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Sample records for 3d coordination polymers

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

    NASA Astrophysics Data System (ADS)

    Singh, Suryabhan; Bhim, Anupam

    2016-12-01

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

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

    SciTech Connect

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

    2012-11-15

    Two new 3D bismuth containing coordination polymers are reported along with their single crystal structures and SHG properties. Compound 1: Bi{sub 2}O{sub 2}(pydc) (pydc=pyridine-2, 5-dicarboxylate), crystallizes in the monoclinic, polar space group, P2{sub 1} (a=9.6479(9) A, b=4.2349(4) A, c=11.9615(11) A, {beta}=109.587(1) Degree-Sign ), which contains Bi{sub 2}O{sub 2} chains that are connected into a 3D structure via the pydc ligands. Compound 2: Bi{sub 4}Na{sub 4}(1R3S-cam){sub 8}(EtOH){sub 3.1}(H{sub 2}O){sub 3.4} (1R3S cam=1R3S-camphoric acid) crystallizes in the monoclinic, polar space group, P2{sub 1} (a=19.0855(7) A, b=13.7706(5) A, c=19.2429(7) A, {beta}=90.701(1) Degree-Sign ) 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 Bi{sup 3+}, a synthetic approach that resulted in polar, non-centrosymmetric, 3D metal-organic coordination polymer. - Graphical Abstract: Structures of two new, polar, 3D Bismuth(III)-based coordination polymers: Bi{sub 2}O{sub 2}(pydc) (compound 1), and Bi{sub 4}Na{sub 4}(1R3S-cam){sub 8}(EtOH){sub 3.1}(H{sub 2}O){sub 3.4} (compound 2). Highlights: Black-Right-Pointing-Pointer New, polar, 3D Bismuth(III)-based coordination polymers. Black-Right-Pointing-Pointer First polar bismuth-based coordination polymers synthesized via a 'hybrid' strategy. Black-Right-Pointing-Pointer Combination of stereochemically-active lone pairs and unsymmetrical or chiral ligands. Black-Right-Pointing-Pointer Synthesis of class C-SHG materials based on Kurtz-Perry categories.

  3. 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.

  4. Unusual Transformation from a Solvent-Stabilized 1D Coordination Polymer to a Metal-Organic Framework (MOF)-Like Cross-Linked 3D Coordination Polymer.

    PubMed

    Lee, Seung-Chul; Choi, Eun-Young; Lee, Sang-Beom; Kim, Sang-Wook; Kwon, O-Pil

    2015-10-26

    An unusual 1D-to-3D transformation of a coordination polymer based on organic linkers containing highly polar push-pull π-conjugated side chains is reported. The coordination polymers are synthesized from zinc nitrate and an organic linker, namely, 2,5-bis{4-[1-(4-nitrophenyl)pyrrolidin-2-yl]butoxy}terephthalic acid, which possesses highly polar (4-nitrophenyl)pyrrolidine groups, with high dipole moments of about 7 D. The coordination polymers exhibit an unusual transformation from a soluble, solvent-stabilized 1D coordination polymer into an insoluble, metal-organic framework (MOF)-like 3D coordination polymer. The coordination polymer exhibits good film-forming ability, and the MOF-like films are insoluble in conventional organic solvents.

  5. Synthesis, structure and properties of a 3D acentric coordination polymer with noninterpenetrated (10,3)-d topology

    NASA Astrophysics Data System (ADS)

    Lun, Huijie; Li, Xuefei; Wang, Xiao; Li, Haiyan; Li, Yamin; Bai, Yan

    2017-01-01

    A new coordination polymer, {[Mn(HPIDC)(H2O)]·2H2O}n (1) (H3PIDC = 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid), has been obtained by hydrothermal method and structurally characterized by X-ray single crystal diffraction, elemental analysis and thermogravimetric analysis (TGA). X-ray single crystal diffraction reveals that compound 1 crystallizing in acentric Pna21 space group, exhibits an ultimate racemic three-dimension framework with rare noninterpenetrated (10,3)-d (or utp) topology due to the alternate array of left- and right-handed helixes. Moreover, compound 1 also features ferroelectric, nonlinear optical (NLO) and antiferromagnetic behaviors.

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

    SciTech Connect

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

    2015-03-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N‧-donor ligands yielded three new coordination polymers as [Cu4(fph)2(bpe)3(H2O)2]·2H2O (fph=4,4‧-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co2(fph)(bpa)2(H2O)2]·3H2O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H2O)(H2oph)(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 Cu2+ ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co2+ 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.

  8. Hydrothermal reactions: From the synthesis of ligand to new lanthanide 3D-coordination polymers

    SciTech Connect

    Silva, Fausthon Fred da; Fernandes de Oliveira, Carlos Alberto; Lago Falcão, Eduardo Henrique; Gatto, Claudia Cristina; Bezerra da Costa, Nivan; Oliveira Freire, Ricardo; Chojnacki, Jarosław; Alves Júnior, Severino

    2013-11-15

    The organic ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) was synthesized under hydrothermal conditions starting from the iminodiacetic acid and catalyzed by oxalic acid. The X-ray powder diffraction data indicates that the compound crystallizes in the P2{sub 1}/c monoclinic system as reported in the literature. The ligand was also characterized by elemental analysis, magnetic nuclear resonance, infrared spectroscopy and thermogravimetric analysis. Two new coordination networks based on lanthanide ions were obtained with this ligand using hydrothermal reaction. In addition to single-crystal X-ray diffraction, the compounds were characterized by infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and elemental analysis. Single-crystal XRD showed that the compounds are isostructural, crystallizing in P2{sub 1}/n monoclinic system with chemical formula [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+}(1) and Eu{sup 3+}(2)).The luminescence properties of both compounds were studied. In the compound (1), a broad emission band was observed at 479 nm, redshifted by 70 nm in comparison of the free ligand. In (2), the typical f–f transition was observed with a maximum peak at 618 nm, related with the red emission of the europium ions. Computational methods were performed to simulate the crystal structure of (2). The theoretical calculations of the intensity parameters are in good agreement with the experimental values. - Graphical abstract: Scheme of obtaining the ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) and two new isostructural 3D-coordination polymers [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+} and Eu{sup 3+}) by hydrothermal synthesis. Display Omitted - Highlights: • The ligand 2,5-piperazinedione-1,4-diacetic acid was synthetized using the hydrothermic method and characterized. • Two new 3D-coordination polymers with this ligand containing Gd{sup 3+} and Eu{sup 3+} ions

  9. Supramolecular self-assembly of 1D and 3D heterometallic coordination polymers with triruthenium building blocks.

    PubMed

    Chan, Sharon Lai-Fung; Gao, Song; Chui, Stephen Sin-Yin; Shek, Lam; Huang, Jie-Sheng; Che, Chi-Ming

    2012-09-03

    Ru(3)(TSA)(6) (1; H(2)TSA=2-thiosalicylic acid), which bears six peripheral carboxylate groups and was isolated in the form [NEt(4)](1.5)[Ru(3)(HTSA)(2)(TSA)(4)](OAc)(0.5)·3.5H(2)O, serves as a building block for assembly of heterometallic coordination polymers. Treatment of 1 with [Fe(acac)(3)] (acac=acetylacetonate) in EG/H(2)O (EG=ethylene glycol) afforded 1D Ru(3)-Fe coordination polymer 2 by means of the connection of the building block 1 through iron centers. Treatment of 1 with MnCl(2) in EG resulted in the formation of 1D Ru(3)-Mn(3) coordination polymer 3, which features self-assembled polynuclear linking units Mn(3)(OCH(2)CH(2)O)(3), each of which contains a planar Mn(3)O(3) ring. By treating 1 with Gd(NO(3))(3) and NaHCO(3) in EG, a 3D Ru(3)-Gd(6) coordination polymer 4 was obtained; this 3D coordination polymer features unprecedented Gd(6)(μ(3)-CO(3))(4) units. The magnetic properties of 1-4, along with DFT calculations on the electronic structure of 1, are also described.

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

    SciTech Connect

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

    2015-04-15

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

  11. Assembly of 3D coordination polymers from 2D sheets by [2+2] cycloaddition reaction.

    PubMed

    Medishetty, Raghavender; Tandiana, Rika; Koh, Lip Lin; Vittal, Jagadese J

    2014-01-27

    The synthesis of three 2D interdigitated Zn(II) coordination polymers (CPs), by using three monotopic ligands containing C=C bonds, is reported. Among these, two CPs with 4spy (4-styryl pyridine) and 2F-4spy (a 2'-fluoro derivative of 4spy) ligands showed quantitative formation of cyclobutane rings, thus demonstrating a unique synthetic procedure to synthesize metal-organic frameworks (MOFs) by using this photochemical reaction. Interestingly, these compounds can also be synthesized by mechanochemical grinding procedures by using Zn(OAc)2. In contrast, Zn(NO3)2 did not yield the required product, unlike in the solution route. In addition, compounds with 4vpy (4-vinylpyridine), 4spy and 2F-4spy ligands created different units in the CPs; 4vpy and 2F-4spy furnished paddle wheel units, whereas 4spy yielded tetrahedral Zn(II) repeating units. Furthermore, the change in coordination geometry manifests in the photoluminescence properties, attributed to the difference in charge-transfer and ligand-centered fluorescent phenomenon.

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

    SciTech Connect

    Qin Junsheng; Du Dongying; Chen Lei; Sun Xiuyun; Lan Yaqian; Su Zhongmin

    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 studied 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.

  13. Hydrothermal reactions: From the synthesis of ligand to new lanthanide 3D-coordination polymers

    NASA Astrophysics Data System (ADS)

    da Silva, Fausthon Fred; de Oliveira, Carlos Alberto Fernandes; Falcão, Eduardo Henrique Lago; Gatto, Claudia Cristina; da Costa, Nivan Bezerra; Freire, Ricardo Oliveira; Chojnacki, Jarosław; Alves Júnior, Severino

    2013-11-01

    The organic ligand 2,5-piperazinedione-1,4-diacetic acid (H2PDA) was synthesized under hydrothermal conditions starting from the iminodiacetic acid and catalyzed by oxalic acid. The X-ray powder diffraction data indicates that the compound crystallizes in the P21/c monoclinic system as reported in the literature. The ligand was also characterized by elemental analysis, magnetic nuclear resonance, infrared spectroscopy and thermogravimetric analysis. Two new coordination networks based on lanthanide ions were obtained with this ligand using hydrothermal reaction. In addition to single-crystal X-ray diffraction, the compounds were characterized by infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and elemental analysis. Single-crystal XRD showed that the compounds are isostructural, crystallizing in P21/n monoclinic system with chemical formula [Ln(PDA)1.5(H2O)](H2O)3 (Ln=Gd3+(1) and Eu3+(2)).The luminescence properties of both compounds were studied. In the compound (1), a broad emission band was observed at 479 nm, redshifted by 70 nm in comparison of the free ligand. In (2), the typical f-f transition was observed with a maximum peak at 618 nm, related with the red emission of the europium ions. Computational methods were performed to simulate the crystal structure of (2). The theoretical calculations of the intensity parameters are in good agreement with the experimental values.

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

    NASA Astrophysics Data System (ADS)

    Xin, Na; Sun, Ya-Qiu; Zheng, Yan-Feng; Xu, Yan-Yan; Gao, Dong-Zhao; Zhang, Guo-Ying

    2016-11-01

    Seven new 3d-4f heterometallic coordination polymers, [Ln(CuL)2(Hbtca)(btca)(H2O)]·2H2O (Ln = TbIII1, PrIII2, SmIII3, EuIII4, YbIII5), [Nd(NiL)(nip)(Rnip)]·0·25H2O·0.25CH3OH (R= 0.6CH3, 0.4H) 6 and [Nd2(NiL)(nip)3(H2O)]·2H2O 7(CuL or NiL, H2L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1, 4, 8, 12-tetraazacyclo-pentadeca-7, 13-dien; H2btca = benzotriazole-5-carboxylic acid; H2nip = 5-nitroisophthalic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1-5 exhibit a double-strand meso-helical chain structures formed by [LnIIICuII2] units via the oxamide and benzotriazole-5-carboxylate bridges, while complex 6 exhibits a four-strand meso-helical chain formed by NdNi unit via the oxamide and 5-nitroisophthalate bridges. Complex 7 consists of a 2D layer framework formed by four-strand meso-helical chain via the nip2- bridges. Moreover, the magnetic properties of them were investigated, and the best-fit analysis of χMT versus T show that the anisotropic contribution of Ln(III) ions (arising from the spin-orbit coupling or the crystal field perturbation) dominates (weak exchange limit) in these complexes(for 3, λ = 214.6 cm-1, zj' = -0.33 cm-1, gav = 1.94; for 5, Δ = 6.98 cm-1, zj' = 1.53 cm-1, gav = 1.85).

  15. In situ Oxidation of phenol and o-aminophenol in the channels of 3d-supramolecular coordination polymers

    NASA Astrophysics Data System (ADS)

    Etaiw, Safaa El-Din H.; Werida, Amal H.

    2010-09-01

    The host attractive properties of supramolecular coordination polymers of the type _infty^3 [(R3Sn)3FeIII(CN)6], where R = methyl (I), n-butyl (II), and phenyl (III), afford the ability to be used as effective oxidizing reagents for phenol and o-aminophenol forming new host-guest supramolecular coordination polymers. Phenol was oxidized to 1,4-benzoquinone while o-aminophenol was oxidized to poly-o-aminophenol by the polymers I and II and to 2-aminophenoxazin-3-one by the polymer III. The oxidation products were investigated by methods of spectroscopy and high-performance liquid chromatography. The redox reactions were characterized by first-order kinetics. Moreover, mechanisms of the oxidation processes of phenol and o-aminophenol have been proposed.

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

    SciTech Connect

    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, [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 groups to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1–4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities. - Graphical abstract: Four 3D microporous lanthanide coordination polymers with reversible structural interconversion have been synthesized. They exhibit characteristic emission bands of the lanthanide ions and possess great thermal stability. - Highlights: • Four lanthanide coordination polymers have been hydrothermal synthesized. • There is an in situ reaction in 1 in which H{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.

  17. 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.

  18. 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

    SciTech Connect

    Fernández-Zapico, Eva; Montejo-Bernardo, Jose; Fernández-González, Alfonso; García, José R. García-Granda, Santiago

    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. 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 of

  19. Structural Modulation from 1D Chain to 3D Framework: Improved Thermostability, Insensitivity, and Energies of Two Nitrogen-Rich Energetic Coordination Polymers.

    PubMed

    Guo, Zhaoqi; Wu, Yunlong; Deng, Chongqing; Yang, Guoping; Zhang, Jiangong; Sun, Zhihua; Ma, Haixia; Gao, Chao; An, Zhongwei

    2016-11-07

    Two new energetic coordination polymers (CPs) [Pb(BT)(H2O)3]n (1) and [Pb3(DOBT)3(H2O)2]n·(4H2O)n (2) with 1D and 3D structures were synthesized by employing two rational designed ligands, 1H,1'H-5,5'-bitetrazole (H2BT) and 1H,1'H-[5,5'-bitetrazole]-1,1'-diol ligands (DHBT), respectively. Thermal analyses and sensitivity tests show that the 3D architecture reinforces the network of 2 which has higher thermal stability and lower sensitivity than that of 1. Through oxygen-bomb combustion calorimetry the molar enthalpy of formation of 2 is derived to be much higher than that of 1 as well as the reported CPs. Herein, more importantly, the heats of detonation (ΔHdet) were calculated according to the decomposition products of TG-DSC-MS-FTIR simultaneous analyses for the first time. The calculated results show that ΔHdet of 2 is 23% higher than that of 1. This research demonstrates that 3D energetic CP with outstanding energetic properties can be obtained through efficient and reasonable design.

  20. Photorefractive Polymers for Updateable 3D Displays

    DTIC Science & Technology

    2010-02-24

    Final Performance Report 3. DATES COVERED (From - To) 01-01-2007 to 11-30-2009 4. TITLE AND SUBTITLE Photorefractive Polymers for Updateable 3D ...ABSTRACT During the tenure of this project a large area updateable 3D color display has been developed for the first time using a new co-polymer...photorefractive polymers have been demonstrated. Moreover, a 6 inch × 6 inch sample was fabricated demonstrating the feasibility of making large area 3D

  1. Synthesis, characterisation and adsorption properties of a porous copper(II) 3D coordination polymer exhibiting strong binding enthalpy and adsorption capacity for carbon dioxide.

    PubMed

    Eckold, Pierre; Gee, William J; Hill, Matthew R; Batten, Stuart R

    2012-11-21

    The synthesis and characterisation of microporous coordination polymers containing copper(II) or cobalt(II) and 2-(pyridin-4-yl)malonaldehyde (Hpma) is described and the gas adsorption properties evaluated. Single-crystal X-ray structure determinations identified the structures as [M(pma)(2)]·2X (M = Cu, 1; Co, 2; X = MeOH, MeCN), which contain 3D networks with rutile topology and continuous 1D rectangular channels with diameters ranging from 3 to 4 Å. The materials exhibit low BET surface areas of 143 m(2) g(-1), but possess large capacities for carbon dioxide capture of 14.1 wt%. The small pore channels are shown to account for this, delivering a particularly strong binding enthalpy to adsorbed CO(2) of 38 kJ mol(-1), and a very large adsorption capacity relative to the low surface area.

  2. 3D polymer scaffold arrays.

    PubMed

    Simon, Carl G; Yang, Yanyin; Dorsey, Shauna M; Ramalingam, Murugan; Chatterjee, Kaushik

    2011-01-01

    We have developed a combinatorial platform for fabricating tissue scaffold arrays that can be used for screening cell-material interactions. Traditional research involves preparing samples one at a time for characterization and testing. Combinatorial and high-throughput (CHT) methods lower the cost of research by reducing the amount of time and material required for experiments by combining many samples into miniaturized specimens. In order to help accelerate biomaterials research, many new CHT methods have been developed for screening cell-material interactions where materials are presented to cells as a 2D film or surface. However, biomaterials are frequently used to fabricate 3D scaffolds, cells exist in vivo in a 3D environment and cells cultured in a 3D environment in vitro typically behave more physiologically than those cultured on a 2D surface. Thus, we have developed a platform for fabricating tissue scaffold libraries where biomaterials can be presented to cells in a 3D format.

  3. Crystal structure and carrier transport properties of a new 3D mixed-valence Cu(I)-Cu(II) coordination polymer including pyrrolidine dithiocarbamate ligand.

    PubMed

    Okubo, Takashi; Tanaka, Naoya; Kim, Kyung Ho; Anma, Haruho; Seki, Shu; Saeki, Akinori; Maekawa, Masahiko; Kuroda-Sowa, Takayoshi

    2011-03-14

    A novel mixed-valence Cu(i)-Cu(ii) coordination polymer having an infinite three-dimensional (3D) structure, {[Cu(I)(4)Cu(II)(2)Br(4)(Pyr-dtc)(4)]·CHCl(3)}(n) (1) (Pyr-dtc(-) = pyrrolidine dithiocarbamate), has been prepared and structurally characterized via X-ray diffraction. This complex consists of 1D Cu(i)-Br chains and bridging mononuclear copper(ii) units of Cu(II)(Pyr-dtc)(2), which form an infinite 3D network. A magnetic study indicates that this complex includes copper(ii) ions exhibiting a weak antiferromagnetic interaction (θ = -0.086 K) between the unpaired electrons of the copper(ii) ions present in the diamagnetic Cu(i)-Br chains. The carrier transport properties of 1 are investigated using an impedance spectroscopy technique and flash-photolysis time-resolved microwave conductivity measurement (FP-TRMC). The impedance spectroscopy reveals that this complex exhibits intriguing semiconducting properties at a small activation energy (E(a) = 0.29 eV (bulk)). The sum of the mobilities of the negative and positive carriers estimated via FP-TRMC is Σμ∼ 0.4 cm(2) V(-1) s(-1).

  4. Self-assembled 3D heterometallic Cu(II)/Fe(II) coordination polymers with octahedral net skeletons: structural features, molecular magnetism, thermal and oxidation catalytic properties.

    PubMed

    Karabach, Yauhen Y; Guedes da Silva, M Fátima C; Kopylovich, Maximilian N; Gil-Hernández, Beatriz; Sanchiz, Joaquin; Kirillov, Alexander M; Pombeiro, Armando J L

    2010-12-06

    The new three-dimensional (3D) heterometallic Cu(II)/Fe(II) coordination polymers [Cu(6)(H(2)tea)(6)Fe(CN)(6)](n)(NO(3))(2n)·6nH(2)O (1) and [Cu(6)(Hmdea)(6)Fe(CN)(6)](n)(NO(3))(2n)·7nH(2)O (2) have been easily generated by aqueous-medium self-assembly reactions of copper(II) nitrate with triethanolamine or N-methyldiethanolamine (H(3)tea or H(2)mdea, respectively), in the presence of potassium ferricyanide and sodium hydroxide. They have been isolated as air-stable crystalline solids and fully characterized including by single-crystal X-ray diffraction analyses. The latter reveal the formation of 3D metal-organic frameworks that are constructed from the [Cu(2)(μ-H(2)tea)(2)](2+) or [Cu(2)(μ-Hmdea)(2)](2+) nodes and the octahedral [Fe(CN)(6)](4-) linkers, featuring regular (1) or distorted (2) octahedral net skeletons. Upon dehydration, both compounds show reversible escape and binding processes toward water or methanol molecules. Magnetic susceptibility measurements of 1 and 2 reveal strong antiferromagnetic [J = -199(1) cm(-1)] or strong ferromagnetic [J = +153(1) cm(-1)] couplings between the copper(II) ions through the μ-O-alkoxo atoms in 1 or 2, respectively. The differences in magnetic behavior are explained in terms of the dependence of the magnetic coupling constant on the Cu-O-Cu bridging angle. Compounds 1 and 2 also act as efficient catalyst precursors for the mild oxidation of cyclohexane by aqueous hydrogen peroxide to cyclohexanol and cyclohexanone (homogeneous catalytic system), leading to maximum total yields (based on cyclohexane) and turnover numbers (TONs) up to about 22% and 470, respectively.

  5. Heterobimetallic MOFs containing tetrathiocyanometallate building blocks: pressure-induced spin crossover in the porous {Fe(II)(pz)[Pd(II)(SCN)4]} 3D coordination polymer.

    PubMed

    Muñoz-Lara, Francisco J; Arcís-Castillo, Zulema; Muñoz, M Carmen; Rodríguez-Velamazán, J Alberto; Gaspar, Ana B; Real, José A

    2012-10-15

    Here we describe the synthesis, structure, and magnetic properties of two related coordination polymers made up of self-assembling Fe(II) ions, pyrazine (pz), and the tetrathiocyanopalladate anion. Compound {Fe(MeOH)(2)[Pd(SCN)(4)]}·pz (1a) is a two-dimensional coordination polymer where the Fe(II) ions are equatorially coordinated by the nitrogen atoms of four [Pd(SCN)(4)](2-) anions, each of which connects four Fe(II) ions, forming corrugated layers {Fe[Pd(SCN)(4)]}(∞). The coordination sphere of Fe(II) is completed by the oxygen atoms of two CH(3)OH molecules. The layers stack one on top of each other in such a way that the included pz molecule establishes strong hydrogen bonds with the coordinated methanol molecules of adjacent layers. Compound {Fe(pz)[Pd(SCN)(4)]} (2) is a three-dimensional porous coordination polymer formed by flat {Fe[Pd(SCN)(4)]}(∞) layers pillared by the pz ligand. Thermal analysis of 1a shows a clear desorption of the two coordinated CH(3)OH molecules giving a rather stable phase (1b), which presumably is a polymorphic form of 2. The magnetic properties of the three derivatives are typical of the high-spin Fe(II) compounds. However, compounds 1b and 2, with coordination sphere [FeN(6)], show thermal spin crossover behavior at pressures higher than ambient pressure (10(5) MPa).

  6. 3D visualization of polymer nanostructure

    SciTech Connect

    Werner, James H

    2009-01-01

    Soft materials and structured polymers are extremely useful nanotechnology building blocks. Block copolymers, in particular, have served as 2D masks for nanolithography and 3D scaffolds for photonic crystals, nanoparticle fabrication, and solar cells. F or many of these applications, the precise 3 dimensional structure and the number and type of defects in the polymer is important for ultimate function. However, directly visualizing the 3D structure of a soft material from the nanometer to millimeter length scales is a significant technical challenge. Here, we propose to develop the instrumentation needed for direct 3D structure determination at near nanometer resolution throughout a nearly millimeter-cubed volume of a soft, potentially heterogeneous, material. This new capability will be a valuable research tool for LANL missions in chemistry, materials science, and nanoscience. Our approach to soft materials visualization builds upon exciting developments in super-resolution optical microscopy that have occurred over the past two years. To date, these new, truly revolutionary, imaging methods have been developed and almost exclusively used for biological applications. However, in addition to biological cells, these super-resolution imaging techniques hold extreme promise for direct visualization of many important nanostructured polymers and other heterogeneous chemical systems. Los Alamos has a unique opportunity to lead the development of these super-resolution imaging methods for problems of chemical rather than biological significance. While these optical methods are limited to systems transparent to visible wavelengths, we stress that many important functional chemicals such as polymers, glasses, sol-gels, aerogels, or colloidal assemblies meet this requirement, with specific examples including materials designed for optical communication, manipulation, or light-harvesting Our Research Goals are: (1) Develop the instrumentation necessary for imaging materials

  7. Self-Construction from 2D to 3D: One-Pot Layer-by-Layer Assembly of Graphene Oxide Sheets Held Together by Coordination Polymers.

    PubMed

    Zakaria, Mohamed B; Li, Cuiling; Ji, Qingmin; Jiang, Bo; Tominaka, Satoshi; Ide, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko; Yamauchi, Yusuke

    2016-07-11

    Deposition of Ni-based cyanide bridged coordination polymer (NiCNNi) flakes onto the surfaces of graphene oxide (GO) sheets, which allows precise control of the resulting lamellar nanoarchitecture by in situ crystallization, is reported. GO sheets are utilized as nucleation sites that promote the optimized crystal growth of NiCNNi flakes. The NiCNNi-coated GO sheets then self-assemble and are stabilized as ordered lamellar nanomaterials. Regulated thermal treatment under nitrogen results in a Ni3 C-GO composite with a similar morphology to the starting material, and the Ni3 C-GO composite exhibits outstanding electrocatalytic activity and excellent durability for the oxygen reduction reaction.

  8. Assembly of 1D, 2D and 3D lanthanum(iii) coordination polymers with perchlorinated benzenedicarboxylates: positional isomeric effect, structural transformation and ring-opening polymerisation of glycolide.

    PubMed

    Chen, Sheng-Chun; Dai, An-Qi; Huang, Kun-Lin; Zhang, Zhi-Hui; Cui, Ai-Jun; He, Ming-Yang; Chen, Qun

    2016-02-28

    Utilizing a series of positional isomers of tetrachlorinated benzenedicarboxylic acid ligands, seven La(iii)-based coordination polymers were solvothermally synthesized and structurally characterized. Their structural dimensionalities varying from 1D double chains, to the 2D 3,4,5-connected network, to 3D 6-connected pcu topological nets are only governed by the positions of carboxyl groups on the tetrachlorinated benzene ring. A comprehensive analysis and comparison reveals that the size of the carbonyl solvent molecules (DMF, DEF, DMA, and NMP) can affect the coordination geometries around the La(iii) ions, the coordination modes of carboxylate groups, the packing arrangements, and the void volumes of the overall crystal lattices. One as-synthesized framework further shows an unprecedented structural transformation from a 3D 6-connected network to a 3D 4,5-connected net through the dissolution and reformation pathway in water, suggesting that these easily hydrolyzed lanthanide complexes may serve as precursors to produce new high-dimensional frameworks. The bulk solvent-free melt polymerisation of glycolide utilizing these La(iii) complexes as initiators has been reported herein for the first time. All complexes were found to promote the polymerization of glycolide over a temperature range of 200 to 220 °C, producing poly(glycolic acid) (PGA) with a molecular weight up to 93,280. Under the same experimental conditions, the different catalytic activities for these complexes may result from their structural discrepancy.

  9. Balance and coordination after viewing stereoscopic 3D television

    PubMed Central

    Read, Jenny C. A.; Simonotto, Jennifer; Bohr, Iwo; Godfrey, Alan; Galna, Brook; Rochester, Lynn; Smulders, Tom V.

    2015-01-01

    Manufacturers and the media have raised the possibility that viewing stereoscopic 3D television (S3D TV) may cause temporary disruption to balance and visuomotor coordination. We looked for evidence of such effects in a laboratory-based study. Four hundred and thirty-three people aged 4–82 years old carried out tests of balance and coordination before and after viewing an 80 min movie in either conventional 2D or stereoscopic 3D, while wearing two triaxial accelerometers. Accelerometry produced little evidence of any change in body motion associated with S3D TV. We found no evidence that viewing the movie in S3D causes a detectable impairment in balance or in visuomotor coordination. PMID:26587261

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

    SciTech Connect

    Xin Lingyun; Liu Guangzhen; Wang Liya

    2011-06-15

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

  11. An unusual 2p-3d-4f heterometallic coordination polymer featuring Ln8Na and Cu8I clusters as nodes

    NASA Astrophysics Data System (ADS)

    Zhao, Mingjuan; Chen, Shimin; Huang, Yutian; Dan, Youmeng

    2017-01-01

    A new cluster-based three-dimensional 2p-3d-4f heterometallic framework {[Ho8Na(OH)6Cu16I2(CPT)24](NO3)9(H2O)6(CH3CN)18}n (1, HCPT = 4-(4-carboxyphenyl)-1,2,4 triazole) has been prepared under solvothermal condition by using a custom-designed bifunctional organic ligand. The single-crystal structure analysis reveals that this framework features novel Ln8Na and Cu8I clusters as nodes, these nodes are further connected by the CPT ligands to give rise to a (6,14)-connected network. The magnetic property of this framework has also been investigated.

  12. 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.

  13. Modelling Polymer Deformation during 3D Printing

    NASA Astrophysics Data System (ADS)

    McIlroy, Claire; Olmsted, Peter

    Three-dimensional printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The fused deposition modelling technique involves melting a thermoplastic, followed by layer-by-layer extrusion to fabricate an object. The key to ensuring strength at the weld between layers is successful inter-diffusion. However, prior to welding, both the extrusion process and the cooling temperature profile can significantly deform the polymer micro-structure and, consequently, how well the polymers are able to ``re-entangle'' across the weld. In particular, polymer alignment in the flow can cause de-bonding of the layers and create defects. We have developed a simple model of the non-isothermal extrusion process to explore the effects that typical printing conditions and material rheology have on the conformation of a polymer melt. In particular, we incorporate both stretch and orientation using the Rolie-Poly constitutive equation to examine the melt structure as it flows through the nozzle, the subsequent alignment with the build plate and the resulting deformation due to the fixed nozzle height, which is typically less than the nozzle radius.

  14. Polymer-Enriched 3D Graphene Foams for Biomedical Applications.

    PubMed

    Wang, Jun Kit; Xiong, Gordon Minru; Zhu, Minmin; Özyilmaz, Barbaros; Castro Neto, Antonio Helio; Tan, Nguan Soon; Choong, Cleo

    2015-04-22

    Graphene foams (GFs) are versatile nanoplatforms for biomedical applications because of their excellent physical, chemical, and mechanical properties. However, the brittleness and inflexibility of pristine GF (pGF) are some of the important factors restricting their widespread application. Here, a chemical-vapor-deposition-assisted method was used to synthesize 3D GFs, which were subsequently spin-coated with polymer to produce polymer-enriched 3D GFs with high conductivity and flexibility. Compared to pGF, both poly(vinylidene fluoride)-enriched GF (PVDF/GF) and polycaprolactone-enriched GF (PCL/GF) scaffolds showed improved flexibility and handleability. Despite the presence of the polymers, the polymer-enriched 3D GF scaffolds retained high levels of electrical conductivity because of the presence of microcracks that allowed for the flow of electrons through the material. In addition, polymer enrichment of GF led to an enhancement in the formation of calcium phosphate (Ca-P) compounds when the scaffolds were exposed to simulated body fluid. Between the two polymers tested, PCL enrichment of GF resulted in a higher in vitro mineralization nucleation rate because the oxygen-containing functional group of PCL had a higher affinity for Ca-P deposition and formation compared to the polar carbon-fluorine (C-F) bond in PVDF. Taken together, our current findings are a stepping stone toward future applications of polymer-enriched 3D GFs in the treatment of bone defects as well as other biomedical applications.

  15. 3D Printing of Biocompatible Supramolecular Polymers and their Composites.

    PubMed

    Hart, Lewis R; Li, Siwei; Sturgess, Craig; Wildman, Ricky; Jones, Julian R; Hayes, Wayne

    2016-02-10

    A series of polymers capable of self-assembling into infinite networks via supramolecular interactions have been designed, synthesized, and characterized for use in 3D printing applications. The biocompatible polymers and their composites with silica nanoparticles were successfully utilized to deposit both simple cubic structures, as well as a more complex twisted pyramidal feature. The polymers were found to be not toxic to a chondrogenic cell line, according to ISO 10993-5 and 10993-12 standard tests and the cells attached to the supramolecular polymers as demonstrated by confocal microscopy. Silica nanoparticles were then dispersed within the polymer matrix, yielding a composite material which was optimized for inkjet printing. The hybrid material showed promise in preliminary tests to facilitate the 3D deposition of a more complex structure.

  16. Holographic imaging of 3D objects on dichromated polymer systems

    NASA Astrophysics Data System (ADS)

    Lemelin, Guylain; Jourdain, Anne; Manivannan, Gurusamy; Lessard, Roger A.

    1996-01-01

    Conventional volume transmission holograms of a 3D scene were recorded on dichromated poly(acrylic acid) (DCPAA) films under 488 nm light. The holographic characterization and quality of reconstruction have been studied by varying the influencing parameters such as concentration of dichromate and electron donor, and the molecular weight of the polymer matrix. Ammonium and potassium dichromate have been employed to sensitize the poly(acrylic) matrix. the recorded hologram can be efficiently reconstructed either with red light or with low energy in the blue region without any post thermal or chemical processing.

  17. Modelling Polymer Deformation and Welding Behaviour during 3D Printing

    NASA Astrophysics Data System (ADS)

    McIlroy, Claire; Olmsted, Peter

    2016-11-01

    3D printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The most common method, fused deposition modelling, involves melting a thermoplastic, followed by layer-by-layer extrusion of the material to fabricate a three-dimensional object. The key to the ensuring strength at the weld between these layers is successful inter-diffusion. However, as the printed layer cools towards the glass transition temperature, the time available for diffusion is limited. In addition, the extrusion process significantly deforms the polymer micro-structure prior to welding and consequently affects how the polymers "re-entangle" across the weld. We have developed a simple model of the non-isothermal printing process to explore the effects that typical printing conditions and amorphous polymer rheology have on the ultimate weld structure. In particular, we incorporate both the stretch and orientation of the polymer using the Rolie-Poly constitutive equation to examine how the melt flows through the nozzle and is deposited onto the build plate. We then address how this deformation relaxes and contributes to the thickness and structure of the weld. National Institute for Standards and Technology (NIST) and Georgetown University.

  18. 3D holographic polymer photonic crystal for superprism application

    NASA Astrophysics Data System (ADS)

    Chen, Jiaqi; Jiang, Wei; Chen, Xiaonan; Wang, Li; Zhang, Sasa; Chen, Ray T.

    2007-02-01

    Photonic crystal based superprism offers a new way to design new optical components for beam steering and DWDM application. 3D photonic crystals are especially attractive as they could offer more control of the light beam based on the needs. A polygonal prism based holographic fabrication method has been demonstrated for a three-dimensional face-centered-cubic (FCC)-type submicron polymer photonic crystal using SU8 as the photo-sensitive material. Therefore antivibration equipment and complicated optical alignment system are not needed and the requirement for the coherence of the laser source is relaxed compared with the traditional holographic setup. By changing the top-cut prism structure, the polarization of the laser beam, the exposure and development conditions we can achieve different kinds of triclinic or orthorhombic photonic crystals on demand. Special fabrication treatments have been introduced to ensure the survivability of the fabricated large area (cm2) nano-structures. Scanning electron microscopy and diffraction results proved the good uniformity of the fabricated structures. With the proper design of the refraction prism we have achieved a partial bandgap for S+C band (1460-1565nm) in the [111] direction. The transmission and reflection spectra obtained by Fourier transform infrared spectroscopy (FTIR) are in good agreement with simulated band structure. The superprism effects around 1550nm wavelength for the fabricated 3D polymer photonic crystal have been theoretically calculated and such effects can be used for beam steering purpose.

  19. 3D print of polymer bonded rare-earth magnets, and 3D magnetic field scanning with an end-user 3D printer

    NASA Astrophysics Data System (ADS)

    Huber, C.; Abert, C.; Bruckner, F.; Groenefeld, M.; Muthsam, O.; Schuschnigg, S.; Sirak, K.; Thanhoffer, R.; Teliban, I.; Vogler, C.; Windl, R.; Suess, D.

    2016-10-01

    3D print is a recently developed technique, for single-unit production, and for structures that have been impossible to build previously. The current work presents a method to 3D print polymer bonded isotropic hard magnets with a low-cost, end-user 3D printer. Commercially available isotropic NdFeB powder inside a PA11 matrix is characterized, and prepared for the printing process. An example of a printed magnet with a complex shape that was designed to generate a specific stray field is presented, and compared with finite element simulation solving the macroscopic Maxwell equations. For magnetic characterization, and comparing 3D printed structures with injection molded parts, hysteresis measurements are performed. To measure the stray field outside the magnet, the printer is upgraded to a 3D magnetic flux density measurement system. To skip an elaborate adjusting of the sensor, a simulation is used to calibrate the angles, sensitivity, and the offset of the sensor. With this setup, a measurement resolution of 0.05 mm along the z-axes is achievable. The effectiveness of our calibration method is shown. With our setup, we are able to print polymer bonded magnetic systems with the freedom of having a specific complex shape with locally tailored magnetic properties. The 3D scanning setup is easy to mount, and with our calibration method we are able to get accurate measuring results of the stray field.

  20. New 3-D microarray platform based on macroporous polymer monoliths.

    PubMed

    Rober, M; Walter, J; Vlakh, E; Stahl, F; Kasper, C; Tennikova, T

    2009-06-30

    Polymer macroporous monoliths are widely used as efficient sorbents in different, mostly dynamic, interphase processes. In this paper, monolithic materials strongly bound to the inert glass surface are suggested as operative matrices at the development of three-dimensional (3-D) microarrays. For this purpose, several rigid macroporous copolymers differed by reactivity and hydrophobic-hydrophilic properties were synthesized and tested: (1) glycidyl methacrylate-co-ethylene dimethacrylate (poly(GMA-co-EDMA)), (2) glycidyl methacrylate-co-glycerol dimethacrylate (poly(GMA-co-GDMA)), (3) N-hydroxyphthalimide ester of acrylic acid-co-glycidyl methacrylate-co-ethylene dimethacrylate (poly(HPIEAA-co-GMA-co-EDMA)), (4) 2-cyanoethyl methacrylate-co-ethylene dimethacrylate (poly(CEMA-co-EDMA)), and (5) 2-cyanoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene dimethacrylate (poly(CEMA-co-HEMA-co-EDMA)). The constructed devices were used as platforms for protein microarrays construction and model mouse IgG-goat anti-mouse IgG affinity pair was used to demonstrate the potential of developed test-systems, as well as to optimize microanalytical conditions. The offered microarray platforms were applied to detect the bone tissue marker osteopontin directly in cell culture medium.

  1. Viewing 3D TV over two months produces no discernible effects on balance, coordination or eyesight

    PubMed Central

    Read, Jenny C.A.; Godfrey, Alan; Bohr, Iwo; Simonotto, Jennifer; Galna, Brook; Smulders, Tom V.

    2016-01-01

    Abstract With the rise in stereoscopic 3D media, there has been concern that viewing stereoscopic 3D (S3D) content could have long-term adverse effects, but little data are available. In the first study to address this, 28 households who did not currently own a 3D TV were given a new TV set, either S3D or 2D. The 116 members of these households all underwent tests of balance, coordination and eyesight, both before they received their new TV set, and after they had owned it for 2 months. We did not detect any changes which appeared to be associated with viewing 3D TV. We conclude that viewing 3D TV does not produce detectable effects on balance, coordination or eyesight over the timescale studied. Practitioner Summary: Concern has been expressed over possible long-term effects of stereoscopic 3D (S3D). We looked for any changes in vision, balance and coordination associated with normal home S3D TV viewing in the 2 months after first acquiring a 3D TV. We find no evidence of any changes over this timescale. PMID:26758965

  2. Viewing 3D TV over two months produces no discernible effects on balance, coordination or eyesight.

    PubMed

    Read, Jenny C A; Godfrey, Alan; Bohr, Iwo; Simonotto, Jennifer; Galna, Brook; Smulders, Tom V

    2016-08-01

    With the rise in stereoscopic 3D media, there has been concern that viewing stereoscopic 3D (S3D) content could have long-term adverse effects, but little data are available. In the first study to address this, 28 households who did not currently own a 3D TV were given a new TV set, either S3D or 2D. The 116 members of these households all underwent tests of balance, coordination and eyesight, both before they received their new TV set, and after they had owned it for 2 months. We did not detect any changes which appeared to be associated with viewing 3D TV. We conclude that viewing 3D TV does not produce detectable effects on balance, coordination or eyesight over the timescale studied. Practitioner Summary: Concern has been expressed over possible long-term effects of stereoscopic 3D (S3D). We looked for any changes in vision, balance and coordination associated with normal home S3D TV viewing in the 2 months after first acquiring a 3D TV. We find no evidence of any changes over this timescale.

  3. 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.

  4. Porphyrin coordination polymer nanospheres and nanorods

    SciTech Connect

    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. 3-dimensional (3D) fabricated polymer based drug delivery systems.

    PubMed

    Moulton, Simon E; Wallace, Gordon G

    2014-11-10

    Drug delivery from 3-dimensional (3D) structures is a rapidly growing area of research. It is essential to achieve structures wherein drug stability is ensured, the drug loading capacity is appropriate and the desired controlled release profile can be attained. Attention must also be paid to the development of appropriate fabrication machinery that allows 3D drug delivery systems (DDS) to be produced in a simple, reliable and reproducible manner. The range of fabrication methods currently being used to form 3D DDSs include electrospinning (solution and melt), wet-spinning and printing (3-dimensional). The use of these techniques enables production of DDSs from the macro-scale down to the nano-scale. This article reviews progress in these fabrication techniques to form DDSs that possess desirable drug delivery kinetics for a wide range of applications.

  6. Towards an efficient compression of 3D coordinates of macromolecular structures

    PubMed Central

    Valasatava, Yana; Bradley, Anthony R.; Rose, Alexander S.; Duarte, Jose M.; Prlić, Andreas

    2017-01-01

    The size and complexity of 3D macromolecular structures available in the Protein Data Bank is constantly growing. Current tools and file formats have reached limits of scalability. New compression approaches are required to support the visualization of large molecular complexes and enable new and scalable means for data analysis. We evaluated a series of compression techniques for coordinates of 3D macromolecular structures and identified the best performing approaches. By balancing compression efficiency in terms of the decompression speed and compression ratio, and code complexity, our results provide the foundation for a novel standard to represent macromolecular coordinates in a compact and useful file format. PMID:28362865

  7. Towards an efficient compression of 3D coordinates of macromolecular structures.

    PubMed

    Valasatava, Yana; Bradley, Anthony R; Rose, Alexander S; Duarte, Jose M; Prlić, Andreas; Rose, Peter W

    2017-01-01

    The size and complexity of 3D macromolecular structures available in the Protein Data Bank is constantly growing. Current tools and file formats have reached limits of scalability. New compression approaches are required to support the visualization of large molecular complexes and enable new and scalable means for data analysis. We evaluated a series of compression techniques for coordinates of 3D macromolecular structures and identified the best performing approaches. By balancing compression efficiency in terms of the decompression speed and compression ratio, and code complexity, our results provide the foundation for a novel standard to represent macromolecular coordinates in a compact and useful file format.

  8. Fused filament 3D printing of ionic polymer-metal composites (IPMCs)

    NASA Astrophysics Data System (ADS)

    Carrico, James D.; Traeden, Nicklaus W.; Aureli, Matteo; Leang, Kam K.

    2015-12-01

    This paper describes a new three-dimensional (3D) fused filament additive manufacturing (AM) technique in which electroactive polymer filament material is used to build soft active 3D structures, layer by layer. Specifically, the unique actuation and sensing properties of ionic polymer-metal composites (IPMCs) are exploited in 3D printing to create electroactive polymer structures for application in soft robotics and bio-inspired systems. The process begins with extruding a precursor material (non-acid Nafion precursor resin) into a thermoplastic filament for 3D printing. The filament is then used by a custom-designed 3D printer to manufacture the desired soft polymer structures, layer by layer. Since at this stage the 3D-printed samples are not yet electroactive, a chemical functionalization process follows, consisting in hydrolyzing the precursor samples in an aqueous solution of potassium hydroxide and dimethyl sulfoxide. Upon functionalization, metal electrodes are applied on the samples through an electroless plating process, which enables the 3D-printed IPMC structures to be controlled by voltage signals for actuation (or to act as sensors). This innovative AM process is described in detail and the performance of 3D printed IPMC actuators is compared to an IPMC actuator fabricated from commercially available Nafion sheet material. The experimental results show comparable performance between the two types of actuators, demonstrating the potential and feasibility of creating functional 3D-printed IPMCs.

  9. Updateable 3D Display Using Large Area Photorefractive Polymer Devices

    DTIC Science & Technology

    2013-04-01

    2011.  C. W. Christenson, et al., " Interdigitated coplanar electrodes for enhanced sensitivity in a photorefractive polymer", Optics Letters, Vol...researcher to tailor the flow of electrons between the electrodes and acts as an insulator to minimize the opportunities for electrical breakdown

  10. Infrared imaging of the polymer 3D-printing process

    NASA Astrophysics Data System (ADS)

    Dinwiddie, Ralph B.; Kunc, Vlastimil; Lindal, John M.; Post, Brian; Smith, Rachel J.; Love, Lonnie; Duty, Chad E.

    2014-05-01

    Both mid-wave and long-wave IR cameras are used to measure various temperature profiles in thermoplastic parts as they are printed. Two significantly different 3D-printers are used in this study. The first is a small scale commercially available Solidoodle 3 printer, which prints parts with layer thicknesses on the order of 125μm. The second printer used is a "Big Area Additive Manufacturing" (BAAM) 3D-printer developed at Oak Ridge National Laboratory. The BAAM prints parts with a layer thicknesses of 4.06 mm. Of particular interest is the temperature of the previously deposited layer as the new hot layer is about to be extruded onto it. The two layers are expected have a stronger bond if the temperature of the substrate layer is above the glass transition temperature. This paper describes the measurement technique and results for a study of temperature decay and substrate layer temperature for ABS thermoplastic with and without the addition of chopped carbon fibers.

  11. 3D Printing of Shape Memory Polymers for Flexible Electronic Devices.

    PubMed

    Zarek, Matt; Layani, Michael; Cooperstein, Ido; Sachyani, Ela; Cohn, Daniel; Magdassi, Shlomo

    2016-06-01

    The formation of 3D objects composed of shape memory polymers for flexible electronics is described. Layer-by-layer photopolymerization of methacrylated semicrystalline molten macromonomers by a 3D digital light processing printer enables rapid fabrication of complex objects and imparts shape memory functionality for electrical circuits.

  12. Adaptive optimal quantization for 3D mesh representation in the spherical coordinate system

    NASA Astrophysics Data System (ADS)

    Ahn, Jeong-Hwan; Ho, Yo-Sung

    1998-12-01

    In recent days, applications using 3D models are increasing. Since the 3D model contains a huge amount of information, compression of the 3D model data is necessary for efficient storage or transmission. In this paper, we propose an adaptive encoding scheme to compress the geometry information of the 3D model. Using the Levinson-Durbin algorithm, the encoder first predicts vertex positions along a vertex spanning tree. After each prediction error is normalized, the prediction error vector of each vertex point is represented in the spherical coordinate system (r,(theta) ,(phi) ). Each r is then quantizes by an optimal uniform quantizer. A pair of each ((theta) ,(phi) ) is also successively encoded by partitioning the surface of the sphere according to the quantized value of r. The proposed scheme demonstrates improved coding efficiency by exploiting the statistical properties of r and ((theta) ,(phi) ).

  13. A new neural net approach to robot 3D perception and visuo-motor coordination

    NASA Technical Reports Server (NTRS)

    Lee, Sukhan

    1992-01-01

    A novel neural network approach to robot hand-eye coordination is presented. The approach provides a true sense of visual error servoing, redundant arm configuration control for collision avoidance, and invariant visuo-motor learning under gazing control. A 3-D perception network is introduced to represent the robot internal 3-D metric space in which visual error servoing and arm configuration control are performed. The arm kinematic network performs the bidirectional association between 3-D space arm configurations and joint angles, and enforces the legitimate arm configurations. The arm kinematic net is structured by a radial-based competitive and cooperative network with hierarchical self-organizing learning. The main goal of the present work is to demonstrate that the neural net representation of the robot 3-D perception net serves as an important intermediate functional block connecting robot eyes and arms.

  14. Polymer physics of chromosome large-scale 3D organisation.

    PubMed

    Chiariello, Andrea M; Annunziatella, Carlo; Bianco, Simona; Esposito, Andrea; Nicodemi, Mario

    2016-07-13

    Chromosomes have a complex architecture in the cell nucleus, which serves vital functional purposes, yet its structure and folding mechanisms remain still incompletely understood. Here we show that genome-wide chromatin architecture data, as mapped by Hi-C methods across mammalian cell types and chromosomes, are well described by classical scaling concepts of polymer physics, from the sub-Mb to chromosomal scales. Chromatin is a complex mixture of different regions, folded in the conformational classes predicted by polymer thermodynamics. The contact matrix of the Sox9 locus, a region linked to severe human congenital diseases, is derived with high accuracy in mESCs and its molecular determinants identified by the theory; Sox9 self-assembles hierarchically in higher-order domains, involving abundant many-body contacts. Our approach is also applied to the Bmp7 locus. Finally, the model predictions on the effects of mutations on folding are tested against available data on a deletion in the Xist locus. Our results can help progressing new diagnostic tools for diseases linked to chromatin misfolding.

  15. Polymer physics of chromosome large-scale 3D organisation

    NASA Astrophysics Data System (ADS)

    Chiariello, Andrea M.; Annunziatella, Carlo; Bianco, Simona; Esposito, Andrea; Nicodemi, Mario

    2016-07-01

    Chromosomes have a complex architecture in the cell nucleus, which serves vital functional purposes, yet its structure and folding mechanisms remain still incompletely understood. Here we show that genome-wide chromatin architecture data, as mapped by Hi-C methods across mammalian cell types and chromosomes, are well described by classical scaling concepts of polymer physics, from the sub-Mb to chromosomal scales. Chromatin is a complex mixture of different regions, folded in the conformational classes predicted by polymer thermodynamics. The contact matrix of the Sox9 locus, a region linked to severe human congenital diseases, is derived with high accuracy in mESCs and its molecular determinants identified by the theory; Sox9 self-assembles hierarchically in higher-order domains, involving abundant many-body contacts. Our approach is also applied to the Bmp7 locus. Finally, the model predictions on the effects of mutations on folding are tested against available data on a deletion in the Xist locus. Our results can help progressing new diagnostic tools for diseases linked to chromatin misfolding.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn-Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi2O(1,3,5-BTC)2]n (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi4O2(COO)12 clusters which are further connected to Mn(COO)6 fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of {413.62}{413.68}{416.65}{418.610}{422.614}{43} corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones.

  17. Optical absorption enhancement in 3D nanofibers coated on polymer substrate for photovoltaic devices.

    PubMed

    Kiani, Amirkianoosh; Venkatakrishnan, Krishnan; Tan, Bo

    2015-06-01

    Recent research in the field of photovoltaics has shown that polymer solar cells have great potential to provide low-cost, lightweight and flexible electronic devices to harvest solar energy. In this paper, we propose a new method for the generation of three-dimensional nanofibers coated on polymer substrate induced by femtosecond laser pulses. In this new method, a thin layer of polymer is irradiated by megahertz femtosecond laser pulses under ambient conditions, and a thin fibrous layer is generated on top of the polymer substrate. This method is single step; no additional materials are added, and the layers of the three-dimensional (3D) polymer nanofibrous structures are grown on top of the substrate after laser irradiation. Light spectroscopy results show significant enhancement of light absorption in the generated 3D nanofibrous layers of polymer. Finally, we suggest how to maximize the light trapping and optical absorption of the generated nanofiber cells by optimizing the laser parameters.

  18. 3D amino-induced electroless plating: a powerful toolset for localized metallization on polymer substrates.

    PubMed

    Garcia, Alexandre; Berthelot, Thomas; Viel, Pascal; Jégou, Pascale; Palacin, Serge

    2011-11-18

    The "3D amino-induced electroless plating" (3D-AIEP) process is an easy and cost-effective way to produce metallic patterns onto flexible polymer substrates with a micrometric resolution and based on the direct printing of the mask with a commercial printer. Its effectiveness is based on the covalent grafting onto substrates of a 3D polymer layer which presents the ability to entrap Pd species. Therefore, this activated Pd-loaded and 3D polymer layer acts both as a seed layer for electroless metal growth and as an interdigital layer for enhanced mechanical properties of the metallic patterns. Consequently, flexible and transparent poly(ethylene terephtalate) (PET) sheets were selectively metalized with nickel or copper patterns. The electrical properties of the obtained metallic patterns were also studied.

  19. Documentation of program AFTBDY to generate coordinate system for 3D after body using body fitted curvilinear coordinates, part 1

    NASA Technical Reports Server (NTRS)

    Kumar, D.

    1980-01-01

    The computer program AFTBDY generates a body fitted curvilinear coordinate system for a wedge curved after body. This wedge curved after body is being used in an experimental program. The coordinate system generated by AFTBDY is used to solve 3D compressible N.S. equations. The coordinate system in the physical plane is a cartesian x,y,z system, whereas, in the transformed plane a rectangular xi, eta, zeta system is used. The coordinate system generated is such that in the transformed plane coordinate spacing in the xi, eta, zeta direction is constant and equal to unity. The physical plane coordinate lines in the different regions are clustered heavily or sparsely depending on the regions where physical quantities to be solved for by the N.S. equations have high or low gradients. The coordinate distribution in the physical plane is such that x stays constant in eta and zeta direction, whereas, z stays constant in xi and eta direction. The desired distribution in x and z is input to the program. Consequently, only the y-coordinate is solved for by the program AFTBDY.

  20. Measuring a hidden coordinate: Rate-exchange kinetics from 3D correlation functions.

    PubMed

    Berg, Mark A; Darvin, Jason R

    2016-08-07

    Nonexponential kinetics imply the existence of at least one slow variable other than the observable, that is, the system has a "hidden" coordinate. We develop a simple, but general, model that allows multidimensional correlation functions to be calculated for these systems. Homogeneous and heterogeneous mechanisms are both included, and slow exchange of the rates is allowed. This model shows that 2D and 3D correlation functions of the observable measure the distribution and kinetics of the hidden coordinate controlling the rate exchange. Both the mean exchange time and the shape of the exchange relaxation are measurable. However, complications arise because higher correlation functions are sums of multiple "pathways," each of which measures different dynamics. Only one 3D pathway involves exchange dynamics. Care must be used to extract exchange dynamics without contamination from other processes.

  1. Testing for memory-free spectroscopic coordinates by 3D IR exchange spectroscopy

    PubMed Central

    Borek, Joanna A.; Perakis, Fivos; Hamm, Peter

    2014-01-01

    Using 3D infrared (IR) exchange spectroscopy, the ultrafast hydrogen-bond forming and breaking (i.e., complexation) kinetics of phenol to benzene in a benzene/CCl4 mixture is investigated. By introducing a third time point at which the hydrogen-bonding state of phenol is measured (in comparison with 2D IR exchange spectroscopy), the spectroscopic method can serve as a critical test of whether the spectroscopic coordinate used to observe the exchange process is a memory-free, or Markovian, coordinate. For the system under investigation, the 3D IR results suggest that this is not the case. This conclusion is reconfirmed by accompanying molecular dynamics simulations, which furthermore reveal that the non-Markovian kinetics is caused by the heterogeneous structure of the mixed solvent. PMID:25002483

  2. 3-D inversion of gravity data in spherical coordinates with application to the GRAIL data

    NASA Astrophysics Data System (ADS)

    Liang, Qing; Chen, Chao; Li, Yaoguo

    2014-06-01

    Three-dimensional (3-D) inversion of gravity data has been widely used to reconstruct the density distributions of ore bodies, basins, crust, lithosphere, and upper mantle. For global model of 3-D density structures of planetary interior, such as the Earth, the Moon, or Mars, it is necessary to use an inversion algorithm that operates in the spherical coordinates. We develop a 3-D inversion algorithm formulated with specially designed model objective function and radial weighting function in the spherical coordinates. We present regional and global synthetic examples to illustrate the capability of the algorithm. The inverted results show density distribution features consistent with the true models. We also apply the algorithm to a set of lunar Bouguer gravity anomaly derived from the Gravity Recovery and Interior Laboratory (GRAIL) gravity field and obtain a lunar 3-D density distribution. High-density anomalies are clearly identified underlying lunar basins, a wide region of the lateral density heterogeneities that exist beneath the South Pole-Aitken basin are found, and low-density anomalies are distributed beneath the Feldspathic Highlands Terrane on the lunar far-side. The consistency of these results with those obtained independently from other existing methods verifies the newly developed algorithm.

  3. Mobile large scale 3D coordinate measuring system based on network of rotating laser automatic theodolites

    NASA Astrophysics Data System (ADS)

    Liu, Zhigang; Liu, Zhongzheng; Wu, Jianwei; Xu, Yaozhong

    2010-08-01

    This paper presents a mobile 3D coordinate measuring system for large scale metrology. This system is composed of a network of rotating laser automatic theodolites (N-RLATs) and a portable touch probe. In the N-RLAT system, each RLAT consists of two laser fans which rotate about its own Z axis at a constant speed and scan the whole metrology space. The optical sensors mounted on the portable touch probe receive the sweeping laser fans and generate the corresponding pulse signals, which establish a relationship between rotating angle of laser fan and time, and then the space angle measurement is converted into the corresponding peak time precision measurement of pulse signal. The rotating laser fans are modeled mathematically as a time varying parametrical vector in its local framework. A two steps on-site calibration method for solving the parameters of each RLAT and coordinate transformation among the N-RLATs. The portable probe is composed of optical sensors array with specified geometrical features and a touch point, on which the coordinates of optical sensors is determined by the N-RLATs and the touch point is estimated by solving a non-linear system. A prototype mobile 3D coordinate measuring system is developed and experiment results show its validity.

  4. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    SciTech Connect

    Nune, Satish K.; Thallapally, Praveen K.; McGrail, Benard Peter; Annapureddy, Harsha V. R.; Dang, Liem X.; Mei, Donghai; Karri, Naveen; Alvine, Kyle J.; Olszta, Matthew J.; Arey, Bruce W.; Dohnalkova, Alice

    2015-10-07

    Nanoscale porous coordination polymers were synthesized using simple wet chemical method. The effect of various polymer surfactants on colloidal stability and shape selectivity was investigated. Our results suggest that the nanoparticles exhibited significantly improved adsorption kinetics compared to bulk crystals due to decreased diffusion path lengths and preferred crystal plane interaction.

