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Sample records for 3d coordination polymers

  1. 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.

  2. A new pillared-layer 3D coordination polymer involving in situ generated formate

    NASA Astrophysics Data System (ADS)

    Xia, Yu-Pei; Li, Yun-Wu; Li, Da-Cheng; Du, Yu-Chang; Yao, Qing-Xia; Dou, Jian-Min

    2015-02-01

    A new Cd-based coordination polymer, [Cd(cpt)(HCOO)]n (1), has been synthesized from 1-(4-carboxyphenyl)-1,2,4-triazole) ligand (Hcpt). The structure was characterized through X-ray crystallography, elemental analysis, and IR spectrum. Compound 1 presents a three-dimensional (3D) pillared-layer structure constructed by metal-formate layers and cpt- ligands. Moreover, the unusual formate anions are generated in situ from the decomposition of DMF precursors. The fluorescence property of 1 in solid state was also researched.

  3. 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.

  4. 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

  5. Coronates, spherical containers, bowl-shaped surfaces, porous 1D-, 2D-, 3D-metallo-coordination polymers, and metallodendrimers.

    PubMed

    Saalfrank, Rolf W; Scheurer, Andreas

    2012-01-01

    Supramolecular coordination cages and polymers bear exceptional advantages over their organic counterparts. They are available in one-pot reactions and in high yields and display physical properties that are generally inaccessible with organic species. Moreover, their weak, reversible, noncovalent bonding interactions facilitate error checking and self-correction. This review emphasizes the achievements in supramolecular coordination container as well as polymer chemistry initiated by serendipity and their materialization based on rational design. The recognition of similarities in the synthesis of different supramolecular assemblies allows prediction of potential structures in related cases. The combination of detailed symmetry considerations with the basic rules of coordination chemistry has only recently allowed for the design of rational strategies for the construction of a variety of nanosized spherical containers, bowls, 1D-, 2D-, and 3D-coordination polymers with specified size and shape. PMID:22160460

  6. Synthesis, structure and fluorescence properties of a novel 3D Sr(II) coordination polymer

    NASA Astrophysics Data System (ADS)

    Tan, Yu-Hui; Xu, Qing; Gu, Zhi-Feng; Gao, Ji-Xing; Wang, Bin; Liu, Yi; Yang, Chang-Shan; Tang, Yun-Zhi

    2016-09-01

    Solvothermal reaction of 2,2‧-bipyridine-5,5‧-dicarboxylic acid (H2bpdc) and SrCl2 affords a novel coordination polymer [Sr(Hbpdc)2]n1. X-ray structure determination shows that 1 exhibits a novel three-dimensional network. The unique Sr II cation sits on a two-fold axis and coordinated by four O-atom donors from four Hbptc- ligands and four N-atom donors from two Hbptc- ligands in distorted dodecahedral geometry. In 1 each Sr II cation connects to six different Hbptc- ligands and each Hbptc- ligand bridges three different Sr II cations which results in the formation of a three-dimensional polymeric structure. Corresponding to the free ligand, the fluorescent emission of complex 1 display remarkable "Einstain" shifts, which may be attributed to the coordination interaction of Sr atoms, thus reduce the rigidity of pyridyl rings.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

    Two new 3-D porous bismuth coordination polymers, (C 5NH 6) 2[Bi 2(H 2O) 2(C 2O 4) 4]·2H 2O 1 and (NH 4)[Bi(C 2O 4) 2]·3H 2O 2, have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic symmetry, P2 1/ c space group with a=10.378(2) Å, b=17.285(3) Å, c=16.563(5) Å, α=90°, β=119.66(2)°, γ=90°, V=2581.8(10) Å 3, Z=4, R1=0.0355 and w R2=0.0658 for unique 4713 reflections I >2 σ( I). Compound 2 crystallizes in the tetragonal symmetry, I4 1/ amd space group with a=11.7026(17) Å, b=11.7026(17) Å, c=9.2233(18) Å, α=90°, β=90°, γ=90°, V=1263.1(4) Å 3, Z=32, R1=0.0208 and w R2=0.0518 for unique 359 reflections I> 2 σ( I). Compounds 1 and 2 are 3-D open-framework structures with a 6 6 uniform net, which consist of honeycomb-like layers connected to each other by oxalate units. While different guest molecules fill in their cavities of honeycomb-like layers, study of ultrasonic treatment on 2 indicates the replacement of NH 4+ by K + on potassium ion exchange. Thermogravimetric analysis indicates that the open-channel frameworks are thermally stable up to 200 °C, and other characterizations are also described by elemental analysis, IR and ultraviolet-visible diffuse reflectionintegral spectrum (UV-Vis DRIS).

  11. A 3D Heterometallic Coordination Polymer Constructed by Trimeric {NiDy2} Single-Molecule Magnet Units.

    PubMed

    Zhang, Shaowei; Li, Han; Duan, Eryue; Han, Zongsu; Li, Leilei; Tang, Jinkui; Shi, Wei; Cheng, Peng

    2016-02-01

    The solvothermal reaction of DyCl3·6H2O, Ni(NO3)2·6H2O, and H4abtc ligands (H4abtc = 3,3',5,5'-azobenzene-tetracarboxylic acid) in the mixed DMF/H2O solvents (DMF = N,N-dimethylformamide) produced a three-dimensional (3D) Ni(II)-Dy(III) heterometallic coordination polymer (HCP) formulated as {[NH2(CH3)2]2[NiDy2(HCOO)2(abtc)2]}n (1). In 1, Dy(III) and Ni(II) ions interconnect through carboxylic O donors of abtc(4-) ligands to generate a linear trimer "Hourglass"-type {NiDy2} cluster, and the adjacent trinuclear {NiDy2} units are bridged by HCOO(-) groups to give a 1D "ladder" chain, which is further bridged by abtc(4-) ligands to form a new topology and named as "zsw3". Alternating-current magnetic susceptibility results indicate that 1 exhibits frequency-dependent out-of-phase signals with two relaxation processes, which suggests that it shows single-molecule magnet (SMM) behavior and represents the first example by using an SMM cluster as the building block to create a 3D Ni-Ln HCP, to the best of our knowledge. The energy barriers for 1 under a 1000 Oe applied direct current magnetic field are estimated from Arrhenius plots to be 40 and 42 K at higher and lower frequencies, respectively. Additionally, the crystalline structure of 1 could be stable to at least 310 °C, supported by thermogravimetric analyses and in situ variable-temperature powder X-ray diffraction patterns. PMID:26751740

  12. 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.

  13. Novel polythreaded coordination polymer: from an armed-polyrotaxane sheet to a 3D polypseudorotaxane array, photo- and thermochromic behaviors.

    PubMed

    Yao, Qing-Xia; Ju, Zhan-Feng; Jin, Xu-Hui; Zhang, Jie

    2009-02-16

    A novel coordination compound, {[Cd(BDC)(Bpybc)(1.5)].10H(2)O}(n), obtained by the reaction of CdCl(2) with 1,1'-bis(4-carboxybenzyl)-4,4'-bipyridinium dichloride (H(2)BpybcCl(2)) and 1,4-benzenedicarboxylic acid (H(2)BDC), contains 1D polymeric chains that are comprised of alternating rings and rods and dangling lateral arms. These 1D polymeric motifs are interlaced via rotaxane-like mechanical linkages to give 2D armed-polyrotaxane sheets, which are further mutually polythreaded via pseudorotaxane-like mechanical linkages to form a 3D polypseudorotaxane array. Notably, a sandwich-type donor-acceptor-donor stacking is formed within each ring as a consequence of both types of polythreading in this species, and photoinduced and thermal-induced reduction of bipyridinium occurs with a color change from light yellow to blue. PMID:19166285

  14. Syntheses, crystal structures and properties of two unusual pillared-layer 3d-4f Ln-Cu heterometallic coordination polymers

    SciTech Connect

    Fan Leqing; Wu Jihuai; Huang Yunfang

    2011-09-15

    Two unusual pillared-layer 3d-4f Ln-Cu heterometallic coordination polymers, {l_brace}[Ln{sub 2}Cu{sub 5}Br{sub 4}(IN){sub 7}(H{sub 2}O){sub 6}].H{sub 2}O{r_brace}{sub n} (Ln=Eu (1) and Gd (2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. The structure determination reveals that 1 and 2 are isostructural and feature a novel three-dimensional pillared-layer hetrometallic structure built upon the linkages of one-dimensional (1D) linear Ln-carboxylate chains, zero-dimensional (0D) Ln-carboxylate Ln{sub 2}(IN){sub 8} dimers, rare 1D zigzag [Cu{sub 5}Br{sub 4}]{sub n} inorganic chains and IN{sup -} pillars. In both 3D structures, there are Ln-carboxylate layers resulted from the connections of 1D Ln-carboxylate chains and 0D Ln{sub 2}(IN){sub 8} dimers through O-H...O hydrogen bondings. The luminescent properties of 1 have been investigated. The magnetic properties of 1 and 2 have also been studied. - Graphical abstract: Two unusual pillared-layer Eu (Gd)-Cu heterometallic coordination polymers have been hydrothermally synthesized. The luminescent properties of Eu-Cu compound and magnetic properties of both compounds are investigated. Highlights: > Two unusual 3D pillared-layer Eu (Gd)-Cu heterometallic coordination polymers have been synthesized. > 1D and 0D Ln-carboxylate motifs construct layers by O-H...O hydrogen bondings. > In both the structures, there are rare 1D zigzag Cu/Br inorganic chains. > Luminescent properties of Eu-Cu compound and magnetic properties of both the compounds are investigated.

  15. Structural variation from 1D to 3D: effects of ligands and solvents on the construction of lead(II)-organic coordination polymers.

    PubMed

    Yang, Jin; Li, Guo-Dong; Cao, Jun-Jun; Yue, Qi; Li, Guang-Hua; Chen, Jie-Sheng

    2007-01-01

    A series of Pb(II) coordination polymers [Pb(ndc)(dpp)] (1), [Pb(ndc)(ptcp)].0.5 H2O (2), [Pb(ndc)(dppz)] (3), [Pb(ndc)(tcpn)(2)] (4), [Pb2(ndc)2(tcpp)] (5), [Pb(Hndc)2].H2O (6), [Pb(ndc)(dma)] (7), [Pb(bdc)(dma)] (8), [Pb(trans-chdc)(H2O)] (9), and [Pb2(cis-chdc)2].NH(CH3)2 (10), where ndc=1,4-naphthalenedicarboxylate, dpp=4,7-diphenyl-1,10-phenanthroline, ptcp=2-phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene, dppz=dipyrido[3,2-a:2',3'-c]phenazine, tcpn=2-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)naphthol, tcpp=4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol, dma=N,N-dimethylacetamide, bdc=1,4-benzenedicarboxylate, and chdc=1,4-cyclohexanedicarboxylate, have been synthesized from a hydrothermal or solvothermal reaction system by varying the ligands or the solvents. Compounds 1-5 crystallize with an N-donor chelating ligand and an aromatic dicarboxylate linker. Compounds 1-4 are 1D polymers with different pi-pi stacking interactions, whereas compound 5 consists of 2D layers. The structures of compounds 7, 8, and 10 are 3D frameworks formed by connection of the Pb(II) centers by organic acid ligands. Compound 7 is chiral although the ndc ligand is achiral, while the framework of 8 is a typical 3D (3,4)-connected net. Compound 10 is the first example of Pb(II) wheel cluster [Pb(8)O(8)] units bridged by carboxylate groups. Compound 6 contains 1D chains which are further extended to a 3D structure by pi-pi interactions. Compound 9 consists of a 2D network constructed by Pb(II) centers and trans-chdc ligands. The structural differences between 7 and 8 and between 9 and 10 indicate the importance of solvents for framework formation of the coordination polymers. By varying the solvent the cis and trans conformations of H(2)chdc in 9 and 10 were separated completely. The photoluminescence and nonlinear optical properties of the coordination polymers have also been investigated. PMID:17212363

  16. Five novel transition metal coordination polymers with 2D/3D framework structure based on flexible H{sub 2}tzda and ancillary ligand bpe

    SciTech Connect

    Wang Yuting; Xu Yan; Fan Yaoting; Hou Hongwei

    2009-10-15

    Five new transition metal coordination polymers based on H{sub 2}tzda and co-ligand bpe, {l_brace}[M(tzda)(bpe)].H{sub 2}O{r_brace}{sub n} [M=Zn(1), Cd(2), Mn(3), Co(4)] and [Ni{sub 2}(tzda){sub 2}(bpe){sub 2}(H{sub 2}O)]{sub n} (5) [H{sub 2}tzda=(1,3,4-thiadiazole-2,5-diyldithio)diacetic acid, bpe=1,2-bis(4-pyridyl)ethane], have been hydrothermally synthesized and structurally characterized. Compounds 1-4 feature a 2D-layered architecture generated from [M(tzda)]{sub n} moiety with double-chain structure cross-linking bpe spacers. However, the conformations bpe adopts in 3 and 4 are different from those in 1 and 2 due to the rotation of C-C single bond in bpe. Polymer 5 exhibits an interesting 3D porous framework with 2-fold interpenetration, in which intriguing 1D double helix chains are observed. The photoluminescence properties of 1 and 2 in the solid-state at room temperature are investigated. In addition, variable-temperature magnetic data show weak antiferromagnetic behavior in 3-5. - Graphical abstract: Five new transition metal coordination polymers based on flexible H{sub 2}tzda and bpe have been hydrothermally synthesized and characterized by X-ray diffraction, luminescent emission spectra and low-temperature magnetic measurements, respectively.

  17. From discrete to infinite 3D coordination polymer: Sonochemical syntheses and structural characterization of a new nano flower lead (II) coordination compound

    NASA Astrophysics Data System (ADS)

    Chung, Jin-Hwan; Min, Bong-Ki; Kim, Young Kyung; Kim, Kyo-Han; Kwon, Tae-Yub

    2014-11-01

    Nano flower of a new discrete Pb (II) coordination compound, [Pb(pcih)2] (1), (pcih = 2-pyridinecarbaldehyde isonicotinoylhy-drazonate), have been synthesized by a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), FT-IR spectroscopy and elemental analyses. Structural determination of compound 1 reveals the Pb (II) ion is six coordinated, bonded to four nitrogen and two oxygen atoms from two “pcih” ligands. Through strong π-π interactions, the overall structure of 1 is 1D supramolecular chain and with other directional intermolecular interactions, it is further extended into a three dimensional (3D) supramolecular structure. Density functional theory calculations (B3LYP functional) have been performed on complex 1 to provide a qualitative theoretical interpretation of their structural parameters, charge distributions and IR spectra. PbO nanoparticles are obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant.

  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. Synthesis, structure and properties of a 3D plywood-like nickel(II) hexaazamacrocyclic coordination polymer constructed from weak Ni\\ctdot O interactions and hydrogen bonding

    NASA Astrophysics Data System (ADS)

    Tao, Bo; Jiang, Xiang; Xia, Hua; Cheng, Hefa

    2012-03-01

    A 3D plywood-like nickel(II) hexaazamacrocyclic coordination polymer {[Ni(hto)(H2btec]}n (2) (hto = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.16,9]octadecane, H4btec = 1,2,4,5-benzenetetracarboxylic acid) was synthesized by a slow diffusion method and characterized by X-ray crystallography and spectroscopic methods. The structure of 2 is made up of [Ni(hto)]2+ cation and H2btec2- anion in a molecular ratio of 1:1. The nickel(II) ions in the complex are bridged by the H2btec2- ligand based on weak Ni⋯O coordination interactions to form a 1D chain. The alternate cross-like 1D chains are packed in a plywood-like structure and interconnected with each other by hydrogen bonding to form a 3D network. Complex 2 exhibits fluorescent emission in the solid state at room temperature.

  20. 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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    Three new zinc(II) coordination polymers, [Zn(HO3PCH2CH2COO)(C12H8N2)(H2O)] (1), [Zn3(O3PCH2CH2COO)2(C12H8N2)](H2O)3.40 (2) and [Zn5(HO3PCH2CH2COO)2(O3PCH2CH2COO)2(C12H8N2)4](H2O)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 (P21/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.

  1. Organic carboxylate ligands tuned structural variations of two new Cd(II) coordination polymers: From 2D layer to 3D framework

    NASA Astrophysics Data System (ADS)

    Lv, Chang-Wei; Li, Jing; Liu, Yan-Wu; Li, Xia; Yuan, Zhi

    2015-11-01

    Two new Cd(II) coordination polymers, namely [Cd(4,4‧-sdb) (biimpy)]n·1.5n(H2O) (1) and [Cd2(Htci)2(biimpy)2]n (2) (4,4‧-H2sdb = 4,4‧-sulfonyldibenzoate, H3tci = tri(2-carboxyethyl)isocyanurate and biimpy = 2,6-bis(1-imdazoly)pyridine), have been synthesized by the hydrothermal reactions of Cd(NO3)2 and the mixed ligands of 4,4‧-H2sdb and biimpy or H3tci and biimpy. Single crystal X-ray structural analyses reveal that compound 1 features a 2D layered structure with 3-connected topology, and compound 2 features a 3D framework with 6-connected 6T8 topology. In addition, the thermal stabilities and luminescent properties of compounds 1 and 2 were also investigated.

  2. A Step-by-Step Assembly of a 3D Coordination Polymer in the Solid-State by Desolvation and [2+2] Cycloaddition Reactions.

    PubMed

    Medishetty, Raghavender; Tandiana, Rika; Wu, Jien; Bai, Zhaozhi; Du, Yonghua; Vittal, Jagadese J

    2015-08-17

    Two solid-state structural transformations that occur in a stepwise and a controlled manner are described. A combination of desolvation and cycloaddition reactions has been employed to synthesise a 3D coordination polymer (CP) from 1D CP [Cd(bdc)(4-spy)2 (H2 O)]⋅2 H2 O⋅2 DMF (bdc=1,4-benzenedicarboxylate, 4-spy=4-styrylpyridine) presumably via a 2D layered structure, [Cd2 (bdc)2 (4-spy)4 ]. In the absence of single crystals to follow the course of the photocycloaddition reaction, thermogravimetry, XAFS and NOESY NMR experiments were used to propose the formation of layered and pillared layered structures. Further, the present strategy enables us to synthesise new multidimensional architectures that are otherwise inaccessible by the self-assembly process. PMID:26150356

  3. 3D-patterned polymer brush surfaces

    NASA Astrophysics Data System (ADS)

    Zhou, Xuechang; Liu, Xuqing; Xie, Zhuang; Zheng, Zijian

    2011-12-01

    Polymer brush-based three-dimensional (3D) structures are emerging as a powerful platform to engineer a surface by providing abundant spatially distributed chemical and physical properties. In this feature article, we aim to give a summary of the recent progress on the fabrication of 3D structures with polymer brushes, with a particular focus on the micro- and nanoscale. We start with a brief introduction on polymer brushes and the challenges to prepare their 3D structures. Then, we highlight the recent advances of the fabrication approaches on the basis of traditional polymerization time and grafting density strategies, and a recently developed feature density strategy. Finally, we provide some perspective outlooks on the future directions of engineering the 3D structures with polymer brushes.

  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

    2010-12-01

    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. PMID:21028781

  5. [Synthesis, crystal structure and spectral properties study of a 3D netlike coordination polymer [Zn(HBIDC) x H2O]n].

    PubMed

    Dong, Yu-Wei; Fan, Rui-Qing; Wang, Ping; Wang, Li-Yuan; Yang, Yu-Lin

    2013-02-01

    The 3D netlike coordination polymer of Zn II with benzimidazole-5,6-dicarboxylic acid (H3BIDC), [Zn(HBIDC) x H2O]n was synthesized by the hydrothermal method through self-assembling. The crystal structure of complex 1 was characterized by single-crystal X-ray diffraction, elemental analysis and IR spectra, and we also studied the fluorescence properties of complex 1 in DMSO and in the solid state with UV-Vis absorption spectra, fluorescence spectra and fluorescence lifetime. Complex 1 has blue luminescence in solutions of DMSO with emission band at 481 nm; and has blue luminescence in the solid state at room temperature with a strong emission band at 493 nm, and these all can be attributed to the pi* --> pi transition based on the benzimidazole-5,6-dicarboxy acid. The experimental results indicate that complex 1 displays higher fluorescence quantum efficiency and can be used as a potential blue luminescence material. PMID:23697137

  6. Mechanochemical and thermal formation of 1H-benzotriazole coordination polymers and complexes of 3d-transition metals with intriguing dielectric properties.

    PubMed

    Brede, Franziska A; Mühlbach, Friedrich; Sextl, Gerhard; Müller-Buschbaum, Klaus

    2016-07-14

    Liquid-assisted grinding (LAG) reactions have been successfully applied to achieve a series of complexes and coordination polymers based on divalent 3d-transition metal chlorides (TM chlorides) and the aromatic ligand 1H-benzotriazole (BtzH). The obtained substances were investigated via single crystal X-ray, powder X-ray determination and simultaneous DTA/TG analysis as model compounds for structural and chemical influences on their dielectric properties. Depending on the synthesis method, different constitutions and structures are observed. Two polymorphous forms of the 1D polymer [MnCl2(BtzH)2] (1 and 2) as well as the complexes [ZnCl2(BtzH)2]·BtzH (3) and [CoCl2(BtzH)2]·BtzH (4) have been obtained as phase-pure bulk substances via the mechanochemical LAG route, and even single crystals are available. For comparison, thermal reactions were also carried out and have led to the formation of the neutral complexes: [CoCl2(BtzH)2] (5) and [CoCl2(BtzH)4]·4BtzH (6), [ZnCl2(BtzH)2] (7) and the anionic complex BtzH2[CoCl3BtzH] (8). In addition, thermal treatment of 3 yields the benzotriazolium salt {(BtzH)2H}Cl (9). The transition metal compounds were additionally analysed regarding their dielectric properties by frequency-dependent as well as temperature-dependent permittivity investigations. It is intriguing that compounds 1 and 3 show remarkably low dielectric constants and loss factors up to 50 °C highlighting them as potential "low-k materials". PMID:27265300

  7. 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

  8. Mechanochemical Synthesis of 3d Transition-Metal-1,2,4-Triazole Complexes as Precursors for Microwave-Assisted and Thermal Conversion to Coordination Polymers with a High Influence on the Dielectric Properties.

    PubMed

    Brede, Franziska A; Heine, Johanna; Sextl, Gerhard; Müller-Buschbaum, Klaus

    2016-02-01

    The complexes [MCl2 (TzH)4 ] (M=Mn (1), Fe (2); TzH=1,2,4-1H-triazole) and [ZnCl2 (TzH)2 ] (3) have been obtained by mechanochemical reactions of the corresponding divalent metal chloride and 1,2,4-1H-triazole. They were successfully used as precursors for the formation of coordination polymers either by a microwave-assisted reaction or by thermal conversion. For manganese, the conversion directly yielded 1∞ [MnCl2 TzH] (4), whereas for the iron-containing precursor, 1∞ [FeCl2 TzH] (6), was formed via the intermediate coordination polymer 1∞ [FeCl(TzH)2 ]Cl (5). For cobalt, the isotypic polymer 1∞ [CoCl(TzH)2 ]Cl (7) was obtained, but exclusively by a microwave-induced reaction directly from CoCl2 . The crystal structures were resolved from single crystals and powders. The dielectric properties were determined and revealed large differences in permittivity between the precursor complexes and the rigid chain-like coordination polymers. Whereas the monomeric complexes exhibit very different dielectric behaviour, depending on the transition metal, from "low-k" to "high-k" with the permittivity ranging from 4.3 to >100 for frequencies of up to 1000 Hz, the coordination polymers and complexes with strong intermolecular interactions are all close to "low-k" materials with very low dielectric constants up to 50 °C. Therefore, the conversion procedures can be used to deliberately influence the dielectric properties from complex to polymer and for different 3d transition-metal ions. PMID:26797710

  9. 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. PMID:27167720

  10. 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. PMID:26811117

  11. Balance and coordination after viewing stereoscopic 3D television.

    PubMed

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

    2015-07-01

    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

  12. 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

  13. A novel 3D Cu(I) coordination polymer based on Cu6Br2 and Cu2(CN)2 SBUs: in situ ligand formation and use as a naked-eye colorimetric sensor for NB and 2-NT.

    PubMed

    Song, Jiang-Feng; Li, Yang; Zhou, Rui-Sha; Hu, Tuo-Ping; Wen, Yan-Liang; Shao, Jia; Cui, Xiao-Bing

    2016-01-14

    A novel coordination polymer with the chemical formula [Cu4Br(CN)(mtz)2]n (mtz = 5-methyl tetrazole) (), has been synthesized under solvothermal conditions and characterized by elemental analysis, infrared (IR) spectroscopy, thermal gravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Interestingly, the Cu(i), CN(-) and mtz(-) in compound are all generated from an in situ translation of the original precursors: Cu(2+), acetonitrile and 1-methyl-5-mercapto-1,2,3,4-tetrazole (Hmnt). The in situ ring-to-ring conversion of Hmnt into mtz(-) was found for the first time. Structural analysis reveals that compound is a novel 3D tetrazole-based Cu(i) coordination polymer, containing both metal halide cluster Cu6Br2 and metal pseudohalide cluster Cu2(CN)2 secondary building units (SBUs), which shows an unprecedented (3,6,10)-connected topology. Notably, a pseudo-porphyrin structure with 16-membered rings constructed by four mtz(-) anions and four copper(i) ions was observed in compound . The fluorescence properties of compound were investigated in the solid state and in various solvent emulsions, the results show that compound is a highly sensitive naked-eye colorimetric sensor for NB and 2-NT (NB = nitrobenzene and 2-NT = 2-nitrotoluene). PMID:26600452

  14. 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.

  15. Time Series Analysis of 3D Coordinates Using Nonstochastic Observations

    NASA Astrophysics Data System (ADS)

    Velsink, Hiddo

    2016-03-01

    Adjustment and testing of a combination of stochastic and nonstochastic observations is applied to the deformation analysis of a time series of 3D coordinates. Nonstochastic observations are constant values that are treated as if they were observations. They are used to formulate constraints on the unknown parameters of the adjustment problem. Thus they describe deformation patterns. If deformation is absent, the epochs of the time series are supposed to be related via affine, similarity or congruence transformations. S-basis invariant testing of deformation patterns is treated. The model is experimentally validated by showing the procedure for a point set of 3D coordinates, determined from total station measurements during five epochs. The modelling of two patterns, the movement of just one point in several epochs, and of several points, is shown. Full, rank deficient covariance matrices of the 3D coordinates, resulting from free network adjustments of the total station measurements of each epoch, are used in the analysis.

  16. Measurement system for 3-D foot coordinates and parameters

    NASA Astrophysics Data System (ADS)

    Liu, Guozhong; Li, Yunhui; Wang, Boxiong; Shi, Hui; Luo, Xiuzhi

    2008-12-01

    The 3-D foot-shape measurement system based on laser-line-scanning principle and the model of the measurement system were presented. Errors caused by nonlinearity of CCD cameras and caused by installation can be eliminated by using the global calibration method for CCD cameras, which based on nonlinear coordinate mapping function and the optimized method. A local foot coordinate system is defined with the Pternion and the Acropodion extracted from the boundaries of foot projections. The characteristic points can thus be located and foot parameters be extracted automatically by the local foot coordinate system and the related sections. Foot measurements for about 200 participants were conducted and the measurement results for male and female participants were presented. 3-D foot coordinates and parameters measurement makes it possible to realize custom-made shoe-making and shows great prosperity in shoe design, foot orthopaedic treatment, shoe size standardization, and establishment of a feet database for consumers.

  17. Luminescent lanthanide coordination polymers

    SciTech Connect

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

    1999-12-13

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

  18. 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. PMID:24901707

  19. 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.

  20. 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

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

    The hydrothermal reactions of Cd, Zn, or Cu(II) acetate salts with H 2PHDA and BPP flexible ligands afford three new coordination polymers, including [Cd(PHDA)(BPP)(H 2O)] n(1), [Zn(PHDA)(BPP)] n(2), and [Cu 2(PHDA) 2(BPP)] n(3) (H 2PHDA=1,2-phenylenediacetic acid, BPP=1,3-bis(4-pyridyl)propane). The single-crystal X-ray diffractions reveal that all three complexes feature various metal carboxylate subunits extended further by the BPP ligands to form a diverse range of structures, displaying a remarked structural sensitivity to metal(II) cation. Complex 1 containing PHDA-bridged binuclear cadmium generates 1D double-stranded chain, complex 2 results in 2D→2D interpenetrated (4,4) grids, and complex 3 displays a 3D self-penetrated framework with 4 86 68 rob topology. In addition, fluorescent analyses show that both 1 and 2 exhibit intense blue-violet photoluminescence in the solid state.

  1. 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. PMID:25822669

  2. Cyano-bridged coordination polymer hydrogel-derived Sn-Fe binary oxide nanohybrids with structural diversity: from 3D, 2D, to 2D/1D and enhanced lithium-storage performance.

    PubMed

    Zhang, Weiyu; Zhu, Xiaoshu; Chen, Xuguang; Zhou, Yiming; Tang, Yawen; Ding, Liangxin; Wu, Ping

    2016-05-14

    Metal oxide nanohybrids with uniform dimensions and controlled architectures possess unique compositional and structural superiorities, and thus harbor promising potential for a series of applications in energy, catalysis, and sensing systems. Herein, we propose a facile, general, and scalable cyano-bridged coordination polymer hydrogel-derived thermal-oxidation route for the construction of main-group metal and transition-metal heterometallic oxide nanohybrids with controlled constituents and architectures. The formation of Sn-Fe binary oxide nanohybrids has been demonstrated as an example by using cyano-bridged Sn(iv)-Fe(ii) bimetallic coordination polymer hydrogels (i.e., SnCl4-K4Fe(CN)6 cyanogels, Sn-Fe cyanogels) as precursors. The physicochemical properties of Sn-Fe cyanogels with different Sn/Fe ratios have been systematically examined, and it is found that perfect Sn-Fe cyanogels without unbridged Sn(iv) or Fe(ii) can be formed with Sn/Fe ratios from 2 : 1 to 1 : 2. More importantly, the simple adjustment of Sn/Fe ratios in the Sn-Fe cyanogel precursors can realize flexible dimensional control of the Sn-Fe binary oxide nanohybrids, and 2D/1D SnO2-Fe2O3 hierarchitectures, 2D SnO2-Fe2O3 nanosheets, and 3D SnO2-Fe2O3 networks have been synthesized using the Sn-Fe 1 : 2, Sn-Fe 1 : 1, and Sn-Fe 2 : 1 cyanogels as precursors, respectively. To demonstrate their compositional/structural superiorities and potential applications, the lithium-storage utilization of the Sn-Fe binary oxide nanohybrids has been selected as an objective application, and the nanohybrids exhibit Sn/Fe ratio-dependent lithium-storage performance. As a representative example, the 2D/1D SnO2-Fe2O3 hierarchitectures manifest markedly enhanced Li-storage performance in terms of reversible capacities and cycling stability in comparison with their constituent units, i.e., bare SnO2 nanosheets and Fe2O3 nanorods. The proposed cyanogel-derived thermal-oxidation strategy could

  3. 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. PMID:26766139

  4. Cyano-bridged coordination polymer hydrogel-derived Sn-Fe binary oxide nanohybrids with structural diversity: from 3D, 2D, to 2D/1D and enhanced lithium-storage performance

    NASA Astrophysics Data System (ADS)

    Zhang, Weiyu; Zhu, Xiaoshu; Chen, Xuguang; Zhou, Yiming; Tang, Yawen; Ding, Liangxin; Wu, Ping

    2016-05-01

    Metal oxide nanohybrids with uniform dimensions and controlled architectures possess unique compositional and structural superiorities, and thus harbor promising potential for a series of applications in energy, catalysis, and sensing systems. Herein, we propose a facile, general, and scalable cyano-bridged coordination polymer hydrogel-derived thermal-oxidation route for the construction of main-group metal and transition-metal heterometallic oxide nanohybrids with controlled constituents and architectures. The formation of Sn-Fe binary oxide nanohybrids has been demonstrated as an example by using cyano-bridged Sn(iv)-Fe(ii) bimetallic coordination polymer hydrogels (i.e., SnCl4-K4Fe(CN)6 cyanogels, Sn-Fe cyanogels) as precursors. The physicochemical properties of Sn-Fe cyanogels with different Sn/Fe ratios have been systematically examined, and it is found that perfect Sn-Fe cyanogels without unbridged Sn(iv) or Fe(ii) can be formed with Sn/Fe ratios from 2 : 1 to 1 : 2. More importantly, the simple adjustment of Sn/Fe ratios in the Sn-Fe cyanogel precursors can realize flexible dimensional control of the Sn-Fe binary oxide nanohybrids, and 2D/1D SnO2-Fe2O3 hierarchitectures, 2D SnO2-Fe2O3 nanosheets, and 3D SnO2-Fe2O3 networks have been synthesized using the Sn-Fe 1 : 2, Sn-Fe 1 : 1, and Sn-Fe 2 : 1 cyanogels as precursors, respectively. To demonstrate their compositional/structural superiorities and potential applications, the lithium-storage utilization of the Sn-Fe binary oxide nanohybrids has been selected as an objective application, and the nanohybrids exhibit Sn/Fe ratio-dependent lithium-storage performance. As a representative example, the 2D/1D SnO2-Fe2O3 hierarchitectures manifest markedly enhanced Li-storage performance in terms of reversible capacities and cycling stability in comparison with their constituent units, i.e., bare SnO2 nanosheets and Fe2O3 nanorods. The proposed cyanogel-derived thermal-oxidation strategy could open up new

  5. Magnetic order in a novel 3D oxalate-based coordination polymer {[Cu(bpy)3][Mn2(C2O4)3]·H2O}n.

    PubMed

    Jurić, Marijana; Pajić, Damir; Žilić, Dijana; Rakvin, Boris; Molčanov, Krešimir; Popović, Jasminka

    2015-12-21

    A heterometallic coordination polymer {[Cu(bpy)3][Mn2(C2O4)3]·H2O}n (1; bpy = 2,2'-bipyridine) was synthesized using a building-block approach and characterized by IR spectroscopy, single-crystal X-ray diffraction, magnetization measurement, and X-band ESR spectroscopy both on a single crystal and a polycrystalline sample. The molecular structure of 1 is made of a three-dimensional (3D) anionic network [Mn2(C2O4)3]n(2n-) and tris-chelated cations [Cu(bpy)3](2+) occupying the vacancies of the framework. In compound 1 magnetic order is confirmed below 12.8 K - magnetization measurements reveal an antiferromagnetic-like network of canted Mn(2+) spins with incorporated paramagnetic Cu(2+) centres. The ESR spectroscopy distinctly shows the phase transition; above T≈ 13 K, single isotropic Lorentzian lines of Mn(2+) ions in the high spin state S = 5/2 were observed, while below this temperature, only characteristic Cu(2+) signals from cations were detected. Thermal decomposition residues of 1 at different temperatures (800-1000 °C) were analyzed by powder X-ray diffraction; by heating the sample up to 1000 °C the spinel oxide CuMn2O4 [94.1(2) wt%] was formed. From the refined structural parameters, it could be seen that the obtained spinel is characterized by the inversion parameter δ∼ 0.8, and therefore the structural formula at room temperature can be written as (tet)[Cu0.17Mn0.83](oct)[Mn1.17Cu0.83]O4. PMID:26564382

  6. Study on portable optical 3D coordinate measuring system

    NASA Astrophysics Data System (ADS)

    Ren, Tongqun; Zhu, Jigui; Guo, Yinbiao

    2009-05-01

    A portable optical 3D coordinate measuring system based on digital Close Range Photogrammetry (CRP) technology and binocular stereo vision theory is researched. Three ultra-red LED with high stability is set on a hand-hold target to provide measuring feature and establish target coordinate system. Ray intersection based field directional calibrating is done for the intersectant binocular measurement system composed of two cameras by a reference ruler. The hand-hold target controlled by Bluetooth wireless communication is free moved to implement contact measurement. The position of ceramic contact ball is pre-calibrated accurately. The coordinates of target feature points are obtained by binocular stereo vision model from the stereo images pair taken by cameras. Combining radius compensation for contact ball and residual error correction, object point can be resolved by transfer of axes using target coordinate system as intermediary. This system is suitable for on-field large-scale measurement because of its excellent portability, high precision, wide measuring volume, great adaptability and satisfying automatization. It is tested that the measuring precision is near to +/-0.1mm/m.

  7. Towards 3-D laser nano patterning in polymer optical materials

    NASA Astrophysics Data System (ADS)

    Scully, Patricia J.; Perrie, Walter

    2015-03-01

    Progress towards 3-D subsurface structuring of polymers using femtosecond lasers is presented. Highly localised refractive index changes can be generated deep in transparent optical polymers without pre doping for photosensitisation or post processing by annealing. Understanding the writing conditions surpasses the limitations of materials, dimensions and chemistry, to facilitate unique structures entirely formed by laser-polymeric interactions to overcome materials, dimensional, refractive index and wavelength constraints.. Numerical aperture, fluence, temporal pulselength, wavelength and incident polarisation are important parameters to be considered, in achieving the desired inscription. Non-linear aspects of multiphoton absorption, plasma generation, filamentation and effects of incident polarisation on the writing conditions will be presented.

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

    SciTech Connect

    Peng, Yi-Ru; Chien, Po-Hsiu; Chung, Huey-Ting; Pan, Pei-Yun; Liu, Yen-Hsiang Yang, En-Che

    2014-04-01

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

  9. 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.

  10. Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2',3'-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

    SciTech Connect

    Liu Guocheng; Chen Yongqiang; Wang Xiuli Chen Baokuan; Lin Hongyan

    2009-03-15

    Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H{sub 2}O){sub 2}][Cd(Dpq)(1,8-NDC)].2H{sub 2}O (1), [Cd(Dpq)(1,4-NDC)(H{sub 2}O)] (2), and [Cd(Dpq)(2,6-NDC)] (3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2',3'-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H{sub 2}NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H{sub 2}NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H{sub 2}NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and {pi}-{pi} stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer {pi}-{pi} stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature. - Graphical abstract: Three novel Cd(II) compounds have been synthesized under hydrothermal conditions exhibiting a systematic variation of architecture by the employment of three structurally related naphthalene-dicarboxylate ligands.

  11. The modeling of portable 3D vision coordinate measuring system

    NASA Astrophysics Data System (ADS)

    Liu, Shugui; Huang, Fengshan; Peng, Kai

    2005-02-01

    The portable three-dimensional vision coordinate measuring system, which consists of a light pen, a CCD camera and a laptop computer, can be widely applied in most coordinate measuring fields especially on the industrial spots. On the light pen there are at least three point-shaped light sources (LEDs) acting as the measured control characteristic points and a touch trigger probe with a spherical stylus which is used to contact the point to be measured. The most important character of this system is that three light sources and the probe stylus are aligned in one line with known positions. In building and studying this measuring system, how to construct the system"s mathematical model is the most key problem called perspective of three-collinear-points problem, which is a particular case of perspective of three-points problem (P3P). On the basis of P3P and spatial analytical geometry theory, the system"s mathematical model is established in this paper. What"s more, it is verified that perspective of three-collinear-points problem has a unique solution. And the analytical equations of the measured point"s coordinates are derived by using the system"s mathematical model and the restrict condition that three light sources and the probe stylus are aligned in one line. Finally, the effectiveness of the mathematical model is confirmed by experiments.

