the samples can be minimized by eliminating the redundant equations among those configured by the experimental data array. The section lengths of the artefact are measured at arranged positions, with which an equation set can be configured to determine the measurement errors at the corresponding positions. With the proposed method, the equation set is short of one equation, which can be supplemented by either measuring the total length of the artefact with a higher-precision CMM or calibrating the single point error at the extreme position with a laser interferometer. In this paper, the latter is selected. With spline interpolation, the error compensation curve can be determined. To verify the proposed method, a simple calibration system was set up on a commercial CMM. Experimental results showed that with the error compensation curve uncertainty of the measurement can be reduced to 50%.

  18. Quantum bright solitons in a quasi-one-dimensional optical lattice

    NASA Astrophysics Data System (ADS)

    Barbiero, Luca; Salasnich, Luca

    2014-06-01

    We study a quasi-one-dimensional attractive Bose gas confined in an optical lattice with a superimposed harmonic potential by analyzing the one-dimensional Bose-Hubbard Hamiltonian of the system. Starting from the three-dimensional many-body quantum Hamiltonian, we derive strong inequalities involving the transverse degrees of freedom under which the one-dimensional Bose-Hubbard Hamiltonian can be safely used. To have a reliable description of the one-dimensional ground state, which we call a quantum bright soliton, we use the density-matrix-renormalization-group (DMRG) technique. By comparing DMRG results with mean-field (MF) ones, we find that beyond-mean-field effects become relevant by increasing the attraction between bosons or by decreasing the frequency of the harmonic confinement. In particular, we find that, contrary to the MF predictions based on the discrete nonlinear Schrödinger equation, average density profiles of quantum bright solitons are not shape-invariant. We also use the time-evolving-block-decimation method to investigate the dynamical properties of bright solitons when the frequency of the harmonic potential is suddenly increased. This quantum quench induces a breathing mode whose period crucially depends on the final strength of the superimposed harmonic confinement.

  19. Comparisons between thermodynamic and one-dimensional combustion models of spark-ignition engines

    NASA Technical Reports Server (NTRS)

    Ramos, J. I.

    1986-01-01

    Results from a one-dimensional combustion model employing a constant eddy diffusivity and a one-step chemical reaction are compared with those of one-zone and two-zone thermodynamic models to study the flame propagation in a spark-ignition engine. One-dimensional model predictions are found to be very sensitive to the eddy diffusivity and reaction rate data. The average mixing temperature found using the one-zone thermodynamic model is higher than those of the two-zone and one-dimensional models during the compression stroke, and that of the one-dimensional model is higher than those predicted by both thermodynamic models during the expansion stroke. The one-dimensional model is shown to predict an accelerating flame even when the front approaches the cold cylinder wall.

  20. One-Dimensional Photonic Crystal Superprisms

    NASA Technical Reports Server (NTRS)

    Ting, David

    2005-01-01

    Theoretical calculations indicate that it should be possible for one-dimensional (1D) photonic crystals (see figure) to exhibit giant dispersions known as the superprism effect. Previously, three-dimensional (3D) photonic crystal superprisms have demonstrated strong wavelength dispersion - about 500 times that of conventional prisms and diffraction gratings. Unlike diffraction gratings, superprisms do not exhibit zero-order transmission or higher-order diffraction, thereby eliminating cross-talk problems. However, the fabrication of these 3D photonic crystals requires complex electron-beam substrate patterning and multilayer thin-film sputtering processes. The proposed 1D superprism is much simpler in structural complexity and, therefore, easier to design and fabricate. Like their 3D counterparts, the 1D superprisms can exhibit giant dispersions over small spectral bands that can be tailored by judicious structure design and tuned by varying incident beam direction. Potential applications include miniature gas-sensing devices.

  1. Core-shell nanoscale coordination polymers combine chemotherapy and photodynamic therapy to potentiate checkpoint blockade cancer immunotherapy

    NASA Astrophysics Data System (ADS)

    He, Chunbai; Duan, Xiaopin; Guo, Nining; Chan, Christina; Poon, Christopher; Weichselbaum, Ralph R.; Lin, Wenbin

    2016-08-01

    Advanced colorectal cancer is one of the deadliest cancers, with a 5-year survival rate of only 12% for patients with the metastatic disease. Checkpoint inhibitors, such as the antibodies inhibiting the PD-1/PD-L1 axis, are among the most promising immunotherapies for patients with advanced colon cancer, but their durable response rate remains low. We herein report the use of immunogenic nanoparticles to augment the antitumour efficacy of PD-L1 antibody-mediated cancer immunotherapy. Nanoscale coordination polymer (NCP) core-shell nanoparticles carry oxaliplatin in the core and the photosensitizer pyropheophorbide-lipid conjugate (pyrolipid) in the shell (NCP@pyrolipid) for effective chemotherapy and photodynamic therapy (PDT). Synergy between oxaliplatin and pyrolipid-induced PDT kills tumour cells and provokes an immune response, resulting in calreticulin exposure on the cell surface, antitumour vaccination and an abscopal effect. When combined with anti-PD-L1 therapy, NCP@pyrolipid mediates regression of both light-irradiated primary tumours and non-irradiated distant tumours by inducing a strong tumour-specific immune response.

  2. Lanthanide co-ordination frameworks: Opportunities and diversity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hill, Robert J.; Long, De-Liang; Hubberstey, Peter

    2005-08-15

    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 moremore » 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.« less

  3. Underwater striling engine design with modified one-dimensional model

    NASA Astrophysics Data System (ADS)

    Li, Daijin; Qin, Kan; Luo, Kai

    2015-09-01

    Stirling engines are regarded as an efficient and promising power system for underwater devices. Currently, many researches on one-dimensional model is used to evaluate thermodynamic performance of Stirling engine, but in which there are still some aspects which cannot be modeled with proper mathematical models such as mechanical loss or auxiliary power. In this paper, a four-cylinder double-acting Stirling engine for Unmanned Underwater Vehicles (UUVs) is discussed. And a one-dimensional model incorporated with empirical equations of mechanical loss and auxiliary power obtained from experiments is derived while referring to the Stirling engine computer model of National Aeronautics and Space Administration (NASA). The P-40 Stirling engine with sufficient testing results from NASA is utilized to validate the accuracy of this one-dimensional model. It shows that the maximum error of output power of theoretical analysis results is less than 18% over testing results, and the maximum error of input power is no more than 9%. Finally, a Stirling engine for UUVs is designed with Schmidt analysis method and the modified one-dimensional model, and the results indicate this designed engine is capable of showing desired output power.

  4. Transient Stress Wave Propagation in One-Dimensional Micropolar Bodies

    DTIC Science & Technology

    2009-02-01

    based on Biot’s theory of poro- elasticity. Two compressional waves were then observed in the resulting one-dimensional model of a poroelastic column...Lisina, S., Potapov, A., Nesterenko, V., 2001. A nonlinear granular medium with particle rotation: a one-dimensional model . Acoustical Physics 47 (5...zones in failed ceramics, may be modeled using continuum theories incorporating additional kinematic degrees of freedom beyond the scope of classical

  5. SU-E-T-243: MonteCarlo Simulation Study of Polymer and Radiochromic Gel for Three-Dimensional Proton Dose Distribution

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Park, M; Jung, H; Kim, G

    2014-06-01

    Purpose: To estimate the three dimensional dose distributions in a polymer gel and a radiochromic gel by comparing with the virtual water phantom exposed to proton beams by applying Monte Carlo simulation. Methods: The polymer gel dosimeter is the compositeness material of gelatin, methacrylic acid, hydroquinone, tetrakis, and distilled water. The radiochromic gel is PRESAGE product. The densities of polymer and radiochromic gel were 1.040 and 1.0005 g/cm3, respectively. The shape of water phantom was a hexahedron with the size of 13 × 13 × 15 cm3. The proton beam energies of 72 and 116 MeV were used in themore » simulation. Proton beam was directed to the top of the phantom with Z-axis and the shape of beam was quadrangle with 10 × 10 cm2 dimension. The Percent depth dose and the dose distribution were evaluated for estimating the dose distribution of proton particle in two gel dosimeters, and compared with the virtual water phantom. Results: The Bragg-peak for proton particles in two gel dosimeters was similar to the virtual water phantom. Bragg-peak regions of polymer gel, radiochromic gel, and virtual water phantom were represented in the identical region (4.3 cm) for 72 MeV proton beam. For 116 MeV proton beam, the Bragg-peak regions of polymer gel, radiochromic gel, and virtual water phantom were represented in 9.9, 9.9 and 9.7 cm, respectively. The dose distribution of proton particles in polymer gel, radiochromic gel, and virtual water phantom was approximately identical in the case of 72 and 116 MeV energies. The errors for the simulation were under 10%. Conclusion: This work indicates the evaluation of three dimensional dose distributions by exposing proton particles to polymer and radiochromic gel dosimeter by comparing with the water phantom. The polymer gel and the radiochromic gel dosimeter show similar dose distributions for the proton beams.« less

  6. One-Dimensional Modelling of Internal Ballistics

    NASA Astrophysics Data System (ADS)

    Monreal-González, G.; Otón-Martínez, R. A.; Velasco, F. J. S.; García-Cascáles, J. R.; Ramírez-Fernández, F. J.

    2017-10-01

    A one-dimensional model is introduced in this paper for problems of internal ballistics involving solid propellant combustion. First, the work presents the physical approach and equations adopted. Closure relationships accounting for the physical phenomena taking place during combustion (interfacial friction, interfacial heat transfer, combustion) are deeply discussed. Secondly, the numerical method proposed is presented. Finally, numerical results provided by this code (UXGun) are compared with results of experimental tests and with the outcome from a well-known zero-dimensional code. The model provides successful results in firing tests of artillery guns, predicting with good accuracy the maximum pressure in the chamber and muzzle velocity what highlights its capabilities as prediction/design tool for internal ballistics.

  7. Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

    NASA Astrophysics Data System (ADS)

    Beheshti, Azizolla; Nozarian, Kimia; Babadi, Susan Soleymani; Noorizadeh, Siamak; Motamedi, Hossein; Mayer, Peter; Bruno, Giuseppe; Rudbari, Hadi Amiri

    2017-05-01

    Two new compounds namely [Cu(SCN)(μ-L)]n (1) and {[Ag (μ2-L)](ClO4)}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 CuS2N 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 AgS4 tetrahedral geometry with 4-membered Ag2S2 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.

  8. Determination of adsorption parameters in numerical simulation for polymer flooding

    NASA Astrophysics Data System (ADS)

    Bao, Pengyu; Li, Aifen; Luo, Shuai; Dang, Xu

    2018-02-01

    A study on the determination of adsorption parameters for polymer flooding simulation was carried out. The study mainly includes polymer static adsorption and dynamic adsorption. The law of adsorption amount changing with polymer concentration and core permeability was presented, and the one-dimensional numerical model of CMG was established under the support of a large number of experimental data. The adsorption laws of adsorption experiments were applied to the one-dimensional numerical model to compare the influence of two adsorption laws on the historical matching results. The results show that the static adsorption and dynamic adsorption abide by different rules, and differ greatly in adsorption. If the static adsorption results were directly applied to the numerical model, the difficulty of the historical matching will increase. Therefore, dynamic adsorption tests in the porous medium are necessary before the process of parameter adjustment in order to achieve the ideal history matching result.