  5. Coordination of gaze and hand movements for tracking and tracing in 3D.

    PubMed

    Gielen, Constantinus C A M; Dijkstra, Tjeerd M H; Roozen, Irene J; Welten, Joke

    2009-03-01

    In this study we have investigated movements in three-dimensional space. Since most studies have investigated planar movements (like ellipses, cloverleaf shapes and "figure eights") we have compared two generalizations of the two-thirds power law to three dimensions. In particular we have tested whether the two-thirds power law could be best described by tangential velocity and curvature in a plane (compatible with the idea of planar segmentation) or whether tangential velocity and curvature should be calculated in three dimensions. We defined total curvature in three dimensions as the square root of the sum of curvature squared and torsion squared. The results demonstrate that most of the variance is explained by tangential velocity and total curvature. This indicates that all three orthogonal components of movements in 3D are equally important and that movements are truly 3D and do not reflect a concatenation of 2D planar movement segments. In addition, we have studied the coordination of eye and hand movements in 3D by measuring binocular eye movements while subjects move the finger along a curved path. The results show that the directional component and finger position almost superimpose when subjects track a target moving in 3D. However, the vergence component of gaze leads finger position by about 250msec. For drawing (tracing) the path of a visible 3D shape, the directional component of gaze leads finger position by about 225msec, and the vergence component leads finger position by about 400msec. These results are compatible with the idea that gaze leads hand position during drawing movement to assist prediction and planning of hand position in 3D space.

  6. Pattern Transformation of Heat-Shrinkable Polymer by Three-Dimensional (3D) Printing Technique

    PubMed Central

    Zhang, Quan; Yan, Dong; Zhang, Kai; Hu, Gengkai

    2015-01-01

    A significant challenge in conventional heat-shrinkable polymers is to produce controllable microstructures. Here we report that the polymer material fabricated by three-dimensional (3D) printing technique has a heat-shrinkable property, whose initial microstructure can undergo a spontaneous pattern transformation under heating. The underlying mechanism is revealed by evaluating internal strain of the printed polymer from its fabricating process. It is shown that a uniform internal strain is stored in the polymer during the printing process and can be released when heated above its glass transition temperature. Furthermore, the internal strain can be used to trigger the pattern transformation of the heat-shrinkable polymer in a controllable way. Our work provides insightful ideas to understand a novel mechanism on the heat-shrinkable effect of printed material, but also to present a simple approach to fabricate heat-shrinkable polymer with a controllable thermo-structural response. PMID:25757881

  7. Infinite Coordination Polymer Nano- and Micro-Particles

    DTIC Science & Technology

    2015-06-12

    SECURITY CLASSIFICATION OF: Infinite coordination polymer (ICP) particles and metal- organic frameworks (MOFs) are attractive materials for a diverse...Coordination Polymer Nano- and Micro- Particles Report Title Infinite coordination polymer (ICP) particles and metal- organic frameworks (MOFs) are...Abstract Infinite coordination polymer (ICP) particles and metal- organic frameworks (MOFs) are attractive materials for a diverse array of

  8. 3D optical printing of piezoelectric nanoparticle-polymer composite materials.

    PubMed

    Kim, Kanguk; Zhu, Wei; Qu, Xin; Aaronson, Chase; McCall, William R; Chen, Shaochen; Sirbuly, Donald J

    2014-10-28

    Here we demonstrate that efficient piezoelectric nanoparticle-polymer composite materials can be optically printed into three-dimensional (3D) microstructures using digital projection printing. Piezoelectric polymers were fabricated by incorporating barium titanate (BaTiO3, BTO) nanoparticles into photoliable polymer solutions such as polyethylene glycol diacrylate and exposing to digital optical masks that could be dynamically altered to generate user-defined 3D microstructures. To enhance the mechanical-to-electrical conversion efficiency of the composites, the BTO nanoparticles were chemically modified with acrylate surface groups, which formed direct covalent linkages with the polymer matrix under light exposure. The composites with a 10% mass loading of the chemically modified BTO nanoparticles showed piezoelectric coefficients (d(33)) of ∼ 40 pC/N, which were over 10 times larger than composites synthesized with unmodified BTO nanoparticles and over 2 times larger than composites containing unmodified BTO nanoparticles and carbon nanotubes to boost mechanical stress transfer efficiencies. These results not only provide a tool for fabricating 3D piezoelectric polymers but lay the groundwork for creating highly efficient piezoelectric polymer materials via nanointerfacial tuning.

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

    SciTech Connect

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

    2015-05-15

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

  10. Suppression of electron-hole correlations in 3D polymer materials.

    PubMed

    Puschnig, Peter; Ambrosch-Draxl, Claudia

    2002-07-29

    We present an ab initio study of the optical absorption spectra of isolated as well as crystalline trans-polyacetylene. We include excitonic effects by solving the Bethe-Salpeter equation for the electron-hole two-particle correlation function. We observe that the strength of the electron-hole interactions drastically reduces when going from an isolated polymer chain to a crystalline arrangement. This is not only a result of enhanced screening in the 3D material, but also of the increased spatial extent of the exciton perpendicular to the polymer chains. We point out that these findings apply to crystalline phases of conjugated polymers and molecular crystals in general.

  11. Reconstruction and Visualization of Coordinated 3D Cell Migration Based on Optical Flow.

    PubMed

    Kappe, Christopher P; Schütz, Lucas; Gunther, Stefan; Hufnagel, Lars; Lemke, Steffen; Leitte, Heike

    2016-01-01

    Animal development is marked by the repeated reorganization of cells and cell populations, which ultimately determine form and shape of the growing organism. One of the central questions in developmental biology is to understand precisely how cells reorganize, as well as how and to what extent this reorganization is coordinated. While modern microscopes can record video data for every cell during animal development in 3D+t, analyzing these videos remains a major challenge: reconstruction of comprehensive cell tracks turned out to be very demanding especially with decreasing data quality and increasing cell densities. In this paper, we present an analysis pipeline for coordinated cellular motions in developing embryos based on the optical flow of a series of 3D images. We use numerical integration to reconstruct cellular long-term motions in the optical flow of the video, we take care of data validation, and we derive a LIC-based, dense flow visualization for the resulting pathlines. This approach allows us to handle low video quality such as noisy data or poorly separated cells, and it allows the biologists to get a comprehensive understanding of their data by capturing dynamic growth processes in stills. We validate our methods using three videos of growing fruit fly embryos.

  12. Continental water storage inferred from 3-D GPS coordinates in Danube Basin

    NASA Astrophysics Data System (ADS)

    van Dam, T. M.; Wang, L.; Weigelt, M. L. B.; Tourian, M. J.; Chen, Q.; Sneeuw, N. J.

    2014-12-01

    GPS coordinates time series contain viable information about continental water storage (CWS) at global and regional scale. The permanent GPS network of GPS stations around the Earth recorded more than 15 years of data, which comprise the elastic response of the bed rock movements induced by mass loading. The inversion of the observed displacements, yields mass variations which can be interpreted as CWS under the condition that no other mass loading is interfering. GPS-derived CWS offers complimentary information to the widely used CWS determination by GRACE but is also able to mitigate a possible loss of data in case the GRACE mission ends before the launch of the GRACE Follow-On mission. GPS also allows increasing the temporal resolution (weekly from GPS versus monthly from GRACE) and the spatial resolution (especially in the regions with dense GPS networks). Here, we determine the weekly mass variations from GPS 3-D coordinates by using mass-loading Green's function in six Danube sub-basins. The results are validated against GRACE and hydro-meteorological models. We also demonstrate the contribution of GPS horizontals for regional water storage and provide insights into the benefits and limitations of 3-D GPS inversions for regional water storage.

  13. Pt-Free Counter Electrodes with Carbon Black and 3D Network Epoxy Polymer Composites

    NASA Astrophysics Data System (ADS)

    Kang, Gyeongho; Choi, Jongmin; Park, Taiho

    2016-03-01

    Carbon black (CB) and a 3D network epoxy polymer composite, representing dual functions for conductive corrosion protective layer (CCPL) and catalytic layer (CL) by the control of CB weight ratio against polymer is developed. Our strategy provides a proper approach which applies high catalytic ability and chemical stability of CB in corrosive triiodide/iodide (I3-/I-) redox electrolyte system. The CB and a 3D network epoxy polymer composite coated on the stainless steel (SS) electrode to alternate counter electrodes in dye sensitized solar cells (DSSCs). A two-step spray pyrolysis process is used to apply a solution containing epoxy monomers and a polyfunctional amine hardener with 6 wt% CB to a SS substrate, which forms a CCPL. Subsequently, an 86 wt% CB is applied to form a CL. The excellent catalytic properties and corrosion protective properties of the CB and 3D network epoxy polymer composites produce efficient counter electrodes that can replace fluorine-doped tin oxide (FTO) with CCPL/SS and Pt/FTO with CL/CCPL/SS in DSSCs. This approach provides a promising approach to the development of efficient, stable, and cheap solar cells, paving the way for large-scale commercialization.

  14. Pt-Free Counter Electrodes with Carbon Black and 3D Network Epoxy Polymer Composites

    PubMed Central

    Kang, Gyeongho; Choi, Jongmin; Park, Taiho

    2016-01-01

    Carbon black (CB) and a 3D network epoxy polymer composite, representing dual functions for conductive corrosion protective layer (CCPL) and catalytic layer (CL) by the control of CB weight ratio against polymer is developed. Our strategy provides a proper approach which applies high catalytic ability and chemical stability of CB in corrosive triiodide/iodide (I3−/I−) redox electrolyte system. The CB and a 3D network epoxy polymer composite coated on the stainless steel (SS) electrode to alternate counter electrodes in dye sensitized solar cells (DSSCs). A two-step spray pyrolysis process is used to apply a solution containing epoxy monomers and a polyfunctional amine hardener with 6 wt% CB to a SS substrate, which forms a CCPL. Subsequently, an 86 wt% CB is applied to form a CL. The excellent catalytic properties and corrosion protective properties of the CB and 3D network epoxy polymer composites produce efficient counter electrodes that can replace fluorine-doped tin oxide (FTO) with CCPL/SS and Pt/FTO with CL/CCPL/SS in DSSCs. This approach provides a promising approach to the development of efficient, stable, and cheap solar cells, paving the way for large-scale commercialization. PMID:26961256

  15. 3D scaffold alters cellular response to graphene in a polymer composite for orthopedic applications.

    PubMed

    Kumar, Sachin; Azam, Dilkash; Raj, Shammy; Kolanthai, Elayaraja; Vasu, K S; Sood, A K; Chatterjee, Kaushik

    2016-05-01

    Graphene-based polymer nanocomposites are being studied for biomedical applications. Polymer nanocomposites can be processed differently to generate planar two-dimensional (2D) substrates and porous three-dimensional (3D) scaffolds. The objective of this work was to investigate potential differences in biological response to graphene in polymer composites in the form of 2D substrates and 3D scaffolds. Polycaprolactone (PCL) nanocomposites were prepared by incorporating 1% of graphene oxide (GO) and reduced graphene oxide (RGO). GO increased modulus and strength of PCL by 44 and 22% respectively, whereas RGO increased modulus and strength by 22 and 16%, respectively. RGO increased the water contact angle of PCL from 81° to 87° whereas GO decreased it to 77°. In 2D, osteoblast proliferated 15% more on GO composites than on PCL whereas RGO composite showed 17% decrease in cell proliferation, which may be attributed to differences in water wettability. In 3D, initial cell proliferation was markedly retarded in both GO (36% lower) and RGO (55% lower) composites owing to increased roughness due to the presence of the protruding nanoparticles. Cells organized into aggregates in 3D in contrast to spread and randomly distributed cells on 2D discs due to the macro-porous architecture of the scaffolds. Increased cell-cell contact and altered cellular morphology led to significantly higher mineralization in 3D. This study demonstrates that the cellular response to nanoparticles in composites can change markedly by varying the processing route and has implications for designing orthopedic implants such as resorbable fracture fixation devices and tissue scaffolds using such nanocomposites.

  16. Fabrication of 3D polymer microstructures using electron beam lithography and nanoimprinting technologies

    NASA Astrophysics Data System (ADS)

    Chen, Kuo-Shen; Lin, I.-Kuan; Ko, Fu-Hsang

    2005-10-01

    Recently, with the advancement in bio-MEMS and micro optoelectromechanical systems (MOEMS), 3D microstructures have become increasingly important and efficient fabrication processes are currently being sought. In this paper, a novel 3D fabrication process has been proposed by utilizing the proximity effect of electron beam lithography (EBL) to create 3D microstructures on negative photoresists as the primary molds, which are subsequently transferred to their corresponding negative molds using nanoimprinting lithography (NIL), and to form the final replicas by either electroforming or polymer spin casting to reduce cost. The effect of electron backscattering on the 3D topography is firstly investigated and the relationship among the spatial distribution of electron beam irradiation, the spot size and the dosage level of irradiation is experimentally characterized in SU-8 to establish a dosage kernel distribution function. A mathematical procedure based on linear operation of this kernel function is then proposed to mimic the EBL fabrication process. The subsequent experiments indicate that the predicted surface profiles agree with the experimental results to large extent and the proposed mathematical operations are valid for the purpose of designing the fabrication process. Finally, the SU-8 primary molds are transferred to NEB to form secondary molds via the nanoimprinting process. It shows that the nanoimprinting process can essentially reproduce the shape and geometry of the primary molds. However, due to the nature of polymer-to-polymer contact printing, the elastic restitution of materials induces a slight deviation of the final device size and a further study should be made in the future to minimize such types of error. Although the above problems are reported, nevertheless, the primary experimental results indicate that this proposed fabrication process is capable of creating 3D shape microstructure in the order of 1 µm and should be useful for related

  17. Imaging Properties of 3D Printed Materials: Multi-Energy CT of Filament Polymers.

    PubMed

    Shin, James; Sandhu, Ranjit S; Shih, George

    2017-02-06

    Clinical applications of 3D printing are increasingly commonplace, likewise the frequency of inclusion of 3D printed objects on imaging studies. Although there is a general familiarity with the imaging appearance of traditional materials comprising common surgical hardware and medical devices, comparatively less is known regarding the appearance of available 3D printing materials in the consumer market. This work detailing the CT appearance of a selected number of common filament polymer classes is an initial effort to catalog these data, to provide for accurate interpretation of imaging studies incidentally or intentionally including fabricated objects. Furthermore, this information can inform the design of image-realistic tissue-mimicking phantoms for a variety of applications, with clear candidate material analogs for bone, soft tissue, water, and fat attenuation.

  18. A coordinate transformation method for calculating the 3D light intensity distribution in ICF hohlraum

    NASA Astrophysics Data System (ADS)

    Lin, Zhili; Li, Xiaoyan; Zhao, Kuixia; Chen, Xudong; Chen, Mingyu; Pu, Jixiong

    2016-06-01

    For an inertial confinement fusion (ICF) system, the light intensity distribution in the hohlraum is key to the initial plasma excitation and later laser-plasma interaction process. Based on the concept of coordinate transformation of spatial points and vector, we present a robust method with a detailed procedure that makes the calculation of the three dimensional (3D) light intensity distribution in hohlraum easily. The method is intuitive but powerful enough to solve the complex cases of random number of laser beams with arbitrary polarization states and incidence angles. Its application is exemplified in the Shenguang III Facility (SG-III) that verifies its effectiveness and it is useful for guiding the design of hohlraum structure parameter.

  19. Measuring large aspherics using a commercially available 3D-coordinate measuring machine

    NASA Astrophysics Data System (ADS)

    Otto, Wolfgang; Matthes, Axel; Schiehle, Heinz

    2000-07-01

    A CNC-controlled precision measuring machine is a very powerful tool in the optical shop not only to determine the surface figure, but also to qualify the radius of curvature and conic constant of aspherics. We used a commercially available 3D-coordinate measuring machine (CMM, ZEISS UPMC 850 CARAT S-ACC) to measure the shape of the GEMINI 1-m convex secondary mirrors at different lapping and polishing stages. To determine the measuring accuracy we compared the mechanical measurements with the results achieved by means of an interferometrical test setup. The data obtained in an early stage of polishing were evaluated in Zernike polynomials which show a very good agreement. The deviation concerning long wave rotational symmetrical errors was 20 nm rms, whereas the accuracy measuring of mid spatial frequency deviations was limited to about 100 nm rms.

  20. Quantitative 3D analysis of complex single border cell behaviors in coordinated collective cell migration.

    PubMed

    Cliffe, Adam; Doupé, David P; Sung, HsinHo; Lim, Isaac Kok Hwee; Ong, Kok Haur; Cheng, Li; Yu, Weimiao

    2017-04-04

    Understanding the mechanisms of collective cell migration is crucial for cancer metastasis, wound healing and many developmental processes. Imaging a migrating cluster in vivo is feasible, but the quantification of individual cell behaviours remains challenging. We have developed an image analysis toolkit, CCMToolKit, to quantify the Drosophila border cell system. In addition to chaotic motion, previous studies reported that the migrating cells are able to migrate in a highly coordinated pattern. We quantify the rotating and running migration modes in 3D while also observing a range of intermediate behaviours. Running mode is driven by cluster external protrusions. Rotating mode is associated with cluster internal cell extensions that could not be easily characterized. Although the cluster moves slower while rotating, individual cells retain their mobility and are in fact slightly more active than in running mode. We also show that individual cells may exchange positions during migration.

  1. A coordinate-free method for the analysis of 3D facial change

    NASA Astrophysics Data System (ADS)

    Mao, Zhili; Siebert, Jan Paul; Cockshott, W. Paul; Ayoub, Ashraf Farouk

    2004-05-01

    Euclidean Distance Matrix Analysis (EDMA) is widely held as the most important coordinate-free method by which to analyze landmarks. It has been used extensively in the field of medical anthropometry and has already produced many useful results. Unfortunately this method renders little information regarding the surface on which these points are located and accordingly is inadequate for the 3D analysis of surface anatomy. Here we shall present a new inverse surface flatness metric, the ratio between the Geodesic and the Euclidean inter-landmark distances. Because this metric also only reflects one aspect of three-dimensional shape, i.e. surface flatness, we have combined it with the Euclidean distance to investigate 3D facial change. The goal of this investigation is to be able to analyze three-dimensional facial change in terms of bilateral symmetry as encoded both by surface flatness and by geometric configuration. Our initial study, based on 25 models of surgically managed children (unilateral cleft lip repair) and 40 models of control children at the age of 2 years, indicates that the faces of the surgically managed group were found to be significantly less symmetric than those of the control group in terms of surface flatness, geometric configuration and overall symmetry.

  2. Facile 3D Metal Electrode Fabrication for Energy Applications via Inkjet Printing and Shape Memory Polymer

    NASA Astrophysics Data System (ADS)

    Roberts, R. C.; Wu, J.; Hau, N. Y.; Chang, Y. H.; Feng, S. P.; Li, D. C.

    2014-11-01

    This paper reports on a simple 3D metal electrode fabrication technique via inkjet printing onto a thermally contracting shape memory polymer (SMP) substrate. Inkjet printing allows for the direct patterning of structures from metal nanoparticle bearing liquid inks. After deposition, these inks require thermal curing steps to render a stable conductive film. By printing onto a SMP substrate, the metal nanoparticle ink can be cured and substrate shrunk simultaneously to create 3D metal microstructures, forming a large surface area topology well suited for energy applications. Polystyrene SMP shrinkage was characterized in a laboratory oven from 150-240°C, resulting in a size reduction of 1.97-2.58. Silver nanoparticle ink was patterned into electrodes, shrunk, and the topology characterized using scanning electron microscopy. Zinc-Silver Oxide microbatteries were fabricated to demonstrate the 3D electrodes compared to planar references. Characterization was performed using 10M potassium hydroxide electrolyte solution doped with zinc oxide (57g/L). After a 300s oxidation at 3Vdc, the 3D electrode battery demonstrated a 125% increased capacity over the reference cell. Reference cells degraded with longer oxidations, but the 3D electrodes were fully oxidized for 4 hours, and exhibited a capacity of 5.5mA-hr/cm2 with stable metal performance.

  3. The fabrication of polymer-nanocone-based 3D Au nanoparticle array and its SERS performance

    NASA Astrophysics Data System (ADS)

    Zhao, Wenning; Wu, Yiyao; Liu, Xiaoguang; Xu, Yebin; Wang, Shuangbao; Xu, Zhimou

    2017-01-01

    By combining conical-pore-AAO template and NIL technology, we realized the transfer of three-dimensional nanoparticle array to polymer materials. Au nanoparticles were deposited on the surface of conical-pore-AAO template, then the nanostructure was duplicated onto the polymer wafer via NIL method and the nanoparticles were inlaid onto the nanocones. Polymer-nanocone-based 3D Au nanoparticle array was obtained. The product possesses excellent flexibility and transparency in visual and infrared range. As a new class of SERS substrate, the product exhibits excellent sensitivity and reproducibility. Compared with the traditional SERS substrates, it provides unique advantages, such as being flexible, transparent, lightweight, portable, easily handled and low cost.

  4. 3D fabrication of all-polymer conductive microstructures by two photon polymerization.

    PubMed

    Kurselis, Kestutis; Kiyan, Roman; Bagratashvili, Victor N; Popov, Vladimir K; Chichkov, Boris N

    2013-12-16

    A technique to fabricate electrically conductive all-polymer 3D microstructures is reported. Superior conductivity, high spatial resolution and three-dimensionality are achieved by successive application of two-photon polymerization and in situ oxidative polymerization to a bi-component formulation, containing a photosensitive host matrix and an intrinsically conductive polymer precursor. By using polyethylene glycol diacrylate (PEG-DA) and 3,4-ethylenedioxythiophene (EDOT), the conductivity of 0.04 S/cm is reached, which is the highest value for the two-photon polymerized all-polymer microstructures to date. The measured electrical conductivity dependency on the EDOT concentration indicates percolation phenomenon and a three-dimensional nature of the conductive pathways. Tunable conductivity, biocompatibility, and environmental stability are the characteristics offered by PEG-DA/EDOT blends which can be employed in biomedicine, MEMS, microfluidics, and sensorics.

  5. 3D Printing: 3D Printing of Shape Memory Polymers for Flexible Electronic Devices (Adv. Mater. 22/2016).

    PubMed

    Zarek, Matt; Layani, Michael; Cooperstein, Ido; Sachyani, Ela; Cohn, Daniel; Magdassi, Shlomo

    2016-06-01

    On page 4449, D. Cohn, S. Magdassi, and co-workers describe a general and facile method based on 3D printing of methacrylated macromonomers to fabricate shape-memory objects that can be used in flexible and responsive electrical circuits. Such responsive objects can be used in the fabrication of soft robotics, minimal invasive medical devices, sensors, and wearable electronics. The use of 3D printing overcomes the poor processing characteristics of thermosets and enables complex geometries that are not easily accessible by other techniques.

  6. Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

    PubMed Central

    Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

    2015-01-01

    The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies. PMID:26677949

  7. 3D printed polymers toxicity profiling: a caution for biodevice applications

    NASA Astrophysics Data System (ADS)

    Zhu, Feng; Skommer, Joanna; Friedrich, Timo; Kaslin, Jan; Wlodkowic, Donald

    2015-12-01

    A recent revolution in additive manufacturing technologies and access to 3D Computer Assisted Design (CAD) software has spurred an explosive growth of new technologies in biomedical engineering. This includes biomodels for diagnosis, surgical training, hard and soft tissue replacement, biodevices and tissue engineering. Moreover, recent developments in high-definition additive manufacturing systems such as Multi-Jet Modelling (MJM) and Stereolithography (SLA), capable of reproducing feature sizes close to 100 μm, promise brand new capabilities in fabrication of optical-grade biomicrofluidic Lab-on-a-Chip and MEMS devices. Compared with other rapid prototyping technologies such as soft lithography and infrared laser micromachining in PMMA, SLA and MJM systems can enable user-friendly production of prototypes, superior feature reproduction quality and comparable levels of optical transparency. Prospectively they can revolutionize fabrication of microfluidic devices with complex geometric features and eliminate the need to use clean room environment and conventional microfabrication techniques. In this work we demonstrate preliminary data on toxicity profiling of a panel of common polymers used in 3D printing applications. The main motivation of our work was to evaluate toxicity profiles of most commonly used polymers using standardized biotests according to OECD guidelines for testing of chemic risk assessment. Our work for the first time provides a multispecies view of potential dangers and limitation for building biocompatible devices using FDM, SLA and MJM additive manufacturing systems. Our work shows that additive manufacturing holds significant promise for fabricating LOC and MEMS but requires caution when selecting systems and polymers due to toxicity exhibited by some 3D printing polymers.

  8. Performance of a commercial optical CT scanner and polymer gel dosimeters for 3-D dose verification.

    PubMed

    Xu, Y; Wuu, Cheng-Shie; Maryanski, Marek J

    2004-11-01

    Performance analysis of a commercial three-dimensional (3-D) dose mapping system based on optical CT scanning of polymer gels is presented. The system consists of BANG 3 polymer gels (MGS Research, Inc., Madison, CT), OCTOPUS laser CT scanner (MGS Research, Inc., Madison, CT), and an in-house developed software for optical CT image reconstruction and 3-D dose distribution comparison between the gel, film measurements and the radiation therapy treatment plans. Various sources of image noise (digitization, electronic, optical, and mechanical) generated by the scanner as well as optical uniformity of the polymer gel are analyzed. The performance of the scanner is further evaluated in terms of the reproducibility of the data acquisition process, the uncertainties at different levels of reconstructed optical density per unit length and the effects of scanning parameters. It is demonstrated that for BANG 3 gel phantoms held in cylindrical plastic containers, the relative dose distribution can be reproduced by the scanner with an overall uncertainty of about 3% within approximately 75% of the radius of the container. In regions located closer to the container wall, however, the scanner generates erroneous optical density values that arise from the reflection and refraction of the laser rays at the interface between the gel and the container. The analysis of the accuracy of the polymer gel dosimeter is exemplified by the comparison of the gel/OCT-derived dose distributions with those from film measurements and a commercial treatment planning system (Cadplan, Varian Corporation, Palo Alto, CA) for a 6 cm x 6 cm single field of 6 MV x rays and a 3-D conformal radiotherapy (3DCRT) plan. The gel measurements agree with the treatment plans and the film measurements within the "3%-or-2 mm" criterion throughout the usable, artifact-free central region of the gel volume. Discrepancies among the three data sets are analyzed.

  9. Massively parallel patterning of complex 2D and 3D functional polymer brushes by polymer pen lithography.

    PubMed

    Xie, Zhuang; Chen, Chaojian; Zhou, Xuechang; Gao, Tingting; Liu, Danqing; Miao, Qian; Zheng, Zijian

    2014-08-13

    We report the first demonstration of centimeter-area serial patterning of complex 2D and 3D functional polymer brushes by high-throughput polymer pen lithography. Arbitrary 2D and 3D structures of poly(glycidyl methacrylate) (PGMA) brushes are fabricated over areas as large as 2 cm × 1 cm, with a remarkable throughput being 3 orders of magnitudes higher than the state-of-the-arts. Patterned PGMA brushes are further employed as resist for fabricating Au micro/nanostructures and hard molds for the subsequent replica molding of soft stamps. On the other hand, these 2D and 3D PGMA brushes are also utilized as robust and versatile platforms for the immobilization of bioactive molecules to form 2D and 3D patterned DNA oligonucleotide and protein chips. Therefore, this low-cost, yet high-throughput "bench-top" serial fabrication method can be readily applied to a wide range of fields including micro/nanofabrication, optics and electronics, smart surfaces, and biorelated studies.

  10. Development of a 3D polymer reinforced calcium phosphate cement scaffold for cranial bone tissue engineering

    NASA Astrophysics Data System (ADS)

    Alge, Daniel L.

    The repair of critical-sized cranial bone defects represents an important clinical challenge. The limitations of autografts and alloplastic materials make a bone tissue engineering strategy desirable, but success depends on the development of an appropriate scaffold. Key scaffold properties include biocompatibility, osteoconductivity, sufficient strength to maintain its structure, and resorbability. Furthermore, amenability to rapid prototyping fabrication methods is desirable, as these approaches offer precise control over scaffold architecture and have the potential for customization. While calcium phosphate cements meet many of these criteria due to their composition and their injectability, which can be leveraged for scaffold fabrication via indirect casting, their mechanical properties are a major limitation. Thus, the overall goal of this work was to develop a 3D polymer reinforced calcium phosphate cement scaffold for use in cranial bone tissue engineering. Dicalcium phosphate dihydrate (DCPD) setting cements are of particular interest because of their excellent resorbability. We demonstrated for the first time that DCPD cement can be prepared from monocalcium phosphate monohydrate (MCPM)/hydroxyapatite (HA) mixtures. However, subsequent characterization revealed that MCPM/HA cements rapidly convert to HA during degradation, which is undesirable and led us to choose a more conventional formulation for scaffold fabrication. In addition, we developed a novel method for calcium phosphate cement reinforcement that is based on infiltrating a pre-set cement structure with a polymer, and then crosslinking the polymer in situ. Unlike prior methods of cement reinforcement, this method can be applied to the reinforcement of 3D scaffolds fabricated by indirect casting. Using our novel method, composites of poly(propylene fumarate) (PPF) reinforced DCPD were prepared and demonstrated as excellent candidate scaffold materials, as they had increased strength and ductility

  11. Estimation of 3-D pore network coordination number of rocks from watershed segmentation of a single 2-D image

    NASA Astrophysics Data System (ADS)

    Rabbani, Arash; Ayatollahi, Shahab; Kharrat, Riyaz; Dashti, Nader

    2016-08-01

    In this study, we have utilized 3-D micro-tomography images of real and synthetic rocks to introduce two mathematical correlations which estimate the distribution parameters of 3-D coordination number using a single 2-D cross-sectional image. By applying a watershed segmentation algorithm, it is found that the distribution of 3-D coordination number is acceptably predictable by statistical analysis of the network extracted from 2-D images. In this study, we have utilized 25 volumetric images of rocks in order to propose two mathematical formulas. These formulas aim to approximate the average and standard deviation of coordination number in 3-D pore networks. Then, the formulas are applied for five independent test samples to evaluate the reliability. Finally, pore network flow modeling is used to find the error of absolute permeability prediction using estimated and measured coordination numbers. Results show that the 2-D images are considerably informative about the 3-D network of the rocks and can be utilized to approximate the 3-D connectivity of the porous spaces with determination coefficient of about 0.85 that seems to be acceptable considering the variety of the studied samples.

  12. Microwave dielectric characterisation of 3D-printed BaTiO3/ABS polymer composites

    PubMed Central

    Castles, F.; Isakov, D.; Lui, A.; Lei, Q.; Dancer, C. E. J.; Wang, Y.; Janurudin, J. M.; Speller, S. C.; Grovenor, C. R. M.; Grant, P. S.

    2016-01-01

    3D printing is used extensively in product prototyping and continues to emerge as a viable option for the direct manufacture of final parts. It is known that dielectric materials with relatively high real permittivity—which are required in important technology sectors such as electronics and communications—may be 3D printed using a variety of techniques. Among these, the fused deposition of polymer composites is particularly straightforward but the range of dielectric permittivities available through commercial feedstock materials is limited. Here we report on the fabrication of a series of composites composed of various loadings of BaTiO3 microparticles in the polymer acrylonitrile butadiene styrene (ABS), which may be used with a commercial desktop 3D printer to produce printed parts containing user-defined regions with high permittivity. The microwave dielectric properties of printed parts with BaTiO3 loadings up to 70 wt% were characterised using a 15 GHz split post dielectric resonator and had real relative permittivities in the range 2.6–8.7 and loss tangents in the range 0.005–0.027. Permittivities were reproducible over the entire process, and matched those of bulk unprinted materials, to within ~1%, suggesting that the technique may be employed as a viable manufacturing process for dielectric composites. PMID:26940381

  13. Microwave dielectric characterisation of 3D-printed BaTiO3/ABS polymer composites

    NASA Astrophysics Data System (ADS)

    Castles, F.; Isakov, D.; Lui, A.; Lei, Q.; Dancer, C. E. J.; Wang, Y.; Janurudin, J. M.; Speller, S. C.; Grovenor, C. R. M.; Grant, P. S.

    2016-03-01

    3D printing is used extensively in product prototyping and continues to emerge as a viable option for the direct manufacture of final parts. It is known that dielectric materials with relatively high real permittivity—which are required in important technology sectors such as electronics and communications—may be 3D printed using a variety of techniques. Among these, the fused deposition of polymer composites is particularly straightforward but the range of dielectric permittivities available through commercial feedstock materials is limited. Here we report on the fabrication of a series of composites composed of various loadings of BaTiO3 microparticles in the polymer acrylonitrile butadiene styrene (ABS), which may be used with a commercial desktop 3D printer to produce printed parts containing user-defined regions with high permittivity. The microwave dielectric properties of printed parts with BaTiO3 loadings up to 70 wt% were characterised using a 15 GHz split post dielectric resonator and had real relative permittivities in the range 2.6–8.7 and loss tangents in the range 0.005–0.027. Permittivities were reproducible over the entire process, and matched those of bulk unprinted materials, to within ~1%, suggesting that the technique may be employed as a viable manufacturing process for dielectric composites.

  14. Microwave dielectric characterisation of 3D-printed BaTiO3/ABS polymer composites.

    PubMed

    Castles, F; Isakov, D; Lui, A; Lei, Q; Dancer, C E J; Wang, Y; Janurudin, J M; Speller, S C; Grovenor, C R M; Grant, P S

    2016-03-04

    3D printing is used extensively in product prototyping and continues to emerge as a viable option for the direct manufacture of final parts. It is known that dielectric materials with relatively high real permittivity-which are required in important technology sectors such as electronics and communications-may be 3D printed using a variety of techniques. Among these, the fused deposition of polymer composites is particularly straightforward but the range of dielectric permittivities available through commercial feedstock materials is limited. Here we report on the fabrication of a series of composites composed of various loadings of BaTiO3 microparticles in the polymer acrylonitrile butadiene styrene (ABS), which may be used with a commercial desktop 3D printer to produce printed parts containing user-defined regions with high permittivity. The microwave dielectric properties of printed parts with BaTiO3 loadings up to 70 wt% were characterised using a 15 GHz split post dielectric resonator and had real relative permittivities in the range 2.6-8.7 and loss tangents in the range 0.005-0.027. Permittivities were reproducible over the entire process, and matched those of bulk unprinted materials, to within ~1%, suggesting that the technique may be employed as a viable manufacturing process for dielectric composites.

  15. 3D-Printed Multidrug-Eluting Stent from Graphene-Nanoplatelet-Doped Biodegradable Polymer Composite.

    PubMed

    Misra, Santosh K; Ostadhossein, Fatemeh; Babu, Ramya; Kus, Joseph; Tankasala, Divya; Sutrisno, Andre; Walsh, Kathleen A; Bromfield, Corinne R; Pan, Dipanjan

    2017-03-21

    Patients with percutaneous coronary intervention generally receive either bare metal stents or drug-eluting stents to restore the normal blood flow. However, due to the lack of stent production with an individual patient in mind, the same level of effectiveness may not be possible in treating two different clinical scenarios. This study introduces for the first time the feasibility of a patient-specific stenting process constructed from direct 3D segmentation of medical images using direct 3D printing of biodegradable polymer-graphene composite with dual drug incorporation. A biodegradable polymer-carbon composite is prepared doped with graphene nanoplatelets to achieve controlled release of combinatorics as anticoagulation and antirestenosis agents. This study develops a technology prototyped for personalized stenting. An in silico analysis is performed to optimize the stent design for printing and its prediction of sustainability under force exerted by coronary artery or blood flow. A holistic approach covering in silico to in situ-in vivo establishes the structural integrity of the polymer composite, its mechanical properties, drug loading and release control, prototyping, functional activity, safety, and feasibility of placement in coronary artery of swine.

  16. Polymer-based mesh as supports for multi-layered 3D cell culture and assays.

    PubMed

    Simon, Karen A; Park, Kyeng Min; Mosadegh, Bobak; Subramaniam, Anand Bala; Mazzeo, Aaron D; Ngo, Philip M; Whitesides, George M

    2014-01-01

    Three-dimensional (3D) culture systems can mimic certain aspects of the cellular microenvironment found in vivo, but generation, analysis and imaging of current model systems for 3D cellular constructs and tissues remain challenging. This work demonstrates a 3D culture system-Cells-in-Gels-in-Mesh (CiGiM)-that uses stacked sheets of polymer-based mesh to support cells embedded in gels to form tissue-like constructs; the stacked sheets can be disassembled by peeling the sheets apart to analyze cultured cells-layer-by-layer-within the construct. The mesh sheets leave openings large enough for light to pass through with minimal scattering, and thus allowing multiple options for analysis-(i) using straightforward analysis by optical light microscopy, (ii) by high-resolution analysis with fluorescence microscopy, or (iii) with a fluorescence gel scanner. The sheets can be patterned into separate zones with paraffin film-based decals, in order to conduct multiple experiments in parallel; the paraffin-based decal films also block lateral diffusion of oxygen effectively. CiGiM simplifies the generation and analysis of 3D culture without compromising throughput, and quality of the data collected: it is especially useful in experiments that require control of oxygen levels, and isolation of adjacent wells in a multi-zone format.

  17. Polymer-Based Mesh as Supports for Multi-layered 3D Cell Culture and Assays

    PubMed Central

    Simon, Karen A.; Park, Kyeng Min; Mosadegh, Bobak; Subramaniam, Anand Bala; Mazzeo, Aaron; Ngo, Phil M.; Whitesides, George M.

    2013-01-01

    Three-dimensional (3D) culture systems can mimic certain aspects of the cellular microenvironment found in vivo, but generation, analysis and imaging of current model systems for 3D cellular constructs and tissues remain challenging. This work demonstrates a 3D culture system – Cells-in-Gels-in-Mesh (CiGiM) – that uses stacked sheets of polymer-based mesh to support cells embedded in gels to form tissue-like constructs; the stacked sheets can be disassembled by peeling the sheets apart to analyze cultured cells—layer-by-layer—within the construct. The mesh sheets leave openings large enough for light to pass through with minimal scattering, and thus allowing multiple options for analysis—(i) using straightforward analysis by optical light microscopy, (ii) by high-resolution analysis with fluorescence microscopy, or (iii) with a fluorescence gel scanner. The sheets can be patterned into separate zones with paraffin film-based decals, in order to conduct multiple experiments in parallel; the paraffin-based decal films also block lateral diffusion of oxygen effectively. CiGiM simplifies the generation and analysis of 3D culture without compromising throughput, and quality of the data collected: it is especially useful in experiments that require control of oxygen levels, and isolation of adjacent wells in a multi-zone format. PMID:24095253

  18. 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.

  19. Mesoscale 3D manufacturing: varying focusing conditions for efficient direct laser writing of polymers

    NASA Astrophysics Data System (ADS)

    Jonušauskas, Linas; Malinauskas, Mangirdas

    2014-05-01

    In this paper, we report a novel approach for efficient fabrication of mesoscale polymer 3D microstructures. It is implemented by direct laser writing varying exposure beam focusing conditions. By carefully optimizing the fabrication parameters (laser intensity, scanning velocity/exposure time, changing objective lens) complex 3D geometries of the microstructures can be obtained rapidly. Additionally, we demonstrate this without the use of the photoinitiator as photosensitizer doped in the pre-polymer material (SZ2080). At femtosecond pulsed irradiation ~TW/cm² intensities the localized free radical polymerization is achieved via avalanche induced bond braking. Such microstructures have unique biocompatibility and optical transparency as well as optical damage threshold value. By creating the bulk part of the structure using low-NA (0.45) objective and subsequently fabricating the fine features using oil immersion high-NA (1.4) objective the manufacturing time is reduced dramatically (30x is demonstrated). Using this two objective method a prototype of functional microdevice was produced: 80 and 85 µm diameter microfluidic tubes with the fine filter consisting of 4 µm period grating structure that has 400 nm wide threads, which corresponds to a feature precision aspect ratio of ~200. Therefore, such method has great potential as a polymer fabrication tool for mesoscale optical, photonic and biomedical applications as well as highly integrated 3D µ-systems. Furthermore, the proposed approach is not limited to lithography and can be implemented in a more general type of laser writing, such as inscription within transparent materials or substractive manufacturing by ablation.

  20. NewVision: a program for interactive navigation and analysis of multiple 3-D data sets using coordinated virtual cameras.

    PubMed

    Pixton, J L; Belmont, A S

    1996-01-01

    We describe "NewVision", a program designed for rapid interactive display, sectioning, and comparison of multiple large three-dimensional (3-D) reconstructions. User tools for navigating within large 3-D data sets and selecting local subvolumes for display, combined with view caching, fast integer interpolation, and background tasking, provide highly interactive viewing of arbitrarily sized data sets on Silicon Graphics systems ranging from simple workstations to supercomputers. Multiple windows, each showing different views of the same 3-D data set, are coordinated through mapping of local coordinate systems to a single global world coordinate system. Mapping to a world coordinate system allows quantitative measurements from any open window as well as creation of linked windows in which operations such as panning, zooming, and 3-D rotations of the viewing perspective in any one window are mirrored by corresponding transformations in the views shown in other linked windows. The specific example of tracing 3-D fiber trajectories is used to demonstrate the potential of the linked window concept. A global overview of NewVision's design and organization is provided, and future development directions are briefly discussed.

  1. A polymer-based Fabry-Perot filter integrated with 3-D MEMS structures

    NASA Astrophysics Data System (ADS)

    Zhang, Ping (Cerina); Le, Kevin; Malalur-Nagaraja-Rao, Smitha; Hsu, Lun-Chen; Chiao, J.-C.

    2006-01-01

    Polymers have been considered as one of the most versatile materials in making optical devices for communication and sensor applications. They provide good optical transparency to form filters, lenses and many optical components with ease of fabrication. They are scalable and compatible in dimensions with requirements in optics and can be fabricated on inorganic substrates, such as silicon and quartz. Recent polymer synthesis also made great progresses on conductive and nonlinear polymers, opening opportunities for new applications. In this paper, we discussed hybrid-material integration of polymers on silicon-based microelectromechanical system (MEMS) devices. The motivation is to combine the advantages of demonstrated silicon-based MEMS actuators and excellent optical performance of polymers. We demonstrated the idea with a polymer-based out-of-plane Fabry-Perot filter that can be self-assembled by scratch drive actuators. We utilized a fabrication foundry service, MUMPS (Multi-User MEMS Process), to demonstrate the feasibility and flexibility of integration. The polysilicon, used as the structural material for construction of 3-D framework and actuators, has high absorption in the visible and near infrared ranges. Therefore, previous efforts using a polysilicon layer as optical interfaces suffer from high losses. We applied the organic compound materials on the silicon-based framework within the optical signal propagation path to form the optical interfaces. In this paper, we have shown low losses in the optical signal processing and feasibility of building a thin-film Fabry-Perot filter. We discussed the optical filter designs, mechanical design, actuation mechanism, fabrication issues, optical measurements, and results.

  2. Sequential Self-Folding Structures by 3D Printed Digital Shape Memory Polymers

    PubMed Central

    Mao, Yiqi; Yu, Kai; Isakov, Michael S.; Wu, Jiangtao; Dunn, Martin L.; Jerry Qi, H.

    2015-01-01

    Folding is ubiquitous in nature with examples ranging from the formation of cellular components to winged insects. It finds technological applications including packaging of solar cells and space structures, deployable biomedical devices, and self-assembling robots and airbags. Here we demonstrate sequential self-folding structures realized by thermal activation of spatially-variable patterns that are 3D printed with digital shape memory polymers, which are digital materials with different shape memory behaviors. The time-dependent behavior of each polymer allows the temporal sequencing of activation when the structure is subjected to a uniform temperature. This is demonstrated via a series of 3D printed structures that respond rapidly to a thermal stimulus, and self-fold to specified shapes in controlled shape changing sequences. Measurements of the spatial and temporal nature of self-folding structures are in good agreement with the companion finite element simulations. A simplified reduced-order model is also developed to rapidly and accurately describe the self-folding physics. An important aspect of self-folding is the management of self-collisions, where different portions of the folding structure contact and then block further folding. A metric is developed to predict collisions and is used together with the reduced-order model to design self-folding structures that lock themselves into stable desired configurations. PMID:26346202

  3. Sequential Self-Folding Structures by 3D Printed Digital Shape Memory Polymers.

    PubMed

    Mao, Yiqi; Yu, Kai; Isakov, Michael S; Wu, Jiangtao; Dunn, Martin L; Jerry Qi, H

    2015-09-08

    Folding is ubiquitous in nature with examples ranging from the formation of cellular components to winged insects. It finds technological applications including packaging of solar cells and space structures, deployable biomedical devices, and self-assembling robots and airbags. Here we demonstrate sequential self-folding structures realized by thermal activation of spatially-variable patterns that are 3D printed with digital shape memory polymers, which are digital materials with different shape memory behaviors. The time-dependent behavior of each polymer allows the temporal sequencing of activation when the structure is subjected to a uniform temperature. This is demonstrated via a series of 3D printed structures that respond rapidly to a thermal stimulus, and self-fold to specified shapes in controlled shape changing sequences. Measurements of the spatial and temporal nature of self-folding structures are in good agreement with the companion finite element simulations. A simplified reduced-order model is also developed to rapidly and accurately describe the self-folding physics. An important aspect of self-folding is the management of self-collisions, where different portions of the folding structure contact and then block further folding. A metric is developed to predict collisions and is used together with the reduced-order model to design self-folding structures that lock themselves into stable desired configurations.

  4. Sequential Self-Folding Structures by 3D Printed Digital Shape Memory Polymers

    NASA Astrophysics Data System (ADS)

    Mao, Yiqi; Yu, Kai; Isakov, Michael S.; Wu, Jiangtao; Dunn, Martin L.; Jerry Qi, H.

    2015-09-01

    Folding is ubiquitous in nature with examples ranging from the formation of cellular components to winged insects. It finds technological applications including packaging of solar cells and space structures, deployable biomedical devices, and self-assembling robots and airbags. Here we demonstrate sequential self-folding structures realized by thermal activation of spatially-variable patterns that are 3D printed with digital shape memory polymers, which are digital materials with different shape memory behaviors. The time-dependent behavior of each polymer allows the temporal sequencing of activation when the structure is subjected to a uniform temperature. This is demonstrated via a series of 3D printed structures that respond rapidly to a thermal stimulus, and self-fold to specified shapes in controlled shape changing sequences. Measurements of the spatial and temporal nature of self-folding structures are in good agreement with the companion finite element simulations. A simplified reduced-order model is also developed to rapidly and accurately describe the self-folding physics. An important aspect of self-folding is the management of self-collisions, where different portions of the folding structure contact and then block further folding. A metric is developed to predict collisions and is used together with the reduced-order model to design self-folding structures that lock themselves into stable desired configurations.

  5. Polymer optical fibers integrated directly into 3D orthogonal woven composites for sensing

    NASA Astrophysics Data System (ADS)

    Hamouda, Tamer; Seyam, Abdel-Fattah M.; Peters, Kara

    2015-02-01

    This study demonstrates that standard polymer optical fibers (POF) can be directly integrated into composites from 3D orthogonal woven preforms during the weaving process and then serve as in-situ sensors to detect damage due to bending or impact loads. Different composite samples with embedded POF were fabricated of 3D orthogonal woven composites with different parameters namely number of y-/x-layers and x-yarn density. The signal of POF was not affected significantly by the preform structure. During application of resin using VARTM technique, significant drop in backscattering level was observed due to pressure caused by vacuum on the embedded POF. Measurements of POF signal while in the final composites after resin cure indicated that the backscattering level almost returned to the original level of un-embedded POF. The POF responded to application of bending and impact loads to the composite with a reduction in the backscattering level. The backscattering level almost returned back to its original level after removing the bending load until damage was present in the composite. Similar behavior occurred due to impact events. As the POF itself is used as the sensor and can be integrated throughout the composite, large sections of future 3D woven composite structures could be monitored without the need for specialized sensors or complex instrumentation.

  6. 3D-printed silicate porous bioceramics using a non-sacrificial preceramic polymer binder.

    PubMed

    Zocca, A; Elsayed, H; Bernardo, E; Gomes, C M; Lopez-Heredia, M A; Knabe, C; Colombo, P; Günster, J

    2015-05-22

    Silicate bioceramics possess an excellent bioactivity; however, shaping them into complex geometries is still challenging. Therefore, this paper aims to present a new strategy for the shaping of a bioglass-ceramic with controlled geometry and properties starting from a glass powder combined with a preceramic polymer, i.e. a silicon resin, and reactive fillers. The powder-based three-dimensional (3D)-printing of wollastonite (CaSiO3)-based silicate bioceramic parts was demonstrated in this work. The resin plays a dual role, as it not only acts as a non-sacrificial binder for the filler powders in the printing process but it also reacts with the fillers to generate the desired bioceramic phases. The mechanical and physical properties, i.e. ball-on-three-balls test, density, porosity and morphology, were evaluated in 3D-printed discs. These samples possessed a total porosity around 64 vol% and a biaxial flexural strength around 6 MPa. The raw materials used in this work also enabled the 3D-printing of scaffolds possessing a designed multi-scale porosity, suitable bioceramic phase assemblage and a compressive strength of 1 MPa (for cylindrical scaffolds with total porosity ~80 vol%). Solubility in TRIS/HCl and in vitro assays, i.e. viability, cytotoxicity and apoptosis assays, were also performed. In vitro tests indicated good cell viability and no cytotoxicity effect on the cells.

  7. Multi-shape active composites by 3D printing of digital shape memory polymers

    NASA Astrophysics Data System (ADS)

    Wu, Jiangtao; Yuan, Chao; Ding, Zhen; Isakov, Michael; Mao, Yiqi; Wang, Tiejun; Dunn, Martin L.; Qi, H. Jerry

    2016-04-01

    Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers – digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications.

  8. Multi-shape active composites by 3D printing of digital shape memory polymers.

    PubMed

    Wu, Jiangtao; Yuan, Chao; Ding, Zhen; Isakov, Michael; Mao, Yiqi; Wang, Tiejun; Dunn, Martin L; Qi, H Jerry

    2016-04-13

    Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers - digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications.

  9. Fabrication of 3D embedded hollow structures inside polymer dielectric PMMA with femtosecond laser

    NASA Astrophysics Data System (ADS)

    Zheng, Chong; Chen, Tao; Hu, Anming; Liu, Shibing; Li, Junwei

    2016-11-01

    Recent progresses in femtosecond laser (fs) manufacturing have already proved that fs laser is a powerful tool in three dimensional internal structure fabrications. However, most studies are mainly focused on realize such structures in inorganic transparent dielectric, such as photosensitive glass and fused silica, etc. In this study, we present two methods to fabricate embedded internal 3D structures in a polymer dielectric material polymethyl methacrylate (PMMA). Both continuous hollow structure such as microfluidic channels and discrete hollow structures such as single microcavities are successfully fabricated with the help of femtosecond lasers. Among them, complicated 3D microchannel with a total length longer than 10mm and diameters around 80μm to 200μm are fabricated with a low repetition rate Ti: sapphire femtosecond laser by direct laser writing at a speed ranging from 25μm/s to 2000μm/s microcavities which function as concave microball lenses (CMBLs) and can be applied in super-wide-angle imaging are fabricated with a high repetition rate femtosecond fiber laser due to the distinct heat accumulation effect after 5s irradiation with the tightly focused fs laser beam. These new approaches proved that femtosecond laser direct writing technology has great application potential in 3D integrated devices manufacturing in the future.

  10. Multi-shape active composites by 3D printing of digital shape memory polymers

    PubMed Central

    Wu, Jiangtao; Yuan, Chao; Ding, Zhen; Isakov, Michael; Mao, Yiqi; Wang, Tiejun; Dunn, Martin L.; Qi, H. Jerry

    2016-01-01

    Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers – digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications. PMID:27071543

  11. Fatigue of a 3D Orthogonal Non-crimp Woven Polymer Matrix Composite at Elevated Temperature

    NASA Astrophysics Data System (ADS)

    Wilkinson, M. P.; Ruggles-Wrenn, M. B.

    2017-02-01

    Tension-tension fatigue behavior of two polymer matrix composites (PMCs) was studied at elevated temperature. The two PMCs consist of the NRPE polyimide matrix reinforced with carbon fibers, but have different fiber architectures: the 3D PMC is a singly-ply non-crimp 3D orthogonal weave composite and the 2D PMC, a laminated composite reinforced with 15 plies of an eight harness satin weave (8HSW) fabric. In order to assess the performance and suitability of the two composites for use in aerospace components designed to contain high-temperature environments, mechanical tests were performed under temperature conditions simulating the actual operating conditions. In all elevated temperature tests performed in this work, one side of the test specimen was at 329 °C while the other side was open to ambient laboratory air. The tensile stress-strain behavior of the two composites was investigated and the tensile properties measured for both on-axis (0/90) and off-axis (±45) fiber orientations. Elevated temperature had little effect on the on-axis tensile properties of the two composites. The off-axis tensile strength of both PMCs decreased slightly at elevated temperature. Tension-tension fatigue tests were conducted at elevated temperature at a frequency of 1.0 Hz with a ratio of minimum stress to maximum stress of R = 0.05. Fatigue run-out was defined as 2 × 105 cycles. Both strain accumulation and modulus evolution during cycling were analyzed for each fatigue test. The laminated 2D PMC exhibited better fatigue resistance than the 3D composite. Specimens that achieved fatigue run-out were subjected to tensile tests to failure to characterize the retained tensile properties. Post-test examination under optical microscope revealed severe delamination in the laminated 2D PMC. The non-crimp 3D orthogonal weave composite offered improved delamination resistance.

  12. Wavelength-scale light concentrator made by direct 3D laser writing of polymer metamaterials.

    PubMed

    Moughames, J; Jradi, S; Chan, T M; Akil, S; Battie, Y; Naciri, A En; Herro, Z; Guenneau, S; Enoch, S; Joly, L; Cousin, J; Bruyant, A

    2016-10-04

    We report on the realization of functional infrared light concentrators based on a thick layer of air-polymer metamaterial with controlled pore size gradients. The design features an optimum gradient index profile leading to light focusing in the Fresnel zone of the structures for two selected operating wavelength domains near 5.6 and 10.4 μm. The metamaterial which consists in a thick polymer containing air holes with diameters ranging from λ/20 to λ/8 is made using a 3D lithography technique based on the two-photon polymerization of a homemade photopolymer. Infrared imaging of the structures reveals a tight focusing for both structures with a maximum local intensity increase by a factor of 2.5 for a concentrator volume of 1.5 λ(3), slightly limited by the residual absorption of the selected polymer. Such porous and flat metamaterial structures offer interesting perspectives to increase infrared detector performance at the pixel level for imaging or sensing applications.

  13. Wavelength-scale light concentrator made by direct 3D laser writing of polymer metamaterials

    PubMed Central

    Moughames, J.; Jradi, S.; Chan, T. M.; Akil, S.; Battie, Y.; Naciri, A. En; Herro, Z.; Guenneau, S.; Enoch, S.; Joly, L.; Cousin, J.; Bruyant, A.

    2016-01-01

    We report on the realization of functional infrared light concentrators based on a thick layer of air-polymer metamaterial with controlled pore size gradients. The design features an optimum gradient index profile leading to light focusing in the Fresnel zone of the structures for two selected operating wavelength domains near 5.6 and 10.4 μm. The metamaterial which consists in a thick polymer containing air holes with diameters ranging from λ/20 to λ/8 is made using a 3D lithography technique based on the two-photon polymerization of a homemade photopolymer. Infrared imaging of the structures reveals a tight focusing for both structures with a maximum local intensity increase by a factor of 2.5 for a concentrator volume of 1.5 λ3, slightly limited by the residual absorption of the selected polymer. Such porous and flat metamaterial structures offer interesting perspectives to increase infrared detector performance at the pixel level for imaging or sensing applications. PMID:27698476

  14. Wavelength-scale light concentrator made by direct 3D laser writing of polymer metamaterials

    NASA Astrophysics Data System (ADS)

    Moughames, J.; Jradi, S.; Chan, T. M.; Akil, S.; Battie, Y.; Naciri, A. En; Herro, Z.; Guenneau, S.; Enoch, S.; Joly, L.; Cousin, J.; Bruyant, A.

    2016-10-01

    We report on the realization of functional infrared light concentrators based on a thick layer of air-polymer metamaterial with controlled pore size gradients. The design features an optimum gradient index profile leading to light focusing in the Fresnel zone of the structures for two selected operating wavelength domains near 5.6 and 10.4 μm. The metamaterial which consists in a thick polymer containing air holes with diameters ranging from λ/20 to λ/8 is made using a 3D lithography technique based on the two-photon polymerization of a homemade photopolymer. Infrared imaging of the structures reveals a tight focusing for both structures with a maximum local intensity increase by a factor of 2.5 for a concentrator volume of 1.5 λ3, slightly limited by the residual absorption of the selected polymer. Such porous and flat metamaterial structures offer interesting perspectives to increase infrared detector performance at the pixel level for imaging or sensing applications.

  15. Hierarchical PEG-Based 3D Patterns Grafting from Polymer Substrate by Surface Initiated Visible Light Photolithography.

    PubMed

    Zhao, Changwen; He, Bin; Wang, Guan; Ma, Yuhong; Yang, Wantai

    2016-10-01

    The precise construction of a hierarchical complex pattern on substrates is required for numerous applications. Here, a strategy to fabricate well-defined hierarchical three dimensional (3D) patterns on polymer substrate is developed. This technique, which combines photolithography and visible light-induced surface initiated living graft crosslinking polymerization (VSLGCP), can effectively graft 3D patterns onto polymer substrate with high fidelity and controllable height. Owing to the living nature of VSLGCP, hierarchical 3D patterns can be prepared when a sequential living graft crosslinking process is performed on the first formed patterns. As a proof-of-concept, a reactive two layer 3D pattern with a morphology of lateral stripe on vertical stripe is prepared and employed to separately immobilize model biomolecules, e.g., biotin and IgG. This two component pattern can specifically interact with corresponding target proteins successfully, indicating that this strategy has potential applications in the fabrication of polymer-based multicomponent biomolecule microarrays.

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

    SciTech Connect

    Zhang, Yingjie; Bhadbhade, Mohan; Karatchevtseva, Inna; Price, Jason R.; Liu, Hao; Zhang, Zhaoming; Kong, Linggen; Čejka, Jiří; Lu, Kim; Lumpkin, Gregory R.

    2015-03-15

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

  17. Shear induced alignment of short nanofibers in 3D printed polymer composites

    NASA Astrophysics Data System (ADS)

    Erdem Yunus, Doruk; Shi, Wentao; Sohrabi, Salman; Liu, Yaling

    2016-12-01

    3D printing of composite materials offers an opportunity to combine the desired properties of composite materials with the flexibility of additive manufacturing in geometric shape and complexity. In this paper, the shear-induced alignment of aluminum oxide nanowires during stereolithography printing was utilized to fabricate a nanowire reinforced polymer composite. To align the fibers, a lateral oscillation mechanism was implemented and combined with wall pattern printing technique to generate shear flow in both vertical and horizontal directions. A series of specimens were fabricated for testing the composite material’s tensile strength. The results showed that mechanical properties of the composite were improved by reinforcement of nanofibers through shear induced alignment. The improvement of tensile strength was approximately ∼28% by aligning the nanowires at 5 wt% (∼1.5% volume fraction) loading of aluminum oxide nanowires.

  18. Shear induced alignment of short nanofibers in 3D printed polymer composites.

    PubMed

    Yunus, Doruk Erdem; Shi, Wentao; Sohrabi, Salman; Liu, Yaling

    2016-12-09

    3D printing of composite materials offers an opportunity to combine the desired properties of composite materials with the flexibility of additive manufacturing in geometric shape and complexity. In this paper, the shear-induced alignment of aluminum oxide nanowires during stereolithography printing was utilized to fabricate a nanowire reinforced polymer composite. To align the fibers, a lateral oscillation mechanism was implemented and combined with wall pattern printing technique to generate shear flow in both vertical and horizontal directions. A series of specimens were fabricated for testing the composite material's tensile strength. The results showed that mechanical properties of the composite were improved by reinforcement of nanofibers through shear induced alignment. The improvement of tensile strength was approximately ∼28% by aligning the nanowires at 5 wt% (∼1.5% volume fraction) loading of aluminum oxide nanowires.