  12. 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. PMID:19463569

  13. Arbitrary and Parallel Nanofabrication of 3D Metal Structures with Polymer Brush Resists.

    PubMed

    Chen, Chaojian; Xie, Zhuang; Wei, Xiaoling; Zheng, Zijian

    2015-12-01

    3D polymer brushes are reported for the first time as ideal resists for the alignment-free nanofabrication of complex 3D metal structures with sub-100 nm lateral resolution and sub-10 nm vertical resolution. Since 3D polymer brushes can be serially fabricated in parallel, this method is effective to generate arbitrary 3D metal structures over a large area at a high throughput. PMID:26439441

  14. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

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

    2012-12-04

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

  15. 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.

  16. Structure and emissive properties of heterobimetallic Ln-Au coordination polymers: role of Tb and Eu in non-aurophilic [nBu4N]2[Ln(NO3)4Au(CN)2] versus aurophilic Ln[Au(CN)2]3·3H2O/3D2O chains.

    PubMed

    Ahern, John C; Roberts, Ryan J; Follansbee, Philip; McLaughlin, Jeffrey; Leznoff, Daniel B; Patterson, Howard H

    2014-07-21

    This investigation is focused on comparing photophysical properties between two series of lanthanide-dicyanoaurate coordination polymers that contain and lack aurophilic interactions, respectively. Luminescence and crystallographic studies have been carried out on five different coordination polymer chain frameworks: the non-aurophilic [(n)Bu4N]2[LnxGd1-x(NO3)4Au(CN)2] (Ln = Eu, Tb; x = 0.01, 0.02, 0.04, 0.08) and[(n)Bu4N]2[EuxTb1-x(NO3)4Au(CN)2] (x = 0.25, 0.5, 0.75), as well as the analogous solid-solutions of aurophilic LnxGd1-x[Au(CN)2]3·3H2O and EuxTb1-x[Au(CN)2]3·3H2O. The single-crystal structures of M[Au(CN)2]3 ·3H2O (M = Eu, Gd) are also reported for comparison. In the aurophilic frameworks the close proximity of gold(I) centers on neighboring chains allows for Au-Au interactions to take place that facilitate energy transfer between lanthanides. Terbium- and europium-doped aurophilic frameworks show energy transfer between one of the lanthanide ions and dicyanoaurate centers as observed via luminescence measurements. In the non-aurophilic frameworks the [(n)Bu4N] cations separate the Au-Au chains, thereby preventing interaction between them, and preventing energy transfer. By preparing the aurophilic EuxTb1-x[Au(CN)2]3·3D2O frameworks, it was shown that the O-H vibrational energy in the hydrated (aurophilic) samples can partially quench the Ln signal. PMID:24968022

  17. 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.

  18. 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. PMID:26402320

  19. 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.

  20. 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.

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

    PubMed Central

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

    2016-01-01

    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. PMID:27405443

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

    PubMed

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

    2016-01-01

    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. PMID:27405443

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

    Berg, Mark A.; Darvin, Jason R.

    2016-08-01

    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.

  6. Two photon polymerization lithography for 3D microfabrication of single wall carbon nanotube/polymer composites

    NASA Astrophysics Data System (ADS)

    Ushiba, Shota; Shoji, Satoru; Kuray, Preeya; Masui, Kyoko; Kono, Junichiro; Kawata, Satoshi

    2013-03-01

    Two photon polymerization (TPP) lithography has been established as a powerful tool to develop 3D fine structures of polymer materials, opening up a wide range applications such as micro-electromechanical systems (MEMS). TPP lithography is also promising for 3D micro fabrication of nanocomposites embedded with nanomaterials such as metal nanoparticles. Here, we make use of TPP lithography to fabricate 3D micro structural single wall carbon nanotube (SWCNT)/polymer composites. SWCNTs exhibit remarkable mechanical, electrical, thermal and optical properties, which leads to enhance performances of polymers by loading SWCNTs. SWCNTs were uniformly dispersed in an acrylate UV-curable monomer including a few amounts of photo-initiator and photo-sensitizer. A femtosecond pulsed laser emitting at 780 nm was focused onto the resin, resulting in the photo-polymerization of a nanometric volume of the resin through TPP. By scanning the focus spot three dimensionally, arbitrary 3D structures were created. The spatial resolution of the fabrication was sub-micrometer, and SWCNTs were embedded in the sub-micro sized structures. The fabrication technique enables one to fabricate 3D micro structural SWCNT/polymer composites into desired shapes, and thus the technique should open up the further applications of SWCNT/polymer composites such as micro sized photomechanical actuators.

  7. 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.

  8. Fabrication of 3D metal/polymer microstructures by site-selective metal coating

    NASA Astrophysics Data System (ADS)

    Takeyasu, N.; Tanaka, T.; Kawata, S.

    2008-02-01

    Three-dimensional silver/polymer conjugated microstructures were fabricated by site-selective metal deposition on photopolymer structures in the sub-micrometer scale. Photopolymerizable resins with and without an amide group were independently prepared, and a three-dimensional polymer structure was fabricated with those resins by means of the two-photon-induced photopolymerization technique to confine the photopolymerization to a sub-micrometer volume. Silver was selectively deposited on the surface of the amide-containing polymer parts by electroless plating. This method can provide 3D arbitrary silver/polymer composite microstructures with sub-micrometer resolution.

  9. Motion error analysis of the 3D coordinates of airborne lidar for typical terrains

    NASA Astrophysics Data System (ADS)

    Peng, Tao; Lan, Tian; Ni, Guoqiang

    2013-07-01

    A motion error model of 3D coordinates is established and the impact on coordinate errors caused by the non-ideal movement of the airborne platform is analyzed. The simulation results of the model show that when the lidar system operates at high altitude, the influence on the positioning errors derived from laser point cloud spacing is small. For the model the positioning errors obey simple harmonic vibration whose amplitude envelope gradually reduces with the increase of the vibration frequency. When the vibration period number is larger than 50, the coordinate errors are almost uncorrelated with time. The elevation error is less than the plane error and in the plane the error in the scanning direction is less than the error in the flight direction. Through the analysis of flight test data, the conclusion is verified.

  10. 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

  11. 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. PMID:25046646

  12. 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.

  13. Comparison of clinical bracket point registration with 3D laser scanner and coordinate measuring machine

    PubMed Central

    Nouri, Mahtab; Farzan, Arash; Baghban, Ali Reza Akbarzadeh; Massudi, Reza

    2015-01-01

    OBJECTIVE: The aim of the present study was to assess the diagnostic value of a laser scanner developed to determine the coordinates of clinical bracket points and to compare with the results of a coordinate measuring machine (CMM). METHODS: This diagnostic experimental study was conducted on maxillary and mandibular orthodontic study casts of 18 adults with normal Class I occlusion. First, the coordinates of the bracket points were measured on all casts by a CMM. Then, the three-dimensional coordinates (X, Y, Z) of the bracket points were measured on the same casts by a 3D laser scanner designed at Shahid Beheshti University, Tehran, Iran. The validity and reliability of each system were assessed by means of intraclass correlation coefficient (ICC) and Dahlberg's formula. RESULTS: The difference between the mean dimension and the actual value for the CMM was 0.0066 mm. (95% CI: 69.98340, 69.99140). The mean difference for the laser scanner was 0.107 ± 0.133 mm (95% CI: -0.002, 0.24). In each method, differences were not significant. The ICC comparing the two methods was 0.998 for the X coordinate, and 0.996 for the Y coordinate; the mean difference for coordinates recorded in the entire arch and for each tooth was 0.616 mm. CONCLUSION: The accuracy of clinical bracket point coordinates measured by the laser scanner was equal to that of CMM. The mean difference in measurements was within the range of operator errors. PMID:25741826

  14. Rapid 3D µ-printing of polymer optical whispering-gallery mode resonators.

    PubMed

    Wu, Jushuai; Guo, Xin; Zhang, A Ping; Tam, Hwa-Yaw

    2015-11-16

    A novel microfabrication method for rapid printing of polymer optical whispering-gallery mode (WGM) resonators is presented. A 3D micro-printing technology based on high-speed optical spatial modulator (SLM) and high-power UV light source is developed to fabricate suspended-disk WGM resonator array using SU-8 photoresist. The optical spectral responses of the fabricated polymer WGM resonators were measured with a biconically tapered optical fiber. Experimental results reveal that the demonstrated method is very flexible and time-saving for rapid fabrication of complex polymer WGM resonators. PMID:26698452

  15. Virtual Spring-Based 3D Multi-Agent Group Coordination

    NASA Astrophysics Data System (ADS)

    Daneshvar, Roozbeh; Shih, Liwen

    As future personal vehicles start enjoying the ability to fly, tackling safe transportation coordination can be a tremendous task, far beyond the current challenge on radar screen monitoring of the already saturated air traffic control. Our focus is on the distributed safe-distance coordination among a group of autonomous flying vehicle agents, where each follows its own current straight-line direction in a 3D space with variable speeds. A virtual spring-based model is proposed for the group coordination. Within a specified neighborhood radius, each vehicle forms a virtual connection with each neighbor vehicle by a virtual spring. As the vehicle changes its position, speed and altitude, the total resultant forces on each virtual spring try to maintain zero by moving to the mechanical equilibrium point. The agents then add the simple total virtual spring constraints to their movements to determine their next positions individually. Together, the multi-agent vehicles reach a group behavior, where each of them keeps a minimal safe-distance with others. A new safe behavior thus arises in the group level. With the proposed virtual spring coordination model, the vehicles need no direct communication with each other, require only minimum local processing resources, and the control is completely distributed. New behaviors can now be formulated and studied based on the proposed model, e.g., how a fast driving vehicle can find its way though the crowd by avoiding the other vehicles effortlessly1.

  16. 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. PMID:26529743

  17. Real-time multicamera system for measurement of 3D coordinates by pattern projection

    NASA Astrophysics Data System (ADS)

    Sainov, Ventseslav; Stoykova, Elena; Harizanova, Jana

    2007-06-01

    The report describes a real-time pattern-projection system for measurement of 3D coordinates with simultaneous illumination and recording of four phase-shifted fringe patterns which are projected at four different wavelengths and captured by four synchronized CCD cameras. This technical solution overcomes the main drawback of the temporal phase-shifting profilometry in which the pattern acquisition is made successively in time. The work considers the use of a sinusoidal phase grating as a projection element which is made by analysis of the frequency content of the projected fringes in the Fresnel diffraction zone and by test measurements of relative 3D coordinates that are performed with interferometrically recorded sinusoidal phase gratings on holographic plates. Finally, operation of a four-wavelength profilometric system with four spatially phase-shifted at π/2 sinusoidal phase gratings illuminated with four diode lasers at wavelengths 790 nm, 810 nm, 850 nm and 910 nm is simulated and the systematical error of the profilometric measurement is evaluated.

  18. 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

  19. 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.

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

    PubMed

    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

  1. Transfer printing of 3D hierarchical gold structures using a sequentially imprinted polymer stamp.

    PubMed

    Zhang, Fengxiang; Low, Hong Yee

    2008-10-15

    Complex three-dimensional (3D) hierarchical structures on polymeric materials are fabricated through a process referred to as sequential imprinting. In this work, the sequentially imprinted polystyrene film is used as a soft stamp to replicate hierarchical structures onto gold (Au) films, and the Au structures are then transferred to a substrate by transfer printing at an elevated temperature and pressure. Continuous and isolated 3D structures can be selectively fabricated with the assistance of thermo-mechanical deformation of the polymer stamp. Hierarchical Au structures are achieved without the need for a corresponding three-dimensionally patterned mold. PMID:21832645

  2. 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. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 732-749, 2016. PMID:26482196

  3. 3D printed sensing patches with embedded polymer optical fibre Bragg gratings

    NASA Astrophysics Data System (ADS)

    Zubel, Michal G.; Sugden, Kate; Saez-Rodriguez, D.; Nielsen, K.; Bang, O.

    2016-05-01

    The first demonstration of a polymer optical fibre Bragg grating (POFBG) embedded in a 3-D printed structure is reported. Its cyclic strain performance and temperature characteristics are examined and discussed. The sensing patch has a repeatable strain sensitivity of 0.38 pm/μepsilon. Its temperature behaviour is unstable, with temperature sensitivity values varying between 30-40 pm/°C.

  4. 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.

  5. EB1-recruited microtubule +TIP complexes coordinate protrusion dynamics during 3D epithelial remodeling

    PubMed Central

    Gierke, Sarah; Wittmann, Torsten

    2012-01-01

    SUMMARY Background Epithelial remodeling, in which apical-basal polarized cells switch to a migratory phenotype, plays a central role in development and disease of multicellular organisms. Although dynamic microtubules (MTs) are required for directed migration on flat surfaces, how MT dynamics are controlled or contribute to epithelial remodeling in a more physiological three-dimensional (3D) environment is not understood. We use confocal live cell imaging to analyze MT function and dynamics during 3D epithelial morphogenesis and remodeling of polarized Madin-Darby canine kidney (MDCK) epithelial cells that undergo partial epithelial-to-mesenchymal transition (EMT) in response to hepatocyte growth factor (HGF). Results We find that HGF treatment increases MT growth rate before morphological changes are evident, and that large numbers of MTs grow into HGF-induced cell extensions independent of centrosome reorientation. Using lentivirus-mediated shRNA, we demonstrate that EB1, an adaptor protein that mediates recruitment of numerous other +TIP proteins to growing MT plus ends, is required for this HGF-induced MT reorganization. We further show that protrusion and adhesion dynamics are disorganized, and that vesicular trafficking to the tip of HGF-induced cell extensions is disrupted in EB1-depleted cells. Conclusions We conclude that EB1-mediated interactions with growing MTs are important to coordinate cell shape changes and directed migration into the surrounding extracellular matrix during epithelial remodeling in a physiological 3D environment. In contrast, EB1 is not required for the establishment or maintenance of apical-basal cell polarity, suggesting different functions of +TIPs and MTs in different types of cell polarity. PMID:22483942

  6. Measuring mandibular asymmetry in Class I normal subjects using 3D novel coordinate system

    PubMed Central

    Kheir, Nadia Abou; Kau, Chung How

    2014-01-01

    Introduction: Orthodontic treatment plays a major role in cosmetic dentistry. A harmonious facial balance is normally the end point in comprehensive orthodontic outcomes. In order to achieve this goal, correct diagnosis of asymmetry should be done starting from the outer facial morphology forms and progressively moving to the dental occlusion. The prime importance of measuring mandibular asymmetry is its tremendous effect on the occlusion. Objective: The aim of this study was to measure mandibular asymmetry in a cohort Class I molar relationship comparing right and left sides using new three-dimensions (3D) imaging technique with the aid of 3D software (in vivo 5.2.3 [San Jose, CA]). Materials and Methods: 35 DICOM files were initially collected retrospectively and seven were excluded due to (1) condylar resorption, (2) history of trauma and (3) unclear DICOM file. A new coordinate system was set for the mid-sagittal plane (MSP), Frankfort horizontal plane and frontal plane (FP). Each cone beam computed tomography (CBCT) was appraised using 16 evaluation criteria bilaterally. Five mandibular landmarks were selected: Condylion_R, Gonion_R, Menton, Gonion_L and Condylion_L. Using these points, the mandible was further divided into four parts: (1) Ramus length right side, body of the mandible right side, body of the Ramus left side and Ramus length left side. The angles between each line and the three different planes were acquired in order to compare each line from a 3D aspect. Mean and standard deviation were calculated for the 28 CBCTs. Results: Significant bilateral differences were reported in the angle between the ramus length and MSP and the ramus length and the FP (P < 0.05). Significant lateroanterior shift of the mandibular ramus on the left side in comparison with the right side. Conclusion: Viewing an object using three different angles between the four parts of the mandible and each plane is a valid method to replicate the actual object. PMID:24987596

  7. 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.

  8. Linkage isomerism in coordination polymers.

    PubMed

    Benmansour, Samia; Setifi, Fatima; Triki, Smail; Gómez-García, Carlos J

    2012-02-20

    The use of the recently prepared polynitrile ligand tcnopr3OH(-) ([(NC)(2)CC(OCH(2)CH(2)CH(2)OH)C(CN)(2)](-)) with different salts of Fe(II), Co(II), and Ni(II) has led to a very rare example of linkage isomerism in a coordination chain. These pairs of linkage isomers can be formulated as [M(tcnopr3OH-κN,κO)(2)(H(2)O)(2)]; M = Fe (1), Co (3), and Ni(5) and [M(tcnopr3OH-κN,κN')(2)(H(2)O)(2)]; M = Fe (2), Co (4), and Ni (6). Compounds 1-2, 3-4, and 5-6 are three pairs of linkage isomers since they present the same formula and chain structure and they only differ in the connectivity of the polynitrile ligand bridging the metal ions in the chain: through a N and an O atom (1κN:2κO-isomer) or through two N atoms (1κN:2κN'-isomer). The magnetic properties show, as expected, very similar behaviors for both isomers. PMID:22296602

  9. Developments for 3D gravity and magnetic modeling in spherical coordinates

    NASA Astrophysics Data System (ADS)

    Lane, R. J.; Liang, Q.; Chen, C.; Li, Y.

    2012-12-01

    for improved management of rock property data and to develop methods to better understand how these data can be used to provide constraints for geophysical modeling. GA are also using the opportunities afforded through the DET CRC to improve documentation and standardization of data and model storage and transfer formats so that the tasks of management, discovery and delivery of modeling inputs and results to various users can be simplified and made more efficient. To provide the foundations of integration and analysis of information in a 3D spatial context, GA are utilizing and customizing 3D visualization software using a Virtual Globe application, NASA World Wind. This will permit us to view the spherical coordinate models and other information at global to local scales in a realistic coordinate framework. The various development activities will together play an important role in the on-going effort by GA to add value to large stores of potential field, rock property, and geological information. This will lead to a better understanding of the geology of the Australian region which will be used in a range of applications, including mineral and energy exploration, natural hazard mitigation, and groundwater management.

  10. 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.

  11. Precision polymers and 3D DNA nanostructures: emergent assemblies from new parameter space.

    PubMed

    Serpell, Christopher J; Edwardson, Thomas G W; Chidchob, Pongphak; Carneiro, Karina M M; Sleiman, Hanadi F

    2014-11-01

    Polymer self-assembly and DNA nanotechnology have both proved to be powerful nanoscale techniques. To date, most attempts to merge the fields have been limited to placing linear DNA segments within a polydisperse block copolymer. Here we show that, by using hydrophobic polymers of a precisely predetermined length conjugated to DNA strands, and addressable 3D DNA prisms, we are able to effect the formation of unprecedented monodisperse quantized superstructures. The structure and properties of larger micelles-of-prisms were probed in depth, revealing their ability to participate in controlled release of their constituent nanostructures, and template light-harvesting energy transfer cascades, mediated through both the addressability of DNA and the controlled aggregation of the polymers. PMID:25325677

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  14. 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

  15. 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. PMID:27273436

  16. Design and verification of an ultra-precision 3D-coordinate measuring machine with parallel drives

    NASA Astrophysics Data System (ADS)

    Bos, Edwin; Moers, Ton; van Riel, Martijn

    2015-08-01

    An ultra-precision 3D coordinate measuring machine (CMM), the TriNano N100, has been developed. In our design, the workpiece is mounted on a 3D stage, which is driven by three parallel drives that are mutually orthogonal. The linear drives support the 3D stage using vacuum preloaded (VPL) air bearings, whereby each drive determines the position of the 3D stage along one translation direction only. An exactly constrained design results in highly repeatable machine behavior. Furthermore, the machine complies with the Abbé principle over its full measurement range and the application of parallel drives allows for excellent dynamic behavior. The design allows a 3D measurement uncertainty of 100 nanometers in a measurement range of 200 cubic centimeters. Verification measurements using a Gannen XP 3D tactile probing system on a spherical artifact show a standard deviation in single point repeatability of around 2 nm in each direction.

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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

    2016-01-01

    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

  3. 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. PMID:26471940

  4. 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

  5. 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.

  6. In vitro and in vivo biocompatibility study on laser 3D microstructurable polymers

    NASA Astrophysics Data System (ADS)

    Malinauskas, Mangirdas; Baltriukiene, Daiva; Kraniauskas, Antanas; Danilevicius, Paulius; Jarasiene, Rasa; Sirmenis, Raimondas; Zukauskas, Albertas; Balciunas, Evaldas; Purlys, Vytautas; Gadonas, Roaldas; Bukelskiene, Virginija; Sirvydis, Vytautas; Piskarskas, Algis

    2012-09-01

    Films and microstructured scaffolds have been fabricated using direct laser writing out of different polymers: hybrid organic-inorganic ORMOCORE b59, acrylate-based AKRE23, novel organic-inorganic Zr containing hybrid SZ2080, and biodegradable PEG-DA-258. Adult myogenic stem cells were grown on these surfaces in vitro. Their adhesion, growth, and viability test results suggest good potential applicability of the materials in biomedical practice. Pieces of these polymers were implanted in rat's paravertebral back tissue. Histological examination of the implants and surrounding tissue ex vivo after 3 weeks of implantation was conducted and results show the materials to be at least as biocompatible as surgical clips or sutures. The applied direct laser writing technique seems to offer good future prospects in a polymeric 3D scaffold design for artificial tissue engineering with autologous stem cells.

  7. 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.

  8. Creeping proteins in microporous structures: polymer brush-assisted fabrication of 3D gradients for tissue engineering.

    PubMed

    Gunnewiek, Michel Klein; Di Luca, Andrea; Bollemaat, Hermannes Z; van Blitterswijk, Clemens A; Vancso, G Julius; Moroni, Lorenzo; Benetti, Edmondo M

    2015-06-01

    Coupling of rapid prototyping techniques and surface-confined polymerizations allows the fabrication of 3D multidirectional gradients of biomolecules within microporous scaffolds. The compositional gradients can be tailored by polymer-brush-assisted diffusion of protein solutions. This technique allows spatial control over stem cells manipulation within 3D environments. PMID:25676461

  9. 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

    2015-01-01

    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

  10. 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

  11. 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.

  12. Inorganic nanoparticles in porous coordination polymers.

    PubMed

    Kim, Cho Rong; Uemura, Takashi; Kitagawa, Susumu

    2016-07-21

    Porous coordination polymers (PCPs) have been recently highlighted because of their high synthetic designability in structure and functions. Because of their ordered nanoporous structures with a large surface area and tunable pore surface functionality, PCPs have emerged as a significant class of nanoporous materials with potential applications in gas storage, separation, catalysis, and chemical sensing. Recent research has shown the utility of PCPs as host materials for the confinement of nanoparticles of inorganic polymers (IPs), such as metals, metal oxides, and metal chalcogenides. The fabrication of IP nanoparticles in PCPs (PCP⊃IP) has been studied for manifesting specific nanosized-dependent properties and host-guest synergistic functions. In this review, we describe the recent progress in the accommodation of IPs in the nanochannels of PCPs and the remarkable functions of the composite materials. PMID:27051891

  13. Plasmon assisted 3D microstructuring of gold nanoparticle-doped polymers

    NASA Astrophysics Data System (ADS)

    Jonušauskas, Linas; Lau, Marcus; Gruber, Peter; Gökce, Bilal; Barcikowski, Stephan; Malinauskas, Mangirdas; Ovsianikov, Aleksandr

    2016-04-01

    3D laser lithography of a negative photopolymer (zirconium/silicon hybrid solgel SZ2080) doped with gold nanoparticles (Au NPs) is performed with a 515 nm and 300 fs laser system and the effect of doping is explored. By varying the laser-generated Au NP doping concentration from 4.8 · 10-6 wt% to 9.8 · 10-3 wt% we find that the fabricated line widths are enlarged by up to 14.8% compared to structures achieved in pure SZ2080. While implicating a positive effect on the photosensitivity, the doping has no adverse impact on the mechanical quality of intricate 3D microstructures produced from the doped nanocompound. Additionally, we found that SZ2080 increases the long term (˜months) colloidal stability of Au NPs in isopropanol. By discussing the nanoparticle-light interaction in the 3D polymer structures we provide implications that our findings might have on other fields, such as biomedicine and photonics.

  14. 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.

  15. 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

    2016-01-01

    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

  16. 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

  17. 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.

  18. Plasmon assisted 3D microstructuring of gold nanoparticle-doped polymers.

    PubMed

    Jonušauskas, Linas; Lau, Marcus; Gruber, Peter; Gökce, Bilal; Barcikowski, Stephan; Malinauskas, Mangirdas; Ovsianikov, Aleksandr

    2016-04-15

    3D laser lithography of a negative photopolymer (zirconium/silicon hybrid solgel SZ2080) doped with gold nanoparticles (Au NPs) is performed with a 515 nm and 300 fs laser system and the effect of doping is explored. By varying the laser-generated Au NP doping concentration from 4.8 · 10(-6) wt% to 9.8 · 10(-3) wt% we find that the fabricated line widths are enlarged by up to 14.8% compared to structures achieved in pure SZ2080. While implicating a positive effect on the photosensitivity, the doping has no adverse impact on the mechanical quality of intricate 3D microstructures produced from the doped nanocompound. Additionally, we found that SZ2080 increases the long term (∼months) colloidal stability of Au NPs in isopropanol. By discussing the nanoparticle-light interaction in the 3D polymer structures we provide implications that our findings might have on other fields, such as biomedicine and photonics. PMID:26925538

  19. 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

    2015-06-01

    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. PMID:26000907

  20. 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.

  1. Permeability modification in 3D porous media due to polymer retention

    NASA Astrophysics Data System (ADS)

    Parsa, Shima; Sizaret, Hubert; Weitz, David

    2015-11-01

    We combine confocal microscopy and bulk transport measurements to quantify the changes in the permeability of a model porous media after flow of a polymer solution. The 3D micromodel is made of closely packed glass beads with diameter of 150 micrometers. By matching the index of refraction of the fluid with beads we are able to measure the fluid velocities at pore level deep in the medium using particle image velocimetry. Our measurement shows that the medium permeability decreases 60% after flow of multiple pore volumes of polymer solution and then flushing with water. At constant flow rate we estimate that the pore velocity increases almost 23% due to this reduction in permeability. Our microscopic measurements of the velocities in pores shows that the average velocity increases considerably more than estimated bulk value. Also the distribution of velocities has a slower decay indicating somewhat higher probability of large velocities in the medium after retention of polymer. These changes in velocities are not uniform and depends on the pore size.

  2. Laser 3D micro/nanofabrication of polymers for tissue engineering applications

    NASA Astrophysics Data System (ADS)

    Danilevičius, P.; Rekštytė, S.; Balčiūnas, E.; Kraniauskas, A.; Širmenis, R.; Baltriukienė, D.; Bukelskienė, V.; Gadonas, R.; Sirvydis, V.; Piskarskas, A.; Malinauskas, M.

    2013-02-01

    In this work, we applied a constructed multi-photon polymerization system based on diode-pumped solid state femtosecond Yb:KGW laser used as pulsed irradiation light source (300 fs, 1030 nm, 200 kHz) in combination with large area high sample translation velocity (up to 300 mm/s) linear motor-driven stages (100×100×50 mm3) designed for high resolution and throughput 3D micro/nanofabrication. It enables rapid prototyping out of most polymers up to cm in scale with sub-micrometer spatial resolution. This can be used for production of three-dimensional artificial polymeric scaffolds applied for cell growth and expansion experiments as well as tissue engineering. Biocompatibilities of different acrylate, hybrid organic-inorganic and biodegradable polymeric materials were evaluated experimentally in vitro. Various in size and form scaffolds of biocompatible photopolymers were successfully fabricated having intricate 3D geometry, thus demonstrating the potential of the applied method. Adult rabbit myogenic stem cell proliferation tests show artificial scaffolds to be applicable for biomedical practice. Additionally, a micromolding technique was used for a rapid multiplication of adequate laser manufactured structures.

  3. On the validity of 3D polymer gel dosimetry: III. MRI-related error sources.

    PubMed

    Vandecasteele, Jan; De Deene, Yves

    2013-01-01

    In MRI (PAGAT) polymer gel dosimetry, there exists some controversy on the validity of 3D dose verifications of clinical treatments. The relative contribution of important sources of uncertainty in MR scanning to the overall accuracy and precision of 3D MRI polymer gel dosimetry is quantified in this study. The performance in terms of signal-to-noise and imaging artefacts was evaluated on three different MR scanners (two 1.5 T and a 3 T scanner). These include: (1) B₀-field inhomogeneity, (2) B₁-field inhomogeneity, (3) dielectric effects (losses and standing waves) and (4) temperature inhomogeneity during scanning. B₀-field inhomogeneities that amount to maximum 5 ppm result in dose deviations of up to 4.3% and deformations of up to 5 pixels. Compensation methods are proposed. B₁-field inhomogeneities were found to induce R₂ variations in large anthropomorphic phantoms both at 1.5 and 3 T. At 1.5 T these effects are mainly caused by the coil geometry resulting in dose deviations of up to 25%. After the correction of the R₂ maps using a heuristic flip angle-R₂ relation, these dose deviations are reduced to 2.4%. At 3 T, the dielectric properties of the gel phantoms are shown to strongly influence B₁-field homogeneity, hence R₂ homogeneity, especially of large anthropomorphic phantoms. The low electrical conductivity of polymer gel dosimeters induces standing wave patterns resulting in dose deviations up to 50%. Increasing the conductivity of the gel by adding NaCl reduces the dose deviation to 25% after which the post-processing is successful in reducing the remaining inhomogeneities caused by the coil geometry to within 2.4%. The measurements are supported by computational modelling of the B₁-field. Finally, temperature fluctuations of 1 °C frequently encountered in clinical MRI scanners result in dose deviations up to 15%. It is illustrated that with adequate temperature stabilization, the dose uncertainty is reduced to within 2.58%. PMID

  4. On the validity of 3D polymer gel dosimetry: III. MRI-related error sources

    NASA Astrophysics Data System (ADS)

    Vandecasteele, Jan; De Deene, Yves

    2013-01-01

    In MRI (PAGAT) polymer gel dosimetry, there exists some controversy on the validity of 3D dose verifications of clinical treatments. The relative contribution of important sources of uncertainty in MR scanning to the overall accuracy and precision of 3D MRI polymer gel dosimetry is quantified in this study. The performance in terms of signal-to-noise and imaging artefacts was evaluated on three different MR scanners (two 1.5 T and a 3 T scanner). These include: (1) B0-field inhomogeneity, (2) B1-field inhomogeneity, (3) dielectric effects (losses and standing waves) and (4) temperature inhomogeneity during scanning. B0-field inhomogeneities that amount to maximum 5 ppm result in dose deviations of up to 4.3% and deformations of up to 5 pixels. Compensation methods are proposed. B1-field inhomogeneities were found to induce R2 variations in large anthropomorphic phantoms both at 1.5 and 3 T. At 1.5 T these effects are mainly caused by the coil geometry resulting in dose deviations of up to 25%. After the correction of the R2 maps using a heuristic flip angle-R2 relation, these dose deviations are reduced to 2.4%. At 3 T, the dielectric properties of the gel phantoms are shown to strongly influence B1-field homogeneity, hence R2 homogeneity, especially of large anthropomorphic phantoms. The low electrical conductivity of polymer gel dosimeters induces standing wave patterns resulting in dose deviations up to 50%. Increasing the conductivity of the gel by adding NaCl reduces the dose deviation to 25% after which the post-processing is successful in reducing the remaining inhomogeneities caused by the coil geometry to within 2.4%. The measurements are supported by computational modelling of the B1-field. Finally, temperature fluctuations of 1 °C frequently encountered in clinical MRI scanners result in dose deviations up to 15%. It is illustrated that with adequate temperature stabilization, the dose uncertainty is reduced to within 2.58%. Both authors contributed

  5. 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.

  6. INS3D: An incompressible Navier-Stokes code in generalized three-dimensional coordinates

    NASA Technical Reports Server (NTRS)

    Rogers, S. E.; Kwak, D.; Chang, J. L. C.

    1987-01-01

    The operation of the INS3D code, which computes steady-state solutions to the incompressible Navier-Stokes equations, is described. The flow solver utilizes a pseudocompressibility approach combined with an approximate factorization scheme. This manual describes key operating features to orient new users. This includes the organization of the code, description of the input parameters, description of each subroutine, and sample problems. Details for more extended operations, including possible code modifications, are given in the appendix.

  7. A reduced-coordinate approach to modeling RNA 3-D structures

    SciTech Connect

    Tung, Chang-Shung

    1997-09-01

    With the realization of RNA molecules capable of performing very specific functions (e.g., catalytic RNAs and RNAs that bind ligand with affinity and specificity of an anti-body) and contrary to the traditional view that structure of RNA molecules being functionally passive, it has become clear that studying the 3-dimensional (3-D) folding of RNA molecules is a very important task. In the absence of sufficient number of experimentally determined RNA structures available up-to-date, folding of RNA structures computationally provides an alternative approach in studying the 3-D structure of RNA molecules. We have developed a computational approach for folding RNA 3-D structures. The method is conceptually simple and general. It consists of two major components. The first being the arrangement of all helices in space. Once the helices are positioned and oriented in space, structures of the connecting loops are modeled and inserted between the helices. Any number of structural constraints derived either experimentally or theoretically can be used to guide the folding processes. A conformational sampling approach is developed with structural equilibration using the Metropolis Monte Carlo simulation. The lengths of various loop sizes (ranging from 1 base to 7 bases) are calculated based on a set of RNA structures deposited in PDB as well as a set of loop structures constructed using our method. The validity of using the averaged loop lengths of the connecting loops as distance constraints for arranging the helices in space is studied.

  8. Effect of polymer brushes on the Self Assembly of 3D Poly(Styrene-Methylmethacrylate) thin films

    NASA Astrophysics Data System (ADS)

    Lwoya, Baraka; Albert, Julie

    2015-03-01

    It would be instrumental to understand the self-assembly capabilities of polymers especially given their industrial capabilities of templating and membrane application .The ability of block copolymers to self assemble into different morphologies is determined by several factor including type of polymer blocks, volume fraction, substrate preference to a polymer and chain architecture . In this paper Poly(Styrene-Methylmethacrylate) (PS-PMMA) was chosen was chosen to further understand the effect polymer brushes on the substrate had on the self assembly of 3D structured PS-PMMA spin coated thin films (30-150 nm). The polymer brushes were grown using surface initiated atomic transfer radical polymerization (SI-ATRP) with the optimal chain length being confirmed by gel permeation chromatography. By using ellipsometer and contact angle measurement the uniformity of the polymer brushes are characterized, while the morphology of the spin coated thin films after thermal annealing would be characterized using atomic force microscopy (AFM).

  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. 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

  11. Proton-Conducting Magnetic Coordination Polymers.

    PubMed

    Biswas, Soumava; Jena, Himanshu Sekhar; Sanda, Suresh; Konar, Sanjit

    2015-09-21

    Three isostructural lanthanide-based two- dimensional coordination polymers (CPs) {[Ln2(L)3(H2O)2]n⋅2n CH3OH)⋅2n H2O} (Ln=Gd(3+) (1), Tb(3+) (2), Dy(3+) (3); H2L=cyclobutane-1,1-dicarboxylic acid) were synthesized by using a low molecular weight dicarboxylate ligand and characterized. Single-crystal structure analysis showed that in complexes 1-3 lanthanide centers are connected by μ3-bridging cyclobutanedicarboxylate ligands along the c axis to form a rod-shaped infinite 1D coordination chain, which is further linked with nearby chains by μ4-connected cyclobutanedicarboxylate ligands to form 2D CPs in the bc plane. Viewing the packing of the complexes down the b axis reveals that the lattice methanol molecules are located in the interlayer space between the adjacent 2D layers and form H-bonds with lattice and coordinated water molecules to form 1D chains. Magnetic properties of complexes 1-3 were thoroughly investigated. Complex 1 exhibits dominant ferromagnetic interaction between two nearby gadolinium centers and also acts as a cryogenic magnetic refrigerant having a significant magnetic entropy change of -ΔSm=32.8 J kg(-1) K(-1) for ΔH=7 T at 4 K (calculated from isothermal magnetization data). Complex 3 shows slow relaxation of magnetization below 10 K. Impedance analysis revealed that the complexes show humidity-dependent proton conductivity (σ=1.5×10(-5) S cm(-1) for 1, σ=2.07×10(-4) S cm(-1) for 2, and σ=1.1×10(-3) S cm(-1) for 3) at elevated temperature (>75 °C). They retain the conductivity for up to 10 h at high temperature and high humidity. Furthermore, the proton conductivity results were correlated with the number of water molecules from the water-vapor adsorption measurements. Water-vapor adsorption studies showed hysteretic and two-step water vapor adsorption (182,000 μL g(-1) for 1, 184,000 μL g(-1) for 2, and 1,874,000 μL g(-1) for 3) in the experimental pressure range. Simulation of

  12. 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. PMID:27007331

  13. Reconstruction Error of Calibration Volume's Coordinates for 3D Swimming Kinematics.

    PubMed

    Figueiredo, Pedro; Machado, Leandro; Vilas-Boas, João Paulo; Fernandes, Ricardo J

    2011-09-01

    The aim of this study was to investigate the accuracy and reliability of above and underwater 3D reconstruction of three calibration volumes with different control points disposal (#1 - on vertical and horizontal rods; #2 - on vertical and horizontal rods and facets; #3 - on crossed horizontal rods). Each calibration volume (3 × 2 × 3 m) was positioned in a 25 m swimming pool (half above and half below the water surface) and recorded with four underwater and two above water synchronised cameras (50 Hz). Reconstruction accuracy was determined calculating the RMS error of twelve validation points. The standard deviation across all digitisation of the same marker was used for assessing the reliability estimation. Comparison among different number of control points showed that the set of 24 points produced the most accurate results. The volume #2 presented higher accuracy (RMS errors: 5.86 and 3.59 mm for x axis, 3.45 and 3.11 mm for y axis and 4.38 and 4.00 mm for z axis, considering under and above water, respectively) and reliability (SD: underwater cameras ± [0.2; 0.6] mm; above water cameras ± [0.2; 0.3] mm) that may be considered suitable for 3D swimming kinematic analysis. Results revealed that RMS error was greater during underwater analysis, possibly due to refraction. PMID:23486761

  14. Reconstruction Error of Calibration Volume’s Coordinates for 3D Swimming Kinematics

    PubMed Central

    Figueiredo, Pedro; Machado, Leandro; Vilas-Boas, João Paulo; Fernandes, Ricardo J.