  9. Pressure-induced amorphization of a dense coordination polymer and its impact on proton conductivity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Umeyama, Daiki; Hagi, Keisuke; Ogiwara, Naoki

    2014-12-01

    The proton conductivity of a dense coordination polymer (CP) was investigated under high-pressure conditions. Impedance measurements under high pressures revealed that the proton conductivity of the CP decreased more than 1000-fold at pressures of 3–7 GPa and that the activation energy for proton conduction almost doubled compared with that at ambient pressure. A synchrotron X-ray study under high pressure identified the amorphization process of the CP during compression, which rationally explains the decrease in conductivity and increase in activation energy. This phenomenon is categorized as reversible pressure-induced amorphization of a dense CP and is regarded as a demonstration of themore » coupling of the mechanical and electrical properties of a CP.« less

  10. Lead(II) coordination polymers based on rigid-flexible 3,5-bis-oxyacetate-benzoic acid: Structural transition driven by temperature control

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Yong-Qiang, E-mail: chenjzxy@126.com; Tian, Yuan

    2017-03-15

    Three Pb(II) complexes ([Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]·H{sub 2}O){sub n} (1), ([Pb{sub 4}(BOABA){sub 2}(µ{sub 4}-O)(H{sub 2}O){sub 2}]·H{sub 2}O){sub n} (2), and [Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]{sub n} (3) (H{sub 3}BOABA=3,5-bis-oxyacetate-benzoic acid) were obtained under the same reaction systems with different temperatures. Complexes 1 and 2 are two dimensional (2D) networks based on Pb-BOABA chains and Pb{sub 4}(µ{sub 4}-O)(COO){sub 6} SBUs, respectively. Complex 3 presents an interesting three dimensional (3D) framework, was obtained by increasing the reaction temperature. Structural transition of the crystallization products is largely dependent on the reaction temperature. Moreover, the fluorescence properties of complexes 1–3 have been investigated. - Graphicalmore » abstract: Three Pb(II) coordination polymers were obtained under the same reaction systems with different temperatures. Both of complexes 1 and 2 are 2D network. 3 presents a 3D framework based on Pb–O–C rods SBUs. The 2D to 3D structures transition between three complexes was achieved successfully by temperature control. - Highlights: • Three Pb(II) complexes were obtained under the same reaction systems with different temperatures. • Structural transition of the crystallization products is largely dependent on the reaction temperature. • The luminescence properties studies reveal that three complexes exhibit yellow fluorescence emission behavior, which might be good candidates for obtaining photoluminescent materials.« less

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Order and chaos in the one-dimensional ϕ4 model: N-dependence and the Second Law of Thermodynamics

    NASA Astrophysics Data System (ADS)

    Hoover, William Graham; Aoki, Kenichiro

    2017-08-01

    We revisit the equilibrium one-dimensional ϕ4 model from the dynamical systems point of view. We find an infinite number of periodic orbits which are computationally stable. At the same time some of the orbits are found to exhibit positive Lyapunov exponents! The periodic orbits confine every particle in a periodic chain to trace out either the same or a mirror-image trajectory in its two-dimensional phase space. These ;computationally stable; sets of pairs of single-particle orbits are either symmetric or antisymmetric to the very last computational bit. In such a periodic chain the odd-numbered and even-numbered particles' coordinates and momenta are either identical or differ only in sign. ;Positive Lyapunov exponents; can and do result if an infinitesimal perturbation breaking a perfect two-dimensional antisymmetry is introduced so that the motion expands into a four-dimensional phase space. In that extended space a positive exponent results. We formulate a standard initial condition for the investigation of the microcanonical chaotic number dependence of the model. We speculate on the uniqueness of the model's chaotic sea and on the connection of such collections of deterministic and time-reversible states to the Second Law of Thermodynamics.

  14. Water stability of microporous coordination polymers and the adsorption of pharmaceuticals from water.

    PubMed

    Cychosz, Katie A; Matzger, Adam J

    2010-11-16

    The stability of a variety of microporous coordination polymers (MCPs) to water-containing solutions was studied using powder X-ray diffraction. It was determined that the stability of the MCP is related to the metal cluster present in the structure with trinuclear chromium clusters more stable than copper paddlewheel clusters which are more stable than basic zinc acetate clusters. Zn(2-methylimidizolate)(2) was found to be more water stable than zinc MCPs with carboxylate linkers; however, extended exposure to water led to decomposition of all zinc-based MCPs. Matériaux de l'Institut Lavoisier (MIL)-100 was also found to be completely water stable and was used to adsorb the pharmaceuticals furosemide and sulfasalazine from water with large uptakes achievable at low concentrations, indicating that the adsorption of wastewater contaminants may be a feasible application for these materials.

  15. Chemically Reacting One-Dimensional Gas-Particle Flows

    NASA Technical Reports Server (NTRS)

    Tevepaugh, J. A.; Penny, M. M.

    1975-01-01

    The governing equations for the one-dimensional flow of a gas-particle system are discussed. Gas-particle effects are coupled via the system momentum and energy equations with the gas assumed to be chemically frozen or in chemical equilibrium. A computer code for calculating the one-dimensional flow of a gas-particle system is discussed and a user's input guide presented. The computer code provides for the expansion of the gas-particle system from a specified starting velocity and nozzle inlet geometry. Though general in nature, the final output of the code is a startline for initiating the solution of a supersonic gas-particle system in rocket nozzles. The startline includes gasdynamic data defining gaseous startline points from the nozzle centerline to the nozzle wall and particle properties at points along the gaseous startline.

  16. Synthesis, X-ray crystal structure, photo luminescent property, antimicrobial activities and DFT computational study of Zn(II) coordination polymer derived from multisite N,O donor Schiff base ligand (H2L1)

    NASA Astrophysics Data System (ADS)

    Majumdar, Dhrubajyoti; Surendra Babu, M. S.; Das, Sourav; Biswas, Jayanta Kumar; Mondal, Monojit; Hazra, Suman

    2017-06-01

    A unique thiocyanato linked 1D chain of Zn(II) coordination polymer [Zn2L1(μ1,3-SCN)(η1SCN)]n (1) has been synthesized using potential multisite compartmental N,O donor Schiff base blocker ligand (L1H2) in presence of Zn(OAc)2 and KSCN. The Schiff base ligand [N, N‧-bis(3-methoxysalicylidenimino)-1,3-daminopropane] (L1H2) is 2:1 M ratio condensation product of O-vaniline and 1,3-diaminopropane in methanol medium. The characterization of Complex 1 was accomplished by means of different micro analytical techniques like elemental analyses, IR, UV-Vis, 1H NMR, emission spectroscopy and Single X-ray crystallographic study. Complex 1 crystallizes in Orthorhombic system, space group Pbca, with values a = 11.579(2), b = 18.538(3), and c = 22.160(4) Å; α = β = γ = 90.00°; V = 4756.6(14) and Z = 8. The single crystal X-ray revealed that the one dimensional chain system with the repeating unit [Zn2(μ1,3-SCN)(η1SCN)(L1)]n bridge by an end to end μ1,3 thiocyanate anion. Within each repeating unit two different types of Zn(II) ions are present. One of these is five-coordinate in a square pyramidal geometry while the other is six-coordinate in an octahedral geometry. A brief but lucid comparative approach has been demonstrated in between Schiff base (L1H2) and complex 1 with respect to their photoluminescence activities. Active luminescence behavior of complex 1 in presence of ligand (L1H2) is due to quenching of PET process which is mediated by 'chelating effect'. Complex 1 exhibits strong antimicrobial efficacy against some important Gram + ve and Gram -ve bacteria. Apart from antimicrobial potential, a combined experimental and theoretical investigation has been performed via DFT on molecular structure of complex 1 with respect to Hirshfeld surface analysis.

  17. Exact solutions to three-dimensional generalized nonlinear Schrödinger equations with varying potential and nonlinearities.

    PubMed

    Yan, Zhenya; Konotop, V V

    2009-09-01

    It is shown that using the similarity transformations, a set of three-dimensional p-q nonlinear Schrödinger (NLS) equations with inhomogeneous coefficients can be reduced to one-dimensional stationary NLS equation with constant or varying coefficients, thus allowing for obtaining exact localized and periodic wave solutions. In the suggested reduction the original coordinates in the (1+3) space are mapped into a set of one-parametric coordinate surfaces, whose parameter plays the role of the coordinate of the one-dimensional equation. We describe the algorithm of finding solutions and concentrate on power (linear and nonlinear) potentials presenting a number of case examples. Generalizations of the method are also discussed.

  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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Arıcı, Mürsel, E-mail: marici@ogu.edu.tr; Zafer Yeşilel, Okan; Büyükgüngör, Orhan

    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 structuremore » 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

  19. Boosted one dimensional fermionic superfluids on a lattice

    NASA Astrophysics Data System (ADS)

    Ray, Sayonee; Mukerjee, Subroto; Shenoy, Vijay B.

    2017-09-01

    We study the effect of a boost (Fermi sea displaced by a finite momentum) on one dimensional systems of lattice fermions with short-ranged interactions. In the absence of a boost such systems with attractive interactions possess algebraic superconducting order. Motivated by physics in higher dimensions, one might naively expect a boost to weaken and ultimately destroy superconductivity. However, we show that for one dimensional systems the effect of the boost can be to strengthen the algebraic superconducting order by making correlation functions fall off more slowly with distance. This phenomenon can manifest in interesting ways, for example, a boost can produce a Luther-Emery phase in a system with both charge and spin gaps by engendering the destruction of the former.

  20. Three-dimensional bioprinting of cell-laden constructs with polycaprolactone protective layers for using various thermoplastic polymers.

    PubMed

    Kim, Byoung Soo; Jang, Jinah; Chae, Suhun; Gao, Ge; Kong, Jeong-Sik; Ahn, Minjun; Cho, Dong-Woo

    2016-08-22

    Three-dimensional (3D) cell-printed constructs have been recognized as promising biological substitutes for tissue/organ regeneration. They provide tailored physical properties and biological cues via multi-material printing process. In particular, hybrid bioprinting, enabling to use biodegradable synthetic polymers as framework, has been an attractive method to support weak hydrogels. The constructs with controlled architecture and high shape fidelity were fabricated through this method, depositing spatial arrangement of multi-cell types into microscale constructs. Among biodegradable synthetic polymers, polycaprolactone (PCL) has been commonly chosen in fabrication of cell-printed constructs because of its low melting temperature of 60 °C to be dispensed with extrusion-based bioprinting system. However, in addition to PCL, various synthetic polymers have been widely applied for tissue regeneration. These polymers have distinctive characteristics essential for tissue/organ regeneration. Nevertheless, it is difficult to use some polymers, such as poly (lactic-co-glycolic acid) (PLGA) and polylactic acid (PLA) with 3D bioprinting technology because of their high melting temperature to be dispensed, which can result in thermal damage to the cells in the printed constructs during the fabrication process. We present a novel bioprinting method to use various synthetic polymers in fabrication of cell-printed constructs. PCL was introduced as a protective layer to prevent thermal damage caused by high temperature of polymers during fabrication. Remarkable improvement in cellular activities in the printed constructs with PCL layers was observed compared with the construct without PCL. This bioprinting method can be applied to fabricate more tissue-like constructs through the use of various biomaterials.

  1. Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

    2002-01-01

    Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

  2. One-Dimensional Oscillator in a Box

    ERIC Educational Resources Information Center

    Amore, Paolo; Fernandez, Francisco M.

    2010-01-01

    We discuss a quantum-mechanical model of two particles that interact by means of a harmonic potential and are confined to a one-dimensional box with impenetrable walls. We apply perturbation theory to the cases of different and equal masses and analyse the symmetry of the states in the latter case. We compare the approximate perturbation results…

  3. Filtration-guided assembly for patterning one-dimensional nanostructures

    NASA Astrophysics Data System (ADS)

    Zhang, Yaozhong; Wang, Chuan; Yeom, Junghoon

    2017-04-01

    Tremendous progress has been made in synthesizing various types of one-dimensional (1D) nanostructures (NSs), such as nanotubes and nanowires, but some technical challenges still remain in the deterministic assembly of the solution-processed 1D NSs for device integration. In this work we investigate a scalable yet inexpensive nanomaterial assembly method, namely filtration-guided assembly (FGA), to place nanomaterials into desired locations as either an individual entity or ensembles, and form functional devices. FGA not only addresses the assembly challenges but also encompasses the notion of green nanomanufacturing, maximally utilizing nanomaterials and eliminating a waste stream of nanomaterials into the environment. FGA utilizes selective filtration of 1D NSs through the open windows on the nanoporous filter membrane whose surface is patterned by a polymer mask for guiding the 1D NS deposition. The modified soft-lithographic technique called blanket transfer (BT) is employed to create the various photoresist patterns of sub-10-micron resolution on the nanoporous filter membrane like mixed cellulose acetate. We use single-walled carbon nanotubes (SWCNTs) as a model 1D NS and demonstrate the fabrication of an array pattern of homogeneous 1D NS network films over an area of 20 cm2 within 10 min. The FGA-patterned SWCNT network films are transferred onto the substrate using the adhesive-based transfer technique, and show the highly uniform film thickness and resistance measurements across the entire substrate. Finally, the electrical performance of the back-gated transistors made from the FGA and transfer method of 95% pure SWCNTs is demonstrated.