  19. 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.

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

    SciTech Connect

    Qin, Ling; Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang

    2016-07-15

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

  1. Embedding silica and polymer fibre Bragg gratings (FBG) in plastic 3D-printed sensing patches

    NASA Astrophysics Data System (ADS)

    Zubel, Michal G.; Sugden, Kate; Webb, David J.; Sáez-Rodríguez, David; Nielsen, Kristian; Bang, Ole

    2016-04-01

    This paper reports the first demonstration of a silica fibre Bragg grating (SOFBG) embedded in an FDM 3-D printed housing to yield a dual grating temperature-compensated strain sensor. We also report the first ever integration of polymer fibre Bragg grating (POFBG) within a 3-D printed sensing patch for strain or temperature sensing. The cyclic strain performance and temperature characteristics of both devices are examined and discussed. The strain sensitivities of the sensing patches were 0.40 and 0.95 pm/μɛ for SOFBG embedded in ABS, 0.38 pm/μɛ for POFBG in PLA, and 0.15 pm/μɛ for POFBG in ABS. The strain response was linear above a threshold and repeatable. The temperature sensitivity of the SOFBG sensing patch was found to be up to 169 pm/°C, which was up to 17 times higher than for an unembedded silica grating. Unstable temperature response POFBG embedded in PLA was reported, with temperature sensitivity values varying between 30 and 40 pm/°C.

  2. Molecular tectonics: pyridyl containing thiacalix[4]arene based tectons for the generation of 2- and 3-D silver coordination networks.

    PubMed

    Ovsyannikov, A; Lang, M N; Ferlay, S; Solovieva, S E; Antipin, I S; Konovalov, A I; Kyritsakas, N; Hosseini, M W

    2013-01-07

    Three new organic tectons (2–4) based on the p-tert-butylthiacalix[4]arene backbone, blocked in the 1,3-alternate conformation, bearing four pyridyl coordinating moieties, have been synthesised and characterised in the solid state. The ligands are positional isomers and differ by the position of the N atom on the pyridyl unit (ortho for 2, meta for 3 and para for 4). Their combination with the Ag+ cation leads, reproducibly, to the formation of 2- and 3-D infinite silver coordination networks. Independent of the nature of the anion, the combination of 2 offering four (N,S) type chelates with the Ag+ cation affords an unprecedented diamond type 3D network. Both 3 and 4, behaving as tetrakis monodentate ligands, lead to the formation of 2-D architectures.

  3. A Lyapunov-Based Approach for Time-Coordinated 3D Path-Following of Multiple Quadrotors

    DTIC Science & Technology

    2012-12-01

    based on neural networks, is introduced in [9] to achieve vertical take-off and landing. Integral sliding mode and reinforcement learning control are...Multi-agent quadrotor testbed control design: integral sliding mode vs reinforcement learning,” in International Conference on Intelligent Robots and...the Time-Coordinated 3D Path-Following task for multiple quadrotor UAVs in the presence of time- varying communication networks and spatial and temporal

  4. Controlled isotropic or anisotropic nanoscale growth of coordination polymers: formation of hybrid coordination polymer particles.

    PubMed

    Lee, Hee Jung; Cho, Yea Jin; Cho, Won; Oh, Moonhyun

    2013-01-22

    The ability to fabricate multicompositional hybrid materials in a precise and controlled manner is one of the primary goals of modern materials science research. In addition, an understanding of the phenomena associated with the systematic growth of one material on another can facilitate the evolution of multifunctional hybrid materials. Here, we demonstrate precise manipulation of the isotropic and/or anisotropic nanoscale growth of various coordination polymers (CPs) to obtain heterocompositional hybrid coordination polymer particles. Chemical composition analyses conducted at every growth step reveal the formation of accurately assembled hybrid nanoscale CPs, and microscopy images are used to examine the morphology of the particles and visualize the hybrid structures. The dissimilar growth behavior, that is, growth in an isotropic or anisotropic fashion, is found to be dependent on the size of the metal ions involved within the CPs.

  5. Development of 3D carbon nanotube interdigitated finger electrodes on polymer substrate for flexible capacitive sensor application.

    PubMed

    Hu, Chih-Fan; Wang, Jhih-Yu; Liu, Yu-Chia; Tsai, Ming-Han; Fang, Weileun

    2013-11-08

    This study reports a novel approach to the implementation of 3D carbon nanotube (CNT) interdigitated finger electrodes on flexible polymer, and the detection of strain, bending curvature, tactile force and proximity distance are demonstrated. The merits of the presented CNT-based flexible sensor are as follows: (1) the silicon substrate is patterned to enable the formation of 3D vertically aligned CNTs on the substrate surface; (2) polymer molding on the silicon substrate with 3D CNTs is further employed to transfer the 3D CNTs to the flexible polymer substrate; (3) the CNT-polymer composite (~70 μm in height) is employed to form interdigitated finger electrodes to increase the sensing area and initial capacitance; (4) other structures such as electrical routings, resistors and mechanical supporters are also available using the CNT-polymer composite. The preliminary fabrication results demonstrate a flexible capacitive sensor with 50 μm high CNT interdigitated electrodes on a poly-dimethylsiloxane substrate. The tests show that the typical capacitance change is several dozens of fF and the gauge factor is in the range of 3.44-4.88 for strain and bending curvature measurement; the sensitivity of the tactile sensor is 1.11% N(-1); a proximity distance near 2 mm away from the sensor can be detected.

  6. Development of 3D carbon nanotube interdigitated finger electrodes on polymer substrate for flexible capacitive sensor application

    NASA Astrophysics Data System (ADS)

    Hu, Chih-Fan; Wang, Jhih-Yu; Liu, Yu-Chia; Tsai, Ming-Han; Fang, Weileun

    2013-11-01

    This study reports a novel approach to the implementation of 3D carbon nanotube (CNT) interdigitated finger electrodes on flexible polymer, and the detection of strain, bending curvature, tactile force and proximity distance are demonstrated. The merits of the presented CNT-based flexible sensor are as follows: (1) the silicon substrate is patterned to enable the formation of 3D vertically aligned CNTs on the substrate surface; (2) polymer molding on the silicon substrate with 3D CNTs is further employed to transfer the 3D CNTs to the flexible polymer substrate; (3) the CNT-polymer composite (˜70 μm in height) is employed to form interdigitated finger electrodes to increase the sensing area and initial capacitance; (4) other structures such as electrical routings, resistors and mechanical supporters are also available using the CNT-polymer composite. The preliminary fabrication results demonstrate a flexible capacitive sensor with 50 μm high CNT interdigitated electrodes on a poly-dimethylsiloxane substrate. The tests show that the typical capacitance change is several dozens of fF and the gauge factor is in the range of 3.44-4.88 for strain and bending curvature measurement; the sensitivity of the tactile sensor is 1.11% N-1 a proximity distance near 2 mm away from the sensor can be detected.

  7. Tour of the World’s Largest 3D Printed Polymer Structure on Display at IBS 2016

    SciTech Connect

    Green, Johney

    2016-01-22

    ORNL’s Johney Green guides a Periscope tour of the 3D printed house and vehicle demonstration called AMIE (Additive Manufacturing Integrated Energy) during the International Builders’ Show 2016 in Las Vegas. See the world’s largest 3D printed polymer structure – made with carbon fiber reinforced ABS plastic, insulated with next-generation vacuum insulation panels, and outfitted with a micro-kitchen by GE Appliances – that was designed to be powered by a 3D printed utility vehicle using bidirectional wireless power technology. Learn more about AMIE at https://www.youtube.com/watch?v=RCkQB... and http://www.ornl.gov/amie.

  8. Virtual 3D tumor marking-exact intraoperative coordinate mapping improve post-operative radiotherapy

    PubMed Central

    2011-01-01

    The quality of the interdisciplinary interface in oncological treatment between surgery, pathology and radiotherapy is mainly dependent on reliable anatomical three-dimensional (3D) allocation of specimen and their context sensitive interpretation which defines further treatment protocols. Computer-assisted preoperative planning (CAPP) allows for outlining macroscopical tumor size and margins. A new technique facilitates the 3D virtual marking and mapping of frozen sections and resection margins or important surgical intraoperative information. These data could be stored in DICOM format (Digital Imaging and Communication in Medicine) in terms of augmented reality and transferred to communicate patient's specific tumor information (invasion to vessels and nerves, non-resectable tumor) to oncologists, radiotherapists and pathologists. PMID:22087558

  9. Using Polymer Confinement for Stem Cell Differentiation: 3D Printed vs Molded Scaffolds

    NASA Astrophysics Data System (ADS)

    Rafailovich, Miriam

    Additive manufacturing technologies are increasingly being used to replace standard extrusion or molding methods in engineering polymeric biomedical implants, which can be further seeded with cells for tissue regeneration. The principal advantage of this new technology is the ability to print directly from a scan and hence produce parts which are an ideal fit for an individual, eliminating much of the sizing and fitting associated with standard manufacturing methods. The question though arises whether devices which may be macroscopically similar, serve identical functions and are produced from the same material, interact in the same manner with cells and living tissue. Here we show that fundamental differences can exist between 3-D printed and extruded scaffolds which can impact stem cell differentiation and lineage selection. We will show how polymer confinement inherent in these methods affect the printed features on multiple length scales. We will also and how the differentiation of stem cells is affected by substrate heterogeneity in both morphological and mechanical features. NSF-Inspire award # 1344267.

  10. 3D printing for the design and fabrication of polymer-based gradient scaffolds.

    PubMed

    Bracaglia, Laura G; Smith, Brandon T; Watson, Emma; Arumugasaamy, Navein; Mikos, Antonios G; Fisher, John P

    2017-03-22

    To accurately mimic the native tissue environment, tissue engineered scaffolds often need to have a highly controlled and varied display of three-dimensional (3D) architecture and geometrical cues. Additive manufacturing in tissue engineering has made possible the development of complex scaffolds that mimic the native tissue architectures. As such, architectural details that were previously unattainable or irreproducible can now be incorporated in an ordered and organized approach, further advancing the structural and chemical cues delivered to cells interacting with the scaffold. This control over the environment has given engineers the ability to unlock cellular machinery that is highly dependent upon the intricate heterogeneous environment of native tissue. Recent research into the incorporation of physical and chemical gradients within scaffolds indicates that integrating these features improves the function of a tissue engineered construct. This review covers recent advances on techniques to incorporate gradients into polymer scaffolds through additive manufacturing and evaluate the success of these techniques. As covered here, to best replicate different tissue types, one must be cognizant of the vastly different types of manufacturing techniques available to create these gradient scaffolds. We review the various types of additive manufacturing techniques that can be leveraged to fabricate scaffolds with heterogeneous properties and discuss methods to successfully characterize them.

  11. Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas

    2005-01-01

    In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect

  12. Protein adsorption resistant surface on polymer composite based on 2D- and 3D-controlled grafting of phospholipid moieties

    NASA Astrophysics Data System (ADS)

    Hoshi, Toru; Matsuno, Ryosuke; Sawaguchi, Takashi; Konno, Tomohiro; Takai, Madoka; Ishihara, Kazuhiko

    2008-11-01

    To prepare the biocompatible surface, a phosphorylcholine (PC) group was introduced on this hydroxyl group generated by surface hydrolysis on the polymer composite composed of polyethylene (PE) and poly (vinyl acetate) (PVAc) prepared by supercritical carbon dioxide. Two different procedures such as two-dimensional (2D) modification and three-dimensional (3D) modification were applied to obtain the steady biocompatible surface. 2D modification was that PC groups were directly anchored on the surface of the polymer composite. 3D modification was that phospholipid polymer was grafted from the surface of the polymer composite by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC). The surfaces were characterized by X-ray photoelectron spectroscopy, dynamic water contact angle measurements, and atomic force microscope. The effects of the poly(MPC) chain length on the protein adsorption resistivity were investigated. The protein adsorption on the polymer composite surface with PC groups modified by 2D or 3D modification was significantly reduced as compared with that on the unmodified PE. Further, the amount of protein adsorbed on the 3D modified surface that is poly(MPC)-grafted surface decreased with an increase in the chain length of the poly(MPC). The surface with an arbitrary structure and the characteristic can be constructed by using 2D and 3D modification. We conclude that the polymer composites of PE/PVAc with PC groups on the surface are useful for fabricating biomedical devices due to their good mechanical and surface properties.

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

    NASA Astrophysics Data System (ADS)

    Chen, Fei-Yan; Lan, You-Zhao; Han, Min-Min; Feng, Yun-Long

    2016-09-01

    Two new coordination polymers [Cd3(D-Tar)3]n ( 1) and [Pb( meso-Tar)]n ( 2) (H2 Tar = tartaric acid) have been synthesized by hydrothermal reaction and characterized by single crystal X-ray diffraction analysis and IR spectra. 1 crystallizes in the C2221 chiral space group and shows a 3D (4,4)-connected net with the (4.6.84)4(4.62.82.10)(4.62.83)(4.63.82)(4.63.82)4(4.85)2 topology. 2 possesses a 3D (4,4)-connected net with the (43.62.8) topology. In addition, the thermogravimetric analyses (TGA) results for polymers are discussed.

  14. A parallel 3D poisson solver for space charge simulation in cylindrical coordinates.

    SciTech Connect

    Xu, J.; Ostroumov, P. N.; Nolen, J.; Physics

    2008-02-01

    This paper presents the development of a parallel three-dimensional Poisson solver in cylindrical coordinate system for the electrostatic potential of a charged particle beam in a circular tube. The Poisson solver uses Fourier expansions in the longitudinal and azimuthal directions, and Spectral Element discretization in the radial direction. A Dirichlet boundary condition is used on the cylinder wall, a natural boundary condition is used on the cylinder axis and a Dirichlet or periodic boundary condition is used in the longitudinal direction. A parallel 2D domain decomposition was implemented in the (r,{theta}) plane. This solver was incorporated into the parallel code PTRACK for beam dynamics simulations. Detailed benchmark results for the parallel solver and a beam dynamics simulation in a high-intensity proton LINAC are presented. When the transverse beam size is small relative to the aperture of the accelerator line, using the Poisson solver in a Cartesian coordinate system and a Cylindrical coordinate system produced similar results. When the transverse beam size is large or beam center located off-axis, the result from Poisson solver in Cartesian coordinate system is not accurate because different boundary condition used. While using the new solver, we can apply circular boundary condition easily and accurately for beam dynamic simulations in accelerator devices.

  15. Coordination polymers undergoing spin crossover and reversible ligand exchange in the solid.

    PubMed

    Galet, Ana; Muñoz, M Carmen; Real, José Antonio

    2006-11-04

    Here we report the synthesis and characterisation of a polymer made up of a system of parallel 2-D grids of Fe(II) ions linked by [Au(CN)2]- bridges and its transformation into a new system of three interpenetrated 3-D coordination open frameworks with the NbO topology. Reversibility of this crystal-to-crystal transformation is evidenced by X-ray crystallographic data and from their spin crossover properties.

  16. Dynamic self-assembly of coordination polymers in aqueous solution.

    PubMed

    Li, Wen; Kim, Yongju; Li, Jingfang; Lee, Myongsoo

    2014-08-07

    The construction of supramolecular polymers has been intensively pursued because the nanostructures formed through weak non-covalent interactions can be triggered by external stimuli leading to smart materials and sensors. Self-assemblies of coordination polymers consisting of metal ions and organic ligands in aqueous solution also provide particular contributions in this area. The main motivation for developing those coordination polymers originates from the value-added combination between metal ions and ligands. This review highlights the recent progress of the dynamic self-assembly of coordination polymers that result from the sophisticated molecular design, towards fabricating stimuli-responsive systems and bio-related materials. Dynamic structural changes and switchable physical properties triggered by various stimuli are summarized. Finally, the outlook for aqueous nanostructures originated from the dynamic self-assembly of coordination polymers is also presented.

  17. Antibacterial activity of silver camphorimine coordination polymers.

    PubMed

    Cardoso, João M S; Galvão, Adelino M; Guerreiro, Soraia I; Leitão, Jorge H; Suarez, Ana C; Carvalho, M Fernanda N N

    2016-04-28

    Five new silver camphorimine complexes of general formula [Ag(NO3)(Y)L] were synthesized and fully characterized using spectroscopic and analytical techniques. The structure of [Ag(NO3)(OC10H14NC6H4NC10H14O)] () was analyzed using single crystal X-ray diffraction, showing that it arranges as a coordination polymer formed by sequential Ag(NO3) units bridged by the bi-camphor ligand (). The antimicrobial properties of the new complexes were screened using the disk diffusion method and their Minimal Inhibitory Concentrations (MIC) were assessed against selected bacterial strains of the Gram-positive Staphylococcus aureus and the Gram-negative Escherichia coli, Pseudomonas aeruginosa, and Burkholderia contaminans. The lowest MICs were observed for , with estimated values of 72, 20, 32 and 19 μg mL(-1) for S. aureus, E. coli, B. contaminans, and P. aeruginosa, respectively. In the case of S. aureus, similar MIC values were obtained for silver nitrate and compound . All five compounds were bactericidal when used in concentrations equal or above the MIC value, as found by enumerating the total colony forming units (CFUs) after incubation in their presence.

  18. Coordination between Understanding Historic Buildings and BIM Modelling: A 3D-Output Oriented and typological Data Capture Method

    NASA Astrophysics Data System (ADS)

    Li, K.; Li, S. J.; Liu, Y.; Wang, W.; Wu, C.

    2015-08-01

    At the present, in trend of shifting the old 2D-output oriented survey to a new 3D-output oriented survey based on BIM technology, the corresponding working methods and workflow for data capture, process, representation, etc. have to be changed.Based on case study of two buildings in the Summer Palace of Beijing, and Jiayuguan Pass at the west end of the Great Wall (both World Heritage sites), this paper puts forward a "structure-and-type method" by means of typological method used in archaeology, Revit family system, and the tectonic logic of building to realize a good coordination between understanding of historic buildings and BIM modelling.

  19. Effect of degree of crosslinking and polymerization of 3D printable polymer/ionic liquid composites on performance of stretchable piezoresistive sensors

    NASA Astrophysics Data System (ADS)

    Lee, Jeongwoo; Faruk Emon, Md Omar; Vatani, Morteza; Choi, Jae-Won

    2017-03-01

    Ionic liquid (IL)/polymer composites (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIMBF4)/2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BACOEA)) were fabricated to use as sensing materials for stretchable piezoresistive tactile sensors. The detectability of the IL/polymer composites was enhanced because the ionic transport properties of EMIMBF4 in the composites were improved by the synergic actions between the coordinate sites generated by the local motion of BACOEA chain segments under enough activation energy. The performance of the piezoresistive sensors was investigated with the degree of crosslinking and polymerization of the IL/polymer composites. As the compressive strain was increased, the distance between two electrodes decreased, and the motion of polymer chains and IL occurred, resulting in a decrease in the electrical resistance of the sensors. We have confirmed that the sensitivity of the sensors are affected by the degree of crosslink and polymerization of the IL/polymer composites. In addition, all of the materials (skins, sensing material, and electrode) used in this study are photo-curable, and thus the stretchable piezoresistive tactile sensors can be successfully fabricated by 3D printing.

  20. Ice-Templated Assembly Strategy to Construct 3D Boron Nitride Nanosheet Networks in Polymer Composites for Thermal Conductivity Improvement.

    PubMed

    Zeng, Xiaoliang; Yao, Yimin; Gong, Zhengyu; Wang, Fangfang; Sun, Rong; Xu, Jianbin; Wong, Ching-Ping

    2015-12-01

    Owing to the growing heat removal issue of modern electronic devices, polymer composites with high thermal conductivity have drawn much attention in the past few years. However, a traditional method to enhance the thermal conductivity of the polymers by addition of inorganic fillers usually creates composite with not only limited thermal conductivity but also other detrimental effects due to large amount of fillers required. Here, novel polymer composites are reported by first constructing 3D boron nitride nanosheets (3D-BNNS) network using ice-templated approach and then infiltrating them with epoxy matrix. The obtained polymer composites exhibit a high thermal conductivity (2.85 W m(-1) K(-1)), a low thermal expansion coefficient (24-32 ppm K(-1)), and an increased glass transition temperature (T(g)) at relatively low BNNSs loading (9.29 vol%). These results demonstrate that this approach opens a new avenue for design and preparation of polymer composites with high thermal conductivity. The polymer composites are potentially useful in advanced electronic packaging techniques, namely, thermal interface materials, underfill materials, molding compounds, and organic substrates.

  1. Preparation and characterization of polymer layer systems for validation of 3D Micro X-ray fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Schaumann, Ina; Malzer, Wolfgang; Mantouvalou, Ioanna; Lühl, Lars; Kanngießer, Birgit; Dargel, Rainer; Giese, Ulrich; Vogt, Carla

    2009-04-01

    For the validation of the quantification of the newly-developed method of 3D Micro X-ray fluorescence spectroscopy (3D Micro-XRF) samples with a low average Z matrix and minor high Z elements are best suited. In a light matrix the interferences by matrix effects are minimized so that organic polymers are appropriate as basis for analytes which are more easily detected by X-ray fluorescence spectroscopy. Polymer layer systems were assembled from single layers of ethylene-propylene-diene rubber (EPDM) filled with changing concentrations of silica and zinc oxide as inorganic additives. Layer thicknesses were in the range of 30-150 μm. Before the analysis with 3D Micro-XRF all layers have been characterized by scanning micro-XRF with regard to filler dispersion, by infrared microscopy and light microscopy in order to determine the layer thicknesses and by ICP-OES to verify the concentration of the X-ray sensitive elements in the layers. With the results obtained for stacked polymer systems the validity of the analytical quantification model for the determination of stratified materials by 3D Micro-XRF could be demonstrated.

  2. One- and three-dimensional silver(I)-5-sulfosalicylate coordination polymers having ligand-supported and unsupported argentophilic interactions

    SciTech Connect

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Yeşilöz, Yeşim; Şahin, Onur

    2014-12-15

    Four new coordination polymers, namely, (Hemim·[Ag(Hssa)(H{sub 2}O)]){sub n} (1), ([Ag(ina){sub 2} Ag(Hssa)]·CH{sub 3}OH·H{sub 2}O){sub n} (2), ([Ag{sub 2}(Hssa)(dmp){sub 1.5}]·2H{sub 2}O){sub n} (3) and [Ag{sub 2}(Hssa)(daoc)]{sub n} (4) (Hssa: 5-Sulfosalicylate, emim: 2-ethyl-4-methylimidazole, ina: isonicotinamide, dmp: 2,5-dimethylpyrazine and daoc: 1,8-diaminooctane) were synthesized and characterized by IR spectroscopy, elemental analysis, single crystal X-ray diffraction, powder X-ray diffraction (PXRD) and thermal analysis techniques. Complexes 1 and 2 are one-dimensional (1D) coordination polymers while complexes 3 and 4 are three-dimensional (3D) coordination polymers. Complex 3 consists of three dimensional (3D) 3,3,6-c net with 3,3,6T37 topology. Complex 4 exhibits a 2-fold interpenetrating 3D framework with tfc topology. Complexes 1–4 contain ligand-supported (1–3) and unsupported (4) argentophilic Ag⋯Ag interactions. Photoluminescence spectra of the complexes demonstrate that photoluminescent properties may be attributed to intraligand transition of coordinated Hssa ligand. - Graphical abstract: In this study, four new Ag(I)-coordination polymers with 5-sulfosalicylate and some N-donor ligands were synthesized and characterized. Complexes 1 and 2 are one-dimensional (1D) coordination polymers while complexes 3 and 4 are three-dimensional (3D) coordination polymers. Complex 3 consists of three dimensional (3D) 3,3,6-c net with 3,3,6T37 topology. Complex 4 exhibits a 2-fold interpenetrating 3D framework with tfc topology. The complexes 1–4 contain ligand-supported (1–3) and unsupported (4) argentophilic Ag⋯Ag interactions. Photoluminescence spectra of the complexes demonstrated that photoluminescent properties may be attributed to intraligand transition of coordinated Hssa ligand. - Highlights: • Four novel Ag(I)-coordination polymers with 5-sulfosalicylate and N-donor ligands. • Complexes 1–4 contain ligand-supported (1–3) and

  3. Representation of protein 3D structures in spherical (ρ, ϕ, θ) coordinates and two of its potential applications.

    PubMed

    Reyes, Vicente M

    2011-09-01

    Three-dimensional objects can be represented using cartesian, spherical or cylindrical coordinate systems, among many others. Currently all protein 3D structures in the PDB are in cartesian coordinates. We wanted to explore the possibility that protein 3D structures, especially the globular type (spheroproteins), when represented in spherical coordinates might find useful novel applications. A Fortran program was written to transform protein 3D structure files in cartesian coordinates (x,y,z) to spherical coordinates (ρ, ϕ, θ), with the centroid of the protein molecule as origin. We present here two applications, namely, (1) separation of the protein outer layer (OL) from the inner core (IC); and (2) identifying protrusions and invaginations on the protein surface. In the first application, ϕ and θ were partitioned into suitable intervals and the point with maximum ρ in each such 'ϕ-θ bin' was determined. A suitable cutoff value for ρ is adopted, and for each ϕ-θ bin, all points with ρ values less than the cutoff are considered part of the IC, and those with ρ values equal to or greater than the cutoff are considered part of the OL. We show that this separation procedure is successful as it gives rise to an OL that is significantly more enriched in hydrophilic amino acid residues, and an IC that is significantly more enriched in hydrophobic amino acid residues, as expected. In the second application, the point with maximum ρ in each ϕ-θ bin are sequestered and their frequency distribution constructed (i.e., maximum ρ's sorted from lowest to highest, collected into 1.50Å-intervals, and the frequency in each interval plotted). We show in such plots that invaginations on the protein surface give rise to subpeaks or shoulders on the lagging side of the main peak, while protrusions give rise to similar subpeaks or shoulders, but on the leading side of the main peak. We used the dataset of Laskowski et al. (1996) to demonstrate both applications.

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

    NASA Astrophysics Data System (ADS)

    Jin, Jing; Han, Xiao; Meng, Qin; Li, Dan; Chi, Yu-Xian; Niu, Shu-Yun

    2013-01-01

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz)2(H2O)]n (1), [Cd1Cd2(btec)(H2O)6]n (2), [Cd(3,4-pdc) (H2O)]n (3), [Zn(2,5-pdc)(H2O)4]·2H2O (4) and {[Zn(2,5-pdc)(H2O)2]·H2O}n (5) (H2bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H4btec=1,2,4,5-benzenetetracarboxylic acid, H2pdc=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 complexes 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.

  5. A 3D pseudospectral method for cylindrical coordinates. Application to the simulations of rotating cavity flows

    NASA Astrophysics Data System (ADS)

    Peres, Noele; Poncet, Sébastien; Serre, Eric

    2012-08-01

    The present work proposes a collocation spectral method for solving the three-dimensional Navier-Stokes equations using cylindrical coordinates. The whole diameter -R⩽r⩽R is discretized with an even number of radial Gauss-Lobatto collocation points and an angular shift is introduced in the Fourier transform that avoid pole and parity conditions usually required. The method keeps the spectral convergence that reduces the number of grid points with respect to lower-order numerical methods. The grid-points distribution densifies the mesh only near the boundaries that makes the algorithm well-suited to simulate rotating cavity flows where thin layers develop along the walls. Comparisons with reliable experimental and numerical results of the literature show good quantitative agreements for flows driven by rotating discs in tall cylinders and thin inter-disc cavities. Associated to a spectral vanishing viscosity [E. Séverac, E. Serre, A spectral vanishing viscosity for the LES of turbulent flows within rotating cavities, J. Comp. Phys. 226 (2007) 1234-1255], the method provides very promising LES results of turbulent cavity flows.

  6. Synthesis and Application of Novel 3D Magnetic Chlorogenic Acid Imprinted Polymers Based on a Graphene-Carbon Nanotube Composite.

    PubMed

    Yan, Liang; Yin, Yuli; Lv, Piaopiao; Zhang, Zhaohui; Wang, Jing; Long, Fang

    2016-04-20

    A novel three-dimensional (3D) magnetic chlorogenic acid (CGA) imprinted polymer (MMIP) was prepared with novel carbon hybrid nanocomposite as the carrier, chlorogenic acid as the template molecule, and methacrylic acid as the functional monomer. The 3D MMIPs were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, vibrating sample magnetometer, and UV spectrometry in detail. The results showed that the imprinted layer was attached successfully on the surface of a 3D magnetic carbon hybrid nanocomposite. The adsorption performance of the 3D MMIPs was investigated, and the results showed that the 3D MMIPs exhibited high adsorption capacity and fast adsorption rate toward CGA with a maximum adsorption capacity of 10.88 mg g(-1). The extraction conditions involving washing solvent, the pH of eluent solvent, elution volume, and desorption time were also investigated in detail. Combined with high-performance liquid chromatography, the 3D MMIPs have been applied to successfully extract CGA from Eucommia leaf extract samples.

  7. 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

    SciTech Connect

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

    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 composite material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.

  8. Tour of the World’s Largest 3D Printed Polymer Structure on Display at IBS 2016

    ScienceCinema

    Green, Johney

    2016-07-12

    ORNL’s Johney Green guides a Periscope tour of the 3D printed house and vehicle demonstration called AMIE (Additive Manufacturing Integrated Energy) during the International Builders’ Show 2016 in Las Vegas. See the world’s largest 3D printed polymer structure – made with carbon fiber reinforced ABS plastic, insulated with next-generation vacuum insulation panels, and outfitted with a micro-kitchen by GE Appliances – that was designed to be powered by a 3D printed utility vehicle using bidirectional wireless power technology. Learn more about AMIE at https://www.youtube.com/watch?v=RCkQB... and http://www.ornl.gov/amie.

  9. 3D Quantification of Low-Coordinate Surface Atom Density: Bridging Catalytic Activity to Concave Facets of Nanocatalysts in Fuel Cells.

    PubMed

    Xia, Ye; Zhong, Xiaoyan; Ke, Xiaoxing; Zhang, Gui-Rong; Cheng, Zhiying; Xu, Bo-Qing

    2016-12-01

    A protocol to quantify the distribution of surface atoms of concave nanocatalysts according to their coordination number is proposed. The 3D surface of an Au@Pd concave nanocube is reconstructed and segmented. The crystallographic coordinates and low-coordinate surface atom densities of the concave facets are determined. The result shows that 32% of the surface atoms are low-coordinated, which may contribute to the high activity.

  10. 3D printing of mineral-polymer bone substitutes based on sodium alginate and calcium phosphate.

    PubMed

    Egorov, Aleksey A; Fedotov, Alexander Yu; Mironov, Anton V; Komlev, Vladimir S; Popov, Vladimir K; Zobkov, Yury V

    2016-01-01

    We demonstrate a relatively simple route for three-dimensional (3D) printing of complex-shaped biocompatible structures based on sodium alginate and calcium phosphate (CP) for bone tissue engineering. The fabrication of 3D composite structures was performed through the synthesis of inorganic particles within a biopolymer macromolecular network during 3D printing process. The formation of a new CP phase was studied through X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. Both the phase composition and the diameter of the CP particles depend on the concentration of a liquid component (i.e., the "ink"). The 3D printed structures were fabricated and found to have large interconnected porous systems (mean diameter ≈800 μm) and were found to possess compressive strengths from 0.45 to 1.0 MPa. This new approach can be effectively applied for fabrication of biocompatible scaffolds for bone tissue engineering constructions.

  11. 3D printing of mineral–polymer bone substitutes based on sodium alginate and calcium phosphate

    PubMed Central

    Egorov, Aleksey A; Fedotov, Alexander Yu; Mironov, Anton V; Popov, Vladimir K; Zobkov, Yury V

    2016-01-01

    We demonstrate a relatively simple route for three-dimensional (3D) printing of complex-shaped biocompatible structures based on sodium alginate and calcium phosphate (CP) for bone tissue engineering. The fabrication of 3D composite structures was performed through the synthesis of inorganic particles within a biopolymer macromolecular network during 3D printing process. The formation of a new CP phase was studied through X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. Both the phase composition and the diameter of the CP particles depend on the concentration of a liquid component (i.e., the “ink”). The 3D printed structures were fabricated and found to have large interconnected porous systems (mean diameter ≈800 μm) and were found to possess compressive strengths from 0.45 to 1.0 MPa. This new approach can be effectively applied for fabrication of biocompatible scaffolds for bone tissue engineering constructions. PMID:28144529

  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. A 3D-printed polymer micro-gripper with self-defined electrical tracks and thermal actuator

    NASA Astrophysics Data System (ADS)

    Alblalaihid, Khalid; Overton, James; Lawes, Simon; Kinnell, Peter

    2017-04-01

    This paper presents a simple fabrication process that allows for isolated metal tracks to be easily defined on the surface of 3D printed micro-scale polymer components. The process makes use of a standard low cost conformal sputter coating system to quickly deposit thin film metal layers on to the surface of 3D printed polymer micro parts. The key novelty lies in the inclusion of inbuilt masking features, on the surface of the polymer parts, to ensure that the conformal metal layer can be effectively broken to create electrically isolated metal features. The presented process is extremely flexible, and it is envisaged that it may be applied to a wide range of sensor and actuator applications. To demonstrate the process a polymer micro-scale gripper with an inbuilt thermal actuator is designed and fabricated. In this work the design methodology for creating the micro-gripper is presented, illustrating how the rapid and flexible manufacturing process allows for fast cycle time design iterations to be performed. In addition the compatibility of this approach with traditional design and analysis techniques such as basic finite element simulation is also demonstrated with simulation results in reasonable agreement with experimental performance data for the micro-gripper.

  14. 3D analysis of posturo-kinetic coordination associated with a climbing task in children and teenagers.

    PubMed

    Testa, M; Martin, L; Debû, B

    2003-01-09

    The aim of this study was to characterize the modifications of the posturo-kinetic coordination during a climbing task as a function of postural and/or movement constraints in children (8-10 years) and adolescents (10-15 years). A 3D-analysis of forces was recorded for different movement amplitudes and types of holds. The results show the involvement of horizontal and vertical forces to maintain equilibrium during the steady state changes for different experimental groups. The contribution of horizontal and vertical forces changes in the course of movement realization. The vertical momentum (Iz) is mainly involved in the movement initiation: this role is mostly meaning for children. The horizontal momentum (Ih) is mainly involved in controlling equilibrium: this role is mostly meaning for adolescents.

  15. 3D tissue culture substrates produced by microthermoforming of pre-processed polymer films.

    PubMed

    Giselbrecht, S; Gietzelt, T; Gottwald, E; Trautmann, C; Truckenmüller, R; Weibezahn, K F; Welle, A

    2006-09-01

    We describe a new technology based on thermoforming as a microfabrication process. It significantly enhances the tailoring of polymers for three dimensional tissue engineering purposes since for the first time highly resolved surface and bulk modifications prior to a microstructuring process can be realised. In contrast to typical micro moulding techniques, the melting phase is avoided and thus allows the forming of pre-processed polymer films. The polymer is formed in a thermoelastic state without loss of material coherence. Therefore, previously generated modifications can be preserved. To prove the feasibility of our newly developed technique, so called SMART = Substrate Modification And Replication by Thermoforming, polymer films treated by various polymer modification methods, like UV-based patterned films, and films modified by the bombardment with energetic heavy ions, were post-processed by microthermoforming. The preservation of locally applied specific surface and bulk features was demonstrated e.g. by the selective adhesion of cells to patterned microcavity walls.

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

    SciTech Connect

    Sezer, Güneş Günay; Yeşilel, Okan Zafer; Erer, Hakan; Şahin, Onur

    2016-01-15

    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 with 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.

  17. Syntheses, structures, and photoluminescence of d 10 coordination architectures: From 1D to 3D complexes based on mixed ligands

    NASA Astrophysics Data System (ADS)

    Yuan, Gang; Shao, Kui-Zhan; Du, Dong-Ying; Wang, Xin-Long; Su, Zhong-Min

    2011-05-01

    Six new compounds, namely, {[Cd 3(Himpy) 3(tda) 2]·3H 2O} n ( 1), {[Zn 3(bipy) 2(tda) 2(H 2O) 2]·4H 2O} n ( 2), {[Cd 3(bipy) 3(tda) 2]·4H 2O} n ( 3), {[Cd 3(tda) 2(H 2O) 3Cl]·H 2O} n ( 4), {[Zn 2(tz)(tda)(H 2O) 2]·H 2O} n ( 5) and {[Cd 7(pz)(tda) 4(OAc)(H 2O) 7]·3H 2O} n ( 6) [H 3tda = 1H-1,2,3-triazole-4,5-dicarboxylic acid, Himpy = 2-(1H-imidazol-2-yl)pyridine, bipy = 2,2'-bipyridine, Htz = 1H-1,2,4-triazole, H 2pz = piperazine] have been prepared under hydrothermal condition and characterized by elemental analyses, infrared spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analyses. Compound 1 is a 1D column-like structure and displays a 3D supramolecular network via the π···π stacking interaction. The compounds 2 and 3 exhibit similar 2D layer-like structure, which further extend to 3D supermolecular structure by the π···π stacking interaction. All of compounds 4- 6 display 3D framework with diverse topology constructed from the tda 3- ligands in different coordination modes and secondary ligands (or bridging atom) connecting metal ions. Furthermore, the thermal stabilities and photoluminescent properties of compounds 1- 6 were studied.

  18. A hierarchical 3D segmentation method and the definition of vertebral body coordinate systems for QCT of the lumbar spine.

    PubMed

    Mastmeyer, André; Engelke, Klaus; Fuchs, Christina; Kalender, Willi A

    2006-08-01

    We have developed a new hierarchical 3D technique to segment the vertebral bodies in order to measure bone mineral density (BMD) with high trueness and precision in volumetric CT datasets. The hierarchical approach starts with a coarse separation of the individual vertebrae, applies a variety of techniques to segment the vertebral bodies with increasing detail and ends with the definition of an anatomic coordinate system for each vertebral body, relative to which up to 41 trabecular and cortical volumes of interest are positioned. In a pre-segmentation step constraints consisting of Boolean combinations of simple geometric shapes are determined that enclose each individual vertebral body. Bound by these constraints viscous deformable models are used to segment the main shape of the vertebral bodies. Volume growing and morphological operations then capture the fine details of the bone-soft tissue interface. In the volumes of interest bone mineral density and content are determined. In addition, in the segmented vertebral bodies geometric parameters such as volume or the length of the main axes of inertia can be measured. Intra- and inter-operator precision errors of the segmentation procedure were analyzed using existing clinical patient datasets. Results for segmented volume, BMD, and coordinate system position were below 2.0%, 0.6%, and 0.7%, respectively. Trueness was analyzed using phantom scans. The bias of the segmented volume was below 4%; for BMD it was below 1.5%. The long-term goal of this work is improved fracture prediction and patient monitoring in the field of osteoporosis. A true 3D segmentation also enables an accurate measurement of geometrical parameters that may augment the clinical value of a pure BMD analysis.

  19. 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.

  20. 3D-printing of pH-responsive and functional polymers on an affordable desktop printer.

    PubMed

    Nadgorny, Milena; Xiao, Zeyun; Chen, Chao; Connal, Luke A

    2016-10-03

    In this work we describe the synthesis, thermal and rheological characterization, hot-melt extrusion and three-dimensional printing (3DP) of poly(2-vinylpyridine) (P2VP). We investigate the effect of thermal processing conditions on physical properties of produced filaments in order to achieve high quality, 3D- printable filaments for fused deposition modeling (FDM). We 3D-print P2VP filaments using an affordable 3D printer. The pyridine moieties are crosslinked and quaternized post-printing to form 3D-printed pH-responsive hydrogels. The printed objects exhibited dynamic and reversible pH-dependent swelling. These hydrogels act as flow regulating valves, controlling the flow rate with pH. Additionally, a macroporous P2VP membrane was 3D-printed and the coordinating ability of the pyridyl groups was harassed to immobilize silver precursors on its surface. After the reduction of silver ions, the structure was used to catalyze the reduction of 4-nitrophenol to 4-aminophenol with a high efficiency. This is a facile technique to print recyclable catalytic objects.

  1. Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides.

    PubMed

    Lamprou, Alexandros; Wang, Hongxia; Saeed, Adeela; Svec, Frantisek; Britt, David; Maya, Fernando

    2015-07-14

    We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process. The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

  2. Determination of Rectification Corrections for Semi Gantry Crane Rail Axes in the Local 3D Coordinate System

    NASA Astrophysics Data System (ADS)

    Filipiak, Daria; Kamiński, Waldemar

    2015-02-01

    Electronic tacheometers are currently the standard instruments used in geodetic work, including also geodetic engineering measurements. The main advantage connected with this equipment is among others high accuracy of the measurement and thus high accuracy of the final determinations represented for example by the points' coordinates. One of many applications of the tacheometers is the measurement of crane rail axes. This measurement is based on polar method and it allows to get the spatial coordinates of points in 3D local system. The standard technology of measurement of crane rail axes and development of its calculations' results is well-known and widely presented in the subject literature. At the same time new methods of observations results evaluation are developing. Some new proposals for the development of measurement results were already presented in (Kamiński, 2013). This paper is a generalisation of the paper quoted above. The authors developed the concept which was presented there by a proposal for determining rectification corrections for semi gantry crane rail axes. To carried out the task, the parametric method with conditions on parameters was used. Moreover the practical tests on simulated measurement results were conducted. The results obtained from alignment confirmed the theoretical assumptions. Despite the fact that analyses were carried out only on the simulated data, it is already possible to say that presented method for determination of rectification corrections for crane rail axes can be used for development of the observations from real measurement.

  3. A σ-coordinate model for 3D free-surface flows using an unstructured finite-volume technique

    NASA Astrophysics Data System (ADS)

    Uh Zapata, Miguel

    2016-11-01

    The aim of this work is to develop a numerical solution of three-dimensional free-surface flows using a σ-coordinate model, a projection method and an unstructured finite-volume technique. The coordinate transformation is used in order to overcome difficulties arising from free surface elevation and irregular geometry. The projection method consists to combine the momentum and continuity equations in order to establish a Poisson-type equation for the non-hydrostatic pressure. A cell-centered finite volume method with a triangular mesh in the horizontal direction is used to simulate the flows with free-surfaces, in which the average values of conserved variables are stored at the centre of each element. A parallel algorithm is also presented for the finite volume discretization of the 3D Navier-Stokes equations. The proposed parallel method is formulated by using a multi-color SOR method, a block domain decomposition and interprocessor data communication techniques with Message Passing Interface. The model has been validated by several benchmarks which numerical simulations are in good agreement with the corresponding analytical and existing experimental results.

  4. 3D Printing of Human Tissue Mimics via Layer-by-Layer Assembly of Polymer/Hydrogel Biopapers

    NASA Astrophysics Data System (ADS)

    Ringeisen, Bradley

    2015-03-01

    The foundations of tissue engineering were built on two fundamental areas of research: cells and scaffolds. Multipotent cells and their derivatives are traditionally randomly seeded into sophisticated polymer or hydrogel scaffolds, ultimately with the goal of forming a tissue-like material through cell differentiation and cell-material interactions. One problem with this approach is that no matter how complex or biomimetic the scaffold is, the cells are still homogeneously distributed throughout this three dimensional (3D) material. Natural tissue is inherently heterogeneous on both a microscopic and macroscopic level. It also contains different types of cells in close proximity, extracellular matrix, voids, and a complex vascularized network. Recently developed 3D cell and organ printers may be able to enhance traditional tissue engineering experiments by building scaffolds layer-by-layer that are crafted to mimic the microscopic and macroscopic structure of natural tissue or organs. Over the past decade, my laboratory has developed a capillary-free, live cell printer termed biological laser printing, or BioLP. We find that printed cells do not express heat shock protein and retain >99% viability. Printed cells also incur no DNA strand fracture and preserve their ability to differentiate. Recent work has used a layer-by-layer approach, stacking sheets of hybrid polymer/hydrogel biopapers in conjunction with live cell printing to create 3D tissue structures. Our specific work is now focused on the blood-brain-barrier and air-lung interface and will be described during the presentation.

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

    NASA Astrophysics Data System (ADS)

    Si, Zhen-Xiu; Xu, Wei; Zheng, Yue-Qing

    2016-07-01

    An uranium coordination polymer, namely [(UO2(pydc)(H2O)]·H2O (1) (H2pydc=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 UO22+ 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 well 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.

  6. 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.

  7. Shape-memory polymer nanocomposites with a 3D conductive network for bidirectional actuation and locomotion application.

    PubMed

    Peng, Qingyu; Wei, Hongqiu; Qin, Yuyang; Lin, Zaishan; Zhao, Xu; Xu, Fan; Leng, Jinsong; He, Xiaodong; Cao, Anyuan; Li, Yibin

    2016-10-27

    Electrical stimulation of shape-memory polymers (SMPs) has many advantages over thermal methods; creating an efficient conductive path through the bulk polymers is essential for developing high performance electroactive systems. Here, we show that a three-dimensional (3D) porous carbon nanotube sponge can serve as a built-in integral conductive network to provide internal, homogeneous, in situ Joule heating for shape-memory polymers, thus significantly improving the mechanical and thermal behavior of SMPs. As a result, the 3D nanocomposites show a fast response and produce large exerting forces (with a maximum flexural stress of 14.6 MPa) during shape recovery. We further studied the construction of a double-layer composite structure for bidirectional actuation, in which the shape change is dominated by the temperature-dependent exerting force from the top and bottom layer, alternately. An inchworm-type robot is demonstrated whose locomotion is realized by such bidirectional shape memory. Our large stroke shape-memory nanocomposites have promising applications in many areas including artificial muscles and bionic robots.

  8. 3D printing PLGA: a quantitative examination of the effects of polymer composition and printing parameters on print resolution.

    PubMed

    Guo, Ting; Holzberg, Timothy R; Lim, Casey G; Gao, Feng; Gargava, Ankit; Trachtenberg, Jordan E; Mikos, Antonios G; Fisher, John P

    2017-04-12

    In the past few decades, 3D printing has played a significant role in fabricating scaffolds with consistent, complex structure that meet patient-specific needs in future clinical applications. Although many studies have contributed to this emerging field of additive manufacturing, which includes material development and computer-aided scaffold design, current quantitative analyses do not correlate material properties, printing parameters, and printing outcomes to a great extent. A model that correlates these properties has tremendous potential to standardize 3D printing for tissue engineering and biomaterial science. In this study, we printed poly(lactic-co-glycolic acid) (PLGA) utilizing a direct melt extrusion technique without additional ingredients. We investigated PLGA with various lactic acid:glycolic acid (LA:GA) molecular weight ratios and end caps to demonstrate the dependence of the extrusion process on the polymer composition. Micro-computed tomography was then used to evaluate printed scaffolds containing different LA:GA ratios, composed of different fiber patterns, and processed under different printing conditions. We built a statistical model to reveal the correlation and predominant factors that determine printing precision. Our model showed a strong linear relationship between the actual and predicted precision under different combinations of printing conditions and material compositions. This quantitative examination establishes a significant foreground to 3D print biomaterials following a systematic fabrication procedure. Additionally, our proposed statistical models can be applied to couple specific biomaterials and 3D printing applications for patient implants with particular requirements.

  9. Microstructure of 3D-Printed Polymer Composites Investigated by Small-Angle Neutron Scattering

    NASA Astrophysics Data System (ADS)

    Kang, Tae Hui; Compton, Brett G.; Heller, William T.; Urban, Voker S.; Duty, Chad E.; Do, Changwoo

    Polymer composites printed from the large scale printer at Manufacturing Demonstration Facility at Oak Ridge National Laboratory have been investigated by small-angle neutron scattering (SANS). For the Acrylonitrile Butadiene Styrene (ABS)/Carbon Fiber (CF) composites, the microstructure of polymer domains and the alignment of CF have been characterized across the layer from the printed piece. CF shows strong anisotropic alignment along the printing direction due to the flow of polymer melt at the nozzle. Order parameter of the anisotropy which ranges from -0.11 to -0.06 exhibits strong correlation with the position within the layer: stronger alignment near the layer interface. It is also confirmed that the existence of CF reduces the polymer domain correlation length significantly and reinforces the mechanical strength of the polymer composites. For the Epoxy/nano-clay platelet composites, the effect of processing condition, nozzle size, and the addition of the another filler, Silicon Carbide (SC), have been investigated by SANS. Nano-clay platelet shows strong anisotropic alignment along the printing direction as well. Order parameter of the anisotropy varies according to nozzle size and presence of the SC, and difference disappears at high Q region. Scientific User Facilities Division and Materials Sciences and Energy Division, Office of Basic Energy Sciences, U.S. Department of Energy.

  10. The history and principles of chemical dosimetry for 3-D radiation fields: gels, polymers and plastics.

    PubMed

    Doran, Simon J

    2009-03-01

    Over recent decades, modern protocols of external beam radiotherapy have been developed that involve very steep dose gradients and are thus extremely sensitive to errors in treatment delivery. A recent credentialling study by the Radiological Physics Center at the MD Anderson Cancer Center (Texas, USA) has noted potentially significant inaccuracies in test treatments at a variety of institutions. 3-D radiation dosimetry (often referred to as "gel dosimetry") may have an important role in commissioning new treatment protocols, to help prevent this type of error. This article discusses the various techniques of 3-D radiation dosimetry, with a focus on the types of radiosensitive samples used and on the optical computed tomography readout technique.

  11. Laser-Micro/Nanofabricated 3D Polymers for Tissue Engineering Applications

    NASA Astrophysics Data System (ADS)

    Danilevičius, P.; Žukauskas, A.; Bičkauskaitė, G.; Purlys, V.; Rutkauskas, M.; Gertus, T.; Paipulas, D.; Matukaitė, J.; Baltriukienė, D.; Malinauskas, M.

    2011-01-01

    A multi-photon polymerization system has been designed based on a pulsed irradiation light source (diode-pumped solid state femtosecond laser Yb:KGW, 300 fs, 1030 nm, 1-200 kHz) in combination with large working area and high precision linear motor driven stages (100×100×50 mm3). The system is intended for high resolution and throughput 3D micro- and nanofabrication and enables manufacturing the polymeric templates up to 1 cm2 areas with sub-micrometer resolution. These can be used for producing 3D artificial polymeric scaffolds to be applied for growing cells, specifically, in the tissue engineering. The bio-compatibility of different acrylate, hybrid organic-inorganic and biodegradable polymeric materials is evaluated experimentally in vitro. Variously sized and shaped polymeric scaffolds of biocompatible photopolymers with intricate 3D geometry were successfully fabricated. Proliferation tests for adult rabbit myogenic stem cells have shown the applicability of artificial scaffolds in biomedicine practice.

  12. Fabrication of 3D polymer photonic crystals for near-IR applications

    NASA Astrophysics Data System (ADS)

    Yao, Peng; Qiu, Liang; Shi, Shouyuan; Schneider, Garrett J.; Prather, Dennis W.; Sharkawy, Ahmed; Kelmelis, Eric

    2008-02-01

    Photonic crystals[1, 2] have stirred enormous research interest and became a growing enterprise in the last 15 years. Generally, PhCs consist of periodic structures that possess periodicity comparable with the wavelength that the PhCs are designed to modulate. If material and periodic pattern are properly selected, PhCs can be applied to many applications based on their unique properties, including photonic band gaps (PBG)[3], self-collimation[4], super prism[5], etc. Strictly speaking, PhCs need to possess periodicity in three dimensions to maximize their advantageous capabilities. However, many current research is based on scaled two-dimensional PhCs, mainly due to the difficulty of fabrication such three-dimensional PhCs. Many approaches have been explored for the fabrication of 3D photonic crystals, including layer-by-layer surface micromachining[6], glancing angle deposition[7], 3D micro-sculpture method[8], self-assembly[9] and lithographical methods[10-12]. Among them, lithographic methods became increasingly accepted due to low costs and precise control over the photonic crystal structure. There are three mostly developed lithographical methods, namely X-ray lithography[10], holographic lithography[11] and two-photon polymerization[12]. Although significant progress has been made in developing these lithography-based technologies, these approaches still suffer from significant disadvantages. X-ray lithography relies on an expensive radiation source. Holographic lithography lacks the flexibility to create engineered defects, and multi-photon polymerization is not suitable for parallel fabrication. In our previous work, we developed a multi-layer photolithography processes[13, 14] that is based on multiple resist application and enhanced absorption upon exposure. Using a negative lift-off resist (LOR) and 254nm DUV source, we have demonstrated fabrication of 3D arbitrary structures with feature size of several microns. However, severe intermixing problem

  13. 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.

  14. A Novel Identification Methodology for the Coordinate Relationship between a 3D Vision System and a Legged Robot.

    PubMed

    Chai, Xun; Gao, Feng; Pan, Yang; Qi, Chenkun; Xu, Yilin

    2015-04-22

    Coordinate identification between vision systems and robots is quite a challenging issue in the field of intelligent robotic applications, involving steps such as perceiving the immediate environment, building the terrain map and planning the locomotion automatically. It is now well established that current identification methods have non-negligible limitations such as a difficult feature matching, the requirement of external tools and the intervention of multiple people. In this paper, we propose a novel methodology to identify the geometric parameters of 3D vision systems mounted on robots without involving other people or additional equipment. In particular, our method focuses on legged robots which have complex body structures and excellent locomotion ability compared to their wheeled/tracked counterparts. The parameters can be identified only by moving robots on a relatively flat ground. Concretely, an estimation approach is provided to calculate the ground plane. In addition, the relationship between the robot and the ground is modeled. The parameters are obtained by formulating the identification problem as an optimization problem. The methodology is integrated on a legged robot called "Octopus", which can traverse through rough terrains with high stability after obtaining the identification parameters of its mounted vision system using the proposed method. Diverse experiments in different environments demonstrate our novel method is accurate and robust.

  15. A Novel Identification Methodology for the Coordinate Relationship between a 3D Vision System and a Legged Robot

    PubMed Central

    Chai, Xun; Gao, Feng; Pan, Yang; Qi, Chenkun; Xu, Yilin

    2015-01-01

    Coordinate identification between vision systems and robots is quite a challenging issue in the field of intelligent robotic applications, involving steps such as perceiving the immediate environment, building the terrain map and planning the locomotion automatically. It is now well established that current identification methods have non-negligible limitations such as a difficult feature matching, the requirement of external tools and the intervention of multiple people. In this paper, we propose a novel methodology to identify the geometric parameters of 3D vision systems mounted on robots without involving other people or additional equipment. In particular, our method focuses on legged robots which have complex body structures and excellent locomotion ability compared to their wheeled/tracked counterparts. The parameters can be identified only by moving robots on a relatively flat ground. Concretely, an estimation approach is provided to calculate the ground plane. In addition, the relationship between the robot and the ground is modeled. The parameters are obtained by formulating the identification problem as an optimization problem. The methodology is integrated on a legged robot called “Octopus”, which can traverse through rough terrains with high stability after obtaining the identification parameters of its mounted vision system using the proposed method. Diverse experiments in different environments demonstrate our novel method is accurate and robust. PMID:25912350

  16. Tracking and quantifying polymer therapeutic distribution on a cellular level using 3D dSTORM

    PubMed Central

    Hartley, Jonathan M.; Zhang, Rui; Gudheti, Manasa; Yang, Jiyuan; Kopeček, Jindřich

    2016-01-01

    We used a single-molecule localization technique called direct stochastic optical reconstruction microscopy (dSTORM) to quantify both colocalization and spatial distribution on a cellular level for two conceptually different N-(2-hydroxypropyl)methacrylamide (HPMA) copolymer conjugates. Microscopy images were acquired of entire cells with resolutions as high as 25 nm revealing the nanoscale distribution of the fluorescently labeled therapeutic components. Drug-free macromolecular therapeutics consisting of two self-assembling nanoconjugates showed slight increase in nanoclusters on the cell surface with time. Additionally, dSTORM provided high resolution images of the nanoscale organization of the self-assembling conjugates at the interface between two cells. A conjugate designed for treating ovarian cancer showed that the model drug (Cy3) and polymer bound to Cy5 were colocalized at an early time point before the model drug was enzymatically cleaved from the polymer. Using spatial descriptive statistics it was found that the drug was randomly distributed after 24 h while the polymer bound dye remained in clusters. Four different fluorescent dyes were used and two different therapeutic systems were tested to demonstrate the versatility and possible general applicability of dSTORM for use in studying drug delivery systems. PMID:26855050

  17. Characterisation of PRESAGE: A new 3-D radiochromic solid polymer dosemeter for ionising radiation.

    PubMed

    Adamovics, J; Maryanski, M J

    2006-01-01

    For the past 50 years there has been interest in developing 3-D dosemeters for ionising radiation. Particular emphasis has been put on those dosemeters that change their optical properties in proportion to the absorbed dose. Many of the dosemeters that have been evaluated have had limitations such as lack of transparency, diffusion of the image of the dose distribution or poor stability of baseline optical density. Many of these performance limitations have been overcome by the development of PRESAGE, an optically clear polyurethane-based radiochromic 3-D dosemeter. The solid PRESAGE dosemeter is formulated with a free radical initiator and a leuco dye and it does not require a container to maintain its shape. The polyurethane matrix is tissue equivalent and prevents the diffusion of the dose distribution image. There is a linear dose-response, which is independent of both photon energy and dose rate. Simple precautions such as preventing long-term exposure to additional ionising radiation including ultraviolet and controlling storage temperatures prevent the bleaching of the radiochromic response field within the irradiated dosemeter.

  18. 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.

  19. Thermal- and pressure-induced cooperative spin transition in the 2D and 3D coordination polymers {Fe(5-Br-pmd)z[M(CN)x]y} (M=AgI, AuI, NiII, PdII, PtII).

    PubMed

    Agustí, Gloria; Gaspar, Ana Belén; Muñoz, M Carmen; Real, José Antonio

    2007-11-12

    A new family of cyanide-based spin-crossover polymers with the general formula {Fe(5-Br-pmd)z[M(CN)x]y} [M=AgI (1), AuI (2), NiII (3), PdII (4), PtII (5); 5-Br-pmd=5-bromopyrimidine; z=1 or 2, x=2 or 4, and y=2 or 1] have been synthesized and characterized using single-crystal X-ray diffraction (XRD), X-ray powder diffraction (XRPD), magnetic susceptibility measurements, and differential scanning calorimetry (DSC). At 293 K, compound 1 presents the monoclinic space group C2/c, whereas at 120 K, it changes to the monoclinic space group P21/c. At 293 K, the crystal structure of 1 displays an uninodal three-dimensional network whose nodes, constituted of FeII, lie at the inversion center of an elongated octahedron. The equatorial bond lengths are defined by the N atoms of four [AgI(CN)2]- groups belonging to two crystallographically nonequivalent AgI atoms, Ag(1) and Ag(2). They are shorter than those of the axial positions occupied by the N atoms of the 5-Br-pmd ligands. The Fe-N average bond length of 2.1657(7) A is consistent with a high-spin (HS) state for the FeII ions. At 120 K, the crystal structure changes refer mainly to the FeII environment. There are two crystallographically independent FeII ions at this temperature, Fe(1) and Fe(2), which adopt the HS and low-spin (LS) states, respectively. The average Fe-N bond length for Fe(1) [2.174(5) A] and Fe(2) [1.955(5) A] agrees well with the reported magnetic data at this temperature. The spin transition of the FeII ions labeled as Fe(1) is found to be centered at Tc downward arrow=149 K and Tc upward arrow=167 K and accompanied by a drastic change of color from orange (HS) to red (LS). Magnetic susceptibility measurements under applied hydrostatic pressure performed on 1 have shown a linear displacement of the transition to higher temperatures while the hysteresis width remains unaltered in the interval of pressures of 105 Pa to 0.34 GPa. A further increase of the pressure induces the spin transition in the Fe(2

  20. A 3D sphere culture system containing functional polymers for large-scale human pluripotent stem cell production.

    PubMed

    Otsuji, Tomomi G; Bin, Jiang; Yoshimura, Azumi; Tomura, Misayo; Tateyama, Daiki; Minami, Itsunari; Yoshikawa, Yoshihiro; Aiba, Kazuhiro; Heuser, John E; Nishino, Taito; Hasegawa, Kouichi; Nakatsuji, Norio

    2014-05-06

    Utilizing human pluripotent stem cells (hPSCs) in cell-based therapy and drug discovery requires large-scale cell production. However, scaling up conventional adherent cultures presents challenges of maintaining a uniform high quality at low cost. In this regard, suspension cultures are a viable alternative, because they are scalable and do not require adhesion surfaces. 3D culture systems such as bioreactors can be exploited for large-scale production. However, the limitations of current suspension culture methods include spontaneous fusion between cell aggregates and suboptimal passaging methods by dissociation and reaggregation. 3D culture systems that dynamically stir carrier beads or cell aggregates should be refined to reduce shearing forces that damage hPSCs. Here, we report a simple 3D sphere culture system that incorporates mechanical passaging and functional polymers. This setup resolves major problems associated with suspension culture methods and dynamic stirring systems and may be optimal for applications involving large-scale hPSC production.