    2011-01-01

    The aim of this study was to investigate the accuracy and reliability of above and underwater 3D reconstruction of three calibration volumes with different control points disposal (#1 - on vertical and horizontal rods; #2 - on vertical and horizontal rods and facets; #3 - on crossed horizontal rods). Each calibration volume (3 × 2 × 3 m) was positioned in a 25 m swimming pool (half above and half below the water surface) and recorded with four underwater and two above water synchronised cameras (50 Hz). Reconstruction accuracy was determined calculating the RMS error of twelve validation points. The standard deviation across all digitisation of the same marker was used for assessing the reliability estimation. Comparison among different number of control points showed that the set of 24 points produced the most accurate results. The volume #2 presented higher accuracy (RMS errors: 5.86 and 3.59 mm for x axis, 3.45 and 3.11 mm for y axis and 4.38 and 4.00 mm for z axis, considering under and above water, respectively) and reliability (SD: underwater cameras ± [0.2; 0.6] mm; above water cameras ± [0.2; 0.3] mm) that may be considered suitable for 3D swimming kinematic analysis. Results revealed that RMS error was greater during underwater analysis, possibly due to refraction. PMID:23486761

  15. Development of the flow behavior model for 3D scaffold fabrication in the polymer deposition process by a heating method

    NASA Astrophysics Data System (ADS)

    Kim, Jong Young; Park, Jung Kyu; Hahn, Sei Kwang; Kwon, Tai Hun; Cho, Dong-Woo

    2009-10-01

    The flow behavior model for 3D scaffold fabrication in the polymer deposition process by the heating method was developed for enhanced efficiency of the deposition process. The analysis of the polymer flow property is very important in the fabrication process of precise micro-structures such as scaffolds. In this study, a deposition model considering fluid mechanics and heat transfer phenomena was built up and introduced for the estimation of the fluid behavior of molten polymer. The effectiveness of the simulation model was verified through comparison with the experimental result in the case of PCL biomaterial. In addition, the effects of various parameters, such as pressure, temperature and nozzle size, were predicted through simulation before experimental approaches. Through the fabrication of 3D scaffold, it is concluded that this model is useful in predicting the flow behavior characteristics in the micro-structure fabrication process, which is based on the heating method.

  16. The model and its solution's uniqueness of a portable 3D vision coordinate measuring system

    NASA Astrophysics Data System (ADS)

    Huang, Fengshan; Qian, Huifen

    2009-11-01

    The portable three-dimensional vision coordinate measuring system, which consists of a light pen, a CCD camera and a laptop computer, can be widely applied in most coordinate measuring fields especially on the industrial spots. On the light pen there are at least three point-shaped light sources (LEDs) acting as the measured control characteristic points and a touch trigger probe with a spherical stylus which is used to contact the point to be measured. The most important character of this system is that three light sources and the probe stylus are aligned in one line with known positions. In building and studying this measuring system, how to construct the system's mathematical model is the most key problem called Perspective of Three-Collinear-points Problem, which is a particular case of Perspective of Three-points Problem (P3P). On the basis of P3P and spatial analytical geometry theory, the system's mathematical model is established. What's more, it is verified that Perspective of Three-Collinear-points Problem has a unique solution. And the analytical equations of the measured point's coordinates are derived by using the system's mathematical model and the restrict condition that three light sources and the probe stylus are aligned in one line. Finally, the effectiveness of the mathematical model is confirmed by experiments.

  17. 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

  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. A theoretical and experimental study on no-guide light pen type 3D-coordinate measurement system

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaofang; Yu, Xin; Jiang, Chengzhi; Wang, Baoguang

    2003-04-01

    A novel no-guide light pen type 3D-coordinate measurement system with three sets of position sensitive devices (PSDs) to realize intersection converge imaging is introduced. It is called as the light pen type measurement system, because the measuring head is shaped as a pen with several light sources on it. The structure design, measurement principle and experimental results are presented. The theoretical analysis and experimental results prove that this system has advanced features of simple structure, high automation, and high accuracy, and can be used in the measurement fields of mechanical manufacture, robot, auto, aviation and medicine effectively.

  20. The study of dual camera 3D coordinate vision measurement system using a special probe

    NASA Astrophysics Data System (ADS)

    Liu, Shugui; Peng, Kai; Zhang, Xuefei; Zhang, Haifeng; Huang, Fengshan

    2006-11-01

    Due to high precision and convenient operation, the vision coordinate measurement machine with one probe has become the research focus in visual industry. In general such a visual system can be setup conveniently with just one CCD camera and probe. However, the price of the system will surge up too high to accept while the top performance hardware, such as CCD camera, image captured card and etc, have to be applied in the system to obtain the high axis-oriented measurement precision. In this paper, a new dual CCD camera vision coordinate measurement system based on redundancy principle is proposed to achieve high precision by moderate price. Since two CCD cameras are placed with the angle of camera axis like about 90 degrees to build the system, two sub-systems can be built by each CCD camera and the probe. With the help of the probe the inner and outer parameters of camera are first calibrated, the system by use of redundancy technique is set up now. When axis-oriented error is eliminated within the two sub-systems, which is so large and always exits in the single camera system, the high precision measurement is obtained by the system. The result of experiment compared to that from CMM shows that the system proposed is more excellent in stableness and precision with the uncertainty beyond +/-0.1 mm in xyz orient within the distance of 2m using two common CCD cameras.

  1. 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. PMID:26479262

  2. Development of a 3D immersive videogame to improve arm-postural coordination in patients with TBI

    PubMed Central

    2011-01-01

    Background Traumatic brain injury (TBI) disrupts the central and executive mechanisms of arm(s) and postural (trunk and legs) coordination. To address these issues, we developed a 3D immersive videogame-- Octopus. The game was developed using the basic principles of videogame design and previous experience of using videogames for rehabilitation of patients with acquired brain injuries. Unlike many other custom-designed virtual environments, Octopus included an actual gaming component with a system of multiple rewards, making the game challenging, competitive, motivating and fun. Effect of a short-term practice with the Octopus game on arm-postural coordination in patients with TBI was tested. Methods The game was developed using WorldViz Vizard software, integrated with the Qualysis system for motion analysis. Avatars of the participant's hands precisely reproducing the real-time kinematic patterns were synchronized with the simulated environment, presented in the first person 3D view on an 82-inch DLP screen. 13 individuals with mild-to-moderate manifestations of TBI participated in the study. While standing in front of the screen, the participants interacted with a computer-generated environment by popping bubbles blown by the Octopus. The bubbles followed a specific trajectory. Interception of the bubbles with the left or right hand avatar allowed flexible use of the postural segments for balance maintenance and arm transport. All participants practiced ten 90-s gaming trials during a single session, followed by a retention test. Arm-postural coordination was analysed using principal component analysis. Results As a result of the short-term practice, the participants improved in game performance, arm movement time, and precision. Improvements were achieved mostly by adapting efficient arm-postural coordination strategies. Of the 13 participants, 10 showed an immediate increase in arm forward reach and single-leg stance time. Conclusion These results support the

  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. PMID

  4. Calcium phosphate cement reinforcement by polymer infiltration and in situ curing: a method for 3D scaffold reinforcement.

    PubMed

    Alge, Daniel L; Chu, Tien-Min Gabriel

    2010-08-01

    This study describes a novel method of calcium phosphate cement reinforcement based on infiltrating a pre-set cement with a reactive polymer and then cross-linking the polymer in situ. This method can be used to reinforce 3D calcium phosphate cement scaffolds, which we demonstrate using poly(ethylene glycol) diacrylate (PEGDA) as a model reinforcing polymer. The compressive strength of a 3D scaffold comprised of orthogonally intersecting beams was increased from 0.31 +/- 0.06 MPa to 1.65 +/- 0.13 MPa using PEGDA 600. In addition, the mechanical properties of reinforced cement were characterized using three PEGDA molecular weights (200, 400, and 600 Da) and three cement powder to liquid (P/L) ratios (0.8, 1.0, and 1.43). Higher molecular weight increased reinforcement efficacy, and P/L controlled cement porosity and determined the extent of polymer incorporation. Although increasing polymer incorporation resulted in a transition from brittle, cement-like behavior to ductile, polymer-like behavior, maximizing polymer incorporation was not advantageous. Polymerization shrinkage produced microcracks in the cement, which reduced the mechanical properties. The most effective reinforcement was achieved with P/L of 1.43 and PEGDA 600. In this group, flexural strength increased from 0.44 +/- 0.12 MPa to 7.04 +/- 0.51 MPa, maximum displacement from 0.05 +/- 0.01 mm to 1.44 +/- 0.17 mm, and work of fracture from 0.64 +/- 0.10 J/m(2) to 677.96 +/- 70.88 J/m(2) compared to non-reinforced controls. These results demonstrate the effectiveness of our novel reinforcement method, as well as its potential for fabricating reinforced 3D calcium phosphate cement scaffolds useful for bone tissue engineering. PMID:20186776

  5. A note on problems in 3D boundary layer computations in streamline coordinates

    NASA Astrophysics Data System (ADS)

    Scholtysik, M.; Bettelini, M.; Fanneløp, T. K.

    1994-01-01

    Turbulent boundary layers with convergent and divergent external streamlines over a flat plate in the neighbourhood of a plane of symmetry have been computed using a finite-difference method based on streamline coordinates. While the results for the divergent case are generally satisfactory, error growth has been observed for the convergent flowfield. This is most pronounced near the lateral boundary of the computational domain, but also occurs in the plane of symmetry. As an ad-hoc engineering solution, a modified and more restrictive definition of the domain of dependence is proposed, which eliminates the part of the computational domain where the largest error growth occurs. The observed tendency to instability in the convergent case is confirmed by a simplified stability analysis after von Neumann of the uncoupled governing equations.

  6. Vorticity vector-potential method for 3D viscous incompressible flows in time-dependent curvilinear coordinates

    NASA Astrophysics Data System (ADS)

    Chen, Yu; Xie, Xilin

    2016-05-01

    E and Liu [J. Comput. Phys. 138 (1997) 57-82] put forward a finite difference method for 3D viscous incompressible flows in the vorticity-vector potential formulation on non-staggered grids. In this paper, we will extend this method to the case of flows in the presence of a deformable surface. By use of two kinds of surface differential operators, the implementation of boundary conditions on a plane is generalized to a curved smooth surface with given velocity distribution, whether this be an inflow/outflow interface or a curved wall. To deal with the irregular and varying physical domain, time-dependent curvilinear coordinates are constructed and the corresponding tensor analysis is adopted in deriving the component form of the governing equations. Therefore, the equations can be discretized and solved in a regular and fixed parametric domain. Numerical results are presented for a 3D lid-driven cavity with a deforming surface and a 3D duct flow with a deforming boundary. A new way to validate numerical simulations is proposed based on an expression for the rate-of-strain tensor on a deformable surface.

  7. 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. PMID:27049929

  8. 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.

  9. 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.

  10. 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

  11. Coordinated assembly of a new 3D mesoporous Fe₃O₄@Cu₂O-graphene oxide framework as a highly efficient and reusable catalyst for the synthesis of quinoxalines.

    PubMed

    Wang, Zhiyi; Hu, Guowen; Liu, Jian; Liu, Weisheng; Zhang, Haoli; Wang, Baodui

    2015-03-25

    A new three-dimensional (3D) mesoporous hybrid framework was synthesized by coordinated layer-by-layer assembly between nanosheets of reduced graphene oxide and Fe3O4@Cu2O. This 3D mesoporous framework shows an excellent catalytic performance with a remarkable activity, selectivity (>99%), and strong durability in the synthesis of quinoxalines. PMID:25712163

  12. 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.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    Two zinc coordination polymers {[Zn2(TPPBDA)(oba)2]·DMF·1.5H2O}n (1), {[Zn(TPPBDA)1/2(tpdc)]·DMF}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 [Zn2(CO2)4] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn2+. 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.

  15. 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.

  16. 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.

  17. Thermal Conductivity of 3D CNT-Polymer Composites with Controlled Dispersion

    NASA Astrophysics Data System (ADS)

    Klittich, Mena; Wang, Xue; Dhinojwala, Ali

    The high thermal conductivity of isolated carbon nanotubes (CNTs) has inspired its use as a thermal filler for insulative polymers. However, the performance of these composites has consistently been sub par. Extensive analyses of these complex systems have resulted in the conclusion that resistance at the CNT/polymer interface due to phonon mismatch and poor physical binding, as well as the weakly bonded tube-tube interactions restrict the effectiveness of CNTs in practice. Experimental comparisons of CNT treatments, coatings, functionalization, and interactions with various polymers have proved challenging, due to the interconnected nature of the composite properties. Here, we have reversed the paradigm and used a constant CNT structure that is then modified post-growth to allow for direct comparisons of polymer composites.

  18. 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.

  19. A CuII coordination polymer based on incorporated carboxylate and sulfonate groups: Synthesis, crystal structure, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Han, Yinfeng; Zheng, Zebao; Wang, Chang'an; Sun, Jiafeng; Li, Xiaoyan; Zhang, Jianping; Xiao, Jing; He, Guofang; Li, Liqing

    2015-01-01

    A CuII coordination polymer, [Cu(sbpc)(phen)(H2O)]ṡH2O 1, has been synthesized and characterized structurally and magnetically (H2sbpc = 4-sulfobiphenyl-4‧-carboxylic acid, phen = 1,10-phenanthroline). Single-crystal structural analysis shows that 1 consists of dinuclear [Cu2(CO2)2] units bridged via sbpc2- to afford a 1-D chain, which then extends into the 3-D coordination polymer supramolecular network by O-H⋯O hydrogen bonds and π⋯π interactions. Magnetic measurements indicate that complex 1 exhibits weak antiferromagnetic coupling.

  20. 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.

  1. How do monomeric components of a polymer gel dosimeter respond to ionising radiation: A steady-state radiolysis towards preparation of a 3D polymer gel dosimeter

    NASA Astrophysics Data System (ADS)

    Kozicki, Marek

    2011-12-01

    Ionising radiation-induced reactions of aqueous single monomer solutions and mixtures of poly(ethylene glycol) diacrylate (PEGDA) and N, N'-methylenebisacrylamide (Bis) in a steady-state condition are presented below and above gelation doses in order to highlight reactions in irradiated 3D polymer gel dosimeters, which are assigned for radiotherapy dosimetry. Both monomers are shown to undergo radical polymerisation and cross-linking, which result in the measured increase in molecular weight and radius of gyration of the formed polydisperse polymer coils. The formation of nanogels was also observed for Bis solutions at a low concentration. In the case of PEGDA-Bis mixtures, co-polymerisation is suggested as well. At a sufficiently high radiation dose, the formation of a polymer network was observed for both monomers and their mixture. For this reason a sol-gel analysis for PEGDA and Bis was performed gravimetrically and a proposition of an alternative to this method employing a nuclear magnetic resonance technique is made. The two monomers were used for preparation of 3D polymer gel dosimeters having the acronyms PABIG and PABIG nx. The latter is presented for the first time in this work and is a type of the formerly established PABIG polymer gel dosimeter. The elementary characteristics of the new composition are presented, underlining the ease of its preparation, low dose threshold, and slightly increased sensitivity but lower quasi-linear range of dose response in comparison to PABIG.

  2. Direct laser writing of 3D polymer micro/nanostructures on metallic surfaces

    NASA Astrophysics Data System (ADS)

    Rekštytė, Sima; Žukauskas, Albertas; Purlys, Vytautas; Gordienko, Yuri; Malinauskas, Mangirdas

    2013-04-01

    Spectra of fields for applications of polymeric 3D micro/nanostructures are rapidly widening thus demanding the development of versatile precise and efficient fabrication methods that can be used to process a variety of materials and could be implemented to form tiny devices on a variety of surfaces without influencing their structural quality. We present the latest results obtained using laser lithography approach: 3D polymeric structures with submicrometer spatial resolution on different opaque surfaces such as semiconductors (Si) and various metals (Cr, Al, Fe and Ti). The photostructuring was performed using a range of photosensitive materials such as acrylate based AKRE23, acrylated biodegradable PEG-DA-258, epoxy based mr-NIL 6000, hybrid organic-inorganic SZ2080 and Ormocore b59.

  3. 3D Conducting Polymer Platforms for Electrical Control of Protein Conformation and Cellular Functions

    PubMed Central

    Wan, Alwin Ming-Doug; Inal, Sahika; Williams, Tiffany; Wang, Karin; Leleux, Pierre; Estevez, Luis; Giannelis, Emmanuel P.; Fischbach, Claudia; Malliaras, George G.; Gourdon, Delphine

    2015-01-01

    We report the fabrication of three dimensional (3D) macroporous scaffolds made from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) via an ice-templating method. The scaffolds offer tunable pore size and morphology, and are electrochemically active. When a potential is applied to the scaffolds, reversible changes take place in their electrical doping state, which in turn enables precise control over the conformation of adsorbed proteins (e.g., fibronectin). Additionally, the scaffolds support the growth of mouse fibroblasts (3T3-L1) for 7 days, and are able to electrically control cell adhesion and pro-angiogenic capability. These 3D matrix-mimicking platforms offer precise control of protein conformation and major cell functions, over large volumes and long cell culture times. As such, they represent a new tool for biological research with many potential applications in bioelectronics, tissue engineering, and regenerative medicine. PMID:26413300

  4. 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.

  5. Mixing of immiscible polymers using nanoporous coordination templates

    PubMed Central

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

    2015-01-01

    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. PMID:26130294

  6. Mixing of immiscible polymers using nanoporous coordination templates.

    PubMed

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

    2015-01-01

    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. PMID:26130294

  7. An Air-Stable Semiconducting Polymer Containing Dithieno[3,2-b:2',3'-d]arsole.

    PubMed

    Green, Joshua P; Han, Yang; Kilmurray, Rebecca; McLachlan, Martyn A; Anthopoulos, Thomas D; Heeney, Martin

    2016-06-13

    Arsole-containing conjugated polymers are a practically unexplored class of materials despite the high interest in their phosphole analogues. Herein we report the synthesis of the first dithieno[3,2-b;2',3'-d]arsole derivative, and demonstrate that it is stable to ambient oxidation in its +3 oxidation state. A soluble copolymer is obtained by a palladium-catalyzed Stille polymerization and demonstrated to be a p-type semiconductor with promising hole mobility, which was evaluated by field-effect transistor measurements. PMID:27121536

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

    SciTech Connect

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

    2014-02-15

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

  9. 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

  10. 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. PMID:27523573

  11. A Zn based coordination polymer exhibiting long-lasting phosphorescence.

    PubMed

    Cepeda, Javier; Sebastian, Eider San; Padro, Daniel; Rodríguez-Diéguez, Antonio; García, Jose A; Ugalde, Jesus M; Seco, Jose M

    2016-07-01

    A new Zn(ii) based coordination polymer (CP) built by the cohesive pilling of 2D Shubnikov type layers is reported. This material exhibits time dependent multicoloured emission, part of which shows a persistent green phosphorescence visible for up to two seconds to the naked eye, which originates from multiple charge transfer mechanisms. PMID:27297330

  12. Coordination polymer particles as potential drug delivery systems.

    PubMed

    Imaz, Inhar; Rubio-Martínez, Marta; García-Fernández, Lorena; García, Francisca; Ruiz-Molina, Daniel; Hernando, Jordi; Puntes, Victor; Maspoch, Daniel

    2010-07-14

    Micro- and nanoscale coordination polymer particles can be used for encapsulating and delivering drugs. In vitro cancer cell cytotoxicity assays showed that these capsules readily release doxorubicin, which shows anticancer efficacy. The results from this work open up new avenues for metal-organic capsules to be used as potential drug delivery systems. PMID:20485835

  13. Layered structures and nanosheets of pyrimidinethiolate coordination polymers.

    PubMed

    Beldon, P J; Tominaka, S; Singh, P; Saha Dasgupta, T; Bithell, E G; Cheetham, A K

    2014-04-18

    We report the synthesis, crystal structure and exfoliation of a new member of an important family of layered compounds: lamellar pyrimidinethiolate coordination polymers. Conductivity measurements and DFT calculations of iron(II) pyrimidine-2-thiolate show that this material and a related compound are insulators. PMID:24599380

  14. 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.

  15. Guiding-centre and full-Lorentz orbit solving in 3D magnetic coordinates for fast particle simulations

    NASA Astrophysics Data System (ADS)

    Cooper, Wilfred A.; Pfefferle, David; Graves, Jonathan P.

    2014-10-01

    Designed to accurately solve the motion of energetic particles in the presence of 3D magnetic fields, the VENUS-LEVIS code leans on a non-canonical general coordinate Lagrangian formulation of the equations of motion. It switches between full-orbit particle following and guiding-centre tracing by verifying the perpendicular variation of magnetic vector field, not only including gradients and curvature terms but also the shearing of field-lines. The criteria is particularly relevant for the study of fast ion redistribution in the kinked core of hybrid plasmas, where the compression of flux-surfaces against the axisymmetric outer mantle creates strongly varying magnetic field-lines and large parallel currents. Slowing-down simulations of NBI fast ions show that co-passing particles helically align in the opposite side of the plasma deformation whereas counter-passing particles are barely affected by the kinked structure. Results are compared with experimental neutron camera traces and FIDA measurements during long-lived modes (LLM).

  16. 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

  17. Application of liquid crystal polymer films for photolithographic fabrication of 3D structures

    NASA Astrophysics Data System (ADS)

    Fox, Anna E.; Fontecchio, Adam K.

    2008-02-01

    In this paper, we demonstrate a silicon etching application of a holographically formed polymer dispersed liquid crystal (H-PDLC) photomask. H-PDLC is a periodically nanostructured material consisting of stratified layers of polymer and liquid crystal. Due to the natural random alignment of the liquid crystal axes with respect to the polymer layers, an index of refraction mismatch exists and a reflection occurs. Application of bias across the film aligns the liquid crystals and eliminates the index mismatch causing the film to become transparent. H-PDLC films have been shown to sufficiently attenuate the UV exposure dose in the photolithographic process when in the unbiased state, and can be electrically controlled to modulate the amount of UV transmission when electric field is applied. We show etch depth profiles of patterns masked on a silicon substrate using the H-PDLC photomask device compared with etch profiles of similar structures patterned with more conventional ink jet printed photomasks and chrome on quartz glass photomasks. We investigate reactive ion etching technique and potassium hydroxide wet etch technique.

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

    PubMed

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

    2016-06-10

    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 25nm 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 24h 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

  19. Polymer optical devices made by reverse and 3D nanoimprint lithography

    NASA Astrophysics Data System (ADS)

    Kehagias, Nikolaos; Zelsmann, Marc; Sotomayor Torres, Clivia M.

    2005-06-01

    Nanoimprint lithography (NIL), with its apparent simplicity and resolution down to 6 nm, has become an attractive flexible and low-cost technique for nanopatterning of thin films, which themselves act as a mask for further nanofabrication steps, or which can be used as-printed thanks to the functionality of the thin film itself. In this work, we focus on the latter approach and report on our experiments carried out to fabricate organic photonic devices. Silicon stamps, with figures down to 100 nm, are fabricated using electron beam lithography and reactive ion etching. Different fabricated stamps include waveguides, gratings, splitters and interferometers. New fabrication techniques are investigated, namely the combination of NIL with optical lithography and reverse NIL. These two techniques allow producing three-dimensional structures. For the combination of NIL with optical lithography, an original approach is used consisting of a polymer stamp on top of a quartz + metal optical mask. In the case of reverse imprint and multilevel structures, particular attention is paid to adhesion between the stamp, the polymer and the substrate on which the layer is reported. These two techniques are very promising for the fabrication of complex polymer optical devices, like distributed feedback structures, in one step.

  20. Spontaneous wrinkling in azlactone-based functional polymer thin films in 2D and 3D geometries for guided nanopatterning

    SciTech Connect

    Ramanathan, Muruganathan; Lokitz, Bradley S.; Messman, Jamie M.; Stafford, Christopher M.; Kilbey II, S. Michael

    2013-01-01

    We report a simple, one step process for developing wrinkling patterns in azlactone-based polymer thin films and brushes in 2D and 3D surfaces. The polymer used in this work wrinkles spontaneously upon deposition and solidification on a substrate without applying any external strain to the substrate, with the mode of deposition defining the direction of the wrinkles. Wrinkle formation is shown to occur on a variety of substrates over large areas. We also find that a very thin brush-like layer of an azlactone-containing block copolymer also exhibits wrinkled topology. Given the spontaneity and versatility of wrinkle formation, we further demonstrate two proofs-of-concept, i) that these periodic wrinkled structures are not limited to planar surfaces, but are also developed in complex geometries including tubes, cones and other 3D structures; and ii) that this one-step wrinkling process can be used to guide the deposition of metal nanoparticles and quantum dots, creating a periodic, nanopatterned film.

  1. Development of patterned carbon nanotubes on a 3D polymer substrate for the flexible tactile sensor application

    NASA Astrophysics Data System (ADS)

    Hu, Chih-Fan; Su, Wang-Shen; Fang, Weileun

    2011-11-01

    This study reports an improved approach to implement a carbon nanotube (CNT)-based flexible tactile sensor, which is integrated with a flexible print circuit (FPC) connector and is capable of detecting normal and shear forces. The merits of the presented tactile sensor by the integration process are as follows: (1) 3D polymer tactile bump structures are naturally formed by the use of an anisotropically etched silicon mold; (2) planar and 3D distributed CNTs are adopted as piezoresistive sensing elements to enable the detection of shear and normal forces; (3) the processes of patterning CNTs and metal routing can be easily batch fabricated on rigid silicon instead of flexible polymer; (4) robust electrical routing is realized using parylene encapsulation to avoid delamination; (5) patterned CNTs, electrical routing and FPC connector are integrated and transferred to a polydimethylsiloxane (PDMS) substrate by a molding process. In application, the CNT-based flexible tactile sensor and its integration with the FPC connector are implemented. Preliminary tests show the feasibility of detecting both normal and shear forces using the presented flexible sensor.

  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. 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

    2014-05-01

    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. PMID:24936458

  4. 3D Mapping of Polymer Crosslink Density with Magnetic Resonance Imaging

    SciTech Connect

    Herberg, J L; Gjersing, E L; Chinn, S C; Maxwell, R S

    2005-03-11

    Magnetic Resonance Imaging (MRI) techniques have been used to detect areas of low crosslink density in damaged silicone parts in an effort to develop a QA/QC protocol to be used in the development of new parts. Model materials of varying crosslink density first demonstrated the applicability of the method. Analysis of damaged pads has been shown to be clearly distinguishable by MRI. It is our belief that both the T{sub 2} weighted SPI NMR and the T{sub 2} weighted water/fat suppression MRI experiments can be used to map out the location of different cross-linking densities, ultimately determining the quality or homogeneity in polymers.

  5. Polymer conformations in internal (polyspherical) coordinates.

    PubMed

    Pesonen, Janne; Henriksson, Krister O E

    2010-07-15

    The small-amplitude conformational changes in macromolecules can be described by the changes in bond lengths and bond angles. The descriptors of large scale changes are torsions. We present a recursive algorithm, in which a bond vector is explicitly written in terms of these internal, or polyspherical coordinates, in a local frame defined by two other bond vectors and their cross product. Conformations of linear and branched molecules, as well as molecules containing rings can be described in this way. The orientation of the molecule is described by the orientation of a body frame. It is parametrized by the instantaneous rotation angle, and the two angles that parametrize the orientation of the instantaneous rotation axis. The reason not to use more conventional Euler angles is due to the fact that Euler angles are not well-defined in gimbal lock (i.e., when a body axis becomes aligned with its space fixed counter part). The position of the molecule is parametrized by its center of mass. Original and calculated positions are compared for several proteins, containing up to about 100,000 atoms. PMID:20082385

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

    SciTech Connect

    Jin Jing; Han Xiao; Meng Qin; Li Dan; Chi Yuxian; Niu Shuyun

    2013-01-15

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

  7. 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

  8. Structural Diversity of Cadmium(II) Coordination Polymers Induced by Tuning the Coordination Sites of Isomeric Ligands.

    PubMed

    Liu, Bo; Zhou, Hui-Fang; Hou, Lei; Wang, Jian-Ping; Wang, Yao-Yu; Zhu, Zhonghua

    2016-09-01

    When the coordination sites of ligands were shifted, the solvothermal reactions of four positional isomeric asymmetrical pyridyldicarboxylatic acids with Cd(NO3)2 generated four new coordination polymers, [Cd(L1)(DMF)3]·DMF·H2O (1), [H2N(CH3)2]2[Cd(L2)2]·3DMF·H2O (2), [Cd(L3)(H2O)2] (3), and [Cd(L4)]·1.5DMF (4), where DMF = N,N-dimethylformamide, H2L1 = 2-(3'-carboxylphenyl)isonicotinic acid, H2L2 = 2-(4'-carboxylphenyl)isonicotinic acid, H2L3 = 5-(3'-carboxylphenyl)nicotic acid, and H2L4 = 2-(3'-pyridyl)terephthalic acid. 1 shows a rare 2D fabric structure. 2 discloses a grid-layer structure with heterochiral helical chains and in which three sets of layers stack in different directions, affording an unprecedented 2D + 2D + 2D → 3D polycatenating framework with 3D intersecting porous systems. 3 also displays a 2D layer possessing strong intralayer π···π interactions and interlayer hydrogen bonds. 4 contains a rare Cd2(COO)4 paddle-wheel unit and forms a 3D framework with 1D open channels. The carboxyl and pyridyl groups of the positional isomeric H2L1-H2L4 ligands show distinct bridging fashions, which leads to the production of versatile architectures of 1-4, and their effects on the crystal structures are discussed. 1-4 reveal solid-state photoluminescence stemming from intraligand charge transfer. 2 and 4 show high selectivity for CO2 over CH4 but with different CO2 adsorption enthalpies. Grand canonical Monte Carlo simulations identified the multiple adsorption sites in 2 for CO2. PMID:27513092

  9. 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.

  10. 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.

  11. 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.

  12. 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. PMID:27323280

  13. Multi-shape memory polymers achieved by the spatio-assembly of 3D printable thermoplastic building blocks.

    PubMed

    Li, Hongze; Gao, Xiang; Luo, Yingwu

    2016-04-01

    Multi-shape memory polymers were prepared by the macroscale spatio-assembly of building blocks in this work. The building blocks were methyl acrylate-co-styrene (MA-co-St) copolymers, which have the St-block-(St-random-MA)-block-St tri-block chain sequence. This design ensures that their transition temperatures can be adjusted over a wide range by varying the composition of the middle block. The two St blocks at the chain ends can generate a crosslink network in the final device to achieve strong bonding force between building blocks and the shape memory capacity. Due to their thermoplastic properties, 3D printing was employed for the spatio-assembly to build devices. This method is capable of introducing many transition phases into one device and preparing complicated shapes via 3D printing. The device can perform a complex action via a series of shape changes. Besides, this method can avoid the difficult programing of a series of temporary shapes. The control of intermediate temporary shapes was realized via programing the shapes and locations of building blocks in the final device. PMID:26924759

  14. 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.

  15. 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.

  16. Arene Selectivity by a Flexible Coordination Polymer Host.

    PubMed

    Wright, James S; Vitórica-Yrezábal, Iñigo J; Thompson, Stephen P; Brammer, Lee

    2016-09-01

    The coordination polymers [Ag4 (O2 CCF3 )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 (O2 CCF3 )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

  17. 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. PMID:27215535

  18. Surface-based matching of 3D point clouds with variable coordinates in source and target system

    NASA Astrophysics Data System (ADS)

    Ge, Xuming; Wunderlich, Thomas

    2016-01-01

    The automatic co-registration of point clouds, representing three-dimensional (3D) surfaces, is an important technique in 3D reconstruction and is widely applied in many different disciplines. An alternative approach is proposed here that estimates the transformation parameters of one or more 3D search surfaces with respect to a 3D template surface. The approach uses the nonlinear Gauss-Helmert model, minimizing the quadratically constrained least squares problem. This approach has the ability to match arbitrarily oriented 3D surfaces captured from a number of different sensors, on different time-scales and at different resolutions. In addition to the 3D surface-matching paths, the mathematical model allows the precision of the point clouds to be assessed after adjustment. The error behavior of surfaces can also be investigated based on the proposed approach. Some practical examples are presented and the results are compared with the iterative closest point and the linear least-squares approaches to demonstrate the performance and benefits of the proposed technique.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    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.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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05912g

  20. Construction of 3D polymer brushes by dip-pen nanodisplacement lithography: understanding the molecular displacement for ultrafine and high-speed patterning.

    PubMed

    Chen, Chaojian; Zhou, Xuechang; Xie, Zhuang; Gao, Tingting; Zheng, Zijian

    2015-02-01

    Dip-pen nanodisplacement lithography (DNL) is a versatile scanning probe-based technique that can be employed for fabricating ultrafine 3D polymer brushes under ambient conditions. Many fundamental studies and applications require the large-area fabrication of 3D structures. However, the fabrication throughput and uniformity are still far from satisfactory. In this work, the molecular displacement mechanism of DNL is elucidated by systematically investigating the synergistic effect of z extension and contact time. The in-depth understanding of molecular displacement results in the successful achievement of ultrafine control of 3D structures and high-speed patterning at the same time. Remarkably, one can prepare arbitrary 3D polymer brushes on a large area (1.3 mm × 1.3 mm), with <5% vertical and lateral size variations, and a patterning speed as much as 200-fold faster than the current state-of-the-art. PMID:25256006

  1. Different dimensional coordination polymers with 4,4'-oxybis(benzoate): Syntheses, structures and properties

    SciTech Connect

    Lun, Huijie; Li, Yamin; Zhang, Xudong; Yang, Jing-He; Xiao, Changyu; Xu, Yanqing; Li, Junrui

    2014-07-01

    Five transition-metal coordination polymers, namely, [Zn{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (1), [Cd{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (2), [Zn(oba)(H{sub 2}O)]{sub n} (3), [Ag{sub 2}(oba)]{sub n} (4) and [Co(oba)(H{sub 2}O){sub 2}]{sub n} (5) (H{sub 2}oba=4,4′-oxydibenzoic acid), have been achieved under hydrothermal conditions 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 isomorphism, featuring pillared-layer 3D motifs, in which the 2D inorganic layers (Zn{sub 6}Cl{sub 7}){sub n} (or (Cd{sub 6}Cl{sub 7}){sub n}) are connected by oba{sup 2−} pillars. Compound 3 exhibits 1D stair-like chain and extends to a 3D network by two different interchain O–H–O hydrogen bonding interactions while compound 4 features wave chains and stretches to 2D layer by interchain Ag–O weak contacts. Compound 5 shows 2D network in which Co-chains are pillared by oba{sup 2−} ligand and then forms a 3D network by four different O–H–O hydrogen bonding interactions. Furthermore, 1–4 exhibit luminescent properties at a solid state and 5 shows antiferromagnetic behavior. - Graphical abstract: Five new transition-metal coordination complexes 1–5 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses (TGA), photoluminescent spectra and magnetic measurement. - Highlights: • Compound 1 exhibits a pillared-layer 3D network. • The photoluminescent properties of 1–4 have been measured. • Compound 5 exhibits antiferromagnetic behavior.

  2. Syntheses, structures, and photoluminescence of three-dimensional lanthanide coordination polymers with 2,5-pyridinedicarboxylic acid

    SciTech Connect

    Huang Yan; Song Yishan; Yan, Bing Shao Min

    2008-08-15

    Four new open-framework coordination polymers of lanthanide 2,5-pyridinedicarboxylates, with the formulas Pr2(pydc){sub 3}(H{sub 2}O){sub 2} (1), Ln(pydc)(Hpydc) (Ln=Tb (2), Er (3), Eu (5)), and Gd(pydc)(nic)(H{sub 2}O) (4) (H{sub 2}pydc=2,5-pyridinedicarboxylic acid, Hnic=nicotinic acid), have been hydrothermally synthesized and four of them (except Eu (5)) have been structurally characterized. Complex 1 consists of two types of ligand-binding modes contributing to link the PrO{sub 7}N(H{sub 2}O) polyhedral chains to three-dimensional (3D) open-framework architecture. Complexes 2 and 3 are isostructural and feature unique 3D cage-like supramolecular frameworks remarkably different from that of 1, owing to the different ligand-bridging pattern. Complex 4, however, has the distinct 3D open-framework architecture due to the presence of unexpected nicotinate ligands, which may be derived from pydc ligands via in-situ decarboxylation under the hydrothermal condition. - Graphical abstract: Four new lanthanide coordination polymers have been hydrothermally synthesized by the reaction of 2,5-pyridinedicarboxylic acid with the corresponding lanthanide nitrates, and they show three types of 3D open-framework architecture. Complexes 2 and 5 show strong characteristic green (or red) luminescence and long lifetimes.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    Four Co(II) coordination polymers, [Co(suc)]n1, [Co(pdc)]n2, {[Co7(suc)4(OH)6(H2O)3] · 8H2O}n3, {[Co(bdc)(phen)(H2O)] · H2O}n4 (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 suc2- and pdc2- anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc2- anions bridging seven-nuclear [Co7(OH)6(H2O)3]3- unit and polymer 4 is a 1D structure bridged by bdc2- 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.

  4. 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. PMID:25280332

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

    SciTech Connect

    Guo Yuanyuan; Ma Pengtao; Wang Jingping; Niu Jingyang

    2011-11-15

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

  6. Comparison of anatomic coordinate systems with rigid multi-resolution 3D registration for the reproducible positioning of analysis volumes of interest in QCT

    NASA Astrophysics Data System (ADS)

    Eisa, Fabian; Museyko, Oleg; Hess, Andreas; Kalender, Willi A.; Engelke, Klaus

    2010-03-01

    In this study we compared two approaches that have recently been used to minimize precision errors in 3D quantitative computed tomography (QCT) images of the hip and the spine in order to optimize the detection of longitudinal changes in bone mineral density (BMD). In 30 subjects we obtained baseline and 1 year follow-up 3D CT scans of the proximal femur and the spine. QCT analysis was applied to a variety of volumes of interest (VOIs) automatically positioned relative to anatomic coordinate systems (ACS). In the first approach (A1) baseline and follow-up scans were analyzed independently. In the second approach (A2) a 3D versor-based rigid intensity registration method was applied to match baseline and follow-up images, and the baseline ACS was mapped on the follow-up image using the registration transformation. Afterwards, the analysis VOIs were again independently calculated for baseline and follow-up images. There were no significant differences of percent BMD changes between baseline and follow-up images between A1 and A2 for any of the VOIs investigated. With advanced image processing methods a time-consuming 3D registration between baseline and follow-up images before the analysis does not improve analysis precision compared to the use of anatomical coordinate systems.

  7. The coordination chemistry and magnetism of some 3d-4f and 4f amino-polyalcohol compounds.

    PubMed

    Sharples, Joseph W; Collison, David

    2014-02-01

    Triethanolamine, teaH3, and diethanolamine, RdeaH2, 3d-4f and 4f compounds demonstrate an enormous variety in their structure and bonding. This review examines the synthetic strategies to these molecules and their magnetic properties, whilst trying to assess these ligands' suitability towards new SMMs and magnetic refrigerants. PMID:25009361

  8. Microporous coordination polymers as efficient sorbents for air dehumidification.

    PubMed

    Guo, Ping; Wong-Foy, Antek G; Matzger, Adam J

    2014-03-01

    Air drying is a widespread and critical industrial process. Removal of water from air is commonly accomplished by passage through a desiccant such as alumina; modest water capacity and energy intensive regeneration are limitations of currently used sorbents. Microporous coordination polymers (MCPs) are demonstrated here to be efficient desiccants for the dehumidification of air, and a comparison of their capacity, regenerability, and efficiency with commercial activated alumina is conducted. Complete regeneration using dry air with mild heating is achieved. The attainment of high capacity for the adsorption of water coupled to facile regeneration indicates that gas dehumidification may be an important application for MCPs. PMID:24517543

  9. 3D polymer gel dosimetry and Geant4 Monte Carlo characterization of novel needle based X-ray source

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Sozontov, E.; Safronov, V.; Gutman, G.; Strumban, E.; Jiang, Q.; Li, S.