  4. Filtration-guided assembly for patterning one-dimensional nanostructures.

    PubMed

    Zhang, Yaozhong; Wang, Chuan; Yeom, Junghoon

    2017-04-07

    Tremendous progress has been made in synthesizing various types of one-dimensional (1D) nanostructures (NSs), such as nanotubes and nanowires, but some technical challenges still remain in the deterministic assembly of the solution-processed 1D NSs for device integration. In this work we investigate a scalable yet inexpensive nanomaterial assembly method, namely filtration-guided assembly (FGA), to place nanomaterials into desired locations as either an individual entity or ensembles, and form functional devices. FGA not only addresses the assembly challenges but also encompasses the notion of green nanomanufacturing, maximally utilizing nanomaterials and eliminating a waste stream of nanomaterials into the environment. FGA utilizes selective filtration of 1D NSs through the open windows on the nanoporous filter membrane whose surface is patterned by a polymer mask for guiding the 1D NS deposition. The modified soft-lithographic technique called blanket transfer (BT) is employed to create the various photoresist patterns of sub-10-micron resolution on the nanoporous filter membrane like mixed cellulose acetate. We use single-walled carbon nanotubes (SWCNTs) as a model 1D NS and demonstrate the fabrication of an array pattern of homogeneous 1D NS network films over an area of 20 cm 2 within 10 min. The FGA-patterned SWCNT network films are transferred onto the substrate using the adhesive-based transfer technique, and show the highly uniform film thickness and resistance measurements across the entire substrate. Finally, the electrical performance of the back-gated transistors made from the FGA and transfer method of 95% pure SWCNTs is demonstrated.

  5. Syntheses, structures and properties of metal-carboxylate chain-based coordination polymers (CPs) with 1,1‧:4‧,1″-terphenyl-2‧,4,4″,5‧-tetracarboxylate

    NASA Astrophysics Data System (ADS)

    Zhou, Xinhui; Song, Lin; Li, Liang; Yang, Tao

    2016-09-01

    Two coordination polymers (CPs) {[Mg2L(μ2-H2O) (μ2-DMA)]·DMA}n (1), and [Ag4L(DMF)2]n (2) (H4L = 1,1‧:4‧,1″-terphenyl-2‧,4,4″,5‧-tetracarboxylic acid, DMA = N,N-dimethylacetamine, DMF = N,N-dimethylformamide) have been synthesized and structurally characterized. In 1 and 2, there exist a series of parallel aligned Msbnd Osbnd C chains, which are linked along two directions by para-terphenyl moieties of L4- ligands to lead to the metal-carboxylate chain-based three-dimensional frameworks. The photoluminescence properties of the compounds 1 and 2 have also been investigated. 1 displays blue-violet light emission with the emission maximum at 380 nm. 2 exhibits a broad emission peak from 300 to 800 nm with an emission maximum at 484 nm and some of the shoulder peaks.

  6. A supramolecular Tröger's base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatic explosives in water.

    PubMed

    Shanmugaraju, Sankarasekaran; Dabadie, Charlyne; Byrne, Kevin; Savyasachi, Aramballi J; Umadevi, Deivasigamani; Schmitt, Wolfgang; Kitchen, Jonathan A; Gunnlaugsson, Thorfinnur

    2017-02-01

    A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker ( L ; bis-[ N -(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[ b , f ][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer ( TB-Zn-CP ) was synthesized in quantitative yield using Zn(OAc) 2 ·2H 2 O and tetraacid linker L (1 : 0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N 2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer-Emmett-Teller (BET) surface area was found to be 72 m 2 g -1 . Furthermore, TB-Zn-CP displayed an excellent CO 2 uptake capacity of 76 mg g -1 at 273 K and good adsorption selectivity for CO 2 over N 2 and H 2 . The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence ( λ max = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid

  7. Quantum logic using correlated one-dimensional quantum walks

    NASA Astrophysics Data System (ADS)

    Lahini, Yoav; Steinbrecher, Gregory R.; Bookatz, Adam D.; Englund, Dirk

    2018-01-01

    Quantum Walks are unitary processes describing the evolution of an initially localized wavefunction on a lattice potential. The complexity of the dynamics increases significantly when several indistinguishable quantum walkers propagate on the same lattice simultaneously, as these develop non-trivial spatial correlations that depend on the particle's quantum statistics, mutual interactions, initial positions, and the lattice potential. We show that even in the simplest case of a quantum walk on a one dimensional graph, these correlations can be shaped to yield a complete set of compact quantum logic operations. We provide detailed recipes for implementing quantum logic on one-dimensional quantum walks in two general cases. For non-interacting bosons—such as photons in waveguide lattices—we find high-fidelity probabilistic quantum gates that could be integrated into linear optics quantum computation schemes. For interacting quantum-walkers on a one-dimensional lattice—a situation that has recently been demonstrated using ultra-cold atoms—we find deterministic logic operations that are universal for quantum information processing. The suggested implementation requires minimal resources and a level of control that is within reach using recently demonstrated techniques. Further work is required to address error-correction.

  8. Syntheses, structures and photoluminescence properties of three M(II)-coordination polymers (M dbnd Zn(II), Mn(II)) based on a pyridine N-oxide bridging ligand

    NASA Astrophysics Data System (ADS)

    Ren, Xiu-Hui; Wang, Peng; Cheng, Jun-Yan; Dong, Yu-Bin

    2018-06-01

    Three M(II)-coordination polymers (M dbnd Zn(II), Mn(II)) were synthesized based on a pyridine N-oxide bridging ligand 3,5-bis(4-carboxylphenyl)-pyridine N-oxide (L1). Compounds 1-3 all have novel complicated structures. Compound 1 (Zn(L1)2(H2O)2) and 2 (Zn2(L1)2(H2O)2) are two single crystals obtained in "one pot" and 1 features 1D double chains motif and 2 features 3D network structure. Compound 3 shows 3D network structure with triangular tunnels. The thermogravimetric analyses and photoluminescence properties were also used to investigate the title compounds.

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

    PubMed

    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.

  10. Three-Dimensional Orthogonal Co-ordinates

    ERIC Educational Resources Information Center

    Astin, J.

    1974-01-01

    A systematic approach to general orthogonal co-ordinates, suitable for use near the end of a beginning vector analysis course, is presented. It introduces students to tensor quantities and shows how equations and quantities needed in classical problems can be determined. (Author/LS)

  11. Configurational Molecular Glue: One Optically Active Polymer Attracts Two Oppositely Configured Optically Active Polymers.

    PubMed

    Tsuji, Hideto; Noda, Soma; Kimura, Takayuki; Sobue, Tadashi; Arakawa, Yuki

    2017-03-24

    D-configured poly(D-lactic acid) (D-PLA) and poly(D-2-hydroxy-3-methylbutanoic acid) (D-P2H3MB) crystallized separately into their homo-crystallites when crystallized by precipitation or solvent evaporation, whereas incorporation of L-configured poly(L-2-hydroxybutanoic acid) (L-P2HB) in D-configured D-PLA and D-P2H3MB induced co-crystallization or ternary stereocomplex formation between D-configured D-PLA and D-P2H3MB and L-configured L-P2HB. However, incorporation of D-configured poly(D-2-hydroxybutanoic acid) (D-P2HB) in D-configured D-PLA and D-P2H3MB did not cause co-crystallization between D-configured D-PLA and D-P2H3MB and D-configured D-P2HB but separate crystallization of each polymer occurred. These findings strongly suggest that an optically active polymer (L-configured or D-configured polymer) like unsubstituted or substituted optically active poly(lactic acid)s can act as "a configurational or helical molecular glue" for two oppositely configured optically active polymers (two D-configured polymers or two L-configured polymers) to allow their co-crystallization. The increased degree of freedom in polymer combination is expected to assist to pave the way for designing polymeric composites having a wide variety of physical properties, biodegradation rate and behavior in the case of biodegradable polymers.

  12. Configurational Molecular Glue: One Optically Active Polymer Attracts Two Oppositely Configured Optically Active Polymers

    NASA Astrophysics Data System (ADS)

    Tsuji, Hideto; Noda, Soma; Kimura, Takayuki; Sobue, Tadashi; Arakawa, Yuki

    2017-03-01

    D-configured poly(D-lactic acid) (D-PLA) and poly(D-2-hydroxy-3-methylbutanoic acid) (D-P2H3MB) crystallized separately into their homo-crystallites when crystallized by precipitation or solvent evaporation, whereas incorporation of L-configured poly(L-2-hydroxybutanoic acid) (L-P2HB) in D-configured D-PLA and D-P2H3MB induced co-crystallization or ternary stereocomplex formation between D-configured D-PLA and D-P2H3MB and L-configured L-P2HB. However, incorporation of D-configured poly(D-2-hydroxybutanoic acid) (D-P2HB) in D-configured D-PLA and D-P2H3MB did not cause co-crystallization between D-configured D-PLA and D-P2H3MB and D-configured D-P2HB but separate crystallization of each polymer occurred. These findings strongly suggest that an optically active polymer (L-configured or D-configured polymer) like unsubstituted or substituted optically active poly(lactic acid)s can act as “a configurational or helical molecular glue” for two oppositely configured optically active polymers (two D-configured polymers or two L-configured polymers) to allow their co-crystallization. The increased degree of freedom in polymer combination is expected to assist to pave the way for designing polymeric composites having a wide variety of physical properties, biodegradation rate and behavior in the case of biodegradable polymers.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhou, Zhi-Hang; Han, Min-Le; Wu, Ya-Pan

    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)more » 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.« less

  14. Directional reversals enable Myxococcus xanthus cells to produce collective one-dimensional streams during fruiting-body formation

    PubMed Central

    Thutupalli, Shashi; Sun, Mingzhai; Bunyak, Filiz; Palaniappan, Kannappan; Shaevitz, Joshua W.

    2015-01-01

    The formation of a collectively moving group benefits individuals within a population in a variety of ways. The surface-dwelling bacterium Myxococcus xanthus forms dynamic collective groups both to feed on prey and to aggregate during times of starvation. The latter behaviour, termed fruiting-body formation, involves a complex, coordinated series of density changes that ultimately lead to three-dimensional aggregates comprising hundreds of thousands of cells and spores. How a loose, two-dimensional sheet of motile cells produces a fixed aggregate has remained a mystery as current models of aggregation are either inconsistent with experimental data or ultimately predict unstable structures that do not remain fixed in space. Here, we use high-resolution microscopy and computer vision software to spatio-temporally track the motion of thousands of individuals during the initial stages of fruiting-body formation. We find that cells undergo a phase transition from exploratory flocking, in which unstable cell groups move rapidly and coherently over long distances, to a reversal-mediated localization into one-dimensional growing streams that are inherently stable in space. These observations identify a new phase of active collective behaviour and answer a long-standing open question in Myxococcus development by describing how motile cell groups can remain statistically fixed in a spatial location. PMID:26246416

  15. One-dimensional ZnO nanostructures.

    PubMed

    Jayadevan, K P; Tseng, T Y

    2012-06-01

    The wide-gap semiconductor ZnO with nanostructures such as nanoparticle, nanorod, nanowire, nanobelt, nanotube has high potential for a variety of applications. This article reviews the fundamentals of one-dimensional ZnO nanostructures, including processing, structure, property, application and their processing-microstructure-property correlation. Various fabrication methods of the ZnO nanostructures including vapor-liquid-solid process, vapor-solid growth, solution growth, solvothermal growth, template-assisted growth and self-assembly are introduced. The characterization and properties of the ZnO nanostructures are described. The possible applications of these nanostructures are also discussed.

  16. Hybrid Semiclassical Theory of Quantum Quenches in One-Dimensional Systems

    NASA Astrophysics Data System (ADS)

    Moca, Cǎtǎlin Paşcu; Kormos, Márton; Zaránd, Gergely

    2017-09-01

    We develop a hybrid semiclassical method to study the time evolution of one-dimensional quantum systems in and out of equilibrium. Our method handles internal degrees of freedom completely quantum mechanically by a modified time-evolving block decimation method while treating orbital quasiparticle motion classically. We can follow dynamics up to time scales well beyond the reach of standard numerical methods to observe the crossover between preequilibrated and locally phase equilibrated states. As an application, we investigate the quench dynamics and phase fluctuations of a pair of tunnel-coupled one-dimensional Bose condensates. We demonstrate the emergence of soliton-collision-induced phase propagation, soliton-entropy production, and multistep thermalization. Our method can be applied to a wide range of gapped one-dimensional systems.

  17. Graphene oxide coated coordination polymer nanobelt composite material: a new type of visible light active and highly efficient photocatalyst for Cr(VI) reduction.

