WorldWideScience

Sample records for coordination polymers assembled

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

    Science.gov (United States)

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

    2010-02-01

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

  2. Assembly and Characterization of Coordination Polymer Nanostructural Materials at Interfaces

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    1 Results Molecular self-assembly of one-/two-dimensional (1D/2D) nanostructures has recently received great interest because the specific structures of crystals determine their unique physical and chemical properties. Coordination polymers contain two central components, connectors and linkers. Transition metal ions are often used as versatile connectors, with coordination numbers ranging from 2 to 7 dependant on the oxidation states of the metal ions. Multidentate ligands are often used as linkers, wh...

  3. The assembly of supramolecular boxes and coordination polymers based on bis-zinc-salphen building blocks

    NARCIS (Netherlands)

    Kuil, M.; Puijk, I.M.; Kleij, A.W.; Tooke, D.M.; Spek, A.L.; Reek, J.N.H.

    2009-01-01

    We report the assembly of supramolecular boxes and coordination polymers based on a rigid bis-zinc(II)-salphen complex and various ditopic nitrogen ligands. The use of the bis-zinc(II)-salphen building block in combination with small ditopic nitrogen ligands gave organic coordination polymers both

  4. The assembly of supramolecular boxes and coordination polymers based on bis-zinc-salphen building blocks.

    Science.gov (United States)

    Kuil, Mark; Puijk, Iris M; Kleij, Arjan W; Tooke, Duncan M; Spek, Anthony L; Reek, Joost N H

    2009-01-05

    We report the assembly of supramolecular boxes and coordination polymers based on a rigid bis-zinc(II)-salphen complex and various ditopic nitrogen ligands. The use of the bis-zinc(II)-salphen building block in combination with small ditopic nitrogen ligands gave organic coordination polymers both in solution as well as in the solid state. Molecular modeling shows that supramolecular boxes with small internal cavities can be formed. However, the inability to accommodate solvent molecules (such as toluene) in these cavities explains why coordination polymers are prevailing over well-defined boxes, as it would lead to an energetically unfavorable vacuum. In contrast, for relatively longer ditopic nitrogen ligands, we observed the selective formation of supramolecular box assemblies in all cases studied. The approach can be easily extended to chiral analogues by using chiral ditopic nitrogen ligands.

  5. Heterotopic silver-NHC complexes: from coordination polymers to supramolecular assemblies

    NARCIS (Netherlands)

    Rubio, M.; Siegler, M. A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    New coordination polymers based on different combinations of silver atoms and pyridyl-substituted N-heterocyclic carbene moieties are described. The addition of Zn(ii) templates leads to Ag-Zn supramolecular assemblies via selective ZnN interactions; a process that can be reverted.

  6. Heterotopic silver-NHC complexes: from coordination polymers to supramolecular assemblies

    NARCIS (Netherlands)

    Rubio, M.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    New coordination polymers based on different combinations of silver atoms and pyridyl-substituted N-heterocyclic carbene moieties are described. The addition of Zn(II) templates leads to Ag-Zn supramolecular assemblies via selective Zn⋯N interactions; a process that can be reverted.

  7. Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers and Assemblies

    OpenAIRE

    E. C. Constable; Housecroft, C. E.

    2016-01-01

    This overview of ligand design focuses on three areas: (i) principles of ligand binding, the formation of complexes, and popular strategies for ligand synthesis; (ii) ligand design in macrocyclic complexes, coordination polymers and networks and metallopolygons, and assembly strategies based upon the use of metalloligand building blocks; (iii) ligand design for the extraction and transport of metals. This area of coordination chemistry is too large to permit a comprehensive survey in the spac...

  8. Coordination polymers assembled through pi-pi interactions

    CERN Document Server

    Plummer, E A

    2001-01-01

    Chapter one is a review of the relevant literature. In chapter two the coordination chemistry of biphenyl-tailed terpyridines with octahedral metal dications is investigated. The effect of different metal ions on their aggregation modes in the solid state is also investigated. In chapter three the coordination chemistry of polyaryl-tailed terpyridines with octahedral metal dications is investigated. The effect of different aryl tails on their aggregation modes in the solid state is investigated. In chapter four the pi-pi aggregation of molecular boxes through biphenyl tails is studied. In chapter five the immobilisation of aryl tailed complexes into polyelectrolyte films has been investigated, and the arrangement of these complexes in the films has been compared with same complexes in the crystal, thus moving from three dimensional aggregation to two dimensions.

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

    Science.gov (United States)

    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.

  10. Linking homogeneous and heterogeneous enantioselective catalysis through a self-assembled coordination polymer.

    Science.gov (United States)

    García, José I; López-Sánchez, Beatriz; Mayoral, José A

    2008-11-01

    Combining the advantages of homogeneous and heterogeneous enantioselective catalysis is possible through self-supported copper coordination polymers, based on a new kind of ditopic chiral ligand bearing two azabis(oxazoline) moieties. When the coordination polymer is used to catalyze a cyclopropanation reaction, it becomes soluble in reaction conditions but precipitates after reaction completion, allowing easy recovery and efficient reuse in the same reaction up to 14 times.

  11. Diffusion-coupled molecular assembly: structuring of coordination polymers across multiple length scales.

    Science.gov (United States)

    Hirai, Kenji; Reboul, Julien; Morone, Nobuhiro; Heuser, John E; Furukawa, Shuhei; Kitagawa, Susumu

    2014-10-22

    Porous coordination polymers (PCPs) are an intriguing class of molecular-based materials because of the designability of framework scaffolds, pore sizes and pore surface functionalities. Besides the structural designability at the molecular scale, the structuring of PCPs into mesoscopic/macroscopic morphologies has attracted much attention due to the significance for the practical applications. The structuring of PCPs at the mesoscopic/macroscopic scale has been so far demonstrated by the spatial localization of coordination reactions on the surface of templates or at the phase boundaries. However, these methodologies have never been applied to the fabrication of solid-solution or multivariate metal-organic frameworks (MOFs), in which multiple components are homogeneously mixed. Herein, we demonstrate the structuring of a box-type superstructure comprising of a solid-solution PCP by integrating a bidirectional diffusion of multiple organic ligands into molecular assembly. The parent crystals of [Zn2(ndc)2(bpy)]n were placed in the DMF solution of additional organic component of H2bdc, and the temperature was rapidly elevated up to 80 °C (ndc = 1,4-naphthalenedicarboxylate, bpy = 4,4'-bipyridyl, bdc = 1,4-benzenedicarboxylate). The dissolution of the parent crystals induced the outward diffusion of components; contrariwise, the accumulation of the other organic ligand of H2bdc induced the inward diffusion toward the surface of the parent crystals. This bidirectional diffusion of multiple components spatially localized the recrystallization at the surface of cuboid parent crystals; therefore, the nanocrystals of a solid-solution PCP ([Zn2(bdc)1.5(ndc)0.5(bpy)]n) were organized into a mesoscopic box superstructure. Furthermore, we demonstrated that the box superstructures enhanced the mass transfer kinetics for the separation of hydrocarbons.

  12. Self-Assembly of Cluster-Based Nanoscopic Supramolecules into One-Dimensional Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Jian-Jun Zhang

    2009-01-01

    (2, and [(4,4′-bpe(Mn(Salen(H2O2]{(4,4′-bpe2[(Mn(Salen(MeOH2(Mn(Salen2(Nb6Cl12(CN6][(Mn(Salen2(Nb6Cl12(CN6]}·16H2O (3. Single crystal X-ray diffraction analyses show that the frameworks of the three coordination polymers are built of heterotrimeric and/or heteropentameric supramolecular species linked by ditopic organic ligands. The framework of 1 consists of anionic chains built of heterotrimeric dianions [(Mn(Salen2(Nb6Cl12(CN6]2− (T linked by 4,4′-dpyo. The chains run along two directions ([0 2 −2] and [0 3 3] leading to the formation of channels along the crystallographic (a direction where the cations [Mn(Salen(S2]+ and solvent molecules are located. Also, 2 was reported earlier, it possesses a neutral 1D chain built of neutral heterpentameric supramolecules: [(Mn(7‐MeSalen2(Mn(7‐MeSalen(S2(Nb6Cl12(CN6] (P linked by 4,4′-bpe ligands. Hydrogen bonds between non-bridging cyanide ligands and coordinated solvent molecules connect the chains into 2D hydrogen-bonded frameworks. Finally, 3 features an anionic chain, built of alternating heterotrimers [(Mn(Salen2(Nb6Cl12(CN6]2− and heteropentamers [(Mn(Salen(S2(Mn(Salen2(Nb6Cl12(CN6] linked by the organic spacer 4,4′-bpe. The anionic charge is compensated by the in situe-assembled [Mn(Salen(S(4,4′‐bpeMn(Salen(S]2+ dimers. Magnetic measurements reveal that the Mn(III ions are well isolated and only weak magnetic interactions are observed. The thermal stability of the three compounds was investigated.

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

    Science.gov (United States)

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

    2017-01-01

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox)0.5(H2O)]n·2n(H2O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H2sfpip)(ox)(H2O)4]n·2n(H2O) (Ln=Nd (8) Sm (9)), [H2ox=oxalic acid, H3sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H3sfpip resulted in two types of structures. Compounds 1-7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox2- anions as linkers to bridge the adjacent layers. Compounds 8-9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1-7 to 8-9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1-9 were also investigated.

  14. Assembling one-dimensional coordination polymers into threedimensional architectures via hydrogen bonds

    Indian Academy of Sciences (India)

    Lalit Rajput; Madhushree Sarkar; Kumar Biradha

    2010-09-01

    The reactions of bis(pyridylcarboxamido)alkanes (amides) and bis(3-pyridyl)alkanediamides (reverse amides) with copper(II) and zinc(II) in the presence of various anions resulted in onedimensional polymeric crystalline complexes with or without guest inclusion. The crystal structure analyses of these complexes reveal that the one-dimensional networks observed here are of three types: simple linear chain, chains with wavy nature and chains containing cavities. The self-complementary amide groups of the ligands assembled these coordination networks into higher dimensional architectures via N-H$\\cdots$O hydrogen bonds.

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

    Science.gov (United States)

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

    2015-01-21

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

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

    Science.gov (United States)

    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.

  17. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Wu, Jiang [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Kirillov, Alexander M. [Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, The University of Lisbon, Av. Rovisco Pais, 1049-001 Lisbon (Portugal); Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    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

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

    Science.gov (United States)

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

    2015-02-07

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

  19. Self-assembled nanoscale coordination polymers carrying siRNAs and cisplatin for effective treatment of resistant ovarian cancer.