  1. Microfluidic assay of endothelial cell migration in 3D interpenetrating polymer semi-network HA-Collagen hydrogel.

    PubMed

    Jeong, Gi Seok; Kwon, Gu Han; Kang, Ah Ran; Jung, Bo Young; Park, Yongdoo; Chung, Seok; Lee, Sang-Hoon

    2011-08-01

    Cell migration through the extracellular matrix (ECM) is one of the key features for physiological and pathological processes such as angiogenesis, cancer metastasis, and wound healing. In particular, the quantitative assay of endothelial cell migration under the well-defined three dimensional (3D) microenvironment is important to analyze the angiogenesis mechanism. In this study, we report a microfluidic assay of endothelial cell sprouting and migration into an interpenetrating polymer semi-network HA-Collagen (SIPNs CH) hydrogel as ECM providing an enhanced in vivo mimicking 3D microenvironment to cells. The microfluidic chip could provide a well-controlled gradient of growth factor to cells, whereas the hydrogel could mimic a well-defined 3D microenvironment in vivo. (In addition/Furthermore, the microfluidic chip gives a well-controlled gradient of growth factor to cells) For this reason, three types of hydrogel, composed of semi-interpenetrating networks of collagen and hyaluronic acid were prepared, and firstly we proved the role of the hydrogel in endothelial cell migration. The diffusion property and swelling ratio of the hydrogel were characterized. It modulated the migration of endothelial cells in quantified manner, also being influenced by additional synthesis of Matrix metalloproteinase(MMP)-sensitive remodeling peptides and Arginine-glycine-lycinee (RGD) cell adhesion peptides. We successfully established a novel cell migration platform by changing major determinants such as ECM material under biochemical synthesis and under growth factor gradients in a microfluidic manner.

  2. 3D Rare earth porous coordination frameworks with formamide generated in situ syntheses: Crystal structure and down- and up-conversion luminescence

    SciTech Connect

    Ma, Xue; Tian, Jing; Yang, Hong-Y.; Zhao, Kai; Li, Xia

    2013-05-01

    The reaction of RE(NO)₃·6H₂O and formamide yielded the coordination polymers, [RE(HCOO)₄]⁻[NH₂CHNH₂]⁺ (RE=Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Er 6, and Yb 7). They possess 3D porous frameworks with the 1D rhombic channels occupied by [NH₂CHNH₂]⁺ cations. Complexes 2 and 4 display the characteristic down-conversion emissions corresponding to ⁵D₀→⁷FJ (J=1–4) transitions of Eu(III) ion and ⁵D₄→⁷FJ (J=6–3) transitions of Tb(III) ion, respectively. Longer lifetime values of 2.128±0.002 ms (⁵D₀) for 2 and 2.132±0.002 ms (⁵D₄) for 4 have been observed. The up-conversion spectra of the Y:Yb,Er and Gd:Yb,Er codoped complexes exhibit three emission bands around 410 (⁴H9/2→⁴I15/2, blue), 518–570 (⁴S3/2, ²H11/2→⁴I15/2, green), and 655 nm (⁴F9/2→⁴I15/2, red). - Graphical Abstract: The complexes [RE(HCOO)₄]⁻[NH₂CHNH₂]⁺ possess 3D porous frameworks. Eu(III) and Tb(III) complexes show characteristic emission of Ln(III) ions. The up-conversion emission of the Y:Yb,Er and Gd:Yb,Er codoped complexes was observed. Highlights: •The reaction of RE(NO)₃·6H₂O and formamide produced complexes [RE(HCOO)₄]⁻[NH₂CHNH₂]⁺. • The complexes possess 3D frameworks with the 1D channels occupied by [NH₂CHNH₂]+ cations. • Eu(III)/Tb(III) complexes display the characteristic down-conversion emission of Ln(III) ions. • The Y:Yb,Er and Gd:Yb,Er doped complexes exhibit the up-conversion emission.

  3. Rendering non-energetic microporous coordination polymers explosive.

    PubMed

    McDonald, Kyle A; Bennion, Jonathan C; Leone, Amanda K; Matzger, Adam J

    2016-09-18

    Adsorption of oxidizing guest molecules into a non-energetic microporous coordination polymer produces explosives with desirable oxygen balance, high heat released upon decomposition, and suppressed vapor pressure of the guest. Here, this results in primary explosives, materials very sensitive to impact, that have the potential to be used as replacements for lead-based initiators.

  4. 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.

  5. Highly conductive self-assembled nanoribbons of coordination polymers.

    PubMed

    Welte, Lorena; Calzolari, Arrigo; Di Felice, Rosa; Zamora, Felix; Gómez-Herrero, Julio

    2010-02-01

    Organic molecules can self-assemble into well-ordered structures, but the conductance of these structures is limited, which is a disadvantage for applications in molecular electronics. Conductivity can be improved by using coordination polymers-in which metal centres are incorporated into a molecular backbone-and such structures have been used as molecular wires by self-assembling them into ordered films on metal surfaces. Here, we report electrically conductive nanoribbons of the coordination polymer [Pt(2)I(S(2)CCH(3))(4)](n) self-assembled on an insulating substrate by direct sublimation of polymer crystals. Conductance atomic force microscopy is used to probe the electrical characteristics of a few polymer chains ( approximately 10) within the nanoribbons. The observed currents exceed those previously sustained in organic and metal-organic molecules assembled on surfaces by several orders of magnitude and over much longer distances. These results, and the results of theoretical calculations based on density functional theory, confirm coordination polymers as candidate materials for applications in molecular electronics.

  6. Quartic canonical force field in curvilinear internal coordinates for XY3 (D3h) molecules. The case of the BH3 molecule.

    PubMed

    Ródenas, Consuelo Rosales; Quesada, Juana Vázquez; Torres, Emilio Martínez; González, Juan Jesús López

    2014-06-01

    Using the canonical force field theory, expressions of quadratic, cubic, and quartic canonical force constants are obtained for XY3 (D3h) molecules in curvilinear redundant coordinates, i.e., simple valence internal coordinates (VICs), in terms of force constants in normal coordinates and in independent symmetry coordinates. To carry out this task, it was previously necessary to obtain for the first time the non-linear redundancy relation and the corresponding orthogonal projection onto the pure vibrational manifold for XY3 (D3h) molecules corresponding to a set of seven VICs. As an application, the quartic canonical force field in curvilinear redundant internal coordinates of BH3 is determined from ab initio force fields in normal coordinates calculated at the coupled-cluster singles and doubles level with perturbative treatment of the triples in conjunction with a triple- and quadruple-ζ size basis set. This anharmonic force field so obtained for the borane molecule, and in general for XY3 (D3h) molecules, is uniquely defined (therefore in an unambiguous form) and depending on the same number of parameters, i.e., force constants, when independent coordinates (natural or symmetry) are used in its description.

  7. Water-Resistant and Transparent Plastic Films from Functionalizable Organic Polymers: Coordination Polymers as Templates for Solid-State [2+2]-Photopolymerization.

    PubMed

    Garai, Mousumi; Biradha, Kumar

    2017-01-05

    An organic polymer containing cyclobutanes and amides as backbones and pyridyl groups as sidearms was synthesized by single-crystal-to-single-crystal (SCSC) [2+2]-photopolymerization in the coordination polymers (CPs) of diene. The diene molecule was photo-inactive in its crystals and formed a triply intertwined 1D-helical CP with Cd(NO3 )2 and Cu(NO3 )2 salts. The 1D-CP was transformed into a coordination polymer of organic polymers containing threefold interpenetrated 3D-networks of CdSO4 topology through a [2+2]-reaction in SCSC manner upon irradiation. The organic polymer was separated from its CPs and found to have an unusually high degree of polymerization for this type of reaction. Furthermore, the organic polymer was amenable for N-alkylation reactions such as methylation, propylation, and decylation. The formate salts of the organic polymer and the methylated polymer were shown to form plastic films with a combination of properties such as high transparency, tensile strengths, gas permeability, thermal stability, water-resistance, and resistance to other organic solvents. The methylated polymer was also able to capture chromate ions and anionic dyes from aqueous solutions.

  8. Small-Field Measurements of 3D Polymer Gel Dosimeters through Optical Computed Tomography

    PubMed Central

    Shih, Cheng-Ting; Lee, Yao-Ting; Wu, Shin-Hua; Yao, Chun-Hsu; Hsieh, Bor-Tsung

    2016-01-01

    With advances in therapeutic instruments and techniques, three-dimensional dose delivery has been widely used in radiotherapy. The verification of dose distribution in a small field becomes critical because of the obvious dose gradient within the field. The study investigates the dose distributions of various field sizes by using NIPAM polymer gel dosimeter. The dosimeter consists of 5% gelatin, 5% monomers, 3% cross linkers, and 5 mM THPC. After irradiation, a 24 to 96 hour delay was applied, and the gel dosimeters were read by a cone beam optical computed tomography (optical CT) scanner. The dose distributions measured by the NIPAM gel dosimeter were compared to the outputs of the treatment planning system using gamma evaluation. For the criteria of 3%/3 mm, the pass rates for 5 × 5, 3 × 3, 2 × 2, 1 × 1, and 0.5 × 0.5 cm2 were as high as 91.7%, 90.7%, 88.2%, 74.8%, and 37.3%, respectively. For the criteria of 5%/5 mm, the gamma pass rates of the 5 × 5, 3 × 3, and 2 × 2 cm2 fields were over 99%. The NIPAM gel dosimeter provides high chemical stability. With cone-beam optical CT readouts, the NIPAM polymer gel dosimeter has potential for clinical dose verification of small-field irradiation. PMID:26974434

  9. Micro-computed tomography image-based evaluation of 3D anisotropy degree of polymer scaffolds.

    PubMed

    Pérez-Ramírez, Ursula; López-Orive, Jesús Javier; Arana, Estanislao; Salmerón-Sánchez, Manuel; Moratal, David

    2015-01-01

    Anisotropy is one of the most meaningful determinants of biomechanical behaviour. This study employs micro-computed tomography (μCT) and image techniques for analysing the anisotropy of regenerative medicine polymer scaffolds. For this purpose, three three-dimensional anisotropy evaluation image methods were used: ellipsoid of inertia (EI), mean intercept length (MIL) and tensor scale (t-scale). These were applied to three patterns (a sphere, a cube and a right prism) and to two polymer scaffold topologies (cylindrical orthogonal pore mesh and spherical pores). For the patterns, the three methods provided good results. Regarding the scaffolds, EI mistook both topologies (0.0158, [-0.5683; 0.6001]; mean difference and 95% confidence interval), and MIL showed no significant differences (0.3509, [0.0656; 0.6362]). T-scale is the preferable method because it gave the best capability (0.3441, [0.1779; 0.5102]) to differentiate both topologies. This methodology results in the development of non-destructive tools to engineer biomimetic scaffolds, incorporating anisotropy as a fundamental property to be mimicked from the original tissue and permitting its assessment by means of μCT image analysis.

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

    NASA Astrophysics Data System (ADS)

    Meundaeng, Natthaya; Rujiwatra, Apinpus; Prior, Timothy J.

    2017-01-01

    We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu2+ coordination polymers with different dimensionality, namely, 1D [Cu2(5-tza)2(1,10-phenanthroline)2(NO3)2] (1), 2D [Cu(5-tza)2(MeOH)2] (2), and 3D [Cu(5-tza)2]·H2O (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)2]·1.5H2O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air.

  11. Syntheses and structures of three transition metal coordination polymers based on 5-Aminonicotinic acid

    NASA Astrophysics Data System (ADS)

    Jiang, Ya-Hui; Wu, Wei-Ping; Yang, Guo-Ping; Jin, Jun-Cheng; Xi, Zheng-Ping; Wang, Yao-Yu

    2015-07-01

    Three new coordination polymers (CPs) based on rigid ligand 5-Aminonicotinic acid (5-anaH), [Cd(5-ana)2]·(H2O)2 (1), [Cd(5-ana)(HCOO) ] (2) and [Cu(5-ana)2] (3), have been synthesized under different solvent media and temperatures. All CPs are characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, powder X-ray diffraction and thermogravimetric analysis. Compound 1 is a two-dimensional (2D) (4,4)-connected layered structure contains 1D open channels. 2 shows a 2-nodal (3,5)-connected three-dimensional (3D) framework with {52·6}{53·63·73·8} topology. While 3 displays a 3D (3,6)-connected homochiral framework with {42·6}2{44·62·85·104} topology. The solid-state photoluminescence for 1 and 2 were also studied.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Yingjie; Bhadbhade, Mohan; Karatchevtseva, Inna; Price, Jason R.; Liu, Hao; Zhang, Zhaoming; Kong, Linggen; Čejka, Jiří; Lu, Kim; Lumpkin, Gregory R.

    2015-03-01

    Three new coordination polymers of uranium(VI) with pyromellitic acid (H4btca) have been synthesized and structurally characterized. (ED)[(UO2)(btca)]·(DMSO)·3H2O (1) (ED=ethylenediammonium; DMSO=dimethylsulfoxide) has a lamellar structure with intercalation of ED and DMSO. (NH4)2[(UO2)6O2(OH)6(btca)]·~6H2O (2) has a 3D framework built from 7-fold coordinated uranyl trinuclear units and btca ligands with 1D diamond-shaped channels (~8.5 Å×~8.6 Å). [(UO2)2(H2O)(btca)]·4H2O (3) has a 3D network constructed by two types of 7-fold coordinated uranium polyhedron. The unique μ5-coordination mode of btca in 3 enables the formation of 1D olive-shaped large channels (~4.5 Å×~19 Å). Vibrational modes, thermal stabilities and fluorescence properties have been investigated.

  13. Tensile strengths of polyamide based 3D printed polymers in liquid nitrogen

    NASA Astrophysics Data System (ADS)

    Cruz, P.; Shoemake, E. D.; Adam, P.; Leachman, J.

    2015-12-01

    Advances in additive manufacturing technology have made 3D printing a viable solution for many industries, allowing for the manufacture of designs that could not be made through traditional subtractive methods. Applicability of additive manufacturing in cryogenic applications is hindered, however, by a lack of accurate material properties information. Nylon is available for printing using fused deposition modeling (FDM) and selective laser sintering (SLS). We selected 5 SLS (DuraForm® EX, DuraForm® HST, DuraForm® PA, PA 640-GSL, and PA 840-GSL) and 2 FDM (Nylon 12, ULTEM) nylon variants based on the bulk material properties and printed properties at room temperature. Tensile tests were performed on five samples of each material while immersed in liquid nitrogen at approximately 77 Kelvin. Samples were tested in XY and, where available, Z printing directions to determine influence on material properties. Results show typical SLS and FDM nylon ultimate strength retention at 77 K, when compared to (extruded or molded) nylon ultimate strength.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg2+, Ca2+ and Ba2+) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO)4, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (44·62)3(49·66)2. The calcium compound consists of 1D infinite "Ca-O" inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D "Ba-O" inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions' influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies.

  15. Temperature Mapping of 3D Printed Polymer Plates: Experimental and Numerical Study

    PubMed Central

    Kousiatza, Charoula; Chatzidai, Nikoleta; Karalekas, Dimitris

    2017-01-01

    In Fused Deposition Modeling (FDM), which is a common thermoplastic Additive Manufacturing (AM) method, the polymer model material that is in the form of a flexible filament is heated above its glass transition temperature (Tg) to a semi-molten state in the head’s liquefier. The heated material is extruded in a rastering configuration onto the building platform where it rapidly cools and solidifies with the adjoining material. The heating and rapid cooling cycles of the work materials exhibited during the FDM process provoke non-uniform thermal gradients and cause stress build-up that consequently result in part distortions, dimensional inaccuracy and even possible part fabrication failure. Within the purpose of optimizing the FDM technique by eliminating the presence of such undesirable effects, real-time monitoring is essential for the evaluation and control of the final parts’ quality. The present work investigates the temperature distributions developed during the FDM building process of multilayered thin plates and on this basis a numerical study is also presented. The recordings of temperature changes were achieved by embedding temperature measuring sensors at various locations into the middle-plane of the printed structures. The experimental results, mapping the temperature variations within the samples, were compared to the corresponding ones obtained by finite element modeling, exhibiting good correlation. PMID:28245557

  16. Temperature Mapping of 3D Printed Polymer Plates: Experimental and Numerical Study.

    PubMed

    Kousiatza, Charoula; Chatzidai, Nikoleta; Karalekas, Dimitris

    2017-02-24

    In Fused Deposition Modeling (FDM), which is a common thermoplastic Additive Manufacturing (AM) method, the polymer model material that is in the form of a flexible filament is heated above its glass transition temperature (Tg) to a semi-molten state in the head's liquefier. The heated material is extruded in a rastering configuration onto the building platform where it rapidly cools and solidifies with the adjoining material. The heating and rapid cooling cycles of the work materials exhibited during the FDM process provoke non-uniform thermal gradients and cause stress build-up that consequently result in part distortions, dimensional inaccuracy and even possible part fabrication failure. Within the purpose of optimizing the FDM technique by eliminating the presence of such undesirable effects, real-time monitoring is essential for the evaluation and control of the final parts' quality. The present work investigates the temperature distributions developed during the FDM building process of multilayered thin plates and on this basis a numerical study is also presented. The recordings of temperature changes were achieved by embedding temperature measuring sensors at various locations into the middle-plane of the printed structures. The experimental results, mapping the temperature variations within the samples, were compared to the corresponding ones obtained by finite element modeling, exhibiting good correlation.

  17. 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.

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

    SciTech Connect

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

    2015-05-15

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

  19. On the development of a VIPAR(nd) radiotherapy 3D polymer gel dosimeter.

    PubMed

    Kozicki, Marek; Jaszczak, Malwina; Maras, Piotr; Dudek, Mariusz; Cłapa, Marian

    2017-02-07

    This work presents an improvement of the VIPAR(nd) ('nd' stands for 'normoxic, double', or VIP) polymer gel dosimeter. The gel composition was altered by increasing the concentration of the monomeric components, N-vinylpyrrolidone (NVP) and N,N'-methylenebisacrylamide (MBA), in co-solvent solutions. The optimal composition (VIPAR(CT), where 'CT' stands for computed tomography, or VIC) comprised: 17% NVP, 8% MBA, 12% t-BuOH, 7.5% gelatine, 0.007% ascorbic acid, 0.0008% CuSO4  ×  5H2O and 0.02% hydroquinone. The following characteristics of VIC were achieved: (i) linear dose range of 0.9(_)30 Gy, (ii) saturation for radiation doses of over 50 Gy, (iii) threshold dose of about 0.5 Gy, (iv) dose sensitivity of 0.171 Gy(-1) s(-1), which is roughly 2.2 times higher than that of VIP (for nuclear magnetic resonance measurements). It was also found that VIC is dose- rate-independent, and its dose response does not alter if the radiation source is changed from electrons to photons for external beam radiotherapy. The gel responded similarly to irradiation with small changes in radiation energy but was sensitive to larger energy changes. The VIC gel retained temporal stability from 20 h until at least 10 d after irradiation, whereas spatial stability was retained from 20 h until at least 6 d after irradiation. The scheme adopted for VIC manufacturing yields repeatable gels in terms of radiation dose response. The VIC was also shown to perform better than VIP using x-ray computed tomography as a readout method; the dose sensitivity of VIC (0.397 HU Gy(-1)) was 1.5 times higher than that of VIP. Also, the dose resolution of VIC was better than that of VIP in the whole dose range examined.

  20. On the development of a VIPARnd radiotherapy 3D polymer gel dosimeter

    NASA Astrophysics Data System (ADS)

    Kozicki, Marek; Jaszczak, Malwina; Maras, Piotr; Dudek, Mariusz; Cłapa, Marian

    2017-02-01

    This work presents an improvement of the VIPARnd (‘nd’ stands for ‘normoxic, double’, or VIP) polymer gel dosimeter. The gel composition was altered by increasing the concentration of the monomeric components, N-vinylpyrrolidone (NVP) and N,N‧-methylenebisacrylamide (MBA), in co-solvent solutions. The optimal composition (VIPARCT, where ‘CT’ stands for computed tomography, or VIC) comprised: 17% NVP, 8% MBA, 12% t-BuOH, 7.5% gelatine, 0.007% ascorbic acid, 0.0008% CuSO4  ×  5H2O and 0.02% hydroquinone. The following characteristics of VIC were achieved: (i) linear dose range of 0.9_30 Gy, (ii) saturation for radiation doses of over 50 Gy, (iii) threshold dose of about 0.5 Gy, (iv) dose sensitivity of 0.171 Gy-1 s-1, which is roughly 2.2 times higher than that of VIP (for nuclear magnetic resonance measurements). It was also found that VIC is dose- rate-independent, and its dose response does not alter if the radiation source is changed from electrons to photons for external beam radiotherapy. The gel responded similarly to irradiation with small changes in radiation energy but was sensitive to larger energy changes. The VIC gel retained temporal stability from 20 h until at least 10 d after irradiation, whereas spatial stability was retained from 20 h until at least 6 d after irradiation. The scheme adopted for VIC manufacturing yields repeatable gels in terms of radiation dose response. The VIC was also shown to perform better than VIP using x-ray computed tomography as a readout method; the dose sensitivity of VIC (0.397 HU Gy-1) was 1.5 times higher than that of VIP. Also, the dose resolution of VIC was better than that of VIP in the whole dose range examined.

  1. Conductive polymer-mediated 2D and 3D arrays of Mn3O4 nanoblocks and mesoporous conductive polymers as their replicas.

    PubMed

    Nakagawa, Yoshitaka; Kageyama, Hiroyuki; Matsumoto, Riho; Oaki, Yuya; Imai, Hiroaki

    2015-11-28

    Orientation-controlled 2D and 3D microarrays of Mn3O4 nanocuboids that were mediated by a conductive polymer were fabricated by evaporation-induced self-assembly of the oxide nanoblocks and subsequent polymerization of pyrrole in the interparticle spaces. Free-standing mesoporous polypyrroles (PPy) having chain- and square-grid-like nanovoid arrays were obtained as replicas of the composite assemblies by dissolving the oxide nanoblocks. The PPy-mediated manganese oxide arrays exhibited stable electrochemical performance as an ultrathin anode of a lithium-ion secondary battery.

  2. 3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells.

    PubMed

    Niemöller, Arvid; Jakes, Peter; Kayser, Steffen; Lin, Yu; Lehnert, Werner; Granwehr, Josef

    2016-08-01

    Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements. In this communication, it is demonstrated that sample containers produced by 3D printing are suitable for EPR applications, with a particular emphasis on electrochemical applications. The housing of a high temperature polymer electrolyte fuel cell (HT-PEFC) with a phosphoric acid doped polybenzimidazole membrane was prepared from polycarbonate by 3D printing. Using a custom glass Dewar, this fuel cell could be operated at temperatures up to 140°C in a standard EPR cavity. The carbon-based gas diffusion layer showed an EPR signal with a characteristic Dysonian line shape, whose evolution could be monitored in-operando in a non-invasive manner.

  3. 3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Niemöller, Arvid; Jakes, Peter; Kayser, Steffen; Lin, Yu; Lehnert, Werner; Granwehr, Josef

    2016-08-01

    Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements. In this communication, it is demonstrated that sample containers produced by 3D printing are suitable for EPR applications, with a particular emphasis on electrochemical applications. The housing of a high temperature polymer electrolyte fuel cell (HT-PEFC) with a phosphoric acid doped polybenzimidazole membrane was prepared from polycarbonate by 3D printing. Using a custom glass Dewar, this fuel cell could be operated at temperatures up to 140 °C in a standard EPR cavity. The carbon-based gas diffusion layer showed an EPR signal with a characteristic Dysonian line shape, whose evolution could be monitored in-operando in a non-invasive manner.

  4. 3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

    PubMed Central

    Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng; Worsley, Marcus A.; Wu, Amanda S.; Kanarska, Yuliya; Horn, John D.; Duoss, Eric B.; Ortega, Jason M.; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A.; King, Michael J.

    2017-01-01

    Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response. PMID:28262669

  5. Developing Customized Dental Miniscrew Surgical Template from Thermoplastic Polymer Material Using Image Superimposition, CAD System, and 3D Printing

    PubMed Central

    Yu, Jian-Hong; Lo, Lun-Jou; Hsu, Pin-Hsin

    2017-01-01

    This study integrates cone-beam computed tomography (CBCT)/laser scan image superposition, computer-aided design (CAD), and 3D printing (3DP) to develop a technology for producing customized dental (orthodontic) miniscrew surgical templates using polymer material. Maxillary bone solid models with the bone and teeth reconstructed using CBCT images and teeth and mucosa outer profile acquired using laser scanning were superimposed to allow miniscrew visual insertion planning and permit surgical template fabrication. The customized surgical template CAD model was fabricated offset based on the teeth/mucosa/bracket contour profiles in the superimposition model and exported to duplicate the plastic template using the 3DP technique and polymer material. An anterior retraction and intrusion clinical test for the maxillary canines/incisors showed that two miniscrews were placed safely and did not produce inflammation or other discomfort symptoms one week after surgery. The fitness between the mucosa and template indicated that the average gap sizes were found smaller than 0.5 mm and confirmed that the surgical template presented good holding power and well-fitting adaption. This study addressed integrating CBCT and laser scan image superposition; CAD and 3DP techniques can be applied to fabricate an accurate customized surgical template for dental orthodontic miniscrews. PMID:28280726

  6. 3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

    NASA Astrophysics Data System (ADS)

    Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng; Worsley, Marcus A.; Wu, Amanda S.; Kanarska, Yuliya; Horn, John D.; Duoss, Eric B.; Ortega, Jason M.; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A.; King, Michael J.

    2017-03-01

    Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.

  7. Hot-melt extruded filaments based on pharmaceutical grade polymers for 3D printing by fused deposition modeling.

    PubMed

    Melocchi, Alice; Parietti, Federico; Maroni, Alessandra; Foppoli, Anastasia; Gazzaniga, Andrea; Zema, Lucia

    2016-07-25

    Fused deposition modeling (FDM) is a 3D printing technique based on the deposition of successive layers of thermoplastic materials following their softening/melting. Such a technique holds huge potential for the manufacturing of pharmaceutical products and is currently under extensive investigation. Challenges in this field are mainly related to the paucity of adequate filaments composed of pharmaceutical grade materials, which are needed for feeding the FDM equipment. Accordingly, a number of polymers of common use in pharmaceutical formulation were evaluated as starting materials for fabrication via hot melt extrusion of filaments suitable for FDM processes. By using a twin-screw extruder, filaments based on insoluble (ethylcellulose, Eudragit(®) RL), promptly soluble (polyethylene oxide, Kollicoat(®) IR), enteric soluble (Eudragit(®) L, hydroxypropyl methylcellulose acetate succinate) and swellable/erodible (hydrophilic cellulose derivatives, polyvinyl alcohol, Soluplus(®)) polymers were successfully produced, and the possibility of employing them for printing 600μm thick disks was demonstrated. The behavior of disks as barriers when in contact with aqueous fluids was shown consistent with the functional application of the relevant polymeric components. The produced filaments were thus considered potentially suitable for printing capsules and coating layers for immediate or modified release, and, when loaded with active ingredients, any type of dosage forms.

  8. 3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties.

    PubMed

    Lewicki, James P; Rodriguez, Jennifer N; Zhu, Cheng; Worsley, Marcus A; Wu, Amanda S; Kanarska, Yuliya; Horn, John D; Duoss, Eric B; Ortega, Jason M; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A; King, Michael J

    2017-03-06

    Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.

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

    SciTech Connect

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-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. - graphical abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated.

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

    SciTech Connect

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

    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 diversities 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.

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

    PubMed

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

    2015-02-07

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

  12. 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.

  13. Arene Selectivity by a Flexible Coordination Polymer Host

    PubMed Central

    Wright, James S.; Vitórica‐Yrezábal, Iñigo J.; Thompson, Stephen P.

    2016-01-01

    Abstract The coordination polymers [Ag4(O2CCF3)4(phen)3]⋅ phen⋅arene (1⋅phen⋅arene) (phen=phenazine; arene=toluene, p‐xylene or benzene) have been synthesised from the solution phase in a series of arene solvents and crystallographically characterised. By contrast, analogous syntheses from o‐xylene and m‐xylene as the solvent yield the solvent‐free coordination polymer [Ag4(O2CCF3)4(phen)2] (2). Toluene, p‐xylene and benzene have been successfully used in mixed‐arene syntheses to template the formation of coordination polymers 1⋅phen⋅arene, which incorporate o‐ or m‐xylene. The selectivity of 1⋅phen⋅arene for the arene guests was determined, through pairwise competition experiments, to be p‐xylene>toluene≈benzene>o‐xylene>m‐xylene. The largest selectivity coefficient was determined as 14.2 for p‐xylene:m‐xylene and the smallest was 1.0 for toluene:benzene. PMID:27483388

  14. Defining the medial-lateral axis of an anatomical femur coordinate system using freehand 3D ultrasound imaging.

    PubMed

    Passmore, Elyse; Sangeux, Morgan

    2016-03-01

    Hip rotation from gait analysis informs clinical decisions regarding correction of femoral torsional deformities. However, it is among the least repeatable due to discrepancies in determining the medial-lateral axis of the femur. Conventional or functional calibration methods may be used to define the axis but there is no benchmark to evaluate these methods. Freehand 3D ultrasound, the coupling of ultrasound with 3D motion capture, may provide such a benchmark. We measured the accuracy in vitro and repeatability in vivo of determining the femur condylar axis from freehand 3D ultrasound. The condylar axis provided the reference medial-lateral axis of the femur and was used to evaluate one conventional method and three functional calibration methods, applied to three calibration movements. Ten healthy subjects (20 limbs) underwent 3D gait analysis and freehand 3D ultrasound. The functional calibration methods were a transformation technique, a geometrical method and a method that minimises variance of knee varus-valgus kinematics (DynaKAD). The conventional method used markers over the femoral epicondyles. The condylar axis determined by 3D ultrasound showed good accuracy in vitro, 1.6° (SD: 0.3°) and good repeatability in vivo, 0.2° (RSMD: 2.3°). The DynaKAD method applied to the walking calibration movement determined the medial-lateral axis closest to the ultrasound reference. The average angular difference in the transverse plane was 3.1° (SD: 6.1°). Freehand 3D ultrasound offers an accurate, non-invasive and relatively fast method to locate the medial-lateral axis of the femur for gait analysis.

  15. Electrical conductivity and luminescence properties of two silver(I) coordination polymers with heterocyclic nitrogen ligands

    SciTech Connect

    Rana, Abhinandan; Kumar Jana, Swapan; Pal, Tanusri; Puschmann, Horst; Zangrando, Ennio; Dalai, Sudipta

    2014-08-15

    The synthesis and X-ray structural characterization of two novel silver(I) coordination polymers, [Ag(NO{sub 3})(quin)]{sub n} (1) and [Ag{sub 8}(HL){sub 2}(H{sub 2}O){sub 4}(mpyz)]·3H{sub 2}O (2) are reported, where quin=5,6,7,8-tetrahydroquinoxaline, H{sub 6}L=cyclohexane-1,2,3,4,5,6-hexacarboxylic acid and mpyz=2-methyl pyrazine. The single crystal diffraction analyses showed that complex 1 is a 2D layered structure, while 2 presents a 3D polymeric architecture. In complex 2 the network is stabilized by argentophilic interactions and hydrogen bonding. Electrical conductivity of order 3×10{sup −4} Scm{sup −1} (1) and 1.6×10{sup −4} Scm{sup −1} (2) is measured on thin film specimen at room temperature. The photoluminescence and thermal properties of the complexes have also been studied. - Graphical abstract: Two new 1D and 3D coordination polymers of Ag(I) have been synthesized and characterized by X-ray analysis. The electrical, luminescence and thermal properties have been studied. - Highlights: • 1 is 2D layered while 2 present a 3D polymeric architecture. • The network in 2 is stabilized by argentophilic interactions and hydrogen bonding. • Electrical conductivity measurement is quite interesting. • Argentophilic interaction and intra-ligand π{sup ⁎}–π CT explains emission behavior of 2.

  16. H2, N2, CO, and CO2 sorption properties of a series of robust sodalite-type microporous coordination polymers.

    PubMed

    Navarro, Jorge A R; Barea, Elisa; Salas, Juan M; Masciocchi, Norberto; Galli, Simona; Sironi, Angelo; Ania, Conchi O; Parra, José B

    2006-03-20

    H2, N2, CO, and CO2 are readily incorporated in the porous, 3D sodalitic frameworks of coordination polymers of the [ML2]n type, with M = Pd(II) or Cu(II) and HL = 2-hydroxypyrimidine or 4-hydroxypyrimidine. The metal ion and ligand functionalization modulate their sorption properties, making these materials suitable for gas storage and separation purposes.

  17. Heteroatom Polymer-Derived 3D High-Surface-Area and Mesoporous Graphene Sheet-Like Carbon for Supercapacitors.

    PubMed

    Sheng, Haiyang; Wei, Min; D'Aloia, Alyssa; Wu, Gang

    2016-11-09

    Current supercapacitors suffer from low energy density mainly due to the high degree of microporosity and insufficient hydrophilicity of their carbon electrodes. Development of a supercapacitor capable of simultaneously storing as much energy as a battery, along with providing sufficient power and long cycle stability would be valued for energy storage applications and innovations. Differing from commonly studied reduced graphene oxides, in this work we identified an inexpensive heteroatom polymer (polyaniline-PANI) as a carbon/nitrogen precursor, and applied a controlled thermal treatment at elevated temperature to convert PANI into 3D high-surface-area graphene-sheet-like carbon materials. During the carbonization process, various transition metals including Fe, Co, and Ni were added, which play critical roles in both catalyzing the graphitization and serving as pore forming agents. Factors including post-treatments, heating temperatures, and types of metal were found crucial for achieving enhanced capacitance performance on resulting carbon materials. Using FeCl3 as precursor along with optimal heating temperature 1000 °C and mixed acid treatment (HCl+HNO3), the highest Brunauer-Emmett-Teller (BET) surface area of 1645 m(2)g(-1) was achieved on the mesopore dominant graphene-sheet-like carbon materials. The unique morphologies featured with high-surface areas, dominant mesopores, proper nitrogen doping, and 3D graphene-like structures correspond to remarkably enhanced electrochemical specific capacitance up to 478 Fg(-1) in 1.0 M KOH at a scan rate of 5 mV s(-1). Furthermore, in a real two-electrode system of a symmetric supercapacitor, a specific capacitance of 235 Fg(-1) using Nafion binder is obtained under a current density of 1 Ag(-1) by galvanostatic charge-discharge tests in 6.0 M KOH. Long-term cycle stability up to 5000 cycles by using PVDF binder in electrode was systematically evaluated as a function of types of metals and current densities.

  18. 3D coordination networks based on supramolecular chains as building units: synthesis and crystal structures of two silver(I) pyridyldiethynides.

    PubMed

    Zhang, Tianle; Kong, Jianxi; Hu, Yuejie; Meng, Xianggao; Yin, Hongbing; Hu, Dongshuang; Ji, Changpeng

    2008-04-21

    Two silver(I) pyridyldiethynides, [Ag2(3,5-C2PyC2).4CF3CO2Ag.4H2O] ( A) and [Ag 2(3,5-C2PyC2).3AgNO3.H2O](B), were synthesized by reactions of 3,5-diethynylpyridine with silver trifluoroacetate and silver nitrate in high yield, respectively. X-ray crystallographic studies revealed that in A pyridyldiethynide groups connect Ag 11 cluster units to generate 1D supramolecular chains as bridging ligands, where each ethynide group interacts with four silver atoms. These supramolecular chains bearing pyridyl groups are linked by silver ions to form wavelike layers, which are further connected by trifluoroacetate ligands to afford a 3D coordination network. However, B exhibits a different structural feature, where two ethynide groups in one pyridyldiethynide ligand coordinate to three and four silver atoms, respectively. These silver ethynide cluster units are linked through silver-ethynide and argentophilic interactions, leading to a double silver chain by sharing silver atoms in these units. In B, the silver double chains are further connected by bridging pyridyldiethynide groups to generate 2D networks, which interact through the Ag-N coordination bonds between silver atoms and pyridyl groups in the adjacent layers to generate a 3D coordination network. In these two compounds, trifluoroacetate and nitrate groups exhibit different bonding modes, indicating that the counterion is an important factor influencing the structures of supramolecular chains and coordination networks.

  19. Spectroscopic properties of a series of Co(II) coordination polymers and the influence of Co(II) coordination environment on photoelectric property.

    PubMed

    Jin, Jing; Gong, Yuanyuan; Li, Lei; Han, Xiao; Meng, Qin; Liu, Yonghua; Niu, Shuyun

    2015-02-25

    Four Co(II) coordination polymers, [Co(suc)]n 1, [Co(pdc)]n 2, {[Co7(suc)4(OH)6(H2O)3]·8H2O}n 3, {[Co(bdc)(phen)(H2O)]·H2O}n 4 (H2suc=succinic acid, H2pdc=pyridine-3,4-dicarboxylic acid, H2bdc=1,2-benzenedicarboxylic acid, phen=1,10-phenanthroline) were hydrothermally synthesized and characterized by X-ray single-crystal diffraction, surface photovoltage spectroscopy (SPS), electrical conductivity, thermogravimetric analysis (TG), ultraviolet visible and near-infrared absorption spectrum (UV-Vis-NIR), infrared spectrum (IR), and elemental analysis. The structural analyses indicate that the coordination numbers of the Co(II) ions are 4, 5, 6 and 6 for the polymers 1-4, respectively. And polymers 1 and 2 exhibit 3D structure formed by suc(2-) and pdc(2-) anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc(2-) anions bridging seven-nuclear [Co7(OH)6(H2O)3](3-) unit and polymer 4 is a 1D structure bridged by bdc(2-) anions. The surface photoelectric properties of the cobalt polymers were mainly studied by SPS. The results of SPS reveal that all polymers possess certain photoelectric conversion property in the range of 300-800 nm. The influences of the structure, coordination micro-environment of central metal ion and structural dimensionality on response bands of SPS were discussed.

  20. Migration of bone marrow stromal cells in 3D: 4 color methodology reveals spatially and temporally coordinated events.

    PubMed

    Thibault, Marc M; Buschmann, Michael D

    2006-12-01

    The cytoskeleton plays a central role in many cell processes including directed cell migration. Since most previous work has investigated cell migration in two dimensions (2D), new methods are required to study movement in three dimensions (3D) while preserving 3D structure of the cytoskeleton. Most previous studies have labeled two cytoskeletal networks simultaneously, impeding an appreciation of their complex and dynamic interconnections. Here we report the development of a 4 color method to simultaneously image vimentin, actin, tubulin and the nucleus for high-resolution confocal microscopy of bone-marrow stromal cells (BMSCs) migrating through a porous membrane. Several methods were tested for structural preservation and labeling intensity resulting in identification of an optimized simultaneous fixation and permeabilization method using glutaraldehyde, paraformaldehyde and Triton X-100 followed by a quadruple fluorescent labeling method. This procedure was then applied at a sequence of time points to migrating cells, allowing temporal progression of migration to be assessed by visualizing all three networks plus the nucleus, providing new insights into 3D directed cell migration including processes such as leading edge structure, cytoskeletal distribution and nucleokinesis. Colocalization of actin and microtubules with distinct spatial arrangements at the cellular leading edge during migration, together with microtubule axial polarization supports recent reports indicating the pivotal role of microtubules in directed cell migration. This study also provides a foundation for 3D migration studies versus 2D studies, providing precise and robust methods to attain new insights into the cellular mechanisms of motility.

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

    SciTech Connect

    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

    2016-03-15

    Three cadmium coordination polymers, [Cd(bismip)]{sub n} (1), {[Cd(bismip)(phen)]·H_2O}{sub n} (2) and {[Cd_2(bismip)_2(4,4′-bipy)]·2H_2O}{sub n} (3) (H{sub 2}bismip=5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid, phen=1,10-phenanthroline, 4,4′-bipy=4,4′-bipyridine) have been prepared under solvothermal conditions. In 1, the [Cd{sub 4}(bismip){sub 3}] units are jointed by bismip ligands to afford a three-dimensional (3D) architecture. Complex 2 exhibits a 3D supramolecular framework based on the interconnection of 1D chains through hydrogen bonding interactions and π-π packing interactions. 3 is a two-fold interpenetrating 3D architecture with a (4·8{sup 2})(4{sup 2}·8{sup 4}) Schläfli symbol in which 2D layers are interlinked by 4,4′-bipy ligands. The diverse structures of compounds 1–3 indicate that the auxiliary ligands have significant effects on the final structures. The photoluminescent properties and photocatalytic properties of these coordination polymers in the solid state were also investigated. Remarkably, 3 shows the wide gap semiconductor nature and exhibit excellent photocatalytic performance. - Graphical abstract: Three cadmium coordination polymers with different architectures based on 5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid have been prepared. Their photoluminescent properties were also investigated. - Highlights: • Three new Cd(II) Cps were synthesized based on H{sub 2}bismip. • Compounds 1 and 3 show 3D networks and 2 exhibits a 1D chain. • Compoud 3 exhibits good catalytic activity of methylene blue photodegradation.

  3. Chemistry and application of flexible porous coordination polymers*

    PubMed Central

    Bureekaew, Sareeya; Shimomura, Satoru; Kitagawa, Susumu

    2008-01-01

    Porous coordination polymers (PCPs), which are microporous materials, have been given much attention from both scientific and commercial aspects regarding their application to gas storage, gas separation and catalytic reaction because of the regularity of their pore shape and pore size, accompanied with the functionality. Moreover, in recent years, flexible PCPs, which are structurally transformable depending upon external stimuli, have been attractive because they provide unique properties, dissimilar to those of zeolites. In this review, the chemistry and application of flexible crystalline PCPs are summarized and discussed. PMID:27877934

  4. Propagation of experimental uncertainties from the tunnel to the body coordinate system in 3-D LDV flow field studies

    NASA Technical Reports Server (NTRS)

    Neuhart, Dan H.

    1994-01-01

    An analysis of experimental laser Doppler velocimetry (LDV) data uncertainties that propagate from measurements in the tunnel coordinate system to results in the model system are provided. Calculations of uncertainties as functions of the variables that comprise the final result requires assessment of the contribution each variable makes. Such an analysis enables and necessitates the experimentalists to identify and address the contributing error sources in the experimental measurement system. This provides an opportunity to improve the quality of data derived from experimental systems. This is especially important in experiments where small changes in test conditions are expected to produce small, detectable changes in results. In addition, the need for high-quality experimental data for CFD method validation demands a thorough assessment of experimental uncertainty. Transforming from one Cartesian coordinate system to another by three sequential rotations, equations were developed to transform the variables initially obtained in the original coordinates into variables in the final coordinate system. Based on the transformation equations, propagation equations for errors in the experimentally-derived flow quantities were derived for a model at angle of attack. Experimental uncertainties were then propagated from the tunnel coordinate system into the model system.

  5. Four homochiral coordination polymers contain N-acetyl-L-tyrosine and different N-donor ligand: Influence of metal cations, ancillary ligands and coordination modes

    SciTech Connect

    Li, Meng-Li; Song, Hui-Hua

    2013-10-15

    Using the chiral ligand N-acetyl-L-tyrosine (Hacty) and maintaining identical reaction conditions, Zn(II), Co(II), and Cd(II) salts provided four novel homochiral coordination polymers ([Zn(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}1, ([Co(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}2, ([Cd(acty){sub 2}(bipy)H{sub 2}O]·H{sub 2}O){sub n}3, and ([Cd(acty)(bpe){sub 2}(Ac)]·6H{sub 2}O){sub n}4 (bipy=4,4′-bipyridine; bpe=1,2-di(4-pyridyl)ethane) in the presence of ancillary ligands. Compounds 1 and 2 are isostructural 1D chain structures. The neighboring chains are further linked into a 3D supramolecular structure via π⋯π stacking and hydrogen bond interactions. Compound 3 shows a 2D network and 4 generates 1D infinite chains along the c-axis. Compounds 3 and 4 are further connected into 3D supramolecular network by hydrogen bond interactions. More importantly, coordination in acyl oxygen atoms and ancillary ligands (bpe) as monodentate decorating ligands in 4 are rarely reported. Ancillary ligands and metal cations significantly influence the structure of the complexes. The photoluminescence properties of 1, 3, and 4 were studied at room temperature. Circular dichroism (CD) of the complexes have been investigated. - Graphical abstract: Four new homochiral coordination polymers were prepared and structurally characterized, which investigate the influence of the ancillary ligands and metal ions on the design and synthesis of coordination polymers. Display Omitted - Highlights: • It is rarely reported that the chiral coordination polymers prepared with N-acetyl-L-tyrosine ligands. • The alkalescent acetyl oxygen atom is difficult to participate in coordination but it is happened in the N-acetyl-L-tyrosine ligands. • The ancillary ligands (4,4′-bipy and bpe) are present in an unusual coordination modes, monodentate decorating ligands in 1, 2 and 4. • Structure comparative analyses results indicate that the

  6. Yttrium-succinates coordination polymers: Hydrothermal synthesis, crystal structure and thermal decomposition

    SciTech Connect

    Amghouz, Zakariae; Roces, Laura; Garcia-Granda, Santiago; Garcia, Jose R.; Souhail, Badredine; Mafra, Luis; Shi, Fa-nian; Rocha, Joao

    2009-12-15

    New polymeric yttrium-succinates, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}, have been synthesized, and their structures (solved by single crystal XRD) are compared with that of Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.H{sub 2}O. Three compounds were obtained as single phases, and their thermal behaviour is described. - Graphical abstract: In the field of coordination polymers or MOF's, few studies report on the polymorphs of Ln(III)-succinic acid. Here, we describe the hydrothermal synthesis and structural characterization of two novel yttrium-succinates coordination polymers, respectively 2D and 3D, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.

  7. Utilization of mixed ligands to construct two new coordination polymers: Syntheses, structures and properties

    NASA Astrophysics Data System (ADS)

    Wang, Yansong; Zhou, Zhimin

    2015-08-01

    The use of triazine and aromatic carboxylic acid as mixed chelating ligands in preparing two coordination polymers is described. Two new transition-metal coordination polymers, namely, [Co2(bpdc)4(phdat)2] (1) and [Zn(bpdc)]n (2) (H2bpdc=2,4-biphenyldicarboxylic acid, phdat=2,4-diamine-6-phenyl-1,3,5-triazine), have been hydrothermally synthesized and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. Compound 1 is a 0D structure and extends to a 3D network by two different N-H···O and N-H···N hydrogen bonds. Compound 2 exhibits a 2D network with 44.62 topological net, which contains two kinds of single helical chains. The interactions within each Co(II)-Co(II) pair of compound 1 are antiferromagnetic (g=2.19, J=-22 K, zj‧=-0.00351 K). Furthermore, the photoluminescence property of 2 was also investigated in the solid state at room temperature.

  8. 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.

  9. Ligand effects on the structural dimensionality and antibacterial activities of silver-based coordination polymers.

    PubMed

    Lu, Xinyi; Ye, Junwei; Sun, Yuan; Bogale, Raji Feyisa; Zhao, Limei; Tian, Peng; Ning, Guiling

    2014-07-14

    Four Ag-based coordination polymers [Ag(Bim)] (1), [Ag2(NIPH)(HBim)] (2), [Ag6(4-NPTA)(Bim)4] (3) and [Ag2(3-NPTA)(bipy)0.5(H2O)] (4) (HBim = 1H-benzimidazole, bipy = 4,4'-bipyridyl, H2NIPH = 5-nitroisophthalic acid, H2NPTA = 3-/4-nitrophthalic acid) have been synthesized by hydrothermal reaction of Ag(i) salts with N-/O-donor ligands. Single-crystal X-ray diffraction indicated that these coordination polymers constructed from mononuclear or polynuclear silver building blocks exhibit three typical structure features from 1-D to 3-D frameworks. These compounds favour a slow release of Ag(+) ions leading to excellent and long-term antimicrobial activities, which is distinguished by their different topological structures, towards both Gram-negative bacteria, Escherichia coli (E. coli) and Gram-positive bacteria, Staphylococcus aureus (S. aureus). In addition, these compounds show good thermal stability and light stability under UV-vis and visible light, which are important characteristics for their further application in antibacterial agents.

  10. Two unusual 12-connected metal–organic coordination polymers with fcu net

    SciTech Connect

    Guo, Sheng-Qi; Tian, Dan; Luo, Yu-Hui; Chen, Xin; Zhang, Hong

    2013-09-15

    Two new three-dimensional 12-connected metal–organic coordination polymers, [Zn{sub 2}(bptc)(H{sub 2}O)]·C{sub 2}H{sub 5}OH·H{sub 2}O (1) and [Cd{sub 4}(bptc){sub 2}(bbi)(H{sub 2}O)]·H{sub 2}O (2) (H4bptc=biphenyl-2,5,2′,5′-tetracarboxylic acid, bbi=1,1′-(1,4-butanediyl)bis(imidazole)), have been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction analyses. All compounds are also characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRD). Topological analysis indicates that both 1 and 2 are 12-connected frameworks with fcu topology, which are based on cuboid cage and rob-like (Cd3) subunit as 12-connected nodes, respectively. Furthermore, the luminescence properties of the two compounds were discussed in detail. - Graphical abstract: Two new compounds with unusual 12-connected fcu topology display intriguing structural feature, as well as luminescence property. Display Omitted - Highlights: • Two new 3D metal–organic coordination polymers based on biphenyl-2,5,2′,5′-tetracarboxylic acid ligand have been synthesized. • Two compounds exhibit rare 12-connected fcu topology. • Photoluminescent property at room temperature has been investigated.

  11. Assembly of three coordination polymers based on a sulfonic-carboxylic ligand showing high proton conductivity.

    PubMed

    Zhao, Shu-Na; Song, Xue-Zhi; Zhu, Min; Meng, Xing; Wu, Lan-Lan; Song, Shu-Yan; Wang, Cheng; Zhang, Hong-Jie

    2015-01-21

    Three new coordination polymers (CPs)/metal-organic frameworks (MOFs) with different structures have been synthesized using 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (H4L) and metal ions, Cu(2+), Ca(2+) and Cd(2+). The Cu compound features a one-dimensional chain structure, further extending into a 2D layer network through H-bond interactions. Both the Ca and Cd compounds show 3D frameworks with (4,4)-connected PtS-type topology and (3,6)-connected bct-type topology, respectively. These CPs/MOFs all exhibit proton conduction behavior, especially for the Cu compound with a proton conductivity of 3.46 × 10(-3) S cm(-1) at 368 K and 95% relative humidity (RH). Additionally, the activation energy (Ea) has also been investigated to deeply understand the proton-conduction mechanism.

  12. Assembly of two novel Lindqvist polyoxoanion-templated coordination polymers with standard honeycomb cavities

    NASA Astrophysics Data System (ADS)

    Sha, Jingquan; Huang, Lin; Peng, Jun; Pang, Haijun; Tian, Aixiang; Zhang, Pengpeng; Chen, Yuan; Zhu, Min

    2009-02-01

    Two novel polyoxometalate(POM)-templated coordination polymers: [Cu 2(phnz) 3][M 6O 19] (M = Mo for 1, W for 2; phnz = phenazine), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In the compounds, Lindqvist POMs as templates induce the [Cu 2(phnz) 3] complexes to 2D hexagonal metal-organic framework (MOF), which represents 6 3 topologies of dimensions ca. 13.515 × 13.515 × 13.515 Å. Furthermore, the 2D sheets are held together by Lindqvist POMs into 3D supramolecular networks with 1D channel, and Lindqvist POMs site in the channels. The successful syntheses and isolation of two compounds provide a novel example of the utility of POM clusters as templates for self-assembly extended framework with cavities.

  13. 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.

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

    SciTech Connect

    Li, Zhao-Hao; Xue, Li-Ping; Miao, Shao-Bin; Zhao, Bang-Tun

    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 were 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.

  15. Synthesis, crystal structure and luminescent properties of one coordination polymer of cadmium(II) with mixed thiocyanate and hexamethylenetetramine ligands.

    PubMed

    Bai, Yan; Shang, Wei-Li; Dang, Dong-Bin; Sun, Ji-De; Gao, Hui

    2009-03-01

    A novel Cd(II) coordination polymer [Cd(SCN)(2)(hmt)(1/2)(H(2)O)](2).H(2)O (hmt=hexamethylenetetramine) has been synthesized and characterized by IR, elemental analysis, TG technique and X-ray crystallography. Cd(II) atom has an distorted octahedral environment with an N(3)S(2)O donor set. Every six Cd(II) centers are linked by hmt and thiocyanato bridges to form a planar 2D coordination polymer containing hexagonal metallocyclic rings [Cd(6)(SCN)(8)(hmt)(2)]. A 2D layer structure is held together with its neighboring ones via a set of hydrogen-bonding interactions to form a 3D supramolecular structure. The luminescent properties of the title complex in the solid state were investigated.

  16. An analogue contact probe using a compact 3D optical sensor for micro/nano coordinate measuring machines

    NASA Astrophysics Data System (ADS)

    Li, Rui-Jun; Fan, Kuang-Chao; Miao, Jin-Wei; Huang, Qiang-Xian; Tao, Sheng; Gong, Er-min

    2014-09-01

    This paper presents a new analogue contact probe based on a compact 3D optical sensor with high precision. The sensor comprises an autocollimator and a polarizing Michelson interferometer, which can detect two angles and one displacement of the plane mirror at the same time. In this probe system, a tungsten stylus with a ruby tip-ball is attached to a floating plate, which is supported by four V-shape leaf springs fixed to the outer case. When a contact force is applied to the tip, the leaf springs will experience elastic deformation and the plane mirror mounted on the floating plate will be displaced. The force-motion characteristics of this probe were investigated and optimum parameters were obtained with the constraint of allowable physical size of the probe. Simulation results show that the probe is uniform in 3D and its contacting force gradient is within 1 mN µm - 1. Experimental results indicate that the probe has 1 nm resolution,  ± 10 µm measuring range in X - Y plane, 10 µm measuring range in Z direction and within 30 nm measuring standard deviation. The feasibility of the probe has been preliminarily verified by testing the flatness and step height of high precision gauge blocks.

  17. A Lyapunov-based Approach for Time-Coordinated 3D Path-Following of Multiple Quadrotors in SO(3)

    DTIC Science & Technology

    2012-12-10

    attention of control community in recent years. Relevant work includes spacecraft formation flying [14], UAV control [15], [16], coordinated control of...introduced in [9] to achieve vertical take off and landing. Finally, integral sliding mode and reinforcement learning control are presented in [10] as...Waslander, G. M. Hoffman, J. S. Jang, and C. J. Tomlin, “Multi-agent quadrotor testbed control design: integral sliding mode vs reinforcement

  18. Synthesis, spectral, X-ray diffraction and thermal studies of new ZnII-pyrazine coordination polymers

    NASA Astrophysics Data System (ADS)

    Marandi, Farzin

    2014-02-01

    Two new zinc(II) coordination polymers with a β-diketone and N-donor ancillary ligands, [Zn(pyz)(ttfa)2]n (1) and [Zn(pyz)(btfa)2]n (2), (Httfa = 2-thenoyltrifluoroacetone, Hbtfa = benzoyltrifluoroacetone and pyz = pyrazine), have been prepared and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy, and studied by thermal gravimetric analysis as well as single crystal X-ray diffraction. The crystal and molecular structures of 1 and 2 have been solved by X-ray diffraction and they turned out to be one-dimensional polymers with linear dispositions of the metal atoms. These one-dimensional polymers are further connected to form a 3D supramolecular network by CH⋯π (only in 1), CH⋯F, π-π and interesting H⋯H (only in 2) interactions.

  19. Documentation of program COORDC to generate and coordinate system for 3D corners with or without fillet using body fitted curvilinear coordinates, part 2

    NASA Technical Reports Server (NTRS)

    Kumar, D.

    1980-01-01

    The computer program COORDC generates a body fitted curvilinear coordinate system for corner geometry with or without corner fillets. It is assumed that at any given xi, x remains constant; consequently the only variation is in y and z. It is also assumed that for all xi's in the physical plane the coordinate system in y-z plane is similar. This enables solution of coordinate system for one particular xi = 1 (x for xi = 1 is arbitrarily chosen to be 0.0) and the solution for all other xi plane can be easily specified once the coordinates in the physical plane on the line 1 or = to xi or = to IMAX, eta = 1, zeta = 1 are specified.

  20. 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.

  1. 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.

  2. Tension-Compression Fatigue Behavior of 2D and 3D Polymer Matrix Composites at Elevated Temperature

    DTIC Science & Technology

    2015-09-21

    performance in elevated temperature environments. High- temperature polymer matrix composites (HTPMCs) are being considered for such applications . However...the polymer matrix in most HTPMCs cannot operate at temperatures required for many aerospace structural applications . Continuous research seeks to...temperature polymer matrix composites (HTPMCs) applications , other polyimide resins replacement are being researched and developed due to the carcinogenic

  3. Self-organizing task modules and explicit coordinate systems in a neural network model for 3-D saccades.

    PubMed

    Smith, M A; Crawford, J D

    2001-01-01

    The goal of this study was to train an artificial neural network to generate accurate saccades in Listing's plane and then determine how the hidden units performed the visuomotor transformation. A three-layer neural network was successfully trained, using back-prop, to take in oculocentric retinal error vectors and three-dimensional eye orientation and to generate the correct head-centric motor error vector within Listing's plane. Analysis of the hidden layer of trained networks showed that explicit representations of desired target direction and eye orientation were not employed. Instead, the hidden-layer units consistently divided themselves into four parallel modules: a dominant "vector-propagation" class (approximately 50% of units) with similar visual and motor tuning but negligible position sensitivity and three classes with specific spatial relations between position, visual, and motor tuning. Surprisingly, the vector-propagation units, and only these, formed a highly precise and consistent orthogonal coordinate system aligned with Listing's plane. Selective "lesions" confirmed that the vector-propagation module provided the main drive for saccade magnitude and direction, whereas a balance between activity in the other modules was required for the correct eye-position modulation. Thus, contrary to popular expectation, error-driven learning in itself was sufficient to produce a "neural" algorithm with discrete functional modules and explicit coordinate systems, much like those observed in the real saccade generator.