    PubMed

    Shi, Gui-Mei; Zhang, Bin; Xu, Xin-Xin; Fu, Yan-Hong

    2015-06-28

    A visible light active photocatalyst was synthesized successfully by coating graphene oxide (GO) on a coordination polymer nanobelt (CPNB) using a simple colloidal blending process. Compared with neat CPNB, the resulting graphene oxide coated coordination polymer nanobelt composite material (GO/CPNB) exhibits excellent photocatalytic efficiency in the reduction of K2Cr2O7 under visible light irradiation. In the composite material, GO performs two functions. Firstly, it cuts down the band gap (E(g)) of the photocatalyst and extends its photoresponse region from the ultraviolet to visible light region. Secondly, GO exhibits excellent electron transportation ability that impedes its recombination with holes, and this can enhance photocatalytic efficiency. For GO, on its surface, the number of functional groups has a great influence on the photocatalytic performance of the resulting GO/CPNB composite material and an ideal GO"coater" to obtain a highly efficient GO/CPNB photocatalyst has been obtained. As a photocatalyst that may be used in the treatment of Cr(VI) in wastewater, GO/CPNB exhibited outstanding stability during the reduction of this pollutant.

  18. Estimation of two-dimensional motion velocity using ultrasonic signals beamformed in Cartesian coordinate for measurement of cardiac dynamics

    NASA Astrophysics Data System (ADS)

    Kaburaki, Kaori; Mozumi, Michiya; Hasegawa, Hideyuki

    2018-07-01

    Methods for the estimation of two-dimensional (2D) velocity and displacement of physiological tissues are necessary for quantitative diagnosis. In echocardiography with a phased array probe, the accuracy in the estimation of the lateral motion is lower than that of the axial motion. To improve the accuracy in the estimation of the lateral motion, in the present study, the coordinate system for ultrasonic beamforming was changed from the conventional polar coordinate to the Cartesian coordinate. In a basic experiment, the motion velocity of a phantom, which was moved at a constant speed, was estimated by the conventional and proposed methods. The proposed method reduced the bias error and standard deviation in the estimated motion velocities. In an in vivo measurement, intracardiac blood flow was analyzed by the proposed method.

  19. Confined One Dimensional Harmonic Oscillator as a Two-Mode System

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gueorguiev, V G; Rau, A P; Draayer, J P

    2005-07-11

    The one-dimensional harmonic oscillator in a box problem is possibly the simplest example of a two-mode system. This system has two exactly solvable limits, the harmonic oscillator and a particle in a (one-dimensional) box. Each of the two limits has a characteristic spectral structure describing the two different excitation modes of the system. Near each of these limits, one can use perturbation theory to achieve an accurate description of the eigenstates. Away from the exact limits, however, one has to carry out a matrix diagonalization because the basis-state mixing that occurs is typically too large to be reproduced in anymore » other way. An alternative to casting the problem in terms of one or the other basis set consists of using an ''oblique'' basis that uses both sets. Through a study of this alternative in this one-dimensional problem, we are able to illustrate practical solutions and infer the applicability of the concept for more complex systems, such as in the study of complex nuclei where oblique-basis calculations have been successful.« less

  20. Surfactant 1-Hexadecyl-3-methylimidazolium Chloride Can Convert One-Dimensional Viologen Bromoplumbate into Zero-Dimensional.

    PubMed

    Liu, Guangfeng; Liu, Jie; Nie, Lina; Ban, Rui; Armatas, Gerasimos S; Tao, Xutang; Zhang, Qichun

    2017-05-15

    A zero-dimensional N,N'-dibutyl-4,4'-dipyridinium bromoplumbate, [BV] 6 [Pb 9 Br 30 ], with unusual discrete [Pb 9 Br 30 ] 12- anionic clusters was prepared via a facile surfactant-mediated solvothermal process. This bromoplumbate exhibits a narrower optical band gap relative to the congeneric one-dimensional viologen bromoplumbates.

  1. One-Dimensional Forward–Forward Mean-Field Games

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gomes, Diogo A., E-mail: diogo.gomes@kaust.edu.sa; Nurbekyan, Levon; Sedjro, Marc

    While the general theory for the terminal-initial value problem for mean-field games (MFGs) has achieved a substantial progress, the corresponding forward–forward problem is still poorly understood—even in the one-dimensional setting. Here, we consider one-dimensional forward–forward MFGs, study the existence of solutions and their long-time convergence. First, we discuss the relation between these models and systems of conservation laws. In particular, we identify new conserved quantities and study some qualitative properties of these systems. Next, we introduce a class of wave-like equations that are equivalent to forward–forward MFGs, and we derive a novel formulation as a system of conservation laws. Formore » first-order logarithmic forward–forward MFG, we establish the existence of a global solution. Then, we consider a class of explicit solutions and show the existence of shocks. Finally, we examine parabolic forward–forward MFGs and establish the long-time convergence of the solutions.« less

  2. One-dimensional GIS-based model compared with a two-dimensional model in urban floods simulation.

    PubMed

    Lhomme, J; Bouvier, C; Mignot, E; Paquier, A

    2006-01-01

    A GIS-based one-dimensional flood simulation model is presented and applied to the centre of the city of Nîmes (Gard, France), for mapping flow depths or velocities in the streets network. The geometry of the one-dimensional elements is derived from the Digital Elevation Model (DEM). The flow is routed from one element to the next using the kinematic wave approximation. At the crossroads, the flows in the downstream branches are computed using a conceptual scheme. This scheme was previously designed to fit Y-shaped pipes junctions, and has been modified here to fit X-shaped crossroads. The results were compared with the results of a two-dimensional hydrodynamic model based on the full shallow water equations. The comparison shows that good agreements can be found in the steepest streets of the study zone, but differences may be important in the other streets. Some reasons that can explain the differences between the two models are given and some research possibilities are proposed.

  3. Versatile hydrothermal synthesis of one-dimensional composite structures

    NASA Astrophysics Data System (ADS)

    Luo, Yonglan

    2008-12-01

    In this paper we report on a versatile hydrothermal approach developed to fabricate one-dimensional (1D) composite structures. Sulfur and selenium formed liquid and adsorbed onto microrods as droplets and subsequently reacted with metallic ion in solution to produce nanoparticles-decorated composite microrods. 1D composites including ZnO/CdS, ZnO/MnS, ZnO/CuS, ZnO/CdSe, and FeOOH/CdS were successfully made using this hydrothermal strategy and the growth mechanism was also discussed. This hydrothermal strategy is simple and green, and can be extended to the synthesis of various 1D composite structures. Moreover, the interaction between the shell nanoparticles and the one-dimensional nanomaterials were confirmed by photoluminescence investigation of ZnO/CdS.

  4. On One-Dimensional Stretching Functions for Finite-Difference Calculations

    NASA Technical Reports Server (NTRS)

    Vinokur, M.

    1980-01-01

    The class of one dimensional stretching function used in finite difference calculations is studied. For solutions containing a highly localized region of rapid variation, simple criteria for a stretching function are derived using a truncation error analysis. These criteria are used to investigate two types of stretching functions. One is an interior stretching function, for which the location and slope of an interior clustering region are specified. The simplest such function satisfying the criteria is found to be one based on the inverse hyperbolic sine. The other type of function is a two sided stretching function, for which the arbitrary slopes at the two ends of the one dimensional interval are specified. The simplest such general function is found to be one based on the inverse tangent. The general two sided function has many applications in the construction of finite difference grids.

  5. CdO-NPs; synthesis from 1D new nano Cd coordination polymer, characterization and application as anti-cancer drug for reducing the viability of cancer cells

    NASA Astrophysics Data System (ADS)

    Afzalian Mend, Behnaz; Delavar, Mahmoud; Darroudi, Majid

    2017-04-01

    The hexagonal CdO nano-particles (CdO-NPs) was prepared using new nano Cd coordination polymer, [Cd(NO3)(bipy)(pzca)]n (1) as a precursor, through direct calcination process at 500 °C. The precursor (1) was synthesized by sonochemical method. The new nano compound (1) was characterized by IR spectroscopy, elemental analyses, X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and thermal gravimetric analyses. The structure of nano coordination polymer was determined by comparing the XRD pattern of nano and single-crystal of compound (1). The nano CdO was characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). In addition, the activity and efficiency of nano CdO as an anti-cancer drug was studied on cancer cells with different concentration. The results shows that the viability of cancer cells reduced above 2 μg/mL of CdO-NPs concentration.

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

    DOEpatents

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

    2015-02-24

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

  7. A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

    NASA Astrophysics Data System (ADS)

    Wang, Jin-Hua; Tang, Gui-Mei; Qin, Ting-Xiao; Yan, Shi-Chen; Wang, Yong-Tao; Cui, Yue-Zhi; Weng Ng, Seik

    2014-11-01

    Four new metal coordination complexes, namely, [Na(BTA)]n (1), [K2(BTA)2(μ2-H2O)]n (2), and [M(BTA)2(H2O)2]n (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1-4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11 nodal net with Schläfli symbol of {318}. Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of {311×42}. Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1-4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail.

  8. Effects of rotational symmetry breaking in polymer-coated nanopores

    NASA Astrophysics Data System (ADS)

    Osmanović, D.; Kerr-Winter, M.; Eccleston, R. C.; Hoogenboom, B. W.; Ford, I. J.

    2015-01-01

    The statistical theory of polymers tethered around the inner surface of a cylindrical channel has traditionally employed the assumption that the equilibrium density of the polymers is independent of the azimuthal coordinate. However, simulations have shown that this rotational symmetry can be broken when there are attractive interactions between the polymers. We investigate the phases that emerge in these circumstances, and we quantify the effect of the symmetry assumption on the phase behavior of the system. In the absence of this assumption, one can observe large differences in the equilibrium densities between the rotationally symmetric case and the non-rotationally symmetric case. A simple analytical model is developed that illustrates the driving thermodynamic forces responsible for this symmetry breaking. Our results have implications for the current understanding of the behavior of polymers in cylindrical nanopores.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Electrospinning bioactive supramolecular polymers from water.

    PubMed

    Tayi, Alok S; Pashuck, E Thomas; Newcomb, Christina J; McClendon, Mark T; Stupp, Samuel I

    2014-04-14

    Electrospinning is a high-throughput, low-cost technique for manufacturing long fibers from solution. Conventionally, this technique is used with covalent polymers with large molecular weights. We report here the electrospinning of functional peptide-based supramolecular polymers from water at very low concentrations (<4 wt %). Molecules with low molecular weights (<1 kDa) could be electrospun because they self-assembled into one-dimensional supramolecular polymers upon solvation and the critical parameters of viscosity, solution conductivity, and surface tension were optimized for this technique. The supramolecular structure of the electrospun fibers could ensure that certain residues, like bioepitopes, are displayed on the surface even after processing. This system provides an opportunity to electrospin bioactive supramolecular materials from water for biomedical applications.

  11. Exact solution of three-dimensional transport problems using one-dimensional models. [in semiconductor devices

    NASA Technical Reports Server (NTRS)

    Misiakos, K.; Lindholm, F. A.

    1986-01-01

    Several parameters of certain three-dimensional semiconductor devices including diodes, transistors, and solar cells can be determined without solving the actual boundary-value problem. The recombination current, transit time, and open-circuit voltage of planar diodes are emphasized here. The resulting analytical expressions enable determination of the surface recombination velocity of shallow planar diodes. The method involves introducing corresponding one-dimensional models having the same values of these parameters.

  12. Bio-inspired Self-healing Composite Hydrogel with Iron Oxide Nanoparticle as Coordination Crosslinker

    NASA Astrophysics Data System (ADS)

    Li, Qiaochu; Barret, Devin G.; Messersmith, Phillip B.; Holten-Andersen, Niels

    2014-03-01

    Polymer-nanoparticle (NP) composites have attracted renewed attention due to enhanced mechanical strength combined with various functionalities, but controlling the interfacial chemistry between NPs and polymer matrix, which is crucial for the composite's mechanical behavior, remains a major challenge. Inspired by the adhesion chemistry of mussel fibers, we investigated a novel approach to incorporate Fe3O4 NPs into hydrogel matrix. A polyethylene glycol polymer is designed with both ends conjugated by catechol groups, which have strong coordination affinity to Fe. The polymer network is crosslinked via coordination bonding at the surface of Fe3O4 NPs, yielding a stiff nanocomposite hydrogel. Due to the reversible nature of coordination bonding, the hydrogel presents self-healing behavior. Oscillatory rheology allows comparative kinetic studies of self-healing driven by catechol bonding at Fe3O4 NP interfaces and by catechol-Fe3+ coordination complexes. Furthermore, the superparamagnetic property of Fe3O4 NP is preserved after gelation, allowing for response to external stimuli. This gelation motif can serve as a versatile platform for tuning functional and mechanical properties for future polymer nanocomposite materials.