    Science.gov (United States)

    He, Chunbai; Liu, Demin; Lin, Wenbin

    2015-01-01

    Resistance to the chemotherapeutic agent cisplatin is a major limitation for the successful treatment of many cancers. Development of novel strategies to overcome intrinsic and acquired resistance to chemotherapy is of critical importance to effective treatment of ovarian cancer and other types of cancers. We have sought to re-sensitize resistant ovarian cancer cells to chemotherapy by co-delivering chemotherapeutics and pooled siRNAs targeting multi-drug resistance (MDR) genes using self-assembled nanoscale coordination polymers (NCPs). In this work, NCP-1 particles with trigger release properties were first constructed by linking cisplatin prodrug-based bisphosphonate bridging ligands with Zn(2+) metal-connecting points and then coated with a cationic lipid layer, followed by the adsorption of pooled siRNAs targeting three MDR genes including survivin, Bcl-2, and P-glycoprotein via electrostatic interactions. The resulting NCP-1/siRNA particles promoted cellular uptake of cisplatin and siRNA and enabled efficient endosomal escape in cisplatin-resistant ovarian cancer cells. By down-regulating the expression of MDR genes, NCP-1/siRNAs enhanced the chemotherapeutic efficacy as indicated by cell viability assay, DNA ladder, and flow cytometry. Local administration of NCP-1/siRNAs effectively reduced tumor sizes of cisplatin-resistant SKOV-3 subcutaneous xenografts. This work shows that the NCP-1/siRNA platform holds great promise in enhancing chemotherapeutic efficacy for the effective treatment of drug-resistant cancers.

  20. Self-assembly of metal-organic coordination polymers constructed from a bent dicarboxylate ligand: diversity of coordination modes, structures, and gas adsorption.

    Science.gov (United States)

    Yang, Wenbin; Lin, Xiang; Blake, Alexander J; Wilson, Claire; Hubberstey, Peter; Champness, Neil R; Schröder, Martin

    2009-12-07

    We have synthesized five new metal-organic coordination polymers incorporating the bent ligand H(2)hfipbb [4,4'-(hexafluoroisopropylidene)bis(benzoic acid)] with different transition metal ions and co-ligands via solvothermal reactions to give [Zn(2)(hfipbb)(2)(py)(2)] x DMF (1), [Zn(2)(hfipbb)(2)(4,4'-bipy)(H(2)O)] (2), [Zn(2)(hfipbb)(2)(bpdab)].2DMF (3), [Cd(2)(hfipbb)(2)(DMF)(2)] x 2 DMF (4), and [Co(hfipbb)(dpp)] x MeOH (5) (py = pyridine, 4,4'-bipy = 4,4'-bipyridine, bpdab = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, dpp = 1,3-di(4-pyridyl)propane). Compound 1 displays a 2-fold 2D-->2D parallel interpenetrated layer network with one-dimensional (1D) helical channels, while 3 exhibits a three-dimensional pillared helical-layer open framework of alpha-Po topology based upon binuclear paddlewheel units. In compounds 2 and 5, binuclear motifs with double carboxylate bridges are linked by hfipbb(2-) ligands into a 1D ribbon, which are further assembled into two-dimensional non-interpenetrated (4,4) layers via bipyridyl co-ligands. However, the different bridging modes of hfipbb(2-) ligands and the different disposition of the coordinated co-ligands around metal ions result in subtle differences in the final architecture. Thus, 2 is based on a binuclear cluster node, double-stranded hfipbb(2-) linkers, and single-stranded 4,4'-bipy linkers, while 5 is based on a binuclear cluster node and hfipbb(2-) and dpp linkers which are both double-stranded. Among these compounds, the Cd(II) complex 4 is possibly the most interesting because it represents a rare example in which metal centers are linked by carboxylate groups into infinite chains further joined together by hfipbb(2-) spacers to form a 2D network with tubular helical channels. All these coordination polymers exhibit low solvent-accessible volumes. Both 3 and 4 retain structural integrity and permanent microporosity upon evacuation of guest molecules, with hydrogen uptakes of 0.57 and 0.78 wt %, respectively, at

  1. Polymer Directed Protein Assemblies

    Directory of Open Access Journals (Sweden)

    Patrick van Rijn

    2013-05-01

    Full Text Available Protein aggregation and protein self-assembly is an important occurrence in natural systems, and is in some form or other dictated by biopolymers. Very obvious influences of biopolymers on protein assemblies are, e.g., virus particles. Viruses are a multi-protein assembly of which the morphology is dictated by poly-nucleotides namely RNA or DNA. This “biopolymer” directs the proteins and imposes limitations on the structure like the length or diameter of the particle. Not only do these bionanoparticles use polymer-directed self-assembly, also processes like amyloid formation are in a way a result of directed protein assembly by partial unfolded/misfolded biopolymers namely, polypeptides. The combination of proteins and synthetic polymers, inspired by the natural processes, are therefore regarded as a highly promising area of research. Directed protein assembly is versatile with respect to the possible interactions which brings together the protein and polymer, e.g., electrostatic, v.d. Waals forces or covalent conjugation, and possible combinations are numerous due to the large amounts of different polymers and proteins available. The protein-polymer interacting behavior and overall morphology is envisioned to aid in clarifying protein-protein interactions and are thought to entail some interesting new functions and properties which will ultimately lead to novel bio-hybrid materials.

  2. Anion-controlled assembly of silver-di(aminophenyl)sulfone coordination polymers: Syntheses, crystal structures, and solid state luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Qi-Long, E-mail: gzuqlzhang@126.com [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Hu, Peng [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Zhao, Yi [Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025 (China); Feng, Guang-Wei [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Zhang, Yun-Qian; Zhu, Bi-Xue; Tao, Zhu [Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025 (China)

    2014-02-15

    Five silver coordination polymers, namely, ([Ag(3,3′-daps){sub 2}]·BF{sub 4}){sub n} (1), ([Ag(3,3′-daps){sub 2}]·NO{sub 3}){sub n} (2), [Ag(3,3′-daps)(CF{sub 3}SO{sub 3})]{sub n} (3), ([Ag(4,4′-daps)]·CF{sub 3}SO{sub 3}){sub n} (4), and ([Ag(4,4′-daps)]·ClO{sub 4}){sub n} (5) (3,3′-daps=di(3′-aminodiphenyl)sulfone, and 4,4′-daps=di(4′-aminodiphenyl)sulfone) have been synthesized and structural characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analyses. Complex 1 displays a 1D ladder-like chain with four-connected Ag ions and bridged 3,3′-daps. Complex 2 shows other 1D ladder chain modified by tentacles. Complex 3 is a 2D layer structure with both Ag ions and 3,3′-daps are 3-connected nodes. Complex 4 is another 1D ladder chain with three-connected Ag ions and 4,4′-daps. Complex 5 shows a 2D 4{sup 4}-sql net with Ag ions and 4,4′-daps as 4-connected nodes. Moreover, their solid state luminescence and thermal stabilities also have been investigated. - Graphical abstract: Pictogram: Synthetic procedures of the five anion controlled silver coordination polymers. We reported the synthetic procedures, structure, and luminescence property of the five anion controlled silver coordination polymers based on two novel di(aminophenyl)sulfone V-shaped ligands. Display Omitted - Highlights: • Five new silver coordination polymers were synthesized and characterized. • Two novel designed V-shaped di(aminophenyl)sulfone ligands were first introduced to coordination chemistry. • Anions play important roles in determining the five silver coordination polymers. • The structural diversity and photoluminescence property were also discussed.

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

    Science.gov (United States)

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

    2008-01-07

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-15

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

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

    Directory of Open Access Journals (Sweden)

    Gonzalo Abellán

    2015-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-02-15

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

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

    Science.gov (United States)

    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.

  8. Self-Assembly of Discrete Metallocycles versus Coordination Polymers Based on Cu(I and Ag(I Ions and Flexible Ligands: Structural Diversification and Luminescent Properties

    Directory of Open Access Journals (Sweden)

    Javier Vallejos

    2016-02-01

    Full Text Available Three new Ag(I and one Cu(I coordination compounds with two different positional isomers, propane-1,3-diyl bis(pyridine-4-carboxylate (L1 and propane-1,3-diyl bis(pyridine-3-carboxylate (L2, of a bis-(pyridyl-carboxylate ligand have been synthesized. X-ray diffraction analysis revealed that the self-assembly of L1 with AgCF3SO3 and AgClO4 salts leads to the formation of discrete binuclear metallocycles {Ag(L1CF3SO3}2 (1 and {Ag(L1ClO4}2 (2, respectively. However, self-assembly of the other ligand, L2, with AgCF3SO3 and CuCl salts, results in a 1-D zig-zag chain {Ag(L2CF3SO3}∞ (3 and a 1-D double-stranded helical chain {Cu2Cl2(L22}∞ (4 coordination polymers, respectively. Solid emission spectra recorded at room temperature show interesting luminescence properties for all four compounds in the range from 438 to 550 nm, especially for compound 4 that was found to change its emission color when the wavelength of the excitation radiation is switched from 332 to 436 nm.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni; Xu, Xiao-Wei; Feng, Yun-Long, E-mail: sky37@zjnu.cn

    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.

  11. A hybrid consisting of coordination polymer and noncovalent organic networks: a highly ordered 2-D phenol network assembled by edge-to-face pi-pi interactions.

    Science.gov (United States)

    Ko, Jung Woo; Min, Kil Sik; Suh, Myunghyun Paik

    2002-04-22

    A 2-D metal-organic open framework having 1-D channels, [Cu(C(10)H(26)N(6))](3)[C(6)H(3)(COO)(3)](2).18H(2)O (1), was constructed by the self-assembly of the Cu(II) complex of hexaazamacrocycle A (A = C(10)H(26)N(6)) with sodium 1,3,5-benzenetricarboxylate (BTC(3)(-)) in DMSO-H(2)O solution. 1 crystallizes in the trigonal space group P with a = b = 17.705(1) A, c = 6.940(1) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1884.0(3) A(3), Z = 1, and rho(calcd) = 1.428 g cm(-3). The X-ray crystal structure of 1 indicates that each Cu(II) macrocyclic unit binds two BTC(3-) ions in a trans position and each BTC(3-) ion coordinates three Cu(II) macrocyclic complexes to form 2-D coordination polymer layers with honeycomb cavities (effective size 8.1 A), and the layers are packed to generate 1-D channels perpendicularly to the 2-D layers. Solid 1 binds guest molecules such as MeOH, EtOH, and PhOH with different binding constant and capacity. By the treatment of 1 with aqueous solution of phenol, a hybrid solid [Cu(C(10)H(26)N(6))](3)[C(6)H(3)(COO)(3)](2).9PhOH.6H(2)O (2) was assembled. 2 crystallizes in the trigonal R3 space group with a = b = 20.461(1) A, c = 24.159(1) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 8759.2(7) A(3), Z = 3, and rho(calcd) = 1.280 g cm(-3). In 2, highly ordered 2-D noncovalent phenol layers are formed by the edge-to-face pi-pi interactions between the phenol molecules and are alternately packed with the coordination polymer layers in the crystal lattice.