  4. Spectroscopic properties and the catalytic activity of new organo-lead supramolecular coordination polymer containing quinoxaline

    NASA Astrophysics Data System (ADS)

    Etaiw, Safaa El-din H.; Abdou, Safaa N.

    2015-01-01

    The 3D-supramolecular coordination polymer (SCP) 3∞[ Cu2(CN)3(Me3Pb)(qox)], 1, as the first example of the CuCN SCP containing the (Me3Pb) fragment, was explored to investigate its catalytic and photo-catalytic activities. The structure of 1 contains two chemically identical but crystallographically different [Cu2(CN)3ṡMe3Pbṡqox]2 units with four Cu(I) sites assuming distorted TP-3 geometry. Two non-linear chains of equal abundance are formed producing corrugated parallel chains which are connected laterally by quinoxaline creating 2D-layers which are arranged parallel in an (AB⋯AB⋯AB)n fashion forming 3D-network. IR, mass, electronic absorption and fluorescence spectra are also investigated. The SCP 1 is diamagnetic and exhibits good catalytic and photo-catalytic activities for the degradation of methylene blue (MB). The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. The efficiency of recycled the 1 and the mechanism of degradation of MB dye were investigated.

  5. A framework for predicting surface areas in microporous coordination polymers.

    PubMed

    Schnobrich, Jennifer K; Koh, Kyoungmoo; Sura, Kush N; Matzger, Adam J

    2010-04-20

    A predictive tool termed the linker to metal cluster (LiMe) ratio is introduced as a method for understanding surface area in microporous coordination polymers (MCPs). Calibrated with geometric accessible surface area computations, the LiMe ratio uses molecular weight of building block components to indicate the maximum attainable surface area for a given linker and metal cluster combination. MOF-5 and HKUST-1 are used as prototypical structures to analyze MCPs with octahedral M(4)O(CO(2)R)(6) and paddlewheel M(2)(CO(2)R)(4) metal clusters. Insight into the effects of linker size, geometry, number of coordinating groups, and framework interpenetration is revealed through the LiMe ratio analysis of various MCPs. Experimental surface area deviation provides indication that a material may suffer from incomplete guest removal, structural collapse, or interpenetration. Because minimal data input are required, the LiMe ratio surface area analysis is suggested as a quick method for experimental verification as well as a guide for the design of new materials.

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

    SciTech Connect

    Lian, Chen; Liu, Liu; Guo, Xu; Long, Yinshuang; Jia, Shanshan; Li, Huanhuan; Yang, Lirong

    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 the 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.

  7. Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

    PubMed

    Lee, Hosoowi; Jeong, Young-Hwan; Kim, Joo-Ho; Kim, Inhye; Lee, Eunji; Jang, Woo-Dong

    2015-09-30

    We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 μM) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased

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

    SciTech Connect

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

    2008-08-15

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

  9. Synthesis and structural characterization of homochiral 2D coordination polymers of zinc and copper with conformationally flexible ditopic imidazolium-based dicarboxylate ligands.

    PubMed

    Nicasio, Antonio I; Montilla, Francisco; Álvarez, Eleuterio; Colodrero, Rosario P; Galindo, Agustín

    2017-01-03

    Different novel coordination polymers containing zinc, 1-4, and copper, 5-8, metals, connected via chiral imidazolium-based dicarboxylate ligands, [L(R)](-), were isolated by reaction between zinc acetate or copper acetate and enantiomerically pure HL(R) compounds. They were characterised and structurally identified by X-ray diffraction methods (single crystal and powder). These compounds are two-dimensional homochiral coordination polymers, [M(L(R))2]n, in which the metal ions are coordinated by the two carboxylate groups of [L(R)](-) anions in a general bridging monodentate μ(2)-κ(1)-O(1),κ(1)-O(3) fashion that afforded tetrahedral metal coordination environments for zinc, 1-4, and square planar for copper, 5-8, complexes. In all the compounds the 3D supramolecular architecture is constructed by non-covalent interactions between the hydrophobic parts (R groups) of the homochiral 2D coordination polymers and, in some cases, by weak C-HO non-classical hydrogen bonds that provided, in general, a dense crystal packing. DFT calculations on the [L(R)](-) anions confirmed their conformational flexibility as ditopic linkers and this fact makes possible the formation of different coordination polymers for four-coordinated metal centers. Preliminary studies on the Zn-catalyzed synthesis of chiral α-aminophosphonates were carried out and, unfortunately, no enantioselectivity was observed in these reactions.

  10. 3D Motions of Iron in Six-Coordinate {FeNO}(7) Hemes by Nuclear Resonance Vibration Spectroscopy.

    PubMed

    Peng, Qian; Pavlik, Jeffrey W; Silvernail, Nathan J; Alp, E Ercan; Hu, Michael Y; Zhao, Jiyong; Sage, J Timothy; Scheidt, W Robert

    2016-04-25

    The vibrational spectrum of a six-coordinate nitrosyl iron porphyrinate, monoclinic [Fe(TpFPP)(1-MeIm)(NO)] (TpFPP=tetra-para-fluorophenylporphyrin; 1-MeIm=1-methylimidazole), has been studied by oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS). The crystal was oriented to give spectra perpendicular to the porphyrin plane and two in-plane spectra perpendicular or parallel to the projection of the FeNO plane. These enable assignment of the FeNO bending and stretching modes. The measurements reveal that the two in-plane spectra have substantial differences that result from the strongly bonded axial NO ligand. The direction of the in-plane iron motion is found to be largely parallel and perpendicular to the projection of the bent FeNO on the porphyrin plane. The out-of-plane Fe-N-O stretching and bending modes are strongly mixed with each other, as well as with porphyrin ligand modes. The stretch is mixed with v50 as was also observed for dioxygen complexes. The frequency of the assigned stretching mode of eight Fe-X-O (X=N, C, and O) complexes is correlated with the Fe-XO bond lengths. The nature of highest frequency band at ≈560 cm(-1) has also been examined in two additional new derivatives. Previously assigned as the Fe-NO stretch (by resonance Raman), it is better described as the bend, as the motion of the central nitrogen atom of the FeNO group is very large. There is significant mixing of this mode. The results emphasize the importance of mode mixing; the extent of mixing must be related to the peripheral phenyl substituents.

  11. INS3D - NUMERICAL SOLUTION OF THE INCOMPRESSIBLE NAVIER-STOKES EQUATIONS IN THREE-DIMENSIONAL GENERALIZED CURVILINEAR COORDINATES (IBM VERSION)

    NASA Technical Reports Server (NTRS)

    Kwak, D.

    1994-01-01

    INS3D computes steady-state solutions to the incompressible Navier-Stokes equations. The INS3D approach utilizes pseudo-compressibility combined with an approximate factorization scheme. This computational fluid dynamics (CFD) code has been verified on problems such as flow through a channel, flow over a backwardfacing step and flow over a circular cylinder. Three dimensional cases include flow over an ogive cylinder, flow through a rectangular duct, wind tunnel inlet flow, cylinder-wall juncture flow and flow through multiple posts mounted between two plates. INS3D uses a pseudo-compressibility approach in which a time derivative of pressure is added to the continuity equation, which together with the momentum equations form a set of four equations with pressure and velocity as the dependent variables. The equations' coordinates are transformed for general three dimensional applications. The equations are advanced in time by the implicit, non-iterative, approximately-factored, finite-difference scheme of Beam and Warming. The numerical stability of the scheme depends on the use of higher-order smoothing terms to damp out higher-frequency oscillations caused by second-order central differencing. The artificial compressibility introduces pressure (sound) waves of finite speed (whereas the speed of sound would be infinite in an incompressible fluid). As the solution converges, these pressure waves die out, causing the derivation of pressure with respect to time to approach zero. Thus, continuity is satisfied for the incompressible fluid in the steady state. Computational efficiency is achieved using a diagonal algorithm. A block tri-diagonal option is also available. When a steady-state solution is reached, the modified continuity equation will satisfy the divergence-free velocity field condition. INS3D is capable of handling several different types of boundaries encountered in numerical simulations, including solid-surface, inflow and outflow, and far

  12. INS3D - NUMERICAL SOLUTION OF THE INCOMPRESSIBLE NAVIER-STOKES EQUATIONS IN THREE-DIMENSIONAL GENERALIZED CURVILINEAR COORDINATES (DEC RISC ULTRIX VERSION)

    NASA Technical Reports Server (NTRS)

    Biyabani, S. R.

    1994-01-01

    INS3D computes steady-state solutions to the incompressible Navier-Stokes equations. The INS3D approach utilizes pseudo-compressibility combined with an approximate factorization scheme. This computational fluid dynamics (CFD) code has been verified on problems such as flow through a channel, flow over a backwardfacing step and flow over a circular cylinder. Three dimensional cases include flow over an ogive cylinder, flow through a rectangular duct, wind tunnel inlet flow, cylinder-wall juncture flow and flow through multiple posts mounted between two plates. INS3D uses a pseudo-compressibility approach in which a time derivative of pressure is added to the continuity equation, which together with the momentum equations form a set of four equations with pressure and velocity as the dependent variables. The equations' coordinates are transformed for general three dimensional applications. The equations are advanced in time by the implicit, non-iterative, approximately-factored, finite-difference scheme of Beam and Warming. The numerical stability of the scheme depends on the use of higher-order smoothing terms to damp out higher-frequency oscillations caused by second-order central differencing. The artificial compressibility introduces pressure (sound) waves of finite speed (whereas the speed of sound would be infinite in an incompressible fluid). As the solution converges, these pressure waves die out, causing the derivation of pressure with respect to time to approach zero. Thus, continuity is satisfied for the incompressible fluid in the steady state. Computational efficiency is achieved using a diagonal algorithm. A block tri-diagonal option is also available. When a steady-state solution is reached, the modified continuity equation will satisfy the divergence-free velocity field condition. INS3D is capable of handling several different types of boundaries encountered in numerical simulations, including solid-surface, inflow and outflow, and far

  13. Tricarboxylate-based Gd(III) coordination polymers exhibiting large magnetocaloric effects.

    PubMed

    Liu, Sui-Jun; Cao, Chen; Xie, Chen-Chao; Zheng, Teng-Fei; Tong, Xiao-Lan; Liao, Jin-Sheng; Chen, Jing-Lin; Wen, He-Rui; Chang, Ze; Bu, Xian-He

    2016-05-31

    Two Gd(III) coordination polymers with the formula [Gd(cit)(H2O)]∞ () and [Gd(nta)(H2O)2]∞ () (H4cit = citric acid, H3nta = nitrilotriacetic acid) have been successfully prepared under hydrothermal conditions. Complex exhibits a three-dimensional (3D) structure based on carboxylate-bridged layers, while complex is a double-layer structure containing eight-coordinated Gd(III). Magnetic investigations reveal that weak antiferromagnetic couplings between adjacent Gd(III) ions in both and with different Weiss values result in large cryogenic magnetocaloric effects. It is notable that the maximum entropy changes (-ΔS) of and reach 31.3 J kg(-1) K(-1) and 32.2 J kg(-1) K(-1) at 2 K for a moderate field change (ΔH = 3 T), and a remarkable -ΔS (41.5 J kg(-1) K(-1) for and 42.0 J kg(-1) K(-1) for ) could be obtained for ΔH = 7 T.

  14. SU-E-CAMPUS-T-05: Validation of High-Resolution 3D Patient QA for Proton Pencil Beam Scanning and IMPT by Polymer Gel Dosimetry

    SciTech Connect

    Cardin, A; Avery, S; Ding, X; Kassaee, A; Lin, L; Maryanski, M

    2014-06-15

    Purpose: Validation of high-resolution 3D patient QA for proton pencil beam scanning and IMPT by polymer gel dosimetry. Methods: Four BANG3Pro polymer gel dosimeters (manufactured by MGS Research Inc, Madison, CT) were used for patient QA at the Robert's Proton Therapy Center (RPTC, Philadelphia, PA). All dosimeters were sealed in identical thin-wall Pyrex glass spheres. Each dosimeter contained a set of markers for 3D registration purposes. The dosimeters were mounted in a consistent and reproducible manner using a custom build holder. Two proton pencil beam scanning plans were designed using Varian Eclipse™ treatment planning system: 1) A two-field intensity modulated proton therapy (IMPT) plan and 2) one single field uniform dose (SFUD) plan. The IMPT fields were evaluated as a composite plan and individual fields, the SFUD plan was delivered as a single field plan.Laser CT scanning was performed using the manufacturer's OCTOPUS-IQ axial transmission laser CT scanner using a 1 mm slice thickness. 3D registration, analysis, and OD/cm to absorbed dose calibrations were perfomed using DICOM RT-Dose and CT files, and software developed by the manufacturer. 3D delta index, a metric equivalent to the gamma tool, was used for dose comparison. Results: Very good agreement with single IMPT fields and with SFUD was obtained. Composite IMPT fields had a less satisfactory agreement. The single fields had 3D delta index passing rates (3% dose difference, 3 mm DTA) of 98.98% and 94.91%. The composite 3D delta index passing rate was 80.80%. The SFUD passing rate was 93.77%. Required shifts of the dose distributions were less than 4 mm. Conclusion: A formulation of the BANG3Pro polymer gel dosimeter, suitable for 3D QA of proton patient plans is established and validated. Likewise, the mailed QA analysis service provided by the manufacturer is a practical option when required resources are unavailable. We fully disclose that the subject of this research regards a production

  15. 3D printing of textile-based structures by Fused Deposition Modelling (FDM) with different polymer materials

    NASA Astrophysics Data System (ADS)

    Melnikova, R.; Ehrmann, A.; Finsterbusch, K.

    2014-08-01

    3D printing is a form of additive manufacturing, i.e. creating objects by sequential layering, for pre-production or production. After creating a 3D model with a CAD program, a printable file is used to create a layer design which is printed afterwards. While often more expensive than traditional techniques like injection moulding, 3D printing can significantly enhance production times of small parts produced in small numbers, additionally allowing for large flexibility and the possibility to create parts that would be impossible to produce with conventional techniques. The Fused Deposition Modelling technique uses a plastic filament which is pushed through a heated extrusion nozzle melting the material. Depending on the material, different challenges occur in the production process, and the produced part shows different mechanical properties. The article describes some standard and novel materials and their influence on the resulting parts.

  16. Syntheses and structural studies of coordination polymers with microporous frameworks

    NASA Astrophysics Data System (ADS)

    Niu, Tianyan

    The purpose of this work is to synthesize microporous solids using coordination chemistry. The syntheses were carried by diffusion method. Starting reagents, solvent, concentration, reaction speed and time, and temperature were the variables used to optimize the syntheses. The resulting products were characterized by single crystal X-ray diffraction to determine their structures. X-ray powder diffraction, TGA, IR, elemental analysis, and electron microprobe were used to provide complementary or supporting information. Exploratory studies were carried out mainly on organotin-cyanometalate compounds [(RmSnIV)x{M(CN)n} y]. The compounds are made up of SnRm cations and M(CN) n anions. The structures adopted are determined by the number and size of the organic ligands attached to the Sn atoms and by the cyanometalate M(CN) n moiety. Several new compounds in this class were synthesized and structurally characterized. They are [(Bu3Sn)3M(CN)6] (M = Fe, Co), [(R2Sn)3{CO(CN)6}2·X] (R = vinyl, butyl, and propyl), and [(Ph3Sn)2Ni(CN) 4 Ph3SnOH·˜0.8CH3CN·˜0.2H 2O]. The compound [(Ph3Sn)2Ni(CN)4·Ph 3SnOH·˜0.8CH3CN·˜0.2H2O] is to our knowledge, the first three dimensional cyanometalate coordination polymer with expanded inorganic NbO structure. The framework is not interpenetrated and the large central cavity in the structure is filled by inclusion of Ph 3SnOH and other solvent molecules during synthesis. In addition to the investigation of organotin-cyanometalate compounds, other approaches to microporous solids were also studied. A new compound [Co(H 2O)2Ni(CN)4·4H2O] in the Hofmann's clathrate family was obtained. Five one dimensional polymers synthesized by the reaction of dirhodium(II) tetraacetate with 1,4-dicyanobenzene in different solvent systems were also synthesized, and the effect of solvent on the resulting structures was investigated.

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

    SciTech Connect

    Lu, Xin-Xin; Luo, Yu-Hui; Lu, Chen; Chen, Xin; Zhang, Hong

    2015-12-15

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

  18. Investigation of cyano-bridged coordination nanoparticles Gd3+/[Fe(CN)6]3-/d-mannitol as T1-weighted MRI contrast agents

    NASA Astrophysics Data System (ADS)

    Perrier, M.; Gallud, A.; Ayadi, A.; Kennouche, S.; Porredon, C.; Gary-Bobo, M.; Larionova, J.; Goze-Bac, Ch.; Zanca, M.; Garcia, M.; Basile, I.; Long, J.; de Lapuente, J.; Borras, M.; Guari, Y.

    2015-07-01

    Cyano-bridged Gd3+/[Fe(CN)6]3- coordination polymer nanoparticles of 3-4 nm stabilized with d-mannitol presenting a high r1 relaxivity value of 11.4 mM-1 s-1 were investigated in vivo as contrast agents (CA) for Magnetic Resonance Imaging (MRI). They allow an increase of the MR image contrast and can act as an efficient intravascular T1 CA with a relatively long blood-circulation lifetime (60 min) without specific toxicity.Cyano-bridged Gd3+/[Fe(CN)6]3- coordination polymer nanoparticles of 3-4 nm stabilized with d-mannitol presenting a high r1 relaxivity value of 11.4 mM-1 s-1 were investigated in vivo as contrast agents (CA) for Magnetic Resonance Imaging (MRI). They allow an increase of the MR image contrast and can act as an efficient intravascular T1 CA with a relatively long blood-circulation lifetime (60 min) without specific toxicity. Electronic supplementary information (ESI) available: Experimental details and procedures, toxicological data, physical characterization. See DOI: 10.1039/c5nr01557j

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

    SciTech Connect

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

    2015-11-15

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

  20. pH-value-controlled assembly of photoluminescent zinc coordination polymers in the mixed-ligand system

    NASA Astrophysics Data System (ADS)

    Liu, Kang; Hu, Hanbin; Sun, Jing; Zhang, Yiheng; Han, Jishu; Wang, Lei

    2017-04-01

    Three novel coordination polymers, [Zn(sdi)2(NO3)(H2O)]·NO3 (1), [Zn(sdi)2(H2O)2]·2NO3 (2) and [Zn(sdi)0.5(H2C3O4)(H2O)] (3), (sdi = N,N‧-sulfuryldiimidazole) have been synthesized and characterized by elemental analysis, IR spectroscopy, single crystal X-ray diffraction, powder X-ray diffraction and thermogravimetric analyses. These compounds have abundant structural chemistry ranging from zero-dimensional (0D) (1), one-dimensional (1D) (2), to three-dimensional (3D) (3) networks. Compound 1 displays a 0D structure which formed by [Zn(sdi)2]2 dimers. Compound 2 possesses 1D chain with closed loops. Notably, compound 3 exhibits a 3D (3,4)-connected net with a (63)(65·8) topology. Interestingly, compounds 1-3 were obtained under similar reaction conditions and the structural diversity of these coordination polymers illustrate the remarkable effect of pH on the self-assembling process. Moreover, the fluorescent properties of these compounds have been investigated.

  1. pySeismicFMM: Python based travel time calculation in regular 2D and 3D grids in Cartesian and geographic coordinates using Fast Marching Method

    NASA Astrophysics Data System (ADS)

    Polkowski, Marcin

    2016-04-01

    Seismic wave travel time calculation is the most common numerical operation in seismology. The most efficient is travel time calculation in 1D velocity model - for given source, receiver depths and angular distance time is calculated within fraction of a second. Unfortunately, in most cases 1D is not enough to encounter differentiating local and regional structures. Whenever possible travel time through 3D velocity model has to be calculated. It can be achieved using ray calculation or time propagation in space. While single ray path calculation is quick it is complicated to find the ray path that connects source with the receiver. Time propagation in space using Fast Marching Method seems more efficient in most cases, especially when there are multiple receivers. In this presentation a Python module pySeismicFMM is presented - simple and very efficient tool for calculating travel time from sources to receivers. Calculation requires regular 2D or 3D velocity grid either in Cartesian or geographic coordinates. On desktop class computer calculation speed is 200k grid cells per second. Calculation has to be performed once for every source location and provides travel time to all receivers. pySeismicFMM is free and open source. Development of this tool is a part of authors PhD thesis. National Science Centre Poland provided financial support for this work via NCN grant DEC-2011/02/A/ST10/00284.

  2. Mechanical, Electromagnetic, and X-ray Shielding Characterization of a 3D Printable Tungsten-Polycarbonate Polymer Matrix Composite for Space-Based Applications

    NASA Astrophysics Data System (ADS)

    Shemelya, Corey M.; Rivera, Armando; Perez, Angel Torrado; Rocha, Carmen; Liang, Min; Yu, Xiaoju; Kief, Craig; Alexander, David; Stegeman, James; Xin, Hao; Wicker, Ryan B.; MacDonald, Eric; Roberson, David A.

    2015-08-01

    Material-extrusion three-dimensional (3D) printing has recently attracted much interest because of its process flexibility, rapid response to design alterations, and ability to create structures "on-the-go". For this reason, 3D printing has possible applications in rapid creation of space-based devices, for example cube satellites (CubeSat). This work focused on fabrication and characterization of tungsten-doped polycarbonate polymer matrix composites specifically designed for x-ray radiation-shielding applications. The polycarbonate-tungsten polymer composite obtained intentionally utilizes low loading levels to provide x-ray shielding while limiting effects on other properties of the material, for example weight, electromagnetic functionality, and mechanical strength. The fabrication process, from tungsten functionalization to filament extrusion and material characterization, is described, including printability, determination of x-ray attenuation, tensile strength, impact resistance, and gigahertz permittivity, and failure analysis. The proposed materials are uniquely advantageous when implemented in 3D printed structures, because even a small volume fraction of tungsten has been shown to substantially alter the properties of the resulting composite.

  3. Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication.

    PubMed

    Reboul, Julien; Furukawa, Shuhei; Horike, Nao; Tsotsalas, Manuel; Hirai, Kenji; Uehara, Hiromitsu; Kondo, Mio; Louvain, Nicolas; Sakata, Osami; Kitagawa, Susumu

    2012-06-24

    The spatial organization of porous coordination polymer (PCP) crystals into higher-order structures is critical for their integration into separation systems, heterogeneous catalysts, ion/electron transport and photonic devices. Here, we demonstrate a rapid method to spatially control the nucleation site, leading to the formation of mesoscopic architecture made of PCPs, in both two and three dimensions. Inspired by geological processes, this method relies on the morphological replacement of a shaped sacrificial metal oxide used both as a metal source and as an 'architecture-directing agent' by an analogous PCP architecture. Spatiotemporal harmonization of the metal oxide dissolution and the PCP crystallization allowed the preservation of very fine mineral morphological details of periodic alumina inverse opal structures. The replication of randomly structured alumina aerogels resulted in a PCP architecture with hierarchical porosity in which the hydrophobic micropores of the PCP and the mesopores/macropores inherited from the parent aerogels synergistically enhanced the material's selectivity and mass transfer for water/ethanol separation.

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

    NASA Astrophysics Data System (ADS)

    Jin, Jing; Chen, Chong; Gao, Yan; Zhao, Ran; Wang, Xiuyan; Lü, Chunxin; Chi, Yuxian; Niu, Shuyun

    2016-03-01

    Six Ln-Ag coordination polymers {[LnAg2(IN)4(H2O)5]·NO3·2H2O}n (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg2(IN)4(H2O)2]·NO3·H2O}n (3), [LnAg(pdc)2]n (Ln=Eu(4) and Pr (5), H2pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc)2(H2O)4]n (6) (H2bidc=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 in 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.

  5. Carbon dioxide (CO2) absorption behavior of mixed matrix polymer composites containing a flexible coordination polymer.

    PubMed

    Culp, Jeffrey T; Sui, Lang; Goodman, Angela; Luebke, David

    2013-03-01

    Mixed matrix membranes (MMMs) comprised of metal organic frameworks (MOFs) dispersed in organic polymers are popular materials under study for potential applications in gas separations. However, research on MMMs containing structurally dynamic sorbents known as flexible MOFs has only very recently appeared in the literature. The thermodynamic requirements of the structure transition between the low porosity and high porosity phases of flexible MOFs may provide a mechanism for high adsorption selectivity in these materials. A fundamental question in MMMs containing flexible MOFs is how the constraint of the polymer matrix on the intrinsic expansion of the flexible MOF particles that occurs during gas adsorption might affect the thermodynamics of this structural phase transition and influence the gas adsorption properties of the embedded MOF. To investigate the fundamental nature of this flexible MOF-polymer interface, thin films of ~20 um thickness were prepared using the flexible linear chain coordination polymer catena-bis(dibenzoylmethanato)-(4,4'bipyridyl)nickel(II) "Ni(Bpy)(DBM)(2)" embedded as 35 wt% dispersions in Matrimid®, polystyrene, and polysulfone. The adsorption of CO(2) in the polymers and embedded particles was studied using in situ ATR-FTIR spectroscopy and variable temperature volumetric CO(2) adsorption/desorption isotherms. Interestingly, no effect of the polymer matrix on the gas adsorption behavior of the embedded Ni(Bpy)(DBM)(2) particles was observed. The composite samples all showed the same threshold pressures for CO(2) absorption and desorption hysteresis associated with the structural phase change in the polymer embedded Ni(Bpy)(DBM)(2) particles as was observed in the pristine polycrystalline sample. The current results contrast those recently reported for a MMM containing the flexible MOF "NH(2)-MIL-53" where a significant increase in the threshold pressure for CO(2) adsorption associated with the structural phase change of the MOF was

  6. Thermo-mechanical Characterization of Metal/Polymer Composite Filaments and Printing Parameter Study for Fused Deposition Modeling in the 3D Printing Process

    NASA Astrophysics Data System (ADS)

    Hwang, Seyeon; Reyes, Edgar I.; Moon, Kyoung-sik; Rumpf, Raymond C.; Kim, Nam Soo

    2015-03-01

    New metal/polymer composite filaments for fused deposition modeling (FDM) processes were developed in order to observe the thermo-mechanical properties of the new filaments. The acrylonitrile butadiene styrene (ABS) thermoplastic was mixed with copper and iron particles. The percent loading of the metal powder was varied to confirm the effects of metal particles on the thermo-mechanical properties of the filament, such as tensile strength and thermal conductivity. The printing parameters such as temperature and fill density were also varied to see the effects of the parameters on the tensile strength of the final product which was made with the FDM process. As a result of this study, it was confirmed that the tensile strength of the composites is decreased by increasing the loading of metal particles. Additionally, the thermal conductivity of the metal/polymer composite filament was improved by increasing the metal content. It is believed that the metal/polymer filament could be used to print metal and large-scale 3-dimensional (3D) structures without any distortion by the thermal expansion of thermoplastics. The material could also be used in 3D printed circuits and electromagnetic structures for shielding and other applications.

  7. Different geometrical arrangements in carboxylate coordination polymers of flexible dicarboxylic acid

    SciTech Connect

    Deka, Himangshu; Sarma, Rupam; Kumari, Satchi; Khare, Alika; Baruah, Jubaraj B.

    2011-07-15

    Dicarboxylate coordination polymers (1-5) of Mn(II), Ni(II), Cu(II), Zn(II) and Cd(II), respectively, derived from (7-carboxymethoxy-naphthalen-2-yloxy)-acetic acid (L{sub 1}H{sub 2}) are synthesized and characterized. Depending on the coordination sites around the metal centers and coordination mode of the ligand, dimensionality of these polymers varies. The dicarboxylates adopt three spatial orientations: in-plane linear coordination, out-of-plane cis coordination and out-of-plane trans coordination mode. Both the cis and trans out-of-plane coordination modes are found to exist only if the ancillary ligand pyridine is coordinated to the metal ion. When the aquoligand coordinates the in-plane linear coordination mode of L{sub 1} predominates. The coordination polymers 4 and 5 show photoluminescence in solution. The dicarboxylate of (5-carboxymethoxy-naphthalen-1-yloxy)-acetic acid (L{sub 2}H{sub 2}) does not form coordination polymer under ambient conditions, but prefers to remain as uncoordinated anion providing hydrophobic confinement to hexa-aquometal(II) cation. Compound 3 crystallizes in P2{sub 1} space group and it shows broadband ultra-violet fluorescence centered at 352.9 nm on focusing 632.8 nm He:Ne laser. - Graphical abstract: Different geometrical arrangements in coordination polymers derived from (7-carboxymethoxy-naphthalen-2-yloxy)-acetic acid of metal ions Mn(II), Ni(II), Cu(II), Zn(II) and Cd(II) are presented. The (5-carboxymethoxy-naphthalen-1-yloxy)-acetic acid led to hexa-aquo cadmium(II) dicarboxylate. Highlights: > Structural and spectroscopic characterizations of five dicarboxylate coordination polymers of (7-carboxymethoxy-naphthalen-2-yloxy)-acetic acid with different metal ions are presented. > Different geometrical arrangements of coordination polymers stabilized in solid state are described. > Photoluminescence properties of the polymers are shown. > NLO property of a copper coordination polymer is described.

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

    SciTech Connect

    Lü, Lei; Mu, Bao; Li, Chang-Xia; Huang, Ru-Dan

    2016-02-15

    A series of metal-organic frameworks (MOFs) have been prepared by tetracarboxylate ligands and Cd(II) ions under the hydrothermal or solvothermal conditions with the formulas of {[Cd_2(L_1)(H_2O)_4]·H_2O}{sub n} (1), {[(CH_3)_2NH_2]_2[Cd(L_1)]}{sub n} (2), [Cd(L{sub 2}){sub 0.5}(H{sub 2}O)]{sub n} (3), {[(CH_3)_2NH_2]_2 [Cd(L_2)]·2DMF}{sub n} (4), [Cd(L{sub 3}){sub 0.5}(H{sub 2}O)]{sub n} (5), {[Cd(L_3)_0_._5(H_2O)]·CH_3OH}{sub n} (6), {[(CH_3)_2NH_2]_2[Cd_3(L_4)_2]}{sub n} (7) (H{sub 4}L{sub 1}=[1,1′:4′,1″-terphenyl]-2,2″,5,5″-tetracarboxylic acid; H{sub 4}L{sub 2}=[1,1′:4′,1″-terphenyl]-2′,4,4″,5′-tetracarboxylic acid; H{sub 4}L{sub 3}=[1,1′:3′,1″-terphenyl]-2′,3,3″,5′-tetracarboxylic acid; H{sub 4}L{sub 4}=[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid), which are characterized by single-crystal X-ray diffraction, elemental analyses, IR, TGA and PXRD. Complex 1 exhibits a three-dimensional (3D) supramolecular framework based on two-dimensional (2D) coordination networks. Complexes 2 and 4 possess 3D framework based on the 1D right-handed helix channels. Complexes 3 and 7 are a 3D architecture containing two different channels. Isostructural complexes 5 and 6 display 3D framework. The different synthetic methods and coordination modes of the tetracarboxylates ligands have effect on formation of various MOFs. Moreover, the luminescent properties and N{sub 2} adsorption behaviors have been reported. - Graphical abstract: A series of cadmium(II) high-dimensional coordination polymers constructed from four different kinds of tetracarboxylate ligands have been successfully prepared under hydrothermal or solvothermal conditions. The effect of solvents, the coordination modes of the tetracarboxylates and positions of carboxylate groups on the architectures of complexes 1–7 have been investigated in detail. The luminescent properties of the part of complexes, N{sub 2} adsorption behaviors of complexes 2, 4–7 have

  9. Coupled 3D time-dependent wave-packet approach in hyperspherical coordinates: application to the adiabatic singlet-state(1(1)A') D(+) + H2 reaction.

    PubMed

    Sahoo, Tapas; Ghosh, Sandip; Adhikari, Satrajit; Sharma, Rahul; Varandas, António J C

    2014-07-03

    We explore a coupled three-dimensional (3D) time-dependent wave packet formalism in hyperspherical coordinates for a 4D reactive scattering problem on the lowest adiabatic singlet surface (1(1)A') of the D(+) + H2 reaction. The coupling among the wavepackets arises through quantization of the rotation matrix, which represents the orientation of the three particles in space. The required transformation from Jacobi to hyperspherical coordinates and vice versa during initialization and projection of the wave packet on the asymptotic state(s), and the coupled equations of motion, are briefly discussed. With the long-range potential known to contribute significantly on the D(+) + H2 system, we demonstrate the workability of our approach, where the convergence profiles of the reaction probability for the reactive noncharge transfer (RNCT) process [D(+) + H2(v=0, j=0,1) → HD(v',j') + H(+)] are shown for three different collisional energies (1.7, 2.1, and 2.5 eV) with respect to the helicity (K) and total angular momentum (J) quantum numbers. The calculated reactive cross-section is presented as a function of the collision energy for two different initial states of the diatom (v = 0, j = 0, 1).

  10. Hydrothermal synthesis of two copper helical coordination polymers with acentric three-dimensional framework constructing from mixed pyridine carboxylates

    SciTech Connect

    Zhang Shuai; Cao Yanning; Zhang Hanhui Chai Xiaochuan; Chen Yiping

    2008-03-15

    Two copper helical coordination polymers, [Cu(2-pc)(3-pc)]{sub n}1 and [Cu(2-pc)(4-pc)]{sub n}2 (2-pc=2-pyridine carboxylate, 3-pc=3-pyridine carboxylate, 4-pc=4-pyridine carboxylate) have been hydrothermally synthesized directly from pyridine carboxylic acids and copper nitrate. The crystal structure were determined by single-crystal X-ray diffraction with the following data: compound 1, orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=6.591(3) A, b=8.692(5) A, c=20.548(9) A, V=1177.2(9) A{sup 3}, Z=4; compound 2, orthorhombic, Pna2{sub 1}, a=21.160(10) A, b=9.095(5) A, c=6.401(3) A, V=1231.9(11) A{sup 3}, Z=4. The acentric three-dimensional (3D) framework of 1 is constructed from right-handed helical Cu(2-pc) chains and left-handed Cu(3-pc) helices. As for 2, Cu(2-pc) helical chains, in which left- and right-handed helices are coexisting, and Cu(4-pc) zigzag chains combined together to form acentric 3D architecture of 2 as well. Additionally, besides general spectral characterization, we first introduce generalized 2D correlation spectroscopy to explore the coordination polymers and ascertain the stretching vibration location of carboxylate groups of compounds 1 and 2. -- Abstract: Two copper helical coordination polymers, [Cu(2-pc)(3-pc)]{sub n}1 and [Cu(2-pc)(4-pc)]{sub n}2 have been obtained by hydrothermal synthesis. Both two compounds crystallized in non-centrosymmetric space groups, P2{sub 1}2{sub 1}2{sub 1} and Pna2{sub 1}, respectively. The 3D framework of 1 is constructed from right-handed helical Cu(2-pc) chains and left-handed Cu(3-pc) helices. As for 2, Cu(2-pc) helical chains, in which left- and right-handed helices are coexisting, and Cu(4-pc) zigzag chains combined together to form 3D architecture of 2 as well.

  11. Two Ag(I) coordination polymers derived from melamine and dicarboxylates: Syntheses, crystal structures and thermal stabilities

    NASA Astrophysics Data System (ADS)

    Li, Yun-Hua; Sun, Di; Luo, Geng-Geng; Liu, Fu-Jing; Hao, Hong-Jun; Wen, Yi-Mei; Zhao, Yang; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-08-01

    Two mixed-ligand Ag(I) coordination polymers (CPs), [(NH 4)Ag 3(MA) 2(suc) 2] n ( 1), [Ag 2(MA) 2(adip)·CH 3OH·H 2O] n ( 2), (where MA = melamine, H 2suc = succinic acid, H 2adip = adipic acid) have been synthesized and structurally characterized by element analysis, IR and X-ray single-crystal diffraction. The CP 1 is a three-dimensional (3D) framework in which the MA acts as a tridentate ligand and suc 2- anion shows three types of coordination modes. Each Ag(I) ion acts as a 4-connected node to generate three- and six-membered cycles, as a result, the network can be simplified to be an overall multi-layered Kagomé topology. The CP 2 is a 2D single-layer structure constructed by tridentate MA ligands and adip 2- anions. The adjacent single-layers are inter-linked to form a double-layer 2D structure through the Ag⋯Ag interactions. Two CPs structurally vary from 2D sheet to 3D framework, which indicates that the different dicarboxylates and coordination modes of MA ligand have significant influence on the final structures. Moreover, the thermal stabilities of them were also discussed.

  12. Metal Coordination Polymers as Potential High-Energy Lithographic Resists

    DTIC Science & Technology

    1989-05-15

    resists,I ~ ~ ~ 1-&obalt polymers--- - dfiroiuinpIrms (CotiueC-positive6 resjits ,-beta- diketones 19 At8tTRACT (Cniu nreverse ifnecessary and odentify by...have synthesized several cobalt(III) coordi- nation polymers, one of which was briefly described earlier (5,6). The general synthesis for three... diketones from ad- jacent units in the polymer chains. The corresponding sulfone polymer can be synthesized from the oxidation of the sulfoxide

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

    SciTech Connect

    Jin, Jing Chen, Chong; Gao, Yan; Zhao, Ran; Wang, Xiuyan; Lü, Chunxin; Chi, Yuxian; Niu, Shuyun

    2016-03-15

    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 in 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 the NIR

  14. Crystal structures and luminescent properties of lanthanide nitrate coordination polymers with structurally related amide type bridging podands

    SciTech Connect

    Wang, Qing; Yan, Xuhuan; Zhang, Hongrui; Liu, Weisheng; Tang, Yu; Tan, Minyu

    2011-01-15

    A one-dimensional linear chain coordination polymer [ErL{sup I}(NO{sub 3}){sub 3}(CH{sub 3}CO{sub 2}Et)]{sub n} (L{sup I}=1,2-bis{l_brace}[(2'-furfurylaminoformyl)phenoxyl]methyl{r_brace}benzene) and a one-dimensional zig-zag coordination polymer {l_brace}[TbL{sup II}(NO{sub 3}){sub 3}(H{sub 2}O)].(H{sub 2}O){r_brace}{sub n} (L{sup II}=1,2-bis{l_brace}[2'-(2-pyridylmethylaminoformyl)phenoxyl]methyl{r_brace}benzene) were assembled by two structurally related bridging podands L{sup I} and L{sup II} which have uniform skeleton and different terminal groups. In {l_brace}[TbL{sup II}(NO{sub 3}){sub 3}(H{sub 2}O)].(H{sub 2}O){r_brace}{sub n}, the neutral chains were linked by the hydrogen bonding interactions between the free and coordinated water molecules from two different directions to interpenetrate into a 3D supramolecular structure. At the same time, the luminescent properties of the solid Tb(III) nitrate complexes of these podands were investigated at room temperature. The lowest triplet state energy levels T{sub 1} of the podands L{sup I} and L{sup II} indicate that the triplet state energy levels of the antennae are both above the lowest excited resonance level of {sup 5}D{sub 4} of Tb{sup 3+} ion. Thus the absorbed energy could be transferred from ligands to the central Tb{sup 3+} ions. And the influence of the hydrogen bonding on the luminescence efficiencies of the coordination polymers was also discussed. -- Graphical Abstract: Two one-dimensional lanthanide coordination polymers were assembled by two structurally related bridging podands, and the effects of the structures on luminescent properties of the solid Tb(III) nitrate complexes were investigated. Display Omitted Research highlights: > Two structurally related amide type bridging ligands were designed and synthesized. > Two one dimensional lanthanide nitrate coordination polymers were obtained. > The structure effects on luminescent properties of the terbium complexes were discussed.

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

    NASA Astrophysics Data System (ADS)

    Wu, Yu; Lu, Lu; Feng, Jianshen; Li, Yulong; Sun, Yanchun; Ma, Aiqing

    2017-01-01

    The reaction of Cu(NO3)2·3H2O/Ni(NO3)2·6H2O with 4‧-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2‧:6‧,4‧‧-terpyridine (H2dbp) gave [Cu0.5(Hdbp)]n (1) and [Ni(dbp)(H2O)]n (2), while the reactions of Co(NO3)2·6H2O with H2dbp in the presence of 4,4‧-bipy and 2,2‧-bpy generated [Co(dbp)(4,4‧-bipy)]n (3) and {[Co(dbp)(2,2‧-bipy)]n·H2O} (4), respectively (4,4‧-bipy=4.4‧-pyridine and 2,2‧-bipy=2,2‧-bipyridine). X-Ray single-crystal analyses reveal that 1 contains a 1D double chain. 2 possesses a 3D architecture with (4.620.83)2 topology that is interpenetrated with each other to form a 2-fold network. In 3, the 2D [Co(dbp)]n sheets are pillared by 4,4‧-bpy to form a 3D framework with 1D open channel. Compound 4 consists of a 1D ladder-like chain. The results showed that the structural diversity of the coordination polymers resulted from the different geometries of metal ions and effect of assistant ligands. Furthermore, the photocatalytic properties of 1-4 for degradation of the methyl violet (MV) have been examined.

  16. Effective Photo- and Triboluminescent Europium(III) Coordination Polymers with Rigid Triangular Spacer Ligands.

    PubMed

    Hasegawa, Yasuchika; Tateno, Shiori; Yamamoto, Masanori; Nakanishi, Takayuki; Kitagawa, Yuichi; Seki, Tomohiro; Ito, Hajime; Fushimi, Koji

    2017-02-21

    Luminescent Eu(III) coordination polymers with rigid triangular spacer ligands are reported. The Eu(III) coordination polymer, [Eu3 (hfa)9 (tppb)2 ]n (hfa: hexafluoroacetylacetonate, tppb: tris(4-diphenylphosphorylphenyl)benzene), shows high thermo-stability (decomposition temperature=354 °C) and photoluminescence quantum yield (Φ4f-4f =82 %, photosensitized energy transfer efficiency=78 %). The triboluminescence efficiency of Eu(III) coordination polymer with triangular spacers under laser pulse irradiation (Nd:YAG, λ=1064 nm, pulse width=5 ns, pulse energy=0.1 mJ) is calculated to be 49 %. Characteristic triangular structure, high emission quantum yield, effective photosensitized energy transfer, and remarkable triboluminescence properties of Eu(III) coordination polymers are demonstrated for the first time.

  17. First high thermally stable organo-inorganic 3D polymer scandium derivative as a heterogeneous Lewis acid catalyst.

    PubMed

    Perles, Josefina; Iglesias, Marta; Ruiz-Valero, Caridad; Snejko, Natalia

    2003-02-07

    Sc2(OOCC2H4COO)2.5(OH), a new hybrid organic-inorganic polymer, has been hydrothermally obtained; the crystal structure of this material has been established by single crystal X-ray diffraction; having high thermal stability it can be used as an effective Lewis acid catalyst and can be easily recycled and reused without any appreciable loss in activity.

  18. A New Structural Family of Gas-Sorbing Coordination Polymers Derived from Phenolic Carboxylic Acids.

    PubMed

    White, Keith F; Abrahams, Brendan F; Babarao, Ravichandar; Dharma, A David; Hudson, Timothy A; Maynard-Casely, Helen E; Robson, Richard

    2015-12-07

    The structure of Li(inox)⋅2/3 DMF (inox(-) =the N-oxide of the isonicotinate anion) consists of a 3D framework with solvent-filled, square cross-section channels of approximate dimensions 5.5×5.5 Å. Unfortunately, the Li(inox) framework is unstable upon removal of DMF from the channels. When the structurally related 4-hydroxybenzoic acid (H2 hba) was used in place of Hinox, and Zn(2+) in place of the Li(+) , a structurally similar but more robust network, Zn(hba), was obtained; the isostructural compound, Co(hba), may also be prepared. Longer ligands with phenolate and carboxylate functional groups at opposite ends, such as the dianions of 4-coumaric acid (H2 cma) and 4'-hydroxy-4-biphenylcarboxylic acid (H2 hbpc), in combination with Zn(2+) yield Zn(cma) and Zn(hbpc) frameworks, respectively, with the same PtS topology but with larger channels. The coordination polymers remain intact after desolvation and exhibit microporosity, showing the ability to sorb significant quantities of CO2 , CH4 , and H2 .

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

    SciTech Connect

    Feng, Xun; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Qiang Shi, Zhi; Wu, Xu-Hong; Ng, Seik-Weng

    2013-10-15

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

  20. A symmetric, triply interlaced 3-D anionic MOF that exhibits both magnetic order and SMM behaviour.

    PubMed

    Campo, J; Falvello, L R; Forcén-Vázquez, E; Sáenz de Pipaón, C; Palacio, F; Tomás, M

    2016-11-14

    A newly prepared 3-D polymer of cobalt citrate cubanes bridged by high-spin Co(ii) centres displays both single-molecule magnet (SMM) behaviour and magnetic ordering. Triple interpenetration of the 3-D diamondoid polymers yields a crystalline solid with channels that host cations and free water molecules, with the SMM behaviour of the Co4O4 cores preserved. The octahedrally coordinated Co(ii) bridges are implicated in the onset of magnetic order at an experimentally accessible temperature.

  1. 3D interconnected ionic nano-channels formed in polymer films: self-organization and polymerization of thermotropic bicontinuous cubic liquid crystals.

    PubMed

    Ichikawa, Takahiro; Yoshio, Masafumi; Hamasaki, Atsushi; Kagimoto, Junko; Ohno, Hiroyuki; Kato, Takashi

    2011-02-23

    Thermotropic bicontinuous cubic (Cub(bi)) liquid-crystalline (LC) compounds based on a polymerizable ammonium moiety complexed with a lithium salt have been designed to obtain lithium ion-conductive all solid polymeric films having 3D interconnected ionic channels. The monomer shows a Cub(bi) phase from -5 to 19 °C on heating. The complexes retain the ability to form the Cub(bi) LC phase. They also form hexagonal columnar (Col(h)) LC phases at temperatures higher than those of the Cub(bi) phases. The complex of the monomer and LiBF(4) at the molar ratio of 4:1 exhibits the Cub(bi) and Col(h) phases between -6 to 19 °C and 19 to 56 °C, respectively, on heating. The Cub(bi) LC structure formed by the complex has been successfully preserved by in situ photopolymerization through UV irradiation in the presence of a photoinitiator. The resultant nanostructured film is optically transparent and free-standing. The X-ray analysis of the film confirms the preservation of the self-assembled nanostructure. The polymer film with the Cub(bi) LC nanostructure exhibits higher ionic conductivities than the polymer films obtained by photopolymerization of the complex in the Col(h) and isotropic phases. It is found that the 3D interconnected ionic channels derived from the Cub(bi) phase function as efficient ion-conductive pathways.

  2. Determination of tetracycline in milk by using nucleotide/lanthanide coordination polymer-based ternary complex.

    PubMed

    Tan, Hongliang; Ma, Chanjiao; Song, Yonghai; Xu, Fugang; Chen, Shouhui; Wang, Li

    2013-12-15

    The meta-organic coordination polymers have been emerged as fascinating nanomaterials because of their tunable nature. In this work, we employed lanthanide coordination polymer self-assembled from adenosine monophosphate (AMP) and europium ion (Eu(3+)) as receptor reagent and citrate (Cit) as ancillary ligand to construct a fluorescent sensor for the detection of tetracycline (Tc) in milk. The co-coordination of Cit and Tc with Eu(3+) on the surface of the coordination polymer AMP/Eu leads to the formation of ternary complex which emitted strong fluorescence due to the removal of coordinated water molecules and an intramolecular energy transfer from Tc to Eu(3+). The fluorescent intensity of Eu(3+) displayed a good linear response to Tc concentrations in the range of 0.1-20 μM with a detection limit of 60 nM. This method was successfully applied to determine the levels of Tc in milk, which is the first application of coordination polymer as a fluorescent sensor in real sample. Compared with other Eu(3+)-based fluorescent methods for Tc detection, the presented method allows simple, direct analysis of Tc without requiring special reaction media or complicated prepreparation processes. This straightforward strategy could be extended to the preparation of other lanthanide coordination polymer-based fluorescent probes for applications in biosensing, imaging, drug delivery, and so on.

  3. One-dimensional alignment of strong Lewis acid sites in a porous coordination polymer.

    PubMed

    Kajiwara, Takashi; Higuchi, Masakazu; Yuasa, Akihiro; Higashimura, Hideyuki; Kitagawa, Susumu

    2013-11-18

    A new lanthanoid porous coordination polymer, La-BTTc (BTTc = benzene-1,3,5-tris(2-thiophene-5-carboxylate)), was synthesized and structurally characterized to have densely aligned one-dimensional open metal sites, which were found to act as strong Lewis acid sites after the removal of the coordinated solvent.

  4. Synthesis and structural characterization of a single-crystal to single-crystal transformable coordination polymer.

    PubMed

    Tian, Yuyang; Allan, Phoebe K; Renouf, Catherine L; He, Xiang; McCormick, Laura J; Morris, Russell E

    2014-01-28

    A single-crystal to single-crystal transformable coordination polymer compound was hydrothermally synthesized. The structural rearrangement is induced by selecting a ligand that contains both strong and weaker coordinating groups. Both hydrated and dehydrated structures were determined by single crystal X-ray analysis.

  5. Coupled 3D Time-Dependent Wave-Packet Approach in Hyperspherical Coordinates: The D(+)+H2 Reaction on the Triple-Sheeted DMBE Potential Energy Surface.

    PubMed

    Ghosh, Sandip; Sahoo, Tapas; Adhikari, Satrajit; Sharma, Rahul; Varandas, António J C

    2015-12-17

    We implement a coupled three-dimensional (3D) time-dependent wave packet formalism for the 4D reactive scattering problem in hyperspherical coordinates on the accurate double many body expansion (DMBE) potential energy surface (PES) for the ground and first two singlet states (1(1)A', 2(1)A', and 3(1)A') to account for nonadiabatic processes in the D(+) + H2 reaction for both zero and nonzero values of the total angular momentum (J). As the long-range interactions in D(+) + H2 contribute significantly due to nonadiabatic effects, the convergence profiles of reaction probabilities for the reactive noncharge transfer (RNCT), nonreactive charge transfer (NRCT), and reactive charge transfer (RCT) processes are shown for different collisional energies with respect to the helicity (K) and total angular momentum (J) quantum numbers. The total and state-to-state cross sections are presented as a function of the collision energy for the initial rovibrational state v = 0, j = 0 of the diatom, and the calculated cross sections compared with other theoretical and experimental results.

  6. Single-Crystal to Single-Crystal Phase Transition and Segmented Thermochromic Luminescence in a Dynamic 3D Interpenetrated Ag(I) Coordination Network.

    PubMed

    Yan, Zhi-Hao; Li, Xiao-Yu; Liu, Li-Wei; Yu, Si-Qi; Wang, Xing-Po; Sun, Di

    2016-02-01

    A new 3D Ag(I)-based coordination network, [Ag2(pz)(bdc)·H2O]n (1; pz = pyrazine and H2bdc = benzene-1,3-dicarboxylic acid), was constructed by one-pot assembly and structurally established by single-crystal X-ray diffraction at different temperatures. Upon cooling from 298 to 93 K, 1 undergo an interesting single-crystal to single-crystal phase transition from orthorhombic Ibca (Z = 16) to Pccn (Z = 32) at around 148 K. Both phases show a rare 2-fold-interpenetrated 4-connected lvt network but incorporate different [Ag2(COO)2] dimeric secondary building units. It is worth mentioning that complex 1 shows red- and blue-shifted luminescences in the 290-170 and 140-80 K temperature ranges, respectively. The variable-temperature single-crystal X-ray crystallographic studies suggest that the argentophilic interactions and rigidity of the structure dominated the luminescence chromism trends at the respective temperature ranges. Upon being mechanically ground, 1 exhibits a slight mechanoluminescence red shift from 589 to 604 nm at 298 K.

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

    SciTech Connect

    Li, Lin; Liu, Chong-Bo; Yang, Gao-Shan; Xiong, Zhi-Qiang; Liu, Hong; Wen, Hui-Liang

    2015-11-15

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

  8. Structural diversity in two-dimensional coordination polymers constructed from simple building-blocks; a rare example of coordination polymer polymorphs structurally characterised from multiple crystals.

    PubMed

    Barnett, Sarah A; Blake, Alexander J; Champness, Neil R; Wilson, Claire

    2005-12-21

    A family of two-dimensional coordination polymers formed from the reaction of Cd(NO(3))(2) with pyrazine or pyrimidine is reported, including rare examples of polymorphic coordination polymers which crystallise as multiple crystals. Six coordination polymers have been structurally characterised, four for pyrazine and two for pyrimidine-based systems, all of which form two-dimensional arrays utilising pyrazine/pyrimidine bridging, in some instances in combination with nitrate bridging. The compounds form either 4(4) grids (1,3,4,5), or in one instance, a 6(3) herringbone sheet structure (2). In the case of 3, two polymorphs have been identified, 3a and 3b, in which the three-dimensional arrangements of the coordination polymers differ only in the relative ordering of adjacent two-dimensional sheets. It was found that these two polymorphs crystallise in a simultaneous fashion such that each crystal studied was found to contain regions of both polymorphs and was believed to be a multiple crystal. Assessment of the phase purity of the product from the reaction of Cd(NO(3))(2) with either pyrazine or pyrimidine indicates that compounds 1and 5 are not formed when the products are formed by rapid precipitation but only when using slow-diffusion methods. It is also apparent that in almost all instances more than one product is formed from a given reaction thereby illustrating the complexity of coordination polymer formation even when using simple building-blocks. For the crystal engineer this complexity is perhaps best illustrated by the simultaneous formation of 3a and 3b where no chemical interactions differentiate the two polymorphs, presenting a seemingly insurmountable complexity in the engineering of these systems.

  9. Micromechanics of Amorphous Metal/Polymer Hybrid Structures with 3D Cellular Architectures: Size Effects, Buckling Behavior, and Energy Absorption Capability.

    PubMed

    Mieszala, Maxime; Hasegawa, Madoka; Guillonneau, Gaylord; Bauer, Jens; Raghavan, Rejin; Frantz, Cédric; Kraft, Oliver; Mischler, Stefano; Michler, Johann; Philippe, Laetitia

    2017-02-01

    By designing advantageous cellular geometries and combining the material size effects at the nanometer scale, lightweight hybrid microarchitectured materials with tailored structural properties are achieved. Prior studies reported the mechanical properties of high strength cellular ceramic composites, obtained by atomic layer deposition. However, few studies have examined the properties of similar structures with metal coatings. To determine the mechanical performance of polymer cellular structures reinforced with a metal coating, 3D laser lithography and electroless deposition of an amorphous layer of nickel-boron (NiB) is used for the first time to produce metal/polymer hybrid structures. In this work, the mechanical response of microarchitectured structures is investigated with an emphasis on the effects of the architecture and the amorphous NiB thickness on their deformation mechanisms and energy absorption capability. Microcompression experiments show an enhancement of the mechanical properties with the NiB thickness, suggesting that the deformation mechanism and the buckling behavior are controlled by the brittle-to-ductile transition in the NiB layer. In addition, the energy absorption properties demonstrate the possibility of tuning the energy absorption efficiency with adequate designs. These findings suggest that microarchitectured metal/polymer hybrid structures are effective in producing materials with unique property combinations.

  10. Synthesis, structure and luminescent properties of rare earth coordination polymers constructed from paddle-wheel building blocks.

    PubMed

    Guo, Xiaodan; Zhu, Guangshan; Fang, Qianrong; Xue, Ming; Tian, Ge; Sun, Jinyu; Li, Xiaotian; Qiu, Shilun

    2005-05-30

    A series of three-dimensional (3D) novel coordination polymers M(bpdc)1.5(H2O) x 0.5DMF (M = Tb (1), Ho (2), Er (3), or Y (4)) have been synthesized by reaction of the rare earth ions (M3+) with 4,4'-biphenyldicarboxylic acid (H2bpdc) in a mixed solution of DMF and C2H5OH. They possess the same 3D architectures and crystallize in monoclinic space group C2/c. Two seven-coordinated metal centers and four dimonodentate bpdc groups construct a paddle-wheel building block. These building blocks connect with two carboxyl groups to lead to a one-dimensional inorganic chain, ---M-O-C-O-M---, along the [001] direction. The inorganic chains are linked with two biphenyl groups to form 25.15 A x 17.09 A rhombic channels along the c axis without interpenetration. These complexes exhibit strong fluorescence in the visible region, and complex 3 shows Er3+ characteristic emission in the range of 1450-1650 nm at room temperature. These complexes could be anticipated as potential fluorescent probes and an IR-emitter, respectively.

  11. Tracer diffusion in a polymer gel: simulations of static and dynamic 3D networks using spherical boundary conditions.

    PubMed

    Kamerlin, Natasha; Elvingson, Christer

    2016-11-30

    We have investigated an alternative to the standard periodic boundary conditions for simulating the diffusion of tracer particles in a polymer gel by performing Brownian dynamics simulations using spherical boundary conditions. The gel network is constructed by randomly distributing tetravalent cross-linking nodes and connecting nearest pairs. The final gel structure is characterised by the radial distribution functions, chain lengths and end-to-end distances, and the pore size distribution. We have looked at the diffusion of tracer particles with a wide range of sizes, diffusing in both static and dynamic networks of two different volume fractions. It is quantitatively shown that the dynamical effect of the network becomes more important in facilitating the diffusional transport for larger particle sizes, and that one obtains a finite diffusion also for particle sizes well above the maximum in the pore size distribution.

  12. 3D Numerical study on the hollow profile polymer extrusion forming based on the gas-assisted technique

    NASA Astrophysics Data System (ADS)

    Ren, Z.; Huang, X. Y.; Liu, H. S.

    2016-07-01

    In this study, gas-assisted extrusion method was introduced into the extrusion of the hollow profiles. To validate the feasibility of the new extrusion method, 3D numerical simulation of the hollow profiles based on gas-assisted technique was carried out by using the finite element method. The Phan-Thien-Tanner (PTT) mode was selected as the construction equation. In the simulations, the physical field distributions of four different extrusion modes were obtained and analyzed. Results showed that the extrudate effect of traditional no gas- assisted mode was poor because the extrudate swell phenomenon is obvious and the physical field values are larger. For the gas-assisted of the inner wall, the extrudate swell of the melt was more obvious than that of the traditional no gas-assisted mode on account of the no-slip boundary condition on the outer wall. For the gas-assisted of the outer wall, the dimple effect of the inner wall is more obvious owing to the no-slip boundary condition on the inner wall. However, the extrusion effect of the double walls gas-assisted mode is very good because of the full-slip effect on the both walls.

  13. Two novel coordination polymers constructed by the same mixed ligands of 1,3-bip and H2bpdc: Syntheses, structures and catalytic properties

    NASA Astrophysics Data System (ADS)

    Lu, Jiu-Fu; Wang, Min-Zhen; Liu, Zhi-Hong

    2015-10-01

    Two novel coordination polymers, namely [Co(1,3-bip)(bpdc)·0.5H2bpdc]n (1), [Cu(1,3-bip)(bpdc)·3H2O]n (2), where 1,3-bip = 1,3-bis(imidazol-1-yl)propane, H2bpdc = biphenyl-4,4‧-dicarboxylic acid, were synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction, powder XRD, FT-IR, TGA and elemental analysis techniques. Single crystal X-ray analysis revealed that complex 1 features a 3D3D fivefold interpenetrating framework. The structure of complex 2 displays a (4,4) grid layer which is further reinforced through strong H-bonding with lattice solvent molecules to form a 3D supramolecular framework. Furthermore, the complexes 1 and 2 exhibit catalytic properties on degradation of methyl orange in Fenton-like process.

  14. 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.