  13. Homoleptic ligands vs heteroleptic ligands on coordination polymerizations: Construction and properties of silver(I) coordination polymers containing dialkylbis(4-pyridy)silanes

    NASA Astrophysics Data System (ADS)

    Park, Minwoo; Jang, Jaeseong; Moon, So Yun; Jung, Ok-Sang

    2014-03-01

    Investigations into pure bidentate ligand vs mixed bidentate ligands on self-assembly of AgPF6 with the respective L1, L2, L3, L1/L2, L1/L3, and L2/L3 (L1 = diethylbis(4-pyridyl)silane; L2 = ethylmethylbis(4-pyridyl)silane; L3 = cyclotetramethylenebis(4-pyridyl)silane) were carried out. The self-assembly reactions of AgPF6 with the respective ligand system produce desirable homoleptic or heteroleptic silver(I) coordination polymers. [Ag(L1)2](PF6) gives rise to a tubular loop chain whereas the other five products lead to a twofold interpenetration diamonoid structure. [Ag(L1)2](PF6) shows a strong blue luminescence at 453 nm (λex = 270 nm), which is useful to recognize alcohols. All products were characterized by thermal analyses, and in particular, calcination of [Ag(L3)2](PF6)ṡCH3OH at 600 °C finally produces silver(0) microcrystalline morphology.

  14. Synthesis of Three-dimensional Polymer Nanostructures via Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Cheng, Kenneth

    Chemical vapor deposition (CVD) is a widely practiced methodology for preparing thin film polymer coatings, and the coatings can be applied to a broad range of materials, including three-dimensional solid structures and low-vapor pressure liquids. Reactive poly(p-xylylene) (PPX) coatings prepared by CVD can be used as a powerful tool for surface functionalization and bio-conjugation. The first portion of this dissertation serves to extend the use of CVD-based reactive PPX coatings as a surface functionalization strategy for the conjugation of biomolecules. Micro-structured PPX coatings having multiple surface reactive groups were fabricated. Multiple orthogonal click reactions were then employed to selectively immobilize galactose and mannobiose to the micro-structured polymer coatings. The presence of different types of carbohydrate enables lectins binding for examining ligands/cell receptor interactions. This dissertation also demonstrates the use of CVD-based reactive PPX coatings as intermediate layers to immobilize adenoviral vectors onto tissue scaffolds. The ability to tether adenoviral vectors on tissue scaffolds localizes the transduction near the scaffold surface and reduces acute toxicity and hepatic pathology cause by direct administration of the viral vector, providing a safe and efficient gene therapy delivery strategy. In the second portion of this dissertation, we explore the CVD of PPX onto surfaces coated with a thin layer of liquid crystal (LC). Instead of forming a conformal PPX coating encapsulating the LC layer, PPX assembled into an array of high-aspect ratio nanofibers inside the LC layer. The LC layer was demonstrated to act as a template where the anisotropic internal ordering of the LC facilitated the formation of nanofibers. The diameter of the nanofibers was in the range of 100 nm and could be tuned by type of LC template used, and the length of the nanofibers could be precisely controlled by varying the thickness of the LC film. The

  15. Three-dimensional smoothed particle hydrodynamics simulation for injection molding flow of short fiber-reinforced polymer composites

    NASA Astrophysics Data System (ADS)

    He, Liping; Lu, Gang; Chen, Dachuan; Li, Wenjun; Lu, Chunsheng

    2017-07-01

    This paper investigates the three-dimensional (3D) injection molding flow of short fiber-reinforced polymer composites using a smoothed particle hydrodynamics (SPH) simulation method. The polymer melt was modeled as a power law fluid and the fibers were considered as rigid cylindrical bodies. The filling details and fiber orientation in the injection-molding process were studied. The results indicated that the SPH method could effectively predict the order of filling, fiber accumulation, and heterogeneous distribution of fibers. The SPH simulation also showed that fibers were mainly aligned to the flow direction in the skin layer and inclined to the flow direction in the core layer. Additionally, the fiber-orientation state in the simulation was quantitatively analyzed and found to be consistent with the results calculated by conventional tensor methods.

  16. A three-dimensional coordination polymer based on 1,2,3-triazole-4,5-dicarboxylic acid (H{sub 3}tda): ([Cd{sub 12}(tda){sub 8}(H{sub 2}O){sub 11}] · (H{sub 2}O)6.25){sub n}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhou, Xin-Hui, E-mail: iamxhzhou@njupt.edu.cn; Chen, Qiang

    The title coordination polymer ([Cd{sub 12}(tda){sub 8}(H{sub 2}O){sub 11}] · (H{sub 2}O){sub 6.25}){sub n} (H{sub 3}tda = 1,2,3-triazole-4,5-dicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex crystallizes in orthorhombic sp. gr. Pmn2{sub 1} with Z = 4. The Cd{sub 2} unit doublebridged by one carboxylate oxygen atom and two neighboring nitrogen atoms from the tda{sup 3–} ligands are linked by the tda{sup 3–}ligands to lead to the 2D (4,4) network in the ac plane. The almost coplanar Cd{sub 2}(μ{sub 5}-tda){sub 2} unit comprised of two Cd ions double-bridged by two tda{sup 3–} ligands through themore » neighboring nitrogen atoms is connected with the other four Cd{sub 2}(μ{sub 5}-tda){sub 2} units form the undulating 2D network in the ac plane. The (4,4) networks and undulating 2D networks are alternatively connected along the b axis by the tda{sup 3–} ligands coordinating to the Cd ions to form the 3D framework.« less

  17. Research of spin-orbit interaction in organic conjugated polymers

    NASA Astrophysics Data System (ADS)

    Li, H.; Zhou, M. Y.; Wu, S. Y.; Liang, X. R.

    2017-06-01

    The effect of spin-orbit interaction on the one-dimensional organic polymer was investigated theoretically. Spin-orbital interaction led to the spatial separation of energy band but did not eliminate spin degeneration, which was different from energy level splitting in the Zeeman Effect. Spin-orbit interaction had little effect on the energy band structure, charge density, and lattice position, etc.; Spin precession was obtained when a polaron was transported along the polymer chain, which theoretically proved that it was feasible to control the spin precession of polaron in organic polymers by the use of external electric field.

  18. Depth-enhanced three-dimensional-two-dimensional convertible display based on modified integral imaging.

    PubMed

    Park, Jae-Hyeung; Kim, Hak-Rin; Kim, Yunhee; Kim, Joohwan; Hong, Jisoo; Lee, Sin-Doo; Lee, Byoungho

    2004-12-01

    A depth-enhanced three-dimensional-two-dimensional convertible display that uses a polymer-dispersed liquid crystal based on the principle of integral imaging is proposed. In the proposed method, a lens array is located behind a transmission-type display panel to form an array of point-light sources, and a polymer-dispersed liquid crystal is electrically controlled to pass or to scatter light coming from these point-light sources. Therefore, three-dimensional-two-dimensional conversion is accomplished electrically without any mechanical movement. Moreover, the nonimaging structure of the proposed method increases the expressible depth range considerably. We explain the method of operation and present experimental results.

  19. Synthesis, Structure, White-Light Emission, and Temperature Recognition Properties of Eu/Tb Mixed Coordination Polymers.

    PubMed

    An, Ran; Zhao, Hui; Hu, Huai-Ming; Wang, Xiaofang; Yang, Meng-Lin; Xue, Ganglin

    2016-01-19

    Two series of Eu(III)/Tb(III) coordination polymers, [LnL(glu)]n·2nH2O (Ln = Eu (1), Tb (2)) and [LnL(glu)(H2O)]n (Ln = Eu (3), Tb (4)) [HL = (2-(2-sulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline, H2glu = glutaric acid] have been hydrothermally synthesized by controlling the pH values and characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. Isomorphic compounds 1 and 2 exhibit 6-connected 3D network with the pcu topological net, containing left- and right-handed helical chains. Isomorphic compounds 3 and 4 show 3,4-connected 2D new topology with the point symbol of (4(2)·6(3)·8)(4(2)·6). Multicolor luminescence can be tailored from red to green regions by singly varying the mixing molar ratio of Eu(III)/Tb(III) cations. The mixing component of 1Eu/2Tb = 4:6 not only achieves white-light emission with the CIE coordinate of (0.323, 0.339) upon excitation at 405 nm but also presents a temperature recognition property with the significantly high sensitivity of 0.68% per K in the 50-225 K temperature range upon excitation at 370 nm.

  20. High Anodic Performance of Co 1,3,5-Benzenetricarboxylate Coordination Polymers for Li-Ion Battery.

    PubMed

    Li, Chao; Lou, Xiaobing; Shen, Ming; Hu, Xiaoshi; Guo, Zhi; Wang, Yong; Hu, Bingwen; Chen, Qun

    2016-06-22

    We report the designed synthesis of Co 1,3,5-benzenetricarboxylate coordination polymers (CPs) via a straightforward hydrothermal method, in which three kinds of reaction solvents are selected to form CPs with various morphologies and dimensions. When tested as anode materials in Li-ion battery, the cycling stabilities of the three CoBTC CPs at a current density of 100 mA g(-1) have not evident difference; however, the reversible capacities are widely divergent when the current density is increased to 2 A g(-1). The optimized product CoBTC-EtOH maintains a reversible capacity of 473 mAh g(-1) at a rate of 2 A g(-1) after 500 galvanostatic charging/discharging cycles while retaining a nearly 100% Coulombic efficiency. The hollow microspherical morphology, accessible specific area, and the absence of coordination solvent of CoBTC-EtOH might be responsible for such difference. Furthermore, the ex situ soft X-ray absorption spectroscopy studies of CoBTC-EtOH under different states-of-charge suggest that the Co ions remain in the Co(2+) state during the charging/discharging process. Therefore, Li ions are inserted to the organic moiety (including the carboxylate groups and the benzene ring) of CoBTC without the direct engagement of Co ions during electrochemical cycling.

  1. Lanthanide-based coordination polymers assembled by a flexible multidentate linker: design, structure, photophysical properties, and dynamic solid-state behavior.

    PubMed

    Marchal, Claire; Filinchuk, Yaroslav; Chen, Xiao-Yan; Imbert, Daniel; Mazzanti, Marinella

    2009-01-01

    Four picolinate building blocks were implemented into the multidentate linker N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl]butylenediamine (H(4)tpabn) with a linear flexible spacer to promote the assembly of lanthanide-based 1D coordination polymers. The role of the linker in directing the geometry of the final assembly is evidenced by the different results obtained in the presence of Htpabn(3-) and tpabn(4-) ions. The tpabn(4-) ion leads to the desired 1D polymer {[Nd(tpabn)]H(3)O x 6 H(2)O}(infinity) (12). The Htpabn(3-) ion leads to the assembly of Tb(III) and Er(III) ions into 1D zigzag chains of the general formula {[M(Htpabn)] x xH(2)O}(infinity) (M = Tb, x = 14 (1); M = Tb, x = 8 (11); M = Er, x = 14 (2); M = Er, x = 5.5 (4)), a 2D network is formed by the Eu(III) ion (i.e., {[Eu(Htpabn)] x 10 H(2)O}(infinity) (7)), and both supramolecular isomers (1D and 2D) are obtained by the Tb(III) ion. The high flexibility of the polymeric chains results in a dynamic behavior with a solvent-induced reversible structural transition. The Tb(III)- and Eu(III)-containing polymers display high-luminescence quantum yields (38 and 18%, respectively). A sizeable near-IR luminescence emission is observed for the Er(III)- and Nd(III)-containing polymers when lattice water molecules are removed.

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

    PubMed

    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.

  3. One-dimensional wave propagation in particulate suspensions

    NASA Technical Reports Server (NTRS)

    Rochelle, S. G.; Peddieson, J., Jr.

    1976-01-01

    One-dimensional small-amplitude wave motion in a two-phase system consisting of an inviscid gas and a cloud of suspended particles is analyzed using a continuum theory of suspensions. Laplace transform methods are used to obtain several approximate solutions. Properties of acoustic wave motion in particulate suspensions are inferred from these solutions.

  4. Polymer Crowding in Confined Polymer-Nanoparticle Mixtures

    NASA Astrophysics Data System (ADS)

    Davis, Wyatt J.; Denton, Alan R.