    2010-11-01

    In the recent years, there have been a few attempts to develop a low energy x-ray radiation sources alternative to conventional radioisotopes used in brachytherapy. So far, all efforts have been centered around the intent to design an interstitial miniaturized x-ray tube. Though direct irradiation of tumors looks very promising, the known insertable miniature x-ray tubes have many limitations: (a) difficulties with focusing and steering the electron beam to the target; (b)necessity to cool the target to increase x-ray production efficiency; (c)impracticability to reduce the diameter of the miniaturized x-ray tube below 4mm (the requirement to decrease the diameter of the x-ray tube and the need to have a cooling system for the target have are mutually exclusive); (c) significant limitations in changing shape and energy of the emitted radiation. The specific aim of this study is to demonstrate the feasibility of a new concept for an insertable low-energy needle x-ray device based on simulation with Geant4 Monte Carlo code and to measure the dose rate distribution for low energy (17.5 keV) x-ray radiation with the 3D polymer gel dosimetry.

  10. 3-D solution of flow in an infinite square array of circular tubes by using boundary-fitted coordinate system

    SciTech Connect

    Chen, B.C.J.; Chien, T.H.; Sha, W.T.; Kim, J.H.

    1982-01-01

    Heat transfer and fluid flow over circular tubes have wide applications in the design of heat exchangers and nuclear reactors. However, it is often difficult to accurately calculate the detailed velocity and temperature distributions of the flow because of the complex geometry involved in the analysis, and a lack of an appropriate coordinate system for the analysis. Boundary conditions on the surfaces of the tubes are often interpolated. This interpolation process introduces inaccuracy. To overcome this difficulty, the present study used the technique of the boundary-fitted coordinate system. In this technique, all the physical boundaries are transformed into constant coordinate lines in the transformed coordinates. Therefore, the boundary conditions can be specified on the grid points without interpolation.

  11. 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

  12. 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}.

  13. 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.

  14. 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.

  15. Magnetic Iron Oxide Nanoparticle Seeded Growth of Nucleotide Coordinated Polymers.

    PubMed

    Liang, Hao; Liu, Biwu; Yuan, Qipeng; Liu, Juewen

    2016-06-22

    The introduction of functional molecules to the surface of magnetic iron oxide nanoparticles (NPs) is of critical importance. Most previously reported methods were focused on surface ligand attachment either by physisorption or covalent conjugation, resulting in limited ligand loading capacity. In this work, we report the seeded growth of a nucleotide coordinated polymer shell, which can be considered as a special form of adsorption by forming a complete shell. Among all of the tested metal ions, Fe(3+) is the most efficient for this seeded growth. A diverse range of guest molecules, including small organic dyes, proteins, DNA, and gold NPs, can be encapsulated in the shell. All of these molecules were loaded at a much higher capacity compared to that on the naked iron oxide NP core, confirming the advantage of the coordination polymer (CP) shell. In addition, the CP shell provides better guest protein stability compared to that of simple physisorption while retaining guest activity as confirmed by the entrapped glucose oxidase assay. Use of this system as a peroxidase nanozyme and glucose biosensor was demonstrated, detecting glucose as low as 1.4 μM with excellent stability. This work describes a new way to functionalize inorganic materials with a biocompatible shell. PMID:27248668

  16. A Lamellar Coordination Polymer with Remarkable Catalytic Activity.

    PubMed

    Mendes, Ricardo F; Antunes, Margarida M; Silva, Patrícia; Barbosa, Paula; Figueiredo, Filipe; Linden, Anthony; Rocha, João; Valente, Anabela A; Almeida Paz, Filipe A

    2016-09-01

    A positively charged lamellar coordination polymer based on a flexible triphosphonic acid linker is reported. [Gd(H4 nmp)(H2 O)2 ]Cl⋅2 H2 O (1) [H6 nmp=nitrilotris(methylenephosphonic acid)] was obtained by a one-pot approach by using water as a green solvent and by forcing the inclusion of additional acid sites by employing HCl in the synthesis. Compound 1 acts as a versatile heterogeneous acid catalyst with outstanding activity in organic reactions such as alcoholysis of styrene oxide, acetalization of benzaldehyde and cyclohexanaldehyde and ketalization of cyclohexanone. For all reaction systems, very high conversions were reached (92-97 %) in only 15-30 min under mild conditions (35 °C, atmospheric pressure). The coordination polymer exhibits a protonic conductivity of 1.23×10(-5)  S cm(-1) at 98 % relative humidity and 40 °C. PMID:27505712

  17. 4,4'-Bipyridazine: a new twist for the synthesis of coordination polymers.

    PubMed

    Domasevitch, Konstantin V; Gural'skiy, Il'ya A; Solntsev, Pavlo V; Rusanov, Eduard B; Krautscheid, Harald; Howard, Judith A K; Chernega, Alexander N

    2007-08-01

    A new polydentate ligand 4,4'-bipyridazine (4,4'-bpdz) was prepared by employing inverse electron demand cycloaddition of 1,2,4,5-tetrazine. A unique combination of structural simplicity, ampolydentate character and efficient donor properties towards Cu(I), Cu(II) and Zn(II) provide wide new possibilities for the synthesis of coordination polymers incorporating the 4,4'-bpdz module either as a bi-, tri- or tetradentate connector between the metal ions. 1D coordination polymers Cu(2)(4,4'-bpdz)(CH(3)CO(2))(4) x 4H(2)O and Zn(4,4'-bpdz)(NO(3))(2), and interpenetrated (4,4)-nets in [Cu(4,4'-bpdz)(2)(H(2)O)(2)]S(2)O(6) were closely related to 4,4'-bipyridine compounds. 1D "ladder-like" polymer Cu(2)(4,4'-bpdz)(3)(CF(3)CO(2))(4) and the unprecedented 3D binodal net ({8(6)}{6(3);8(3)}) in [Cu(3)(4,4'-bpdz)(6)(H(2)O)(4)](BF(4))(6) x 6H(2)O were based upon a combination of linear and angular organic bridges. Complex [Cu(3)(OH)(2)(4,4'-bpdz)(3)(H(2)O)(2){CF(3)CO(2)}(2)](CF(3)CO(2))(2) x 2H(2)O has a "NbO-like" 3D topology incorporating discrete dihydroxotricopper(II) clusters linked by tri- and tetradentate ligands. The tetradentate function of the 4,4'-bpdz ligand was especially relevant for copper(I) complexes, which adopt layered Cu(2)X(2)(4,4'-bpdz) (X = Cl, Br) or 3D chiral framework (X = I) structures based upon infinite (CuX)(n) chains. The electron deficient character of the ligand was manifested by short anion-pi interactions (O-pi 3.02-3.20; Cl-pi 3.35 A), which may be involved as a factor for controlling the supramolecular structure. PMID:17637989

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    Two novel coordination polymers, namely, [Ca(NCP)2]∞ (I) and [Sr(NCP)2]∞ (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-)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- which stabilize the frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability.

  19. Ultrasound-assisted fabrication of a new nano-rods 3D copper(II)-organic coordination supramolecular compound.

    PubMed

    Hanifehpour, Younes; Safarifard, Vahid; Morsali, Ali; Mirtamizdoust, Babak; Joo, Sang Woo

    2016-07-01

    High-energy ultrasound irradiation has been used for the synthesis of a new copper(II) coordination supramolecular compound, [Cu2(μ-O2CCH3)2(μ-OOCCH3)(phen)2](BF4) (1), ("phen" is 1,10-phenanthroline) with nano-rods morphology. The new nano-structure was characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. Compound 1 was structurally characterized by single crystal X-ray diffraction. The utilization of high intensity ultrasound has found as a facile, environmentally friendly, and versatile synthetic tool for the supramolecular coordination compounds. PMID:26964941

  20. Cu{sup II} coordination polymers based on 5-methoxyisophthalate and flexible N-donor ligands: Structures and magnetic properties

    SciTech Connect

    Chang, Xin-Hong; Qin, Jian-Hua; Ma, Lu-Fang; Wang, Li-Ya

    2014-04-01

    Three Cu{sup II} coordination polymers, ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib)]){sub n} (1), ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib){sub 2}]){sub n} (2) and ([Cu(CH{sub 3}O-ip)(bbip)]∙2H{sub 2}O){sub n} (3) (CH{sub 3}O-H{sub 2}ip is 5-methoxyisophthalic acid, bmib is 1,4-bis(2-methylimidazol-1-yl)butane and bbip is 1,3-bis(1H-benzimidazolyl)propane), have been synthesized by hydrothermal methods. Complexes 1–3 were structurally characterized by elemental analysis, infrared (IR) spectra and X-ray single-crystal diffraction. Complex 1 shows a 3D six-connected self-penetrating network based on paddlewheel secondary building units. Complex 2 has a 3-fold interpenetrating 3D diamond framework. Complex 3 possesses a 1D tube-like chain. Thermo-gravimetric and magnetic properties of 1–3 were also investigated. - Graphical abstract: Structures and magnetic properties of copper(II) coordination polymers constructed from 5-methoxyisophthalate linker and two flexible N-donor ancillary ligands. Three copper(II) coordination polymers with 5-methoxyisophthalate and two related flexible N-donor ancillary ligands have been synthesized and structurally characterized. Moreover, thermal behaviors and magnetic properties of these complexes have also been investigated. - Highlights: • Three Cu(II) coordination polymers were synthesized. • The conformations of N-donor ligands and pH value have an effect on the final structures. • The magnetic properties of 1–3 have been investigated.

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

    PubMed

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

    2016-06-01

    The effect of pressure on the crystal structure of a coordination polymer, emim[Mn(II)(btc)] (emim = 1-ethyl,3-methyl imidazolium cation, btc = 1,3,5-benzene-tricarboxylate), was investigated with single-crystal X-ray diffraction. At 4.3 GPa the unit-cell volume had decreased by 14% compared with ambient conditions. The unit-cell contraction is highly anisotropic, with the a- and b-axes decreasing by 5.5 and 9.5%, respectively, and the c-axis compressing a mere 0.25% up to 1.7 GPa followed by a 0.2% expansion between 1.7 and 4.3 GPa. The 0.2% increase in length of the c-axis in this interval happens above the quasi-hydrostatic limit of the pressure-transmitting medium and therefore it might be a consequence of strain gradients. Under ambient conditions, two MnO6 units are connected by two carboxylate ligands to form dimeric units. On increasing pressure, a non-bonded O atom from a bridging carboxylate group approaches the Mn atom, with the Mn-O distance decreasing from 2.866 (1) Å at 0.3 GPa to 2.482 (6) Å at 4.3 GPa, increasing the coordination environment of the Mn ion from six- to seven-coordinated. PMID:27240770

  2. New 4,5-dichlorophthalhydrazidate-bridged chained coordination polymers

    NASA Astrophysics Data System (ADS)

    Jin, Juan; Wu, Di; Jia, Ming-Jun; Peng, Yu; Yu, Jie-Hui; Wang, Yu-Chang; Xu, Ji-Qing

    2011-03-01

    The hydrothermal self-assemblies of Pb 2+/Cd 2+ salt, 4,5-dichlorophthalic acid (dcpha), N 2H 4·H 2O together with 1,10-phenanthroline·H 2O (phen) or 2,2'-bipyridine (bpy) generated two new monoacylhydrazidate-bridged 1-D chained coordination polymers [Pb 2(DCPTH) 4(phen) 2] 1 and [Cd 3(DCPTH) 2(dcph) 2(bpy) 2] 2 (DCPTH=4,5-dichlorophthalhydrazidate, dcph=4,5-dichlorophthalate). The monoacylhydrazidate ligand DCPTH originated from the hydrothermal in situ acylation reaction between dcpha and N 2H 4·H 2O. In compound 1, two types of coordination modes for DCPTH are found, which link alternately the Pb(II) centers into a 1-D chain structure of compound 1 with ancillary phen molecules. In compound 2, DCPTH and dcph as the mixed bridges extend the Cd(II) centers into a 1-D chain structure of compound 2 with auxiliary bpy molecules. DCPTH in compound 2 shows a different coordination mode from those observed in compound 1.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Three cadmium coordination polymers, [Cd(bismip)]n (1), {[Cd(bismip)(phen)]·H2O}n (2) and {[Cd2(bismip)2(4,4‧-bipy)]·2H2O}n (3) (H2bismip=5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid, phen=1,10-phenanthroline, 4,4‧-bipy=4,4‧-bipyridine) have been prepared under solvothermal conditions. In 1, the [Cd4(bismip)3] units are jointed by bismip ligands to afford a three-dimensional (3D) architecture. Complex 2 exhibits a 3D supramolecular framework based on the interconnection of 1D chains through hydrogen bonding interactions and π-π packing interactions. 3 is a two-fold interpenetrating 3D architecture with a (4·82)(42·84) Schläfli symbol in which 2D layers are interlinked by 4,4‧-bipy ligands. The diverse structures of compounds 1-3 indicate that the auxiliary ligands have significant effects on the final structures. The photoluminescent properties and photocatalytic properties of these coordination polymers in the solid state were also investigated. Remarkably, 3 shows the wide gap semiconductor nature and exhibit excellent photocatalytic performance.

  6. 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.

  7. 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.

  8. Self-assembly of a unique 3d/4f heterometallic square prismatic box-like coordination cage.

    PubMed

    Li, Li; Zhang, Yingjie; Avdeev, Maxim; Lindoy, Leonard F; Harman, David G; Zheng, Rongkun; Cheng, Zhenxiang; Aldrich-Wright, Janice R; Li, Feng

    2016-06-21

    We present the synthesis and characterization of a unique, slightly distorted square prismatic, box-like coordination cage of type [Cu6Dy8L8(MeOH)8(H2O)6](NO3)12·χsolvent obtained via the supramolecular assembly between a non-centrosymmetric Dy(iii) metalloligand and Cu(ii) nitrate. Magnetic susceptibility measurements indicate that the complex behaves as a single-molecule magnet. PMID:27227419

  9. Five new Mn(II)/Co(II) coordination polymers constructed from flexible multicarboxylate ligands with varying magnetic properties

    SciTech Connect

    Liu, Sui-Jun; Zeng, Yong-Fei; Hu, Xin; Xue, Li; Han, Song-De; Jia, Ji-Min; Hu, Tong-Liang

    2013-08-15

    Five new Mn(II)/Co(II) coordination polymers [Mn{sub 2}(Adi){sub 2}(DMA)]{sub n} (1), [Mn{sub 2}(Adi){sub 2}(DMF)]{sub n} (2), [Mn{sub 4}(Adi){sub 4}(DMF){sub 2}]{sub n} (3), [Co{sub 4}(Adi){sub 4}(DMF){sub 2}]{sub n} (4) and ([Co{sub 3}(Cit){sub 2}(H{sub 2}O){sub 3}]·(H{sub 2}O)){sub n} (5) [Adi=adipate anion, Cit=citrate anion, DMA=N,N′-dimethylacetamide and DMF=N,N′-dimethylformamide] have been successfully constructed from two flexible multicarboxylate ligands under solvothermal conditions. Complexes 1 and 2 exhibit 2-D network featured 1-D Mn{sup II} chain, 3 and 4 are 3-D frameworks containing different 1-D carboxylate–metal chain, while 5 shows a 3-D structure based on Co{sub 6} wheel clusters. Magnetic investigations indicate antiferromagnetic behaviors for 1–4 and weak ferromagnetic behavior for 5 because of distinct linkage modes of metal ions. - Graphical abstract: Five new Mn(II)/Co(II) coordination polymers display 2-D/3-D structures containing 1-D carboxylate–metal chains or wheel clusters. Magnetic analyses reveal that they show antiferromagnetic, canted antiferromagnetic and weak ferromagnetic behaviors, respectively. Highlights: ●Five new Mn(II)/Co(II) coordination polymers have been synthesized. ●A complex-based Co{sub 6} wheel cluster was obtained. ●The different magnetic properties of the complexes are discussed.

  10. Metal dicyanamide layered coordination polymers with cyanopyridine co-ligands: Synthesis, crystal structures and magnetism

    SciTech Connect

    Du Miao . E-mail: dumiao@public.tpt.tj.cn; Wang Qian; Wang Ying; Zhao Xiaojun; Ribas, Joan

    2006-12-15

    A series of metal dicyanamide (dca) coordination polymers combined with cyanopyridine (cypy) terminal co-ligands, namely, [Co{sub 2}(dca){sub 4}(4-cypy){sub 4}] {sub n} (1), [Cd(dca){sub 2}(4-cypy){sub 2}] {sub n} (2), [Fe(dca){sub 2}(3-cypy){sub 2}] {sub n} (3) and [Co(dca){sub 2}(3-cypy){sub 2}] {sub n} (4), have been synthesized at the ambient conditions. X-ray single crystal diffraction reveals that complexes 1-4 have similar metal-dca coordination layers in which the octahedral metal centers are connected by {mu} {sub 1,5}-dca linkers. Notably, three types of 3-D packing lattices are observed for these layered arrays. The thermal stabilities of such new crystalline materials have been studied by thermogravimetric analysis of mass loss. The magnetic properties of the Co{sup II} and Fe{sup II} complexes have been investigated and discussed in detail. A discrete mononuclear molecule [Cd(dca){sub 2}(pyom){sub 2}] (5) is also described, in which the chelated ligand O-methyl picolinimidate (pyom) arises from the addition of methanol solvent across the C{identical_to}N bond of 2-cypy. - Graphical abstract: A series of new metal dicyanamide complexes with cyanopyridine terminal co-ligands have been prepared and structurally determined by X-ray single-crystal diffraction. The magnetic properties of the Co{sup II} and Fe{sup II} layered coordination polymers are also discussed.

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

    SciTech Connect

    Wang, Yansong; Zhou, Zhimin

    2015-08-15

    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, [Co{sub 2}(bpdc){sub 4}(phdat){sub 2}] (1) and [Zn(bpdc)]{sub n} (2) (H{sub 2}bpdc=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 4{sup 4}.6{sup 2} 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. - Graphical abstract: Two polymeric metal compounds based on mixed-ligands were synthesized and characterized. The use of different metal ions results in distinct structures. The magnetic and fluorescent properties were also studied. - Highlights: • The first bpdc{sup 2−}/phdat-based 0D discrete coordination complex. • A new 2D architecture with two kinds of helical chains. • The structure-dependent magnetism and photoluminescence properties.

  12. 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.

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

    PubMed

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

    2015-01-25

    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)3⋅Me3Pb⋅qox]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. PMID:25124847

  14. Synthesis and crystal structures of two nickel coordination polymers generated from asymmetric malate ligand

    SciTech Connect

    Guo Yaqin; Xiao Dongrong; Wang Enbo . E-mail: wangenbo@public.cc.jl.cn; Lu Ying; Lue Jian; Xu Xinxin; Xu Lin

    2005-03-15

    Two nickel coordination polymers [Ni(H{sub 2}O)(C{sub 4}H{sub 4}O{sub 5})].H{sub 2}O 1 and [Ni(H{sub 2}O)(mal)(phen)] 2, have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data for 1: C{sub 4}H{sub 8}O{sub 7}Ni, monoclinic Cc, a=13.156(3)A, b=7.5436(15)A, c=9.6982(19)A, {beta}=130.96(3){sup o}, Z=4. Crystal data for 2: C{sub 16}H{sub 14}N{sub 2}O{sub 6}Ni, orthorhombic Pna2{sub 1}, a=9.6113(19)A, b=19.691(4)A, c=8.0944(16)A, Z=4. Compound 1 is constructed from [Ni(H{sub 2}O)(C{sub 4}H{sub 4}O{sub 5})] sheets pillared through {beta}-carboxylate groups into a 3D framework, which exhibits a diamond-like network. Compound 2 exhibits a 3D supramolecular network. To our knowledge, compound 1 represents the first diamond-like topology in the system of metal-malate. Other characterizations by elemental analysis, IR and TG are also described. The magnetic behavior of compound 1 has been studied.

  15. Unravelling the Proton Conduction Mechanism from Room Temperature to 553 K in a 3D Inorganic Coordination Framework.

    PubMed

    Wang, Yaxing; Tao, Zetian; Yin, Xuemiao; Shu, Jie; Chen, Lanhua; Sheng, Daopeng; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2015-10-19

    The preparation of proton-conducting materials that are functional and stable at intermediate temperatures (393-573 K) is a focal point of fuel cell development. The purely inorganic material, HNd(IO3)4, which possesses a dense 3D framework structure, can reach a maximum of 4.6 × 10(-4) S·cm(-1) at 353 K and 95% relative humidity and exhibit a high conductivity of 8.0 × 10(-5) S·cm(-1) from 373 to 553 K under the flow of wet N2. HNd(IO3)4 exhibits a variety of improvements including high thermal stability, low solubility in water, and resistance to reducing atmosphere. The proton conductivity in such a wide temperature range originates from the intrinsic liberated protons in the structure and the resulting 1D hydrogen-bonding network confirmed by bond valence sum calculation and solid-state NMR analysis. Moreover, two different activation energies are observed in different temperature regions (0.23 eV below 373 K and 0.026 eV from 373 to 553 K), indicating that two types of proton motion are responsible for proton diffusion, as further domenstrated by temperature-dependent open-circuit voltage hysteresis in a tested fuel cell assembly as well as variable-temperature and double quantum filtered solid-state NMR measurements. PMID:26444097

  16. Heterometallic Fe(III) /K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature.

    PubMed

    Kang, Soonchul; Shiota, Yoshihito; Kariyazaki, Akira; Kanegawa, Shinji; Yoshizawa, Kazunari; Sato, Osamu

    2016-01-11

    The anionic Fe(III) complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5-Brthsa)2 ] (5-Brthsa-H2 =5-bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one-step transition in heating mode and a two-step transition in cooling mode. X-ray structure analysis showed that the coexistence of hydrogen bond and cation-π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of Fe(II) spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π-π stacking or hydrogen-bond networks. As a consequence, the importance, or the very good suitability of alkali metal-based coordination bonds and cation-π interactions for communicating cooperative interactions in spin-crossover (SCO) compounds must be reconsidered. PMID:26564335

  17. 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

  18. Three new homochiral coordination polymers involving two three-dimensional structural architectures: Syntheses, structures and magnetic properties

    SciTech Connect

    Chao, Tzu-Ling; Yang, Chen-I.

    2014-03-15

    The preparations and properties of three new homochiral three-dimensional (3D) coordination polymers, [M(D-cam)(pyz)(H{sub 2}O){sub 2}]{sub n} (M=Co (1) and Ni (2); D-H{sub 2}cam=(+) D-camphoric acid; pyz=pyrazine) and [Mn{sub 2}(D-cam){sub 2}(H{sub 2}O){sub 2}] (3), under solvothermal conditions is described. Single-crystal X-ray diffraction analyses revealed that all of compounds are homochiral 3D structure. 1 and 2 are isostructural and crystallize in the trigonal space group P3{sub 2}21, while 3 crystallizes in monoclinic space group P2{sub 1}. The structure of 1 and 2 consists of metal-D-cam helical chains which are pillared with pyrazine ligands into a 3D framework structure and 3 features a 3D homochiral framework involving one-dimensional manganese-carboxylate chains that are aligned parallel to the b axis. Magnetic susceptibility data of all compounds were collected. The findings indicate that μ{sub 2}-pyrazine dominate weak antiferromagnetic coupling within 1 and 2, while 3 exhibits antiferromagnetic behavior through the carboxylate groups of D-cam ligand. -- Graphical abstract: The preparations and properties of three new homochiral three-dimensional (3D) coordination polymers, [M(D-cam)(pyz)(H{sub 2}O){sub 2}]{sub n} (M=Co (1) and Ni (2); D-H{sub 2}cam=(+) D-camphoric acid; pyz=pyrazine) and [Mn{sub 2}(D-cam){sub 2}(H{sub 2}O){sub 2}] (3), under solvothermal conditions is described. Single-crystal X-ray diffraction analyses revealed that all of compounds are homochiral 3D structure. 1 and 2 are isostructural and crystallize in the trigonal space group P3{sub 2}21, while 3 crystallizes in monoclinic space group P2{sub 1}. The structure of 1 and 2 consists of metal-D-cam helical chains which are pillared with pyrazine ligands into a 3D framework structure and 3 features a 3D homochiral framework involving one-dimensional manganese-carboxylate chains that are aligned parallel to the b axis. Magnetic susceptibility data of all compounds were collected. The

  19. pH- and mol-ratio dependent formation of zinc(II) coordination polymers with iminodiacetic acid: Synthesis, spectroscopic, crystal structure and thermal studies

    SciTech Connect

    Ni Lubin; Zhang Ronghua; Liu Qiongxin; Xia Wensheng; Wang Hongxin; Zhou Zhaohui

    2009-10-15

    Three novel zinc coordination polymers (NH{sub 4}){sub n}[Zn(Hida)Cl{sub 2}]{sub n} (1), [Zn(ida)(H{sub 2}O){sub 2}]{sub n} (2), [Zn(Hida){sub 2}]{sub n}.4nH{sub 2}O (3) (H{sub 2}ida=iminodiacetic acid) and a monomeric complex [Zn(ida)(phen)(H{sub 2}O)].2H{sub 2}O (4) (phen=1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction methods. 1 and 2 form one-dimensional (1-D) chain structures, whereas 3 exhibits a three-dimensional (3-D) diamondoid framework with an open channel. The mononuclear complex 4 is extended into a 3-D supramolecular architecture through hydrogen bonds and pi-pi stacking. Interestingly, cyclic nonplanar tetrameric water clusters are observed that encapsulated in the 3-D lattice of 4. Based on {sup 1}H and {sup 13}C NMR observations, there is obvious coordination of complex 2 in solution, while 1 and 3 decompose into free iminodiacetate ligand. Monomer [Zn(ida)(H{sub 2}O){sub 3}] (5) is considered as a possible discrete species from 2. These coordination polymers can serve as good molecular precursors for zinc oxide. - Text3: Reaction of zinc salt with iminodiacetic acid afforded three new coordination polymers 1-3 and a monomer 4, which is dependent on pH value and molar ratio of the reactants.

  20. 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.

  1. A new three-dimensional Zn2 + coordination polymer constructed from oxalate and 1,2,4-triazolate

    NASA Astrophysics Data System (ADS)

    Wang, Yan-Ning; Zhu, Wan-Chun; Huo, Qi-Sheng; Yu, Jie-Hui; Xu, Ji-Qing

    2016-05-01

    A new 3-D Zn2 + coordination polymer (CP) [(CH3)2NH2]3[Zn6(ox)4.5(trz)6]ṡ 4H2O (ox = oxalate; trz = 1,2,4-triazolate) 1 was obtained by a simple solvothermal self-assembly. The crystal structural analysis demonstrates that the trz molecules link the Zn2 + ions into a two-dimensional (2-D) layer network, which is based on the trinuclear Zn3(trz)6 clusters. The ox molecules serve as the linkers to propagate the 2-D layers into a three-dimensional (3-D) network of 1. The thermogravimetry (TG) behavior, photoluminescence property, and the sensing ability of 1 are investigated. The sensing experiment on nitrobenzene (NB) reveals that 1 can serve as a fluorescence probe to detect NB at the ppm concentration.

  2. A new three-dimensional Zn(2+) coordination polymer constructed from oxalate and 1,2,4-triazolate.

    PubMed

    Wang, Yan-Ning; Zhu, Wan-Chun; Huo, Qi-Sheng; Yu, Jie-Hui; Xu, Ji-Qing

    2016-05-15

    A new 3-D Zn(2+) coordination polymer (CP) [(CH3)2NH2]3[Zn6(ox)4.5(trz)6]⋅4H2O (ox=oxalate; trz=1,2,4-triazolate) 1 was obtained by a simple solvothermal self-assembly. The crystal structural analysis demonstrates that the trz molecules link the Zn(2+) ions into a two-dimensional (2-D) layer network, which is based on the trinuclear Zn3(trz)6 clusters. The ox molecules serve as the linkers to propagate the 2-D layers into a three-dimensional (3-D) network of 1. The thermogravimetry (TG) behavior, photoluminescence property, and the sensing ability of 1 are investigated. The sensing experiment on nitrobenzene (NB) reveals that 1 can serve as a fluorescence probe to detect NB at the ppm concentration. PMID:26971022

  3. 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. PMID:27171744

  4. Magnetic and Photochromic Properties of a Manganese(II) Metal-Zwitterionic Coordination Polymer.

    PubMed

    Gong, Teng; Yang, Xiao; Sui, Qi; Qi, Yan; Xi, Fu-Gui; Gao, En-Qing

    2016-01-01

    The solvothermal reaction of Mn(ClO4)2, NaN3, and a rigid viologen-tethered tetracarboxylic acid (1,1'-bis(3,5-dicarboxyphenyl)-4,4'-bipyridinium chloride, [H4L]Cl2) led to a coordination polymer of formula [Mn4(L)(N3)6(H2O)2]n. X-ray analysis revealed a 3D coordination structure. The Mn(II) ions are connected by mixed azide and carboxylate bridges to give 2D layers, which are pillared by the viologen tether of the zwitterionic ligand. Magnetic analyses suggested that the compound features antiferromagnetism and field-induced metamagnetism. The compound also shows photochromic and photomagnetic properties. The long-range magnetic ordering is owed to the spin-canting structure of the Mn(II)-azide-carboxylate layer; the photochromism involves the formation of viologen radicals via photoinduced electron transfer, and the photomagnetism is related to the interactions between the metal ion and the photogenerated radicals. The study demonstrates a strategy for the design of new multifunctional materials with photoresponsive properties. PMID:26671046

  5. 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

  6. Nanoscale coordination polymers exhibiting luminescence properties and NMR relaxivity

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  7. 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. PMID:26999733

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

    PubMed

    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

    2015-07-28

    Cyano-bridged Gd(3+)/[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. PMID:25967733

  9. 3D surface coordinate inspection of formed sheet material parts using optical measurement systems and virtual distortion compensation

    NASA Astrophysics Data System (ADS)

    Weckenmann, Albert A.; Gall, P.; Gabbia, A.

    2005-02-01

    Modern forming technology allows the production of highly sophisticated free form sheet material components, affording great flexibility to the design and manufacturing processes across a wide range of industries. This increased design and manufacturing potential places an ever growing demand on the accompanying inspection metrology. As a consequence of their surface shape, these parts underlie a reversible geometrical deformation caused by variations of the material and the manufacturing process, as well as by gravity. This distortion is removed during the assembly process, usually performed in automated robotic processes. For this reason, the part's tolerated parameters have to be inspected in a defined state, simulating the assembly process' boundary conditions. Thus, the inspection process chain consists of six steps: picking the workpiece up, manual fixation of the workpiece, tactile measurement of the surface's coordinates using a defined measurement strategy, manual removal of the fixation and removal of the workpiece from the inspection area. These steps are both laborious and time consuming (for example, the inspection of a car door can take up to a working day to complete). Using optical measuring systems and virtual distortion compensation, this process chain can be dramatically shortened. Optical measuring systems provide as a measurement result a point cloud representing a sample of all nearest surfaces in the measuring range containing the measurand. From this data, a surface model of the measurand can be determined, independent of its position in the measuring range. For thin sheet material parts an approximating finite element model can be deduced from such a surface model. By means of pattern recognition, assembly relevant features of the measurand can be identified and located on this model. Together with the boundary conditions given by the assembly process, the shape of the surface in its assembled state can be calculated using the finite

  10. Structural Design Parameters for Highly Birefringent Coordination Polymers.

    PubMed

    Thompson, John R; Katz, Michael J; Williams, Vance E; Leznoff, Daniel B

    2015-07-01

    A series of coordination polymer materials incorporating the highly anisotropic 2-(2-pyridyl)-1,10-phenanthroline (phenpy) building block have been synthesized and structurally characterized. M(phenpy)[Au(CN)2]2 (M = Cd, Mn) are isostructural and form a 1-D chain through bridging [Au(CN)2](-) units and extend into a 2-D sheet through aurophilic interactions. M(phenpy)(H2O)[Au(CN)2]2·2H2O (M = Cd, Mn, and Zn) are also isostructural but differ from the first set via the inclusion of a water molecule into the coordination sphere, resulting in a 1-D topology through aurophilic interactions. In(phenpy)(Cl)2[Au(CN)2]·0.5H2O forms a dimer through bridging chlorides and contains a free [Au(CN)2](-) unit. In the plane of the primary crystal growth direction, the birefringence values (Δn) of 0.37(2) (Cd(phenpy)[Au(CN)2]2), 0.50(3) (In(phenpy)(Cl)2[Au(CN)2]·0.5H2O), 0.56(3) and 0.59(6) (M(phenpy)(H2O)[Au(CN)2]2·2H2O M = Cd and Zn, respectively) were determined. β, a structural parameter defined by phenpy units rotated in the A-C plane relative to the light propagation (C) direction, was found to correlate to Δn magnitudes. The addition of a carbon-carbon double bond to terpy has increased the molecular polarizability anisotropy of the building block, and all structures have reduced deviation from planarity in comparison to terpy and terpy derivative structures, leading to these higher Δn values, which are among the highest reported for crystalline solids. PMID:26098267

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

    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 ( L1H2) 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 L1 predominates. The coordination polymers 4 and 5 show photoluminescence in solution. The dicarboxylate of (5-carboxymethoxy-naphthalen-1-yloxy)-acetic acid ( L2H2) 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 1 space group and it shows broadband ultra-violet fluorescence centered at 352.9 nm on focusing 632.8 nm He:Ne laser.

  12. Syntheses, crystal structure and properties of two novel coordination polymers with the flexible tetrazole-1-acetic acid (Htza)

    SciTech Connect

    Dong Wenwen; Zhao Jun; Xu Li

    2008-05-15

    Two new coordination polymers, [Ag(tza)]{sub {infinity}} (1) (Htza=tetrazole-1-acetic acid) and [Cu(tza){sub 2}]{sub {infinity}} (2) have been prepared at room temperature and characterized by X-ray crystallography, IR, UV-vis, fluorescence spectra and magnetism analysis. Compound 1 exhibits extended helical chains through bridging ligand tza. The Ag{center_dot}{center_dot}{center_dot}Ag interactions between the adjacent chains form a 3-D framework featuring the extended tza-connected Ag chains that obviously affect the photoluminescent property. Compound 2 features undulated layered structure with hourglass-shaped [Cu{sub 4}(tza){sub 4}] as subunits with the weak ferromagnetic interactions between Cu(II) ions, which are further stabilized by inter-lamellar C-H{center_dot}{center_dot}{center_dot}O hydrogen bonds in the resulting 3-D supramolecular framework. - Graphical abstract: Two novel coordination polymers, [Ag(tza)]{sub {infinity}} (1) and [Cu(tza){sub 2{infinity}} (2) have been prepared and characterized. Compound 1 features extended double-stranded helical chains. Compound 2 features undulated layered structure with hourglass-shaped [Cu{sub 4}(tza){sub 4}] as subunits with the weak ferromagnetic interactions between Cu(II) ions.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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 63, 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 EuIII, TbIII and DyIII 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 EuIII, TbIII and DyIII complexes can be efficiently sensitized by the ligand.

  14. 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.

  15. Polymer complexes. LX. Supramolecular coordination and structures of N(4-(acrylamido)-2-hydroxybenzoic acid) polymer complexes

    NASA Astrophysics Data System (ADS)

    Ghoneim, M. M.; El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.; Serag, L. S.

    2015-04-01

    A number of novel polymer complexes of various anions of copper(II), cobalt(II), nickel(II) and uranyl(II) with N(4-(acrylamido)-2-hydroxy benzoic acid) (ABH) have been synthesized and characterized by elemental analysis, IR, 1H NMR, magnetic susceptibility measurements, electronic spin resonance, vibrational spectra and thermal analysis. The molecular structures of the ligand are optimized theoretically and the quantum chemical parameters are calculated. Tentative structures for the polymeric metal complexes due to their potential application are also suggested. The IR data exhibit the coordination of ONO2/OAc/SO4 with the metal ions in the polymeric metal complex. Vibrational spectra indicate coordination of carboxylate oxygen and phenolic OH of the ligand giving a MO4 square planar chromophore. Ligand field ESR spectra support square planar geometry around Cu(II). The thermal decomposition of the polymer complexes were discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated applying Coast-Redfern and Horowitz-Metzger methods.

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

    NASA Astrophysics Data System (ADS)

    Li, Meng-Li; Song, Hui-Hua

    2013-10-01

    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)2(H2O)2]·NO3·2H2O}n1, {[Co(acty)(bipy)2(H2O)2]·NO3·2H2O}n2, {[Cd(acty)2(bipy)H2O]·H2O}n3, and {[Cd(acty)(bpe)2(Ac)]·6H2O}n4 (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.

  17. 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

  18. Soluble porous coordination polymers by mechanochemistry: from metal-containing films/membranes to active catalysts for aerobic oxidation.

    PubMed

    Zhang, Pengfei; Li, Haiying; Veith, Gabriel M; Dai, Sheng

    2015-01-14

    Soluble porous coordination polymers from mechanochemical synthesis are presented through a coordination polymerization between highly contorted, rigid tetraphenol and a broad variety of transition metal ions. These polymers can be easily cast as metal-containing films or freestanding membranes. Importantly, as-made coordination polymers are highly active and stable in the aerobic oxidation of allylic C-H bonds. PMID:25389070

  19. 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.

  20. 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.

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

    PubMed Central

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

    2010-01-01

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

  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. 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.

  4. New silver(I) coordination polymers constructed from pyrazine derivatives and aromatic carboxylic acids: Syntheses, structures and photoluminescence

    NASA Astrophysics Data System (ADS)

    Zhang, Ting; Huang, Hua-Qi; Mei, Hong-Xin; Wang, Dan-Feng; Wang, Xiao-Xiang; Huang, Rong-Bin; Zheng, Lan-Sun

    2015-11-01

    Five one-dimensional to three-dimensional coordination polymers have been synthesized by 2-chlorobenzoic acid (HL1), 2-nitrobenzoic acid (HL2), o-toluic acid (HL3), 2,3,5-trimethylpyrazine (tpyz) and 2,3,5,6-tetramethylpyrazine (mpyz) in the presence of NH3·H2O in mixed solvents systems, namely, {Ag4(tpyz)2(L1)4}n (1), {Ag2(tpyz) (L2)2}n (2), {Ag2(tpyz) (L3)2}n (3), {Ag2(mpyz) (L1)2}n (4), {Ag(mpyz) (L2) (H2O)}n (5). All the complexes have been characterized by elemental analyses, IR spectra and X-ray diffraction. Compound 1 shows a 3D framework. The tpyz ligand links 1D chain which was connected by silver atom and L1 anion into 3D framework. Compounds 2 and 4 possess a similar 2D network with (4, 4) topology. Complex 3 also exhibits a two-dimensional structure. There is a 1D silver chain in 3, which is the main difference from 2 and 4. So, 3 shows three-connected (4 8, 3) topology. For 5, only one oxygen of L2 coordinated to Ag(I) ions. The L2 anions were arranged in both sides of the chain, which was connected by silver atoms and mpyz ligands. Then, the uncoordinated carboxylate oxygen with coordinated water 1molecule oxygen through the hydrogen bond made the resultant structure to a 3D framework. Complexes 1-5 spanning from one-dimensional chains to three-dimensional framework suggest that carboxylates and the kinds of pyrazine derivatives play significant roles in the formation of such coordination architectures. The photoluminescence and thermogravimetric analysis (TGA) of the complexes were also investigated.