  12. Hydrothermal Synthesis and Crystal Structure of Manganese(Ⅱ) Coordination Polymer Assembled by 4-Sulfophthalate and 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ Introduction The rational design and synthesis of metal-directed supramolecular framework compounds have received much attention in coordination chemistry because of their potential applications in catalysis, molecular selection, nonlinear optics, ion exchange, and microelectronics[1-4].

  13. A series of chiral coordination polymers containing helicals assembled from a new chiral (R)-2-(4'-(4''-carboxybenzyloxy)phenoxy)propanoic acid: syntheses, structures and photoluminescent properties.

    Science.gov (United States)

    He, Wei-Wei; Yang, Jin; Yang, Yan; Liu, Ying-Ying; Ma, Jian-Fang

    2012-08-28

    Ten new chiral coordination polymers, namely, [Ni(L)(H(2)O)(2)] (1), [Co(L)(H(2)O)(2)] (2), [Cd(L)(H(2)O)] (3), [Cd(L)(phen)] (4), [Mn(2)(L)(2) (phen)(2)]·H(2)O (5), [Cd(2)(L)(2)(biim-4)(2)] (6), [Zn(2)(L)(2)(biim-4)(2)] (7), [Cd(L)(pbib)] (8), [Cd(L)(bbtz)] (9) and [Cd(L)(biim-6)] (10), where phen = 1,10-phenathroline, biim-4 = 1,1'-(1,4-butanediyl)bis(imidazole), pbib = 1,4-bis(imidazole-1-ylmethyl)benzene, bbtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, biim-6 = 1,1'-(1,6-hexanedidyl)bis(imidazole), and H(2)L = (R)-2-(4'-(4''-carboxybenzyloxy)phenoxy)propanoic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra (IR), powder X-ray diffraction (PXRD), elemental analyses and thermogravimetric (TG) analyses. Compounds 1 and 2 exhibit similar 1D left-handed helical chains, which are further extended into 3D supramolecular structures through O-H···O hydrogen-bonding interactions, respectively. Compound 3 shows a 2D double-layer architecture containing helical chains. Compound 4 features two types of 2D undulated sheets with helical chains, which are stacked in an ABAB fashion along the c direction. Compound 5 possesses a 1D double chain ribbon structure containing unusual meso-helical chains, which is linked by π-π interactions into a 2D supramolecular layer. These layers are further extended by hydrogen-bonding interactions to form a 3D supramolecular assembly. Compounds 6 and 7 are isostructural and exhibit 2D (4(4))-sql networks with helical chains. Neighboring sheets are further linked by C-H···O hydrogen-bonding interactions to generate 3D supramolecular architectures. Compounds 8-10 are isostructural and display 3D 3-fold interpenetrating diamond frameworks with helical chains. The effects of coordination modes of L anions, metal ions and N-donor ligands on the structures of the coordination polymers have been

  14. Self-assembly of iron coordination polymer of bowl-shaped N-ligand and dodecamolybdosilicate anion

    Science.gov (United States)

    Tang, Qun; Chen, Ya-Guang

    2014-06-01

    [FeII2(ttmb)2(H2O)6][SiMo12O40]·4H2O (1) (ttmb = 1,3,5-tris(triazol-1-ylmethyl) benzene) was synthesized under hydrothermal conditions and characterized by IR spectroscopy, TG analysis and X-ray diffraction method. In 1 the bowl-like tridentate ligand, ttmb, bridges Fe2+ ions forming a coordination polymeric layer, [FeII2(ttmb)2(H2O)6]n4n+, with a large dimensional grid of 7.00 × 7.11 Å, in the presence of Keggin-type polyoxoanion as a template. The coordination polymeric layers and the polyoxoanions are fused into an inorganic-organic hybrid by hydrogen bonds. The photoluminescent spectrum of 1 in solid state at room temperature shows that the coordination of ttmb to Fe2+ ion results in a quench of the ttmb intramolecular fluorescence and a weak O-Mo LMCT fluorescent emission was observed at 520 nm.

  15. Polymer Directed Protein Assemblies

    NARCIS (Netherlands)

    van Rijn, Patrick

    2013-01-01

    Protein aggregation and protein self-assembly is an important occurrence in natural systems, and is in some form or other dictated by biopolymers. Very obvious influences of biopolymers on protein assemblies are, e. g., virus particles. Viruses are a multi-protein assembly of which the morphology is

  16. Polymer Directed Protein Assemblies

    NARCIS (Netherlands)

    van Rijn, Patrick

    Protein aggregation and protein self-assembly is an important occurrence in natural systems, and is in some form or other dictated by biopolymers. Very obvious influences of biopolymers on protein assemblies are, e. g., virus particles. Viruses are a multi-protein assembly of which the morphology is

  17. Assembly, crystal structure, and luminescent properties of three-dimensional (10,3)-a netted rare earth coordination polymers

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Solid complexes [REL(NO3)3]n with novel (10,3)-a type three-dimensional networks structure have been assembled using rare earth nitrates and an amide type semirigid tripodal bridging ligand, 1,3,5-tris {[(2′-benzylaminoformyl)phenoxyl]methyl}benzene (L), as building blocks. The complexes were crys- tallized in the orthorhombic system with chiral space group P212121. The whole structure consists of an infinite array of trigonal RE(III) ions bridged by tridentate ligands, and a novel (10,3)-a net is formed, which is very uncommon in the rare earth complexes. At room temperature, the Sm(III), Eu(III), Tb(III), Dy(III) complexes all exhibited characteristic luminescence emissions of central metal ions under UV light excitation.

  18. Six Zn(II) and Cd(II) coordination polymers assembled from a similar binuclear building unit: tunable structures and luminescence properties.

    Science.gov (United States)

    Zhang, Liyan; Rong, Lulu; Hu, Guoli; Jin, Suo; Jia, Wei-Guo; Liu, Ji; Yuan, Guozan

    2015-04-21

    Six Zn(ii) and Cd(ii) coordination polymers were constructed by treating a 2-substituted 8-hydroxyquinolinate ligand containing a pyridyl group with zinc or cadmium salts, and characterized by a variety of techniques. Interestingly, based on a similar binuclear Zn(ii) or Cd(ii) building unit, the supramolecular structures of the six coordination polymers () exhibit an unprecedented structural diversification due to the different choices of metal salts. and represent a novel 2D framework containing 1D infinite right- and left-handed helical chains. and are 2D coordination frameworks based on binuclear Cd(ii) building units. For and , the L ligands can bridge binuclear building units forming a 1D infinite chain. Interestingly, the adjacent Cd2O2 planes of the 1D chain in are in parallel with each other, while the dihedral angle between the two Zn2O2 planes in is 83.43°. Photoluminescence properties revealed that the six coordination polymers exhibit redshifted emission maximum compared with the free ligand HL, which can be ascribed to an increased conformational rigidity and the fabrication of coplanar binuclear building units M2L2 in . Coordination polymers also display distinct fluorescence lifetimes and quantum yields because of their different metal centers and supramolecular structures.

  19. Solvent-regulated assemblies of four Zn(II) coordination polymers constructed by flexible tetracarboxylates and pyridyl ligands

    Science.gov (United States)

    Fang, Kang; He, Xiang; Shao, Min; Li, Ming-Xing

    2016-08-01

    Four unique complexes with diverse coordination architectures were synthesized upon complexation of 5,5-(1,4-phenylenebis (methylene))bis (oxy)- diisophthalic acid (H4L) with zinc ions by using different solvent. namely, {[Zn(H2L) (bpp)]·DEF}n (1), {[Zn2(L) (bpp)2]·4H2O}n (2), {[Zn2(L) (pdp)2]·3H2O·DEF}n (3), {[Zn2(L) (pdp)2].4H2O}n (4). Complexes 1,2 and 3,4 are obtained by varying solvents to control their structures. The size of solvent molecular plays an important role to control different structure of these compounds. Compound 1 is 2D waved framework with (4, 4) grid layer as sql topology. Compound 3 displays a (4,6)-connected 2-nodal net with a fsc topology. Compounds 2 and 4 are all three-dimensional network simplified as (4,4)-connected 2-nodal net with a bbf topology. The photochemical properties of compounds 1-4 were tested in the solid state at room temperature, owing to their strong luminescent emissions, complexes 1-4 are good candidates for photoactive materials.

  20. Porphyrin coordination polymer nanospheres and nanorods

    Science.gov (United States)

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

    2012-12-04

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

  1. Porphyrin coordination polymer nanospheres and nanorods

    Science.gov (United States)

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

    2013-09-10

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

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

    Science.gov (United States)

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

    2010-12-06

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhao-Hao [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Xue, Li-Ping, E-mail: lpxue@163.com [College of Food and Drug, Luoyang Normal University, Luoyang 471934 (China); Miao, Shao-Bin [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Zhao, Bang-Tun, E-mail: zbt@lynu.edu.cn [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China)

    2016-08-15

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

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

    Science.gov (United States)

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

    2013-01-22

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

  5. Nitrate-Bridged One-Dimension Coordination Polymer Self-Assembled from a N4O2-Tetraiminodiphenolate Dicopper(II Macrocyclic Complex

    Directory of Open Access Journals (Sweden)

    Julio Cesar da Rocha

    2015-01-01

    Full Text Available Herein we report on the synthesis and single crystal X-ray structure characterization of [{Cu2(tidf(μ-NO3}∞]ClO4 (tidf = a Robson type macrocyclic ligand obtained upon condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane. The coordination geometry around the copper(II is square-pyramidal and has [Cu2(tidf]2+ units connected to each other through nitrate bridges extending as a one-dimension coordination polymer. The compound exhibits an extensive supramolecular structure supported by nonclassic hydrogen bonding between C-H⋯Operchlorate and C-H⋯Onitrate.