    Crowding can influence the conformations and thus functionality of macromolecules in quasi-two-dimensional environments, such as DNA or proteins confined to a cell membrane. We explore such crowding within a model of polymers as penetrable ellipses, whose shapes are governed by the statistics of a 2D random walk. The principal radii of the polymers fluctuate according to probability distributions of the eigenvalues of the gyration tensor. Within this coarse-grained model, we perform Monte Carlo simulations of mixtures of polymers and hard nanodisks, including trial changes in polymer conformation (shape and orientation). Penetration of polymers by nanodisks is incorporated with a free energy cost predicted by polymer field theory. Over ranges of size ratio and nanodisk density, we analyze the influence of crowding on polymer shape by computing eigenvalue distributions, mean radius of gyration, and mean asphericity of the polymer. We compare results with predictions of free-volume theory and with corresponding results in three dimensions. Our approach may help to interpret recent (and motivate future) experimental studies of biopolymers interacting with cell membranes, with relevance for drug delivery and gene therapy. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

  5. Novel bipyridinyl oxadiazole-based metal coordination complexes: High efficient and green synthesis of 3,4-dihydropyrimidin-2(1H)-ones through the Biginelli reactions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Jin-Hua; Zhang, E.; Tang, Gui-Mei, E-mail: meiguit@163.com

    2016-09-15

    Three new metal coordination complexes, namely, [Co(BPO){sub 2}(H{sub 2}O){sub 4}](BS){sub 2}(H{sub 2}O){sub 2} (1), [Co(BPO){sub 2}(H{sub 2}O){sub 4}](ABS){sub 2}(H{sub 2}O){sub 2} (2), [Co(BPO){sub 2}(H{sub 2}O){sub 4}](MBS){sub 2}(H{sub 2}O){sub 2} (3) [BPO=2,5-di(pyridin-4-yl)-1,3,4-oxadiazole, BS=benzenesulphonate, ABS=4-aminobenzenesulphonate, MBS=4-methylbenzenesulphonate] were obtained under hydrothermal conditions. Complexes 1–3 were structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR and thermogravimetric analyses (TGA). All of them display a zero-dimensional motif, in which strong intermolecular hydrogen bonding interactions (O–H···O/N) and packing interactions (C–H···π and π···π) make them achieve a three-dimensional supramolecular architecture. The primary catalytic results of these three complexes show that high efficiency for the green synthesismore » of a variety of 3,4-dihydropyrimidin-2(1H)-ones was observed under solvent free conditions through Biginelli reactions. The present catalytic protocols exhibit advantages such as excellent yield, easy isolation, eco-friendly conditions, and short reaction time. - Graphical abstract: Three new metal coordination complexes with bipyridinyl-oxadiazole were obtained under hydrothermal conditions, which display a zero-dimensional motif, and show high efficiency for the green synthesis of a variety of 3,4-dihydropyrimidin-2(1H)-ones under solvent free conditions through Biginelli reactions. The present catalytic protocols exhibit advantages such as excellent yield, easy isolation, eco-friendly conditions, and short reaction time. Display Omitted.« less

  6. One-dimensional analysis of supersonic two-stage HVOF process

    NASA Astrophysics Data System (ADS)

    Katanoda, Hiroshi; Hagi, Junichi; Fukuhara, Minoru

    2009-12-01

    The one-dimensional calculation of the gas/particle flows of a supersonic two-stage high-velocity oxy-fuel (HVOF) thermal spray process was performed. The internal gas flow was solved by numerically integrating the equations of the quasi-one-dimensional flow including the effects of pipe friction and heat transfer. As for the supersonic jet flow, semi-empirical equations were used to obtain the gas velocity and temperature along the center line. The velocity and temperature of the particle were obtained by an one-way coupling method. The material of the spray particle selected in this study is ultra high molecular weight polyethylene (UHMWPE). The temperature distributions in the spherical UHMWPE particles of 50 and 150µm accelerated and heated by the supersonic gas flow was clarified.

  7. A disorder-enhanced quasi-one-dimensional superconductor

    PubMed Central

    Petrović, A. P.; Ansermet, D.; Chernyshov, D.; Hoesch, M.; Salloum, D.; Gougeon, P.; Potel, M.; Boeri, L.; Panagopoulos, C.

    2016-01-01

    A powerful approach to analysing quantum systems with dimensionality d>1 involves adding a weak coupling to an array of one-dimensional (1D) chains. The resultant quasi-1D (q1D) systems can exhibit long-range order at low temperature, but are heavily influenced by interactions and disorder due to their large anisotropies. Real q1D materials are therefore ideal candidates not only to provoke, test and refine theories of strongly correlated matter, but also to search for unusual emergent electronic phases. Here we report the unprecedented enhancement of a superconducting instability by disorder in single crystals of Na2−δMo6Se6, a q1D superconductor comprising MoSe chains weakly coupled by Na atoms. We argue that disorder-enhanced Coulomb pair-breaking (which usually destroys superconductivity) may be averted due to a screened long-range Coulomb repulsion intrinsic to disordered q1D materials. Our results illustrate the capability of disorder to tune and induce new correlated electron physics in low-dimensional materials. PMID:27448209

  8. A disorder-enhanced quasi-one-dimensional superconductor.

    PubMed

    Petrović, A P; Ansermet, D; Chernyshov, D; Hoesch, M; Salloum, D; Gougeon, P; Potel, M; Boeri, L; Panagopoulos, C

    2016-07-22

    A powerful approach to analysing quantum systems with dimensionality d>1 involves adding a weak coupling to an array of one-dimensional (1D) chains. The resultant quasi-1D (q1D) systems can exhibit long-range order at low temperature, but are heavily influenced by interactions and disorder due to their large anisotropies. Real q1D materials are therefore ideal candidates not only to provoke, test and refine theories of strongly correlated matter, but also to search for unusual emergent electronic phases. Here we report the unprecedented enhancement of a superconducting instability by disorder in single crystals of Na2-δMo6Se6, a q1D superconductor comprising MoSe chains weakly coupled by Na atoms. We argue that disorder-enhanced Coulomb pair-breaking (which usually destroys superconductivity) may be averted due to a screened long-range Coulomb repulsion intrinsic to disordered q1D materials. Our results illustrate the capability of disorder to tune and induce new correlated electron physics in low-dimensional materials.

  9. One dimensional wavefront distortion sensor comprising a lens array system

    DOEpatents

    Neal, Daniel R.; Michie, Robert B.

    1996-01-01

    A 1-dimensional sensor for measuring wavefront distortion of a light beam as a function of time and spatial position includes a lens system which incorporates a linear array of lenses, and a detector system which incorporates a linear array of light detectors positioned from the lens system so that light passing through any of the lenses is focused on at least one of the light detectors. The 1-dimensional sensor determines the slope of the wavefront by location of the detectors illuminated by the light. The 1 dimensional sensor has much greater bandwidth that 2 dimensional systems.

  10. One dimensional wavefront distortion sensor comprising a lens array system

    DOEpatents

    Neal, D.R.; Michie, R.B.

    1996-02-20

    A 1-dimensional sensor for measuring wavefront distortion of a light beam as a function of time and spatial position includes a lens system which incorporates a linear array of lenses, and a detector system which incorporates a linear array of light detectors positioned from the lens system so that light passing through any of the lenses is focused on at least one of the light detectors. The 1-dimensional sensor determines the slope of the wavefront by location of the detectors illuminated by the light. The 1 dimensional sensor has much greater bandwidth that 2 dimensional systems. 8 figs.

  11. Silicon/Carbon Anodes with One-Dimensional Pore Structure for Lithium-Ion Batteries

    DTIC Science & Technology

    2012-02-28

    REPORT Silicon/Carbon Anodes with One-Dimensional Pore Structure for Lithium - Ion Batteries 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: A series of...Dimensional Pore Structure for Lithium - Ion Batteries Report Title ABSTRACT A series of composite electrode materials have been synthesized and...1 Silicon/Carbon Anodes with One-Dimensional Pore Structure for Lithium - Ion Batteries Grant # W911NF1110231 Annual Progress report June

  12. One-Dimensional Scanning Approach to Shock Sensing

    NASA Technical Reports Server (NTRS)

    Tokars, Roger; Adamovsky, Girgory; Floyd, Bertram

    2009-01-01

    Measurement tools for high speed air flow are sought both in industry and academia. Particular interest is shown in air flows that exhibit aerodynamic shocks. Shocks are accompanied by sudden changes in density, pressure, and temperature. Optical detection and characterization of such shocks can be difficult because the medium is normally transparent air. A variety of techniques to analyze these flows are available, but they often require large windows and optical components as in the case of Schlieren measurements and/or large operating powers which precludes their use for in-flight monitoring and applications. The one-dimensional scanning approach in this work is a compact low power technique that can be used to non-intrusively detect shocks. The shock is detected by analyzing the optical pattern generated by a small diameter laser beam as it passes through the shock. The optical properties of a shock result in diffraction and spreading of the beam as well as interference fringes. To investigate the feasibility of this technique a shock is simulated by a 426 m diameter optical fiber. Analysis of results revealed a direct correlation between the optical fiber or shock location and the beam s diffraction pattern. A plot of the width of the diffraction pattern vs. optical fiber location reveals that the width of the diffraction pattern was maximized when the laser beam is directed at the center of the optical fiber. This work indicates that the one-dimensional scanning approach may be able to determine the location of an actual shock. Near and far field effects associated with a small diameter laser beam striking an optical fiber used as a simulated shock are investigated allowing a proper one-dimensional scanning beam technique.

  13. Entanglement entropy of one-dimensional gases.

    PubMed

    Calabrese, Pasquale; Mintchev, Mihail; Vicari, Ettore

    2011-07-08

    We introduce a systematic framework to calculate the bipartite entanglement entropy of a spatial subsystem in a one-dimensional quantum gas which can be mapped into a noninteracting fermion system. To show the wide range of applicability of the proposed formalism, we use it for the calculation of the entanglement in the eigenstates of periodic systems, in a gas confined by boundaries or external potentials, in junctions of quantum wires, and in a time-dependent parabolic potential.

  14. Exploration properties of biased evanescent random walkers on a one-dimensional lattice

    NASA Astrophysics Data System (ADS)

    Esguerra, Jose Perico; Reyes, Jelian

    2017-08-01

    We investigate the combined effects of bias and evanescence on the characteristics of random walks on a one-dimensional lattice. We calculate the time-dependent return probability, eventual return probability, conditional mean return time, and the time-dependent mean number of visited sites of biased immortal and evanescent discrete-time random walkers on a one-dimensional lattice. We then extend the calculations to the case of a continuous-time step-coupled biased evanescent random walk on a one-dimensional lattice with an exponential waiting time distribution.

  15. Three-Dimensional Non-Fermi-Liquid Behavior from One-Dimensional Quantum Critical Local Moments

    DOE PAGES

    Classen, Laura; Zaliznyak, Igor; Tsvelik, Alexei M.

    2018-04-10

    We study the temperature dependence of the electrical resistivity in a system composed of critical spin chains interacting with three dimensional conduction electrons and driven to criticality via an external magnetic field. The relevant experimental system is Yb 2Pt 2Pb, a metal where itinerant electrons coexist with localized moments of Yb-ions which can be described in terms of effective S = 1/2 spins with dominantly one-dimensional exchange interaction. The spin subsystem becomes critical in a relatively weak magnetic field, where it behaves like a Luttinger liquid. We theoretically examine a Kondo lattice with different effective space dimensionalities of the twomore » interacting subsystems. Lastly, we characterize the corresponding non-Fermi liquid behavior due to the spin criticality by calculating the electronic relaxation rate and the dc resistivity and establish its quasi linear temperature dependence.« less

  16. Three-Dimensional Non-Fermi-Liquid Behavior from One-Dimensional Quantum Critical Local Moments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Classen, Laura; Zaliznyak, Igor; Tsvelik, Alexei M.

    We study the temperature dependence of the electrical resistivity in a system composed of critical spin chains interacting with three dimensional conduction electrons and driven to criticality via an external magnetic field. The relevant experimental system is Yb 2Pt 2Pb, a metal where itinerant electrons coexist with localized moments of Yb-ions which can be described in terms of effective S = 1/2 spins with dominantly one-dimensional exchange interaction. The spin subsystem becomes critical in a relatively weak magnetic field, where it behaves like a Luttinger liquid. We theoretically examine a Kondo lattice with different effective space dimensionalities of the twomore » interacting subsystems. Lastly, we characterize the corresponding non-Fermi liquid behavior due to the spin criticality by calculating the electronic relaxation rate and the dc resistivity and establish its quasi linear temperature dependence.« less

  17. Three-Dimensional Non-Fermi-Liquid Behavior from One-Dimensional Quantum Critical Local Moments

    NASA Astrophysics Data System (ADS)

    Classen, Laura; Zaliznyak, Igor; Tsvelik, Alexei M.