  5. Two new pyridine-2,3-dicarboxylate coordination polymers prepared from zerovalent metal precursor: Syntheses, luminescent and magnetic properties

    NASA Astrophysics Data System (ADS)

    Semerci, Fatih; Yeşilel, Okan Zafer; Soylu, Mustafa Serkan; Yerli, Yusuf; Dal, Hakan

    2014-02-01

    Two new K+/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), {K2[Cu(μ-pydc)2]·3H2O}n (1) and {[Zn(μ-pydc)(H2O)(4-mim)]·H2O}n (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. In the sandwiched 3D anionic framework of 1, pydc ligands exhibit hexadentate coordination; tridentate coordination bond with Cu(II) and tridentate ionic interaction with K+ ions. {K2[Cu(μ-pydc)2]·3H2O}n shows a rare topology consists of three dimensional (3,4,5)-connected network with the point symbol of {42.6}2{42.84}{43.6.86}2. The distorted square pyramidal geometry of 2 is completed with an nitrogen atom from 4-mim and aqua ligand to form a 1D polynuclear structure. The hydrogen bonds link the 1D chains into 3D architecture. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin; Luan, Jian; Qu, Yun; Wang, Xiu-Li

    2014-04-01

    Five new metal-organic coordination polymers {[Cu3(μ2-OH)2(atrz)2(nph)2(H2O)2]·2H2O}n (1), {[Cu2(μ3-OH)(atrz)(1,2,4-btc)]·2H2O}n (2), {[Cu2(μ3-OH)(atrz)(1,2,4-btc)(H2O)]·H2O}n (3), [Cu(dth)0.5(nph)(H2O)]n (4) and [Cu(dth)(Hnip)2]n (5) [atrz=4-amino-1,2,4-triazole, dth=N,N'-di(4H-1,2,4-triazole)hexanamide, H2nph=3-nitrophthalic acid, 1,2,4-H3btc=1,2,4-benzenetricarboxylic acid and H2nip=5-nitroisophthalic acid] were hydrothermally synthesized and structurally characterized. Polymer 1 shows a one-dimensional (1D) chain. Polymers 2 and 3 exhibit similar tetranuclear CuII4 cluster-based three-dimensional (3D) frameworks with the same components. Polymer 4 possesses a 3D framework with a 412·63-pcu topology. Polymer 5 displays a 3D framework with a 44·610·8-mab topology. The magnetic properties of 1-4 were investigated.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  9. 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

    2015-12-01

    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 . PMID:26525776

  10. 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.

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

    SciTech Connect

    Fang, Wei-Hui; Yang, Guo-Yu

    2014-04-01

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

  12. Multi-responsive coordination polymers utilising metal-stabilised, dynamic covalent imine bonds.

    PubMed

    García, Fátima; Pelss, Janis; Zuilhof, Han; Smulders, Maarten M J

    2016-07-12

    We report how the combination of dynamic covalent imine bonds and coordination bonds in a single polymer material not only imparts enhanced stability to the final polymer, but also allows the material to be sensitive to a range of stimuli, offering more fine-grained control over its properties. PMID:26879208

  13. Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake.

    PubMed

    Leroux, Maxime; Mercier, Nicolas; Allain, Magali; Dul, Marie-Claire; Dittmer, Jens; Kassiba, Abdel Hadi; Bellat, Jean-Pierre; Weber, Guy; Bezverkhyy, Igor

    2016-09-01

    The zwitterionic bipyridinium carboxylate ligand 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium (pc1) in the presence of cadmium chloride affords novel porous coordination polymers (PCPs): [Cd4(pc1)3Cl6]·CdCl4·guest (1) crystallizing in the P3̅1c space group. In the structure, [Cd4Cl6(CO2)6] building units are linked together by six pc1 ligands, leading to a 3D high-symmetrical network exhibiting hexagonal channels along the c axis. The walls of this PCP consist of cationic electron-acceptor bipyridinium units. The PCP 1 reversibly adsorbs H2O and CH3OH up to about 0.1 g/g at saturation showing the adsorption isotherms characteristic of a moderately hydrophilic sorbent. Adsorption of ammonia (NH3) follows a different pattern, reaching an exceptional uptake of 0.39 g/g (22.3 mmol/g) after the first adsorption cycle. Although the crystalline structure of 1 collapses after the first adsorption, the solid can be regenerated and maintains the capacity of 0.29 g/g (17 mmol/g) in the following cycles. We found that the high NH3 uptake is due to a combination of pore filling taking place below 150 h·Pa and chemisorption occurring at higher pressures. The latter process was shown to involve two phenomena: (i) coordination of NH3 molecules to Cd(2+) cations as follows from (113)Cd NMR and (ii) strong donor-acceptor interactions between NH3 molecules and pc1 ligands. PMID:27500980

  14. Comparison of 3D dose distributions for HDR 192Ir brachytherapy sources with normoxic polymer gel dosimetry and treatment planning system.

    PubMed

    Senkesen, Oznur; Tezcanli, Evrim; Buyuksarac, Bora; Ozbay, Ismail

    2014-01-01

    Radiation fluence changes caused by the dosimeter itself and poor spatial resolution may lead to lack of 3-dimensional (3D) information depending on the features of the dosimeter and quality assurance of dose distributions for high-dose rate (HDR) iridium-192 ((192)Ir) brachytherapy sources is challenging and experimental dosimetry methods used for brachytherapy sources are limited. In this study, we investigated 3D dose distributions of (192)Ir brachytherapy sources for irradiation with single and multiple dwell positions using a normoxic gel dosimeter and compared them with treatment planning system (TPS) calculations. For dose calibration purposes, 100-mL gel-containing vials were irradiated at predefined doses and then scanned in an magnetic resonance (MR) imaging unit. Gel phantoms prepared in 2 spherical glasses were irradiated with (192)Ir for the calculated dwell positions, and MR scans of the phantoms were obtained. The images were analyzed with MATLAB software. Dose distributions and profiles derived with 1-mm resolution were compared with TPS calculations. Linearity was observed between the delivered dose and the reciprocal of the T2 relaxation time constant of the gel. The x-, y-, and z-axes were defined as the sagittal, coronal, and axial planes, respectively, the sagittal and axial planes were defined parallel to the long axis of the source while the coronal plane was defined horizontally to the long axis of the source. The differences between measured and calculated profile widths of 3-cm source length and point source for 70%, 50%, and 30% isodose lines were evaluated at 3 dose levels using 18 profiles of comparison. The calculations for 3-cm source length revealed a difference of > 3mm in 1 coordinate at 50% profile width on the sagittal plane and 3 coordinates at 70% profile width and 2 coordinates at 50% and 30% profile widths on the axial plane. Calculations on the coronal plane for 3-cm source length showed > 3-mm difference in 1 coordinate at

  15. Comparison of 3D dose distributions for HDR {sup 192}Ir brachytherapy sources with normoxic polymer gel dosimetry and treatment planning system

    SciTech Connect

    Senkesen, Oznur; Tezcanli, Evrim; Buyuksarac, Bora; Ozbay, Ismail

    2014-10-01

    Radiation fluence changes caused by the dosimeter itself and poor spatial resolution may lead to lack of 3-dimensional (3D) information depending on the features of the dosimeter and quality assurance of dose distributions for high–dose rate (HDR) iridium-192 ({sup 192}Ir) brachytherapy sources is challenging and experimental dosimetry methods used for brachytherapy sources are limited. In this study, we investigated 3D dose distributions of {sup 192}Ir brachytherapy sources for irradiation with single and multiple dwell positions using a normoxic gel dosimeter and compared them with treatment planning system (TPS) calculations. For dose calibration purposes, 100-mL gel-containing vials were irradiated at predefined doses and then scanned in an magnetic resonance (MR) imaging unit. Gel phantoms prepared in 2 spherical glasses were irradiated with {sup 192}Ir for the calculated dwell positions, and MR scans of the phantoms were obtained. The images were analyzed with MATLAB software. Dose distributions and profiles derived with 1-mm resolution were compared with TPS calculations. Linearity was observed between the delivered dose and the reciprocal of the T2 relaxation time constant of the gel. The x-, y-, and z-axes were defined as the sagittal, coronal, and axial planes, respectively, the sagittal and axial planes were defined parallel to the long axis of the source while the coronal plane was defined horizontally to the long axis of the source. The differences between measured and calculated profile widths of 3-cm source length and point source for 70%, 50%, and 30% isodose lines were evaluated at 3 dose levels using 18 profiles of comparison. The calculations for 3-cm source length revealed a difference of > 3 mm in 1 coordinate at 50% profile width on the sagittal plane and 3 coordinates at 70% profile width and 2 coordinates at 50% and 30% profile widths on the axial plane. Calculations on the coronal plane for 3-cm source length showed > 3-mm difference in 1

  16. Polymer Coatings in 3D-Printed Fluidic Device Channels for Improved Cellular Adherence Prior to Electrical Lysis.

    PubMed

    Gross, Bethany C; Anderson, Kari B; Meisel, Jayda E; McNitt, Megan I; Spence, Dana M

    2015-06-16

    This paper describes the design and fabrication of a polyjet-based three-dimensional (3D)-printed fluidic device where poly(dimethylsiloxane) (PDMS) or polystyrene (PS) were used to coat the sides of a fluidic channel within the device to promote adhesion of an immobilized cell layer. The device was designed using computer-aided design software and converted into an .STL file prior to printing. The rigid, transparent material used in the printing process provides an optically transparent path to visualize endothelial cell adherence and supports integration of removable electrodes for electrical cell lysis in a specified portion of the channel (1 mm width × 0.8 mm height × 2 mm length). Through manipulation of channel geometry, a low-voltage power source (500 V max) was used to selectively lyse adhered endothelial cells in a tapered region of the channel. Cell viability was maintained on the device over a 5 day period (98% viable), though cell coverage decreased after day 4 with static media delivery. Optimal lysis potentials were obtained for the two fabricated device geometries, and selective cell clearance was achieved with cell lysis efficiencies of 94 and 96%. The bottleneck of unknown surface properties from proprietary resin use in fabricating 3D-printed materials is overcome through techniques to incorporate PDMS and PS. PMID:25973637

  17. Valence Tautomerism in One-Dimensional Coordination Polymers.

    PubMed

    Drath, Olga; Gable, Robert W; Moubaraki, Boujemaa; Murray, Keith S; Poneti, Giordano; Sorace, Lorenzo; Boskovic, Colette

    2016-05-01

    The combination of the divergent bis-pyridyl linking ligands 1,2-bis(4-pyridyl)ethane (1,2-bpe), 4,4'-trans-azopyridine (azpy), and 1,3-bis(4-pyridyl)propane (1,3-bpp) with cobalt and 3,5-di-tert-butyldioxolene (3,5-dbdiox) ligands has afforded the complexes [Co(3,5-dbdiox)2(1,2-bpe)]∞ (1), [Co(3,5-dbdiox)2(azpy)]∞ (2), [trans-Co(3,5-dbdiox)2(1,3-bpp)]∞ (3a), and [cis-Co(3,5-dbdiox)2(1,3-bpp)]∞ (3b). All species are 1D coordination polymers that crystallize as solvated forms; the geometric isomers 3a,b cocrystallize. Complexes 1, 2, and 3a exhibit around the Co centers a trans disposition of the N-donor atoms from the pyridyl linkers, while an unusual cis disposition is evident in 3b. Single-crystal X-ray structural analysis at 100 or 130 K of solvated forms of these complexes indicates that all complexes possess the {Co(III)(3,5-dbcat)(3,5-dbsq)} (3,5-dbcat = 3,5-di-tert-butylcatecholate; 3,5-dbsq = 3,5-di-tert-butylsemiquinonate) charge distribution at the temperature of data collection. Variable-temperature magnetic susceptibility studies reveal that 1, 1·1.5MeCN·2H2O, 2·2EtOH, and 3·MeCN·H2O (3 = 3a·3b) all exhibit thermally induced valence tautomeric (VT) transitions above 200 K. Multiple heating and cooling cycles indicate that in some cases the behavior is strongly dependent on desolvation processes. Most notably, further desolvation of 1·1.5MeCN·2H2O above 340 K affords χmT values that suggest unusual ferromagnetic coupling in the {hs-Co(II)(3,5-dbsq)2} valence tautomer. Compound 3·MeCN·H2O exhibits a two-step VT transition that may be ascribed to the presence of the cis and trans geometric isomers. Compounds 1, 1·1.5MeCN·2H2O, 2·2EtOH, and 3·MeCN·H2O all also exhibit a single photoinduced VT transition, comparable to those generally observed for nonpolymeric cobalt-dioxolene complexes. PMID:27058604

  18. Modeling of mesoscale dispersion effect on the piezoresistivity of carbon nanotube-polymer nanocomposites via 3D computational multiscale micromechanics methods

    NASA Astrophysics Data System (ADS)

    Ren, Xiang; Chaurasia, Adarsh K.; Oliva-Avilés, Andrés I.; Ku-Herrera, José J.; Seidel, Gary D.; Avilés, Francis

    2015-06-01

    In uniaxial tension and compression experiments, carbon nanotube (CNT)-polymer nanocomposites have demonstrated exceptional mechanical and coupled electrostatic properties in the form of piezoresistivity. In order to better understand the correlation of the piezoresistive response with the CNT dispersion at the mesoscale, a 3D computational multiscale micromechanics model based on finite element analysis is constructed to predict the effective macroscale piezoresistive response of CNT/polymer nanocomposites. The key factors that may contribute to the overall piezoresistive response, i.e. the nanoscale electrical tunneling effect, the inherent CNT piezoresistivity and the CNT mesoscale network effect are incorporated in the model based on a 3D multiscale mechanical-electrostatic coupled code. The results not only explain how different nanoscale mechanisms influence the overall macroscale piezoresistive response through the mesoscale CNT network, but also give reason and provide bounds for the wide range of gauge factors found in the literature offering insight regarding how control of the mesoscale CNT networks can be used to tailor nanocomposite piezoresistive response.

  19. pH- and mol-ratio dependent formation of zinc(II) coordination polymers with iminodiacetic acid: synthesis, spectroscpic, crystal structure and thermal studies

    PubMed Central

    Ni, Lu-Bin; Zhang, Rong-Hua; Liu, Qiong-Xin; Xia, Wen-Sheng; Wang, Hongxin; Zhou, Zhao-Hui

    2009-01-01

    Three novel zinc coordination polymers (NH4)n[Zn(Hida)Cl2]n (1), [Zn(ida)(H2O)2]n (2), [Zn(Hida)2]n·4nH2O (3) (H2ida = iminodiacetic acid) and a monomeric complex [Zn(ida)(phen)(H2O)]·2H2O (4) (phen=1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction methods. 1 and 2 form one-dimensional (1-D) chain structures, whereas 3 exhibits a three-dimensional (3-D) diamondoid framework with an open channel. The mononuclear complex 4 is extended into a 3-D supramolecular architecture through hydrogen bonds and π-π stacking. Interestingly, cyclic nonplanar tetrameric water clusters are observed that encapsulated in the 3-D lattice of 4. Based on 1H and 13C NMR observations, there is obvious coordination of complex 2 in solution, while 1 and 3 decompose into free iminodiacetate ligand. Monomer [Zn(ida)(H2O)3] (5) is considered as a possible discrete species from 2. These coordination polymers can serve as good molecular precursors for zinc oxide. PMID:20161370

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

    Four coordination polymers, [Zn(pda)(bpy)(H 2O)] n· nH 2O ( 1), [Cd(pda)(prz)(H 2O)] n ( 2), [Co 3( μ3-OH) 2(pda) 2(pyz)] n·2 nH 2O ( 3) and [Pr 2(pda) 3(H 2O) 2] n ( 4) (H 2pda=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 π- π 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 3 mol -1 K, and θ=-23.9 and -46.3 K, respectively.

  1. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven self-assembly and host/guest interactions.

    PubMed

    Yan, Xuzhou; Cook, Timothy R; Pollock, J Bryant; Wei, Peifa; Zhang, Yanyan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2014-03-26

    An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal-ligand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel-sol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained. PMID:24621148

  2. 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. PMID:26436891

  3. 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. PMID:26828950

  4. 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.

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

    SciTech Connect

    Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin; Luan, Jian; Qu, Yun; Wang, Xiu-Li

    2014-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    The reaction of Cd(NO3)2·4H2O, 2,5-thiophenedicarboxylic acid (H2tdc) 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 [Cd2(CO2)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.

  7. 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.

  8. 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

  9. 3D printed titanium micro-bore columns containing polymer monoliths for reversed-phase liquid chromatography.

    PubMed

    Gupta, Vipul; Talebi, Mohammad; Deverell, Jeremy; Sandron, Sara; Nesterenko, Pavel N; Heery, Brendan; Thompson, Fletcher; Beirne, Stephen; Wallace, Gordon G; Paull, Brett

    2016-03-01

    The potential of 3D selective laser melting (SLM) technology to produce compact, temperature and pressure stable titanium alloy chromatographic columns is explored. A micro bore channel (0.9 mm I.D. × 600 mm long) was produced within a 5 × 30 × 30 mm titanium alloy (Ti-6Al-4V) cuboid, in form of a double handed spiral. A poly(butyl methacrylate-co-ethyleneglycoldimethacrylate) (BuMA-co-EDMA) monolithic stationary phase was thermally polymerised within the channel for application in reversed-phase high-performance liquid chromatography. The prepared monolithic column was applied to the liquid chromatographic separation of intact proteins and peptides. Peak capacities of 69-76 (for 6-8 proteins respectively) were observed during isothermal separation of proteins at 44 °C which were further increased to 73-77 using a thermal step gradient with programmed temperature from 60 °C to 35 °C using an in-house built direct-contact heater/cooler platform based upon matching sized Peltier thermoelectric modules. Rapid temperature gradients were possible due to direct-contact between the planar metal column and the Peltier module, and the high thermal conductivity of the titanium column as compared to a similar stainless steel printed column. The separation of peptides released from a digestion of E.coli was also achieved in less than 35 min with ca. 40 distinguishable peaks at 210 nm. PMID:26873472

  10. Detection of human genome mutations associated with pregnancy complications using 3-D microarray based on macroporous polymer monoliths.

    PubMed

    Glotov, A S; Sinitsyna, E S; Danilova, M M; Vashukova, E S; Walter, J G; Stahl, F; Baranov, V S; Vlakh, E G; Tennikova, T B

    2016-01-15

    Analysis of variations in DNA structure using a low-density microarray technology for routine diagnostic in evidence-based medicine is still relevant. In this work the applicability of 3-D macroporous monolithic methacrylate-based platforms for detection of different pathogenic genomic substitutions was studied. The detection of nucleotide replacements in F5 (Leiden G/A, rs6025), MTHFR (C/T, rs1801133) and ITGB3 (T/C, rs5918), involved in coagulation, and COMT (C/G, rs4818), TPH2 (T/A, rs11178997), PON1 (T/A rs854560), AGTR2 (C/A, rs11091046) and SERPINE1 (5G/4G, rs1799889), associated with pregnancy complications, was performed. The effect of such parameters as amount and type of oligonucleotide probe, amount of PCR product on signal-to-noise ratio, as well as mismatch discrimination was analyzed. Sensitivity and specificity of mutation detections were coincided and equal to 98.6%. The analysis of SERPINE1 and MTHFR genotypes by both NGS and developed microarray was performed and compared. PMID:26592644

  11. Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)-Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands

    SciTech Connect

    Li, Xinfa; Cao, Rong

    2012-12-15

    Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers (HCPs), formulated as [Ln{sub 2}Ag(hma){sub 2}(ina)(H{sub 2}O){sub 2}]{sub n} nH{sub 2}O [Ln=La(1), Pr(2), Nd(3); Hina=isonicotinic acid, H{sub 3}hma=hemimellitic acid], have been synthesized under hydrothermal conditions. Single-crystal and powder X-ray diffractions confirm that they are isostructural, which features a three-dimensional (3D) pillared-layer heterometallic structure built upon the strictly alternate arrangement of lanthanide-organic layers and [Ag(ina)] pillars. The layers and pillars are connected to each other by Ln-O and Ag-O coordination bonds. The photoluminescent property of the Nd derivative (3) has also been investigated. - Graphical abstract: Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers have been synthesized and structurally characterized. Highlights: Black-Right-Pointing-Pointer Three 3D pillared-layer 4d-4f HCPs were synthesized by hydrothermal reactions. Black-Right-Pointing-Pointer The synergistic coordination strategy was employed. Black-Right-Pointing-Pointer It opens new perspective for the construction of structurally diversified 4d-4f HCPs.

  12. 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.

  13. 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.

  14. A series of coordination polymers based on a V-shaped multicarboxylate and bisimidazole ligands: Synthesis, characterization and luminescent properties

    NASA Astrophysics Data System (ADS)

    Guo, Huadong; Yan, Yongnian; Guo, Xianmin; Wang, Nan; Qi, Yanjuan

    2016-03-01

    Based on a V-shaped multicarboxylic acid and various bisimidazole ligands, six new coordination polymers, namely, [Zn4(otba) (1,4-bix)4]·3H2O (1), [Ni4(otba)2(1,4-bix)3(H2O)2]·2H2O (2), [Zn2(H2otba)2(bib) (H2O)2] (3), [Cd2(H2otba)2(bib)]·2H2O (4), [Zn3(otba)2(bidpe)2(H2O)2] (5), [Ni2(H2otba)2(bidpe)3(H2O)2]·H2O (6) (H4otba = 3,5,3‧,5‧-oxytetrabenzoic acid, 1,4-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazol-1-yl)benzene and bidpe = 4,4'-bis(imidazol-1-yl)diphenyl ether) have been hydrothermally synthesized and structurally characterized. Compound 1 displays an uncommon hexanodal 3D 4-connected network. Compound 2 features a trinodal 3D (4, 4, 6)-connected framework. Compound 3 shows an interesting polythreaded 1D→3D species. Compound 4 exhibits a binodal 3D (3, 8)-connected network. Compound 5 displays a three-fold interpenetration of trinodal (3, 3, 4)-connected network. Compound 6 shows a five-fold interpenetration of five-connected bilayer network. The luminescent properties of compounds 1, 3, 4 and 5 were also measured.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    SciTech Connect

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Keskin, Seda; Şahin, Onur

    2014-02-15

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

  18. Loading of a coordination polymer nanobelt on a functional carbon fiber: a feasible strategy for visible-light-active and highly efficient coordination-polymer-based photocatalysts.

    PubMed

    Xu, Xin-Xin; Yang, Hong-Yu; Li, Zhen-Yu; Liu, Xiao-Xia; Wang, Xiu-Li

    2015-02-23

    To improve the photocatalytic properties of coordination polymers under irradiation in the visible-light region, coordination polymer nanobelts (CPNB) were loaded on functional carbon fiber (FCF) through the use of a simple colloidal blending process. The resulting coordination polymer nanobelt loaded functional carbon fiber composite material (CPNB/FCF) exhibited dramatically improved photocatalytic activity for the degradation of rhodamine B (RhB) under visible-light irradiation. Optical and electrochemical methods illustrated the enhanced photocatalytic activity of CPNB/FCF originated from high separation efficiency of photogenerated electrons and holes on the interface of CPNB and FCF, which was produced by the synergy effect between them. In the composite material, the role of FCF could be described as photosensitizer and good electron transporter. For FCF, the number of functional groups on its surface has a significant influence on the photocatalytic performance of the resulting CPNB/FCF composite material, and an ideal FCF carrier was obtained as a highly efficient CPNB/FCF photocatalyst. CPNB/FCF showed outstanding stability during the degradation of rhodamine B (RhB); thus, the material is suitable for use as a photocatalyst in the treatment of organic dyes in water. PMID:25641070

  19. 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

  20. A series of M-M' heterometallic coordination polymers: syntheses, structures and surface photoelectric properties (M=Ni/Co, M'=Cd/Zn)

    SciTech Connect

    Li, Lei; Niu, Shu-Yun; Jin, Jing; Meng, Qin; Chi, Yu-Xian; Xing, Yong-Heng; Zhang, Guang-Ning

    2011-05-15

    Four new heterometallic polymers, [NiCd(mal){sub 2}(H{sub 2}O){sub 2}]n.2nH{sub 2}O 1, [NiZn{sub 2}(Hcit){sub 2}(H{sub 2}O){sub 2}]n 2, [CoCd{sub 2}(Hcit){sub 2}(H{sub 2}O){sub 2}]n 3, [CoZn{sub 2}(Hcit){sub 2}(H{sub 2}O){sub 2}]n 4 (H{sub 2}mal=malonic acid, H{sub 4}cit=citric acid) were synthesized and characterized. The photoelectric properties of the polymers were discussed by the surface photovoltage spectroscopy (SPS). The structural analyses indicate 1 is a Ni-Cd heterometallic polymer with 3D structure bridged by the mal{sup 2-} group. 2-4 are all heterometallic polymers with 2D structures bridged by the Hcit{sup 3-} group. The results of SPS for the four polymers reveal that there are wide photovoltage response bands in the range of 300-800 nm, which indicates that they all possess photoelectric conversion properties. By the introduction of the other metals, the SPS of heterometallic polymers are broadened obviously than the SPS of monometallic complexes. Moreover, the relationships between SPS and UV-Vis absorption spectra have been discussed. -- Graphical Abstract: Four heterometallic polymers, Ni-Cd, Ni-Zn, Co-Cd, Co-Zn, were synthesized and characterized. The photoelectric properties of heterometallic polymers were discussed by SPS. The introduction of heterometallic ions will broaden the SPS of corresponded monometallic complexes. Display Omitted highlights: > Four new heterometallic coordination polymers were reported. > The surface photoelectric properties of heterometallic polymers were studied by SPS. > They all possess photoelectric conversion properties. > The SPS of heterometallic polymers are broadened than that of monometallic complexes.

  1. Amphiphilic nanocapsules entangled with organometallic coordination polymers for controlled cargo release.

    PubMed

    Liang, Guodong; Ni, Huan; Bao, Suping; Zhu, Fangming; Gao, Haiyang; Wu, Qing; Tang, Ben Zhong

    2014-06-01

    A class of new amphiphilic nanocapsules entangled with organometallic coordination polymers has been developed for the first time. Poly(2-(N,N-dimethyl amino)ethyl methacrylate)-b-polystyrene capped with β-cyclodextrin (β-CD) (CD-PDMAEMA-b-PS) is first synthesized using sequent RAFT polymerization of styrene and 2-(N,N-dimethyl amino)ethyl methacrylate with xanthate modified β-CD as chain transfer agent. The end group of β-CD is allowed to include 4,4'-bipyridine through host-guest inclusion to yield PDMAEMA-b-PS terminated with an inclusion complex of β-CD and bipyridine (bpy-PDMAEMA-b-PS), which is then used as surfactant to prepare emulsion droplets in toluene/water mixture. Upon addition of Ni(II), bipyridine coordinates with Ni(II) to form coordination polymers in the periphery of emulsion droplets, affording amphiphilic capsules entangled with organometallic coordination polymers, as confirmed by GPC, (1)H NMR, SEM, TEM, DLS, and so on. The organometallic coordination polymer capsules are capable of encapsulating organic cargoes. Interestingly, encapsulated cargoes can be extracted from the capsules without damaging the capsules. Such capsules are potential candidates for encapsulating and controlled release of organic cargoes. PMID:24828951

  2. Unprecedented layered coordination polymers of dithiolene group 10 metals: magnetic and electrical properties.

    PubMed

    Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martín, Avelino; Zamora, Félix

    2016-04-21

    One-pot reactions between Ni(ii), Pd(ii) or Pt(ii) salts and 3,6-dichloro-1,2-benzenedithiol (HSC6H2Cl2SH) in KOH medium under argon lead to a series of bis-dithiolene coordination polymers. X-ray analysis shows the presence of a common square planar complex [M(SC6H2Cl2S)2](2-) linked to potassium cations forming either a two-dimensional coordination polymer network for {[K2(μ-H2O)2(μ-thf)(thf)2][M(SC6H2Cl2S)2]}n [M = Ni () and Pd ()] or a one-dimensional coordination polymer for {[K2(μ-H2O)2(thf)6][Pt(SC6H2Cl2S)2]}n (). In the coordination environment of the potassium ions may slightly change leading to the two-dimensional coordination polymer {[K2(μ-H2O)(μ-thf)2][Pt(SC6H2Cl2S)2]}n () that crystallizes together with . The physical characterization of compounds show similar trends, they are diamagnetic and behave as semiconductors. PMID:26974399

  3. 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. PMID:26322715

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

    PubMed Central

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

    2015-01-01

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

  5. 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.

  6. 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. PMID:23921454

  7. 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. PMID:26264525

  8. Hydration-dependent anomalous thermal expansion behaviour in a coordination polymer.

    PubMed

    Lama, Prem; Alimi, Lukman O; Das, Raj Kumar; Barbour, Leonard J

    2016-02-21

    A coordination polymer is shown to possess anomalous anisotropic thermal expansion. Guest water molecules present in the as-synthesised material can be removed upon activation without loss of crystal singularity. The fully dehydrated form shows considerably different thermal expansion behaviour as compared to the hydrate. PMID:26810007

  9. 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

    2016-03-01

    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. PMID:26865502

  10. Novel photochromic infinite coordination polymer particles derived from a diarylethene photoswitch.

    PubMed

    Hu, Xiao Guang; Li, XiaoLiang; Yang, Sung Ik

    2015-07-01

    A novel infinite coordination polymer (DAE-ICP) based on zinc nitrite and a diarylethene photoswitch, with reversible photochromic properties in solution and the solid state upon applying photostimuli, was synthesized and characterized by FT-IR, EDX, FE-SEM and FE-TEM. PMID:26041619

  11. Coordination power adjustment of surface-regulating polymers for shaping gold polyhedral nanocrystals.

    PubMed

    Lee, Seon Joo; Park, Garam; Seo, Daeha; Ka, Duyoun; Kim, Sang Youl; Chung, Im Sik; Song, Hyunjoon

    2011-07-18

    PVP (poly(vinyl pyrrolidone)) is a common polymer that behaves as a surface-regulating agent that shapes metal nanocrystals in the polyol process. We have used different polymers containing tertiary amide groups, namely PVCL (poly(vinyl caprolactam)) and PDMAm (poly(N,N-dimethyl acrylamide)), for the synthesis of gold polyhedrons, including octahedrons, cuboctahedrons, cubes, and higher polygons, under the present polyol reaction conditions. The basicity and surface coordination power of the polymers are in the order of PVCL, PVP, and PDMAm. A correlation is observed between the coordination power of the polymers and the resulting gold nanocrystal size. Strong coordination and electron donation from the polymer functional groups to the gold surface restrict particle growth rates, which leads to small nanocrystals. The use of PVCL can yield gold polyhedral structures with small sizes, which cannot be achieved in the reactions with PVP. Simultaneous hydrolysis of the amide group in PDMAm leads to carboxylate functionality, which is very useful for generating chemical and bioconjugates through the formation of ester and amide bonds. PMID:21656861

  12. 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%). PMID:27377859

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    Hydrothermal reactions of 2,2‧-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H2L) and zinc ions in the presence of N-donor ancillary ligands afford four novel coordination polymers, namely, [Zn2(μ2-OH)(μ4-O)0.5(L)]·0.5H2O (1), [Zn(L)(2,2‧-bipy)(H2O)] (2), [Zn3(L)3(phen)2]·H2O (3) and [Zn2(L)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 [Zn4(μ4-O)(μ2-OH)2]4+ clusters, and exhibits a novel (3,8)-connected topological net with the Schläfli symbol of {3·4·5}2{34·44·52·66·710·82}, 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 {44·62} 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 {44·62} square structure with left- and right-handed helical chains. Moreover, the luminescent properties of 1-4 have been investigated.

  14. Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studies.

    PubMed

    Hawes, Chris S; Chilton, Nicholas F; Moubaraki, Boujemaa; Knowles, Gregory P; Chaffee, Alan L; Murray, Keith S; Batten, Stuart R; Turner, David R

    2015-10-28

    The synthesis and structural, magnetic and gas adsorption properties of a series of coordination polymer materials prepared from a new, highly flexible and internally functional tetrakis-carboxybenzyl ligand H4L derived from 1,2-diaminoethane have been examined. The compound poly-[Ni3(HL)2(OH2)4]·2DMF·2H2O 1, a two-dimensional coordination polymer, contains aqua- and carboxylato-bridged trinuclear Ni(II) clusters, the magnetic behaviour of which can be well described through experimental fitting and ab initio modelling to a ferromagnetically coupled trimer with a positive axial zero-field splitting parameter D. Compound poly-[Zn2L]·2DMF·3H2O 2, a three-dimensional coordination polymer displaying frl topology, contains large and well-defined solvent channels, which are shown to collapse on solvent exchange or drying. Compound poly-[Zn2(L)(DMSO)4]·3DMSO·3H2O 3, a highly solvated two-dimensional coordination polymer, displayed poor stability characteristics, however a structurally related material poly-[Zn2(L)(bpe)(DMSO)2]·DMSO·3H2O 4 was prepared under similar synthetic conditions by including the 1,2-bis(4-pyridyl)ethylene bpe co-ligand. Compound 4, containing small one-dimensional solvent channels, shows excellent structural resilience to solvent exchange and evacuation, and the evacuated material displays selective adsorption of CO2 over N2 at 273 K in the pressure range 0-1 atm. Each of the coordination polymers displays subtle differences in the conformation and binding mode of the ligand species, with switching between two distinct conformers (X-shaped and H-shaped), as well as a variable protonation state of the central core, with significant effects on the resulting network structures and physical properties of the materials. PMID:26223788

  15. Synthesis and characterization of nanowire coils of organometallic coordination polymers for controlled cargo release.

    PubMed

    Liang, Guodong; Ni, Huan; Bao, Suping; Zhu, Fangming; Gao, Haiyang; Wu, Qing

    2014-06-12

    Nanowire coils of organometallic coordination polymers have been synthesized for the first time by using the emulsion periphery polymerization technique. An amphiphilic triblock copolymer terminated with inclusion complex of β-cyclodextrin and 4,4'-bipyridine self-assembles into oil-in-water emulsion in a toluene/water mixture. Subsequent coordination of bipyridine with Ni(II) in periphery of emulsions results in the formation of coordination polymer nanowire coils. The nanowire coils are composed of nanowires with diameter of 2 nm. Nanowire coils exhibit enhanced thermal stability in contrast to their parent triblock copolymer. Interestingly, nanowire coils are capable of encapsulating organic cargoes. Encapsulated cargoes can be selectively extracted from nanowire coils without damaging nanowire coils. Nanowire coils are potential candidates for encapsulating and controlled release of organic cargoes. PMID:24842771

  16. Synthesis, Structure, White-Light Emission, and Temperature Recognition Properties of Eu/Tb Mixed Coordination Polymers.

    PubMed

    An, Ran; Zhao, Hui; Hu, Huai-Ming; Wang, Xiaofang; Yang, Meng-Lin; Xue, Ganglin

    2016-01-19

    Two series of Eu(III)/Tb(III) coordination polymers, [LnL(glu)]n·2nH2O (Ln = Eu (1), Tb (2)) and [LnL(glu)(H2O)]n (Ln = Eu (3), Tb (4)) [HL = (2-(2-sulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline, H2glu = glutaric acid] have been hydrothermally synthesized by controlling the pH values and characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. Isomorphic compounds 1 and 2 exhibit 6-connected 3D network with the pcu topological net, containing left- and right-handed helical chains. Isomorphic compounds 3 and 4 show 3,4-connected 2D new topology with the point symbol of (4(2)·6(3)·8)(4(2)·6). Multicolor luminescence can be tailored from red to green regions by singly varying the mixing molar ratio of Eu(III)/Tb(III) cations. The mixing component of 1Eu/2Tb = 4:6 not only achieves white-light emission with the CIE coordinate of (0.323, 0.339) upon excitation at 405 nm but also presents a temperature recognition property with the significantly high sensitivity of 0.68% per K in the 50-225 K temperature range upon excitation at 370 nm. PMID:26750629

  17. 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

  18. 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.

  19. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    PubMed

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  20. Two one-dimensional d10-metal coordination polymers based on polydentate Schiff-base ligand: Synthesis, crystal structure and luminescent properties

    NASA Astrophysics Data System (ADS)

    Niu, Wei-Jia; Wang, Jun-Li; Bai, Yan; Dang, Dong-Bin

    2012-06-01

    Two one-dimensional d10-metal coordination polymers {[AgL(H2O)]2[AgL(NO3)]2(NO3)2L(H2O)2}n (1) and [ZnLCl2]n (2) (L = N,N'-bis-(1-pyridin-4-yl-ethylidene)-hydrazine) have been synthesized and characterized by IR, elemental analysis, TG technique, XRPD and X-ray crystallography. Polymer 1 contains two types of 1D Ag-double-chain units. Ag(1)-double-chain unit is formed by linking two adjacent Ag(1)-L-chains through face-to-face π⋯π interactions, while Ag(2)-double-chain unit is formed through the combination of coordinating NO3- anions bridging interactions and π⋯π interactions between two adjacent Ag(2)-L-chains. Free ligands interact with the adjacent Ag(1)-double-chain units and Ag(2)-double-chain units to form a 3D supramolecular structure through multiform hydrogen bonds. For polymer 2, each ligand acts as a bis-monodentate bridging ligand to bind adjacent Zn(II) centers forming a one-dimensional chain structure. Furthermore, 1D chain is held together with its neighboring ones via Csbnd H⋯π interactions. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature.