  6. Anion-directed assembly and crystal transformation of Ag(I) coordination polymers with a versatile tripyridyltriazole ligand 3,4-bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole

    Science.gov (United States)

    Li, Cheng-Peng; Chen, Jing; Guo, Wei; Du, Miao

    2015-03-01

    A series of distinct Ag(I) coordination polymers, namely {[Ag2(L224)(H2O)3](SiF6)(H2O)4}n (1), {[Ag2(L224)2(NO3)](NO3)(H2O)}n (3), {[Ag2(L224)(OOCC6H5)(H2O)](NO3)(H2O)2}n (4), and {[Ag(L224)2](CF3SO3)(H2O)0.25}n (5) have been synthesized by assembling a versatile ligand 3,4-bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (L224) with different Ag(I) salts. Their diverse 1D and 2D coordination arrays indicate the critical role of counterions in structural assemblies. Interestingly, single-crystal-to-single-crystal (SC-SC) transformation from 1 to {[Ag2(L224)(CF3COO)2(H2O)](H2O)}n (2) will occur in the water solution of Ag(CF3COO). Structural comparison and mechanism of SC-SC transformation are discussed. These Ag(I) coordination polymers show enhanced ligand-based solid-state fluorescent emissions.

  7. Self-assembly, structures and properties of three new Ni(II) coordination polymers derived from two different bis-pyridyl-bis-amide ligands and two aromatic polycarboxylates

    Indian Academy of Sciences (India)

    HONGYAN LIN; JUNJUN SUN; GUOCHENG LIU; XIANG WANG; PANWEN CHEN

    2017-01-01

    Three new Ni(II) coordination polymers exhibiting different 1D and 2D framework structures have been hydrothermally synthesized: [Ni(L ¹)(1,3-BDC)(H ₂O) ₃]•H ₂O (1), [Ni(L ¹)(1,3,5-HBTC)(H ₂O) ₃] (2), [Ni ₃ (L ²)3(1,3,5-BTC) ₂ (H ₂O)8]•12H ₂ ₂O (3) [L ¹ = N,N_-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide, L ² = N,N’-bis(3-pyridyl)octandiamide, 1,3-H ₂BDC = 1,3-benzenedicarboxylic acid, 1,3,5-H3BTC = 1,3,5- benzenetricarboxylic acid]. X-ray single crystal diffraction analyses revealed that polymer 1 is a 2D interlaced layer based on the 1D [Ni(L ¹)(1,3-BDC)(H ₂O) ₃] meso-helical chains. Polymer 2 is a 1D wave-shaped chain derived from the 1D [Ni(L ¹)]n chain and monodentate coordinated 1,3,5-HBTC anions. Polymer 3 possesses an interesting 2D layer containing the trinuclear [Ni ₃ (1,3,5-BTC) ₂] substructural unit and 1D zigzag [Ni(L ²)]n chain, representing a 3,4-connected {6•8 ²} ₂{6 ² •8 ² • 10• 12} topology. Finally, the adjacent 1D chains or the 2D layers are connected through hydrogen bonding interactions to construct 3D supramolecular networks. Further, the thermal stability, solid state fluorescent property and photocatalytic activity of 1–3 have been investigated.

  8. Metal ions directed assembly of two coordination polymers based on an organic phosphonate anion and a multidentate N-donor ligand

    Science.gov (United States)

    Kan, Wei-Qiu; Xu, Ji-Ming; Wen, Shi-Zheng; Yang, Lin

    2017-01-01

    Two new coordination polymers [Cd(4,4‧-tmbpt)(HL)(H2O)] (1) and [Cu(4,4‧-tmbpt)(HL)]·H2O (2) (H3L = 2‧-carboxybiphenyl-4-ylmethylphosphonic and 4,4‧-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole) have been synthesized hydrothermally. The two compounds have the same metal to ligand ratio, but different metal ions. As a result, the two compounds display different 2D layer structures, which is mainly caused by the different coordination numbers of the different metal ions. The effects of the metal ions on the structures, the optical band gaps and photoluminescent and photocatalytic properties of the compounds have been studied.

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

    Science.gov (United States)

    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.

  10. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-08-15

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

  13. Influence of pseudohalide anions on the structural assembly of Cd(II) coordination polymers with 3,4-bis(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole

    Science.gov (United States)

    Chen, Jing; Li, Ming-Ze; Sun, Nan; Guo, Jian-Hua

    2016-02-01

    Four CdII coordination polymers, namely {[Cd(L334)(Cl)2](CH3OH)}n (1), [Cd(L334)(Cl)(dca)]n (2), {[Cd(L334)(Cl)1.33(N3)0.67](H2O)}n (3), and {[Cd(L334)(SCN)2(H2O)](H2O)1.5(CH3OH)}n (4), have been synthesized by the conventional reactions of CdCl2 and 3,4-bis(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (L334) or in the presence of different pseudohalides dicyanamide (dca), azide (N3), and thiocyanate (SCN), respectively as auxiliary ligands. Complexes 1-3 exhibit the isostructural 2D layered network structures, whereas complex 4 shows a distinct 2D network with dimeric CdII subunits. The structural discrepancy in 1-4 indicates the significant influence of pseudohalide anions on the structural assembly of CdII coordination polymers with 3,4-bis(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole. In addition, thermogravimetric and fluorescent properties for all complexes and the ligand have also been investigated.

  14. Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Coordination Polymer Assembled by Phthalate and 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    LI Xiu-Mei; WANG Qing-Wei; CUI Yun-Cheng; LI Chuan-Bi; WANG Ren-Zhang; LIU Bo

    2006-01-01

    A metal-organic coordination polymer {[Zn(Pht)(4,4′-bipy)(H2O)2]·2H2O}n (Pht = phthalate, 4,4′-bipy = 4,4′-bipyridine) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in the monoclinic system, space group P2/n, a = 7.6346(14), b = 11.316(2), c = 10.8133(19) (A), β = 92.444(3)o, V = 933.3(3)(A)3, C18H20N2O8Zn, Mr = 457.73, Dc = 1.629 g/cm3, F(000) = 472, Z = 2, μ(MoKα) = 1.367 mm-1, the final R = 0.0323 and wR = 0.0821 for 1859 observed reflections (I > 2σ(I)). The structure of 1 exhibits a two-dimensional bilayer framework formed by hydrogen bonding interactions. Furthermore, 1 shows yellow photoluminescent pro- perty at room temperature.

  15. Toward the self-assembly of metal-organic nanotubes using metal-metal and π-stacking interactions: bis(pyridylethynyl) silver(I) metallo-macrocycles and coordination polymers.

    Science.gov (United States)

    Kilpin, Kelly J; Gower, Martin L; Telfer, Shane G; Jameson, Geoffrey B; Crowley, James D

    2011-02-07

    Shape-persistent macrocycles and planar organometallic complexes are beginning to show considerable promise as building blocks for the self-assembly of a variety of supramolecular materials including nanofibers, nanowires, and liquid crystals. Here we report the synthesis and characterization of a family of planar di- and tri-silver(I) containing metallo-macrocycles designed to self-assemble into novel metal-organic nanotubes through a combination of π-stacking and metal-metal interactions. The silver(I) complexes have been fully characterized by elemental analysis, high resolution electrospray ionization mass spectrometry (HR-ESI-MS), IR, (1)H and (13)C NMR spectroscopy, and the solution data are consistent with the formation of the metallo-macrocycles. Four of the complexes have been structurally characterized using X-ray crystallography. However, only the di-silver(I) complex formed with 1,3-bis(pyridin-3-ylethynyl)benzene is found to maintain its macrocyclic structure in the solid state. The di-silver(I) shape-persistent macrocycle assembles into a nanoporous chicken-wire like structure, and ClO(4)(-) anions and disordered H(2)O molecules fill the pores. The silver(I) complexes of 2,6-bis(pyridin-3-ylethynyl)pyridine and 1,4-di(3-pyridyl)buta-1,3-diyne ring-open and crystallize as non-porous coordination polymers.

  16. Metallogels from Coordination Complexes, Organometallic, and Coordination Polymers.

    Science.gov (United States)

    Dastidar, Parthasarathi; Ganguly, Sumi; Sarkar, Koushik

    2016-09-20

    A supramolecular gel results from the immobilization of solvent molecules on a 3D network of gelator molecules stabilized by various supramolecular interactions that include hydrogen bonding, π-π stacking, van der Waals interactions, and halogen bonding. In a metallogel, a metal is a part of the gel network as a coordinated metal ion (in a discrete coordination complex), as a cross-linking metal node with a multitopic ligand (in coordination polymer), and as metal nanoparticles adhered to the gel network. Although the field is relatively new, research into metallogels has experienced a considerable upsurge owing to its fundamental importance in supramolecular chemistry and various potential applications. This focus review aims to provide an insight into the development of designing metallogelators. Because of the limited scope, discussions are confined to examples pertaining to metallogelators derived from discrete coordination complexes, organometallic gelators, and coordination polymers. This review is expected to enlighten readers on the current development of designing metallogelators of the abovementioned class of molecules. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Assemblies of a new flexible multicarboxylate ligand and d10 metal centers toward the construction of homochiral helical coordination polymers: structures, luminescence, and NLO-active properties.

    Science.gov (United States)

    Zang, Shuangquan; Su, Yang; Li, Yizhi; Ni, Zhaoping; Meng, Qingjin

    2006-01-01

    Hydro(solvo)thermal reactions between a new flexible multicarboxylate ligand of 2,2',3,3'-oxydiphthalic acid (2,2',3,3'-H(4)ODPA) and M(NO(3))(2).xH(2)O (M = Zn, x = 6; M = Cd, x = 4) in the presence of 4,4'-bipyridine (bpy) afford two novel homochiral helical coordination polymers [[Zn(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 1 and [Cd(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 2]. Though having almost the same chemical formula, they have different space groups (P2(1)2(1)2(1) for 1 and P2(1) for 2) and different bridging modes of the 2,2',3,3'-ODPA ligand. Two kinds of homochiral helices (right-handed) are found in both 1 and 2, each of which discriminates only one kind of crystallographical nonequivalent metal atom. 1 has a 2D metal-organic framework and can be seen as the unity of two parallel homochiral Zn1 and Zn2 helices, in which the nodes are etheric oxygen atoms. In contrast, 2 has a 3D metal-organic framework and consists of two partially overlapped homochiral Cd1 and Cd2 helices in the two dimensions. Moreover, metal-ODPA helices give a 2D chiral herringbone structural motif in both 1 and 2 in the two dimensions, which are further strengthened by the second ligand of bpy. Bulk materials for 1 and 2 all have good second-harmonic generation activity, approximately 1 and 0.8 times that of urea.