  15. First examples of ternary lanthanide 5-aminoisophthalate complexes: Hydrothermal syntheses and structures of lanthanide coordination polymers with 5-aminoisophthalate and oxalate

    NASA Astrophysics Data System (ADS)

    Liu, Chong-Bo; Wen, Hui-Liang; Tan, Sheng-Shui; Yi, Xiu-Guang

    2008-05-01

    Two new lanthanide coordination polymers with mixed-carboxylates, [Ln(OX)(HAPA)(H 2O)] n[Ln = Eu ( 1), Ho ( 2); H 2APA = 5-aminoisophthalic acid; OX = oxalate] were obtained by hydrothermal reactions, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Complexes 1 and 2 are both 3-D supramolecular structure, in which lanthanide ions are bridged by oxalate and 5-aminoisophthalate ligands forming 2-D metal-organic framework, and 2-D networks are further architectured to form 3-D supramolecular structures by hydrogen bonds. The two carboxylate groups of H 2APA ligand are all deprotonated and exhibit chelating and bridging bidentate coordination modes, respectively, and the amino group in HAPA presents - NH3+ in the titled complexes. The thermogravimetric analysis was carried out to examine the thermal stability of the titled complexes. And the photoluminescence property of 1 was investigated.

  16. Copper(II)-lanthanide(III) coordination polymers constructed from pyridine-2,5-dicarboxylic acid: Preparation, crystal structure and photoluminescence

    SciTech Connect

    Xia Zhengqiang; Wei Qing; Chen Sanping; Feng Xinming; Xie Gang; Qiao Chengfang; Zhang Guochun; Gao Shengli

    2013-01-15

    A series of 3d-4f heterometallic coordination polymers, formulated as {l_brace} [Cu{sub 3}Ln{sub 2}(pydc){sub 6}(H{sub 2}O){sub 12}]{center_dot}4H{sub 2}O{r_brace} {sub n} [Ln=Tb (1), Eu (2), Dy (3), Ho (4), Lu (5)], {l_brace} [CuNd{sub 2}(pydc){sub 4}(H{sub 2}O){sub 3}]{center_dot}H{sub 2}O{r_brace} {sub n} (6) and {l_brace} [Cu{sub 3}Pr{sub 2}(pydc){sub 6}(H{sub 2}O){sub 13}]{center_dot}4H{sub 2}O{r_brace} {sub n} (7) (where H{sub 2}pydc=pyridine-2,5-dicarboxylic acid), have been hydrothermally prepared by reactions of H{sub 2}pydc ligand with lanthanide ions in the presence of Cu(II) ion. X-ray crystal structure analysis reveals that these compounds exhibit rich structural chemistry. 1-5 are isomorphous and present a two-dimensional network constructed from Ln{sub 2}Cu{sub 2}L{sub 2}(H{sub 2}O){sub 2} SBU rings and CuL{sub 2}(H{sub 2}O) building blocks. In 6, two-dimensional ladder-like layers based on Nd(III) belts and CuL{sub 2}O{sub 2} units are assembled by H{sub 2}pydc ligands into a three-dimensional open framework. Polymer 7 displays a two-dimensional wave-like layer structure containing two distinct ring units, in which a new coordination mode of the pydc{sup 2-} ligand is observed. The results indicate that the coordination flexibility of the pydc{sup 2-} ligand and lanthanide contraction effect play cooperative roles in the formation of coordination polymers with different polymeric architectures. Compounds 1-2 exhibit intense green and red luminescence emission characteristics of Tb(III) and Eu(III), respectively. Furthermore, elemental analyses (EA), infrared spectra (IR) and thermogravimetric analyses (TGA) of these compounds were also studied. - Graphical abstract: Seven 3d-4f heterometallic coordination polymers were synthesized by reactions of H{sub 2}pydc with lanthanide metal ions in the presence of Cu{sup 2+}, the effects of Cu{sup 2+} on the structures and photoluminescent properties of Ln-pydc{sup 2-} systems were investigated. Highlights

  17. Polymer model with Epigenetic Recoloring Reveals a Pathway for the de novo Establishment and 3D Organization of Chromatin Domains

    NASA Astrophysics Data System (ADS)

    Michieletto, D.; Orlandini, E.; Marenduzzo, D.

    2016-10-01

    One of the most important problems in development is how epigenetic domains can first be established, and then maintained, within cells. To address this question, we propose a framework that couples three-dimensional chromatin folding dynamics to a "recoloring" process modeling the writing of epigenetic marks. Because many intrachromatin interactions are mediated by bridging proteins, we consider a "two-state" model with self-attractive interactions between two epigenetic marks that are alike (either active or inactive). This model displays a first-order-like transition between a swollen, epigenetically disordered phase and a compact, epigenetically coherent chromatin globule. If the self-attraction strength exceeds a threshold, the chromatin dynamics becomes glassy, and the corresponding interaction network freezes. By modifying the epigenetic read-write process according to more biologically inspired assumptions, our polymer model with recoloring recapitulates the ultrasensitive response of epigenetic switches to perturbations and accounts for long-lived multidomain conformations, strikingly similar to the topologically associating domains observed in eukaryotic chromosomes.

  18. Selective CO2 adsorption in a robust and water-stable porous coordination polymer with new network topology.

    PubMed

    Nagarkar, Sanjog S; Chaudhari, Abhijeet K; Ghosh, Sujit K

    2012-01-02

    A robust and water-stable porous coordination polymer [Cd(NDC)(0.5)(PCA)]·G(x) (1) (H(2)NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) with new network topology has been synthesized solvothermally. The framework is 3D porous material and forms a 1D channel along the c-axis, with the channel dimensions ~9.48 × 7.83 Å(2). The compound has high selectivity in uptake of CO(2) over other gases (H(2), O(2), Ar, N(2), and CH(4)). The framework is highly stable in presence of water vapor even at 60 °C. The high CO(2) selectivity over other gases and water stability makes the compound promising candidate for industrial postcombustion gas separation application.

  19. Characterising the structural properties of polymer separators for lithium-ion batteries in 3D using phase contrast X-ray microscopy

    NASA Astrophysics Data System (ADS)

    Finegan, Donal P.; Cooper, Samuel J.; Tjaden, Bernhard; Taiwo, Oluwadamilola O.; Gelb, Jeff; Hinds, Gareth; Brett, Dan J. L.; Shearing, Paul R.

    2016-11-01

    Separators are an integral component for optimising performance and safety of lithium-ion batteries; therefore, a clear understanding of how their microstructure affects cell performance and safety is crucial. Phase contrast X-ray microscopy is used here to capture the microstructures of commercial monolayer, tri-layer, and ceramic-coated lithium-ion battery polymer separators. Spatial variations in key structural parameters, including porosity, tortuosity factor and pore size distribution, are determined through the application of 3D quantification techniques and stereology. The architectures of individual layers in multi-layer membranes are characterised, revealing anisotropy in porosity, tortuosity factor and mean pore size of the three types of separator. Detailed structural properties of the individual layers of multi-layered membranes are then related with their expected effect on safety and rate capability of cells.

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

    SciTech Connect

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

    2016-03-15

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

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

    SciTech Connect

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

    2014-10-15

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

  2. Direct synthesis of nanoporous carbon nitride fibers using Al-based porous coordination polymers (Al-PCPs).

    PubMed

    Hu, Ming; Reboul, Julien; Furukawa, Shuhei; Radhakrishnan, Logudurai; Zhang, Yuanjian; Srinivasu, Pavuluri; Iwai, Hideo; Wang, Hongjing; Nemoto, Yoshihiro; Suzuki, Norihiro; Kitagawa, Susumu; Yamauchi, Yusuke

    2011-07-28

    We report a new synthetic route for preparation of nanoporous carbon nitride fibers with graphitic carbon nitride polymers, by calcination of Al-based porous coordination polymers (Al-PCPs) with dicyandiamide (DCDA) under a nitrogen atmosphere.

  3. Synthesis, structures, luminescent and magnetic properties of four coordination polymers with the flexible 1,3-phenylenediacetate ligands

    SciTech Connect

    Gu, Jin-Zhong; Lv, Dong-Yu; Gao, Zhu-Qing; Liu, Jian-Zhao; Dou, Wei; Tang, Yu

    2011-03-15

    Four coordination polymers, [Zn(pda)(bpy)(H{sub 2}O)]{sub n}.nH{sub 2}O (1), [Cd(pda)(prz)(H{sub 2}O)]{sub n} (2), [Co{sub 3}({mu}{sub 3}-OH){sub 2}(pda){sub 2}(pyz)]{sub n}.2nH{sub 2}O (3) and [Pr{sub 2}(pda){sub 3}(H{sub 2}O){sub 2}]{sub n} (4) (H{sub 2}pda=1,3-phenylendiacetic acid, bpy=4,4'-bipyridine, prz=piperazine and pyz=pyrazine) have been hydrothermally synthesized and characterized. Complex 1 is a 1D wheel-like chain structure, which is further extended into a 3D metal-organic supramolecular framework by H-bonds and {pi}-{pi} stacking interactions. Complex 2 is a 1D ladder-like chain structure, which is also further extended into a 3D metal-organic supramolecular framework by H-bonds. Complex 3 possess a 2D sheet structure with infrequent two pairs of double-helix chains. Complex 4 features a 3D structure. Both 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of complexes 3 and 4 exhibit antiferromagnetic interactions between the nearest metal ions, with C=9.99 and 3.43 cm{sup 3} mol{sup -1} K, and {theta}=-23.9 and -46.3 K, respectively. -- Graphical abstract: Four new coordination polymers with 1,3-phenylenediacetate ligands have been hydrothermally synthesized and characterized. Complexes 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of 3 and 4 exhibit antiferromagnetic interactions between the nearest metal centers. Display Omitted Research highlights: > Coordinative property of H{sub 2}pda ligand was shown when bonded by different block metals. > Careful selection of co-ligand and metals resulted in dramatic framework evolution. > (c) The compounds constructed with Zn{sup 2+} and Cd{sup 2+} exhibit strong blue fluorescent emission. > The magneto-structural correlation of the complexes constructed with Co{sup 2+} and Pr{sup 3+} was elucidated.

  4. Synthesis, structures and photocatalytic properties of two new Co(II) coordination polymers based on 5-(benzyloxy)isophthalate ligand

    NASA Astrophysics Data System (ADS)

    Li, Xia; Li, Jing; Li, Ming-Kai; Fei, Zhou

    2014-02-01

    Two new Co(II) coordination polymer, namely [Co2(L)2(H2O)]n (1) and [Co(L)(phen)(H2O)]n·xH2O (2) (H2L = 5-(benzyloxy)isophthalic acid, phen = 1,10-phenanthroline) have been hydrothermally synthesized and characterized by elemental analysis, powder X-ray diffraction, thermal analysis and single crystal X-ray analysis. The molecular structure of 1 contains two Co(II) ions, two L2- ligands and one coordinated water molecule, which further extends into a complicated 3D framework with the tails of L2- ligands filling in the hexagonal channels, and the molecular structure of 2 contains one Co(II) ions, one L2- ligands, one phen ligands, one coordinated water molecule and half of the water molecule of crystallization, which further extends into a 1D chain structure. In addition, photocatalytic investigation on compounds 1 and 2 reveals that they are active catalyst for degradation of methyl blue.

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

    SciTech Connect

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

    2015-07-15

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

  6. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

    NASA Astrophysics Data System (ADS)

    He, Tian; Yue, Ke-Fen; Zhao, Yi-xing; Chen, San-Ping; Zhou, Chun-sheng; Yan, Ni

    2016-07-01

    Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H2O}n (1), {[Zn(bib)(atbip)]·H2O}n (2), [Zn(bib)(2,2‧-tda)]}n (3) and {[Zn(bib)(5-tbipa)]·EtOH}n (4), (H2atibdc=5-amino-2,4,6-triiodoisophthalic acid, H2atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2‧-H2tad=2,2‧-thiodiacetic acid, 5-H2tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1-4. The fluorescent properties of complexes 1-4 were studied. In addition, the thermal decompositions properties of 1-4 were investigated by simultaneous TG/DTG-DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1-4 are calculated by the integral Kissinger's method and Ozawa-Doyle's method. The activation energy E (E1=209.658 kJ·mol-1, E2=250.037 kJ mol-1, E3=225.300 kJ mol-1, E4=186.529 kJ·mol-1) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH‡, ΔG‡ and ΔS‡) at the peak temperatures of the DTG curves were also calculated. ΔG‡>0 indicates that the skeleton collapse is not spontaneous. ΔHd>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The structural stability could be illustrated from the point of thermodynamics and kinetics.

  7. Porphyrin-Cored Polymer Nanoparticles: Macromolecular Models for Heme Iron Coordination.

    PubMed

    Rodriguez, Kyle J; Hanlon, Ashley M; Lyon, Christopher K; Cole, Justin P; Tuten, Bryan T; Tooley, Christian A; Berda, Erik B; Pazicni, Samuel

    2016-10-03

    Porphyrin-cored polymer nanoparticles (PCPNs) were synthesized and characterized to investigate their utility as heme protein models. Created using collapsible heme-centered star polymers containing photodimerizable anthracene units, these systems afford model heme cofactors buried within hydrophobic, macromolecular environments. Spectroscopic interrogations demonstrate that PCPNs display redox and ligand-binding reactivity similar to that of native systems and thus are potential candidates for modeling biological heme iron coordination.

  8. Influence of the supramolecular order on the electrical properties of 1D coordination polymers based materials

    NASA Astrophysics Data System (ADS)

    Musumeci, Chiara; Osella, Silvio; Ferlauto, Laura; Niedzialek, Dorota; Grisanti, Luca; Bonacchi, Sara; Jouaiti, Abdelaziz; Milita, Silvia; Ciesielski, Artur; Beljonne, David; Hosseini, Mir Wais; Samorì, Paolo

    2016-01-01

    The generation, under self-assembly conditions, of coordination polymers on surface based combinations of a terpyridine-antracene-pyridine based tecton and Co(ii) or Pd(ii) cations is primarily governed by the coordination geometry of the metal center (octahedral and square planar respectively). While the octahedral Co(ii) based polymer self-assembles in insulating films exhibiting randomly oriented crystalline domains, the planarity of Pd(ii) based polymers leads to the formation of conductive π-π stacked fibrillar structures exhibiting anisotropically oriented domains. In the latter case, the favorable Pd-Pd and anthracene-anthracene wavefunction overlaps along the fiber direction are responsible for the large electronic couplings between adjacent chains, whereas small electronic couplings are instead found along individual polymer chains. These results provide important guidelines for the design of conductive metal coordination polymers, highlighting the fundamental role of both intra- as well as inter-chain interactions, thus opening up new perspectives towards their application in functional devices.The generation, under self-assembly conditions, of coordination polymers on surface based combinations of a terpyridine-antracene-pyridine based tecton and Co(ii) or Pd(ii) cations is primarily governed by the coordination geometry of the metal center (octahedral and square planar respectively). While the octahedral Co(ii) based polymer self-assembles in insulating films exhibiting randomly oriented crystalline domains, the planarity of Pd(ii) based polymers leads to the formation of conductive π-π stacked fibrillar structures exhibiting anisotropically oriented domains. In the latter case, the favorable Pd-Pd and anthracene-anthracene wavefunction overlaps along the fiber direction are responsible for the large electronic couplings between adjacent chains, whereas small electronic couplings are instead found along individual polymer chains. These results

  9. Ultralarge 3d/4f Coordination Wheels: From Carboxylate/Amino Alcohol-Supported {Fe4Ln2} to {Fe18Ln6} Rings

    PubMed Central

    2017-01-01

    A family of wheel-shaped charge-neutral heterometallic {FeIII4LnIII2}- and {FeIII18MIII6}-type coordination clusters demonstrates the intricate interplay of solvent effects and structure-directing roles of semiflexible bridging ligands. The {Fe4Ln2}-type compounds [Fe4Ln2(O2CCMe3)6(N3)4(Htea)4]·2(EtOH), Ln = Dy (1a), Er (1b), Ho (1c); [Fe4Tb2(O2CCMe3)6(N3)4(Htea)4] (1d); [Fe4Ln2(O2CCMe3)6(N3)4(Htea)4]·2(CH2Cl2), Ln = Dy (2a), Er (2b); [Fe4Ln2(O2CCMe3)4(N3)6(Htea)4]·2(EtOH)·2(CH2Cl2), Ln = Dy (3a), Er (3b) and the {Fe18M6}-type compounds [Fe18M6(O2CCHMe2)12(Htea)18(tea)6(N3)6]·n(solvent), M = Dy (4, 4a), Gd (5), Tb (6), Ho (7), Sm (8), Eu (9), and Y (10) form in ca. 20–40% yields in direct reaction of trinuclear FeIII pivalate or isobutyrate clusters, lanthanide/yttrium nitrates, and bridging triethanolamine (H3tea) and azide ligands in different solvents: EtOH for the smaller {Fe4Ln2} wheels and MeOH/MeCN or MeOH/EtOH for the larger {Fe18M6} wheels. Single-crystal X-ray diffraction analyses revealed that 1–3 consist of planar centrosymmetric hexanuclear clusters built from FeIII and LnIII ions linked by an array of bridging carboxylate, azide, and aminopolyalcoholato-based ligands into a cyclic structure with a cavity, and with distinct sets of crystal solvents (2 EtOH per formula unit in 1a–c, 2 CH2Cl2 in 2, and 2 EtOH and 2 CH2Cl2 in 3). In 4–10, the largest 3d/4f wheels currently known, nearly linear Fe3 fragments are joined via mononuclear Ln/Y units by a set of isobutyrates and amino alcohol ligands into virtually planar rings. The magnetic properties of 1–10 reveal slow magnetization relaxation for {Fe4Tb2} (1d) and slow relaxation for {Fe4Ho2} (1c), {Fe18Dy6} (4), and {Fe18Tb6} (6). PMID:28135085

  10. 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

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

    PubMed

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

    2015-12-01

    In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or block copolymer design. 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 is general and may inform the design of soft materials for use in complex mechanical environments. Three examples that demonstrate this are provided.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or block copolymer design. 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 is general and may inform the design of soft materials for use in complex mechanical environments. Three examples that demonstrate this are provided.

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

    NASA Astrophysics Data System (ADS)

    Lu, Xin-Xin; Luo, Yu-Hui; Lu, Chen; Chen, Xin; Zhang, Hong

    2015-12-01

    Three new silver coordination polymers, namely, {Ag3(bpy)6[PW12O40]} (1), {Ag5(H2biim)2(Hbiim-NO2)2[PW12O40]} (2), {Ag7(pytz)4[PW12O40]} (3) (bpy=2,2‧-bipyridine, H2biim=2,2‧-biimidazole, pytz=4-(1H-tetrazol-5-yl)pyridine), have been synthesized under hydrothermal condition. Compound 1 shows a 3D supramolecular framework based on 0D moieties. Compound 2 exhibits an attractive 2D biologic screw axis. Compound 3 displays a 3D structure, which consists of Ag(I)···π interactions, π···π stacking and weak Ag···Ag interactions. It is noteworthy that nitration happens to compound 2 during the hydrothermal condition, which is quite rare. Through contrasting the antibacterial activities of gram negative and gram positive bacteria, we find compounds 1-3 have better antibacterial property in gram negative bacteria than gram positive bacteria. In addition, compounds 1-3 also exhibit efficiency of photocatalytic decomposition of organic dyes. Those compounds may be used as potential multifunctional materials in wastewater treatment, because they not only can kill bacteria but also degrade organic pollutants.

  14. Synthesis of a 3D graphite microball using a microfluidic droplet generator and its polymer composite with core-shell structure.

    PubMed

    Han, Dong Ju; Jung, Jae Hwan; Choi, Jong Seob; Kim, Yong Tae; Seo, Tae Seok

    2013-10-21

    Spherical 3D graphite microballs (3D GMs) and their nanohybrids (3D GM-Fe3O4 nanoparticles) were synthesized by using a microfluidic droplet generator and a thermal evaporation-induced capillary compression method. Using the 3D GM-Fe3O4 nanoparticle as a support for polymerization, 3D GM-polypyrrole composites were produced with a unique core-shell structure.

  15. SU-E-T-678: Response Calibration Using Electron Depth-Dose Data for MRI-Based 3D Polymer Gel Dosimetry

    SciTech Connect

    Watanabe, Y; Warmington, L; Gopishankar, N

    2015-06-15

    Purpose: To evaluate a calibration method using the depth-dose data of an electron beam for MRI-based polymer gel dosimetry. Methods: MAGAT was manufactured in-house to fill two 400mL-cylindrical phantoms and nine 22mL-glass vials. Phantom-A was irradiated along the cylinder axis with a 9MeV electron beam of 6 cm x 6 cm field size (FS). Phantom-B was irradiated with a 6MV photon beam of 3 cm x 3 cm FS by a 360-degree arc technique. Eight vials were irradiated in a water-bath to various doses with a 20 cm x 20 cm FS 6MV photon beam. All irradiated phantoms and one un-irradiated vial were scanned with a 3T MRI scanner to obtain the spin-spin relaxation rate (R2) distributions. By comparing the measured R2-to-depth data with the known depth-dose data for Phantom-A, R2-to-dose calibration data were obtained (e-beam method). Another calibration data were obtained from the 9 vials data (9-vial method). We tested two regression equations, i.e., third-order polynomial and tangent functions, and two dose normalization methods, i.e., one-point and two-point methods. Then, these two calibration methods were used to obtain the 3D dose distribution of Phantom-B and evaluated by comparing the measured data with the dose distribution from a treatment planning system. The comparison was made with gamma passing rate (2%/2mm criteria). Results: We did not observe a clear advantage of the e-beam method over the 9-vial method for the 3D dose comparison with the test case. Nevertheless, we found that the e-beam method required a smaller dose scaling for the dose comparison. Furthermore, the tangent function showed better data fitting than the polynomial function with smaller uncertainty of the estimated coefficients. Conclusions: Considering the overall superior performance, we recommend the e-beam method with the tangent function as the regression equation and one-point dose normalization for the MRI-based polymer gel dosimetry.

  16. Two 2D Cd(II) coordination polymers based on asymmetrical Schiff-base ligand: synthesis, crystal structures and luminescent properties.

    PubMed

    Dang, Dong-Bin; Li, Meng-Meng; Bai, Yan; Zhou, Rui-Min

    2013-02-15

    Two new two-dimensional coordination polymers [Cd(3)L(2)(SCN)(6)](n) (1) and [CdLI(2)](n) (2) have been synthesized and characterized by IR spectroscopy, elemental analysis, TG technique, XRPD and complete single crystal structure analysis, where L is 4-(pyridine-2-yl)methyleneamino-1,2,4-trizaole. Asymmetrical Schiff-base ligand L with five- and six-membered N-containing heterocyclic rings acts as a tridentate bridging ligand to bind two Cd(II) centers through one terminal N(triazolyl) and one pyridylimine chelate unit in 1 and 2. For polymer 1, tridentate bridging ligands link Cd-(1,3-μ-SCN(-)) 1D inorganic chains to form a 2D layer network. The existence of C-H···π and π-π stacking interactions between 2D hybrid layers further gives rise to a 3D supramolecular network. In comparison with 1, polymer 2 shows a 2D layer network containing hexanuclear macrometallacyclic units. The 2D layers are staggered together through the combination of C-H···π and π-π stacking interactions and forming a 3D supramolecular structure. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature.

  17. Host-Guest Engineering of Coordination Polymers for Highly Tunable Luminophores Based on Charge Transfer Emissions.

    PubMed

    Zhao, Bei; Li, Na; Wang, Xi; Chang, Ze; Bu, Xian-He

    2017-01-25

    Aiming at the targeted construction of coordination polymer luminophores, the engineering of host-guest architectures with charge transfer based emissions is performed by utilizing the interactions between the electron-deficient 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) and electron-rich polycyclic aromatic hydrocarbons (PAHs) motifs as acceptors and donors, respectively. Through guest modulation of a prototype coordination polymer [Cd(tpt)(1,4-pda)(H2O)2]·(tpt)·(H2O)2 (1) (1,4-H2pda = 1,4-phenylenediacetic acid), a series of coordination polymers with different PAHs as guests, [Cd2(tpt)2(1,4-pda)2]·guest (2-5) (guest = triphenylene for 2, pyrene for 3, coronene for 4, and perylene for 5), are successfully fabricated. Distinct from 1, coordination polymers 2-5 reveal unique bilayer structures with PAHs interlayer and good stability, owing to the enhanced stacking interactions between tpt motifs and PAH guests. Moreover, their emissions cover a wide range of wavelength due to the effective guest to host charge transfer interactions between donor and acceptor motifs. Their readily tunable host-guest charge transfer based emissions make them good candidates as potential luminophores.

  18. Reversible stimulus-responsive Cu(I) iodide pyridine coordination polymer.

    PubMed

    Amo-Ochoa, P; Hassanein, K; Gómez-García, C J; Benmansour, S; Perles, J; Castillo, O; Martínez, J I; Ocón, P; Zamora, F

    2015-10-01

    We present a structurally flexible copper-iodide-pyridine-based coordination polymer showing drastic variations in its electrical conductivity driven by temperature and sorption of acetic acid molecules. The dramatic effect on the electrical conductivity enables the fabrication of a simple and robust device for gas detection. X-ray diffraction studies and DFT calculations allow the rationalisation of these observations.

  19. A barium based coordination polymer for the activity assay of deoxyribonuclease I.

    PubMed

    Song, Chan; Wang, Guan-Yao; Wang, Ya-Ling; Kong, De-Ming; Wang, Yong-Jian; Li, Yue; Ruan, Wen-Juan

    2014-10-04

    A new coordination polymer which shows an unusual 2D inorganic connectivity was constructed. This compound exhibits distinct fluorescence quenching ability to the dye-labeled single-stranded DNA probes with different lengths, based on which an analytical method was developed for the activity assay of deoxyribonuclease I.

  20. Enhanced bistability by guest inclusion in Fe(II) spin crossover porous coordination polymers.

    PubMed

    Muñoz Lara, Francisco J; Gaspar, Ana B; Aravena, Daniel; Ruiz, Eliseo; Muñoz, M Carmen; Ohba, Masaaki; Ohtani, Ryo; Kitagawa, Susumu; Real, José A

    2012-05-16

    Inclusion of thiourea guest molecules in the tridimensional spin crossover porous coordination polymers {[Fe(pyrazine)[M(CN)(4)]} (M = Pd, Pt) leads to novel clathrates exhibiting unprecedented large thermal hysteresis loops of ca. 60 K wide centered near room temperature.

  1. New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide.

    PubMed

    Monreal, Marisa J; Seaman, Lani A; Goff, George S; Michalczyk, Ryszard; Morris, David E; Scott, Brian L; Kiplinger, Jaqueline L

    2016-03-07

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge.

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

    PubMed

    Boeckmann, Jan; Näther, Christian

    2011-07-07

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

  3. Intraoral 3D scanner

    NASA Astrophysics Data System (ADS)

    Kühmstedt, Peter; Bräuer-Burchardt, Christian; Munkelt, Christoph; Heinze, Matthias; Palme, Martin; Schmidt, Ingo; Hintersehr, Josef; Notni, Gunther

    2007-09-01

    Here a new set-up of a 3D-scanning system for CAD/CAM in dental industry is proposed. The system is designed for direct scanning of the dental preparations within the mouth. The measuring process is based on phase correlation technique in combination with fast fringe projection in a stereo arrangement. The novelty in the approach is characterized by the following features: A phase correlation between the phase values of the images of two cameras is used for the co-ordinate calculation. This works contrary to the usage of only phase values (phasogrammetry) or classical triangulation (phase values and camera image co-ordinate values) for the determination of the co-ordinates. The main advantage of the method is that the absolute value of the phase at each point does not directly determine the coordinate. Thus errors in the determination of the co-ordinates are prevented. Furthermore, using the epipolar geometry of the stereo-like arrangement the phase unwrapping problem of fringe analysis can be solved. The endoscope like measurement system contains one projection and two camera channels for illumination and observation of the object, respectively. The new system has a measurement field of nearly 25mm × 15mm. The user can measure two or three teeth at one time. So the system can by used for scanning of single tooth up to bridges preparations. In the paper the first realization of the intraoral scanner is described.

  4. Seawater-Assisted Self-Healing of Catechol Polymers via Hydrogen Bonding and Coordination Interactions.

    PubMed

    Li, Jincai; Ejima, Hirotaka; Yoshie, Naoko

    2016-07-27

    It is highly desirable to prevent crack formation in polymeric materials at an early stage and to extend their lifespan, particularly when repairs to these materials would be difficult for humans. Here, we designed and synthesized catechol-functionalized polymers that can self-heal in seawater through hydrogen bonding and coordination. These bioinspired acrylate polymers are originally viscous materials, but after coordination with environmentally safe, common metal cations in seawater, namely, Ca(2+) and Mg(2+), the mechanical properties of the polymers were greatly enhanced from viscous to tough, hard materials. Reduced swelling in seawater compared with deionized water owing to the higher osmotic pressure resulted in greater toughness (∼5 MPa) and self-healing efficiencies (∼80%).

  5. 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.

  6. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

    SciTech Connect

    He, Tian; Yue, Ke-Fen; Zhao, Yi-xing; Chen, San-Ping; Zhou, Chun-sheng; Yan, Ni

    2016-07-15

    Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The

  7. Dextran and polymer polyethylene glycol (PEG) coating reduce both 5 and 30 nm iron oxide nanoparticle cytotoxicity in 2D and 3D cell culture.

    PubMed

    Yu, Miao; Huang, Shaohui; Yu, Kevin Jun; Clyne, Alisa Morss

    2012-01-01

    Superparamagnetic iron oxide nanoparticles are widely used in biomedical applications, yet questions remain regarding the effect of nanoparticle size and coating on nanoparticle cytotoxicity. In this study, porcine aortic endothelial cells were exposed to 5 and 30 nm diameter iron oxide nanoparticles coated with either the polysaccharide, dextran, or the polymer polyethylene glycol (PEG). Nanoparticle uptake, cytotoxicity, reactive oxygen species (ROS) formation, and cell morphology changes were measured. Endothelial cells took up nanoparticles of all sizes and coatings in a dose dependent manner, and intracellular nanoparticles remained clustered in cytoplasmic vacuoles. Bare nanoparticles in both sizes induced a more than 6 fold increase in cell death at the highest concentration (0.5 mg/mL) and led to significant cell elongation, whereas cell viability and morphology remained constant with coated nanoparticles. While bare 30 nm nanoparticles induced significant ROS formation, neither 5 nm nanoparticles (bare or coated) nor 30 nm coated nanoparticles changed ROS levels. Furthermore, nanoparticles were more toxic at lower concentrations when cells were cultured within 3D gels. These results indicate that both dextran and PEG coatings reduce nanoparticle cytotoxicity, however different mechanisms may be important for different size nanoparticles.

  8. Novel electrochemical sensing platform based on a molecularly imprinted polymer decorated 3D nanoporous nickel skeleton for ultrasensitive and selective determination of metronidazole.

    PubMed

    Li, Yingchun; Liu, Yuan; Yang, Yang; Yu, Feng; Liu, Jie; Song, Han; Liu, Jiang; Tang, Hui; Ye, Bang-Ce; Sun, Zhipeng

    2015-07-22

    A novel electrochemical sensor has been developed by using a composite element of three-dimensional (3D) nanoporous nickel (NPNi) and molecularly imprinted polymer (MIP). NPNi is introduced in order to enhance the electron-transport ability and surface area of the sensor, while the electrosynthesized MIP layer affords simultaneous identification and quantification of the target molecule by employing Fe(CN)6(3-/4-) as the probe to indicate the current intensity. The morphology of the hybrid film was observed by scanning electron microscopy, and the properties of the sensor were examined by cyclic voltammetry and electrochemical impedance spectroscopy. By using metronidazole (MNZ) as a model analyte, the sensor based on the MIP/NPNi hybrid exhibits great features such as a remarkably low detection limit of 2 × 10(-14) M (S/N = 3), superb selectivity in discriminating MNZ from its structural analogues, and good antiinterference ability toward several coexisting substances. Moreover, the proposed method also demonstrates excellent repeatability and stability, with relative standard deviations of less than 1.12% and 1.4%, respectively. Analysis of MNZ in pharmaceutical dosage form and fish tissue is successfully carried out without assistance of complicated pretreatment. The MIP/NPNi composite presented here with admirable merits makes it a promising candidate for developing electrochemical sensor devices and plays a role in widespread fields.

  9. Biomechanical Evaluation of a Tooth Restored with High Performance Polymer PEKK Post-Core System: A 3D Finite Element Analysis

    PubMed Central

    Shin, Joo-Hee; Kim, Jong-Eun; Kim, Jee-Hwan; Lee, Won-Chang; Shin, Sang-Wan

    2017-01-01

    The aim of this study was to evaluate the biomechanical behavior and long-term safety of high performance polymer PEKK as an intraradicular dental post-core material through comparative finite element analysis (FEA) with other conventional post-core materials. A 3D FEA model of a maxillary central incisor was constructed. A cyclic loading force of 50 N was applied at an angle of 45° to the longitudinal axis of the tooth at the palatal surface of the crown. For comparison with traditionally used post-core materials, three materials (gold, fiberglass, and PEKK) were simulated to determine their post-core properties. PEKK, with a lower elastic modulus than root dentin, showed comparably high failure resistance and a more favorable stress distribution than conventional post-core material. However, the PEKK post-core system showed a higher probability of debonding and crown failure under long-term cyclic loading than the metal or fiberglass post-core systems. PMID:28386547

  10. An investigation into the use of polymer blends to improve the printability of and regulate drug release from pharmaceutical solid dispersions prepared via fused deposition modeling (FDM) 3D printing.

    PubMed

    Alhijjaj, Muqdad; Belton, Peter; Qi, Sheng

    2016-11-01

    FDM 3D printing has been recently attracted increasing research efforts towards the production of personalized solid oral formulations. However, commercially available FDM printers are extremely limited with regards to the materials that can be processed to few types of thermoplastic polymers, which often may not be pharmaceutically approved materials nor ideal for optimizing dosage form performance of poor soluble compounds. This study explored the use of polymer blends as a formulation strategy to overcome this processability issue and to provide adjustable drug release rates from the printed dispersions. Solid dispersions of felodipine, the model drug, were successfully fabricated using FDM 3D printing with polymer blends of PEG, PEO and Tween 80 with either Eudragit E PO or Soluplus. As PVA is one of most widely used polymers in FDM 3D printing, a PVA based solid dispersion was used as a benchmark to compare the polymer blend systems to in terms of processability. The polymer blends exhibited excellent printability and were suitable for processing using a commercially available FDM 3D printer. With 10% drug loading, all characterization data indicated that the model drug was molecularly dispersed in the matrices. During in vitro dissolution testing, it was clear that the disintegration behavior of the formulations significantly influenced the rates of drug release. Eudragit EPO based blend dispersions showed bulk disintegration; whereas the Soluplus based blends showed the 'peeling' style disintegration of strip-by-strip. The results indicated that interplay of the miscibility between excipients in the blends, the solubility of the materials in the dissolution media and the degree of fusion between the printed strips during FDM process can be used to manipulate the drug release rate of the dispersions. This brings new insight into the design principles of controlled release formulations using FDM 3D printing.

  11. Synthesis of Coordination Polymers of Tetravalent Actinides (Uranium and Neptunium) with a Phthalate or Mellitate Ligand in an Aqueous Medium.

    PubMed

    Martin, Nicolas P; März, Juliane; Volkringer, Christophe; Henry, Natacha; Hennig, Christoph; Ikeda-Ohno, Atsushi; Loiseau, Thierry

    2017-03-06

    Four metal-organic coordination polymers bearing uranium or neptunium have been hydrothermally synthesized from a tetravalent actinide chloride (AnCl4) and phthalic (1,2-H2bdc) or mellitic (H6mel) acid in aqueous media at 130 °C. With the phthalate ligand, two analogous assemblies ([AnO(H2O)(1,2-bdc)]2·H2O; An = U(4+) (1) or Np(4+) (2)) have been isolated, in which the square-antiprismatic polyhedra of AnO8 are linked to each other via μ3-oxo groups with an edge-sharing mode to materialize infinite zigzag ribbons. The phthalate molecules play a role in connecting the adjacent zigzag chains to build a two-dimensional (2D) network. Water molecules are bonded to the actinide center or found intercalated between the layers. With the mellitate ligand, two distinct structures have been identified. The uranium-based compound [U2(OH)2(H2O)2(mel)] (3) exhibits a three-dimensional (3D) structure composed of the dinuclear units of UO8 polyhedra (square antiprism), which are further linked via the μ2-hydroxo groups. The mellitate linkers use their carboxylate groups to connect the dinuclear units, eventually building a 3D framework. The compound obtained for the neptunium mellitate ([(NpO2)10(H2O)14(Hmel)2]·12H2O (4)) reveals oxidation of the initial Np(IV) to Np(V) under the applied hydrothermal synthetic conditions, yielding the neptunyl(V) (NpO2(+)) unit with a pentagonal-bipyramidal NpO7 environment. This further leads to the formation of a layered assembly of the square-frame NpO7 sheets via the bridging oxygen atoms from the neptunyl oxo groups, which further coordinate to the pentagonal equatorial coordination plane of the adjacent neptunium unit (i.e., cation-cation interactions). In compound 4, the mellitate molecules act as bridging linkers between the NpO7 sheets by using four of their carboxylage groups, eventually building up a 3D structure.

  12. Structure modulation of manganese coordination polymers consisting of 1,4-naphthalene dicarboxylate and 1,10-phenanthroline.

    PubMed

    Lou, Yongbing; Wang, Jingjing; Tao, Yinhua; Chen, Jinxi; Mishima, Akio; Ohba, Masaaki

    2014-06-14

    Three new manganese coordination polymers, {[Mn2(1,4-NDC)2(phen)2](H2O)}n (1), [Mn2(1,4-NDC)2(phen)(H2O)]n (2) and {[Mn4(1,4-NDC)4(phen)4](DMF)2}n (3) (1,4-H2NDC = 1,4-naphthalene dicarboxylic acid; phen = 1,10-phenanthroline; DMF = N,N-dimethylformamide), have been synthesized solvo/hydrothermally. 1,4-NDC(2-) ligands adopt different coordination modes under different solvents and concentrations which promotes different crystal structure formation. X-ray crystal structural data reveal that compounds 1, 2 and 3 crystallize in monoclinic space groups C2/c, P21/c and C2/c, respectively. Compound 1 has Mn2 dimers connected by 1,4-NDC(2-) linkers, packing into a 2D structure in a grid pattern. Compound 2 has a three-dimensional (3D) structure which is constructed by Mn2 dimers and 1,4-NDC(2-) linkers. Each MnO4N2 node of compound 3 is linked to another by 1,4-NDC(2-) ligands to form a two-dimensional (2D) structure. Variable-temperature magnetic susceptibilities of compounds 1-3 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions.

  13. Lanthanide coordination polymers based on 5-(2'-carboxylphenyl) nicotinate: syntheses, structure diversity, dehydration/hydration, luminescence and magnetic properties.

    PubMed

    Gu, Jin-Zhong; Wu, Jiang; Lv, Dong-Yu; Tang, Yu; Zhu, Kongyang; Wu, Jincai

    2013-04-14

    Twelve lanthanide coordination polymers associated with the organic ligand 5-(2′-carboxylphenyl) nicotinic acid (H2cpna): {[Ln(Hcpna)(cpna)(phen)]·H2O}n (Ln = Sm (1), Tb (2), Ho (3), phen = 1,10-phenanthroline), {[Sm(Hcpna)(cpna)(phen)]·2H2O}n (4), {[Ln2(cpna)3(H2O)3]·4H2O}n (Ln = Y (5), Tb(6), Dy (7), Ho (8)), [Lu2(cpna)3(H2O)2]n (9), {[Y2(cpna)3(phen)2(H2O)]·H2O}n (10), and [Ln(cpna)(phen)(NO3)]n (Ln = Tm (11), Lu (12)) have been prepared by hydrothermal methods and structurally characterized. The structure analyses reveal that complexes 1–3 are isostructural and possess unique three-dimensional (3D) frameworks based on the dodecanuclear Sm/Tb/Ho macrocycles. Complex 4 exhibits a one-dimensional (1D) wheel-chain structure, which further builds three-dimensional (3D) supramolecular architecture via O–HN hydrogen-bonding interactions. Complexes 5–8 are also isostructural and display three-dimensional (3D) open frameworks, which possess two types of channels along the a- and b-axis, respectively. Complexes 9 and 10 feature three-dimensional (3D) frameworks and are created from tetranuclear and dinuclear units, respectively. Complexes 11 and 12 are isostructural and demonstrate one-dimensional (1D) double chain structures, which further build three-dimensional (3D) supramolecular architecture via C–H···O hydrogen-bonding. The results show that the pH value of the reaction system, anion, auxiliary ligand and lanthanide contraction play a significant role in determining the structures of the complexes. In addition, the results of luminescent measurements for compounds 2 and 6 in the solid state at room temperature indicate that the different types of structures have a dissimilar influence on their characteristic luminescence. The magnetic properties of compounds 1, 3, 4, 7 and 11 have been investigated. Furthermore, thermal stabilities for 1–12 and the dehydration/hydration properties of compound 6 have also been studied.

  14. Three Mn(II) coordination polymers with a bispyridyl-based quinolinate ligand: the anion-controlled tunable structural and magnetic properties.

    PubMed

    Yuan, Guozan; Shan, Weilong; Liu, Bin; Rong, Lulu; Zhang, Liyan; Zhang, Hui; Wei, Xianwen

    2014-07-07

    Three new Mn(ii) coordination polymers, namely [Mn3L6·2H2O] (), [MnL2] (), and [MnL2·2H2O] (), were prepared by solvothermal reactions of Mn(ii) salts with a bispyridyl-based quinolinate ligand. All complexes were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray crystallography. Single crystal X-ray studies show that these coordination polymers exhibit a structural diversification due to the different counteranions (OAc(-), Cl(-), and NO3(-)). Complex has a 2D supramolecular structure with a cyclic tetramer Mn3L6 secondary building unit. Complex possesses a rhombohedral grid network containing a type of meso-helical chain (P + M) constructed via the metal-ligand coordination interaction. Complex features a 3D non-porous structure based on the arrangement of 2D grids. Magnetic susceptibility measurements indicate that the three Mn(ii) polymers show disparate magnetic properties due to their different supramolecular structures.

  15. Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

    SciTech Connect

    Lin, Hong-Yan; Lu, Huizhe; Le, Mao; Luan, Jian; Wang, Xiu-Li; Liu, Guocheng; Zhang, Juwen

    2015-03-15

    Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){sub 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8

  16. Tunable white-light emission PMMA-supported film materials containing lanthanide coordination polymers: preparation, characterization, and properties.

    PubMed

    Chen, Wei; Fan, Ruiqing; Zhang, Huijie; Dong, Yuwei; Wang, Ping; Yang, Yulin

    2017-03-27

    A series of lanthanide coordination polymers(LnCPs) containing both light and heavy rare-earth elements, namely {[Eu2(pydc)3(H2O)]·2H2O}n (1-Eu, H2pydc = pyridine-2,3-dicarboxylic acid), [Ln(pyc)2(Hpyc)(NO3)]n (Ln = Nd (2-Nd), Sm (3-Sm), Eu (4-Eu), Gd (5-Gd), Tb (6-Tb), Ho (7-Ho), and Er (8-Er), Hpyc = pyridine-3-carboxylic acid), has been synthesized under hydro(solvo)thermal conditions and fully characterized. The crystal structure analysis indicates that in situ decarboxylation of H2pydc occurred in the synthesis process of 2-Nd-8-Er. Coordination polymer 1-Eu displays a 3-D pcu network with central-symmetric quad-core structural units [Eu4(COO)6] linked by 1-D chains. 2-Nd-8-Er are of triple helical chain enantiomeric pair 61/65 axis, and can be further linked through two separate kinds of Hbonding interaction to form a mirror symmetrical 3-D framework; the final topological symbol of the jointly connected network is rare {4(7)·6(8)}. Solid-state luminescence studies show that the emission spectra of these LnCPs cover both the visible and near-infrared luminescence region. 2-Nd exhibits characteristic (4)F3/2 → (4)IJ/2 (J = 9, 11, 13) transition NIR emission. 1-Eu and 4-Eu provide characteristic (5)D0 → (7)FJ intense and bright red luminescence, while 4-Eu exhibits better luminescence performance because of the presence of the O-H oscillators within 1-Eu. 6-Tb exhibits characteristic (5)D4 → (7)FJ intense and bright green luminescence. Furthermore, through doping with PMMA polymer, the luminescence properties of 4-Eu and 6-Tb are all improved. The results show the best doping concentration is 4%. The thermal stabilities of 4-Eu-PMMA and 6-Tb-PMMA increased from 270 to 315 °C when compared with single coordination polymers 4-Eu and 6-Tb. The co-doping of 4-Eu, 5-Gd, and 6-Tb (0.92/0.04/0.04) with PMMA at a total concentration of 4% resulted in a tunable luminescence material W(4-Eu,5-Gd,6-Tb)-PMMA film. When excited at 285 nm, W(4-Eu,5-Gd,6-Tb

  17. Bio-Inspired Composite Interfaces: Controlling Hydrogel Mechanics via Polymer-Nanoparticle Coordination Bond Dynamics

    NASA Astrophysics Data System (ADS)

    Holten-Andersen, Niels

    2015-03-01

    In soft nanocomposite materials, the effective interaction between polymer molecules and inorganic nanoparticle surfaces plays a critical role in bulk mechanical properties. However, controlling these interfacial interactions remains a challenge. Inspired by the adhesive chemistry in mussel threads, we present a novel approach to control composite mechanics via polymer-particle interfacial dynamics; by incorporating iron oxide nanoparticles (Fe3O4 NPs) into a catechol-modified polymer network the resulting hydrogels are crosslinked via reversible coordination bonds at Fe3O4 NP surfaces thereby providing a dynamic gel network with robust self-healing properties. By studying the thermally activated composite network relaxation processes we have found that the polymer-NP binding energy can be controlled by engineering both the organic and inorganic side of the interface.

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

    PubMed

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

    2010-02-01

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

  19. Coordination Architectures of energetic Cd (II) coordination polymers constructed by the bifunctional substituted-tetrazole-carboxylate ligands

    NASA Astrophysics Data System (ADS)

    Shen, Lei; Bai, Yu; Min, Yu-Ting; Jia, Tian-Tian; Wu, Qi; Wang, Jing; Geng, Fei; Cheng, Hong-Jian; Zhu, Dun-Ru; Yang, Jie; Yang, Gao-Wen

    2016-12-01

    Three different tetrazole-carboxylate ligands, monotetrazole-carboxylate H2tza (H2tza=1,5-tetrazole-diacetic acid), Hpztza (Hpztza=5-(2-pyrazinyl)tetrazole-2(1-methyl)acetic acid), ditetrazole-carboxylate H2tzpha (H2tzpha=1,3-di(tetrazole-5-yl)benzene-N2,N2‧-diacetic acid) have been chosen to react with CdCl2·6H2O, resulting in the formation of three new compounds [Cd2(tza)2] (1), [Cd(pztza)2] (2) and [Cd(tzpha)(CH3OH)2] (3). The coordinate sites of the three ligands are major influenced by the different substituted group of tetrazole ring. These compounds have been characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 displays a complex 3D structure; compound 2 shows a 3D network and compound 3 features a 2D layer network. Furthermore, the luminescence properties investigated at room temperature in the solid state showed excellent ligand-centered luminescence. The obvious enhancement in luminescence makes these compounds potential materials for optical use. The differential scanning calorimetry (DSC) and thermogravimetric-differential thermogravimetric (TG-DTG) analyses were applied to evaluate the thermal decomposition behavior of such compounds, showing that compounds 2 and 3 can be used as potential energetic materials. The relevant thermodynamic parameters ΔH, ΔS and ΔG were calculated as well.

  20. Self-assembly of flexible one-dimensional coordination polymers on metal surfaces.

    PubMed

    Heim, Daniel; Ecija, David; Seufert, Knud; Auwärter, Willi; Aurisicchio, Claudia; Fabbro, Chiara; Bonifazi, Davide; Barth, Johannes V

    2010-05-19

    We employed a de novo synthesized porphyrin module to construct one-dimensional (1D) Cu-coordinated polymers on Cu(111) and Ag(111) surfaces. The programmed geometry and functionality of the molecular module together with its conformational flexibility and substrate interaction yields sinuous metal-organic polymeric assemblies, based on an unusual two-fold Cu-pyridyl coordination motif. An analysis of scanning tunneling microscopy (STM) data reveals the occurrence of two enantiomers, resulting from the surface confinement that deconvolutes the module in 2D-chiral conformational isomers. The stereoisomers exhibit site-specific surface anchoring, from whence three discrete orientations are possible for each species. Their sequence and mutual arrangement determine direction and curvature of the metal-organic chains. The Cu-coordinated polymers are very similar on both Cu(111) and Ag(111), where their formation is induced by intrinsic and coevaporated adatoms, respectively, which indicates that the lateral bonding motif is predominantly independent of the substrate. In addition, molecular manipulation experiments show the collective motion of entire segments of the Cu-coordinated multi-porphyrin polymers.

  1. Enantioselective synthesis of a chiral coordination polymer with circularly polarized visible laser.

    PubMed

    Wu, Shu-Ting; Cai, Zhen-Wen; Ye, Qiao-Yan; Weng, Chen-Hao; Huang, Xi-He; Hu, Xiao-Lin; Huang, Chang-Cang; Zhuang, Nai-Feng

    2014-11-17

    Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL-responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL-induced enantioselective synthesis. By irradiation with either left-handed or right-handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left-handed CPL resulted in crystals with a left-handed helical structure, and right-handed CPL led to crystals with a right-handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.

  2. Vapochromic Behaviour of M[Au(CN)2]2-Based Coordination Polymers (M = Co, Ni)

    PubMed Central

    Lefebvre, Julie; Korčok, Jasmine L.; Katz, Michael J.; Leznoff, Daniel B.

    2012-01-01

    A series of M[Au(CN)2]2(analyte)x coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), pyridine; x = 2 or 4) was prepared and characterized. Addition of analyte vapours to solid M(μ-OH2)[Au(CN)2]2 yielded visible vapochromic responses for M = Co but not M = Ni; the IR νCN spectral region changed in every case. A single crystal structure of Zn[Au(CN)2]2(DMSO)2 revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II) salt and K[Au(CN)2] in DMSO yielded the isostructural Ni[Au(CN)2]2(DMSO)2 product. Co[Au(CN)2]2(DMSO)2 and M[Au(CN)2]2(DMF)2 (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH2)[Au(CN)2]2 and from DMSO or DMF solution synthesis. Co[Au(CN)2]2(pyridine)4 is generated via vapour absorption by Co(μ-OH2)[Au(CN)2]2; the analogous Ni complex is synthesized by immersion of Ni(μ-OH2)[Au(CN)2]2 in 4% aqueous pyridine. Similar immersion of Co(μ-OH2)[Au(CN)2]2 yielded Co[Au(CN)2]2(pyridine)2, which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH2)[Au(CN)2]2 was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN)2]2 was prepared by dehydration of Co(μ-OH2)[Au(CN)2]2 at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate. PMID:22737031

  3. Three-dimensional conformal setup (3D-CSU) of patients using the coordinate system provided by three internal fiducial markers and two orthogonal diagnostic X-ray systems in the treatment room

    SciTech Connect

    Shirato, Hiroki . E-mail: hshirato@radi.med.hokudai.ac.jp; Oita, Masataka; Fujita, Katsuhisa; Shimizu, Shinichi; Onimaru, Rikiya; Uegaki, Shinji; Watanabe, Yoshiharu; Kato, Norio; Miyasaka, Kazuo

    2004-10-01

    Purpose: To test the accuracy of a system for correcting for the rotational error of the clinical target volume (CTV) without having to reposition the patient using three fiducial markers and two orthogonal fluoroscopic images. We call this system 'three-dimensional conformal setup' (3D-CSU). Methods and materials: Three 2.0-mm gold markers are inserted into or adjacent to the CTV. On the treatment couch, the actual positions of the three markers are calculated based on two orthogonal fluoroscopies crossing at the isocenter of the linear accelerator. Discrepancy of the actual coordinates of gravity center of three markers from its planned coordinates is calculated. Translational setup error is corrected by adjustment of the treatment couch. The rotation angles ({alpha}, {beta}, {gamma}) of the coordinates of the actual CTV relative to the planned CTV are calculated around the lateral (x), craniocaudal (y), and anteroposterior (z) axes of the planned CTV. The angles of the gantry head, collimator, and treatment couch of the linear accelerator are adjusted according to the rotation of the actual coordinates of the tumor in relation to the planned coordinates. We have measured the accuracy of 3D-CSU using a static cubic phantom. Results: The gravity center of the phantom was corrected within 0.9 {+-} 0.3 mm (mean {+-} SD), 0.4 {+-} 0.2 mm, and 0.6 {+-} 0.2 mm for the rotation of the phantom from 0-30 degrees around the x, y, and z axes, respectively, every 5 degrees. Dose distribution was shown to be consistent with the planned dose distribution every 10 degrees of the rotation from 0-30 degrees. The mean rotational error after 3D-CSU was -0.4 {+-} 0.4 (mean {+-} SD), -0.2 {+-} 0.4, and 0.0 {+-} 0.5 degrees around the x, y, and z axis, respectively, for the rotation from 0-90 degrees. Conclusions: Phantom studies showed that 3D-CSU is useful for performing rotational correction of the target volume without correcting the position of the patient on the treatment couch

  4. Molecular tectonics: control of pore size and polarity in 3-D hexagonal coordination networks based on porphyrins and a zinc cation.

    PubMed

    Kühn, Elisabeth; Bulach, Véronique; Hosseini, Mir Wais

    2008-11-07

    In the crystalline phase, porphyrin derivatives based on two 4-pyridyl units at the 5 and 15 meso positions and two 4-aryl moieties bearing various groups (CN, OMe, OH and CF(3)) at the 10 and 20 meso positions lead, in the presence of a zinc dication, to the formation of robust 3-D networks presenting hexagonal channels: both the size and the polarity of the pores were tuned by the nature of the substituents attached to the two aryl groups.

  5. A 3D CFD Simulation and Analysis of Flow-Induced Forces on Polymer Piezoelectric Sensors in a Chinese Liquors Identification E-Nose

    PubMed Central

    Gu, Yu; Wang, Yang-Fu; Li, Qiang; Liu, Zu-Wu

    2016-01-01

    Chinese liquors can be classified according to their flavor types. Accurate identification of Chinese liquor flavors is not always possible through professional sommeliers’ subjective assessment. A novel polymer piezoelectric sensor electric nose (e-nose) can be applied to distinguish Chinese liquors because of its excellent ability in imitating human senses by using sensor arrays and pattern recognition systems. The sensor, based on the quartz crystal microbalance (QCM) principle is comprised of a quartz piezoelectric crystal plate sandwiched between two specific gas-sensitive polymer coatings. Chinese liquors are identified by obtaining the resonance frequency value changes of each sensor using the e-nose. However, the QCM principle failed to completely account for a particular phenomenon: we found that the resonance frequency values fluctuated in the stable state. For better understanding the phenomenon, a 3D Computational Fluid Dynamics (CFD) simulation using the finite volume method is employed to study the influence of the flow-induced forces to the resonance frequency fluctuation of each sensor in the sensor box. A dedicated procedure was developed for modeling the flow of volatile gas from Chinese liquors in a realistic scenario to give reasonably good results with fair accuracy. The flow-induced forces on the sensors are displayed from the perspective of their spatial-temporal and probability density distributions. To evaluate the influence of the fluctuation of the flow-induced forces on each sensor and ensure the serviceability of the e-nose, the standard deviation of resonance frequency value (SDF) and the standard deviation of resultant forces (SDFy) in y-direction (Fy) are compared. Results show that the fluctuations of Fy are bound up with the resonance frequency values fluctuations. To ensure that the sensor's resonance frequency values are steady and only fluctuate slightly, in order to improve the identification accuracy of Chinese liquors using

  6. A 3D CFD Simulation and Analysis of Flow-Induced Forces on Polymer Piezoelectric Sensors in a Chinese Liquors Identification E-Nose.

    PubMed

    Gu, Yu; Wang, Yang-Fu; Li, Qiang; Liu, Zu-Wu

    2016-10-20

    Chinese liquors can be classified according to their flavor types. Accurate identification of Chinese liquor flavors is not always possible through professional sommeliers' subjective assessment. A novel polymer piezoelectric sensor electric nose (e-nose) can be applied to distinguish Chinese liquors because of its excellent ability in imitating human senses by using sensor arrays and pattern recognition systems. The sensor, based on the quartz crystal microbalance (QCM) principle is comprised of a quartz piezoelectric crystal plate sandwiched between two specific gas-sensitive polymer coatings. Chinese liquors are identified by obtaining the resonance frequency value changes of each sensor using the e-nose. However, the QCM principle failed to completely account for a particular phenomenon: we found that the resonance frequency values fluctuated in the stable state. For better understanding the phenomenon, a 3D Computational Fluid Dynamics (CFD) simulation using the finite volume method is employed to study the influence of the flow-induced forces to the resonance frequency fluctuation of each sensor in the sensor box. A dedicated procedure was developed for modeling the flow of volatile gas from Chinese liquors in a realistic scenario to give reasonably good results with fair accuracy. The flow-induced forces on the sensors are displayed from the perspective of their spatial-temporal and probability density distributions. To evaluate the influence of the fluctuation of the flow-induced forces on each sensor and ensure the serviceability of the e-nose, the standard deviation of resonance frequency value (SDF) and the standard deviation of resultant forces (SDFy) in y-direction (Fy) are compared. Results show that the fluctuations of Fy are bound up with the resonance frequency values fluctuations. To ensure that the sensor's resonance frequency values are steady and only fluctuate slightly, in order to improve the identification accuracy of Chinese liquors using

  7. Synthesis, structure and magnetic properties of 5-(4-Sulfophenylazo) salicylate-bridged 1D coordination polymers containing linear trinuclear metal clusters

    NASA Astrophysics Data System (ADS)

    Liu, Hong; Song, Li-jun; Ju, Zhan-feng; Li, Wei; Zhang, Jie

    2008-03-01

    Three new trinuclear metal complexes with an azobenzene-containing ligand [M 3(Sasa) 2(Py) 2(H 2O) 8] (Na 2HSasa = 5-(4-Sulfophenylazo) salicylic acid disodium salt; Py = pyridine; M = Cu, Co, Zn), are synthesized through the interface diffusion and structurally characterized by single crystal X-ray diffraction, XRPD analysis and spectral methods. The metal ions in distorted octahedral coordination environments are connected by Sasa ligands to form 1D coordination polymer chain containing the linear trinuclear units with single syn-anti carboxylate bridges. The extensive hydrogen bonding interactions hold these chains together into 3D supramolecular network. Weak antiferromagnetic interactions between adjacent metal ions with J = -1.85 cm -1 and J = -2.81 cm -1 dominate the magnetic properties of Cu(II) and Co(II) complexes, separately.

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

    SciTech Connect

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

    2014-12-15

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

  9. Spherical 3D isotropic wavelets

    NASA Astrophysics Data System (ADS)

    Lanusse, F.; Rassat, A.; Starck, J.-L.