  1. Nicotine molecularly imprinted polymer: synergy of coordination and hydrogen bonding.

    PubMed

    Huynh, Tan-Phat; B K C, Chandra; Sosnowska, Marta; Sobczak, Janusz W; Nesterov, Vladimir N; D'Souza, Francis; Kutner, Wlodzimierz

    2015-02-15

    Two new bis(2,2'-bithienyl)methane derivatives, one with the zinc phthalocyanine substituent (ZnPc-S16) and the other with the 2-hydroxyethyl substituent (EtOH-S4), were synthesized to serve as functional monomers for biomimetic recognition of nicotine (Nic) by molecular imprinting. Formation of a pre-polymerization complex of the Nic template with ZnPc-S16 and EtOH-S4 was confirmed by both the high negative Gibbs free energy gain, ΔG = -115.95 kJ/mol, calculated using the density functional theory at the B3LYP/3-21G* level, and the high stability constant, Ks = 4.67 × 10(5) M(-1), determined by UV-vis titration in chloroform. A solution of this complex was used to deposit a Nic-templated molecularly imprinted polymer (MIP-Nic) film on an Au electrode of a quartz crystal resonator of EQCM by potentiodynamic electropolymerization. The imprinting factor was as high as ~9.9. Complexation of the Nic molecules by the MIP cavities was monitored with X-ray photoelectron spectroscopy (XPS), as manifested by a negative shift of the binding energy of the Zn 2p3/2 electron of ZnPc-S16 after Nic templating. For sensing applications, simultaneous chronoamperometry (CA) and piezoelectric microgravimetry (PM) measurements were performed under flow-injection analysis conditions. The limit of detection of the CA and PM chemosensing was as low as 40 and 12 µM, respectively. Among them, the CA chemosensing was more selective to the cotinine and myosmine interferences due to the 1.10 V vs. Ag/AgCl discriminating potential of nicotine electro-oxidation applied. Differences in selectivity to the analyte and interferences were interpreted by modeling complexation of Nic and, separately, each of the interferences with a "frozen" MIP-Nic molecular cavity. PMID:25441415

  2. Different aliphatic dicarboxylates affected assemble of new coordination polymers constructed from flexible-rigid mixed ligands

    SciTech Connect

    Xu Xinxin; Ma Ying; Wang Enbo

    2007-11-15

    In this article, seven coordination polymers: [Cd(C{sub 5}H{sub 6}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (1), [Zn(C{sub 5}H{sub 6}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (2), [Cd(C{sub 6}H{sub 8}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (3), {l_brace}[Mn(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O){sub 4}] (C{sub 4}H{sub 4}O{sub 4}).4H{sub 2}O{r_brace}{sub n} (4), [Mn{sub 5}(C{sub 4}H{sub 4}O{sub 4}){sub 4}(O)]{sub n} (5), [Cd(C{sub 4}H{sub 4}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O)]{sub n} (6) and [Zn(C{sub 6}H{sub 6}O{sub 4})(C{sub 12}H{sub 8}N{sub 2})(H{sub 2}O)]{sub n} (7) were synthesized and characterized by single-crystallographic X-ray diffraction. Compounds 1 and 2 are two-dimensional layers connected by glutarate anions and 4,4'-bpy. Unlike compounds 1 and 2, compound 3 is a two-fold interpenetration network. Compound 4 is a one-dimensional chain-like structure, which is further extended to two-dimensional supramolecular layer structure with hydrogen bond. During the synthesis of compound 4, to our surprise, we got compound 5; compound 5 is an interesting three-dimensional network composed of pentanuclear Mn(II) building units and succinate anions. Compound 6 is also a two-dimensional supramolecular layer structure composed of one-dimensional chain-like structure with hydrogen bonds and {pi}-{pi} interactions. Compound 7 is also a one-dimensional chain-like structure, which is further connected with the same kind of interaction to generate two-dimensional supramolecular layer structure. Furthermore, compounds 1 and 2 both exhibit fluorescent property at room temperature. - Graphical abstract: Seven complexes composed by 3D metal ions, aliphatic acid ligand and rigid bidentate nitrogen ligands: 4,4'-bpy, 2,2'-bpy and 1,10'-phen. With the change of the carbon number of the backbone of aliphatic dicarboxylate ligand, we can synthesize different complexes with various structures.

  3. 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.

  4. 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. Their thermal decompositions properties of 1-4 were

  5. Syntheses, crystal structures and luminescent properties of two new 1D d {sup 1} coordination polymers constructed from 2,2'-bibenzimidazole and 1,4-benzenedicarboxylate

    SciTech Connect

    Wen Lili; Li Yizhi; Dang Dongbin; Tian Zhengfang; Ni Zhaoping; Meng Qingjin . E-mail: mengqj@nju.edu.cn

    2005-11-15

    Two novel interesting d {sup 1} metal coordination polymers, [Zn(H{sub 2}bibzim)(BDC)] {sub n} (1) and [Cd(H{sub 2}bibzim)(BDC)] {sub n} (2) [H{sub 2}bibzim=2,2'-bibenzimidazole, BDC=1,4-benzenedicarboxylate] have been synthesized under solvothermal conditions and structurally characterized. Both 1 and 2 are constructed from infinite neutral zigzag-like one-dimensional (1D) chains. The {pi}-{pi} interactions and interchain hydrogen-bonding interactions further extend the 1D arrangement to generate a 3D supramolecular architecture for 1 and 2. Both complexes have high thermal stability and display strong blue fluorescent emissions in the solid state upon photo-excitation at 365 nm at room temperature. They are the first two examples that 2,2'-bibenzimidazole has been introduced into the d {sup 1} coordination polymeric framework.

  6. 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

  7. Separation of gas mixtures using Co(II) carborane-based porous coordination polymers

    SciTech Connect

    Bae, Youn-Sang; Spokoyny, Alexander M.; Farha, Omar K.; Snurr, Randall Q.; Hupp, Joseph T.; Mirkin, Chad A.

    2010-01-01

    Separations of CO{sub 2}/CH{sub 4}, CO{sub 2}/N{sub 2}, and O{sub 2}/N{sub 2} mixtures were studied in three porous coordination polymers made of the same carborane ligand and Co(II) nodes. High selectivities for CO{sub 2} over CH{sub 4} (~47) and CO{sub 2} over N{sub 2} (~95) were obtained, especially in the material with coordinated pyridine. Unusual selectivity for O{sub 2} over N{sub 2} (as high as 6.5) was demonstrated in the materials with open Co(II) sites.

  8. 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.

  9. Sonochemical synthesis and characterization of new one-dimensional manganese(II) coordination polymer nanostructures.

    PubMed

    Morsali, Ahmad; Hosseini-Monfared, Hassan; Morsali, Ali; Mayer, Peter

    2015-05-01

    A new Mn(II) coordination polymer, [Mn (L1)2(NCS)2]n (1) [L1=3,4-bis(4-pyridyl)-5-(2-pyridyl)-1,2,4-triazole] was synthesized by the reaction of ligand L1 and mixtures of manganese(II) acetate and potassium thiocyanate using the heat gradient method. Compound 1 has been characterized by IR spectroscopy, elemental analyses and X-ray crystallography. The crystal structure of compound 1 was determined by single-crystal X-ray diffraction and shows a new interesting one-dimensional coordination polymer. Nanostructures of compound 1 have been synthesized by sonochemical method. The products were characterized by X-ray powder diffraction, scanning electron microscopy (SEM), and IR spectroscopy. The thermal stability of nano particles of compound 1 was studied by thermal gravimetric and differential thermal analyses. PMID:25483353

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

    SciTech Connect

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

    2009-08-15

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

  11. 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. PMID:27377646

  12. Design of 2D Porous Coordination Polymers Based on Metallacrown Units.

    PubMed

    Atzeri, Corrado; Marchiò, Luciano; Chow, Chun Y; Kampf, Jeff W; Pecoraro, Vincent L; Tegoni, Matteo

    2016-05-01

    A 12-metallacrown-4 (MC) complex was designed and employed as the building block in the synthesis of coordination polymers, one of which is the first permanently porous MC architecture. The connection of the four-fold symmetric MC subunits by Cu(II) nodes led to the formation of 2D layers of metallacrowns. Channels are present in the crystalline architecture, which exhibits permanent porosity manifested in N2 and CO2 uptake capacity. PMID:26951956

  13. 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.

  14. 4,2':6',4''-Terpyridines: diverging and diverse building blocks in coordination polymers and metallomacrocycles.

    PubMed

    Housecroft, Catherine E

    2014-05-14

    4,2':6',4''-Terpyridine (4,2':6',4''-tpy) is one of the less well documented isomers of the well-established bis-chelating 2,2':6',2''-terpyridine. The N-donors of the outer rings in 4,2':6',4''-tpy subtend an angle of 120°, leading to a description of 4,2':6',4''-tpy as a divergent ligand. Because it typically binds metal ions through the outer N-donors only, 4,2':6',4''-tpy is an ideal linker for combination with metal nodes (often geometrically flexible d(10) ions) in coordination polymers and metallomacrocyclic complexes. The facile functionalization of terpyridines in the 4'-position allows access to a suite of 4'-X-4,2':6',4''-tpy ligands in which the 4'-substituent, X, can be selected to assist in directing the metal-ligand assembly process. This overview of recent advances in the chemistry of 4,2':6',4''-tpy and its 4'-substituted derivatives looks at relationships within a series of chiral polymers, competition between the formation of metallocyclic complexes versus polymers, and the use of extended aryl systems to encourage the formation of coordination polymers in which π-stacking of arene domains dominates in the assembly process. Use of metal(ii) acetates is key to the formation of paddle-wheel and larger cluster nodes that direct the assembly of both predetermined and unexpected architectures. PMID:24522847

  15. Crystal structures of coordination polymers from CaI2 and proline

    PubMed Central

    Lamberts, Kevin; Englert, Ulli

    2015-01-01

    Completing our reports concerning the reaction products from calcium halides and the amino acid proline, two different solids were found for the reaction of l- and dl-proline with CaI2. The enanti­opure amino acid yields the one-dimensional coordination polymer catena-poly[[aqua-μ3-l-proline-tetra-μ2-l-proline-dicalcium] tetra­iodide 1.7-hydrate], {[Ca2(C5H9NO2)5(H2O)]I4·1.7H2O}n, (1), with two independent Ca2+ cations in characteristic seven- and eightfold coordination. Five symmetry-independent zwitterionic l-proline mol­ecules bridge the metal sites into a cationic polymer. Racemic proline forms with Ca2+ cations heterochiral chains of the one-dimensional polymer catena-poly[[di­aquadi-μ2-dl-proline-calcium] diiodide], {[Ca(C5H9NO2)2(H2O)2]I2}n, (2). The centrosymmetric structure is built by one Ca2+ cation that is bridged towards its symmetry equivalents by two zwitterionic proline mol­ecules. In both structures, the iodide ions remain non-coordinating and hydrogen bonds are formed between these counter-anions, the amino groups, coordinating and co-crystallized water mol­ecules. While the overall composition of (1) and (2) is in line with other structures from calcium halides and amino acids, the diversity of the carboxyl­ate coordination geometry is quite surprising. PMID:26090148

  16. Investigations of bridging ligands for the synthesis of bimetallic coordination polymers

    NASA Astrophysics Data System (ADS)

    Glynn, Christopher W.

    The synthesis and study of new transition metal coordination complexes that display spontaneous magnetic moments is the goal of the present research. Materials of this kind represent a new class of magnetic compounds, molecular-based magnets. For our purposes, transition metal ions provide the source of the magnetic moments, which are bridged by organic ligands. The systems we have designed are bimetallic coordination polymers with two alternating transition metal ions, M1 and M2, with inequivalent non-zero moments. The primary difficulty encountered in the design strategy is how to arrange two chemically similar transition metal ions in an alternating pattern. The organic ligands 2,6-bis-(1'-triazolo)-pyridine (btpy), 2,6-bis(4'-imidazolo)pyridine (H2bimpy), 2,2'-biimidazole (2,2'-H2biim), 4,4'-biimidazole (4,4'-H2biim), and 2,6-diacetylpyridine dioxime (H2dapd) were investigated for use in constructing site-ordered bimetallic coordination polymers. All five ligands share the following characteristics: a polydentate internal binding site, the possibility of external binding sites in a square-planar or octahedral arrangement and the potential to mediate magnetic exchange between the transition metals ions coordinated to the distinct internal and external binding sites. The systems based on H2bimpy and 4,4'-H 2biim are promising, but difficulties in the preparation of the ligands have prevented the realization of these systems. Transition metal complexes for the ligands btpy, 2,2'-H2biim and H 2dapd have been prepared and characterized. Although to date no bimetallic materials have been constructed through the use of these ligands, the data presented indicates their viability for the construction of bimetallic coordination polymers.

  17. Two polyoxometalate-based coordination polymers constructed from Mn(II)-4,4'-bipyridine-N,N'-dioxide building blocks and Keggin-type clusters: Syntheses, crystal structures and spectral properties.

    PubMed

    Bai, Yan; Li, Meng-Meng; Huang-Fu, You-Jing; Dang, Dong-Bin

    2013-11-01

    Two polyoxometalate-based coordination polymers {[Mn2(dpdo)4(H2O)6](GeMo12O40)(H2O)4}n (1) and {[Mn2(dpdo)4(H2O)6](GeW12O40)(H2O)3}n (2) (dpdo=4,4'-bipyridine-N,N'-dioxide) have been synthesized and characterized by IR, elemental analysis, XRPD, TG technique and X-ray crystallography. The polymers 1 and 2 are basically isostructural and feature a 3D supramolecular framework decorated with Keggin-type polyanion clusters based on one-dimension polymeric chains, which formed through the coordination interaction of Mn(II) and dpdo. The luminescent properties of the polymers were investigated in the solid state at room temperature. PMID:23880411

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  19. 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…

  20. Coordination polymer gels: soft metal-organic supramolecular materials and versatile applications.

    PubMed

    Sutar, Papri; Maji, Tapas Kumar

    2016-06-21

    In recent times, significant attention has been paid to the development of functional coordination polymer gels (CPGs) from rationally designed low molecular weight gelators (LMWGs) and metal ions. Coordination of metal ions to LMWGs provides an opportunity to emulate metal based redox, optical, electronic and magnetic properties in soft CPG materials. The metal-LMWG interactions allow controlled growth of CPGs with different nanostructures such as fibers, tubes, rings, ribbons and vesicles. Furthermore, the nanoscale periodicity of metal ions and LWMGs in CPGs is of paramount importance for different optoelectronic applications. The easy processability and dynamic nature of CPGs are explored for application in diverse fields, including drug-delivery, gas storage, optoelectronics, chemo-sensing, self-healing, etc. Also, by taking advantage of dynamic metal-ligand coordination bonds various stimuli-responsive multi-functional CPGs are developed. In this feature article, we cover important examples of newly developed CPGs, which show potential applications in different fields. PMID:27203359

  1. A responsive supramolecular polymer formed by orthogonal metal-coordination and cryptand-based host-guest interaction.

    PubMed

    Wei, Peifa; Xia, Binyuan; Zhang, Yanyan; Yu, Yihua; Yan, Xuzhou

    2014-04-18

    Herein, a cation responsive linear supramolecular polymer was constructed in an orthogonal fashion by unifying the themes of coordination-driven self-assembly and cryptand-based host-guest interaction. PMID:24609282

  2. 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.

  3. HCl chemisorption-induced drastic magneto-structural transformation in a layered cobalt-phosphonotriazolate coordination polymer.

    PubMed

    Zhang, Weiquan; Wang, Dianpeng; Zhu, Lin; Zhai, Fupeng; Weng, Linhong; Sun, Jinyu; Ling, Yun; Chen, Zhenxia; Zhou, Yaming

    2016-07-14

    The chemisorption of gaseous HCl molecules in a two-dimensional coordination polymer results in subtle changes in its structure and instigates a drastic modification from antiferro- to ferromagnetic properties. PMID:27294584

  4. 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.

  5. Synthesis and structural characterization of new bismuth (III) nano coordination polymer: A precursor to produce pure phase nano-sized bismuth (III) oxide

    NASA Astrophysics Data System (ADS)

    Hanifehpour, Younes; Mirtamizdoust, Babak; Hatami, Masoud; Khomami, Bamin; Joo, Sang Woo

    2015-07-01

    A novel bismuth (III) nano coordination polymer, {[Bi (pcih)(NO3)2]ṡMeOH}n (1), ("pcih" is the abbreviations of 2-pyridinecarbaldehyde isonicotinoylhydrazoneate) were synthesized by a sonochemical method. The new nano-structure was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray powder diffraction, elemental analyses and IR spectroscopy. Single crystalline material was obtained using a heat gradient applied to a solution of the reagents. Compound 1 was structurally characterized by single crystal X-ray diffraction. The determination of the structure by single crystal X-ray crystallography shows that the complex forms a zig-zag one dimensional polymer in the solid state and the coordination number of BiIII ions is seven, (BiN3O4), with three N-donor and one O-donor atoms from two "pcih" and three O-donors from nitrate anions. It has a hemidirected coordination sphere. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The chains interact with each other through π-π stacking interactions creating a 3D framework. After thermolysis of 1 at 230 °C with oleic acid, pure phase nano-sized bismuth (III) oxide was produced. The morphology and size of the prepared Bi2O3 samples were further observed using SEM.

  6. Synthesis, crystal structures, luminescence and catalytic properties of two d¹⁰ metal coordination polymers constructed from mixed ligands.

    PubMed

    Wang, Xiao-xiao; Zhang, Ming-xi; Yu, Baoyi; Van Hecke, Kristof; Cui, Guang-hua

    2015-03-15

    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 6(6) 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. PMID:25576941

  7. Design and synthesis of two luminescent Zn(II)-based coordination polymers with different structures regulated by different solvent system

    NASA Astrophysics Data System (ADS)

    Wu, Wei-Ping; Wen, Gui-Lin; Liao, Yi; Wang, Jun; Lu, Lu; Wu, Yu; Xie, Bin

    2016-08-01

    Two new coordination polymers (CPs) [Zn(HL)(H2O)]n (1) and [Zn3(L)2(H2O)2]n·(H2O)n (2), based on a multifunctional ligand combined carboxylate groups and a nitrogen donor group 5-(6-carboxypyridin-2-yl)isophthalic acid (H3L), have been synthesized under different solvent media and fully characterized by powder X-ray diffraction (PXRD), infrared (IR) spectra, elemental analyses (EA) and thermogravimetric analyses (TGA). Single-crystal X-ray diffraction analysis reveals that 1 shows 1D dimeric chain structure, while 2 gives a 3D dense packing framework. Topology analysis illustrates that 2 can be simplified as a 3-nodal net (4, 5, 6-connected net) with the point symbol of {44·62}{46·64}2{48·66·8}. In addition, solid state luminescent properties of two complexes have also been studied in detail, which may act as the potential optical materials.

  8. 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.

  9. 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

  10. Forward Modeling Method of Gravity and Magnetic Fields and Their Gradient Tensors Based on 3-D Delaunay Discretization in Cartesian and Spherical Coordinate Systems

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Chen, C.; Du, J.; Sun, S.; Liang, Q.

    2015-12-01

    In the study of the inversion of gravity and magnetic data, the discretization of underground space is usually achieved by the use of structured grids. For instance, using the regular block as the module unit to divide model space in Cartesian coordinate system and the tesseroid in spherical coordinate system. Structured grids show clear spatial structures and mathematical properties. However, the block can only provide a rough approximation to the given terrain and using the tesseroid to approximate the terrain even seems impracticable. These shape determining errors cause the reduction of forward modeling precision. Moreover, the precision decreases again while using the tesseroid as no analytical algorithm has been acquired. On the other hand, since most terrain data has a limited resolution, unstructured grids, based on the polyhedron or tetrahedron, could fill the space completely, which allows us to reduce errors in shape determination to the minima. In addition, the analytical algorithms for polyhedron have been proposed. In our study, we use the tetrahedron as the module unit to divide the underground space. Moreover, based on the former researches, we supplement new analytical algorithms for tetrahedron to forward modeling gravity and magnetic fields and their gradient tensors in both Cartesian and spherical coordinate systems. The algorithm is testified by comparing the forward gravity and magnetic data of a block with the data obtained using the existed algorithms. The absolute difference between these two data is under 10e-9 mGal. Our approach is suitable for the inversion of gravity and magnetic data in both Cartesian and spherical coordinate systems.This study is supported by Natural Science Fund of Hubei Province (Grant No.: 2015CFB361) and International Cooperation Project in Science and Technology of China (Grant No.: 2010DFA24580).

  11. Two new pyridine-2,3-dicarboxylate coordination polymers prepared from zerovalent metal precursor: Syntheses, luminescent and magnetic properties

    SciTech Connect

    Semerci, Fatih; Yeşilel, Okan Zafer; Soylu, Mustafa Serkan; Yerli, Yusuf; Dal, Hakan

    2014-02-15

    Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. In the sandwiched 3D anionic framework of 1, pydc ligands exhibit hexadentate coordination; tridentate coordination bond with Cu(II) and tridentate ionic interaction with K{sup +} ions. (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows a rare topology consists of three dimensional (3,4,5)-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The distorted square pyramidal geometry of 2 is completed with an nitrogen atom from 4-mim and aqua ligand to form a 1D polynuclear structure. The hydrogen bonds link the 1D chains into 3D architecture. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. - Graphical abstract: Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. The water soluble (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows three dimensional a rare 3,4,5-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. Display Omitted - Highlights: • Water

  12. Thiazolo[5,4-d]thiazole-2,5-dicarboxylic acid, C 6H 2N 2O 4S 2, and its coordination polymers

    NASA Astrophysics Data System (ADS)

    Aprea, Alessia; Colombo, Valentina; Galli, Simona; Masciocchi, Norberto; Maspero, Angelo; Palmisano, Giovanni

    2010-05-01

    Thiazolo[5,4-d]thiazole-2,5-dicarboxylic acid, C 6H 2N 2O 4S 2, was isolated as a polycrystalline material, and its crystal structure was determined by ab-initio X-ray powder diffraction (XRPD) methods. This species, upon deprotonation, was subsequently used in preparing the new coordination polymers Ag 2(C 6N 2O 4S 2), Mn(C 6N 2O 4S 2)(H 2O) 2, Co(C 6N 2O 4S 2)(H 2O) 2, Cu(C 6N 2O 4S 2)(H 2O) and Zn(C 6N 2O 4S 2)(H 2O) 2, fully characterized by analytical, thermal and XRPD structural methods - including in situ thermodiffractometry and simultaneous TGA and DSC. In the first-row transition metal derivatives, the [C 6N 2O 4S 2] 2- anion systematically prefers the N, O-chelating, vs. the expected O, O'-bridging, coordination mode, not allowing the formation of porous 3D frameworks. Indeed, these species are dense 1D coordination polymers. At variance, the silver derivative possesses a complex, dense 3D framework, due to the presence of μ 6-[C 6N 2O 4S 2] 2- ligands showing two μ 2-bridging carboxylates and two monohapto N-donor sites. When dehydration is viable, materials of E n(C 6N 2O 4S 2) formulation are irreversibly recovered ( n = 1 for E = Mn, Co, Zn, Cu; n = 2, for E = H).

  13. SNL3dFace

    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 featuresmore » 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.« less

  14. 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.

  15. 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.

  16. Coordination polymers assembled from semirigid fluorene-based ligand: A couple of enantiomers

    NASA Astrophysics Data System (ADS)

    Li, Liang; Wang, Zihao; Chen, Qiang; Zhou, Xinhui; yang, Tao; Zhao, Qiang; Huang, Wei

    2015-11-01

    A couple of Mg(II)-based coordination polymer enantiomers [MgL(DMF)(H2O)3]n (R-MgL and S-MgL), and a Zn(II)-based coordination polymer [ZnL(DMF)]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 (H2L) 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 P21 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.

  17. 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.

  18. 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

  19. 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

    2015-04-01

    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. PMID:25781213

  20. Semiconductive and magnetic one-dimensional coordination polymers of Cu(II) with modified nucleobases.

    PubMed

    Amo-Ochoa, Pilar; Castillo, Oscar; Gómez-García, Carlos J; Hassanein, Khaled; Verma, Sandeep; Kumar, Jitendra; Zamora, Félix

    2013-10-01

    Four new copper(II) coordination complexes, obtained by reaction of CuX2 (X = acetate or chloride) with thymine-1-acetic acid and uracil-1-propionic acid as ligands, of formulas [Cu(TAcO)2(H2O)4]·4H2O (1), [Cu(TAcO)2(H2O)2]n (2), [Cu3(TAcO)4(H2O)2(OH)2]n·4H2O (3), and [Cu3(UPrO)2Cl2(OH)2(H2O)2]n (4) (TAcOH = thymine-1-acetic acid, UPrOH = uracil-1-propionic acid) are described. While 1 is a discrete complex, 2-4 are one-dimensional coordination polymers. Complexes 2-4 present dc conductivity values between 10(-6) and 10(-9) S/cm(-1). The magnetic behavior of complex 2 is typical for almost isolated Cu(II) metal centers. Moderate-weak antiferromagnetic interactions have been found in complex 3, whereas a combination of strong and weak antiferromagnetic interactions have been found in complex 4. Quantum computational calculations have been done to estimate the individual "J" magnetic coupling constant for each superexchange pathway in complexes 3 and 4. Compounds 2-4 are the first known examples of semiconductor and magnetic coordination polymers containing nucleobases. PMID:24040754

  1. Understanding the Structure of Reversible Coordination Polymers Based on Europium in Electrostatic Assemblies Using Time-Resolved Luminescence.

    PubMed

    Xu, Limin; Xie, Mengqi; Huang, Jianbin; Yan, Yun

    2016-06-14

    In situ characterization of the structure of reversible coordination polymers remains a challenge because of their dynamic and concentration-responsive nature. It is especially difficult to determine these structures in their self-assemblies where their degree of polymerization responds to the local concentration. In this paper, we report on the structure of reversible lanthanide coordination polymers in electrostatic assemblies using time-resolved luminescence (TRL) measurement. The reversible coordinating system is composed of the bifunctional ligand 1,11-bis(2,6-dicarboxypyridin-4-yloxy)-3,6,9-trioxaundecane (L2EO4) and europium ion Eu(3+). Upon mixing with the positively charged diblock copolymer poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP41-b-PEO205), electrostatic polyion micelles are formed and the negatively charged L2EO4-Eu coordination complex simultaneously transforms into coordination "polymers" in the micellar core. By virtue of the water-sensitive luminescence of Eu(3+), we are able to obtain the structural information of the L2EO4-Eu coordination polymers before and after the formation of polyion micelles. Upon analyzing the fluorescence decay curves of Eu(3+) before and after micellization, the fraction of Eu(3+) fully coordinated with L2EO4 is found to increase from 32 to 83%, which verifies the occurrence of chain extension of the L2EO4-Eu coordination polymers in the micellar core. Our work provides a qualitative picture for the structure change of reversible coordination polymers, which allows us to look into these "invisible" structures. PMID:27228142

  2. 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.

  3. 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. PMID:26388327

  4. 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

  5. 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.

  6. Coordination polymers built from 1,4-bis(imidazol-1-ylmethyl)benzene: from crystalline to amorphous.

    PubMed

    Adarsh, N N; Novio, Fernando; Ruiz-Molina, Daniel

    2016-07-28

    The supramolecular chemistry of the bis-imidazole ligand 1,4-bis(imidazol-1-ylmethyl)benzene, popularly known as bix, has been explored by various researchers in order to synthesize functional coordination polymers (CPs). The flexibility of the bix ligand, its unpredictable conformation and its coordination behaviour with transition metal ions have resulted in a huge number of structurally diverse and functionally intriguing CPs. In this perspective review we discuss the progress in CPs of bix between 1997 and today. More precisely, this review emphasizes the developments in functional supramolecular coordination polymers built from the bix ligand, from crystalline materials to amorphous nanomaterials. PMID:27335273

  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. Two double and triple interpenetrated Cd(II) and Zn(II) coordination polymers based on mixed O- and N-donor ligands: Syntheses, crystal structures and luminescent properties

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Li, Xiaohui; Zhang, Yan

    2016-01-01

    Two interpenetrated 3D coordination polymers, namely [Cd2(tdc)2(bpp) (DMA)]n (1) and [Zn2(tdc)2(bib)2]n·2n(DMA) (2) (H2tdc = 2,5-thiophenedicarboxylic acid, bpp = 1,3-di(4-pyridyl)propane, bib = 1, 4-bis(imidazolyl)butane, DMA = N,N-dimethylacetamide), have been solvothermally synthesized by the self-assembly of flexible N-donor and dicarboxylate ligands. Single crystal X-ray diffraction analyses revealed that compound 1 features a 2-fold interpenetrated 3D framework based on dinuclear [Cd2(COO)3] subunits and can be simplified into a 6-connected pcu topology, and compound 2 features a 3-fold interpenetrated 3D framework with 4-connected dia topology. Moreover, the thermal stabilities and luminescent properties of these two compounds were also investigated.

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

    SciTech Connect

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

    2013-09-15

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

  10. 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.

  11. A novel 2D porous indium coordination polymer with tunable luminescent property

    NASA Astrophysics Data System (ADS)

    Li, Xuejiao; Wang, Fangfang; Yang, He; Xu, Bo; Li, Cuncheng

    2016-08-01

    A new Indium coordination polymer [In(pda)1.5(phen)]n1 based on 1,4-phenylenediacetic acid (H2pda) and phen = 1,10-phenanthroline was obtained under hydrothermal condition and further characterized by single crystal X-ray analysis and other physicochemical studies such as infrared spectrum (IR), elemental analysis, thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Structure analysis reveals that complex 1 exhibits 2D porous (6,3) connected layer structure. Luminescent property of 1 was investigated both in the solid state and in different solvents and the results indicated that complex 1 demonstrates distinct solvent dependent luminescent property.

  12. 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.

  13. Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

    SciTech Connect

    Uemura, Kazuhiro; Onishi, Fumiaki; Yamasaki, Yukari; Kita, Hidetoshi

    2009-10-15

    NO{sub 2} containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO{sub 2}) and 2,5-dinitroterephthalate (bdc-(NO{sub 2}){sub 2}), afford porous coordination polymers, {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (2 contains solvents) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (3 contains solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn{sub 2} units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2 contains solvents and 3 contains solvents, a rectangle pore surrounded by eight Zn{sub 2} corners contains two and four NO{sub 2} moieties, respectively. Thermal gravimetry (TG) and X-ray powder diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me{sub 2}CO. Adsorption measurements reveal that dried 2 and 3 adsorb H{sub 2}O molecules to be {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].4H{sub 2}O{r_brace}{sub n} (2 contains 4H{sub 2}O) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].6H{sub 2}O{r_brace}{sub n} (3 contains 6H{sub 2}O), showing the pore hydrophilicity enhancement caused by NO{sub 2} group introduction. - Graphical abstract: Two hydrophilic porous coordination polymers, [Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)]{sub n} (2, bdc-NO{sub 2}=nitroterephthalate, dabco=1,4-diazabicyclo[2.2.2]octane) and [Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)]{sub n} (3, bdc-(NO{sub 2}){sub 2}=2,5-dinitroterephthalate), have been synthesized and characterized by single X-ray analyses, thermal gravimetry, and adsorption measurements.

  14. 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. PMID:27483139

  15. 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

    2015-09-01

    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. PMID:26258593

  16. 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.

  17. 1D coordination polymers with polychalcogenides as linkers between metal atoms

    SciTech Connect

    Kysliak, Oleksandr; Beck, Johannes

    2013-07-15

    The reactions of zinc metal with elemental selenium and selenium/sulfur mixtures in liquid ammonia or methylamine under solvothermal conditions in closed glass ampoules at 50 °C lead within some days specifically to [Zn(NH{sub 3}){sub 2}Se{sub 4}]{sub n} (1), [Zn(MeNH{sub 2}){sub 2}Se{sub 4}]{sub n} (2), [Zn(NH{sub 3}){sub 2}Se{sub 2.23}S{sub 1.77}]{sub n} (3). From MnCl{sub 2}, Rb{sub 2}Se and excess Se in n-butylamine [Mn({sup n}BuNH{sub 2}){sub 4}Se{sub 6}]{sub n} (4) is obtained after prolonged reaction time at ambient temperature. The compounds are sensitive towards air and loss of NH{sub 3} or the amine ligands. The crystal structures were determined by single crystal diffraction at low temperatures. As a common structural feature, all compounds represent 1D coordination polymers with polychalcogenide chains as linkers between the metal atoms and consist of infinite [M–Ch{sub m}–]{sub n} chains (M=Zn, Mn; Ch{sub m}=Se{sub 4}, (S/Se){sub 4}, Se{sub 6}). The Zn central atoms in 1–3 have tetrahedral coordination with two amine ligands, the Mn atoms in 4 have octahedral coordination with four amine ligands and cis position of the two Se atoms. Raman spectra of 1–3 show the stretching mode vibrations of the Ch{sub 4} groups. The observation of S–S, S–Se, and Se–Se vibration bands in the spectrum of 3 indicates the presence of mixed S/Se polyanions. An optical band gap of 1.86(5) eV was determined for 2 by diffuse reflectance spectroscopy. - Graphical abstract: The reaction of Zn and Se in liquid methylamine yields dark red [Zn(NH{sub 2}CH{sub 3})Se{sub 4}], a 1D coordination polymer consisting of helical Zn–Se{sub 4}–Zn– chains. - Highlights: • A series of 1D coordination polymers consisting of metal amine complexes concatenated by polychalcogenide ions is presented. • Syntheses were performed as solvothermal reactions in liquid ammonia, liquid methylamine and n-butylamine. • Crystal structures are dominated by helices [M–Ch{sub m

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

    SciTech Connect

    Liu, Yong-Liang; Wu, Ya-Pan; Li, Dong-Sheng; Dong, Wen-Wen; Zhou, Chun-Sheng

    2015-03-15

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

  19. The Enhancement on Proton Conductivity of Stable Polyoxometalate-Based Coordination Polymers by the Synergistic Effect of MultiProton Units.

    PubMed

    Li, Jing; Cao, Xue-Li; Wang, Yuan-Yuan; Zhang, Shu-Ran; Du, Dong-Ying; Qin, Jun-Sheng; Li, Shun-Li; Su, Zhong-Min; Lan, Ya-Qian

    2016-06-27

    Two novel polyoxometalate (POM)-based coordination polymers, namely, [Co(bpz)(Hbpz)][Co(SO4 )0.5 (H2 O)2 (bpz)]4 [PMo(VI) 8 Mo(V) 4 V(IV) 4 O42 ]⋅13 H2 O (NENU-530) and [Ni2 (bpz)(Hbpz)3 (H2 O)2 ][PMo(VI) 8 Mo(V) 4 V(IV) 4 O44 ]⋅8 H2 O (NENU-531) (H2 bpz=3,3',5,5'-tetramethyl-4,4'-bipyrazole), were isolated by hydrothermal methods, which represented 3D networks constructed by POM units, the protonated ligand and sulfate group. In contrast with most POM-based coordination polymers, these two compounds exhibit exceptional excellent chemical and thermal stability. More importantly, NENU-530 shows a high proton conductivity of 1.5×10(-3)  S cm(-1) at 75 °C and 98 % RH, which is one order of magnitude higher than that of NENU-531. Furthermore, structural analysis and functional measurement successfully demonstrated that the introduction of sulfate group is favorable for proton conductivity. Herein, the syntheses, crystal structures, proton conductivity, and the relationship between structure and property are presented. PMID:27243145

  20. 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.

  1. Employing linear tetranuclear [Zn4(COO)4(OH)2] clusters as building subunits to construct a new Zn(II) coordination polymer with tunable luminescent properties

    NASA Astrophysics Data System (ADS)

    Li, Wu-Wu; Zhang, Zun-Ting

    2016-02-01

    A new Zn(II) coordination polymer, [Zn2(btc) (biimpy) (OH)]n (1 H3btc = 1,3,5-benzenetricarboxylic acid, biimpy = 2,6-bis(1-imdazoly)pyridine) has been successfully synthesized and characterized by elemental analysis, powder single crystal X-ray diffraction analyses. Compound 1 features a 3D framework employing linear tetranuclear [Zn4(COO)4(OH)2] cluster as building subunits. Topological analysis reveals it represents a (3,10)-connected structural topology by viewing btc3-, linear tetranuclear clusters and biimpy as 3-connected nodes, 10-connected nodes, linear linkers, respectively. Moreover, the thermal stability and luminescent property of compound 1 have been well investigated.

  2. Synthesis, Structure and Spectroscopy Study of a 1D Copper Coordination Polymer Based on a Carboxybenzyl Viologen Ligand and SCN-Anion.

    PubMed

    Qiu, Li-xia; Wan, Fang; Zhu, Bin-bin; Sun, Yan-qiong; You, Yi; Chen, Yi-ping

    2015-05-01

    A zwitterionic viologen derivative ligand, 1,1'-bis(4-carboxybenzyl)-4 4'-bipyridinium dichloride (H2BpybcCl2) as a multifunctional ligand, has been synthesized incorporating a 4,4'-bipyridine core with two carboxylate groups as a. building block, specifically designed for the rational construction of metal-organic frameworks. H2BpybcCl2 ligand is a multifunctional ligand that contains viologen's specific functions and carboxylate coordination groups. The coordination polymers of viologen carboxylate with copper thiocyanate are not reported to date. A novel copper coordination polymer, [Cu(SCN)2 (Bpybc)] (I) was by solution diffusion method and characterized by single-crystal X-ray diffraction, XRD, elemental analyses, IR spectroscopy, UV-Vis DRS, TG analysis and liquid-state luminescent properties. Compound I crystallized in the monoclinic system with C2/c space group. Crystal data for complex I is as follow: a=19. 508(4) A, b=9. 474(2) Å, c =16. 963(3) Å, α=90°, β=124. 92(3)°, γ=90°. Two SCN-anions were coordinated to the Cu2+ cation forming a [Cu(SCN)2] unit. Complex I was built up by [Cu(SCN)2] units bridged sequentially by ladder-shaped Bpybc ligands to form one-dimensional zigzag chains running along the [203] direction. The chains were held together by π-π interaction between the pyridine rings and phenyl rings, thus yielding a 3-D extended supramolecular network. The UV-Visible absorption spectra show the absorption bands of π-π* transitions of Bpybc ligands and d-->d transition of Cu2+. The liquid-state luminescent property of compound I was investigated at room temperature. Attractively, the complex exhibits strong blue emission peak at 533 nm (λEx=360 nn) that can be assigned to intraligand transition of Bpybc ligand when it was excited at 360 nm. PMID:26415457

  3. Structure and efficient luminescence upconversion of Ln(iii) aromatic N-oxide coordination polymers.

    PubMed

    Chong, Bowie S K; Moore, Evan G

    2016-08-14

    A series of lanthanide-based coordination polymers {[Yb1-xErx(4,4'-bpdo)3(H2O)2](CF3SO3)3}∞ were synthesised by solvent diffusion techniques, where 4,4'-bpdo = 4,4'-bipyridine-N,N'-dioxide, and using differing mole fractions of Yb(iii) and Er(iii) which were systematically varied (x = 0, 0.05, 0.20, 0.50 and 1). All of the materials obtained were characterised using elemental analyses, single-crystal X-ray diffraction (SXRD) and solid-state photoluminescence studies. Structurally, the coordination polymers crystallise as an isomorphous series of infinite 2D sheets, which contain two inner sphere water molecules, and are isostructural with a previously characterised homometallic Yb(iii) compound. In addition to the normal Near Infra-Red (NIR) luminescence, these compounds also demonstrate upconversion emission upon 980 nm excitation. Upconversion luminescence measurements reveal visible emission in the red, green, and blue regions corresponding to the (2)H11/2→(4)I15/2, (4)F9/2→(4)I15/2 and (2)H9/2→(4)I15/2 transitions of the Er(iii) cation upon two and three-photon excitation. We also observed weak emission from the Er(iii) cation in the UV region for the first time in a Ln-MOF based material. PMID:27411484

  4. Facile fabrication of MIL-103(Eu) porous coordination polymer nanostructures and their sorption and sensing properties.