  18. Polymer Self-assembly on Carbon Nanotubes

    Science.gov (United States)

    Giulianini, Michele; Motta, Nunzio

    This chapter analyses the poly(3-hexylthiophene) self-assembly on carbon nanotubes and the interaction between the two materials forming a new hybrid nanostructure. The chapter starts with a review of the several studies investigating polymers and biomolecules self-assembled on nanotubes. Then conducting polymers and polythiophenes are briefly introduced. Accordingly, carbon nanotube structure and properties are reported in Sect. 3. The experimental section starts with the bulk characterisation of polymer thin films with the inclusion of uniformly distributed carbon nanotubes. By using volume film analysis techniques (AFM, TEM, UV-Vis and Raman), we show how the polymer's higher degree of order is a direct consequence of interaction with carbon nanotubes. Nevertheless, it is through the use of nanoscale analysis and molecular dynamic simulations that the self-assembly of the polymer on the nanotube surface can be clearly evidenced and characterised. In Sect. 6, the effect of the carbon templating structure on the P3HT organisation on the surface is investigated, showing the chirality-driven polymer assembly on the carbon nanotube surface. The interaction between P3HT and CNTs brings also to charge transfer, with the modification of physical properties for both species. In particular, the alteration of the polymer electronic properties and the modification of the nanotube mechanical structure are a direct consequence of the P3HT π-π stacking on the nanotube surface. Finally, some considerations based on molecular dynamics studies are reported in order to confirm and support the experimental results discussed.

  19. Topochemical control in desolvation of coordination polymers

    OpenAIRE

    Matteo Lusi

    2015-01-01

    Reactions in the solid state are at the core of crystal engineering as they can result in new crystalline phases that are not always accessible by traditional solution methods. The work of Brammer and co-workers [Wright et al. (2015), IUCrJ, 2, 188–197] represents a clear example of this potential as applied to the synthesis of a silver–phenazine coordination polymer.

  20. Nanometrization of Lanthanide-Based Coordination Polymers.

    Science.gov (United States)

    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.

  1. Protein-responsive assemblies from catechol-metal ion supramolecular coordination.

    Science.gov (United States)

    Yuan, C; Chen, J; Yu, S; Chang, Y; Mao, J; Xu, Y; Luo, W; Zeng, B; Dai, L

    2015-03-21

    Supramolecular self-assembly driven by catechol-metal ion coordination has gained great success in the fabrication of functional materials including adhesives, capsules, coatings and hydrogels. However, this route has encountered a great challenge in the construction of nanoarchitectures in the absence of removable templates, because of the uncontrollable crosslinking of catechol-metal ion coordination. Herein, we show that a supramolecular approach, combining both catechol-metal ion coordination and polymer self-assembly together, can organize polymers into hybrid nanoassemblies ranging from solid particles, homogeneous vesicles to Janus vesicles. Without the introduction of a specific binding ligand or complicated molecular design, these assemblies can totally disassemble in response to proteins. UV/vis absorption, fluorescence quenching and recovery investigations have confirmed that proteins can seize metal ions from the hybrid nanoassemblies, thus causing the degradation of catechol-metal ion coordination networks.

  2. Topologically unique heterometallic Cu(II)/Li coordination polymers self-assembled from N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid biobuffer: versatile catalyst precursors for mild hydrocarboxylation of alkanes to carboxylic acids.

    Science.gov (United States)

    Kirillova, Marina V; Kirillov, Alexander M; Martins, André N C; Graiff, Claudia; Tiripicchio, Antonio; Pombeiro, Armando J L

    2012-05-07

    The facile aqueous medium reactions of copper(II) nitrate with BES biobuffer [(HOCH(2)CH(2))(2)N(CH(2)CH(2)SO(3)H), hereinafter referred as H(3)bes] in the presence of various benzenecarboxylic acids [benzoic (Hba), 3-hydroxybenzoic (Hhba), and 3,5-dihydroxybenzoic (Hdhba) acid] and lithium hydroxide gave rise to the self-assembly generation of three new heterometallic Cu(II)/Li materials, [Li(H(2)O)(4)][Cu(4)(μ(2)-Hbes)(4)(μ(2)-ba)]·H(2)O (1) and [Cu(4)(μ(3)-Hbes)(4)(L){Li(H(2)O)(2)}](n)·3nH(2)O {L = μ(2)-hba (2) and μ(2)-dhba (3)}. They were isolated as air-stable crystalline solids and fully characterized by infrared (IR) and UV-vis spectroscopy and electrospray ionization (ESI)-MS(±), elemental, thermal, and single-crystal X-ray diffraction analyses. The latter revealed that 1-3 have comparable packing patterns and unit cell parameters, being composed of similar [Cu(4)(μ-Hbes)(4)(μ-carboxylate)](-) cores and [Li(H(2)O)(4)](+) cations (in 1) or [μ-Li(H(2)O)(2)](+) groups (in 2 and 3), which are arranged into discrete 0D aggregates in 1 or infinite 3D noninterpenetrating metal-organic networks in 2 and 3. The topological analysis of the coordination polymers 2 and 3 disclosed the trinodal 3,3,4-connected underlying nets with an unprecedented topology defined by the point symbol of (4.6.8)(4)(4(2).6)(2)(6(2).16(2).18(2)), further simplification of which resulted in the binodal 4,4-connected nets with the pts (PtS) topology. Apart from representing very rare examples of coordination compounds derived from H(3)bes, 1-3 feature solubility in water and were applied as efficient and versatile catalyst precursors for the mild (60 °C) single-pot hydrocarboxylation, by CO and H(2)O, of various gaseous, linear, and cyclic C(n) (n = 2-9) alkanes into the corresponding C(n+1) carboxylic acids, in H(2)O/MeCN medium under homogeneous conditions and in the presence of potassium peroxodisulfate. Total yields (based on alkane) of carboxylic acids up to 78% were

  3. New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide.

    Science.gov (United States)

    Monreal, Marisa J; Seaman, Lani A; Goff, George S; Michalczyk, Ryszard; Morris, David E; Scott, Brian L; Kiplinger, Jaqueline L

    2016-03-07

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge.

  4. Ytterbium Coordination Polymer with Four Different Coordination Numbers: The First Structural Characterization of Lanthanide Phthalate Complex

    Institute of Scientific and Technical Information of China (English)

    WAN,Yong-Hong(万永红); JIN,Lin-Pei(金林培); WANG,Ke-Zhi(王科志)

    2002-01-01

    The novel ytterbium coordination polymer is a two-dimensional framework in which the central metal ions have four different coordination numhers and form four kinds of coordination polyhedra. The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms

  5. Supramolecular assembly in telechelic polymer blends

    Science.gov (United States)

    Elliott, R.; Fredrickson, Glenn H.

    2009-10-01

    Equilibrium, supramolecular assembly in melt blends of two species of telechelic polymers with reversible bonding sites at both ends is theoretically investigated. The bonding between polymers, whether between like or dislike chains, is controlled by affinities of chain bonding set by specified bond energies. Low affinities, or low overall bond strength, results in a monodisperse population of unlinked chains while larger affinities cause longer chains to assemble, forming a polydisperse blend. We investigate sequentially blends with only homobonding (like chain), only heterobonding (dislike chain), and finally a mixed homo- and heterobonding melt. In the first case, the effects of longer chain assembly and polydispersity in a homogeneous melt and its bulk demixing transition are explored. In contrast with the homobonding case, large heterobonding affinities cause alternating blocks to assemble into multiblock copolymers, which can lead to mesophases. The weak bonding region between bulk phase separation and mesophase stability is investigated and a novel Lifshitz point is found indicating a region prone to emulsify. Mixed homo- and heterobonding systems are also examined. Polymeric segments of both species are modeled as flexible Gaussian threads and nonspecific interactions between dissimilar blocks are contactlike Flory-Huggins repulsions. The melts are assumed to be incompressible and all calculations are carried out within mean-field theory. A new integral equation formalism is developed for enumerating all linear species in these complex supramolecular systems, and the random phase approximation and numerical self-consistent field theory are invoked in this context to map out a variety of phase diagrams.

  6. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro

    2013-05-01

    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  7. Expanding coordination chemistry from protein to protein assembly.

    Science.gov (United States)

    Sanghamitra, Nusrat J M; Ueno, Takafumi

    2013-05-14

    Bioinorganic chemistry is of growing importance in the fields of nanomaterial science and biotechnology. Coordination of metals by biological systems is a crucial step in intricate enzymatic reactions such as photosynthesis, nitrogen fixation and biomineralization. Although such systems employ protein assemblies as molecular scaffolds, the important roles of protein assemblies in coordination chemistry have not been systematically investigated and characterized. Many researchers are joining the field of bioinorganic chemistry to investigate the inorganic chemistry of protein assemblies. This area is emerging as an important next-generation research field in bioinorganic chemistry. This article reviews recent progress in rational design of protein assemblies in coordination chemistry for integration of catalytic reactions using metal complexes, preparation of mineral biomimetics, and mechanistic investigations of biomineralization processes with protein assemblies. The unique chemical properties of protein assemblies in the form of cages, tubes, and crystals are described in this review.

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

    Science.gov (United States)

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

    2013-12-15

    The meta-organic coordination polymers have been emerged as fascinating nanomaterials because of their tunable nature. In this work, we employed lanthanide coordination polymer self-assembled from adenosine monophosphate (AMP) and europium ion (Eu(3+)) as receptor reagent and citrate (Cit) as ancillary ligand to construct a fluorescent sensor for the detection of tetracycline (Tc) in milk. The co-coordination of Cit and Tc with Eu(3+) on the surface of the coordination polymer AMP/Eu leads to the formation of ternary complex which emitted strong fluorescence due to the removal of coordinated water molecules and an intramolecular energy transfer from Tc to Eu(3+). The fluorescent intensity of Eu(3+) displayed a good linear response to Tc concentrations in the range of 0.1-20 μM with a detection limit of 60 nM. This method was successfully applied to determine the levels of Tc in milk, which is the first application of coordination polymer as a fluorescent sensor in real sample. Compared with other Eu(3+)-based fluorescent methods for Tc detection, the presented method allows simple, direct analysis of Tc without requiring special reaction media or complicated prepreparation processes. This straightforward strategy could be extended to the preparation of other lanthanide coordination polymer-based fluorescent probes for applications in biosensing, imaging, drug delivery, and so on. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Dynamic assembly of molecularly imprinted polymer nanoparticles.