    2018-04-01

    We study the temperature dependence of the electrical resistivity in a system composed of critical spin chains interacting with three-dimensional conduction electrons and driven to criticality via an external magnetic field. The relevant experimental system is Yb2 Pt2 Pb , a metal where itinerant electrons coexist with localized moments of Yb ions which can be described in terms of effective S =1 /2 spins with a dominantly one-dimensional exchange interaction. The spin subsystem becomes critical in a relatively weak magnetic field, where it behaves like a Luttinger liquid. We theoretically examine a Kondo lattice with different effective space dimensionalities of the two interacting subsystems. We characterize the corresponding non-Fermi liquid behavior due to the spin criticality by calculating the electronic relaxation rate and the dc resistivity and establish its quasilinear temperature dependence.

  18. Detection of Macromolecular Fractions in HCN Polymers Using Electrophoretic and Ultrafiltration Techniques.

    PubMed

    Marín-Yaseli, Margarita R; Cid, Cristina; Yagüe, Ana I; Ruiz-Bermejo, Marta

    2017-02-01

    Elucidating the origin of life involves synthetic as well as analytical challenges. Herein, for the first time, we describe the use of gel electrophoresis and ultrafiltration to fractionate HCN polymers. Since the first prebiotic synthesis of adenine by Oró, HCN polymers have gained much interest in studies on the origins of life due to the identification of biomonomers and related compounds within them. Here, we demonstrate that macromolecular fractions with electrophoretic mobility can also be detected within HCN polymers. The migration of polymers under the influence of an electric field depends not only on their sizes (one-dimensional electrophoresis) but also their different isoelectric points (two-dimensional electrophoresis, 2-DE). The same behaviour was observed for several macromolecular fractions detected in HCN polymers. Macromolecular fractions with apparent molecular weights as high as 250 kDa were detected by tricine-SDS gel electrophoresis. Cationic macromolecular fractions with apparent molecular weights as high as 140 kDa were also detected by 2-DE. The HCN polymers synthesized were fractionated by ultrafiltration. As a result, the molecular weight distributions of the macromolecular fractions detected in the HCN polymers directly depended on the synthetic conditions used to produce these polymers. The implications of these results for prebiotic chemistry will be discussed. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

  19. In Vitro Cytocompatibility of One- and Two-Dimensional Nanostructure-Reinforced Biodegradable Polymeric Nanocomposites

    PubMed Central

    Farshid, Behzad; Lalwani, Gaurav; Sitharaman, Balaji

    2015-01-01

    This study investigates the in vitro cytocompatibility of one- and two-dimensional (1-D and 2-D) carbon and inorganic nanomaterial reinforced polymeric nanocomposites fabricated using biodegradable polymer poly (propylene fumarate), crosslinking agent N-vinyl pyrrolidone (NVP) and following nanomaterials: single- and multi- walled carbon nanotubes, single- and multi- walled graphene oxide nanoribbons, graphene oxide nanoplatelets, molybdenum disulfide nanoplatelets, or tungsten disulfide nanotubes dispersed between 0.02–0.2 wt% concentrations in the polymer. The extraction media of unreacted components, crosslinked nanocomposites and their degradation products between 1X-100X dilutions were examined for effects on viability and attachment employing two cell lines: NIH3T3 fibroblasts and MC3T3 pre-osteoblasts. The extraction media of unreacted PPF/NVP elicited acute dose-dependent cytotoxicity attributed to leaching of unreacted components into cell culture media. However, extraction media of crosslinked nanocomposites showed no dose dependent adverse effects. Further, all crosslinked nanocomposites showed high viability (78–100%), high cellular attachment (40–55%), and spreading that was confirmed by confocal and scanning electron microscopy. Degradation products of nanocomposites showed a mild dose-dependent cytotoxicity possibly due to acidic degradation components of PPF. In general, compared to PPF control, none of the nanocomposites showed significant differences in cellular response to the unreacted components, crosslinked nanocomposites and their degradation products. The initial minor cytotoxic response and lower cell attachment numbers were observed only for a few nanocomposite groups; these effects were absent at later time points for all PPF nanocomposites. The favorable cytocompatibility results for all the nanocomposites opens avenues for in vivo safety and efficacy studies for bone tissue engineering applications. PMID:25367032

  20. Quasi-one-dimensional Hall physics in the Harper–Hofstadter–Mott model

    NASA Astrophysics Data System (ADS)

    Kozarski, Filip; Hügel, Dario; Pollet, Lode

    2018-04-01

    We study the ground-state phase diagram of the strongly interacting Harper–Hofstadter–Mott model at quarter flux on a quasi-one-dimensional lattice consisting of a single magnetic flux quantum in y-direction. In addition to superfluid phases with various density patterns, the ground-state phase diagram features quasi-one-dimensional analogs of fractional quantum Hall phases at fillings ν = 1/2 and 3/2, where the latter is only found thanks to the hopping anisotropy and the quasi-one-dimensional geometry. At integer fillings—where in the full two-dimensional system the ground-state is expected to be gapless—we observe gapped non-degenerate ground-states: at ν = 1 it shows an odd ‘fermionic’ Hall conductance, while the Hall response at ν = 2 consists of the transverse transport of a single particle–hole pair, resulting in a net zero Hall conductance. The results are obtained by exact diagonalization and in the reciprocal mean-field approximation.

  1. Crystal structure of catena-poly[[aquadi-n-propyl­tin(IV)]-μ-oxalato

    PubMed Central

    Reichelt, Martin; Reuter, Hans

    2014-01-01

    The title compound, [Sn(C3H7)2(H2O)(C2O4)]n, represents the first diorganotin(IV) oxalate hydrate to be structurally characterized. The tin(IV) atom of the one-dimensional coordination polymer is located on a twofold rotation axis and is coordinated by two chelating oxalate ligands with two slightly different Sn—O bond lengths of 2.290 (2) and 2.365 (2) Å, two symmetry-related n-propyl groups with a Sn—C bond lengths of 2.127 (3) Å, and a water mol­ecule with a Sn—O bond length of 2.262 (2) Å. The coordination polyhedron around the SnIV atom is a slightly distorted penta­gonal bipyramid with a nearly linear axis between the trans-oriented n-propyl groups [C—Sn—C = 176.8 (1)°]. The bond angles between the oxygen atoms of the equatorial plane range from 70.48 (6)° to 76.12 (8)°. A one-dimensional coordination polymer results from the less asymmetric bilateral coordination of the centrosymmetric oxalate anion, inter­nally reflected by two slightly different C—O bond lengths of 1.248 (3) and 1.254 (3) Å. The chains of the polymer propagate parallel to [001] and are held together by hydrogen bonds between water mol­ecules and oxalate anions of neighboring chains, leading to a two-dimensional network parallel to (100). PMID:25249862

  2. Effects of rotational symmetry breaking in polymer-coated nanopores

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Osmanović, D.; Hoogenboom, B. W.; Ford, I. J.

    2015-01-21

    The statistical theory of polymers tethered around the inner surface of a cylindrical channel has traditionally employed the assumption that the equilibrium density of the polymers is independent of the azimuthal coordinate. However, simulations have shown that this rotational symmetry can be broken when there are attractive interactions between the polymers. We investigate the phases that emerge in these circumstances, and we quantify the effect of the symmetry assumption on the phase behavior of the system. In the absence of this assumption, one can observe large differences in the equilibrium densities between the rotationally symmetric case and the non-rotationally symmetricmore » case. A simple analytical model is developed that illustrates the driving thermodynamic forces responsible for this symmetry breaking. Our results have implications for the current understanding of the behavior of polymers in cylindrical nanopores.« less

  3. Elastic dependence of defect modes in one-dimensional photonic crystals with a cholesteric elastomer slab

    NASA Astrophysics Data System (ADS)

    Avendanño, Carlos G.; Martínez, Daniel

    2018-07-01

    We studied the transmission spectra in a one-dimensional dielectric multilayer photonic structure containing a cholesteric liquid crystal elastomer layer as a defect. For circularly polarized incident electromagnetic waves, we analyzed the optical defect modes induced in the band gap spectrum as a function of the incident angle and the axial strain applied along the same axis as the periodic medium. The physical parameters of the structure were chosen in such a way the photonic band gap of the cholesteric elastomer lies inside that of the multilayer. We found that, in addition to the defect modes associated with the thickness of the defect layer and the anisotropy of the elastic polymer, two new defect modes appear at both band edges of the cholesteric structure, whose amplitudes and spectral positions can be elastically tuned. Particularly, we showed that, at normal incidence, the defect modes shift toward the long-wavelength region with the strain; whereas, for constant elongation, such defects move toward larger frequencies with the incidence angle.

  4. DNA/RNA binding and anticancer/antimicrobial activities of polymer-copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Lakshmipraba, Jagadeesan; Arunachalam, Sankaralingam; Riyasdeen, Anvarbatcha; Dhivya, Rajakumar; Vignesh, Sivanandham; Akbarsha, Mohammad Abdulkader; James, Rathinam Arthur

    2013-05-01

    Water soluble polymer-copper(II) complexes with various degrees of coordination in the polymer chain were synthesized and characterized by elemental analysis, IR, UV-visible and EPR spectra. The DNA/RNA binding behavior of these polymer-copper(II) complexes was examined by UV-visible absorption, emission and circular dichroism spectroscopic methods, and cyclic voltammetry techniques. The binding of the polymer-copper(II) complexes with DNA/RNA was mainly through intercalation but some amount of electrostatic interaction was also observed. This binding capacity increased with the degree of coordination of the complexes. The polymer-copper(II) complex having the highest degree of coordination was subjected to analysis of cytotoxic and antimicrobial properties. The cytotoxicity study indicated that the polymer-copper(II) complexes affected the viability of MCF-7 mammary carcinoma cells, and the cells responded to the treatment with mostly through apoptosis although a few cells succumbed to necrosis. The antimicrobial screening showed activity against some human pathogens.

  5. Electrical tuning of three-dimensional photonic crystals using polymer dispersed liquid crystals

    NASA Astrophysics Data System (ADS)

    McPhail, Dennis; Straub, Martin; Gu, Min

    2005-01-01

    Electrically tunable three-dimensional photonic crystals with a tunable wavelength range of over 70nm of stop gaps between 3 and 4μm have been generated in a liquid crystal-polymer composite. The photonic crystals were fabricated by femtosecond-laser direct writing of void channels in an inverse woodpile configuration with 20 layers providing an extinction of infrared light transmission of 70% in the stacking direction. Stable structures could be manufactured up to a liquid crystal concentration of 24%. Applying a direct voltage of several hundred volts in the stacking direction of the photonic crystal changes the alignment of the liquid crystal directors and hence the average refractive index of the structure. This mechanism permits the direct tuning of the photonic stop gap.

  6. Porphyrin framework solids. Synthesis and structure of hybrid coordination polymers of tetra(carboxyphenyl)porphyrins and lanthanide-bridging ions.

    PubMed

    Muniappan, Sankar; Lipstman, Sophia; George, Sumod; Goldberg, Israel

    2007-07-09

    New types of porphyrin-based framework solids were constructed by reacting meso-tetra(3-carboxyphenyl)porphyrin and meso-tetra(4-carboxyphenyl)metalloporphyrins with common salts of lanthanide metal ions. The large size, high coordination numbers and strong affinity for oxo ligands of the latter, combined with favorable hydrothermal reaction conditions, allowed the formation of open three-dimensional single-framework architectures by coordination polymerization, in which the tetradentate porphyrin units are intercoordinated by multinuclear assemblies of the bridging metal ions. The latter serve as construction pillars of the supramolecular arrays, affording stable structures. Several modes of coordination polymerization were revealed by single-crystal X-ray diffraction. They differ by the spatial functionality of the porphyrin building blocks, the coordination patterns of the lanthanide-carboxylate assemblies, and the topology of the resulting frameworks. The seven new reported structures exhibit periodically spaced 0.4-0.6 nm wide channel voids that perforate the respective crystalline polymeric architectures and are accessible to solvent components. Materials based on the m-carboxyphenyl derivative reveal smaller channels than those based on the p-carboxyphenyl analogues. An additional complex of the former with a smaller third-row transition metal (Co) is characterized by coordination connectivity in two dimensions only. Thermal and powder-diffraction analyses confirm the stability of the lanthanide-TmCPP (TmCPP=tetra(m-carboxyphenyl)porphyrin) frameworks.