    PubMed

    Liu, Qing; Yang, Ji-Min; Guo, Fan; Jin, Li-Na; Sun, Wei-Yin

    2016-04-01

    Nano/microscale lanthanide porous coordination polymer MIL-103(Eu) [Eu(BTB)] (H3BTB = 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid) crystals have been fabricated at room temperature by a facile, convenient and environmentally friendly method. The structures of the products were confirmed by powder X-ray diffraction, and the crystal morphologies, including microrods, nanorods and nanospheres, were characterized by scanning electron microscopy. It is found that the addition of sodium acetate and the concentration of the reactants have an important impact on the morphology and size of the MIL-103(Eu) crystals. Gas adsorption measurements reveal that the products show high specific surface areas among the rare earth based coordination polymers and the MIL-103(Eu) nanorods can selectively adsorb CO2 over N2 under ambient conditions. Furthermore, all the products exhibit red emission corresponding to the (5)D0→(7)F2 transition of the Eu(iii) ion, and MIL-103(Eu) nanorods display sensitive and selective sensing for Cu(ii) ions and acetone molecules in solution. PMID:26940895

  5. 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.

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

    SciTech Connect

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

    2015-05-15

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

  7. 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.

  8. Localized cell stimulation by nitric oxide using a photoactive porous coordination polymer platform

    NASA Astrophysics Data System (ADS)

    Diring, Stéphane; Wang, Dan Ohtan; Kim, Chiwon; Kondo, Mio; Chen, Yong; Kitagawa, Susumu; Kamei, Ken-Ichiro; Furukawa, Shuhei

    2013-10-01

    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.

  9. 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

  10. Design of Advanced MnO/N-Gr 3D Walls through Polymer Cross-Linking for High-Performance Supercapacitor.

    PubMed

    Tran, Ngoc Quang; Kang, Bong Kyun; Tiruneh, Sintayehu Nibret; Yoon, Dae Ho

    2016-01-26

    Three-dimensional, vertically aligned MnO/nitrogen-doped graphene (3D MnO/N-Gr) walls were prepared through facile solution-phase synthesis followed by thermal treatment. Polyvinylpyrrolidone (PVP) was strategically added to generate cross-links to simultaneously form 3D wall structures and to incorporate nitrogen atoms into the graphene network. The unique wall features of the as-prepared 3D MnO/N-Gr hybirdes provide a large surface area (91.516 m(2) g(-1)) and allow for rapid diffusion of the ion electrolyte, resulting in a high specific capacitance of 378 F g(-1) at 0.25 A g(-1) and an excellent charge/discharge stability (93.7% capacity retention after 8000 cycles) in aqueous 1 m Na2 SO4 solution as electrolyte. Moreover, the symmetric supercapacitors that were rationally designed by using 3D MnO/N-Gr hybrids exhibit outstanding electrochemical performance in an organic electrolyte with an energy density of 90.6 Wh kg(-1) and a power density of 437.5 W kg(-1). PMID:26689298

  11. Multifunctional sensing ability of a new Pt/Zn-based luminescent coordination polymer.

    PubMed

    Kobayashi, Atsushi; Hara, Hirofumi; Noro, Shin-Ichiro; Kato, Masako

    2010-04-14

    We synthesized a new Pt/Zn-based coordination polymer, {Zn[Pt(CN)(2)(5,5'-dcbpy)].4H(2)O}(n), (5,5'-H(2)dcbpy = 5,5'-dicarboxy-2,2'-bipyridine), which exhibits reversible colour changes in response to temperature change or exposure to chemical vapours and liquids. Such chromic behaviour shows promise for sensing not only changes in temperature but also for detecting chemical solvents and vapours. The single crystal X-ray structure indicates that one-dimensional coordination polymeric chains formed by an alternating arrangement of [Zn(H(2)O)(3)](2+) and [Pt(CN)(2)(5,5'-dcbpy)](2-) stacked to produce moderate metallophilic interactions between the Pt(ii) ions. Thermogravimetric analysis and water vapour adsorption measurements show that both the crystal water and water coordinated to Zn(ii) ions can be removed and re-adsorbed reversibly by heating or under vacuum. Emission spectra at various temperatures and/or in the presence of vapours or liquids reveal that the complex exhibits thermochromic and solvatochromic-like behaviours, with the emission band shifting between 616 and 671 nm. IR spectroscopy and powder X-ray diffraction measurements suggest that this multichromic behaviour is a result of the cooperative phenomena of water adsorption/desorption around the Zn(ii) ions and the modification of the metallophilic interaction. PMID:20379533

  12. 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. PMID:26920783

  13. 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.

  14. A visual and reversible assay for temperature using thioflavin T-doped lanthanide/nucleotide coordination polymers.

    PubMed

    Li, Yan-Yun; Jiang, Xiao-Qin; Zhang, Min; Shi, Guoyue

    2016-04-21

    In this work, we prepared a type of thioflavin T (ThT)-doped lanthanide/nucleotide coordination polymer by the self-assembly of ThT, europium ions (Eu(3+)) and nucleotides (guanosine monophosphate, GMP) in aqueous solution (i.e. ThT/Eu/GMP). The Eu/GMP coordination polymers show excellent adaptive inclusion properties for ThT in a convenient one-step approach, which can readily enhance the fluorescence of ThT via the restricted effect. Moreover, the as-prepared hydrophilic ThT/Eu/GMP coordination polymers have the capability to act as a temperature-sensitive, visual and reversible sensor in aqueous solution under the irradiation of visible light. Our proposed design is cost-effective and simple to prepare without chemical modification or fluorescence labeling. PMID:27010102

  15. Electrochemical Li-Ion Intercalation in Octacyanotungstate-Bridged Coordination Polymer with Evidence of Three Magnetic Regimes.

    PubMed

    Long, Jérôme; Asakura, Daisuke; Okubo, Masashi; Yamada, Atsuo; Guari, Yannick; Larionova, Joulia

    2016-08-01

    Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)5[W(CN)8] operates as a Li(+)-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li(+) ion in the solid-state redox reaction between paramagnetic [W(V)(CN)8](3-) and diamagnetic [W(IV)(CN)8](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved. PMID:27420412

  16. Temperature-dependent polymorphism and magnetic properties of three-dimensional copper pyromellitate coordination polymers containing 4,4′-dipyridylamine

    SciTech Connect

    Mizzi, Jessica E.; Staples, Richard J.; LaDuca, Robert L.

    2015-05-15

    A pair of three-dimensional divalent copper pyromellitate (1,2,4,5-benzene-tetracarboxylate, pyro) coordination polymers containing 4,4′-dipyridylamine (dpa) was hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction. The higher-temperature phase ([H{sub 2}dpa][Cu{sub 3}(pyro){sub 2}(H{sub 2}O){sub 3}]·2.5H{sub 2}O){sub n} (1) displays an acentric 3-D 4,4,6-connected anionic network with (4{sup 4}5.6)(5{sup 4}8{sup 2})(4{sup 4}5{sup 4}6{sup 3}7{sup 4}) topology, featuring (Cu{sub 2}(OCO){sub 4}) paddlewheel dimers and isolated copper ions. Charge-balancing H{sub 2}dpa cations are embedded in incipient voids. Prepared at lower temperature, ([Cu{sub 3}(pyro){sub 2}(dpa){sub 2}(dpaH){sub 2}]·3H{sub 2}O){sub n} (2) manifests a 3-D 4,4,4-connected neutral network with uncommon (4{sup 2}6{sup 4}){sub 4}(6{sup 4}8{sup 2}) frl topology based on (Cu{sub 3}(OCO){sub 2}) linear trimers. Antiferromagnetic coupling (J=–82(5) cm{sup –1}) was observed within the (Cu{sub 2}(OCO){sub 4}) dimeric units in 1, while weak ferromagnetic coupling (J=1.0(4) cm{sup –1}) was evident for the (Cu{sub 3}(OCO){sub 2}) linear trimers in 2. Thermal degradation behavior of these new materials is also presented. - Graphical abstract: Two copper pyromellitate coordination polymers containing 4,4′-dipyridylamine were prepared. The higher-temperature phase ([H{sub 2}dpa][Cu{sub 3}(pyro){sub 2}(H{sub 2}O){sub 3}]∙2.5H{sub 2}O){sub n} displays an acentric 3-D trinodal anionic network with (4{sup 4}5.6)(5{sup 4}8{sup 2})(4{sup 4}5{sup 4}6{sup 3}7{sup 4}) topology, featuring antiferromagnetically coupled (Cu{sub 2}(OCO){sub 4}) paddlewheel dimers and isolated copper ions. - Highlights: • Copper pyromellitate (pyro) coordination polymers with 4,4′-dipyridylamine (dpa). • Higher-temperature phase 1 has 3-D anionic trinodal network with H{sub 2}dpa cations. • Lower-temperature phase 2 has rare 3-D frl network. • Dimers and chains in 1 show

  17. 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.

  18. 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%. PMID:27247213

  19. Synthesis and crystal structure of new lanthanide coordination polymers with Pyridine-2, 6-dicarboxylic acid

    NASA Astrophysics Data System (ADS)

    Du, Rui-Zhi; Wang, Yan-Yan; Xie, Yu-Yu; Li, Hao-Tian; Liu, Tian-Fu

    2016-03-01

    Reactions between Ln(NO3)3 aq (Ln = La (1), Ce (2), Pr (3) and Nd(4)), pyridine-2, 6-dicarboxylic acid (2, 6-pdc), and sodium nitroprusside Na2[Fe(CN)5NO] lead to three-dimensional network structures: {[Ln2(2, 6-pdc)2(H2O)8][Fe(CN)5NO]·4H2O}n (Ln = La (1), Ce (2), Pr (3) and Nd(4)). The complexes 1 and 2 crystallize in the monoclinic space group Cc while complexes 3 and 4 crystallize in the monoclinic space group I2. The Ln(III) ion is nine-coordinate by four oxygen atoms of three 2, 6-pdc ligands, four oxygen of water and one nitrogen atom of 2, 6-pdc. Ln(III) ions are bridged by 2, 6-pdc ligands via bridging/chelating-bridging pentadentate coordination to form 3-D framework structures. Hydrogen bonds provide additional stabilization of the crystal structures. The magnetic properties of 2-4 have been investigated.

  20. 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

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

    PubMed

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

    2014-04-25

    The compound (C4C1py)[Cu(SCN)2], (C4C1py = 1-Butyl-4-methyl-pyridinium), which can be obtained from CuSCN and the ionic liquid (C4C1py)(SCN), turns out to be a new organic-inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)2](-) units, in which the thiocyanates bridge the copper ions in a μ1,3-fashion. The resulting one-dimensional chains run along the a axis, separated by the C4C1py counterions. Powder X-ray diffraction not only confirms the single-crystal X-ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature-dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100 °C point towards the formation of polyanionic chain fragments in the melt. Solid-state UV/Vis spectroscopy shows a broad absorption band around 18,870 cm(-1) (530 nm) and another strong one below 20,000 cm(-1) (<500 nm). The latter is attributed to the d(Cu(I))→π*(SCN)-MLCT (metal-to-ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15,870 cm(-1) (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases. PMID:24644064

  2. 3d-3d correspondence revisited

    NASA Astrophysics Data System (ADS)

    Chung, Hee-Joong; Dimofte, Tudor; Gukov, Sergei; Sułkowski, Piotr

    2016-04-01

    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. We also consider the cutting and gluing of 3-manifolds along smooth boundaries and the role played by all flat connections in this operation.

  3. 3D dose verification with polymer gel detectors of brain-spine match line for proton pencil beam cranio-spinal: A preliminary study

    NASA Astrophysics Data System (ADS)

    Avery, S.; Cardin, A.; Lin, L.; Kirk, M.; Kassaee, A.; Maryanski, M. J.

    2015-01-01

    This paper is intended as a preliminary study to demonstrate the quality assurance benefits from polymer gel detectors for proton pencil beam cranio-spinal treatments. A stable gel type was selected for protons to suppress the LET dependence at the end of the Bragg peak. The depth dose distributions in the gels were examined with regard of its dose dependences and compared to baseline measurements. The preliminary experimental results indicate polymer gel detectors may be able to verify dose in three dimensions along match line for proton therapy treatments.

  4. Crystal structures, fluorescent and magnetic properties of five new coordination polymers based on biphenyl-3,4 Prime ,5-tricarboxylic acid

    SciTech Connect

    Lu Yingli; Zhao Wenjie; Liu Yu; Liu Bin; Feng Xing; Tan Jinting; Li Xia; Yang Xuwu

    2012-08-15

    Five new coordination polymers, {l_brace}[Cd{sub 3}(bpt){sub 2}(DMF){sub 2}]{center_dot}(H{sub 2}O){sub 2}{r_brace}{sub n} (1), [Cd(Hbpt)(bipy){sub 0.5}(H{sub 2}O)]{sub n} (2), [Cd{sub 2}(bpt)(phen){sub 2}Cl]{sub n} (3), {l_brace}[Cu{sub 2}(bpt)(phen)({mu}{sub 2}-OH)(H{sub 2}O)]{center_dot}(H{sub 2}O){sub 2}{r_brace}{sub n} (4) and {l_brace}[Mn{sub 5}(Hbpt){sub 4}(phen){sub 4}({mu}{sub 2}-OH){sub 2}(H{sub 2}O){sub 2}]{center_dot}(H{sub 2}O){sub 2}(CH{sub 3}CN){sub 2}{r_brace}{sub n} (5) have been prepared through hydro(solvo)thermal reactions of H{sub 3}bpt (H{sub 3}bpt=biphenyl-3,4 Prime ,5-tricarboxylic acid) with different pyridyl-containing auxiliary ligands (bipy=4,4 Prime -bipyridine and phen=1,10-phenanthroline). Compound 1 represents a 3D ladder-like framework composed of rod-shaped infinite chains. In 2, the bridging ligand bipy links binuclear cadmium ions to generate a 2D layer. Compound 3 features a 1D ladder structure and further linked by {pi}-{pi} stacking interaction to form a 3D supramolecular network. Compound 4 exhibits a binodal 3-connected net which features the Schlafli symbol of (4{center_dot}8{sup 2}). Compound 5 contains trimetallic cluster and binuclear unite which are further linked by Hbpt ligand to form a 2D layer. Moreover, photoluminescent properties of compounds 1-3 were studied in the solid state. Magnetic susceptibility measurements indicate that compound 4 exhibits ferromagnetic exchange interactions, whereas compound 5 displays antiferromagnetic exchange interactions. - Graphical abstract: Five new coordination polymers have been prepared through reactions of H{sub 3}bpt with different pyridyl-containing auxiliary ligands. The bpt exhibits four new kinds of coordination modes with 'V or Y shape'. Highlights: Black-Right-Pointing-Pointer 1 represents a unique (4{center_dot}8)-connected network with a Schlafli symbol (4{sup 6})(4{sup 12}{center_dot}6{sup 12}{center_dot}8{sup 4}). Black-Right-Pointing-Pointer Compound 4 shows

  5. 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.

  6. Bright luminescence in lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand.

    PubMed

    Sobieray, Miriam; Gode, Jens; Seidel, Christiane; Poß, Marieke; Feldmann, Claus; Ruschewitz, Uwe

    2015-04-01

    Ten new coordination polymers of the general compositions ∞²[Ln(III)(tfBDC)(NO3)(DMF)2]·DMF with Ln(III) = Eu(3+) (1), Gd(3+) (2), Tb(3+) (3), Ho(3+) (4), Tm(3+) (5), ∞²[Ln(III)(tfBDC)(CH3COO)(FA)3]·3FA with Ln(III) = Sm(3+) (6), Eu(3+) (7) and ∞²[Ln(III)(tfBDC)(NO3)(DMSO)2] with Ln(III) = Ho(3+) (8), Er(3+) (9) and Tm(3+) (10) were synthesized and structurally characterized by X-ray single crystal diffraction (tfBDC(2-) = 2,3,5,6-tetrafluoroterephthalate, DMF = N,N'-dimethylformamide, FA = formamide, DMSO = dimethyl sulfoxide). 1-5 crystallize in the monoclinic space group C2/c with Z = 8, 6 and 7 in P1̄ with Z = 2 and 8-10 in Pbca with Z = 8. All crystal structures contain binuclear lanthanide nodes that are connected by 2,3,5,6-tetrafluoroterephthalates (tfBDC(2-)) to form two-dimensional polymeric structural units. Despite this common structural feature the coordination within these binuclear units is quite different in detail, e.g. CN = 9 for 1-7 and CN = 8 for 8-10. The emission spectra of the europium (1, 7) and terbium (3) compounds reveal bright red and green emission in the visible region. The resulting high quantum yields of 53% (1) and 67% (3) at room temperature show that the replacement of organic ligands with C-H groups by perfluorinated ligands leads to compounds with intense emission, as vibrational quenching is reduced. On the other hand, the influence of the coordinating solvent and additional ligands cannot be neglected, as the replacement of DMF by FA and NO3(-) by CH3COO(-) in 7 leads to a reduced quantum yield of only 10%. Thermoanalytical investigations show that all compounds are stable up to 100-150 °C, before a stepwise release of solvent molecules starts followed by a decomposition of the coordination polymer. PMID:25740408

  7. 3D graphene oxide-polymer hydrogel: near-infrared light-triggered active scaffold for reversible cell capture and on-demand release.

    PubMed

    Li, Wen; Wang, Jiasi; Ren, Jinsong; Qu, Xiaogang

    2013-12-10

    An active cell scaffold based on a graphene-polymer hydrogel has been successfully fabricated. The macroporous hydrogel can efficiently capture cells not only through the bioadhesive ligand RGD but also through on-demand release of cells with an NIR light stimulus. The latter process shows better dynamic control over cells than traditional passive-hydrogel-based cell depots. PMID:24123218

  8. Two-semiconductive-component hybrid coordination polymers with controllable photo-induced electron-transfer properties.

    PubMed

    Liu, Jian-Jun; Chen, Yong; Lin, Mei-Jin; Huang, Chang-Cang; Dai, Wen-Xin

    2016-04-12

    Two semiconductive inorganic-organic hybrid coordination polymers constructed from metal iodide clusters and naphthalene diimide semiconductive components, [Cu2I2(DPNDI)]n () and [PbI2(DPNDI)]n () (DPNDI = N,N'-di-(4-pyridyl)-1,4,5,8-naphthalene diimide), have been synthesized and characterized. Although possessing similar 2D heterostructures, hybrids exhibited different photo-induced electron-transfer properties. Due to the higher HOMO energy level of the [Cu2I2]n chain than that of the [PbI2]n cluster, only hybrid can easily undergo intramolecular electron transfer to form a long-lived charge separated state, which may be applied in artificial photosynthesis. PMID:26985714

  9. 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

  10. A Highly Water-Tolerant Magnesium(II) Coordination Polymer Derived from a Flexible Layered Structure.

    PubMed

    Ochi, Rika; Noro, Shin-Ichiro; Kamiya, Yuichi; Kubo, Kazuya; Nakamura, Takayoshi

    2016-07-25

    A two-dimensional (2D) layered Mg(II) coordination polymer (CP) with a high tolerance for H2 O was designed, synthesised, and crystallographically characterised. The synthesis was achieved by the introduction of a flexible 2D layered structure composed of Mg(II) ions and isonicotinate N-oxide ligands. Owing to its high H2 O tolerance, the obtained 2D layered structure has the flexibility to repeatedly adsorb a large amount of H2 O associated with interlayer expansion and enable the removal of H2 O from a H2 O/2-propanol mixed vapour. These results indicate that the CP could be an excellent dehydrating agent. PMID:27373696

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

    PubMed

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

    2015-11-28

    A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g(-1) at a current density of 1 A g(-1) in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles. PMID:26487265

  12. Two new luminescent Zn(II) coordination polymers with different interpenetrated motifs

    NASA Astrophysics Data System (ADS)

    Song, Changying; Liu, Qifeng; Liu, Wei; Cao, Ziqing; Ren, Yuanyuan; Zhou, Qichao; Zhang, Li

    2015-11-01

    Solvothermal reactions of Zn(NO3)2, H2tdc and bib in the presence of different solvents (DMF = N,N'- dimethylformamide or DMA = N,N'- dimethylacetamide) have given rise to two new coordination polymers, namely [Zn2(tdc)2(bib)2]n·2n(H2O) (1) and [Zn(tdc)(bib)0.5(H2O)]n (2) (H2tdc = 2,5-thiophenedicarboxylic acid, bib = 1, 4-bis(imidazolyl)butane). The structures were determined by single crystal X-ray diffraction and characterized by elemental analysis, powder X-ray diffraction and infrared spectroscopy. Compound 1 exhibits a 4-fold interpenetrated dia topological network, and compound 2 features a 8-fold interpenetrated ths topological network. In addition, thermal stabilities and solid state luminescent properties of these two compounds were also investigated.

  13. Catalytic glucose isomerization by porous coordination polymers with open metal sites.

    PubMed

    Akiyama, George; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu

    2014-10-01

    Highly efficient catalytic isomerization reactions from glucose to fructose in aqueous media using porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is reported for the first time. The catalytic activity of PCPs functionalized with -NH2, -(CH3)2, -NO2, and -SO3H groups on the pore surface is systematically tested. The catalytic activity can be tuned by the acidity of open metal sites (OMSs) by modifying the organic linkers with the functional groups. As a result, it is demonstrated that MIL-101 functionalized with -SO3H not only shows high conversion of glucose but also selectively produces fructose. Further, catalytic one-pot conversion of amylose to fructose is achieved, thanks to the high stability of the framework in an acidic solution. These results show that MOF/PCP compounds having OMSs are promising materials for various useful heterogeneous catalytic reactions, in particular in the biomass field. PMID:25080129

  14. 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

  15. 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. PMID:27344485

  16. A novel copper(II) coordination polymer with carboxylate and isoindol backbones of a bifunctional ligand

    NASA Astrophysics Data System (ADS)

    Patra, Ayan; Sen, Tamal K.; Musie, Ghezai T.; Mandal, Swadhin K.; Bera, Manindranath

    2013-09-01

    The reaction of a bifunctional ligand, 3-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (Hpda) with Cu(NO3)2ṡ3H2O in methanol-water in the presence of NaOH at room temperature produces a novel dinuclear copper(II) coordination polymer [Cu2(pda)4]n. The complex is fully characterized in the solid state as well as in solution using various analytical techniques including single crystal X-ray diffraction study. The single crystal X-ray structure analysis reveals that the monomeric unit of complex consists of Cu2(O2CR)4 paddlewheel building unit, where the two copper centers acquire a distorted square pyramidal geometry with amide oxygen of the isoindol ring of an adjacent Hpda ligand sitting on the axial positions.

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    Two new three-dimensional 12-connected metal-organic coordination polymers, [Zn2(bptc)(H2O)]·C2H5OH·H2O (1) and [Cd4(bptc)2(bbi)(H2O)]·H2O (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.

  19. Bismuth-Based Coordination Polymers with Efficient Aggregation-Induced Phosphorescence and Reversible Mechanochromic Luminescence.

    PubMed

    Toma, Oksana; Allain, Magali; Meinardi, Francesco; Forni, Alessandra; Botta, Chiara; Mercier, Nicolas

    2016-07-01

    Two bismuth coordination polymers (CPs), (TBA)[BiBr4 (bp4mo)] (TBA=tetrabutylammonium) and [BiBr3 (bp4mo)2 ], which are based on the rarely used simple ditopic ligand N-oxide-4,4'-bipyridine (bp4mo), show mechanochromic luminescence (MCL). High solid-state phosphorescence quantum yields of up to 85 % were determined for (TBA)[BiBr4 (bp4mo)] (λem =540 nm). Thorough investigations of the luminescence properties combined with DFT and TDDFT calculations revealed that the emission is due to aggregation-induced phosphorescence (AIP). Upon grinding, both samples became amorphous, and their luminescence changed from yellow to orange and red, respectively. Heating or exposure to water vapor led to the recovery of the initial luminescence. These materials are the first examples of mechanochromic phosphors based on bismuth(III). PMID:27166740

  20. 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.

  1. 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. PMID:26368067

  2. Glass Formation of a Coordination Polymer Crystal for Enhanced Proton Conductivity and Material Flexibility.

    PubMed

    Chen, Wenqian; Horike, Satoshi; Umeyama, Daiki; Ogiwara, Naoki; Itakura, Tomoya; Tassel, Cédric; Goto, Yoshihiro; Kageyama, Hiroshi; Kitagawa, Susumu

    2016-04-18

    The glassy state of a two-dimensional (2D) Cd(2+) coordination polymer crystal was prepared by a solvent-free mechanical milling process. The glassy state retains the 2D structure of the crystalline material, albeit with significant distortion, as characterized by synchrotron X-ray analyses and solid-state multinuclear NMR spectroscopy. It transforms to its original crystal structure upon heating. Thus, reversible crystal-to-glass transformation is possible using our new processes. The glass state displays superior properties compared to the crystalline state; specifically, it shows anhydrous proton conductivity and a dielectric constant two orders of magnitude greater than the crystalline material. It also shows material flexibility and transparency. PMID:26990042

  3. Anion-dependent construction of a series of fluorescent coordination polymers based on 1D zinc∩4,4‧-bis(imidazol-1-yl)-biphenyl substrates

    NASA Astrophysics Data System (ADS)

    Zou, Kang-Yu; Zou, Qian; Han, Tong; Liu, Yi-Chen; Wang, Jun-Jie; Zhang, Xue; Li, Zuo-Xi

    2016-03-01

    In this work, the rod-like ligand 4,4‧-bis(imidazol-1-yl)-biphenyl (bibp) has been utilized as a building block to carry out counterion effects on the structural diversities of coordination polymers. A series of new zinc complexes, [Zn(trans-bibp)Cl2]∞ (1), [Zn(trans-bibp)Br2]∞ (2), {[Zn(cis-bibp)(Ac)2]·(H2O)}∞ (3), [Zn(trans-bibp)SO4]∞ (4), {[Zn2(cis-bibp)2(ipa)2]·(H2O)}∞ (5, H2ipa=isophthalic acid) and {[Zn(trans-bibp)(cis-bibp)]·(ClO4)2(CHCl3)2(CH3OH)}∞ (6) have been successfully synthesized. Complexes 1 and 2 are iso-structural, which show a 1D W-type chain [Zn(trans-bibp)]∞. Complex 3 exhibits a 2D wave-like layer formed by the hydrogen bond among the 1D linear chain [Zn(cis-bibp)]∞. Complex 4 displays a 2D fish-bone lattice, which is generated from connecting the 1D W-type chain [Zn(trans-bibp)]∞ by the μ2-SO42- . Complex 5 presents an interesting 2D-3D 65·8 architecture, including two 1D chains [Zn(ipa)]∞ and [Zn(cis-bibp)]∞. Complex 6 demonstrates a 2D wave-like layer [Zn(trans-bibp)(cis-bibp)]∞. The structural diversities among 1-6 have been carefully discussed, and the role of counterion in the self-assembly of coordination polymer have also been well documented from the coordination affinity and bridging mode. Furthermore, the solid-state fluorescence properties of 1-6 at room temperature have been studied.

  4. 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

  5. Anion effect on the topological frameworks of a series of manganese coordination polymers based on 1,4-bis(imidazol-1-yl)-benzene: Syntheses, crystal structures and magnetic properties

    NASA Astrophysics Data System (ADS)

    Ye, Gan; Zou, Kang-Yu; Yang, Ying; Wang, Jun-Jie; Gou, Xiao-Feng; Li, Zuo-Xi

    2015-05-01

    In this work, the rod-like ligand 1,4-bis(imidazol-1-yl)-benzene (bib) has been utilized as a building block to perform counterion researches on the structural diversities of coordination polymers. A series of new manganese compounds, {[Mn(bib)3(ClO4)2](CHCl3)2}n (1), [Mn(bib)2(N3)2]n (2), [Mn(bib)2(HCO2)2]n (3), [Mn(bib)2(Ac)2]n (4), {[Mn(bib)2(CF3SO3)2](CH2Cl2)4}n (5), and [Mn(bib)2(SO4)]n (6) have been successfully synthesized. Compound 1 shows a 3D interpenetrating α-Po network only based on the bib linker. Compounds 2 and 3 exhibit a 2D (4,4) layer with parallel and incline interpenetration, respectively. Compounds 4 and 5 display a parallel-packing 2D (4,4) layer with the porosity of 23.4% and 61.4%, respectively. Compound 6 furnishes a 3D α-Po framework with a 2D (4,4) layer pillared by the μ2-SO42- ion. The structural diversities among 1-6 have been carefully discussed, and the roles of counterions (from coordination affinity and molecular size) in the self-assembly of coordination polymers have also been well documented. Furthermore, magnetic properties of 6 have been carefully studied.

  6. Lanthanide Coordination Polymer Nanoparticles as an Excellent Artificial Peroxidase for Hydrogen Peroxide Detection.

    PubMed

    Zeng, Hui-Hui; Qiu, Wei-Bin; Zhang, Li; Liang, Ru-Ping; Qiu, Jian-Ding

    2016-06-21

    Lanthanide coordination polymer nanoparticles (Ln-CPNs) have been recently demonstrated as excellent platforms for biomolecule detection. In this work, we synthesized novel cerium coordination polymer nanoparticles ATP-Ce-Tris CPNs in a simple and quick way using ATP molecules as the biocompatible ligands to Ce(3+) ions in tris(hydroxymethyl)aminomethane hydrochloric (Tris-HCl) solution. In view of the excellent free radical scavenging property of cerium compounds, which is ascribed to the mixed valence state (Ce(3+), Ce(4+)) and the reversible switch from Ce(3+) to Ce(4+), the synthesized ATP-Ce-Tris CPNs was used as artificial peroxidase to selectively and sensitively detect H2O2. The sensing mechanism depends on the oxidation of the fluorescent ATP-Ce(III)-Tris CPNs to nonfluorescent ATP-Ce(IV)-Tris CPNs by H2O2. Compared with those inorganic cerium oxide sensors, this kind of fluoresence ATP-Ce-Tris CPNs sensor needs no additional organic redox dye, such as ABTS (2,20-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid), TMB (3,3,5,5-tetramethylbenzidine), or fluorescein as signal molecules. Moreover, such ATP-Ce-Tris CPNs sensor exhibited a more sensitive response to H2O2 with a detection limit down to 0.6 nM, which is 2 orders of magnitude lower than those of cerium oxide sensors. This sensing platform was further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) for the oxidation of glucose and formation of H2O2. PMID:27220993

  7. Syntheses and crystal structures of four 1-D or 2-D coordination polymers based on 1-((benzotriazol-1-yl)methyl)-1 H-1,3-imidazole

    NASA Astrophysics Data System (ADS)

    Zhou, Xiaoli; Li, Weiqiang; Jin, Guanghua; Zhao, Dong; Zhu, Xiaoqing; Meng, Xiangru; Hou, Hongwei

    2011-05-01

    In this paper, four coordination polymers, {[Ag(bmi)]·NO 3} n ( 1), [Co(N 3) 2(bmi) 2] n ( 2), [Cu(SCN) 2(bmi) 2] n ( 3), and {[Cu(bmi) 2(CH 3OH)(H 2O)]·(ClO 4) 2} n ( 4) have been synthesized through the reactions of an unsymmetrical ligand 1-((benzotriazol-1-yl)methyl)-1 H-1,3-imidazole (bmi) with Ag(I), Co(II) and Cu(II) salts at room temperature. X-ray diffraction analyses showed that compound 1 exhibits double-stranded helical chain. Compounds 2- 4 display 2-D rhombus grid network structure. The rhombus grid consists of 32-membered rings, and gives the dimensions of ca. 8.9 × 8.9 Å for compound 2, ca. 10.1 × 10.1 Å for compound 3, and ca. 9.7 × 9.5 Å for compound 4. In addition, the 2-D layers of compound 3 are stacked into 3-D structure via π- π interactions, while the 3-D architecture of compound 4 is realized through complicated hydrogen bonds and π- π interactions. The thermal analyses of compounds 1 and 3 indicate that they have high thermal stability and are stable up to 259 °C.

  8. pH-Dependent two novel heteronuclear Cu(II)/Sr(II) coordination polymers constructed from 1,3,5-benzenetricarboxylic acid: Synthesis, crystal structures and properties

    NASA Astrophysics Data System (ADS)

    Sun, Qiao-Zhen; Yin, Yi-Biao; Pan, Jun-Qiao; Chai, Li-Yuan; Su, Nan; Liu, Hui; Zhao, Yi-Lin; Liu, Xing-Tao

    2016-02-01

    Two novel heteronuclear coordination polymers, namely, [CuSr2(BTC)2]·10H2O (1) and [Cu2Sr(H4TMA)2]·4H2O (2) (H3BTC = 1,3,5-benzenetricarboxylic acid, H4TMA = 2-hydroxytrimesic acid) were hydrothermally synthesized as pH-dependent products and characterized by elemental analysis (EA), infrared spectroscopy (IR) and single crystal X-ray diffraction. For compound 1, it displays a 3D structure with (2,5,6)-connected net topology. For 2, the H3BTC ligand is oxidized into H4TMA and compound 2 features a 2D layer structure, which is further linked by Cu⋯Cu and Cu⋯O supramolecular interactions into a 3D structure. The results show that the pH plays a crucial role in determining the structure of the compounds. In addition, thermalgravimetric analysis of compounds 1-2 and luminescence property of 1 are also investigated.

  9. Two new Zn(II) coordination polymers based on mixed pipemidic acid and flexible aromatic dicarboxylic acid ligands: Syntheses, crystal structures and luminescent properties

    NASA Astrophysics Data System (ADS)

    Jia, Yanxia; Zhou, Pingping

    2016-09-01

    Two new Zn(II) coordination polymers, namely [Zn(4,4‧-sdb) (HPPA)]n (1) and [Zn(2,2‧-bpdc)0.5(PPA)]n (2) (4,4‧-H2sdb = 4,4‧-sulfonyldibenzoate, 2,2‧-H2bpdc = 2,2‧-biphenyldicarboxylic acid, HPPA = pipemidic acid) were successfully obtained under hydrothermal conditions. These two compounds were further characterized by single-crystal X-ray diffraction analyses, elemental analyses, powder X-ray diffraction (PXRD) analyses and IR spectra. Compound 1 features a 1D chain structure, which further extended into a 3D supramolecular framework via intermolecular hydrogen bonds and weak van der Waals interactions, and compound 2 features a 3D framework with 6-connected α-Po-type topology. The structural regulation for these two compounds was successfully achieved by changing the flexible aromatic dicarboxylic acid ligand. Moreover, the thermal stabilities and luminescent properties for these two compounds were also investigated.

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

    NASA Astrophysics Data System (ADS)

    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

    2015-12-01

    Solvothermal reactions of Zn(NO3)2·6H2O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H2bdc), p-phenylenediacetic acid (p-H2pda), benzophenone-4,4-dicarboxylic acid (H2bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]n (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H2O}n (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H2O}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.

  11. 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?

  12. 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.

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

    PubMed

    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 (S2(2-)) 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. PMID:26974410

  14. Controllable synthesis of Zn/Cd(ii) coordination polymers: dual-emissive luminescent properties, and tailoring emission tendency under varying excitation energies.

    PubMed

    Xing, Kai; Fan, Ruiqing; Gao, Song; Wang, Xinming; Du, Xi; Wang, Ping; Fang, Ru; Yang, Yulin

    2016-03-21

    Based on a new asymmetric semi-rigid V-shaped tricarboxylate ligand 3-(2',3'-dicarboxylphenoxy)benzoic acid (H3dpob), a series of zinc/cadmium(ii) coordination polymers, {[Cd(Hdpob)(H2O)3]·H2O}n (1), [Cd(Hdpob)(bib)]n (2), [Zn(Hdpob)(bib)0.5]n (3), {[Cd1.5(dpob)(2,2'-bipy)]·0.5H2O}2n (4) and {[Cd3(dpob)2(4,4'-bipy)2]·3H2O}n (5) [bib = 1,4-bis(1-imidazolyl)benzene; 2,2'-bipy = 2,2'-bipyridine; 4,4'-bipy = 4,4'-bipyridine], have been successfully synthesized via hydro(solvo)thermal reactions. 1 forms a three dimensional (3D) supramolecular structure linked by two types of intermolecular hydrogen bonds based on zig-zag 1D chains, whereas 2 and 3 are obtained with a similar 2D layer structure by the same ligands and further connected into a 3D structure through hydrogen bonds. 4 displays a homochiral 2D structure though two achiral ligands 2,2'-bipy and H3dpob, which contains right-handed helical infinite chains. 5 is a 3D structure containing 2D metal-pyridine layer motifs, which are further pillared by beaded dpob(3-) ligands to complete the structure and form a 6-connected pcu (primitive cubic) net. In DMSO solvent, 1-5 illustrate dual-emission properties but have different low-energy emission (LE) intensities relatively. Extraordinarily, the difference resulting from central metals between 2 and 3 makes the intensity of LE dramatically enhanced and quenched. In this regard, the luminescence of 2 and 3 can be tuned between blue and green regions by varying the excitation light, and the tuning tendency can be tailored with inverse directions. Comparing their tunable-sensitivity to energy quantitatively, the theoretical calculation displays that 3 (4.29%) is little higher than 2 (3.59%) in a relative lower excitation wavelength zone. Meanwhile, five coordination polymers show distinct luminescence thermochromism in the solid state. When the temperature decreases from 298 K to 77 K, the red-shift from blue/green to the pure yellow light region is highlighted. The

  15. 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.

  16. 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.

  17. Emission behaviour of a series of bimetallic Cd(ii)-Au(i) coordination polymers.

    PubMed

    Yamagishi, Akihiko; Kawasaki, Takeshi; Hiruma, Kei; Sato, Hisako; Kitazawa, Takafumi

    2016-05-01

    A series of bimetallic coordination polymers with the elemental composition of [Cd(II)L2][Au(CN)2]2, (L = 3-methylpyridine, 4-ethylpyridine, 3,5-lutidine and 3-fluoropyridine) were synthesized and their crystal structures were determined. In all of the investigated compounds, there existed a pair of Au-Au atoms whose interatomic distance was shorter than the sum of van der Waals radii (0.36 nm) as an indication of the aurophilic interaction. The compounds were emissive under the irradiation at 370 nm. The emission spectra recorded in the temperature range of 183-363 K were characterized by the vibronic structures with a peak spacing (Δν) of ca. 2000 cm(-1). The value of Δν was close to the stretching vibration of the coordinated C[triple bond, length as m-dash]N (2150-2170 cm(-1)). It was postulated that C[triple bond, length as m-dash]N groups participated in the emission processes through their vibronic coupling. In the case of L = 4-ethylpyridine, the lifetime of emission was measured in the same temperature range, leading to the conclusion that the activation energy of the non-radiative processes (ΔEa) was estimated to be 20 kJ mol(-1). PMID:27063188

  18. Gram-scale synthesis of coordination polymer nanodots with renal clearance properties for cancer theranostic applications

    PubMed Central

    Liu, Fuyao; He, Xiuxia; Chen, Hongda; Zhang, Junping; Zhang, Huimao; Wang, Zhenxin

    2015-01-01

    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. PMID:26245151

  19. Gram-scale synthesis of coordination polymer nanodots with renal clearance properties for cancer theranostic applications.