    Science.gov (United States)

    Gong, Haiyue; Hajizadeh, Solmaz; Jiang, Lingdong; Ma, Huiting; Ye, Lei

    2017-09-11

    Manipulation of specific binding and recycling of materials are two important aspects for practical applications of molecularly imprinted polymers. In this work, we developed a new approach to control the dynamic assembly of molecularly imprinted nanoparticles by surface functionalization. Molecularly imprinted polymer nanoparticles with a well-controlled core-shell structure were synthesized using precipitation polymerization. The specific binding sites were created in the core during the first step imprinting reaction. In the second polymerization step, epoxide groups were introduced into the particle shell to act asan intermediate linker to immobilize phenylboronic acids, as well as to introduce cis-diol structures on surface. The imprinted polymer nanoparticles modified with boronic acid and cis-diol structures maintained high molecular binding specificity, and the nanoparticles could be induced to form dynamic particle aggregation that responded to pH variation and chemical stimuli. The possibility of modulating molecular binding and nanoparticle assembly in a mutually independent fashion can be exploited in a number of applications where repeated use of precious nanoparticles is needed. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. CO2-stimulated diversiform deformations of polymer assemblies.

    Science.gov (United States)

    Yan, Qiang; Zhao, Yue

    2013-11-01

    Use of a given physiological stimulus to delicately deform polymer assemblies is a challenging topic. Here we develop synthetic block copolymers to construct a series of CO2-sensitive self-assembled nanostructures that can simulate controllable deformations of the organelles in different ways. By controlling the CO2 stimulation levels, one can modulate the size, shape, and morphology of the polymer aggregates, which is conducive to understanding the stimuli-triggered dynamic reshaping process of polymer assemblies in aqueous solution.

  11. Coordinating the interruption of assembly workers in manufacturing.

    Science.gov (United States)

    Kolbeinsson, Ari; Thorvald, Peter; Lindblom, Jessica

    2017-01-01

    This paper examines how interruptions from information and communications technology systems affect errors and the time to complete tasks for assembly workers. Interruptions have previously been examined in laboratory experiments and office environments, but not much work has been performed in other authentic environments. This paper contains the results of an experiment that was performed in a simulated manufacturing assembly environment, which tested the effects of interruptions on a manual assembly task. The experiment used existing interruption coordination methods as a basis, and the results showed a difference in the effect of interruptions and interruption coordination between cognitively complex laboratory tasks and manual assembly tasks in an authentic environment. Most notably, the negative effects of interruptions delivered without consideration were smaller in this experiment. Based on these findings, recommendations were developed for designing interruption systems for minimizing the costs (errors and time) imposed by interruptions during assembly tasks in manufacturing.

  12. Hydrothermal Assembly and Structural Characterization of a Novel 3D Coordination Polymer: [Cd2Zn(BTC)2(H2O)4]n·2nH2O

    Institute of Scientific and Technical Information of China (English)

    陈建新; 刘世雄

    2005-01-01

    A hydrothermal reaction of 1,3,5-benzene-tricarboxylic acid (H3BTC) with cad- mium acetate, zinc acetate and pyridine led to the formation of pink crystals of [Cd2Zn(BTC)2- (H2O)4]n·2nH2O 1. Single-crystal X-ray diffraction analysis has revealed that 1 (Cd2ZnC18H18O18) crystallizes in the monoclinic system, space group C2/c with a = 19.4328(7), b = 7.1420(3), c = 18.0426(5)(A), β = 118.035(1)o, V = 2210.3(1) (A)3, Mr = 812.49, Dc = 2.442 g/cm3, Z = 4, μ(MoKα) = 3.081 mm-1 and F(000) =1584. A total of 10735 reflections were collected, of which 2544 were unique. The structure was refined to R = 0.0200 and wR = 0.0603 for 2388 observed reflections with I>2σ(I). The crystal structure consists of cadmium(II)/zinc(II) carboxylates of BTC as well as coordination and discrete water molecules. Extension of the coordination geometry around three metal centers (Cd(1), Cd(2) and Zn(1)), two BTC3- ligands and four coordinated water molecules generates a three-dimensional coordination polymer.

  13. Stable Polymer Micelles Formed by Metal Coordination

    NARCIS (Netherlands)

    Wang, Junyou; Stuart, Martien A. Cohen; Marcelis, Antonius T. M.; Colomb-Delsuc, Mathieu; Otto, Sijbren; van der Gucht, Jasper

    2012-01-01

    Metal-containing polymer micelles have attracted much attention due to their potential for medical and nanotechnological applications. In this paper, we present a method to prepare stable metal-containing polymer micelles. A diblock copolymer poly(4-vinylpyridine)-b-poly(ethylene oxide) (P4VP(48)-b-

  14. Nanoscale coordination polymers for anticancer drug delivery

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    Yuheng Deng

    2010-05-01

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

  16. Non covalent assembly of coordination superstructures

    CERN Document Server

    Khlobystov, A N

    2002-01-01

    The main topic of this work is the design of discrete and polymeric multi-component coordination structures using non-covalent interactions between organic and inorganic molecular components. All of the structures described herein are based on transition metal cations and N-donor heterocyclic bis-exodentate ligands with different geometries and various spacer functionalities. The predominant method used for the structural characterisation of the complexes was single crystal X-ray crystallography. X-ray powder diffraction, IR and NMR spectroscopies and TEM and AFM imaging were used to characterise the bulk products from the reactions. Chapter 1 is a comparative review of non-covalent interactions relevant to coordination superstructures and covers the latest developments in the area of crystal engineering and supramolecular chemistry. The nature, geometry and relative energy of the non-covalent interactions are considered in detail in order to reveal their influence on the structure and properties of complexes...

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

    Science.gov (United States)

    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.

  18. Hybrid Thin Films Based Upon Polyoxometalates-Polymer Assembly

    Science.gov (United States)

    Qi, Na; Jing, Benxin; Zhu, Yingxi

    2014-03-01

    Block copolymers (BCPs) and polyoxometalates (POMs) have been used individually as building blocks for design and synthesis of novel functional materials. POM nanoclusters, the assemblies of transition metal oxides with well-defined atomic coordination structure, have been recently explored as novel nanomaterials... for catalysis, semiconductors, and even anti-cancer treatment due to their unique chemical, optical and electrical characteristics. We have explored the blending of inorganic POM nanocluster with BCPs into hierarchaically structured inorganic-organic hybrid nanocomposites. Using polystyrene-b-poly(ethylene oxide) (PS-b-PEO) thin films as the template, we have observed that the spatial organization of BCP thin films is modified by molybdenum based POM nanocluster to form 2D in-plane hexagonal ordered or 3D ordered network of POM-BCP assemblies, depending on the concentration ratio of POM to PS-b-PEO. The dielectric properties of such hybrid thin films can be enhanced by embedded POMs but show a strong dependence on the supramolecular structures of POM-polymer complexes. The assembly of nanoclusters in BCP-templated thin films could pave a new path to design new hybrid nanocomposites with uniquely combined functionality and material properties.

  19. Polymer Directed Self-Assembly of pH-Responsive Antioxidant Nanoparticles

    Science.gov (United States)

    Tang, Christina; Amin, Devang; Messersmith, Phillip B.; Anthony, John E.; Prud’homme, Robert K.

    2015-01-01

    We have developed pH-responsive, multifunctional nanoparticles based on encapsulation of an antioxidant, tannic acid (TA), using Flash NanoPrecipitation, a polymer directed self-assembly method. Formation of insoluble coordination complexes of tannic acid and iron during mixing drives nanoparticle assembly. Tuning the core material to polymer ratio, the size of the nanoparticles can be readily tuned between 50 and 265 nm. The resulting nanoparticle is pH-responsive, i.e. stable at pH 7.4 and soluble under acidic conditions due to the nature of the coordination complex. Further, the coordination complex can be coprecipitated with other hydrophobic materials such as therapeutics or imaging agents. For example, coprecipitation with a hydrophobic fluorescent dye creates fluorescent nanoparticles. In vitro, the nanoparticles have low cytotoxicity show antioxidant activity. Therefore, these particles may facilitate intracellular delivery of antioxidants. PMID:25760226

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-15

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

  1. Nanostructured photovoltaic materials using block polymer assemblies

    Science.gov (United States)

    Mastroianni, Sarah Elizabeth

    Despite its potential as an abundant, sustainable alternative to non-renewable energy sources, solar energy currently is underutilized. Photovoltaics, which convert energy from sunlight into electricity, commonly are made from inorganic semiconductor materials that require expensive manufacturing and processing techniques. Alternatively, organic materials can be used to produce flexible and lightweight organic photovoltaic (OPV) devices, which can be prepared using solution-based processing techniques. However, OPV devices are limited by low efficiencies and short lifetimes compared to their inorganic counterparts. In OPV systems, charge carriers are generated in the active layer via the separation of excitons (electron-hole pairs) at interfaces between donor and acceptor materials. Because excitons have a limited diffusion length (˜10 nm), they may recombine before reaching a donor-acceptor interface if domain sizes are large. This exciton recombination can limit device efficiency; thus, the design parameters for improved active layer morphologies include large interfacial areas, small size scales, and continuous conducting pathways. Currently, most OPV devices are prepared by blending donor and acceptor materials in bulk heterojunction (BHJ) devices, often resulting in non-ideal, process-dependent morphologies. Alternatively, the self-assembly of block polymers (BP)s offers a reproducible means to generate nanostructured active layers. The work presented in this dissertation examines the synthetic approaches to preparing BPs containing different electroactive materials: non-conjugated, amorphous poly(vinyl-m-triphenylamine) [PVmTPA] and conjugated poly(3-alkythiophene) [P3AT] p-type materials as well as fullerene-based n-type materials. The synthesis and self-assembly of a model poly(methyl methacrylate)- b-PVmTPA system is presented. This work was extended to synthesize PVmTPA BPs with complementary poly(methyl methacrylate- co-hydroxyethyl methacrylate) [P

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

    Science.gov (United States)

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

    2004-09-20

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

  3. Copper-based coordination polymers from thiophene and furan dicarboxylates with high isosteric heats of hydrogen adsorption

    NARCIS (Netherlands)

    Yang, J.; Lutz, M.; Grzech, A.; Mulder, F.M.; Dingemans, T.J.*

    2014-01-01

    Self-assembled Cu-based coordination polymers derived from thiophene-2,5-dicarboxylic acid (Cu-TDC) and furan-2,5-dicarboxylic acid (Cu-FDC) were synthesized via a solvothermal method and their H2 adsorption behaviour was investigated and contrasted with isophthalic acid (Cu-m-BDC) and terephthalic

  4. Electronic polymers and DNA self-assembled in nanowire transistors.

    Science.gov (United States)

    Hamedi, Mahiar; Elfwing, Anders; Gabrielsson, Roger; Inganäs, Olle

    2013-02-11

    Aqueous self-assembly of DNA and molecular electronic materials can lead to the creation of innumerable copies of identical devices, and inherently programmed complex nanocircuits. Here self-assembly of a water soluble and highly conducting polymer PEDOT-S with DNA in aqueous conditions is shown. Orientation and assembly of the conducting DNA/PEDOT-S complex into electrochemical DNA nanowire transistors is demonstrated.