    2012-04-01

    Context. Future cosmological surveys will provide 3D large scale structure maps with large sky coverage, for which a 3D spherical Fourier-Bessel (SFB) analysis in spherical coordinates is natural. Wavelets are particularly well-suited to the analysis and denoising of cosmological data, but a spherical 3D isotropic wavelet transform does not currently exist to analyse spherical 3D data. Aims: The aim of this paper is to present a new formalism for a spherical 3D isotropic wavelet, i.e. one based on the SFB decomposition of a 3D field and accompany the formalism with a public code to perform wavelet transforms. Methods: We describe a new 3D isotropic spherical wavelet decomposition based on the undecimated wavelet transform (UWT) described in Starck et al. (2006). We also present a new fast discrete spherical Fourier-Bessel transform (DSFBT) based on both a discrete Bessel transform and the HEALPIX angular pixelisation scheme. We test the 3D wavelet transform and as a toy-application, apply a denoising algorithm in wavelet space to the Virgo large box cosmological simulations and find we can successfully remove noise without much loss to the large scale structure. Results: We have described a new spherical 3D isotropic wavelet transform, ideally suited to analyse and denoise future 3D spherical cosmological surveys, which uses a novel DSFBT. We illustrate its potential use for denoising using a toy model. All the algorithms presented in this paper are available for download as a public code called MRS3D at http://jstarck.free.fr/mrs3d.html

  10. Application of a silver-olefin coordination polymer as a catalytic curing agent for self-healing epoxy polymers

    NASA Astrophysics Data System (ADS)

    Everitt, D. T.; Coope, T. S.; Trask, R. S.; Wass, D. F.; Bond, I. P.

    2015-05-01

    A silver-olefin based coordination polymer was prepared in a simple, one step process to act as an initiator to facilitate the ring-opening polymerization of epoxides. Thermal analysis found the complex to be capable of curing a range of commercially available epoxy resins used in the manufacture of conventional composite materials. Curing of the oligomeric diglycidyl ether bisphenol A resin, Epon 828, in combination with a non-toxic solvent, ethyl phenylacetate, was studied by differential scanning calorimetry. The mechanical characterization of the resultant cured polymers was conducted by single lap shear tests. Tapered double cantilever beam (TDCB) test specimens containing 2.5 pph of silver-olefin initiator, both with and without embedded microcapsules, were analyzed for their healing performance. Healing efficiency values were found to be strongly dependent on the applied healing temperature. A mean recovery of 74% fracture load was found in TDCB samples after being healed at 70 °C for 48 h.

  11. Magnetite nanoparticle-supported coordination polymer nanofibers: synthesis and catalytic application in Suzuki-Miyaura coupling.

    PubMed

    Liao, Yetong; He, Lisi; Huang, Jing; Zhang, Jianyong; Zhuang, Lin; Shen, Hui; Su, Cheng-Yong

    2010-08-01

    Functional nanoscale coordination polymers are receiving growing scientific interest because of their potential applications in many domains. In this paper, we demonstrated that a nanofibrous networked metal-organic gel (G1-MNPs) was formed by simply mixing 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris(N-(pyridin-3-ylmethyl)benzamide) (L) and Pd(COD)(NO(3))(2) in CHCl(3)-MeOH with a Pd/L molar ratio of 1:1 in the presence of magnetite nanoparticle (MNPs). The self-assembly behavior of nanofibers was not significantly effected by the introduction of magnetite nanoparticles. The xerogel of G1-MNPs was superparamagnetic and showed catalytic activity in Suzuki-Miyaura C-C coupling reactions. The Pd(II) xerogel could be magnetically isolated and recycled with a permanent magnet. It represents a novel strategy to introduce nanoparticles into functional coordination polymers for multifunctional materials.

  12. 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.

  13. 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.

  14. A series of divalent metal coordination polymers based on isomeric tetracarboxylic acids: synthesis, structures and magnetic properties.

    PubMed

    Han, Min-Le; Duan, Ya-Ping; Li, Dong-Sheng; Xu, Guo-Wang; Wu, Ya-Pan; Zhao, Jun

    2014-12-14

    Five new coordination polymers, namely, [Mn(2,2′-bipy)(H2O)2(H2L1)]n (1), {[Co(btb)(H2O)2(H2L1)]·0.5H2O}n (2), [Co(bib)(H2O)2(H2L1)]n (3), [Ni2(bpm)(H2O)3(L2)]n (4), and {[Co2(H2O)3(OH)(HL2)]·H2O}n (5), (H4L1 = 1,1′:2′,1′′-terphenyl-4,4′,4′′,5′-tetracarboxylic acid, H4L2 = 1,1′:2′,1′′-terphenyl-3,3′′,4′,5′-tetracarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bib = 1,4-bis(imidazol-1-yl)butane, bpm = bis(4-pyridyl)amine), have been obtained under hydrothermal conditions. Complex 1 exhibits a 3D supramolecular framework based on 1D chains. Both complexes 2 and 3 are 3D supramolecular frameworks constructed from 1D zig-zag chains. Complex 4 features a 3D tetra-nodal (3,4,4,5)-connected architecture containing 1D μ-COO bridged chains with (5(2)·6(2)·7.9)(5(2)·6(4)·7(3)·8)2(5(2)·6)2(6(3)·7(2)·9) topology. Complex 5 shows a 3D penta-nodal (3,4,4,6,6)-connected net containing 1D μ-OH/μ-COO bridged chains and mononuclear Co(II) nodes with a (4(2)·6(3)·8)(4(3))2(4(4)·6(2))2(4(4)·6(6)·8(5))2(4(4)·6(7)·8(4)) topology. Variable-temperature magnetic susceptibility measurements reveal that complexes 2 and 3 show antiferromagnetic interactions between the adjacent Co(II) ions, whereas 4 is a ferromagnetic system.

  15. Sequestering aromatic molecules with a spin-crossover Fe(II) microporous coordination polymer.

    PubMed

    Muñoz-Lara, Francisco J; Gaspar, Ana B; Muñoz, M Carmen; Arai, Masashi; Kitagawa, Susumu; Ohba, Masaaki; Real, José Antonio

    2012-06-25

    All in a spin: A series of three-dimensional porous coordination polymer {Fe(dpe)[Pt(CN)(4)]}⋅G (dpe = 1,2-di(4-pyridyl)ethylene; G = phenazine, anthracene, or naphthalene) exhibiting spin crossover and host-guest functions is reported. The magnetic properties of the framework are very sensitive to the chemical nature (aromatic or hydroxilic solvents) and the size of the included guest molecules.

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

    SciTech Connect

    Hazari, Debdoot; Jana, Swapan Kumar; Fleck, Michel; Zangrando, Ennio; Dalai, Sudipta

    2014-11-15

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

  17. Lateralized Effects of Categorical and Coordinate Spatial Processing of Component Parts on the Recognition of 3D Non-Nameable Objects

    ERIC Educational Resources Information Center

    Saneyoshi, Ayako; Michimata, Chikashi

    2009-01-01

    Participants performed two object-matching tasks for novel, non-nameable objects consisting of geons. For each original stimulus, two transformations were applied to create comparison stimuli. In the categorical transformation, a geon connected to geon A was moved to geon B. In the coordinate transformation, a geon connected to geon A was moved to…

  18. Terbium-based coordination polymer nanoparticles for detection of ciprofloxacin in tablets and biological fluids.

    PubMed

    Tan, Hongliang; Zhang, Li; Ma, Chanjiao; Song, Yonghai; Xu, Fugang; Chen, Shouhui; Wang, Li

    2013-11-27

    The metal-organic coordination polymers with tunable structures and properties have been rapidly emerging as very important functional materials. In this work, we prepared terbium (Tb(3+))-based coordination polymer nanoparticles (CPNPs) by employing adenine (Ad) as bridging ligands. The CPNPs was further used as a receptor reagent for ciprofloxacin (CF) detection in aqueous solution. Addition of CF induces a typical emission of Tb(3+) due to the formation of Ad/Tb-CF complex and the sensitization of CF. The fluorescent intensity of Tb(3+) was enhanced linearly with increasing the CF concentration from 60 nM to 14 μM. The detection limit for CF in aqueous solution is 60 nM. The Ad/Tb CPNPs was successfully applied to detect CF in tablet and urine samples and showed a satisfactory result. Compared with other methods, the proposed method is advantageous because that it provides a very simple strategy for CF detection, which does not require complicated sample pretreatment processes or special reaction media. The proposed strategy could be contributed to expand the potential applications of lanthanide coordination polymers in biological and environmental fields.

  19. Synthesis of Highly Porous Coordination Polymers with Open Metal Sites for Enhanced Gas Uptake and Separation.

    PubMed

    Song, Kyung Seob; Kim, Daeok; Polychronopoulou, Kyriaki; Coskun, Ali

    2016-10-12

    Metal-containing amorphous microporous polymers are an emerging class of functional porous materials in which the surface properties and functions of polymers are dictated by the nature of the metal ions incorporated into the framework. In an effort to introduce coordinatively unsaturated metal sites into the porous polymers, we demonstrate herein an aqueous-phase synthesis of porous coordination polymers (PCPs) incorporating bis(o-diiminobenzosemiquinonato)-Cu(II) or -Ni(II) bridges by simply reacting hexaminotriptycene with CuSO4·5H2O [Cu(II)-PCP] or NiCl2·6H2O [Ni(II)-PCP] in H2O. The resulting polymers showed surface areas of up to 489 m(2) g(-1) along with a narrow pore size distribution. The presence of open metal sites significantly improved the gas affinity of these frameworks, leading to an exceptional isosteric heat of adsorption of 10.3 kJ·mol(-1) for H2 at zero coverage. The high affinities of Cu(II)- and Ni(II)-PCPs toward CO2 prompted us to investigate the removal of CO2 from natural and landfill gas conditions. We found that the higher affinity of Cu(II)-PCP compared to that of Ni(II)-PCP not only allowed for the tuning of the affinity of CO2 molecules toward the sorbent, but also led to an exceptional CO2/CH4 selectivity of 35.1 for landfill gas and 20.7 for natural gas at 298 K. These high selectivities were further verified by breakthrough measurements under the simulated natural and landfill gas conditions, in which both Cu(II)- and Ni(II)-PCPs showed complete removal of CO2. These results clearly demonstrate the promising attributes of metal-containing porous polymers for gas storage and separation applications.

  20. Design, synthesis, and optimization of nanostructured calcium phosphates (NanoCaPs) and natural polymer based 3-D non-viral gene delivery systems

    NASA Astrophysics Data System (ADS)

    Ko, Hsu-Feng

    Sustained delivery of therapeutic genes from a three-dimensional (3-D) scaffold and subsequent gene expression capable of triggering the regeneration of damaged tissues is a tissue engineering strategy that has been gaining increased attention. Nanostructured calcium phosphates (NanoCaPs) are biocompatible and non-toxic biomaterials. Furthermore, their efficient transfection in vitro have rendered them attractive gene delivery carriers compared to other viral- or lipid-based agents that tend to be immunogenic or cytotoxic, leading to undesirable responses when utilized above a critical threshold. However, NanoCaPs are typically characterized by variable transfection and short shelf life due to particle aggregation. A viable solution to this problem is the incorporation of NanoCaPs into 3-D scaffolds. The main objectives of this research are therefore two-fold: (1) Examination of the potential of achieving optimized transfection of NanoCaPs via anionic substitution and (2) high throughput synthesis and screening of non-viral gene delivery systems (GDS) comprised of naturally-derived polymers as scaffolds containing NanoCaPs gene carriers. Results indicated that in addition to the excellent transfection levels exhibited by NanoCaPs in vitro, an additional 20-30% increase was observed for NanoCaPs with 10-25 mol% anion substitution. In contrast, high anion substitution (>60%) yielded a drastic decline in transfection. Structural characterizations verified successful anion substitution with a noticeable increase in lattice parameters indicative of an expanded unit cell due to ionic substitution. All of the anion substituted calcium phosphates exhibited the primary phase of hydroxyapatite. For the first time, GDS composed of various concentrations of alginate (AA), fibronectin (FN), and NanoCaPs-DNA complexes were demonstrated. The presence of AA and FN was effective in immobilizing NanoCaPs and reducing the aggregation. High throughput synthesis and screening

  1. Micromolding of a Highly Fluorescent Reticular Coordination Polymer: Solvent-Mediated Reconfigurable Polymerization in a Soft Lithographic Mold

    SciTech Connect

    Y You; H Yang; J Chung; J Kim; Y Jung; S Park

    2011-12-31

    Coordination polymerization of pyridine-based ligands and zinc or silver ions was controlled by soft lithographic micromolding in capillaries. The polymer patterns that are produced are highly fluorescent and supramolecularly structured.

  2. Ultrasonic assisted synthesis of two new coordination polymers and their applications as precursors for preparation of nano-materials.

    PubMed

    Masoomi, Mohammad Yaser; Morsali, Ali; Junk, Peter C; Wang, Jun

    2017-01-01

    Two new isostructural coordination polymers, [Zn3(Oba)4][Me2NH2)2]·6DMF·3H2O (1) and [Cd3(Oba)4][Me2NH2)2]·2DMF·2H2O (2), were synthesized using the nonlinear dicarboxylate ligand, 4,4'-oxybis(benzoic acid) (H2oba) and characterized by IR spectroscopy and single-crystal X-ray crystallography. Single-crystal X-ray data show that 1 and 2 are two-dimensional coordination polymers that can be extended to three-dimensional supramolecular networks by CH…O interactions. These two new coordination polymers were also sonochemically synthesized while sonication time and power of irradiation influencing size and morphology of nano-structured compounds were also studied. Moreover, calcination of these coordination polymers creates ZnO and CdO nanostructures.

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

    SciTech Connect

    Lun, Huijie; Yang, Jinghe; Jin, Linyu; Cui, Sasa; Bai, Yanlong; Zhang, Xudong; Li, Yamin

    2015-05-15

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

  4. SNL3dFace

    SciTech Connect

    Russ, Trina; Koch, Mark; Koudelka, Melissa; Peters, Ralph; Little, Charles; Boehnen, Chris; Peters, Tanya

    2007-07-20

    This software distribution contains MATLAB and C++ code to enable identity verification using 3D images that may or may not contain a texture component. The code is organized to support system performance testing and system capability demonstration through the proper configuration of the available user interface. Using specific algorithm parameters the face recognition system has been demonstrated to achieve a 96.6% verification rate (Pd) at 0.001 false alarm rate. The system computes robust facial features of a 3D normalized face using Principal Component Analysis (PCA) and Fisher Linear Discriminant Analysis (FLDA). A 3D normalized face is obtained by alighning each face, represented by a set of XYZ coordinated, to a scaled reference face using the Iterative Closest Point (ICP) algorithm. The scaled reference face is then deformed to the input face using an iterative framework with parameters that control the deformed surface regulation an rate of deformation. A variety of options are available to control the information that is encoded by the PCA. Such options include the XYZ coordinates, the difference of each XYZ coordinates from the reference, the Z coordinate, the intensity/texture values, etc. In addition to PCA/FLDA feature projection this software supports feature matching to obtain similarity matrices for performance analysis. In addition, this software supports visualization of the STL, MRD, 2D normalized, and PCA synthetic representations in a 3D environment.

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

    SciTech Connect

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

    2016-06-15

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

  6. Synthesis, crystal structures, luminescence and catalytic properties of two d10 metal coordination polymers constructed from mixed ligands

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-xiao; Zhang, Ming-xi; Yu, Baoyi; Van Hecke, Kristof; Cui, Guang-hua

    2015-03-01

    Two new coordination polymers [Cd(bmb)(hmph)]n (1), {[Ag(bmb)]·H2btc}n (2) (bmb = 1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2hmph = homophthalic acid, H3btc = 1,3,5-benzenetetracarboxylic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction methods, IR spectroscopy, TGA, XRPD and elemental analysis. Complex 1 features a 3D threefold interpenetrating dia array with a 4-connected 66 topology. Complex 2 shows a 1D helix chain structure connected by L1 ligands, which is finally extended into a rarely 2D 4L2 supramolecular network via C-H⋯O hydrogen bond interactions. In addition, the luminescence and catalytic properties of the two complexes for the degradation of the methyl orange azo dye in a Fenton-like process were presented. The degradation efficiency of the methyl orange azo dye for 1 and 2 are 56% and 96%, respectively.

  7. New oxalate-propagated layered Mn2+/Fe2+-4,4‧-sulfoyldiphthalhydrazidate coordination polymers

    NASA Astrophysics Data System (ADS)

    Jin, Juan; Yan, Wen-Fu; Yang, Qing-Feng; Yu, Xiao-Yang; Sun, Li-Xiang; Xu, Ji-Qing; Chen, Zi-Ao; Li, Chuan-Zhao

    2017-01-01

    Based on the hydrothermal in situ acylation reaction of 4,4‧-sulfoyldiphthalic anhydride (sdpha) with N2H4ṡH2O, two isostructural oxalate-propagated Mn2+/Fe2+-diacylhydrazidate coordination polymers, [M3(sdpth)2(ox)(H2O)2]ṡ2H2O (M2+ = Mn2+1, Fe2+2; sdpth = 4,4‧-sulfoyldiphthalhydrazidate, ox = oxalate), were obtained and characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. In both compounds, ox ligands act as the second linkers, extending the metal-diacylhydrazidate chains into a 2-D layer. Via Nsbnd H⋯O interactions, compounds 1 and 2 self-assemble into 3-D supramolecular networks. The magnetic analyses indicate that there are antiferromagnetic interactions between magnetic centers in compounds 1 and 2. The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution.

  8. Four new coordination polymers based on carboxyphenyl-substituted dipyrazinylpyridine ligand: Syntheses, structures, magnetic and luminescence properties

    NASA Astrophysics Data System (ADS)

    Yuan, Fei; Zhang, Lu; Hu, Huai-Ming; Bai, Chao; Xue, Ganglin

    2017-01-01

    Four new coordination polymers, namely, [Co(L)2]n (1) and [Co(L)(tp)0.5]n·nH2O (2), [Zn(L)2]n·0.5nH2O (3) and [Zn(L)(suc)0.5]n·nH2O (4) (HL = 4-(3-carboxyphenyl)-2,6-di(pyrazinyl)pyridine, H2tp = benzene-1,4-dicarboxylic acid, H2suc = succinic acid), were constructed by changing metal ion and introducing auxiliary ligand under hydrothermal condition. X-ray single diffraction studies reveal that compounds 1 and 3 have similar structures and crystallized in the monoclinic system with P21/c space group, which show infinite zigzag chains and are further extended into a 2D supramolecular layer by inter-molecular hydrogen bonds. Compounds 2 and 4 display infinite ladder chains and are further extended into a 3D supramolecular network by inter-molecular hydrogen bonds. Additionally, magnetic and photoluminescence properties of 1-4 have been investigated.

  9. 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.

  10. Halochromic coordination polymers based on a triarylmethane dye for reversible detection of acids.

    PubMed

    Zavakhina, Marina S; Yushina, Irina V; Samsonenko, Denis G; Dybtsev, Danil N; Fedin, Vladimir P; Argent, Stephen P; Blake, Alexander J; Schröder, Martin

    2017-01-03

    Chromeazurol B (Na2HL) is a pH-sensitive (halochromic) dye based on a hydroxytriarylmethane core and two carboxylate functional groups, which makes it suitable for the synthesis of coordination polymers. Two new coordination polymers [NaZn4(H2O)3(L)3]·3THF·3H2O (1) and [Zn3(H2O)3(μ2-OH2)(μ3-OH)(HL)2(H2L)]·2THF·3H2O (2) incorporating Chromeazurol B linkers have been prepared and characterised. The structure of 1 comprises pentanuclear heterometallic {Zn4Na} nodes linked by six L(3-) anions to give a layered structure with a honeycomb topology. 2 crystallizes as a double-chain ribbon (ladder) structure with two types of metal node: a mononuclear Zn(ii) cation and tetranuclear {Zn(ii)}4 cluster. Chromeazurol B anions link each tetranuclear cluster to four individual Zn(ii) cations and each Zn(ii) cation with four tetranuclear clusters. Both compounds show pH-sensitivity in water solution which can be observed visually, giving the first example of a halochromic coordination polymer. The halochromic properties of 1 towards HCl vapors were systematically investigated. As-synthesized violet-grey 1 reversibly changes color from orange to pink in the presence of vapors of 2 M and 7 M HCl, respectively. The coordination of the Chromeazurol B anion at each color stage was examined by diffuse reflectance spectroscopy and FT-IR measurements. The remarkable stability of 1 to acid and the observed reversible and reproducible color changes provide a new design for multifunctional sensor materials.

  11. Facile fabrication and adsorption property of a nano/microporous coordination polymer with controllable size and morphology.

    PubMed

    Liu, Qing; Jin, Li-Na; Sun, Wei-Yin

    2012-09-11

    A porous coordination polymer [Cu(3)(btc)(2)] with controllable size and morphology from nanocube to microoctahedron was readily synthesized in an ethanol-water mixture at room temperature by adjusting the concentration of the surfactant and the polymer shows size- and morphology-dependent sorption properties.

  12. Synthesis, spectral characterization and thermal aspects of coordination polymers of some transition metal ions with adipoyl bis(isonicotinoylhydrazone)

    NASA Astrophysics Data System (ADS)

    Haque, Mahejabeen Azizul; Paliwal, L. J.

    2017-04-01

    A series of metal coordination polymers of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), obtained by the reaction of metal acetate with newly synthesized adipoyl bis(isonicotinoylhydrazone) (ADBI) have been investigated. The ligand has been characterized by 1H NMR, 13C NMR, FTIR, and ESI mass spectra. Structural and spectroscopic characterization of the coordination polymers have been carried out using elemental analysis, XRD, SEM, infrared and diffused reflectance spectra, magnetic susceptibility measurements and thermogravimetric analytical techniques. Each metal ion is coordinated to the ligand through oxygen of carbonyl group and the nitrogen of azomethine group of ligand forming a stable 5-membered heterocyclic ring. The synthesized ligand coordinates in an octadentate manner. Magnetic and diffused reflectance spectral studies reveal octahedral geometry of Co(II), Cu(II), Fe(II) and Ni(II) coordination polymers and tetrahedral geometry of Mn(II) and Zn(II) coordination polymers. The thermal stability and decomposition steps of all coordination polymers have been studied using TG, DTG and DTA techniques. Moreover, the kinetic parameters such as activation energy (Ea*), order of reaction (n), Arrhenius factor (A), change in entropy (ΔS*), change in enthalpy (ΔH*) and free energy change (ΔG*) were evaluated at each stage of decomposition curve using Coats-Redfern method.

  13. Preparation and characterization of lanthanide-azo-dye coordination polymers and polymer thin films via layer-by-layer depositions.

    PubMed

    Han, Li-Wei; Lü, Jian; Liu, Tian-Fu; Gao, Shui-Ying; Cao, Rong

    2010-12-07

    A series of tartrazine-lanthanide dye compounds has been synthesized and characterized. Structural studies reveal that the light rare-earth elements La, Ce, Pr and Nd form coordination compounds with tartrazine ligands in a 1:1 ratio and result in 1-D 'fish-bone' chain-like structures having uncoordinated organosulfonate groups on each side of the chain. However, reactions of tartrazine and heavy rare-earth elements Ho, Er, Tm and Yb, in the presence of auxiliary 1,10-phenanthroline, give new 1-D coordination polymers in which uncoordinated organosulfonate groups are located on the same side of the chains. The tartrazine ligands display similar but slightly different coordination modes in both types of structures and the 1,10-phenanthroline plays a vital role in the formation of heavy rare-earth dye compounds. Based on the knowledge of their structures, the light rare-earth dye compounds were utilized to assemble with positively-charged PEI into multilayer thin films by means of layer-by-layer depositions. The as-synthesized thin films showed enhanced stability and consistency on solid surfaces.

  14. A flexible pro-porous coordination polymer: non-conventional synthesis and separation properties towards CO(2)/CH(4) mixtures.

    PubMed

    Barea, Elisa; Tagliabue, Giulia; Wang, Wen-Guo; Pérez-Mendoza, Manuel; Mendez-Liñan, Laura; López-Garzon, Francisco J; Galli, Simona; Masciocchi, Norberto; Navarro, Jorge A R

    2010-01-18

    The novel coordination polymers [Cu(Hoxonic)(H(2)O)](n) (1) and [Cu(Hoxonic)(bpy)(0.5)](n)1.5 n H(2)O (2 subsetH(2)O) (H(3)oxonic: 4,6-dihydroxy-1,3,5-triazine-2-carboxylic acid; bpy: 4,4'-bipyridine) have been isolated and structurally characterised by ab initio X-ray powder diffraction. The dense phase 1 contains 1D zig-zag chains in which Hoxonic dianions bridge square-pyramidal copper(II) ions, apically coordinated by water molecules. On the contrary, 2 subsetH(2)O, prepared by solution and solventless methods, is based on 2D layers of octahedral copper(II) ions bridged by Hoxonic ligands, further pillared by bpy spacers. The resulting pro-porous 3D network possesses small hydrated cavities. The reactivity, thermal, magnetic and adsorptive properties of these materials have been investigated. Notably, the adsorption studies on 2 show that this material possesses unusual adsorption behaviour. Indeed, guest uptake is facilitated by increasing the thermal energy of both the guest and the framework. Thus, neither N(2) at 77 K nor CO(2) at 195 K are incorporated, and CH(4) is only minimally adsorbed at 273 K and high pressures (0.5 mmol g(-1) at 2500 kPa). By contrast, CO(2) is readily incorporated at 273 K (up to 2.5 mmol g(-1) at 2500 kPa). The selectivity of 2 towards CO(2) over CH(4) has been investigated by means of variable-temperature zero coverage adsorption experiments and measurement of breakthrough curves of CO(2)/CH(4) mixtures. The results show the highly selective incorporation of CO(2) in 2, which can be rationalised on the basis of the framework flexibility and polar nature of its voids.

  15. Euro3D Science Conference

    NASA Astrophysics Data System (ADS)

    Walsh, J. R.

    2004-02-01

    The Euro3D RTN is an EU funded Research Training Network to foster the exploitation of 3D spectroscopy in Europe. 3D spectroscopy is a general term for spectroscopy of an area of the sky and derives its name from its two spatial + one spectral dimensions. There are an increasing number of instruments which use integral field devices to achieve spectroscopy of an area of the sky, either using lens arrays, optical fibres or image slicers, to pack spectra of multiple pixels on the sky (``spaxels'') onto a 2D detector. On account of the large volume of data and the special methods required to reduce and analyse 3D data, there are only a few centres of expertise and these are mostly involved with instrument developments. There is a perceived lack of expertise in 3D spectroscopy spread though the astronomical community and its use in the armoury of the observational astronomer is viewed as being highly specialised. For precisely this reason the Euro3D RTN was proposed to train young researchers in this area and develop user tools to widen the experience with this particular type of data in Europe. The Euro3D RTN is coordinated by Martin M. Roth (Astrophysikalisches Institut Potsdam) and has been running since July 2002. The first Euro3D science conference was held in Cambridge, UK from 22 to 23 May 2003. The main emphasis of the conference was, in keeping with the RTN, to expose the work of the young post-docs who are funded by the RTN. In addition the team members from the eleven European institutes involved in Euro3D also presented instrumental and observational developments. The conference was organized by Andy Bunker and held at the Institute of Astronomy. There were over thirty participants and 26 talks covered the whole range of application of 3D techniques. The science ranged from Galactic planetary nebulae and globular clusters to kinematics of nearby galaxies out to objects at high redshift. Several talks were devoted to reporting recent observations with newly

  16. A facile route for preparing a mesoporous palladium coordination polymer as a recyclable heterogeneous catalyst.

    PubMed

    Zhang, Siyong; Liu, Qinghua; Shen, Ming; Hu, Bingwen; Chen, Qun; Li, Hexing; Amoureux, Jean-Paul

    2012-04-21

    To overcome the separation difficulty of the palladium-based homogeneous catalyst, the palladium complex can be anchored on various supports such as silica, polymers and nanoparticles. For the same purpose, we describe a general and facile method to immobilize palladium bis(phosphine) complexes on the basis of the technique widely used for metal-organic framework (MOF) synthesis, yielding a mesoporous coordination polymer palladium-CP1. Although palladium complexes are generally not stable enough to allow further manipulation, we succeeded in preparation of a palladium coordination polymer without by-product Pd clusters or nanoparticles. The fresh palladium-CP1 catalyst exhibits a yield close to 55% for tolane at room temperature and 24 h in Sonogashira coupling of iodobenzene and phenylacetylene, as compared with a yield of 89% for its homogeneous counterpart [Pd(PPh(3))(2)Cl(2)]. Furthermore, this catalyst is stable enough to be reused more than four times with no Pd and Zn leaching. Therefore this new immobilization method offers great promise for the produce of recyclable palladium heterogeneous catalysts with higher activity and higher thermal and chemical stability in the future.

  17. Hierarchical effect behind the supramolecular chirality of silver(I)-cysteine coordination polymers.

    PubMed

    Randazzo, Rosalba; Di Mauro, Alessandro; D'Urso, Alessandro; Messina, Gabriele C; Compagnini, Giuseppe; Villari, Valentina; Micali, Norberto; Purrello, Roberto; Fragalà, Maria Elena

    2015-04-09

    Cysteine is a sulfur-containing amino acid that easily coordinates to soft metal ions and grafts to noble metal surfaces. Recently, chiroptical activity of Ag(+)/cysteine coordination polymers has been widely studied, while, on the other hand, the appearance of a plasmon-enhanced circular dichroic signal (PECD) at the plasmonic spectral region (λ > 400 nm) has been observed for AgNPs capped with chiral sulfur-containing amino acids. These two events are both potentially exploited for sensing applications. However, the presence of Ag(+) ions in AgNP colloidal solution deals with the competition of cysteine grafting at the metal NP surface and/or metal ion coordination. Herein we demonstrate that the chiroptical activity observed by adding cysteine to AgNP colloids prepared by pulsed laser ablation in liquids (PLAL) is mainly related to the formation of CD-active Ag(+)/cysteine supramolecular polymers. The strict correlation between supramolecular chirality and hierarchical effects, driven by different chemical environments experienced by cysteine when different titration modalities are used, is pivotal to validate cysteine as a fast and reliable probe to characterize the surface oxidation of AgNPs prepared by pulsed laser ablation in liquids by varying the laser wavelengths.

  18. Hydrothermal synthesis of copper coordination polymers based on molybdates: Chemistry issues

    NASA Astrophysics Data System (ADS)

    Pavani, K.; Ramanan, A.; Whittingham, M. S.

    2006-08-01

    Crystal engineering of metal organic coordination polymers or metal organic frameworks have been attracting unprecedented efforts in the past few years due to potential applications in the area of catalysis, gas separation and storage. Hydrothermal synthesis is a popular soft chemical route employed by a number of researchers to grow suitable single crystals for unambiguous structural characterization. The structural diversity of the various solid frameworks is attributed to the choice of metal, its ability to exist in multiple oxidation states exhibiting different coordination geometry and multidentate nature of organic ligands. Polyoxomolybdate is another interesting class of inorganic materials that are potential catalysts. A contemporary theme is to develop porous solids combining the acidic properties of oligomeric molybdates integrated with first-row transition metal ions that can form coordination polymers with suitable multidentate ligands. A bottleneck to this problem is to develop reliable synthetic protocols that can produce reproducible materials with designed structural characteristics. In this paper, we present our results on the formation of self-assembled metal organic hybrid solids from acidified aqueous molybdate solution containing cupric ions and one of the multidentate organic ligands (pyrazine, 2-pyrazine carboxylic acid or isonicotinic acid). We propose a molecular mechanism to rationalize the formation of solids.

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

    SciTech Connect

    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

    2015-05-15

    Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2{sub 1} helical chains. While the Nd(III) ions are bridged through μ{sub 2}-HIDC{sup 2−} and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2{sub 1} helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2{sub 1} helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.

  20. Picogram sensing of trinitrophenol in aqueous medium through a water stable nanoscale coordination polymer

    NASA Astrophysics Data System (ADS)

    Asha, K. S.; Vaisakhan, G. S.; Mandal, Sukhendu

    2016-06-01

    A water stable nanoscale coordination polymer (CP) can detect trinitrophenol (TNP) in an aqueous medium at a record-picogram level (~1.66 pg cm-2) with a detection limit of 1.66 ppb. This is a simple and low-cost method for the detection of TNP in aqueous media in contact mode, taking advantage of the unique structural arrangement of the as-synthesized CP and the associated photophysical properties.A water stable nanoscale coordination polymer (CP) can detect trinitrophenol (TNP) in an aqueous medium at a record-picogram level (~1.66 pg cm-2) with a detection limit of 1.66 ppb. This is a simple and low-cost method for the detection of TNP in aqueous media in contact mode, taking advantage of the unique structural arrangement of the as-synthesized CP and the associated photophysical properties. Electronic supplementary information (ESI) available: Experimental section, a scheme for nano CP synthesis, a table for crystallographic data and selected bond lengths, figures of coordination modes of metal and ligand, IR, TGA, DLS and PXRD characterization of the micro/nano sample, SEM and TEM images, N2 adsorption-desorption plot, the optical properties of 1 in DMF and photophysical studies and NMR studies of the compound. See DOI: 10.1039/c5nr08159a

  1. Synthesis, structures and properties of a family of four two-dimensional coordination polymers constructed from 5-hydroxyisophthalate

    SciTech Connect

    Zhang, Kou-Lin; Zhang, Jing-Bo; Jing, Chu-Yue; Zhang, Lei; Walton, Richard I.; Zhu, Peizhi; Ng, Seik Weng

    2014-03-15

    Four 2D coordination polymers (CPs) with different structures containing the multifunctional ligand 5-hydroxyisophthalate (5-OH-BDC{sup 2−}), [Zn(5-OH-BDC)(btb)]·2H{sub 2}O (1), [Cd(5-OH-BDC)(btp)(H{sub 2}O)]·3H{sub 2}O (2), [Cd(5-OH-BDC)(bth){sub 2}(H{sub 2}O)]·H{sub 2}O (3) and [Pb(5-OH-BDC)]·H{sub 2}O (4) [btp=1, 3-bis(1,2,4-triazol-1-yl)propane, btb=1,4-bis(1,2,4-triazol-1-yl)butane, bth=1, 6-bis(1,2,4-triazol-1-yl)hexane] were obtained. 1–3 were synthesised hydrothermally, while 4 was obtained under ambient condition. The adjacent (2D→2D) polycatenated 2D layers of 1 polythread in a parallel manner to form an unusual 2D→3D polythreaded framework. 2 contains an undulated 2D (4, 4) network and further extends into an “embracing” double-layer structure through the C–H···π and π···π stacking interactions. 3 exhibits a non-interpenetrating 2D (4, 4)-network. 4 exhibits a 2D double-layered binodal (4, 4)-net containing oblong nanochannels with symbol (4{sup 3}6{sup 3}){sub 2}. Reversible dehydration–rehydration is observed in 1, 2 and 4, which fall within the category of “recoverable collapsing” and “guest-induced re-formation” frameworks, while 3 exhibits irreversible dehydration–rehydration behaviour. The solid state fluorescent properties of 1–4 have been investigated. -- Graphical abstract: Among four 2D CPs reported, 1 is an unusual 2D→3D polythreaded framework. 4 exhibits 2D double-layered binodal (4, 4)-net containing nanochannels. Reversible dehydration–rehydration is observed in 1, 2 and 4. Highlights: • Four 2D CPs based on 5-hydroxyisophthalate with d{sup 10} and Pb(II) ions were reported. • 1 is an unusual 2D→3D polythreaded framework. • 4 shows a binodal (4, 4)-connected 2D double-layer network with nanochannels. • The materials 1, 2 and 4 show reversible dehydration–rehydration behaviours. • Solid state fluorescent properties were investigated.

  2. New five coordinated supramolecular structured cadmium complex as precursor for CdO nanoparticles: Synthesis, crystal structure, theoretical and 3D Hirshfeld surface analyses

    NASA Astrophysics Data System (ADS)

    Ghanbari Niyaky, S.; Montazerozohori, M.; Masoudiasl, A.; White, J. M.

    2017-03-01

    In this paper, a combined experimental and theoretical study on a new CdLBr2 complex (L = N1-(2-bromobenzylidene)-N2-(2-((E)-(2-bromobenzylidene) amino)ethyl) ethane-1,2-diamine) synthesized via template method, is described. The crystal structure analysis of the complex indicates that, the Cd(II) ion is centered in a distorted square pyramidal space constructed by three iminic nitrogens of the ligand as well as two bromide anions. More analysis of crystal packing proposed a supramolecular structure stabilized by some non-covalent interactions such as Br⋯Br and Xsbnd H⋯Br (X = N and C) in solid state. Furthermore, 3D Hirshfeld surface analyses and DFT studies were applied for theoretical investigation of the complexes. Theoretical achievements were found in a good agreement with respect to the experimental data. To evaluate the nature of bonding and the strength of the intra and inter-molecular interactions a natural bond orbital (NBO) analysis on the complex structure was performed. Time dependent density functional theory (TD-DFT) was also applied to predict the electronic spectral data of the complex as compared with the experimental ones. CdLBr2 complex as nano-structure compound was also prepared under ultrasonic conditions and characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRPD). Finally, it was found that the cadmium complex can be used as a suitable precursor for preparation of CdO nanoparticles via calcination process at 600 °C under air atmosphere.

  3. Nickel(II) and copper(II) coordination polymers with 1,2-bis(tetrazol-1-yl)ethane and thiocyanate: Structure, supramolecular isomerism and magnetism

    NASA Astrophysics Data System (ADS)

    Liu, Pei-Pei; Wang, Yan-Qin; Tian, Chun-Yan; Peng, Hui-Qi; Gao, En-Qing

    2009-02-01

    Two heteroleptic coordination polymers with the flexible 1,2-bis(tetrazol-1-yl)ethane (btze) ligand, [Ni(btze) 2(SCN) 2] n ( 1) and [Cu(btze)(SCN) 2] n ( 2), have been synthesized in presence of thiocyanate. Compound 1 is composed of 1D chains with double btze bridges in the V-shaped gauche conformation, while 2 exhibits 2D coordination networks in which 1D chains with double N, S-thiocyanate bridges are cross-linked by btze bridges in the Z-shaped transoid conformation. In both compounds, the coordination motifs are stacked into 3D architectures through S···S and C-H···N interactions. The structures of 1 and a previously reported compound illustrate an interesting type of supramolecular isomerism. The two isomers exhibit almost identical 1D coordination structure and 2D hydrogen bonded superstructure, and the difference lies only in the interlayer packing associated with S···S contacts. Compound 2 exhibits weak antiferromagnetic interactions with J = 0.29 cm -1, consistent with the structural observation that the thiocyanate bridge adopts an equatorial-axial disposition between Cu(II) ions.

  4. Copper(II)-Thymine Coordination Polymer Nanoribbons as Potential Oligonucleotide Nanocarriers.

    PubMed

    Vegas, Verónica G; Lorca, Romina; Latorre, Ana; Hassanein, Khaled; Gómez-García, Carlos J; Castillo, Oscar; Somoza, Álvaro; Zamora, Félix; Amo-Ochoa, Pilar

    2017-01-19

    The direct reaction between copper nitrate, thymine-1-acetic acid, and 4,4'-bipyridine in water leads to the formation of a blue colloid comprising uniform crystalline nanoribbons (length >1 μm; width ca. 150-185 nm; diameter ca. 15-60 nm) of a coordination polymer. The polymer displays a thymine-based structure freely available for supramolecular interactions. These nanostructures show significant selective interaction with single-stranded oligonucleotides based on adenine. Remarkably, they present low cell toxicity in three cell lines-despite the copper(II) content-and can be used as nanocarriers of oligonucleotides. These results suggest the potential of these types of nanostructures in several biological applications.

  5. Facile preparation and dual catalytic activity of copper(I)-metallosalen coordination polymers.

    PubMed

    Hou, Yun-Long; Li, Sheng-Xia; Sun, Raymond Wai-Yin; Liu, Xin-Yuan; Weng Ng, Seik; Li, Dan

    2015-10-21

    Three copper(i)-metallosalen coordination polymers (CPs), {[Ni(II)(SalImCy)]2(Cu(I)CN)9}n (1), {[Cu(II)(SalImCy)]2(Cu(I)CN)9}n (2) and {[Ni(II)(SalImCy)](Cu(I)I)2·DMF}n (3) were prepared by direct combination of Ni(II)/Cu(II)(salen) motifs with [Cu(I)CN]n chains and Cu2I2 clusters via the metalloligand strategy. The mixed-valence and mixed-metal CPs could effectively catalyze both the oxidation of aromatic alcohols to ketones and aldehydes under mild conditions and photocatalytic degradation of organic dye methylene blue (MB). This work demonstrates the effective integration of transition metal catalytic Ni(II)/Cu(II)(salen) units and photoactive copper(i) species in a single solid polymer to meet the demand for catalytic materials with the dual catalytic properties.

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

    SciTech Connect

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

    2015-05-15

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

  7. Two unprecedented 1D coordination polymer chains based on tetranuclear copper(II) building blocks

    SciTech Connect

    Li Gaijuan; Xing Yan Song Shuyan; Xu Ning; Liu Xianchun; Su Zhongmin

    2008-09-15

    The reaction of copper(II) sulfate with pyridine in DMF or methanol yield two unprecedented Cu(II) coordination polymers {l_brace}[Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}][{mu}-Cu(py)(DMF){sub 2}]{r_brace}{sub n}(1) and {l_brace}[Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}][{mu}-Cu(py){sub 4}]{r_brace}{sub n}(2), respectively. Single-crystal X-ray diffraction indicated that compound 1 crystallizes in the monoclinic system, space group p2(1)/n, a=14.542(5) A, b=16.359(5) A, c=18.951(5) A, {beta}=92.047(5){sup o}, V=4505(2) A{sup 3}, Z=4 while 2 is monoclinic C2/c, a=23.078(5) A, b=10.214(5) A, c=23.142(5) A, {beta}=115.471(5){sup o}, V=4925(3) A{sup 3}, Z=4. Both of the two compounds consist of tetrahedral tetranuclear [Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}] clusters that are bridged by pentacoordinated Cu atom for 1 or hexacoordinated Cu atoms for 2 through the sulfate oxygen to form the infinite one-dimensional polymer chains. - Graphical abstract: Two unprecedented Cu(II) coordination polymers have been prepared by using solvothermal method; they consist of tetrahedral tetranuclear clusters that are bridged by unique Cu(II) atom through the sulfate oxygen to form the infinite one-dimensional polymer chains (a) for complex 1 and (b) for complex 2.

  8. 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.

  9. Guest-Dependent Spin-Transition Behavior of Porous Coordination Polymers.

    PubMed

    Ohtani, Ryo; Hayami, Shinya

    2017-02-16

    The host-guest composites of Hofmann-type iron(II) spin-transition (ST) porous coordination polymers incorporating guest molecules show guest-dependent ST behavior in accordance with the respective guest species, which may be a gas, solvent, halogen, or organic molecule. The guest also works as a chemical stimulant to switch the spin state of the host between high and low spin at room temperature. In this review, we discuss guest properties including size, shape, flexibility, chemical properties, and pore loading content, which impact the spin states of the host framework and the ST behavior exhibited by the host-guest composites.

  10. Synthesis and characterization of 1D iron(II) spin crossover coordination polymers with hysteresis.

    PubMed

    Bauer, Wolfgang; Lochenie, Charles; Weber, Birgit

    2014-02-07

    Purposeful ligand design was used for the synthesis of eight new 1D iron(II) spin crossover coordination polymers aiming for cooperative spin transitions with hysteresis. The results from magnetic measurements and X-ray structure analysis show that the combination of rigid linkers and a hydrogen bond network between the 1D chains is a promising tool to reach this goal. Five of the eight new samples show a cooperative spin transition with hysteresis with up to 43 K wide hysteresis loops.

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

    SciTech Connect

    Chiruta, Daniel; Jureschi, Catalin-Maricel; Rotaru, Aurelian E-mail: rotaru@eed.usv.ro; Linares, Jorge E-mail: rotaru@eed.usv.ro; Garcia, Yann

    2014-02-07

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

  12. Soluble Metal-Nanoparticle-Decorated Porous Coordination Polymers for the Homogenization of Heterogeneous Catalysis.

    PubMed

    Huang, Yuan-Biao; Wang, Qiang; Liang, Jun; Wang, Xusheng; Cao, Rong

    2016-08-17

    Ultrasmall metal nanoparticles (MNPs) were decorated on soluble porous coordination polymers (PCPs) with high metal loadings. The solubility of the composite and the size of the MNPs can be controlled by varying the ratio of the precursors to the supports. The soluble PCPs can serve as a platform to homogenize heterogeneous MNPs catalysts, which exhibited excellent activity and recyclability in C-H activation and Suzuki reactions. This strategy combines the advantages of homogeneous and heterogeneous catalysis and may bring new inspiration to catalysis.

  13. Synthesis, crystal structure, and porosity estimation of hydrated erbium terephthalate coordination polymers.

    PubMed

    Daiguebonne, Carole; Kerbellec, Nicolas; Bernot, Kevin; Gérault, Yves; Deluzet, André; Guillou, Olivier

    2006-07-10

    The reaction of the Er3+ ion with polycarboxylate ligands in gel media leads to coordination polymers exhibiting various structural types and dimensionalities. Five Er3+/1,4-benzenedicarboxylate-based coordination polymers have been obtained in such conditions. Four out of the five are new. Their crystal structures are reported and compared herein. Compound 1, namely, Er2Ter3(H2O)6, where H2Ter symbolizes the terephthalic acid, crystallizes in the space group P1 (No. 2) with a = 7.8373(10) A, b = 9.5854(2) A, c = 10.6931(2) A, alpha = 68.7770(8) degrees, beta = 70.8710(8) degrees, and gamma = 75.3330(12) degrees. It has already been reported elsewhere. The last four compounds are new. Compound 2, namely, Er2Ter3(H2O)6 x 2 H2O, crystallizes in the space group P121/a1 (No. 14) with a = 6.7429(2) A, b = 22.4913(7) A, c = 9.6575(3) A, and beta = 91.6400(18) degrees. Compound 3, namely Er2Ter3(H2O)8 x 2 H2O crystallizes in the space group P1 (No. 2) with a = 7.5391(2) A, b = 10.0533(3) A, c = 10.4578(3) A, alpha = 87.7870(10) degrees, beta = 82.5510(11) degrees, and gamma = 86.2800(16) degrees. Compound 4, namely, Er2Ter3(H2O)6 x 2 H2O crystallizes in the space group C2/c (No. 15) with a = 38.5123(13) A, b = 11.1241(4) A, c = 7.0122(2) A, and beta = 98.634(2) degrees. Compound 5, namely, Er2Ter3(H2O)6 x H2O, crystallizes in the space group P1 (No. 2) with a = 6.8776(10) A, b = 11.0420(2) A, c = 18.5675(3) A, alpha = 84.7240(6) degrees, beta = 81.8380(6) degrees, and gamma = 84.1770(8) degrees. A computational method has also been developed to evaluate the potential porosity of the coordination polymers. This method is described and then applied to the different Er2Ter3(H2O)n coordination polymers previously described.

  14. Selective Adsorption of CO2 from Light Gas Mixtures Using a Structurally Dynamic Porous Coordination Polymer**

    SciTech Connect

    Kristi L. Kauffman, Jeffrey T. Culp, Andrew J. Allen, Laura Espinal, Winnie Wong-Ng, Thomas D. Brown, Angela Goodman, Mark P. Bernardo, Russel J. Pancoast, Danielle Chirdon, Christopher Matranga*

    2010-01-01

    The selective adsorption of CO{sub 2} from mixtures with N{sub 2}, CH{sub 4}, and N{sub 2}O in a dynamic porous coordination polymer (see monomer structure) was evaluated by ATR-FTIR spectroscopy, GC, and SANS. All three techniques indicate highly selective adsorption of CO{sub 2} from CO{sub 2}/CH{sub 4} and CO{sub 2}/N{sub 2} mixtures at 30 C, with no selectivity observed for the CO{sub 2}/N{sub 2}O system.

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

    NASA Astrophysics Data System (ADS)

    Chiruta, Daniel; Jureschi, Catalin-Maricel; Linares, Jorge; Garcia, Yann; Rotaru, Aurelian

    2014-02-01

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

  16. Formation of Highly Thermostable Copper-Containing Energetic Coordination Polymers Based on Oxidized Triaminoguanidine.

    PubMed

    Yan, Qi-Long; Cohen, Adva; Petrutik, Natan; Shlomovich, Avital; Zhang, Jian-Guo; Gozin, Michael

    2016-08-24

    A series of novel highly thermostable energetic coordination polymers (ECPs), with promising mechanical sensitivity properties, were prepared by an in situ oxidation-coordination reaction of triaminoguanidine hydrochloride with copper nitrate in aqueous solution. The molecular structures and properties of these ECPs could be tuned, by varying the ratios and concentrations of the starting materials. Our ECPs exhibit remarkable thermostability (>390 °C) and very low sensitivity to impact (Im > 98 J). The best-performing material (ECP-5) has a calculated detonation velocity of 8969 m·s(-1) and a decomposition peak temperature of 396.9 °C, demonstrating an outstanding balance between two inherently contradicting properties: high detonation performance and very low sensitivity.

  17. Hysteretic Spin Crossover in Two-Dimensional (2D) Hofmann-Type Coordination Polymers.

    PubMed

    Liu, Wei; Wang, Lu; Su, Yu-Jun; Chen, Yan-Cong; Tucek, Jiri; Zboril, Radek; Ni, Zhao-Ping; Tong, Ming-Liang

    2015-09-08

    Three new two-dimensional (2D) Hofmann-type coordination polymers with general formula [Fe(3-NH2py)2M(CN)4] (3-NH2py = 3-aminopyridine, M = Ni (1), Pd (2), Pt (3)) have been synthesized. Magnetic susceptibility measurements show that they exhibited cooperative spin crossover (SCO) with remarkable hysteretic behaviors. Their hysteresis widths are 25, 37, and 30 K for 1-3, respectively. The single-crystal structure of 1 suggest that the pseudo-octahedral Fe sites are equatorially bridged by [M(CN)4](2-) to form 2D grids and axially coordinated by 3-NH2py ligands. The intermolecular interactions between layers (the offset face-to-face π···π interactions, hydrogen bonds, and weak N(amino)···Ni(II) contacts) together with the covalent bonds bridged by [M(CN)4](2-) units are responsible to the significant cooperativity.

  18. Crystal-chemical role of malonate ions in the structure of coordination polymers

    NASA Astrophysics Data System (ADS)

    Serezhkin, V. N.; Medvedkov, Ya. A.; Serezhkina, L. B.; Pushkin, D. V.

    2015-06-01

    In the crystal structures of the malonate-containing compounds of d- or f-metals, the C3H2O{4/2-} anions were found to exhibit 17 topologically different types of coordination to the metal atoms A, playing the role of mono-, bi-, tri-, or tetradentate ligands and forming one to seven O-A bonds. The C-C-C bond angle in the malonate ions changed from 103° to 126° and depended linearly on the dihedral angle (φCOO) between the planes of the two carboxyl groups of the anion. At φCOO < 60°, the malonate ions in the crystal structures always form six-membered metallocycles with d- or f-metal atoms, while at φCOO > 67°, they can form only four-membered metallocycles. The factors that influence the conformation of malonate ions in the structures of coordination polymers were discussed.

  19. Europeana and 3D

    NASA Astrophysics Data System (ADS)

    Pletinckx, D.

    2011-09-01

    The current 3D hype creates a lot of interest in 3D. People go to 3D movies, but are we ready to use 3D in our homes, in our offices, in our communication? Are we ready to deliver real 3D to a general public and use interactive 3D in a meaningful way to enjoy, learn, communicate? The CARARE project is realising this for the moment in the domain of monuments and archaeology, so that real 3D of archaeological sites and European monuments will be available to the general public by 2012. There are several aspects to this endeavour. First of all is the technical aspect of flawlessly delivering 3D content over all platforms and operating systems, without installing software. We have currently a working solution in PDF, but HTML5 will probably be the future. Secondly, there is still little knowledge on how to create 3D learning objects, 3D tourist information or 3D scholarly communication. We are still in a prototype phase when it comes to integrate 3D objects in physical or virtual museums. Nevertheless, Europeana has a tremendous potential as a multi-facetted virtual museum. Finally, 3D has a large potential to act as a hub of information, linking to related 2D imagery, texts, video, sound. We describe how to create such rich, explorable 3D objects that can be used intuitively by the generic Europeana user and what metadata is needed to support the semantic linking.

  20. Lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand: thermal and optical properties.

    PubMed

    Seidel, Christiane; Lorbeer, Chantal; Cybińska, Joanna; Mudring, Anja-Verena; Ruschewitz, Uwe

    2012-04-16

    By slow diffusion of triethylamine into a solution of 2,3,5,6-tetrafluoroterephthalic acid (H2tfBDC) and the respective lanthanide salt in EtOH/DMF single crystals of seven nonporous coordination polymers, (∞)(2)[Ln(tfBDC)(NO(3))(DMF)(2)]·DMF (Ln(3+) = Ce, Pr, Nd, Sm, Dy, Er, Yb; C2/c, Z = 8) have been obtained. In the crystal structures, two-dimensional square grids are found, which are composed of binuclear lanthanide nodes connected by tfBDC(2-) as a linking ligand. The coordination sphere of each lanthanide cation is completed by a nitrate anion and two DMF molecules (CN = 9). This crystal structure is unprecedented in the crystal chemistry of coordination polymers based on nonfluorinated terephthalate (BDC(2-)) as a bridging ligand; as for tfBDC(2-), a nonplanar conformation of the ligand is energetically more favorable, whereas for BDC(2-), a planar conformation is preferred. Differential thermal analysis/thermogravimetric analysis (DTA/TGA) investigations reveal that the noncoordinating DMF molecule is released first at temperatures of 100-200 °C. Subsequent endothermal weight losses correspond to the release of the coordinating DMF molecules. Between 350 and 400 °C, a strong exothermal weight loss is found, which is probably due to a decomposition of the tfBDC(2-) ligand. The residues could not be identified. The emission spectra of the (∞)(2)[Ln(tfBDC)(NO(3))(DMF)(2)]·DMF compounds reveal intense emission in the visible region of light for Pr, Sm, and Dy with colors from orange, orange-red, to warm white.

  1. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    NASA Astrophysics Data System (ADS)

    Vlassa, Mihaela; Bende, Attila

    2015-08-01

    Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet-triplet transition was studied in details and the corresponding spin-orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  2. In situ hydrothermal synthesis of tetrazole coordination polymers with interesting physical properties.

    PubMed

    Zhao, Hong; Qu, Zhi-Rong; Ye, Heng-Yun; Xiong, Ren-Gen

    2008-01-01

    Tetrazole compounds have been studied for more than one hundred years and applied in various areas. Several years ago Sharpless and his co-workers reported an environmentally friendly process for the preparation of 5-substituted 1H-tetrazoles in water with zinc salt as catalysts. To reveal the exact role of the zinc salt in this reaction, a series of hydrothermal reactions aimed at trapping and characterizing the solid intermediates were investigated. This study allowed us to obtain a myriad interesting metal-organic coordination polymers that not only partially showed the role of the metal species in the synthesis of tetrazole compounds but also provided a class of complexes displaying interesting chemical and physical properties such as second harmonic generation (SHG), fluorescence, ferroelectric and dielectric behaviors. In this tutorial review, we will mainly focus on tetrazole coordination compounds synthesized by in situ hydrothermal methods. First, we will discuss the synthesis and crystal structures of these compounds. Their various properties will be mentioned and we will show the applications of tetrazole coordination compounds in organic synthesis. Finally, we will outline some expectations in this area of chemistry. The direct coordination chemistry of tetrazoles to metal ions and in situ synthesis of tetrazole through cycloaddition between organotin azide and organic cyano group will be not discussed in this review.

  3. Effect of substituent on structures and catalytic properties of cobalt(II) isophthalate coordination polymers with a semi-rigid bis(benzimidazole)

    NASA Astrophysics Data System (ADS)

    Zhang, Xu; Meng, Xiang-Li; Huang, Cui-Miao; Cui, Guang-Hua

    2015-11-01

    Three Co(II) coordination polymers based on flexible bis(2-dimethylbenzimidazole) and the derivatives of the familiar isophthalate co-ligands, namely [Co(L)(ip)]n (1), [Co2(L)2(nip)2]n (2) and [Co2(L)2(tbip)2·2H2O]n (3) (L = 1,2-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2ip = isophthalic acid, H2nip = 5-nitroisophthalic acid, H2tbip = 5-tert-butylisophthalic acid) have been synthesized by hydrothermal methods and characterized by elemental analyses, IR spectra, thermogravimetric analyses and single-crystal X-ray diffraction. Both complexes 1 and 2 exhibit a 2-fold interpenetrating 3D network with 66-dia topology, whereas complex 3 is bridged by the L and tbip2- ligands to form a rarely tri-nodal (3,3,5) layer with 3,3,5L18 topology. The results indicate that Co(II) mixed coordination polymers structurally modulated by the substituent effect of isophthalate-involved co-ligands. In addition, the fluorescence and catalytic activity of the complexes for the degradation of methyl orange by the sodium persulfate in a Fenton-like process have been investigated.

  4. Assembly, structures and properties of four Cu(II) coordination polymers based on a semi-rigid bis-pyridyl-bis-amide ligand and different polycarboxylates

    NASA Astrophysics Data System (ADS)

    Wang, Xiu-Li; Luan, Jian; Lin, Hong-Yan; Lu, Qi-Lin; Le, Mao; Liu, Guo-Cheng

    2014-09-01

    Four new Cu(II) coordination polymers, namely, [Cu(3-bpah)(1,4-NDC)(H2O)]·3H2O (1), [Cu2(3-bpah)(1,4-NDC)2]·(1,4-H2NDC)·3H2O (2), [Cu(3-bpah)(3-NIP)] (3), [Cu(3-bpah)(1,3,5-HBTC)]·2H2O (4), where 3-bpah = N,N‧-bis(3-pyridinecarboxamide)-1,2-cyclohexane, 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid, 3-H2NIP = 3-nitrophthalic acid, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid, have been synthesized under hydrothermal conditions. The structures of 1-4 have been determined by single crystal X-ray diffraction and were further characterized by infrared spectroscopy (IR) and thermogravimetric analyses (TGA). Complex 1 displays a 1D double strand. Complex 2 shows a 3D α-Po framework with 1,4-H2NDC guest molecules inside the cages. Complex 3 reveals a 2D wave-like network. Complex 4 exhibits a 2D sql topology. The structural discrepancies of complexes 1-4 imply that the O-donor ancillary ligands play an important role in the formation of the resultant structures of the title coordination polymers. The fluorescent, electrochemical and photocatalytic properties of complexes 1-4 have been studied.

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

    NASA Astrophysics Data System (ADS)

    Lun, Huijie; Yang, Jinghe; Jin, Linyu; Cui, Sasa; Bai, Yanlong; Zhang, Xudong; Li, Yamin

    2015-05-01

    By hydrothermal method, two new coordination polymers [Co(ca)(phdat)]n (1), [Ni(ca)(phdat).0.125H2O]n (2) (H2ca=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 Co2(CO2)4/Ni2(CO2)4 SBUs by ca2- ligand. In the existence of π…π stacking interactions between triazine rings and phenyl rings, the 3D networks are constructed with the hanging phdat filled between the neighboring layers. Furthermore, compounds 1-2 exhibit antiferromagnetic behavior and compound 2 displays a good activity for methanol oxidation.

  6. Electrical bistability around room temperature in an unprecedented one-dimensional coordination magnetic polymer.

    PubMed

    Amo-Ochoa, Pilar; Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martin, Avelino; Zamora, Félix

    2013-05-20

    The synthesis, crystal structure, and physical properties of an unprecedented one-dimensional (1D) coordination polymer containing [Fe2(S2C6H2Cl2)4](2-) entities bridged by dicationic [K2(μ-H2O)2(THF)4](2+) units are described. The magnetic properties show that the title compound presents pairwise Fe-Fe antiferromagnetic interactions that can be well reproduced with a S = 1/2 dimer model with an exchange coupling, J = -23 cm(-1). The electrical conductivity measurements show that the title compound is a semiconductor with an activation energy of about 290 meV and two different transitions, both with large hysteresis of about 60 and 30 K at 260-320 K and 350-380 K, respectively. These two transitions are assumed to be due to slight structural changes in the cation-anion interactions. Differential Scanning Calorimetry confirms the presence of both transitions. This compound represents the first sample of a coordination polymer showing electrical bistability.