    PubMed

    Liu, Fuyao; He, Xiuxia; Chen, Hongda; Zhang, Junping; Zhang, Huimao; Wang, Zhenxin

    2015-01-01

    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 Fe(3+), 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. PMID:26245151

  20. Software for 3D radiotherapy dosimetry. Validation

    NASA Astrophysics Data System (ADS)

    Kozicki, Marek; Maras, Piotr; Karwowski, Andrzej C.

    2014-08-01

    The subject of this work is polyGeVero® software (GeVero Co., Poland), which has been developed to fill the requirements of fast calculations of 3D dosimetry data with the emphasis on polymer gel dosimetry for radiotherapy. This software comprises four workspaces that have been prepared for: (i) calculating calibration curves and calibration equations, (ii) storing the calibration characteristics of the 3D dosimeters, (iii) calculating 3D dose distributions in irradiated 3D dosimeters, and (iv) comparing 3D dose distributions obtained from measurements with the aid of 3D dosimeters and calculated with the aid of treatment planning systems (TPSs). The main features and functions of the software are described in this work. Moreover, the core algorithms were validated and the results are presented. The validation was performed using the data of the new PABIGnx polymer gel dosimeter. The polyGeVero® software simplifies and greatly accelerates the calculations of raw 3D dosimetry data. It is an effective tool for fast verification of TPS-generated plans for tumor irradiation when combined with a 3D dosimeter. Consequently, the software may facilitate calculations by the 3D dosimetry community. In this work, the calibration characteristics of the PABIGnx obtained through four calibration methods: multi vial, cross beam, depth dose, and brachytherapy, are discussed as well.

  1. Design of Stable and Powerful Nanobiocatalysts, Based on Enzyme Laccase Immobilized on Self-Assembled 3D Graphene/Polymer Composite Hydrogels.

    PubMed

    Ormategui, Nerea; Veloso, Antonio; Leal, Gracia Patricia; Rodriguez-Couto, Susana; Tomovska, Radmila

    2015-07-01

    Graphene-based materials appear as a suitable answer to the demand for novel nanostructured materials for effective nanobiocatalytic systems design. In this work, a design of stable and efficient nanobiocatalysts made of enzyme laccase immobilized on composite hydrogels [reduced graphene oxide (rGO)/polymer] is presented. The composite hydrogel supports were synthesized by self-assembly of graphene oxide nanoplatelets in the frame of a polymer latex matrix, where the polymer nanoparticles were adsorbed onto the GO surface, creating hybrid nanoplatelets. These hybrids self-assembled when ascorbic acid was added as a GO reducing agent and formed three-dimensional porous structures, greatly swollen with water, e.g., the composite hydrogels. The hydrogels were used as a support for covalent immobilization of the laccase. The performance of the nanobiocatalysts was tested in the oxidative degradation of the recalcitrant synthetic dye Remazol Brilliant Blue R in aqueous solutions. The biocatalysts showed strong dye discoloration ability and high stability as they preserved their catalytic action in four successive batches of dye degradation. The presented biocatalysts offer possibilities for overcoming the main disadvantages of the enzyme catalysts (fragile nature, high cost, and high loading of the enzyme), which would lead to a step forward toward their industrial application. PMID:26075472

  2. 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

  3. New method of 3-D object recognition

    NASA Astrophysics Data System (ADS)

    He, An-Zhi; Li, Qun Z.; Miao, Peng C.

    1991-12-01

    In this paper, a new method of 3-D object recognition using optical techniques and a computer is presented. We perform 3-D object recognition using moire contour to obtain the object's 3- D coordinates, projecting drawings of the object in three coordinate planes to describe it and using a method of inquiring library of judgement to match objects. The recognition of a simple geometrical entity is simulated by computer and studied experimentally. The recognition of an object which is composed of a few simple geometrical entities is discussed.

  4. Nucleotide/Tb³⁺ coordination polymer nanoparticles as luminescent sensor and scavenger for nitrite ion.

    PubMed

    Qi, Zewan; You, Qi; Chen, Yang

    2016-01-01

    Newly emerged metal organic coordination polymers have aroused the great interest in designing tailored functional materials. In this study, multiple functional components, luminescent Tb(3+) ion, nucleobase and antenna molecule, were integrated in a single material and prepared into a responsive nanoparticle for nitrite. The terbium coordination polymer nanoparticles made of this kind of material have the dual functions of recognition and transduction and obey a preset sensing mechanism without a post-functionalization of common materials. As the result of the tailored, the terbium coordination polymer nanoparticles are highly sensitive and selective to nitrite by means of Dexter energy transfer between Tb(3+) ion and nitrite, and can be used for the scavenger for nitrite in aqueous solution. The detection limit, dynamic range and removal capacity of U-Tb-OBBA CPNPs for nitrite are 0.3 µM, 0.3-470 µM and 4.44 mg per gram of particles, respectively. Metal organic coordination polymers show an attractive potential in constructing smart sensing materials. PMID:26703267

  5. Ultrasound-driven preparation and pair distribution function-assisted structure solution of a copper-based layered coordination polymer.

    PubMed

    Mohideen, M Infas; Allan, Phoebe K; Chapman, Karena W; Hriljac, Joseph A; Morris, Russell E

    2014-07-21

    Nanoparticles of a copper-based layered coordination polymer, STAM-2, have been prepared via an ultrasound mediated transformation from a layered metal-organic framework, STAM-1. The structure of the material was then solved using pair distribution function analysis to identify the structural units present and the final structural model refined against the pair distribution function data. PMID:24310447

  6. 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.

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

    SciTech Connect

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

    2010-09-15

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

  8. Optoplasmonics: hybridization in 3D

    NASA Astrophysics Data System (ADS)

    Rosa, L.; Gervinskas, G.; Žukauskas, A.; Malinauskas, M.; Brasselet, E.; Juodkazis, S.

    2013-12-01

    Femtosecond laser fabrication has been used to make hybrid refractive and di ractive micro-optical elements in photo-polymer SZ2080. For applications in micro- uidics, axicon lenses were fabricated (both single and arrays), for generation of light intensity patterns extending through the entire depth of a typically tens-of-micrometers deep channel. Further hybridisation of an axicon with a plasmonic slot is fabricated and demonstrated nu- merically. Spiralling chiral grooves were inscribed into a 100-nm-thick gold coating sputtered over polymerized micro-axicon lenses, using a focused ion beam. This demonstrates possibility of hybridisation between optical and plasmonic 3D micro-optical elements. Numerical modelling of optical performance by 3D-FDTD method is presented.

  9. The influence of different coordination environments on one-dimensional Cu(ii) coordination polymers for the photo-degradation of organic dyes.

    PubMed

    Hussain, Navid; Bhardwaj, Vimal K

    2016-05-01

    Three new Cu(ii) coordination polymers, namely, {[Cu3(L(1))(NO3)2(DMF)(H2O)]·3(DMF)}n (), [Cu3(L(1))(Cl)2(DMF)2]n () and [Cu3(L(2))(NO3)4(H2O)4]n (), were synthesized from pyridine-2,6-dicarbohydrazide based imine linked tritopic ligands. All the complexes were characterized using elemental analysis, IR, UV-vis spectroscopy and ESI-MS. The solid state structures of complexes were determined using single crystal X-ray crystallography. The complexes contain trinuclear copper units connected through different anions that lead to the formation of one dimensional (ID) chain structures. Depending upon the anion of the copper salt and donor atoms of the ligands used in complexation, a small variation in the structures was observed. In complex , the trinuclear copper units are connected by phenoxo-bridging (μ2-O(-)) along with one coordinated water molecule, whereas complex is connected through chloride bridging (μ2-Cl) and complex is connected through nitrate ions (μ-[O-N-O]) along with four water molecules. Photo-catalytic activities of the synthesized complexes () were investigated. All the complexes were found to be photo-catalytically active; however, the distinct coordination environment of the metal ions (i.e. difference in the coordinated water molecules and donor sites of ligands) played a significant role in the catalytic activities. Therefore, this study presents comparative photo-catalytic studies of different coordination environments of metal ions in one-dimensional Cu(ii) coordination polymers. The results provide a potential pathway for the rational design of more efficient photo-catalysts. PMID:27054292

  10. Syntheses, structures and properties of 3D inorganic-organic hybrid frameworks constructed from lanthanide polymer and Keggin-type tungstosilicate

    SciTech Connect

    Gao Yuanzhe; Xu Yanqing; Han Zhangang; Li Chunhong; Cui, Fengyun; Chi Yingnan; Hu Changwen

    2010-05-15

    Inorganic-organic hybrid frameworks, namely [Ce(H{sub 2}O){sub 3}(pdc)]{sub 4}[SiW{sub 12}O{sub 40}].6H{sub 2}O 1, [M(H{sub 2}O){sub 4}(pdc)]{sub 4}[SiW{sub 12}O{sub 40}].2H{sub 2}O (M=Ce for 2a, La for 2b, Nd for 2c; H{sub 2}pdc=pyridine-2,6-dicarboxylic acid) were assembled through incorporation of Keggin-type heteropolyanion [SiW{sub 12}O{sub 40}]{sup 4-} within the voids of lanthanides-pdc network as pillars or guests under hydrothermal condition. Single-crystal X-ray analyses of these crystals reveal that compound 1 presents 3D pillar-layered framework with the [SiW{sub 12}O{sub 40}]{sup 4-} anions located on the square voids of the two-dimensional Ce-pdc bilayer. Compounds 2a-c are isostructural and constructed from 3D Ln-pdc-based metal-organic framework (MOF) incorporating noncoordinating guests Keggin structure [SiW{sub 12}O{sub 40}]{sup 4-}. Solid-state properties of compounds 1 and 2a-c such as thermal stability and photoluminescence have been further investigated. - Graphical abstract: Two types of new inorganic-organic hybrid frameworks through incorporation of Keggin-type heteropolyanion [SiW{sub 12}O{sub 40}]{sup 4-} within the voids of lanthanides-pdc network as pillars or guests under hydrothermal condition were successfully assembled. Solid-state properties of compounds 1 and 2a such as thermal stability and photoluminescence have been further investigated.

  11. Three coordination polymers based on different carboxylates, metals and a tri(4-imidazolylphenyl)amine ligand

    NASA Astrophysics Data System (ADS)

    Wu, Hua; Shi, Chenjie; Zhao, Yanqing; Jiang, Yutong; Tao, Yuehong

    2015-04-01

    In this paper, three new coordination complexes based on a flexible tri(4-imidazolylphenyl)amine (Tipa) ligand, namely [Co(Tipa)(L1)2]·H2O (1), [Zn2(Tipa)(L1)4(H2O)]·2H2O (2) and [Mn(Tipa)(L2)]·2H2O (3), where HL1 = benzoic acid H2L2 = 5-OH-1,3-benzenedicarboxylic acid and Tipa = tri(4-imidazolylphenyl)amine, have been synthesized under the hydrothermal condition and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectra. Compound 1 exhibits a 1D ladder chain with the benzoic anions hanging on the two sides of the chain. For compound 2, it shows a fascinating 1D zigzag chain. Compound 3 displays (3,5)-connected (42·6)(42·67·8) topology, where the identical 2D networks entangle in highly rare parallel fashions to give a fascinating 2D → 3D framework with polycatenation and polyrotaxane characters. Moreover, the photoluminescent properties for the compounds 2 and 3 were also investigated.

  12. 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.

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

    PubMed

    Wright, James S; Vitórica-Yrezábal, Iñigo J; Adams, Harry; Thompson, Stephen P; Hill, Adrian H; Brammer, Lee

    2015-03-01

    A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene) n ]·m(arene), 1 (arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2], 2a and/or 2b , with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b , not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η(1),η(1) manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations. PMID:25866656

  14. 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

  15. 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)

  16. 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

  17. Luminescent coordination polymers for the VIS and NIR range constituting LnCl3 and 1,2-bis(4-pyridyl)ethane.

    PubMed

    Dannenbauer, N; Matthes, P R; Müller-Buschbaum, K

    2016-04-12

    A series of 14 lanthanide containing coordination polymers LnCl3 with 1,2-bis(4-pyridyl)ethane (bpe) was synthesized from either thiazole or pyridine. Depending on the ligand content, a structural diversity from 3D-frameworks [LnCl3(bpe)2]·thz, Ln = Ce-Lu, to 1D-strands [La2Cl6(bpe)2(thz)6] and [LnCl3(bpe)(py)2]·(bpe/py), Ln = Gd, Er, was obtained and characterized by X-ray single crystal diffraction, powder diffraction, differential thermal analysis and thermogravimetry (DTA/TG), IR-spectroscopy and photoluminescence spectroscopy. The compounds exhibit a variety of luminescence properties and different phenomena. This includes ligand centred fluorescence, metal-centred 5d-4f/4f-4f emission in the visible and the NIR range, antenna effects via Dexter and Förster energy transfer mechanisms, excitation dependent emission with a correlating shift of the chromaticity coordinates and inner filter effects by combined re-absorption/emission. PMID:26956557

  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

    Wang, Xiaohong; Schröder, Heinz C; Grebenjuk, Vladislav; Diehl-Seifert, Bärbel; Mailänder, Volker; Steffen, Renate; Schloßmacher, Ute; Müller, Werner E G

    2014-02-01

    , 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. 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

  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

    2016-01-01

    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

  2. A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

    NASA Astrophysics Data System (ADS)

    Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

    2016-04-01

    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.

  3. Validation of high-resolution 3D patient QA for proton PBS and IMPT using laser CT of improved polymer gel dosimeters

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    Laser CT scanning of LET-independent BANG3-Pro2® polymer gel dosimeters has recently shown potential in proton dosimetry. However, raw materials' impurities impart some variability. This study aimed to validate a new method of compensating for this variability, and to validate the suitability of the improved dosimeter for patient-specific QA in pencil beam scanning (PBS) and IMPT. Six modifications of the BANG3-Pro2® gel dosimeter were analysed for their sensitivity to proton dose and to LET. One formulation was selected for a clinical QA feasibility study, in which one composite IMPT plan, two single-field IMPT plans, and one SFUD plan were delivered to identical gel phantoms. New commercial VOLQATM software (beta version) was used for data analysis. Both validations were successful.

  4. Ultralong Persistent Room Temperature Phosphorescence of Metal Coordination Polymers Exhibiting Reversible pH-Responsive Emission.

    PubMed

    Yang, Yongsheng; Wang, Ke-Zhi; Yan, Dongpeng

    2016-06-22

    Ultra-long-persistent room temperature phosphorescence (RTP) materials have attracted much attention and present various applications in illumination, displays, and the bioimaging field; however, the persistent RTP is generally from the inorganic phosphor materials to date. Herein, we show that the metal coordination polymers (CPs) could be new types of emerging long-lived RTP materials for potential sensor applications. First, two kinds of Cd-based CPs, Cd(m-BDC)(H2O) (1) and Cd(m-BDC)(BIM) (2) (m-BDC = 1,3-benzenedicarboxylic acid; BIM = benzimidazole), were obtained through a hydrothermal process, and the samples were found to exhibit two-dimensional layered structures, which are stabilized by interlayer C-H···π interaction and π···π interaction, respectively. The CPs show unexpected second-time-scale ultra-long-persistent RTP after the removal of UV excitation, and this persistent emission can be detected easily on a time scale of 0-10 s. The CPs also feature a tunable luminescence decay lifetime by adjusting their coordination situation and packing fashion of ligands. Theoretical calculation further indicates that the introduction of the second ligand could highly influence the electronic structure and intermolecular electron transfer toward tailoring the RTP of the CP materials. Moreover, CP 2 exhibits well-defined pH- and temperature-dependent phosphorescence responses. Therefore, this work provides a facile way to develop new type of CPs with steady-state and dynamic tuning of the RTP properties from both experimental and theoretical perspectives, which have potential applications in the areas of displays, pH/temperature sensors, and phosphorescence logic gates. On account of suitable incorporation of inorganic and organic building blocks, it can be expected that the ultra-long-persistent RTP CPs can be extended to other similar systems due to the highly tunable structures and facile synthesis routes. PMID:27253185

  5. Self-assembled copper(II) coordination polymers derived from aminopolyalcohols and benzenepolycarboxylates: structural and magnetic properties.

    PubMed

    Kirillov, Alexander M; Karabach, Yauhen Y; Haukka, Matti; Guedes da Silva, M Fatima C; Sanchiz, Joaquin; Kopylovich, Maximilian N; Pombeiro, Armando J L

    2008-01-01

    The new copper(II) or copper(II)/sodium(I) 1D coordination polymers [Cu2(Hmdea)2(mu-H2O)(mu2-tpa)]n.2nH2O (1), [Cu2(H2tipa)2(mu2-ipa)]n.4nH2O (2), [Cu2(H2tea)2Na(H2O)2(mu2-tma)]n.6nH2O (3), [Cu2(H2tea)2(mu2-ipa)]n.nH2O (4a), and [Cu2(H2tea)2{mu3-Na(H2O)3}(mu3-ipa)]n(NO3)n.0.5nH2O (4b) have been prepared in aqueous medium by self-assembly from copper(II) nitrate, aminopolyalcohols [methyldiethanolamine (H2mdea), triisopropanolamine (H3tipa), and triethanolamine (H3tea)] as main chelating ligands and benzenepolycarboxylic acids [terephthalic (H2tpa), isophthalic (H2ipa), and trimesic (H3tma) acid] as spacers. They have been characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses, the latter indicating the formation of unusual multinuclear metal cores interconnected by various benzenepolycarboxylate spacers, leading to distinct wavelike, zigzag, or linear 1D polymeric metal-organic chains. These are further extended to 2D or 3D hydrogen-bonded supramolecular networks via extensive interactions with the intercalated crystallization water molecules. The latter are associated, also with aqua ligands, by hydrogen bonds resulting in acyclic (H2O)3 clusters in 1, (H2O)8 clusters in 2, infinite 1D water chains in 3, and disordered water-nitrate associates in 4b, all playing a key role in the structure stabilization and its extension to further dimensions. Variable-temperature magnetic susceptibility measurements have shown that 1-4 exhibit a moderately strong ferromagnetic coupling through the alkoxo bridge. The small Cu-O-Cu bridging angle and the large out-of-plane displacement of the carbon atom of the alkoxo group accounts for this behavior. The magnetic data have been analyzed by means of a dinuclear and a 1D chain model, and the magnetic parameters have been determined. The magnetic exchange coupling in 3, to our knowledge, is the highest found in alkoxo-bridged copper(II) complexes. PMID:18069826

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

    SciTech Connect

    Zhuang Guilin; Chen Wulin; Zheng Jun; Yu Huiyou; Wang Jianguo

    2012-08-15

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

  7. Sonochemical synthesis of tri-nuclear lead(II)-azido nano rods coordination polymer with 3,4,7,8-tetramethyl-1,10-phenanthroline (tmph): Crystal structure determination and preparation of nano lead(II) oxide

    NASA Astrophysics Data System (ADS)

    Hanifehpour, Younes; Morsali, Ali; Mirtamizdoust, Babak; Joo, Sang Woo

    2015-01-01

    Preparation of rod-shaped nanostructure of a new 1D lead(II) tri nuclear coordination polymer containing the Pb2-(μ-N3)2 and Pb2-(μ-N3)(NO3) motifs [Pb3(tmph)4(μ-N3)5(μ-NO3)]n (1) where "tmph" is the abbreviation of 3,4,7,8-tetramethyl-1,10-phenanthroline, using a sonochemical method is described. The new coordination polymer is characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), elemental analysis and infrared spectroscopy. The single crystalline material is obtained using a heat gradient applied to a solution of the reagents. Single-crystal XRD analysis indicates three different lead(II) centers in the structure with coordination numbers of seven and eight with a holo and hemidirected coordination geometry. They also show that the chains interact with each other through π-π stacking interactions creating a 3D framework. PbO nanoparticles are obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirm formation of PbO particles around 10-20 nm.

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

    SciTech Connect

    Yang, Gao-Shan; Liu, Chong-Bo; Liu, Hong; Robbins, Julianne; Zhang, Z. John; Yin, Hong-Shan; Wen, Hui-Liang; Wang, Yu-Hua

    2015-05-15

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

  9. Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand.

    PubMed

    Noro, Shin-ichiro; Mizutani, Junya; Hijikata, Yuh; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu; Sugimoto, Kunihisa; Inubushi, Yasutaka; Kubo, Kazuya; Nakamura, Takayoshi

    2015-01-01

    The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. PMID:25592677

  10. Surfactant-Assisted Nanocrystalline Zinc Coordination Polymers: Controlled Particle Sizes and Synergistic Effects in Catalysis.

    PubMed

    Huang, Chao; Wang, Huarui; Wang, Xiaolu; Gao, Kuan; Wu, Jie; Hou, Hongwei; Fan, Yaoting

    2016-04-25

    Different morphologies and particle sizes of two crystalline zinc-based coordination polymers (CPs), [Zn(pytz)H2 O]n (1; H2 pytz=2,6-bis(tetrazole)pyridine) and [Zn2 (pytz)2 4 H2 O] (2), from the bulk scale to the nanoscale, could be obtained under solvothermal conditions with different surfactants (polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) 2000) as templates. PVP and PEG 2000 could act as capping and structure-directing agents, respectively, to influence the growth of crystalline particles and control their sizes. CP 1 exhibits a two-dimensional framework with window-like units and 2 shows a bimetallic structure. Nanocrystalline 1 and 2 were used as heterogeneous catalysts to study how adjacent catalytic active sites synergistically effected their catalytic reactivities in the direct catalytic conversion of aromatic dinitriles into oxazolines. The results showed that 1 produced bis-oxazolines as the sole products, whereas 2 gave the mono-oxazolines as the major products under the same reaction conditions. PMID:26997347

  11. Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand

    PubMed Central

    Noro, Shin-ichiro; Mizutani, Junya; Hijikata, Yuh; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu; Sugimoto, Kunihisa; Inubushi, Yasutaka; Kubo, Kazuya; Nakamura, Takayoshi

    2015-01-01

    The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. PMID:25592677

  12. Self-assembled nanoscale coordination polymers with trigger release properties for effective anticancer therapy

    NASA Astrophysics Data System (ADS)

    Liu, Demin; Poon, Christopher; Lu, Kuangda; He, Chunbai; Lin, Wenbin

    2014-06-01

    Nanoscale coordination polymers (NCPs) are self-assembled from metal ions and organic bridging ligands, and can overcome many drawbacks of existing drug delivery systems by virtue of tunable compositions, sizes and shapes, high drug loadings, ease of surface modification and intrinsic biodegradability. Here we report the self-assembly of zinc bisphosphonate NCPs that carry 48±3 wt% cisplatin prodrug and 45±5 wt% oxaliplatin prodrug. In vivo pharmacokinetic studies in mice show minimal uptake of pegylated NCPs by the mononuclear phagocyte system and excellent blood circulation half-lives of 16.4±2.9 and 12.0±3.9 h for the NCPs carrying cisplatin and oxaliplatin, respectively. In all tumour xenograft models evaluated, including CT26 colon cancer, H460 lung cancer and AsPC-1 pancreatic cancer, pegylated NCPs show superior potency and efficacy compared with free drugs. As the first example of using NCPs as nanotherapeutics with enhanced antitumour activities, this study establishes NCPs as a promising drug delivery platform for cancer therapy.

  13. Uniform Cerium-Based Coordination Polymer Microsnheres: Preoaration and Upconversion Emission.

    PubMed

    Nie, Zhi-Wen; Zeng, Cheng-Hui; Xie, Gang; Zhong, Sheng-Liang

    2016-04-01

    Homogeneously doped Yb3+ and Er3+ cerium-based coordination polymer (CP) microspheres have been successfully synthesized on a large scale through a simple solvothermal route with 2,5-pyridinedicarboxylic acid (2,5-H2PDC) as the organic linker. CeO2: Yb3+, Er3+ porous microspheres were obtained by annealing the corresponding CP microspheres at 600 °C for 4 h under atmospheric pressure. These as-prepared products were characterized by Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), energy-dispersion X-ray (EDX) spectroscopy, Thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis. The room temperature upconversion luminescent spectra of the as-prepared microspheres were carried out by 980 nm NIR light excitation. Interestingly, Yb3+ and Er3+ codoped CP microspheres give a single-band emission centered at 673 nm, while the CeO2: Yb3+, Er3+ microspheres give emission in green and red region, with red being the dominant emission. The emission intensity of the CeO2: Yb3+, Er3+ microspheres were much stronger than that of the Yb3+ and Er3+ codoped CP microspheres. PMID:27451693

  14. Preparation of nanocrystalline metal oxides and intermetallic phases by controlled thermolysis of organometallic coordination polymers

    NASA Astrophysics Data System (ADS)

    Rehbein, Marcus; Epple, Matthias; Fischer, R. Dieter

    2000-06-01

    Organometallic coordination polymers of the super-Prussian blue type [(Me 3Sn) nM(CN) 6] (Me=CH 3; n=3, 4; M=Fe, Co, Ru) were subjected to thermolysis in different atmospheres (air, argon, hydrogen/nitrogen). In air, oxides were found: Fe 2O 3/SnO 2 (crystalline and nanocrystalline), Co 2SnO 4 and RuO 2. In argon and in hydrogen, the intermetallic phases FeSn 2, CoSn 2, Ru 3Sn 7 and Fe 3SnC were obtained. A detailed mechanistic study was carried out using thermogravimetry (TG), X-ray diffraction (XRD), X-ray absorption spectroscopy (EXAFS) at Fe, Co, Ru and Sn K-edges, infrared spectroscopy (IR) and elemental analysis. Below 250°C, Me 3SnCN and (CN) 2 are released, whereas above 250°C oxidation or pyrolysis leads to the corresponding oxides or intermetallic phases. Polymeric cyanides containing at least two metals have turned out to be suitable precursors to prepare well-defined oxides and intermetallic phases at comparatively low temperature.

  15. Hydrothermal synthesis and structural characterization of two novel lanthanide supramolecular coordination polymers with nano-chains

    NASA Astrophysics Data System (ADS)

    Wan, Yong-Hong; Jin, Lin-Pei; Wang, Ke-Zhi

    2003-04-01

    Two novel lanthanide supramolecular coordination polymers, {[Nd 2(phth) 3(phen)(H 2O)]·H 2O} n ( 1, phth=phthalate, phen=1,10-phenanthroline) and {[Ho 2(phth) 3(phen)(H 2O) 2]·3H 2O} n ( 2), have been synthesized by hydrothermal method and characterized by X-ray diffraction. The results show that complex 1 crystallizes in triclinic space group P 1¯ with a=7.605(2) Å, b=12.972(4) Å, c=18.773(6) Å, α=109.778(5)°, β=91.657(5)°, γ=103.951(5)° and Z=2. Complex 1 has a one-dimentional nano-chain structure and the existence of hydrogen bonds and π- π interactions results in 2D network structure. Complex 2 crystallizes in triclinic space group P 1¯ with a=11.695(2) Å, b=13.488(3) Å, c=13.761(3) Å, α=87.09(3)°, β=67.40(3)°, γ=67.41(3)° and Z=2. Complex 2 features a zigzag double-chain and the hydrogen bonds lead to the formation of a three-dimensional network. Both Complex 1 and 2 have two metal environments.

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

    PubMed

    Janiak, Christoph; Henninger, Stefan K

    2013-01-01

    Porous coordination polymers (PCPs)/metal-organic frameworks (MOFs) are inorganic-organic hybrid materials with a permanent three-dimensional porous metal-ligand network. PCPs or MOFs are inorganic-organic analogs of zeolites in terms of porosity and reversible guest exchange properties. Microporous water-stable PCPs with high water uptake capacity are gaining attention for low temperature heat transformation applications in thermally driven adsorption chillers (TDCs) or adsorption heat pumps (AHPs). TDCs or AHPs are an alternative to traditional air conditioners or heat pumps operating on electricity or fossil fuels. By using solar or waste heat as the operating energy TDCs or AHPs can significantly help to minimize primary energy consumption and greenhouse gas emissions generated by industrial or domestic heating and cooling processes. TDCs and AHPs are based on the evaporation and consecutive adsorption of coolant liquids, preferably water, under specific conditions. The process is driven and controlled by the microporosity and hydrophilicity of the employed sorption material. Here we summarize the current investigations, developments and possibilities of PCPs/MOFs for use in low-temperature heat transformation applications as alternative materials for the traditional inorganic porous substances like silica gel, aluminophosphates or zeolites. PMID:23945102

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  18. Two coordination polymers of manganese(II) isophthalate and their preparation, structures, and magnetic properties

    SciTech Connect

    Chen Jinxi; Wang Jingjing; Ohba, Masaaki

    2012-01-15

    Two manganese coordination polymers, [Mn{sub 2}(ip){sub 2}(dmf)]{center_dot}dmf (1) and [Mn{sub 4}(ip){sub 4}(dmf){sub 6}]{center_dot}2dmf (2) (ip=isophthalate; dmf=N,N-dimethylformamide), have been synthesized and characterized. X-ray crystal structural data reveal that compound 1 crystallizes in triclinic space group P-1, a=9.716(3) A, b=12.193(3) A, c=12.576(3) A, {alpha}=62.19(2) Degree-Sign , {beta}=66.423(17) Degree-Sign , {gamma}=72.72(2) Degree-Sign , Z=2, while compound 2 crystallizes in monoclinic space group Cc, a=19.80(3) A, b=20.20(2) A, c=18.01(3) A, {beta}=108.40(4) Degree-Sign , Z=4. Variable-temperature magnetic susceptibilities of compounds 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions. - Graphical abstract: Three-dimensional porous and two-dimensional layered manganese isophthalates have been prepared. Magnetic susceptibility measurements exhibit overall weak antiferromagnetic interactions between the Mn(II) ions in both compounds. Highlights: Black-Right-Pointing-Pointer Two manganese isophthalates have been prepared. Black-Right-Pointing-Pointer Compound 1 adopts a three-dimensional porous structure. Black-Right-Pointing-Pointer Compound 2 adopts a two-dimensional layered structure. Black-Right-Pointing-Pointer Magnetic properties of both compounds are investigated.

  19. Self-assembled nanoscale coordination polymers with trigger release properties for effective anticancer therapy

    PubMed Central

    Liu, Demin; Poon, Christopher; Lu, Kuangda; He, Chunbai; Lin, Wenbin

    2014-01-01

    Nanoscale coordination polymers (NCPs) are self-assembled from metal ions and organic bridging ligands, and can overcome many drawbacks of existing drug delivery systems by virtue of tunable compositions, sizes, and shapes; high drug loadings; ease of surface modification; and intrinsic biodegradability. Here we report the self-assembly of zinc bisphosphonate NCPs that carry 48±3 wt% cisplatin prodrug and 45±5 wt% oxaliplatin prodrug. In vivo pharmacokinetic studies in mice show minimal uptake of pegylated NCPs by the mononuclear phagocyte system and excellent blood circulation half-lives of 16.4±2.9 and 12.0±3.9 h for the NCPs carrying cisplatin and oxaliplatin, respectively. In all tumor xenograft models evaluated, including CT26 colon cancer, H460 lung cancer, and AsPC-1 pancreatic cancer, pegylated NCPs show superior potency and efficacy compared to free drugs. As the first example of using NCPs as nanotherapeutics with enhanced antitumor activities, this study establishes NCPs as a promising drug delivery platform for cancer therapy. PMID:24964370

  20. TRACE 3-D documentation

    SciTech Connect

    Crandall, K.R.

    1987-08-01

    TRACE 3-D is an interactive beam-dynamics program that calculates the envelopes of a bunched beam, including linear space-charge forces, through a user-defined transport system. TRACE 3-D provides an immediate graphics display of the envelopes and the phase-space ellipses and allows nine types of beam-matching options. This report describes the beam-dynamics calculations and gives detailed instruction for using the code. Several examples are described in detail.

  1. In vitro and in vivo evaluation of porous PCL-PLLA 3D polymer scaffolds fabricated via salt leaching method for bone tissue engineering applications.

    PubMed

    Sadiasa, Alexander; Nguyen, Thi Hiep; Lee, Byong-Taek

    2014-01-01

    Three dimensional porous scaffolds composed of various ratios of polycaprolactone and poly(L-lactic acid) (PLLA) were prepared using salt leaching method for bone regeneration applications. Surfaces of the scaffolds were visualized using scanning electron microscope (SEM) and the combination of the polymers was confirmed by FT-IR. Addition of PLLA increased the porosity and pore sizes of the scaffolds and also the scaffolds' compressive strength initially. Osteoblast-like cells were used and it was found that the samples' cell biocompatibility was further promoted with the increase in PLLA content as observed via cell proliferation assays using MTT, gene expression with RT-PCR, and micrographs from SEM and confocal microscopy. Samples were then implanted into male rabbits for 2 months, and histological staining and micro-CT histomorphometry show that new bone formations were detected in the site containing the implants of the scaffolds and that bone regeneration was further promoted with the increased concentration of PLLA in the scaffold. PMID:24138179

  2. Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal

    SciTech Connect

    Llano-Tomé, Francisco; Bazán, Begoña; Urtiaga, Miren-Karmele; Barandika, Gotzone; Antonia Señarís-Rodríguez, M.; and others

    2015-10-15

    Combination of polycarboxylate anions and dipyridyl ligands is an effective strategy to produce solid coordination frameworks (SCF) which are crystalline materials based on connections between metal ions through organic ligands. In this context, this work is focused on two novel Cu{sup II}-based SCFs exhibiting PDC (2,5-pyridinedicarboxylate) and bpa (1,2-di(4-pyridyl)ethane), being the first structures reported in literature containing both ligands. Chemical formula are [Cu{sub 2}[(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·3H{sub 2}O·DMF (1), and [Cu{sub 2}(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·7H{sub 2}O (2), where DMF is dimethylformamide. Compounds 1 and 2 have been characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric (TG) analysis, differential thermal analysis (DTA) and dielectric measurements. The crystallographic analysis revealed that compounds 1 and 2 can be described as herringbone-type layers formed by helicoidal Cu-PDC-Cu chains connected through bpa ligands. Solvent molecules are crystallized between the layers, providing the inter-layer connections through hydrogen bonds. Differences between both compounds are attributable to the flexibility of bpa (in 2D) as well as to the 3D packing of the layers which is solvent dependent. This fact results in the fact that compound 2 is the most regular 3-c herringbone array reported so far. The structural dynamism of these networks is responsible for the crystalline to-amorphous to-crystalline (CAC) transformation from compound 1 to compound 2. Crystallochemical features for both compounds have also been studied and compared to similar 3-connected herringbone-arrays. - Graphical abstract: Cu-PDC-bpa 3-c herringbone arrays. - Highlights: • The most ideal herringbone array reported so far is a Cu-PDC-bpa SCF. • Conformational freedom of bpa results in 2D and 3D flexibility of the SCFs. • The flexibility of the SCFs is related to a phase transformation. • Dielectric

  3. 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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    Three new coordination polymers, namely, {[Ni(H2L)(bix)(H2O)2]·2h2O}n (1), {[Ni(HL)(Hdpa)(H2O)2]·H2O}n (2), {[Ni(L)0.5(bpp)(H2O)]·H2O}n (3) (H4L=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 H4L ligand and different N-donor co-ligands, have been synthesized under hydrothermal conditions. Compound 1 features a 3D 4-connected 66-dia-type framework with H4L ligand adopts a μ2-bridging mode with two symmetry-related carboxylate groups in μ1-η1:η0 monodentate mode. Compound 2 displays a 1D [Ni(HL)(Hdpa)]n ribbon chains motif, in which the H4L ligand adopts a μ2-bridging mode with two carboxylate groups in μ1-η1:η1 and μ1-η1:η0 monodentate modes, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology, with H4L ligand displays a μ4-bridging coordination mode. The H4L 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.

  4. Highly effective heterogeneous chemosensors of luminescent silica@coordination polymer core-shell micro-structures for metal ion sensing

    NASA Astrophysics Data System (ADS)

    Cho, Won; Lee, Hee Jung; Choi, Sora; Kim, Yoona; Oh, Moonhyun

    2014-10-01

    Heterogeneous solid sensors are regarded as promising next-generation sensor due to their excellent chemical stability, low contamination, and excellent recyclability, despite their low sensitivity and weak signal. The dispersity and signals specifically from the exterior of solid sensors are critical aspects which define the sensing sensitivity and selectivity. A novel strategy for the preparation of ideal heterogeneous sensors based upon luminescent lanthanide coordination polymers (LnCP) has been demonstrated. Ideal heterogeneous sensors are systematically achieved by producing the sensors in small, uniform, and thin core-shell particles (silica@LnCP, Ln = Eu, Tb). Eventually, we found that the extremely small amount of well-structured silica@LnCP microsphere, less than ca. 1/400 compared to the amount of several known coordination polymer-based sensors, was sufficient to achieve a reliable Cu2+ sensing with even much greater sensitivity (ca. 550% improvement).

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

    PubMed

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

    2016-11-01

    An innovative approach is proposed for the recycling of metals from a simulant lithium-ion battery (LIBs) waste aqueous solution. Phosphonate organic linkers are introduced as precipitating agents to selectively react with the metals to form coordination polymers from an aqueous solution containing Ni, Mn and Co in a hydrothermal process. The supernatant is analyzed by ICP-AES to quantify the efficiency and the selectivity of the precipitation and the materials are characterized by Scanning Electron Microscopy (SEM), Powder X-Ray Diffraction (PXRD), Thermogravimetric Analyses (TGA) and nitrogen gas sorption (BET). Conditions have been achieved to selectively precipitate Manganese or Manganese/Cobalt from this solution with a high efficiency. This work describes a novel method to obtain potentially valuable coordination polymers from a waste metal solution that can be generalized on any waste solution. PMID:27362538

  6. Fabrication of chain-like Mn 2O 3 nanostructures via thermal decomposition of manganese phthalate coordination polymers

    NASA Astrophysics Data System (ADS)

    Salavati-Niasari, Masoud; Mohandes, Fatemeh; Davar, Fatemeh; Saberyan, Kamal

    2009-12-01

    A novel manganese coordination polymer [Mn(Pht)(H 2O)] n as a precursor was obtained by chemical precipitation involving an aqueous solution of anhydrous manganese acetate and phthalate anion as a potential O-banded ligand. Fourier transform infrared (FT-IR) results proved that phthalate anions coordinate to metal cations as a chelating bidentate ligand, making polymeric structure. The Mn 2O 3 nanostructures have been prepared via thermal decomposition of as-prepared manganese phthalate polymers as precursor in the presence of oleic acid (OA) and triphenylphosphine (TPP) as a stabilizer and capping. Different approaches such as FT-IR, X-ray diffraction (XRD), X-ray photoelectron sp