  7. Free-standing membrane polymer laser on the end of an optical fiber

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhai, Tianrui, E-mail: trzhai@bjut.edu.cn, E-mail: zhangxinping@bjut.edu.cn; Li, Songtao; Hu, Yujie

    2016-01-25

    One- and two-dimensional distributed feedback cavities were constructed on free-standing polymer membranes using spin-coating and lift-off techniques. Low threshold lasing was generated through feedback amplification when the 290-nm membrane device was optically pumped, which was attributed to the strong confinement mechanism provided by the active waveguide layer without a substrate. The free-standing membrane polymer laser is flexible and can be transplanted. Single- and dual-wavelength fiber lasers were achieved by directly attaching the membrane polymer laser on the optical fiber end face. This technique provides potential to fabricate polymer lasers on surfaces with arbitrary shapes.

  8. Path description of coordinate-space amplitudes

    NASA Astrophysics Data System (ADS)

    Erdoǧan, Ozan; Sterman, George

    2017-06-01

    We develop a coordinate version of light-cone-ordered perturbation theory, for general time-ordered products of fields, by carrying out integrals over one light-cone coordinate for each interaction vertex. The resulting expressions depend on the lengths of paths, measured in the same light-cone coordinate. Each path is associated with a denominator equal to a "light-cone deficit," analogous to the "energy deficits" of momentum-space time- or light-cone-ordered perturbation theory. In effect, the role played by intermediate states in momentum space is played by paths between external fields in coordinate space. We derive a class of identities satisfied by coordinate diagrams, from which their imaginary parts can be derived. Using scalar QED as an example, we show how the eikonal approximation arises naturally when the external points in a Green function approach the light cone, and we give applications to products of Wilson lines. Although much of our discussion is directed at massless fields in four dimensions, we extend the formalism to massive fields and dimensional regularization.

  9. Conducting polymer nanostructures for photocatalysis under visible light

    NASA Astrophysics Data System (ADS)

    Ghosh, Srabanti; Kouamé, Natalie A.; Ramos, Laurence; Remita, Samy; Dazzi, Alexandre; Deniset-Besseau, Ariane; Beaunier, Patricia; Goubard, Fabrice; Aubert, Pierre-Henri; Remita, Hynd

    2015-05-01

    Visible-light-responsive photocatalysts can directly harvest energy from solar light, offering a desirable way to solve energy and environment issues. Here, we show that one-dimensional poly(diphenylbutadiyne) nanostructures synthesized by photopolymerization using a soft templating approach have high photocatalytic activity under visible light without the assistance of sacrificial reagents or precious metal co-catalysts. These polymer nanostructures are very stable even after repeated cycling. Transmission electron microscopy and nanoscale infrared characterizations reveal that the morphology and structure of the polymer nanostructures remain unchanged after many photocatalytic cycles. These stable and cheap polymer nanofibres are easy to process and can be reused without appreciable loss of activity. Our findings may help the development of semiconducting-based polymers for applications in self-cleaning surfaces, hydrogen generation and photovoltaics.

  10. Poisson Coordinates.

    PubMed

    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.

  11. Three d10 coordination polymers assembled from 3,5-bis(imidazole-1-yl)pyridine and different polycarboxylates: Syntheses, structures and luminescence properties

    NASA Astrophysics Data System (ADS)

    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.

  12. Reactive scattering with row-orthonormal hyperspherical coordinates. 4. Four-dimensional-space Wigner rotation function for pentaatomic systems.

    PubMed

    Kuppermann, Aron

    2011-05-14

    The row-orthonormal hyperspherical coordinate (ROHC) approach to calculating state-to-state reaction cross sections and bound state levels of N-atom systems requires the use of angular momentum tensors and Wigner rotation functions in a space of dimension N - 1. The properties of those tensors and functions are discussed for arbitrary N and determined for N = 5 in terms of the 6 Euler angles involved in 4-dimensional space.

  13. Anomalous critical behavior in the polymer collapse transition of three-dimensional lattice trails.

    PubMed

    Bedini, Andrea; Owczarek, Aleksander L; Prellberg, Thomas

    2012-07-01

    Trails (bond-avoiding walks) provide an alternative lattice model of polymers to self-avoiding walks, and adding self-interaction at multiply visited sites gives a model of polymer collapse. Recently a two-dimensional model (triangular lattice) where doubly and triply visited sites are given different weights was shown to display a rich phase diagram with first- and second-order collapse separated by a multicritical point. A kinetic growth process of trails (KGTs) was conjectured to map precisely to this multicritical point. Two types of low-temperature phases, a globule phase and a maximally dense phase, were encountered. Here we investigate the collapse properties of a similar extended model of interacting lattice trails on the simple cubic lattice with separate weights for doubly and triply visited sites. Again we find first- and second-order collapse transitions dependent on the relative sizes of the doubly and triply visited energies. However, we find no evidence of a low-temperature maximally dense phase with only the globular phase in existence. Intriguingly, when the ratio of the energies is precisely that which separates the first-order from the second-order regions anomalous finite-size scaling appears. At the finite-size location of the rounded transition clear evidence exists for a first-order transition that persists in the thermodynamic limit. This location moves as the length increases, with its limit apparently at the point that maps to a KGT. However, if one fixes the temperature to sit at exactly this KGT point, then only a critical point can be deduced from the data. The resolution of this apparent contradiction lies in the breaking of crossover scaling and the difference in the shift and transition width (crossover) exponents.

  14. Recurrence relations in one-dimensional Ising models.

    PubMed

    da Conceição, C M Silva; Maia, R N P

    2017-09-01

    The exact finite-size partition function for the nonhomogeneous one-dimensional (1D) Ising model is found through an approach using algebra operators. Specifically, in this paper we show that the partition function can be computed through a trace from a linear second-order recurrence relation with nonconstant coefficients in matrix form. A relation between the finite-size partition function and the generalized Lucas polynomials is found for the simple homogeneous model, thus establishing a recursive formula for the partition function. This is an important property and it might indicate the possible existence of recurrence relations in higher-dimensional Ising models. Moreover, assuming quenched disorder for the interactions within the model, the quenched averaged magnetic susceptibility displays a nontrivial behavior due to changes in the ferromagnetic concentration probability.

  15. Coordinated path following of multiple underacutated marine surface vehicles along one curve.

    PubMed

    Liu, Lu; Wang, Dan; Peng, Zhouhua

    2016-09-01

    This paper investigates the coordinated path following problem for a fleet of underactuated marine surface vehicles (MSVs) along one curve. The dedicated control design is divided into two tasks. One is to steer individual underactuated MSV to track the given spatial path, and the other is to force the vehicles dispersed on a parameterized path subject to the constraints of a communication network. Specifically, a robust individual path following controller is developed based on a line-of-sight (LOS) guidance law and a reduced-order extended state observer (ESO). The vehicle sideslip angle due to environmental disturbances can be exactly identified. Then, the vehicle coordination is achieved by a path variable containment approach, under which the path variables are evenly dispersed between two virtual leaders. Another reduced-order ESO is developed to identify the composite disturbance related to the speed of virtual leaders and neighboring vehicles. The proposed coordination design is distributed since the reference speed does not need to be known by all vehicles as a priori. The input-to-state stability of the closed-loop network system is established via cascade theory. Simulation results demonstrate the effectiveness of the proposed design method. Copyright © 2016 ISA. Published by Elsevier Ltd. All rights reserved.

  16. Calculation of three-dimensional compressible laminar and turbulent boundary flows. Three-dimensional compressible boundary layers of reacting gases over realistic configurations

    NASA Technical Reports Server (NTRS)

    Kendall, R. M.; Bonnett, W. S.; Nardo, C. T.; Abbett, M. J.

    1975-01-01

    A three-dimensional boundary-layer code was developed for particular application to realistic hypersonic aircraft. It is very general and can be applied to a wide variety of boundary-layer flows. Laminar, transitional, and fully turbulent flows of compressible, reacting gases are efficiently calculated by use of the code. A body-oriented orthogonal coordinate system is used for the calculation and the user has complete freedom in specifying the coordinate system within the restrictions that one coordinate must be normal to the surface and the three coordinates must be mutually orthogonal.

  17. One-dimensional/two-dimensional hybridization for self-supported binder-free silicon-based lithium ion battery anodes.

    PubMed

    Wang, Bin; Li, Xianglong; Luo, Bin; Jia, Yuying; Zhi, Linjie

    2013-02-21

    A unique silicon-based anode for lithium ion batteries is developed via the facile hybridization of one-dimensional silicon nanowires and two-dimensional graphene sheets. The resulting paper-like film holds advantages highly desirable for not only accommodating the volume change of silicon, but also facilitating the fast transport of electron and lithium ions.

  18. Impact of styrenic polymer one-step hyper-cross-linking on volatile organic compound adsorption and desorption performance.

    PubMed

    Ghafari, Mohsen; Atkinson, John D

    2018-06-05

    A novel one-step hyper-cross-linking method, using 1,2-dichloroethane (DCE) and 1,6-dichlorohexane (DCH) cross-linkers, expands the micropore volume of commercial styrenic polymers. Performance of virgin and modified polymers was evaluated by measuring hexane, toluene, and methyl-ethyl-ketone (MEK) adsorption capacity, adsorption/desorption kinetics, and desorption efficiency. Hyper-cross-linked polymers have up to 128% higher adsorption capacity than virgin polymers at P/P 0  = 0.05 due to micropore volume increases up to 330%. Improvements are most pronounced with the DCE cross-linker. Hyper-cross-linking has minimal impact on hexane adsorption kinetics, but adsorption rates for toluene and MEK decrease by 6-41%. Desorption rates decreased (3-36%) for all materials after hyper-cross-linking, with larger decreases for DCE hyper-cross-linked polymers due to smaller average pore widths. For room temperature desorption, 20-220% more adsorbate remains in hyper-cross-linked polymers after regeneration compared to virgin materials. DCE hyper-cross-linked polymers have 13-92% more residual adsorbate than DCH counterparts. Higher temperatures were required for DCE hyper-cross-linked polymers to completely desorb VOCs compared to the DCH hyper-cross-linked and virgin counterparts. Results show that the one-step hyper-cross-linking method for modifying styrenic polymers improves adsorption capacity because of added micropores, but decreases adsorption/desorption kinetics and desorption efficiency for large VOCs due to a decrease in average pore width. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. Using an effective dimensionality to map the force-extension relation for a semi-flexible polymer in a nanoslit

    NASA Astrophysics Data System (ADS)

    de Haan, Hendrick

    2015-03-01

    The force-extension relation for a semi-flexible polymer is well described by the Marko-Siggia equation in both two and three dimensions. However, while of interest for experimental systems such as DNA in nanopits, the behaviour between these limiting dimensionalities is less understood. I will present results from simulations of a polymer subject to a stretching force F confined in nanoslits of varying heights h. Going from the 3D case to the 2D case, both the coefficients of the equation and the relevant persistence length are shown to change. This observation leads to the definition of an effective dimensionality, deff, to characterize the system. At low F, using deff in a generalized form of the Marko-Siggia relation provides good agreement with the simulation curves. However, at high F, deff drifts back towards d = 3 . 0 . The reason behind this F dependence is discussed. Semi-empirical forms for strong and weak confinement regimes will be presented and shown to give good agreement across all slit heights and stretching forces. deff is thus dependent on h and F and provides a cohesive physical picture for all regimes.

  20. Large-displacement statistics of the rightmost particle of the one-dimensional branching Brownian motion.

    PubMed

    Derrida, Bernard; Meerson, Baruch; Sasorov, Pavel V

    2016-04-01

    Consider a one-dimensional branching Brownian motion and rescale the coordinate and time so that the rates of branching and diffusion are both equal to 1. If X_{1}(t) is the position of the rightmost particle of the branching Brownian motion at time t, the empirical velocity c of this rightmost particle is defined as c=X_{1}(t)/t. Using the Fisher-Kolmogorov-Petrovsky-Piscounov equation, we evaluate the probability distribution P(c,t) of this empirical velocity c in the long-time t limit for c>2. It is already known that, for a single seed particle, P(c,t)∼exp[-(c^{2}/4-1)t] up to a prefactor that can depend on c and t. Here we show how to determine this prefactor. The result can be easily generalized to the case of multiple seed particles and to branching random walks associated with other traveling-wave equations.