  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 [Cu3 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 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, 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.

  8. True 3d Images and Their Applications

    NASA Astrophysics Data System (ADS)

    Wang, Z.; wang@hzgeospace., zheng.

    2012-07-01

    A true 3D image is a geo-referenced image. Besides having its radiometric information, it also has true 3Dground coordinates XYZ for every pixels of it. For a true 3D image, especially a true 3D oblique image, it has true 3D coordinates not only for building roofs and/or open grounds, but also for all other visible objects on the ground, such as visible building walls/windows and even trees. The true 3D image breaks the 2D barrier of the traditional orthophotos by introducing the third dimension (elevation) into the image. From a true 3D image, for example, people will not only be able to read a building's location (XY), but also its height (Z). true 3D images will fundamentally change, if not revolutionize, the way people display, look, extract, use, and represent the geospatial information from imagery. In many areas, true 3D images can make profound impacts on the ways of how geospatial information is represented, how true 3D ground modeling is performed, and how the real world scenes are presented. This paper first gives a definition and description of a true 3D image and followed by a brief review of what key advancements of geospatial technologies have made the creation of true 3D images possible. Next, the paper introduces what a true 3D image is made of. Then, the paper discusses some possible contributions and impacts the true 3D images can make to geospatial information fields. At the end, the paper presents a list of the benefits of having and using true 3D images and the applications of true 3D images in a couple of 3D city modeling projects.

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

    SciTech Connect

    Cheng, Hong-Jian Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin

    2015-12-15

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

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

    SciTech Connect

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

    2010-06-15

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

  11. A novel polythreading Ag(I) coordination polymer with blue photoluminescence

    SciTech Connect

    Duan, Xian-Ying; Yao, Jing; Lu, Chang-Sheng; Meng, Qing-Jin

    2013-04-15

    One new compound, [Ag(p-bix)]{sub 3}[Ag(Hbtc){sub 2}]·2H{sub 2}O (H{sub 3}btc=1,2,4-benzenetricarboxylate, p-bix=1,4-bis(imidazol-1-ylmethyl)-benzene), has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PXRD, luminescent analysis, and single-crystal X-ray diffraction. X-ray structural analysis revealed that 0-D unit [Ag(Hbtc){sub 2}]{sup 3−} and two kinds of 1-D linear chain [Ag(p-bix)]{sub ∞}{sup +}, can be found within the crystal structure. The combination of 0-D [Ag(Hbtc){sub 2}]{sup 3−} unit and 1-D undulated chain [Ag1(p{sub 1}-bix)]{sub ∞}{sup +} through weak Ag–O bond gave rise to 2-D anionic supramolecular doublelayer. Then the grids of the 2-D layer are threaded by 1-D linear cationic chain [Ag2(p{sub 2}-bix)]{sub ∞}{sup +} to generate entangled 3-D architecture with unusual poly(pseudo-rotaxane)-type arrangements. Luminescent properties of the title complex were also studied in this paper. - Graphical abstract: Novel 3D polythreading supramolecular architecture was constructed, in which 1D linear cationic chains [Ag(p{sub 2}-bix)]{sub ∞}{sup +} threaded into the grid of weak Ag–O bonded anionic 2D sheet. Highlights: ► Novel 1D{sup +}+2D{sup −}→3D polythreading coordination complex was reported. ► Diverse conformations of p-bix result in different 1D [Ag(p-bix)]{sub ∞}{sup +} chains. ► The title complex displayed blue photoluminescence at room temperature.

  12. Localized cell stimulation by nitric oxide using a photoactive porous coordination polymer platform

    PubMed Central

    Diring, Stéphane; Wang, Dan Ohtan; Kim, Chiwon; Kondo, Mio; Chen, Yong; Kitagawa, Susumu; Kamei, Ken-ichiro; Furukawa, Shuhei

    2013-01-01

    Functional cellular substrates for localized cell stimulation by small molecules provide an opportunity to control and monitor cell signalling networks chemically in time and space. However, despite improvements in the controlled delivery of bioactive compounds, the precise localization of gaseous biomolecules at the single-cell level remains challenging. Here we target nitric oxide, a crucial signalling molecule with site-specific and concentration-dependent activities, and we report a synthetic strategy for developing spatiotemporally controllable nitric oxide-releasing platforms based on photoactive porous coordination polymers. By organizing molecules with poor reactivity into polymer structures, we observe increased photoreactivity and adjustable release using light irradiation. We embed photoactive polymer crystals in a biocompatible matrix and achieve precisely controlled nitric oxide delivery at the cellular level via localized two-photon laser activation. The biological relevance of the exogenous nitric oxide produced by this strategy is evidenced by an intracellular change in calcium concentration, mediated by nitric oxide-responsive plasma membrane channel proteins. PMID:24158008

  13. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    NASA Astrophysics Data System (ADS)

    Gu, Jin-Zhong; Wu, Jiang; Kirillov, Alexander M.; Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai

    2014-05-01

    A series of six coordination compounds {[Zn(5-Brnic)2]·1.5H2O}n (1), [Cd(5-Brnic)2]n (2), [Co(5-Brnic)2(H2O)2]n (3), [Zn(5-Brnic)2(H2biim)]n (4), {[Cd(5-Brnic)2(phen)]·H2O}n (5), and [Pb(5-Brnic)2(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2‧-biimidazole (H2biim) ligand. All the products 1-6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N-H⋯O and C-H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail.

  14. 3D measurement for rapid prototyping

    NASA Astrophysics Data System (ADS)

    Albrecht, Peter; Lilienblum, Tilo; Sommerkorn, Gerd; Michaelis, Bernd

    1996-08-01

    Optical 3-D measurement is an interesting approach for rapid prototyping. On one hand it's necessary to get the 3-D data of an object and on the other hand it's necessary to check the manufactured object (quality checking). Optical 3-D measurement can realize both. Classical 3-D measurement procedures based on photogrammetry cause systematic errors at strongly curved surfaces or steps in surfaces. One possibility to reduce these errors is to calculate the 3-D coordinates from several successively taken images. Thus it's possible to get higher spatial resolution and to reduce the systematic errors at 'problem surfaces.' Another possibility is to process the measurement values by neural networks. A modified associative memory smoothes and corrects the calculated 3-D coordinates using a-priori knowledge about the measurement object.

  15. 3d-3d correspondence revisited

    DOE PAGES

    Chung, Hee -Joong; Dimofte, Tudor; Gukov, Sergei; ...

    2016-04-21

    In fivebrane compactifications on 3-manifolds, we point out the importance of all flat connections in the proper definition of the effective 3d N = 2 theory. The Lagrangians of some theories with the desired properties can be constructed with the help of homological knot invariants that categorify colored Jones polynomials. Higgsing the full 3d theories constructed this way recovers theories found previously by Dimofte-Gaiotto-Gukov. As a result, we also consider the cutting and gluing of 3-manifolds along smooth boundaries and the role played by all flat connections in this operation.

  16. Homochiral nickel coordination polymers based on salen(Ni) metalloligands: synthesis, structure, and catalytic alkene epoxidation.

    PubMed

    Huang, Yuanbiao; Liu, Tianfu; Lin, Jingxiang; Lü, Jian; Lin, Zujin; Cao, Rong

    2011-03-21

    One-dimensional (1D) homochiral nickel coordination polymers [Ni(3)(bpdc)(RR-L)(2)·(DMF)](n) (2R, RR-L = (R,R)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene), bpdc = 4,4'-biphenyldicarboxylic acid) and [Ni(3)(bpdc)(SS-L)(2)·(DMF)](n) (2S, SS-L = (S,S)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) based on enantiopure pyridyl-functionalized salen(Ni) metalloligand units NiL ((1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene))Ni(II)) have been synthesized and characterized by microanalysis, IR spectroscopy, solid-state UV-vis spectroscopy, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, cyclic voltammetric measurement, and powder and single crystal X-ray diffraction. Each NiL as unbridging pendant metalloligand uses one terminal pyridyl group to coordinate achiral unit (nickel and bpdc(2-)) building a helical chain, while the other pyridyl group remains uncoordinated. Both 2R and 2S contain left- and right-handed helical chains made of the achiral building blocks, while the NiL as remote external chiral source is perpendicular to the backbone of the helices. The nickel coordination polymers 2R and 2S containing unsaturated active nickel center in metalloligand NiL can be used as self-supported heterogeneous catalysts. They show catalytic activity comparable with their homogeneous counterpart in alkene epoxidation and exhibit great potential as recyclable catalysts.

  17. Coordination polymers assembled from semirigid fluorene-based ligand: A couple of enantiomers

    SciTech Connect

    Li, Liang; Wang, Zihao; Chen, Qiang; Zhou, Xinhui; Yang, Tao; Zhao, Qiang; Huang, Wei

    2015-11-15

    A couple of Mg(II)-based coordination polymer enantiomers [MgL(DMF)(H{sub 2}O){sub 3}]{sub n} (R-MgL and S-MgL), and a Zn(II)-based coordination polymer [ZnL(DMF)]{sub n} (ZnL) have been synthesized by the solvothermal reactions between the achiral ligand 4,4′-(9,9-dimethyl-9H-fluorene-2,7-diyl)dibenzoic acid (H{sub 2}L) and the corresponding metal salts. The MgL was obtained as the racemic conglomerate from the one pot reaction. The single crystal X-ray structural analyses reveal that MgL crystallize in the chiral space group P2{sub 1} and possesses the right- or left-handed homochiral 1D Mg–O–C helical chain. The ZnL crystallize in the non-centrosymmetrical space group Aba2 and possesses the 2D network comprised of 1D Zn–O–C meso-helical chains and ligands. The MgL and ZnL complexes exhibit strong coordination-perturbed ligand-centered blue emissions when excited at 320 nm. Their second-order nonlinear optical effects and thermal properties have also been studied. - Highlights: • A couple of Mg(II)-based enantiomers were obtained as the racemic conglomerate. • The ligand is 4,4′-(9,9-dimethyl-9H-fluorene-2,7-diyl)dibenzoic acid. • MgL features the right- or left-handed homochiral 1D Mg–O–C helical chain. • ZnL features the 1D Zn–O–C meso-helical chain. • Both MgL and ZnL display the intense solid-state blue emissions.

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

    PubMed

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

    2016-03-17

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

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

    SciTech Connect

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min

    2014-11-15

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

  20. Transition metal coordination polymers based on tetrabromoterephthalic and bis(imidazole) ligands: Syntheses, structures, topological analysis and photoluminescence properties

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaowei; Xing, Peiqi; Geng, Xiujuan; Sun, Daofeng; Xiao, Zhenyu; Wang, Lei

    2015-09-01

    Eight new coordination polymers (CPs), namely, [Zn(1,2-mbix)(tbtpa)]n (1), [Co(1,2-mbix)(tbtpa)]n (2), [CdCl(1,2-mbix)(tbtpa)0.5]n (3), {[Cd(1,2-bix)(tbtpa)]·H2O}n (4), {[Cd0.5(1,2-bix)(tbtpa)0.5]·H2O}n (5), {[Co0.5(1,2-bix)(tbtpa)0.5]·2H2O}n (6), {[Co(1,2-bix)(tbtpa)]·H2O}n (7) and {[Co(1,2-bix)(tbtpa)]·Diox·2H2O}n (8), were synthesized under solvothermal conditions based on mix-ligand strategy (H2tbtpa=tetrabromoterephthalic acid and 1,2-mbix=1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,2-bix=1,2-bis(imidazol-1-ylmethyl)benzene). All of the CPs have been structurally characterized by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). X-ray diffraction analyses show that 1 and 2 are isotypics which have 2D highly undulated networks with (4,4)-sql topology with the existence of C-H ⋯Br interactions; for 3, it has a 2D planar network with (4,4)-sql topology with the occurrence of C-H ⋯Cl interactions other than C-H ⋯Br interactions; 4 shows a 3D 2-fold interpenetrated nets with rare 65·8-mok topology which has a self-catention property. As the same case as 1 and 2, 5 and 6 are also isostructural with planar layers with 44-sql topology which further assembled into 3D supramolecular structure through the interdigitated stacking fashion and the C-Br ⋯Cph interactions. As for 7, it has a 2D slightly undulated networks with (4,4)-sql topology which has one dimension channel. While 8 has a 2-fold interpenetrated networks with (3,4)-connect jeb topology with point symbol {63}{65·8}. And their structures can be tuned by conformations of bis(imidazol) ligands and solvent mixture. Besides, the TGA properties for all compounds and the luminescent properties for 1, 3, 4, 5 are discussed in detail.

  1. Three Pb{sup II} coordination polymers based on 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid: Syntheses, crystal structures, and fluorescent properties

    SciTech Connect

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

    2013-08-15

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

  2. 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%.

  3. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    SciTech Connect

    Gu, Jin-Zhong; Wu, Jiang; Kirillov, Alexander M.; Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai

    2014-05-01

    A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network

  4. 3D and Education

    NASA Astrophysics Data System (ADS)

    Meulien Ohlmann, Odile

    2013-02-01

    Today the industry offers a chain of 3D products. Learning to "read" and to "create in 3D" becomes an issue of education of primary importance. 25 years professional experience in France, the United States and Germany, Odile Meulien set up a personal method of initiation to 3D creation that entails the spatial/temporal experience of the holographic visual. She will present some different tools and techniques used for this learning, their advantages and disadvantages, programs and issues of educational policies, constraints and expectations related to the development of new techniques for 3D imaging. Although the creation of display holograms is very much reduced compared to the creation of the 90ies, the holographic concept is spreading in all scientific, social, and artistic activities of our present time. She will also raise many questions: What means 3D? Is it communication? Is it perception? How the seeing and none seeing is interferes? What else has to be taken in consideration to communicate in 3D? How to handle the non visible relations of moving objects with subjects? Does this transform our model of exchange with others? What kind of interaction this has with our everyday life? Then come more practical questions: How to learn creating 3D visualization, to learn 3D grammar, 3D language, 3D thinking? What for? At what level? In which matter? for whom?

  5. Hand Ground Nanoscale Zn(II)-Coordination Polymers Derived from NSAIDs: Cell Migration Inhibition of Human Breast Cancer Cells.

    PubMed

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

    2017-02-25

    Increased level of intracellular prostaglandin E2 (PGE2) has 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 responsible for increased PGE2 concentration in inflammated as well as cancer cells. In this article, we demonstrated that NSAID derived Zn(II)-coordination polymers were able to inhibit cell migration of human breast cancer cells. Various NSAIDs were anchored to a series of 1D Zn(II)-coordination polymers via carboxylate-Zn coordination and fully characterized by single crystal X-ray diffraction. Hand grinding in laboratory mortar and pastel resulted in nano-scale coordination polymers, for the first time, suitable for biological studies. Two such hand ground nano-scale coordination polymers namely NCP1a and NCP2a containing naproxen (a well-studied NSAID) were successfully internalized within the human breast cancer cells MDA-MD-231 as evident from cellular imaging using fluorescence microscope, were able to kill the cancer cells (MTT assay) more efficiently than the corresponding mother drug naproxen and most importantly inhibited significantly the cancer cell migration thereby displaying anti-cancer activity.

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

    SciTech Connect

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

    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} (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.

  7. The perils and opportunities of reactive building blocks: Attempted synthesis of new Hg(CN) 2-based coordination polymers and the structures of the resulting products

    NASA Astrophysics Data System (ADS)

    Leznoff, Daniel B.; Katz, Michael J.; Cheng, Leslie K. L.; Draper, Neil D.; Batchelor, Raymond J.

    2006-08-01

    The addition of Hg(CN) 2 to an aqueous solution of CoBr 2 and tris(2-aminoethyl)amine (tren) yields an oxidized peroxocobalt(III)-containing ionic complex {[Co(tren)(CN)] 2(μ-O 2)}[HgBr 4], which has been characterized structurally. The bromide ligands have migrated to the Lewis acidic Hg(CN) 2 moiety with concomitant transfer of the cyanide groups to the cobalt(III) centre. The potentially non-innocent nature of the Hg(CN) 2 building block is also manifested in its reaction with CuCl 2 and N, N-dimethylethylenediamine (dmeda); recrystallization of the initial precipitate from ammonia yielded the oxalate-containing coordination polymer {(dmeda) 2Cu 2(μ-C 2O 4)[Hg(CN) 2Cl] 2Hg(CN) 2}·(H 2O) 1.5. The structure consists of 1D chains of [(dmeda) 2Cu 2(μ-C 2O 4)][Hg(CN) 2Cl] 2 units, which are formed by mercury-bridging chloride ligands as well as N-cyano coordination to the opposing sites of the copper dimer. The chains are connected into a 3D CdSO 4-type array via the second Hg(CN) 2 unit binding to the chlorides; adjacent chains are inclined at 59.0°. The structure can also be considered as a pair of inclined (4,4)-grids fused at [Hg(CN) 2Cl 2] 2- centroids. The oxalate might be generated in situ as a result of the NH 3-triggered release of CN - from Hg(CN) 2, its reaction with available copper(II) to yield cyanogen, and the subsequent hydrolysis of (CN) 2. These two products illustrate examples of potentially undesirable side-reactivities of building blocks that must be considered when rationally designing the synthesis of new coordination polymers.

  8. Influence of the steric effect of flexible isomeric phenylenediacetic acids on the resultant lead(II) coordination polymers

    SciTech Connect

    Wu, Yunlong; Zhao, Yanqing; Yang, Guo-Ping Guo, Yanjun; Wang, Yao-Yu Shi, Qi-Zhen

    2015-03-15

    To study the steric effect of the flexible dicarboxylate ligands on the resultant formations of coordination polymers (CPs), four new Pb{sup II} CPs [Pb(1,2-pda)(H{sub 2}O)]{sub n} (1), [Pb(1,3-pda)]{sub n}·nH{sub 2}O (2), [Pb{sub 2}(1,4-pda){sub 2}(H{sub 2}O)]{sub n}·2nH{sub 2}O (3a and 3b) have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The X-ray crystallography study reveals that CP 1 is a two-dimensional (2D) 4-connected sql (4{sup 4}.6{sup 2}) network via the weak Pb···O interactions built on 1D chain-like structure. CP 2 crystallizes in orthorhombic system with chiral space group P2{sub 1}2{sub 1}2{sub 1}, showing a 4-connected sra (4{sup 2}.6{sup 3}.8) framework where a left-handed helical motif is formed by Pb{sup II} ions and trans-1,3-pda ligands. More interestingly, CPs 3a and 3b are two true 3D polymorphs and have the different morphology. Topologically, the framework of 3a exhibits a 4-connected lon 6{sup 6} motif, while that of 3b is a (4,6)-connected fsh (4{sup 3}.6{sup 3}){sub 2}(4{sup 6}.6{sup 6}.8{sup 3}) net. It is found that the three isomeric pda anions display the various coordination fashions in four CPs. The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Graphical abstract: Four new Pb{sup II}-based CPs have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Highlights: • Four Pb{sup II}-based coordination polymers were produced by phenylenediacetic acids. • The crystal and topological structures of the

  9. Structures and magnetic properties of two noncentrosymmetric coordination polymers based on carboxyphosphinate ligand

    NASA Astrophysics Data System (ADS)

    Li, Jianyong; Xue, Chao-Chao; Liu, Siming; Wang, Zhao-Xi

    2016-11-01

    Two novel coordination polymers have been hydrothermally synthesized by reactions of Cu(II), Mn(II) salt with 2-carboxyethyl(phenyl)phosphinic acid (H2L), namely, [Cu(L)(H2O)]n (1) and [Mn(HL)2]n (2). Both compounds were well characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopic, power X-ray diffraction and magnetic studies. Compound 1 crystallizes in a noncentrosymmetric monoclinic Cc space group and presents an inorganic two-dimensional (2D) network, whereas compound 2 adopts a noncentrosymmetric Pca21 space group and exhibits a 2D layer structure. Magnetic studies reveal a dominant ferromagnetic interaction in 1, and weak antiferromagnetic coupling between the Mn(II) ions in 2 mediated by phosphinico group, respectively.

  10. A novel coordination polymer containing both interdigitated 1D chains and interpenetrated 2D grids.

    PubMed

    Ayyappan, Ponnaiyan; Evans, Owen R; Lin, Wenbin

    2002-07-01

    A hydro(solvo)thermal reaction between zinc perchlorate and ethyl ester of a new pyridinecarboxylate bridging ligand of approximately 17.6 A in length yields a unique coordination polymer which contains both interdigitated infinite 1D chains and interpenetrated 2D rhombohedral grids [Zn(2.5)(L)(4)(mu(3)-OH)] x (H(2)O)(5), 1, where L is 3-[[4-(4-pyridylethenyl)phenyl]ethenyl]benzoate. The 1D chains contain mu(3)-bridged hydroxy groups and have a [Zn(4)(mu(3)-OH)(2)(L)(6)] stoichiometry, while the 2D grids have a Zn(L)(2) formula and diagonal distances of 31.7 and 25.2 A. Crystal data for 1: monoclinic space group P2/c, a = 15.686(2) A, b = 12.6103(16) A, c = 38.999(5) A, beta = 98.397(2) degrees, and Z = 4.

  11. A systematic study on the stability of porous coordination polymers against ammonia.

    PubMed

    Kajiwara, Takashi; Higuchi, Masakazu; Watanabe, Daisuke; Higashimura, Hideyuki; Yamada, Teppei; Kitagawa, Hiroshi

    2014-11-17

    To establish a strategy for designing porous coordination polymers (PCPs) for ammonia capture, the first systematic study on the stability of PCPs against ammonia was conducted. Various types of PCPs were investigated by comparing their powder XRD patterns before and after treatment with ammonia. Among the PCPs tested, ZIF-8, MIL-53(Al), Al-BTB, MOF-76(M) (M=Y or Yb), MIL-101(Cr), and MOF-74(Mg) were stable up to 350 °C under an ammonia atmosphere at ambient pressure. The origin of the stability of PCPs is discussed from the viewpoint of their components, metal cations, and organic linkers. Furthermore, adsorption isotherm measurements show that the adsorptive behavior of PCPs is independent of their stability.

  12. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    PubMed

    Rood, Jeffrey A; Huttenstine, Ashley L; Schmidt, Zachery A; White, Michael R; Oliver, Allen G

    2014-06-01

    Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF is N,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT-IR and (1)H NMR spectroscopy and elemental analyses.

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

    PubMed Central

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

    2015-01-01

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

  14. Coordination polymer core/shell structures: Preparation and up/down-conversion luminescence.

    PubMed

    Li, Bingmei; Xu, Hualan; Xiao, Chen; Shuai, Min; Chen, Weimin; Zhong, Shengliang

    2016-10-01

    Coordination polymer (CP) core-shell nanoparticles with Gd-based CP (GdCP) as core and Eu-based CP (EuCP) as shell have been successfully prepared. Allantoin was employed as the organic building block without the assistance of any template. The composition, size and structure of the core-shell nanospheres were well characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TG). Results show that the resultant cores are uniform nanospheres with diameter of approximately 45nm, while the diameters of the core-shell nanospheres are increased to approximately 60nm. The core-shell products show enhanced luminescence efficiency than the core under 980nm laser excitation and decreased down-conversion luminescence when excited at 394nm.

  15. Coordination Polymer Nanoglue: Robust Adhesion Based on Collective Lamellar Stacking of Nanoplates.

    PubMed

    Zhao, Yanyi; Li, Wenwu; Jiang, Xiangfen; Li, Fengqiong; Li, Xin; Zhang, Wei; Jiang, Ji-Sen; Liu, Jian; Ariga, Katsuhiko; Hu, Ming

    2017-03-15

    Despite a continuously growing interest in integration of coordination polymers (CPs) colloids towards functional materials, collective properties of the CPs colloids have rarely been addressed mainly due to the difficulty in assembling pure CPs colloids into superstructures with impressive mechanical strength. We demonstrated that CPs nanoplates could stack together spontaneously upon drying of the slurry of the nanoplates. The stacked CPs nanoplates could work like polymeric adhesives. Versatile articles could be glued when the CPs nanoplates were sandwiched between two substrates. In addition, the CPs nanoplates themselves could form well-defined bulk-structures without using any additional adhesives. The anisotropic shape together with the lamellar stacking way of the CPs nanoplates were found to be the key points in leading to the adhesion and cohesion effect. The reasonable adhesion strength of the CPs nanoglues can allow the exploration of further application of integrated CPs colloids in the future.

  16. Flexible Two-Dimensional Square-Grid Coordination Polymers: Structures and Functions

    PubMed Central

    Kajiro, Hiroshi; Kondo, Atsushi; Kaneko, Katsumi; Kanoh, Hirofumi

    2010-01-01

    Coordination polymers (CPs) or metal-organic frameworks (MOFs) have attracted considerable attention because of the tunable diversity of structures and functions. A 4,4′-bipyridine molecule, which is a simple, linear, exobidentate, and rigid ligand molecule, can construct two-dimensional (2D) square grid type CPs. Only the 2D-CPs with appropriate metal cations and counter anions exhibit flexibility and adsorb gas with a gate mechanism and these 2D-CPs are called elastic layer-structured metal-organic frameworks (ELMs). Such a unique property can make it possible to overcome the dilemma of strong adsorption and easy desorption, which is one of the ideal properties for practical adsorbents. PMID:21152303

  17. Control of molecular rotor rotational frequencies in porous coordination polymers using a solid-solution approach.

    PubMed

    Inukai, Munehiro; Fukushima, Tomohiro; Hijikata, Yuh; Ogiwara, Naoki; Horike, Satoshi; Kitagawa, Susumu

    2015-09-30

    Rational design to control the dynamics of molecular rotors in crystalline solids is of interest because it offers advanced materials with precisely tuned functionality. Herein, we describe the control of the rotational frequency of rotors in flexible porous coordination polymers (PCPs) using a solid-solution approach. Solid-solutions of the flexible PCPs [{Zn(5-nitroisophthalate)x(5-methoxyisophthalate)1-x(deuterated 4,4'-bipyridyl)}(DMF·MeOH)]n allow continuous modulation of cell volume by changing the solid-solution ratio x. Variation of the isostructures provides continuous changes in the local environment around the molecular rotors (pyridyl rings of the 4,4'-bipyridyl group), leading to the control of the rotational frequency without the need to vary the temperature.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C6H2O5)(C6H3O5)(H2O)]n (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented.

  19. Chemistry of porous coordination polymers having multimodal nanospace and their multimodal functionality.

    PubMed

    Seo, Joobeom; Sakamoto, Hirotoshi; Matsuda, Ryotaro; Kitagawa, Susumu

    2010-01-01

    Remarkable advances in the recent development of porous coordination polymers (PCPs) or metal organic frameworks (MOFs) have paved the way toward functional chemistry having potential application such as molecular storage, separation, and catalysis. Moreover flexible PCPs, which are structurally transformable depending upon guest molecules adsorption/desorption, have received much attention because they provide unique properties, dissimilar to those of zeolites. PCPs can be categorized into structurally monomodal and multimodal classes. Monomodal PCPs possess single uniform pores in the framework. In contrast, multimodal PCPs have more than two types of pores in the framework. Interpenetrated PCPs can possess more than two types of pores with different sizes and shapes in the same framework depending on relative position of individual motifs, resulting in multimodal PCPs. Moreover, interpenetrated PCPs have several advantages, such as high thermal stability, flexibility, and ultramicropore for effective adsorption. In this review, chemistry of PCPs based on monomodal and multimodal PCPs are summarized and discussed.

  20. 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.

  1. Cyano-Bridged Trimetallic Coordination Polymer Nanoparticles and Their Thermal Decomposition into Nanoporous Spinel Ferromagnetic Oxides.

    PubMed

    Zakaria, Mohamed B; Hossain, Md Shahriar A; Shiddiky, Muhammad J A; Shahabuddin, Mohammed; Yanmaz, Ekrem; Kim, Jung Ho; Belik, Alexei A; Ide, Yusuke; Hu, Ming; Tominaka, Satoshi; Yamauchi, Yusuke

    2016-10-10

    The synthesis of a novel family of cyano-bridged trimetallic coordination polymers (CPs) with various compositions and shapes has been reported by changing the compositional ratios of Fe, Co, and Ni species in the reaction system. In order to efficiently control the nucleation rate and the crystal growth, trisodium citrate dihydrate plays an important role as a chelating agent. After the obtained cyano-bridged trimetallic CPs undergo thermal treatment in air at three different temperatures (250, 350, and 450 °C), nanoporous spinel metal oxides are successfully obtained. Interestingly, the obtained nanoporous metal oxides are composed of small crstalline grains, and the grains are oriented in the same direction, realizing pseudo-single crystals with nanopores. The resultant nanoporous spinel oxides feature interesting magnetic properties. Cyano-bridged multimetallic CPs with various sizes and shapes can provide a pathway toward functional nanoporous metal oxides that are not attainable from simple cyano-bridged CPs containing single metal ions.

  2. Modular design of domain assembly in porous coordination polymer crystals via reactivity-directed crystallization process.

    PubMed

    Fukushima, Tomohiro; Horike, Satoshi; Kobayashi, Hirokazu; Tsujimoto, Masahiko; Isoda, Seiji; Foo, Maw Lin; Kubota, Yoshiki; Takata, Masaki; Kitagawa, Susumu

    2012-08-15

    The mesoscale design of domain assembly is crucial for controlling the bulk properties of solids. Herein, we propose a modular design of domain assembly in porous coordination polymer crystals via exquisite control of the kinetics of the crystal formation process. Employing precursors of comparable chemical reactivity affords the preparation of homogeneous solid-solution type crystals. Employing precursors of distinct chemical reactivity affords the preparation of heterogeneous phase separated crystals. We have utilized this reactivity-directed crystallization process for the facile synthesis of mesoscale architecture which are either solid-solution or phase-separated type crystals. This approach can be also adapted to ternary phase-separated type crystals from one-pot reaction. Phase-separated type frameworks possess unique gas adsorption properties that are not observed in single-phasic compounds. The results shed light on the importance of crystal formation kinetics for control of mesoscale domains in order to create porous solids with unique cooperative functionality.

  3. A luminescent coordination polymer based on a π-conjugated ligand: Syntheses, structure and luminescent property

    NASA Astrophysics Data System (ADS)

    Li, Dan-Yang; Xie, Hua; Yao, Xiao-Qiang; Ma, Heng-Chang; Lei, Zi-Qiang; Liu, Jia-Cheng

    2017-04-01

    A new cadmium coordination polymer [Cd(DPFE)(adip)0.5(NO3)]n (1) has been synthesized hydrothermally from the self-assembly of the Cd2+ ion with a new π-conjugated rigid ligand DPFE and the adipic acid, where DPFE = 2,7-di(pyridin-4-yl)-9H-fluorene and H2adip = adipic acid. The structure of 1 was full characterized by elemental analysis, FT-IR spectroscopy and single crystal X-ray diffraction. Structural analysis reveals compound 1 is a dinuclear Cd(II) based two-dimensional (4,4) layer and two kinds of strong intramolecular π-π stacking interactions exist between pyridyl rings and benzene rings. In addition, the thermogravimetric analysis and solid-state luminescent properties have also been investigated.

  4. Pressure-induced amorphization of a dense coordination polymer and its impact on proton conductivity

    SciTech Connect

    Umeyama, Daiki; Hagi, Keisuke; Ogiwara, Naoki; Horike, Satoshi E-mail: kitagawa@icems.kyoto-u.ac.jp; Tassel, Cedric; Kageyama, Hiroshi; Higo, Yuji; Kitagawa, Susumu E-mail: kitagawa@icems.kyoto-u.ac.jp

    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 the coupling of the mechanical and electrical properties of a CP.

  5. Geometric accuracy of 3D coordinates of the Leksell stereotactic skull frame in 1.5 Tesla- and 3.0 Tesla-magnetic resonance imaging: a comparison of three different fixation screw materials

    PubMed Central

    Nakazawa, Hisato; Mori, Yoshimasa; Yamamuro, Osamu; Komori, Masataka; Shibamoto, Yuta; Uchiyama, Yukio; Tsugawa, Takahiko; Hagiwara, Masahiro

    2014-01-01

    We assessed the geometric distortion of 1.5-Tesla (T) and 3.0-T magnetic resonance (MR) images with the Leksell skull frame system using three types of cranial quick fixation screws (QFSs) of different materials—aluminum, aluminum with tungsten tip, and titanium—for skull frame fixation. Two kinds of acrylic phantoms were placed on a Leksell skull frame using the three types of screws, and were scanned with computed tomography (CT), 1.5-T MR imaging and 3.0-T MR imaging. The 3D coordinates for both strengths of MR imaging were compared with those for CT. The deviations of the measured coordinates at selected points (x = 50, 100 and 150; y = 50, 100 and 150) were indicated on different axial planes (z = 50, 75, 100, 125 and 150). The errors of coordinates with QFSs of aluminum, tungsten-tipped aluminum, and titanium were <1.0, 1.0 and 2.0 mm in the entire treatable area, respectively, with 1.5 T. In the 3.0-T field, the errors with aluminum QFSs were <1.0 mm only around the center, while the errors with tungsten-tipped aluminum and titanium were >2.0 mm in most positions. The geometric accuracy of the Leksell skull frame system with 1.5-T MR imaging was high and valid for clinical use. However, the geometric errors with 3.0-T MR imaging were larger than those of 1.5-T MR imaging and were acceptable only with aluminum QFSs, and then only around the central region. PMID:25034732

  6. From 3D view to 3D print

    NASA Astrophysics Data System (ADS)

    Dima, M.; Farisato, G.; Bergomi, M.; Viotto, V.; Magrin, D.; Greggio, D.; Farinato, J.; Marafatto, L.; Ragazzoni, R.; Piazza, D.

    2014-08-01

    In the last few years 3D printing is getting more and more popular and used in many fields going from manufacturing to industrial design, architecture, medical support and aerospace. 3D printing is an evolution of bi-dimensional printing, which allows to obtain a solid object from a 3D model, realized with a 3D modelling software. The final product is obtained using an additive process, in which successive layers of material are laid down one over the other. A 3D printer allows to realize, in a simple way, very complex shapes, which would be quite difficult to be produced with dedicated conventional facilities. Thanks to the fact that the 3D printing is obtained superposing one layer to the others, it doesn't need any particular work flow and it is sufficient to simply draw the model and send it to print. Many different kinds of 3D printers exist based on the technology and material used for layer deposition. A common material used by the toner is ABS plastics, which is a light and rigid thermoplastic polymer, whose peculiar mechanical properties make it diffusely used in several fields, like pipes production and cars interiors manufacturing. I used this technology to create a 1:1 scale model of the telescope which is the hardware core of the space small mission CHEOPS (CHaracterising ExOPlanets Satellite) by ESA, which aims to characterize EXOplanets via transits observations. The telescope has a Ritchey-Chrétien configuration with a 30cm aperture and the launch is foreseen in 2017. In this paper, I present the different phases for the realization of such a model, focusing onto pros and cons of this kind of technology. For example, because of the finite printable volume (10×10×12 inches in the x, y and z directions respectively), it has been necessary to split the largest parts of the instrument in smaller components to be then reassembled and post-processed. A further issue is the resolution of the printed material, which is expressed in terms of layers

  7. Synthesis of Biocompatible Nanoparticulate Coordination Polymers for Diagnostic and Therapeutic Applications

    NASA Astrophysics Data System (ADS)

    Kandanapitiye, Murthi S.

    The combination of nanotechnology with medicinal chemistry has developed into a burgeoning research area. Nanomaterials (NMs) could be seamlessly interfaced with various facets in biology, biochemistry, medicinal chemistry and environmental chemistry that may not be available to the same material in the bulk scale. This dissertation research has focused on the development of nanoparticulate coordination polymers for diagnostic and therapeutic applications. Modern imaging techniques include X-ray computed tomography (CT), magnetic resonance imaging (MRI), single photon emission computed tomography (SPECT) and positron emission tomography (PET). We have successfully developed several types of nanoparticulate diagnostics and therapeutics that have some potential usefulness in biomedicine. Synthesis and characterization of nanoparticulate based PET (Positron emission tomography)/SPECT (Single photon emission computed tomography) are discussed in chapter 3. In chapter 4, preparation and potential utility of non-gadolinium based MRI contrast agent are reported for T1-weighted application. As far as the solely effectiveness of relaxation is concerned, Gd-based T 1-weighted MRI contrast agents have excellent enhancement of image contrast but they have risks of biological toxicity. Consequently, the search for T 1-weighted CAs with high efficacy and low toxicity has gained attention toward the Mn(II) and Fe(III). Fe(III) is considered to be more toxic to cells because free ferric or ferrous ions can catalyze the production of reactive oxygen species via the Fenton reactions. Paramagnetic chelates of Mn(II) could be employed as T1-weighted CAs. However, it is challenging to design and synthesize highly stable Mn(II) complexes that could maintain the integrity when administered to living system. Chapter 4 describes the synthesis and utility of nanoparticulate Mn analogue of Prussian blue (K2Mn 3[FeII(CN)6]2) as an effective T1 MRI contrast agent for cellular imaging X

  8. Studies on three-dimensional coordination polymer [Cd2(N2H4)2(N3)4]n: crystal structure, thermal decomposition mechanism and explosive properties.

    PubMed

    Liu, Zhenhua; Zhang, Tonglai; Zhang, Jianguo; Wang, Shaozong

    2008-06-15

    A 3D coordination polymer of cadmium(II) hydrazine azide, [Cd2(N2H4)2(N3)4]n, was synthesized and characterized by elemental analysis and Fourier transform infrared (FT-IR) spectrum. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to monoclinic, P2(1)/c space group, a=12.555(2)A, b=11.724(2)A, c=7.842(1)A, beta=94.56(2) degrees and Z=4. The crystal contains two crystallographically independent sets of distorted octahedral Cd(II) atoms and dimeric units of Cd2N2, Cd2(NNN)2, Cd2(NN)2 through double micro-1, 1 azide bridges, micro-1, 3 azide bridges and bidentate bridging hydrazine ligands, respectively, and thus generating a 3D network structure. The thermal decomposition mechanism of the complex was studied by using differential scanning calorimetry (DSC), thermogravimetry-derivative thermogravimetry (TG-DTG) and FT-IR techniques. Under nitrogen atmosphere with a heating rate of 10 degrees C/min, the thermal decomposition of the complex contained two intense exothermic decomposition processes in the range of 150-304 degrees C in the DSC curve, and the final decomposed residue at 500 degrees C was Cd. Sensitivity tests revealed that the title complex is very insensitive to external stimuli.

  9. Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; New precursor for the preparation of nano-materials.

    PubMed

    Mirtamizdoust, Babak

    2017-03-01

    Nano-sheets of a novel Pb(II)-based 3D metal-organic coordination polymer [Pb2(nih)2(NO3)4(CH3OH)]n (1) were synthesized by a branched-tube method and sonochemical reaction. The synthesis was done using various times, concentrations of initial reagents, and irradiation power. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray powder diffraction (XRD), and single-crystal X-ray analysis. The X-ray analysis of the structures revealed the composition and stereochemistry of the basic building block, which had with a formula of {Pb2(nih)2(NO3)4(CH3OH)}. These blocks are connected by covalent bonds originating from the nih and nitrate ligands and form infinite 3D metal-organic polymeric chains. The effect of triethylamine on the speed of nucleation was also investigated. Lead oxide nanoparticles were obtained by thermolysis of 1 at 180°C using oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XRD to be 36nm. The morphology and size of the PbO nanoparticles were also studied using SEM.

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

    NASA Astrophysics Data System (ADS)

    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

    2016-06-01

    Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The 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 exhibits 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 optimization of this HER electrocatalyst as an alternative to platinum.

  11. 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.

  12. Divergent layer topologies in divalent metal aliphatic dicarboxylate coordination polymers containing 3-pyridylmethylnicotinamide

    NASA Astrophysics Data System (ADS)

    White, Charmaine L.; Torres Salgado, Maria D.; Mizzi, Jessica E.; LaDuca, Robert L.

    2015-12-01

    Hydrothermal reaction of the requisite metal salt, an aliphatic dicarboxylic acid, and the hydrogen-bonding capable dipyridylamide ligand 3-pyridylmethylnicotinamide (3-pmna) resulted in four coordination polymers whose connectedness and layer topology depend on the metal coordination environment and dicarboxylate binding mode. These new crystalline phases were characterized by single crystal X-ray diffraction. [Cu(ox)(3-pmna)]n (1, ox = oxalate) manifests stacked 3-connected (6,3) herringbone layer motifs. {[Cd(mal)(3-pmna)(H2O)]·3H2O}n (2, mal = malonate) shows a 4-connected (4,4) grid topology with entrained water molecule trimeric chains in the interlamellar regions. {[Cd2(suc)2(3-pmna)(H2O)2]·3H2O}n (3, suc = succinate) possesses {Cd2O2} dimer-based [Cd(suc)]n layers pillared by 3-pmna ligands into a 5-connected sandwich motif with 4862 topology. {[Cd(glu)(3-pmna)(H2O)]·3H2O}n (4, glu = glutarate) manifests a rippled (4,4) grid topology. Luminescent behavior in the cadmium complexes is ascribed to intra-ligand molecular orbital transitions. Thermal decomposition behavior is also discussed herein.

  13. 3D Imaging.

    ERIC Educational Resources Information Center

    Hastings, S. K.

    2002-01-01

    Discusses 3 D imaging as it relates to digital representations in virtual library collections. Highlights include X-ray computed tomography (X-ray CT); the National Science Foundation (NSF) Digital Library Initiatives; output peripherals; image retrieval systems, including metadata; and applications of 3 D imaging for libraries and museums. (LRW)

  14. Polarized 3D Raman and nanoscale near-field optical microscopy of optically inscribed surface relief gratings: chromophore orientation in azo-doped polymer films.

    PubMed

    Di Florio, Giuseppe; Bründermann, Erik; Yadavalli, Nataraja Sekhar; Santer, Svetlana; Havenith, Martina

    2014-03-14

    We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.

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

    PubMed Central

    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. PMID:28115934

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

    SciTech Connect

    Lytvynenko, Anton S.; Kiskin, Mikhail A.; Dorofeeva, Victoria N.; Mishura, Andrey M.; Titov, Vladimir E.; Kolotilov, Sergey V.; Eremenko, Igor L.; Novotortsev, Vladimir M.

    2015-03-15

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

  17. The marine sponge-derived inorganic polymers, biosilica and polyphosphate, as morphogenetically active matrices/scaffolds for the differentiation of human multipotent stromal cells: potential application in 3D printing and distraction osteogenesis.

    PubMed

    Wang, Xiaohong; Schröder, Heinz C; Grebenjuk, Vladislav; Diehl-Seifert, Bärbel; Mailänder, Volker; Steffen, Renate; Schloßmacher, Ute; Müller, Werner E G

    2014-02-21

    , supplemented with polyP and/or biosilica, is a suitable biomaterial that promotes the growth and differentiation of hMSCs and might be beneficial for application in 3D tissue printing of hMSCs and for the delivery of hMSCs in fractures, surgically created during distraction osteogenesis.

  18. The Marine Sponge-Derived Inorganic Polymers, Biosilica and Polyphosphate, as Morphogenetically Active Matrices/Scaffolds for the Differentiation of Human Multipotent Stromal Cells: Potential Application in 3D Printing and Distraction Osteogenesis

    PubMed Central

    Wang, Xiaohong; Schröder, Heinz C.; Grebenjuk, Vladislav; Diehl-Seifert, Bärbel; Mailänder, Volker; Steffen, Renate; Schloßmacher, Ute; Müller, Werner E. G.

    2014-01-01

    , supplemented with polyP and/or biosilica, is a suitable biomaterial that promotes the growth and differentiation of hMSCs and might be beneficial for application in 3D tissue printing of hMSCs and for the delivery of hMSCs in fractures, surgically created during distraction osteogenesis. PMID:24566262

  19. Ion conductivity and transport by porous coordination polymers and metal-organic frameworks.

    PubMed

    Horike, Satoshi; Umeyama, Daiki; Kitagawa, Susumu

    2013-11-19

    Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have been recognized for their easy design and the dynamic behavior of the ionic components in the structures. These PCP/MOFs consist of metal ions (or clusters) and organic ligands structured via coordination bonds. They could have highly concentrated mobile ions with dynamic behavior, and their characteristics have inspired the design of a new class of ion conductors and transporters. In this Account, we describe the state-of-the-art of studies of ion conductivity by PCP/MOFs and nonporous coordination polymers (CPs) and offer future perspectives. PCP/MOF structures tend to have high hydrophilicity and guest-accessible voids, and scientists have reported many water-mediated proton (H(+)) conductivities. Chemical modification of organic ligands can change the hydrated H(+) conductivity over a wide range. On the other hand, the designable structures also permit water-free (anhydrous) H(+) conductivity. The incorporation of protic guests such as imidazole and 1,2,4-triazole into the microchannels of PCP/MOFs promotes the dynamic motion of guest molecules, resulting in high H(+) conduction without water. Not only the host-guest systems, but the embedding of protic organic groups on CPs also results in inherent H(+) conductivity. We have observed high H(+) conductivities under anhydrous conditions and in the intermediate temperature region of organic and inorganic conductors. The keys to successful construction are highly mobile ionic species and appropriate intervals of ion-hopping sites in the structures. Lithium (Li

  20. A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

    PubMed Central

    Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

    2016-01-01

    Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability. PMID:27080134

  1. A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation.

    PubMed

    Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

    2016-04-15

    Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors' knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

  2. Complementary in situ reactivity of isomeric dipyridylamide precursors and its effect on dimensionality of cadmium 5-nitroisophthalate coordination polymers

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    Hydrothermal treatment of cadmium nitrate, 5-nitroisophthalic acid (H2nip) and one of two isomeric dipyridylamides resulted in coordination polymer crystalline solids that manifested different in situ reactivity and dimensionality, as ascertained by single crystal X-ray diffraction. Hydrolysis of 3-pyridylisonicotinamide (3-pina) afforded the 3-aminopyridine (3-ampyr) ligands observed in the 1-D ladder polymer {[Cd(nip)(3-ampyr)(H2O)]ṡ2H2O}n (1). Conversely, hydrolysis of the isomeric precursor 3-pyridylnicotinamide (3-pna) generated the monoanionic nicotinate ligands in the 2-D coordination polymer [Cd2(nip)(nic)2(H2O)2]n (2). Compound 2 displays {Cd2(OCO)2} eight-membered ring dimeric units linked into (6,3) graphite-type slab motifs. Luminescent properties of these two new materials are also presented.

  3. Calculations of the integral invariant coordinates I and L* in the magnetosphere and mapping of the regions where I is conserved, using a particle tracer (ptr3D v2.0), LANL*, SPENVIS, and IRBEM

    NASA Astrophysics Data System (ADS)

    Konstantinidis, K.; Sarris, T.

    2015-09-01

    The integral invariant coordinate I and Roederer's L or L* are proxies for the second and third adiabatic invariants, respectively, that characterize charged particle motion in a magnetic field. Their usefulness lies in the fact that they are expressed in more instructive ways than their counterparts: I is equivalent to the path length of the particle motion between two mirror points, whereas L*, although dimensionless, is equivalent to the distance from the center of the Earth to the equatorial point of a given field line, in units of Earth radii, in the simplified case of a dipole magnetic field. However, care should be taken when calculating the above invariants, as the assumption of their conservation is not valid everywhere in the Earth's magnetosphere. This is not clearly stated in state-of-the-art models that are widely used for the calculation of these invariants. The purpose of this work is thus to investigate where in the near-Earth magnetosphere we can safely calculate I and L* with tools with widespread use in the field of space physics, for various magnetospheric conditions and particle initial conditions. More particularly, in this paper we compare the values of I and L* as calculated using LANL*, an artificial neural network developed at the Los Alamos National Laboratory, SPENVIS, a space environment online tool, IRBEM, a software library dedicated to radiation belt modeling, and ptr3D, a 3-D particle tracing code that was developed for this study. We then attempt to quantify the variations between the calculations of I and L* of those models. The deviation between the results given by the models depends on particle initial position, pitch angle and magnetospheric conditions. Using the ptr3D v2.0 particle tracer we map the areas in the Earth's magnetosphere where I and L* can be assumed to be conserved by monitoring the constancy of I for energetic protons propagating forwards and backwards in time. These areas are found to be centered on the noon

  4. 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.

  5. [Synthesis and structure of silver(I) coordination polymers with bis(pyridyl) ligands linked by an aromatic sulfonamide].

    PubMed

    Katagiri, Kosuke

    2014-01-01

    Aromatic sulfonamides exist in a synclinal conformation with the twisted structure arising from rotation around the S-N bond in both the solid state and in solution. Simple bidentate ligands containing the sulfonamide moiety can be extended to form elongated ligands, and optically active components can be added to form a versatile building block for the construction of coordination polymers with many structures. Mixing the simple ligands 1 and 2 and the elongated ligands 3 and 4 with different Ag(I) salts yielded the corresponding complexes [Ag(1)OTf]n (1a), [Ag(2)]n•nOTf(2a), [Ag(3)OTf]n (3a), [Ag(3)]n•nBF₄ (3b), [Ag(4)CH₃CN]n•nBF₄•nCHCl₃ (4b), and [Ag(4)]n•nSbF₆•nCH₄O (4c). Straight chains and racemic helical polymers were observed in the crystal structure of complexes 1a and 2a, respectively. In the crystal structures of complexes 3a and 4b, infinite 1D straight chains containing a T-shaped coordination geometry about the Ag(I) centers were formed by the reaction of ligands 3 or 4 with Ag(I) salts in CH₃CN/CHCl₃. A continuous 1D coordination polymer containing a racemic mixture of left- and right-handed helices formed in the crystal structure of complex 3b. Furthermore, a layered coordination polymer consisting of a racemic mixture of left- and right-handed polymers was observed from the crystal structure of complex 4c. The construction of optically pure left- or right-handed 1D helical polymers via the introduction of chiral functional groups on the nitrogen atom of the sulfonamide ligand is currently under investigation in our laboratory.

  6. Synthesis, crystal structures and characterization of four coordination polymers based on 5-amino-2,4,6-triiodoisophthalic acid

    SciTech Connect

    Zhang Koulin; Chang Yan; Zhang Jingbo; Yuan Limin; Deng Ye; Diao Guowang; Ng, Seik Weng

    2011-05-15

    One homochiral 1D coordination polymer [Cu(ATIBDC)(2,2'-bipy)].3H{sub 2}O.CH{sub 3}OH (1) and three achiral 1D coordination polymers: [Cd(ATIBDC)(2,2'-bipy)(H{sub 2}O)].3H{sub 2}O (2), [Cd(ATIBDC)(phen)(H{sub 2}O)].4H{sub 2}O (3), and [Mn(ATIBDC)(phen){sub 2}].5H{sub 2}O (4) have been synthesized and characterized (H{sub 2}ATIBDC=5-amino-2,4,6-triiodoisophthalic acid, 2,2'-bipy=2,2'-bipyridine, and phen=1,10-phenanthroline). Extended high dimensional network architectures are further constructed with the help of weak secondary interactions, such as hydrogen bonding, aromatic stacking, and halogen bonding (C-I..{pi} and C-I...N/O). Complex 1 crystallizes in the monoclinic system with chiral space group P2(1) and exhibits a right-handed 2{sub 1} helical chain structure. The homochirality of 1 was confirmed by CD spectrum. Interestingly, two new configurations of decameric water cluster are found in 3 and 4. The acyclic tetrameric cluster (H{sub 2}O){sub 3}(CH{sub 3}OH) in 1 and (H{sub 2}O){sub 4} in 2 array into highly ordered helical infinite chains. Thermal stabilities of all the complexes have been studied. Solid state fluorescent properties of the Cd(II) complexes have been explored. -- Graphical abstract: The synthesis, crystal structures and characterization of one 1D homochiral coordination polymer and three achiral 1D coordination polymers with 5-amino-2,4,6-triiodoisophthalic acid (H{sub 2}ATIBDC) are reported. Display Omitted highlights: > Four 1D coordination polymers with 5-amino-2,4,6-triiodoisophthalate are reported. > The halogen bonds play important roles in the supramolecular assembly. > Solid state fluorescent properties of the Cd(II) complexes are explored.

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    Two new lanthanide coordination polymers based on a semirigid bridging thenylsalicylamide ligand {[Ln2L3(NO3)6]·(C4H8O2)2}∞ were obtained and characterized by elemental analysis, X-ray diffraction, IR and TGA measurements. The two compounds are isostructure and possess one dimensional trapezoid ladder-like chain built up from the connection of isolated LnO3(NO3)3 polyhedra (distorted monocapped antisquare prism) through the ligand. The photoluminescence analysis suggest that there is an efficient ligand-to-Ln(III) energy transfer in Tb(III) complex and the ligand is an efficient "antenna" for Tb(III). From a more general perspective, the results demonstrated herein provide the possibility of controlling the formation of the desired lanthanide coordination structure to enrich the crystal engineering strategy and enlarge the arsenal for developing excellent luminescent lanthanide coordination polymers.

  8. Chiral one- and two-dimensional silver(I)-biotin coordination polymers.

    PubMed

    Altaf, Muhammad; Stoeckli-Evans, Helen

    2013-02-01

    Reaction of biotin {C(10)H(16)N(2)O(3)S, HL; systematic name: 5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoic acid} with silver acetate and a few drops of aqueous ammonia leads to the deprotonation of the carboxylic acid group and the formation of a neutral chiral two-dimensional polymer network, poly[[{μ(3)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}silver(I)] trihydrate], {[Ag(C(10)H(15)N(2)O(3)S)]·3H(2)O}(n) or {[Ag(L)]·3H(2)O}(n), (I). Here, the Ag(I) cations are pentacoordinate, coordinated by four biotin anions via two S atoms and a ureido O atom, and by two carboxylate O atoms of the same molecule. The reaction of biotin with silver salts of potentially coordinating anions, viz. nitrate and perchlorate, leads to the formation of the chiral one-dimensional coordination polymers catena-poly[[bis[nitratosilver(I)]-bis{μ(3)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}] monohydrate], {[Ag(2)(NO(3))(2)(C(10)H(16)N(2)O(3)S)(2)]·H(2)O}(n) or {[Ag(2)(NO(3))(2)(HL)(2)]·H(2)O}(n), (II), and catena-poly[bis[perchloratosilver(I)]-bis{μ(3)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}], [Ag(2)(ClO(4))(2)(C(10)H(16)N(2)O(3)S)(2)](n) or [Ag(2)(ClO(4))(2)(HL)(2)](n), (III), respectively. In (II), the Ag(I) cations are again pentacoordinated by three biotin molecules via two S atoms and a ureido O atom, and by two O atoms of a nitrate anion. In (I), (II) and (III), the Ag(I) cations are bridged by an S atom and are coordinated by the ureido O atom and the O atoms of the anions. The reaction of biotin with silver salts of noncoordinating anions, viz. hexafluoridophosphate (PF(6)(-)) and hexafluoridoantimonate (SbF(6)(-)), gave the chiral double-stranded helical structures catena-poly[[silver(I)-bis{μ(2)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}] hexafluoridophosphate], {[Ag(C(10)H(16)N(2)O(3)S)(2)](PF(6))}(n) or {[Ag(HL)(2)](PF(6

  9. Solvothermal self-assembly of Cd(2+) coordination polymers with supramolecular networks involving N-donor ligands and aromatic dicarboxylates: synthesis, crystal structure and photoluminescence studies.

    PubMed

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

    2017-03-14

    Two cadmium(ii) coordination polymers (CPs) of compositions {[Cd(H2O)4(4-BPDB)][BPDC]}n (CP1) and {[Cd(H2O)(BrIP)(BTTMB)]·4MeOH}n (CP2) have been synthesized by solvothermal methods and characterized by several analytical methods including SXRD (Single Crystal X-ray Diffraction). The structure of CP1 can be described as a 1D cationic chain, {[Cd(H2O)4(4-BPDB)](2+)}n and discrete BPDC counter anions. The structure of CP2 revealed an undulated 2D sql net comprising Cd(2+) nodes bridged by the ditopic N-donor, BTTMB and dicarboxylate BrIP involved in μ2-η(1)η(1)η(1)η(1) coordination. Supramolecular interactions in both CPs generate 3D hydrogen bonded architectures. The solid state fluorescence properties of these d(10) metal ion containing CPs have been investigated. Fluorescence emission of CP1 suspended in acetonitrile is observed to be selectively quenched by acetone (LOD = 0.15 mM) over other common laboratory solvents.

  10. Increased dimensionalities of zinc-diphenic acid coordination polymers by simultaneous or subsequent addition of neutral bridging ligands.

    PubMed

    Dietzel, Pascal D C; Blom, Richard; Fjellvåg, Helmer

    2006-01-28

    Three coordination polymers containing zinc and diphenic acid (H2dpa) were synthesised by solvothermal reaction. Zn(dpa)(H2O) is a one-dimensional coordination polymer that consists of parallel ladder-like chains. One carboxylate group of the diphenic acid coordinates two zinc atoms forming a dinuclear unit which composes the steps of the ladder. The other carboxylate connects to a zinc atom in the next step of the ladder. The fourth coordination site at the zinc atom is occupied by water. Attempts to crosslink the chains by replacing the water molecule with the neutral ligands triethylenediamine (dabco) or 4,4'-bipyridyl lead to the compounds Zn2(dpa)2(dabco) and Zn(dpa)(4,4'-bpy). Their structures can be rationalised as being derived from action of the neutral ligand on Zn(dpa)(H2O), and while they are most conveniently prepared in a one-pot synthesis, it is also possible to obtain them by exposing Zn(dpa)(H2O) to the respective neutral ligand. Zn2(dpa)2(dabco) is a layered two-dimensional coordination polymer in which dinculear zinc carboxylate paddle wheel units and the dabco ligand form infinite linear chains. The chains are interconnected by the dpa unit. The structure of Zn(dpa)(4,4'-bpy) consists of two identical interpenetrating three-dimensional networks. In the network, helical Zn(dpa) chains are interconnected by the rigid 4,4'-bipyridine ligand. Thermogravimetric analysis indicates a high thermal stability of this coordination polymer with decomposition occurring in the range 350-450 degrees C. This is complemented by X-ray thermodiffractometry that indicates a phase transition at 337 degrees C and the final loss of crystallinity at 427 degrees C. The room temperature phase expands drastically along one axis and contracts along the other two axes on heating.

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

    SciTech Connect

    Hu, Dong-Cheng; Fan, Yan; Si, Chang-Dai; Wu, Ya-Jun; Dong, Xiu-Yan; Yang, Yun-Xia; Yao, Xiao-Qiang; Liu, Jia-Cheng

    2016-09-15

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

  12. AE3D

    SciTech Connect

    Spong, Donald A

    2016-06-20

    AE3D solves for the shear Alfven eigenmodes and eigenfrequencies in a torodal magnetic fusion confinement device. The configuration can be either 2D (e.g. tokamak, reversed field pinch) or 3D (e.g. stellarator, helical reversed field pinch, tokamak with ripple). The equations solved are based on a reduced MHD model and sound wave coupling effects are not currently included.

  13. Performance evaluation of an improved optical computed tomography polymer gel dosimeter system for 3D dose verification of static and dynamic phantom deliveries

    SciTech Connect

    Lopatiuk-Tirpak, O.; Langen, K. M.; Meeks, S. L.; Kupelian, P. A.; Zeidan, O. A.; Maryanski, M. J.

    2008-09-15

    The performance of a next-generation optical computed tomography scanner (OCTOPUS-5X) is characterized in the context of three-dimensional gel dosimetry. Large-volume (2.2 L), muscle-equivalent, radiation-sensitive