  5. Polymer cantilever platform for dielectrophoretic assembly of carbon nanotubes

    DEFF Research Database (Denmark)

    Johansson, Alicia; Calleja, M.; Dimaki, Maria;

    2004-01-01

    A polymer cantilever platform for dielectrophoretic assembly of carbon nanotubes has been designed and realized. Multi-walled carbon nanotubes from aqueous solution have been assembled between two metal electrodes that are separated by 2 mu m and embedded in the polymer cantilever. The entire chip......, except for the metallic electrodes and wiring, was fabricated in the photoresist SU-8. SU-8 allows for an inexpensive, flexible and fast fabrication method, and the cantilever platform provides a hydrophobic surface that should be well suited for nanotube assembly. The device can be integrated in a micro...

  6. Self-Organization in Coordination-Driven Self-Assembly

    Science.gov (United States)

    Northrop, Brian H.; Zheng, Yao-Rong; Chi, Ki-Whan; Stang, Peter J.

    2009-01-01

    Conspectus Self-assembly allows for the preparation of highly complex molecular and supramolecular systems from relatively simple starting materials. Typically, self-assembled supramolecules are constructed by combining complementary pairs of two highly symmetric molecular components, thus limiting the chances of forming unwanted side products. Combining asymmetric molecular components or multiple complementary sets of molecules in one complex mixture can produce myriad different ordered and disordered supramolecular assemblies. Alternatively, spontaneous self-organization phenomena can promote the formation of specific product(s) out of a collection of multiple possibilities. Self-organization processes are common throughout much of nature and are especially common in biological systems. Recently, researchers have studied self-organized self-assembly in purely synthetic systems. This Account describes our investigations of self-organization in the coordination-driven self-assembly of platinum(II)-based metallosupramolecules. The modularity of the coordination-driven approach to self-assembly has allowed us to systematically study a wide variety of different factors that can control the extent of supramolecular self-organization. In particular, we have evaluated the effects of the symmetry and polarity of ambidentate donor subunits, differences in geometrical parameters (e.g. the size, angularity, and dimensionality) of Pt(II)-based acceptors and organic donors, the influence of temperature and solvent, and the effects of intermolecular steric interactions and hydrophobic interactions on self-organization. Our studies have shown that the extent of self-organization in the coordination-driven self-assembly of both 2D polygons and 3D polyhedra ranges from no organization (a statistical mixture of multiple products), to amplified organization (wherein a particular product or products are favored over others), and all the way to the absolute self-organization of

  7. Self-organization in coordination-driven self-assembly.

    Science.gov (United States)

    Northrop, Brian H; Zheng, Yao-Rong; Chi, Ki-Whan; Stang, Peter J

    2009-10-20

    Self-assembly allows for the preparation of highly complex molecular and supramolecular systems from relatively simple starting materials. Typically, self-assembled supramolecules are constructed by combining complementary pairs of two highly symmetric molecular components, thus limiting the chances of forming unwanted side products. Combining asymmetric molecular components or multiple complementary sets of molecules in one complex mixture can produce myriad different ordered and disordered supramolecular assemblies. Alternatively, spontaneous self-organization phenomena can promote the formation of specific product(s) out of a collection of multiple possibilities. Self-organization processes are common throughout much of nature and are especially common in biological systems. Recently, researchers have studied self-organized self-assembly in purely synthetic systems. This Account describes our investigations of self-organization in the coordination-driven self-assembly of platinum(II)-based metallosupramolecules. The modularity of the coordination-driven approach to self-assembly has allowed us to systematically study a wide variety of different factors that can control the extent of supramolecular self-organization. In particular, we have evaluated the effects of the symmetry and polarity of ambidentate donor subunits, differences in geometrical parameters (e.g., the size, angularity, and dimensionality) of Pt(II)-based acceptors and organic donors, the influence of temperature and solvent, and the effects of intermolecular steric interactions and hydrophobic interactions on self-organization. Our studies have shown that the extent of self-organization in the coordination-driven self-assembly of both 2D polygons and 3D polyhedra ranges from no organization (a statistical mixture of multiple products) to amplified organization (wherein a particular product or products are favored over others) and all the way to the absolute self-organization of discrete

  8. Double-electrochromic coordination polymer network films.

    Science.gov (United States)

    Maier, Anna; Cheng, Kalie; Savych, Julia; Tieke, Bernd

    2011-07-01

    Formation and characteristic properties of organized double-electrochromic films consisting of electrochromic poly(4-(2,2':6,2″-terpyridyl)phenyliminofluorene) (P-1)-zinc ion complexes and electrochromic anions are reported. The anions are 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonate) (ABTS) and poly((4-sulfonatophenyl)iminofluorene) (P-2). The films were prepared upon multiple sequential adsorption of P-1 and the zinc salts of ABTS and P-2 on solid supports using coordinative interactions between the Zn ions and the terpyridine (tpy) ligands. The ABTS and P-2 ions are incorporated in the films via electrostatic forces neutralizing the charge of the complexed divalent zinc (Zn(2+)) ions. The optical, electrochemical, and electrochromic properties of the films are described. Films consisting of the Zn ion complex of P-1 and ABTS are yellow in the neutral state and change their color to brownish gray and finally blue, if anodically oxidized at ∼640 mV vs FOC. Films containing the Zn ion complex of P-1, with P-2 as a counterion, are yellow in the neutral state and change color to dark red and finally blue, if anodically oxidized at ∼450 mV vs FOC. Compared with previously reported films of the Zn ion complex of P-1 with nonelectroactive hexafluorophosphate as the counterion, the new films exhibit faster response times, as well as higher contrast, and the colors in the oxidized state are modified. The films are stable under ambient conditions and might be useful as active layers in electrochromic devices.

  9. A lanthanum pyromellitate coordination polymer with threedimensional structure

    Indian Academy of Sciences (India)

    S V Ganesan; Srinivasan Natarajan

    2004-03-01

    A new three-dimensional metal-organic coordination polymer, [La2(H2O)2(H2BTEC)(BTEC)], 1, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. The threedimensional framework is built up from La2O16 dimers connected by carboxylate anions. The polymer exhibits strong photoluminescence at room temperature with the main emission band at 390 nm (ex = 338 nm). Crystal data: triclinic, space group (-1), = 6.4486(3), = 9.4525(5), = 9.6238(5) Å, = 88.24(1), = 74.67(2), = 76.76(1)°, = 550.45(5).

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

    Science.gov (United States)

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

    2015-10-26

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

  11. Ytterbium Coordination Polymer with Four Different Coordination Numbers:The First Structural Characterization of Lanthanide Phthalate Complex

    Institute of Scientific and Technical Information of China (English)

    万永红; 金林培; 等

    2002-01-01

    The novel ytterbium coordination polymer is a t4wo-dimensional framework in which the central metal ions have four different coordination numbers and form four kinds of coordination poly-hedra,The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms.

  12. Studies on the Coordination Polymer of Copper Electropolyurushiol

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The coordination polymer of copper electropolyurushiol(EPU-Cu2+) was obtained by the reaction of copper chloride with electropolyurushiol (EPU) in an isopropyl alcohol solution. The properties of EPU-Cu2+ were studied by means of ESR, FTIR, XPS, DMTA and TG-DTA.The results of AES show that the content of Cu2+ was 8.63%. The electric resistances of EPUCu2+ and EPU were determined to be 9.37×1010Ω and 7.90×1010Ω respectively. It was also ascertained that in EPU-Cu2+ each Cu2+ is coordinated with two units hydroxyl in EPU, making the EPU-Cu2+ cross-link further. As a result, the title polymer exhibits an insolubility in most of organic solutions, a higher glass transition temperature and thermal resistance.

  13. Interpenetration in coordination polymers: structural diversities toward porous functional materials

    Directory of Open Access Journals (Sweden)

    Ritesh Haldar

    2015-03-01

    Full Text Available Interpenetration is a natural phenomenon frequently encountered in porous coordination polymers (PCPs or metal-organic frameworks (MOFs. Traditionally interpenetration has been considered as a threat to permanent porosity and several strategies have been adopted to control the framework interpenetration. Recent literature reports have unveiled that interpenetration has paramount importance in several material properties particularly in storage and separation of small gas molecules. Such frameworks also show interesting structural flexibility based on shearing or movement of the nets and also reveals guest induced dynamic structural transformation for modulated specific functions. In this review, we will emphasize several interpenetration phenomena observed in coordination polymers, their intriguing structural aspects and fascinating material properties.

  14. Self-Assembled Conjugated Polymer Nanometer Scale Devices

    Institute of Scientific and Technical Information of China (English)

    Wenping Hu; Hiroshi Nakashima; Keiichi Torimitsu; Yunqi Liu; Daoben Zhu

    2005-01-01

    @@ 1Introduction Nanometer scale devices, as the next generation devices of electronics, have got a worldwide attention and rapid development recently. Simultaneously, conjugated polymers have been applied in organic electronics successfully because of their outstanding electronic-photonic properties. However, as far as we know few reports have dealt with the fabrication of nanometer scale devices by using conjugated polymers, although the combination of nanometer scale devices and polymers will not only extend conjugated polymers to Nanoelectronics, but also excavate the behaviors of polymer molecules at nano-molecular level, such as the electron transport through polymer molecules. One reason for this case is due to the lack of rigidity for most polymers.It results in the failure to bridge them between electrodes or to stand on substrates, therefore, fails to be characterized by scanning probe microscopy. Another reason is that the non-functionalized end-group of most polymers is impossible to graft on substrates through chemical bonds. Here, we introduce a self-assembled conjugated polymer can be used to fabricate nanodevices by self-assembly. The conjugated polymer is a derivative of poly(p-phenyleneethynylene)s (PPE) with thioacetyl end groups (Fig. 1). In general, it is known that for self-assembling ideal nanojunctions the materials should possess: a) conductivity, b) rigidity (for wiring and bridging between electrodes), and c) connectivity (for covalent attachment to metallic or semiconductor solid surfaces). PPE provides good conductivity owing to its special π-conjugated configuration. It is also believed that in principle PPE molecules possess rigidity because of the presence of the triple bond in their molecules,which prevents the rotation of adjacent phenyl rings with respect to each other.

  15. Design of Self-Assembling Protein-Polymer Conjugates.

    Science.gov (United States)

    Carter, Nathan A; Geng, Xi; Grove, Tijana Z

    Protein-polymer conjugates are of particular interest for nanobiotechnology applications because of the various and complementary roles that each component may play in composite hybrid-materials. This chapter focuses on the design principles and applications of self-assembling protein-polymer conjugate materials. We address the general design methodology, from both synthetic and genetic perspective, conjugation strategies, protein vs. polymer driven self-assembly and finally, emerging applications for conjugate materials. By marrying proteins and polymers into conjugated bio-hybrid materials, materials scientists, chemists, and biologists alike, have at their fingertips a vast toolkit for material design. These inherently hierarchical structures give rise to useful patterning, mechanical and transport properties that may help realize new, more efficient materials for energy generation, catalysis, nanorobots, etc.

  16. Design directed self-assembly of donor-acceptor polymers.

    Science.gov (United States)

    Marszalek, Tomasz; Li, Mengmeng; Pisula, Wojciech

    2016-09-21

    Donor-acceptor polymers with an alternating array of donor and acceptor moieties have gained particular attention during recent years as active components of organic electronics. By implementation of suitable subunits within the conjugated backbone, these polymers can be made either electron-deficient or -rich. Additionally, their band gap and light absorption can be precisely tuned for improved light-harvesting in solar cells. On the other hand, the polymer design can also be modified to encode the desired supramolecular self-assembly in the solid-state that is essential for an unhindered transport of charge carriers. This review focuses on three major factors playing a role in the assembly of donor-acceptor polymers on surfaces which are (1) nature, geometry and substitution position of solubilizing alkyl side chains, (2) shape of the conjugated polymer defined by the backbone curvature, and (3) molecular weight which determines the conjugation length of the polymer. These factors adjust the fine balance between attractive and repulsive forces and ensure a close polymer packing important for an efficient charge hopping between neighboring chains. On the microscopic scale, an appropriate domain formation with a low density of structural defects in the solution deposited thin film is crucial for the charge transport. The charge carrier transport through such thin films is characterized by field-effect transistors as basic electronic elements.

  17. Stability of complex coacervate core micelles containing metal coordination polymer.

    Science.gov (United States)

    Yan, Yun; de Keizer, Arie; Cohen Stuart, Martien A; Drechsler, Markus; Besseling, Nicolaas A M

    2008-09-01

    We report on the stability of complex coacervate core micelles, i.e., C3Ms (or PIC, BIC micelles), containing metal coordination polymers. In aqueous solutions these micelles are formed between charged-neutral diblock copolymers and oppositely charged coordination polymers formed from metal ions and bisligand molecules. The influence of added salt, polymer concentration, and charge composition was investigated by using light scattering and cryo-TEM techniques. The scattering intensity decreases strongly with increasing salt concentration until a critical salt concentration beyond which no micelles exist. The critical micelle concentration increases almost exponentially with the salt concentration. From the scattering results it follows that the aggregation number decreases with the square root of the salt concentration, but the hydrodynamic radius remains constant or increases slightly. It was concluded that the density of the core decreases with increasing ionic strength. This is in agreement with theoretical predictions and is also confirmed by cryo-TEM measurements. A complete composition diagram was constructed based on the composition boundaries obtained from light scattering titrations.

  18. A Novel Coordination Polymer Based on 4,4'-(Hexauoroisopropylidene)diphthalic Acid: Synthesis, Structure and Physical Properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun; Tao, Jianqing; Xu, Xiaojuan; Tan, Chunyun [Yancheng Teachers' College, Yancheng (China)

    2012-11-15

    The design and synthesis of coordination polymers is an attractive area of research, not only owing to their diverse topology and intriguing structures but also due to their potential applications in many fields, such as ion-exchange, catalysis, luminescence, magnets, and gas storage. The mainstream method of constructing such coordination polymers is to utilize organic ligands with aromatic polycarboxylate groups, because of their excellent coordination capability and flexible coordination patterns. Among them, aromatic polycarboxylic derivatives, such as 1,2,4,5-benzenetetracarboxylic acid, 4,4'-oxydiphthalic acid, 4,4'-(hexauoroisopropylidene) diphthalic acid (H{sub 4}FA), and so on, have been extensively used to prepare coordination polymers. Meanwhile, the flexible 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene (BTX) as an excellent derivative of triazole not only possesses the merits of triazole, but also can adopt different conformations compared with the corresponding 1,2,4-triazole ligand on the basis of the relative orientations of its CH{sub 2} groups.10 Taking these into consideration, we explored the self-assembly of Cd(II) ion, H{sub 4}FA, and BTX under hydrothermal conditions, and obtained a novel 3D coordination polymer: [Cd{sub 3}(BTX){sub 2}(HFA){sub 2}·{sub 2}H{sub 2}O]{sub n}. Herein, we report the synthesis, crystal structure, and physical properties.

  19. Convective polymer assembly for the deposition of nanostructures and polymer thin films on immobilized particles

    Science.gov (United States)

    Richardson, Joseph J.; Björnmalm, Mattias; Gunawan, Sylvia T.; Guo, Junling; LiangPresent Address: Csiro Process Science; Engineering, Clayton, Victoria 3168, Australia, Kang; Tardy, Blaise; SekiguchiPresent Address: Graduate School Of Chemical Sciences; Engineering, Hokkaido University, Sapporo, Japan, Shota; Noi, Ka Fung; Cui, Jiwei; EjimaPresent Address: Institute Of Industrial Science, The University Of Tokyo, Tokyo, Japan, Hirotaka; Caruso, Frank

    2014-10-01

    We report the preparation of polymer particles via convective polymer assembly (CPA). Convection is used to move polymer solutions and cargo through an agarose gel that contains immobilized template particles. This method both coats and washes the particles in a process that is amenable to automation, and does not depend on passive diffusion or electrical currents, thus facilitating incorporation of fragile and nanoscale objects, such as liposomes and gold nanoparticles, into the thin polymer films. Template dissolution leads to the formation of stable polymer particles and capsules.We report the preparation of polymer particles via convective polymer assembly (CPA). Convection is used to move polymer solutions and cargo through an agarose gel that contains immobilized template particles. This method both coats and washes the particles in a process that is amenable to automation, and does not depend on passive diffusion or electrical currents, thus facilitating incorporation of fragile and nanoscale objects, such as liposomes and gold nanoparticles, into the thin polymer films. Template dissolution leads to the formation of stable polymer particles and capsules. Electronic supplementary information (ESI) available: Detailed experimental/instrumental information and supporting figures. See DOI: 10.1039/c4nr04348k

  20. Bottlebrush Polymers: Synthesis, Rheology, and Self-Assembly

    Science.gov (United States)

    Dalsin, Samuel J.

    Bottlebrush polymers are comb-like molecules with a high density of side chains grafted along a central backbone. Due to their unique conformational properties, bottlebrush polymers have become attractive candidates for developing new photonic bandgap materials, nanotubes and nanowires, or drug delivery vehicles, to name a few. This dissertation primarily investigates the rheological properties and self-assembly behavior of bottlebrush polymer molecules made using a variety of different polymerization routes. A considerable portion of the work is directed towards the linear rheology of model, polyolefin-based bottlebrush polymers with independently varied branch and backbone lengths. These studies demonstrate how the tight spacing between branch points effectively precludes backbone entanglement in the polymer melts, but it does not inhibit the formation of entanglements among the branched side chains. Furthermore, the relaxation profiles reveal transient scaling behavior in which the dynamics transition from Zimm-like to Rouse-like at increasing relaxation times. These results highlight the distinct conformational character of bottlebrushes at different length scales. The latter parts of this work report on the self-assembly behavior of bottlebrush diblock polymers composed of atactic polypropylene and polystyrene side chains. The diblock samples are analyzed using small-angle X-ray scattering and atomic force microscopy. Nearly all of the samples display strong segregation between the two blocks, owing to the large molar mass of typical bottlebrush polymers. Consequently, only one experimental sample displays an accessible order-disorder transition temperature. The strong segregation is also shown to affect the ability of large bottlebrush diblocks to readily achieve well-ordered nanostructures by self-assembly. Finally, results of the most symmetric (by volume fraction) diblock samples are compared with predictions of a newly developed self-consistent field

  1. New Metal-organic Polymers Through Subcomponent Self-Assembly

    Science.gov (United States)

    2012-07-27

    material using subcomponent self-assembly. We developed the synthesis of double helical polymeric species according to the general procedure...to use - diketones as subcomponents for polymers. She then shifted her efforts to other projects, funded by the European Research Council. Because

  2. Thermal expansion of d10 dicyanometallate-based coordination polymers

    OpenAIRE

    Korcok, Jasmine Lynn

    2010-01-01

    The thermal expansion of several new d10, dicyanometallate-based coordination polymers was examined by powder and single-crystal X-ray diffraction. In isostructural KNi[Au(CN)2]3, KCd[M(CN)2]3, and In[M(CN)2]3 (M=Ag(I), Au(I)), extremely large positive and negative thermal expansion (PTE/NTE) coefficients were discovered. Weaker metallophilic interactions promote larger PTE and NTE. Similarly, the M[Au(CN)2]2 series (M=Mn, Fe, Co, Zn, Hg) showed sizeable PTE and NTE effects. HgCN(NO3) exhibit...

  3. Polymer electrolyte membrane assembly for fuel cells

    Science.gov (United States)

    Yen, Shiao-Ping S. (Inventor); Kindler, Andrew (Inventor); Yavrouian, Andre (Inventor); Halpert, Gerald (Inventor)

    2002-01-01

    An electrolyte membrane for use in a fuel cell can contain sulfonated polyphenylether sulfones. The membrane can contain a first sulfonated polyphenylether sulfone and a second sulfonated polyphenylether sulfone, wherein the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone have equivalent weights greater than about 560, and the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone also have different equivalent weights. Also, a membrane for use in a fuel cell can contain a sulfonated polyphenylether sulfone and an unsulfonated polyphenylether sulfone. Methods for manufacturing a membrane electrode assemblies for use in fuel cells can include roughening a membrane surface. Electrodes and methods for fabricating such electrodes for use in a chemical fuel cell can include sintering an electrode. Such membranes and electrodes can be assembled into chemical fuel cells.

  4. Designer coordination polymers: dimensional crossover architectures and proton conduction.

    Science.gov (United States)

    Yamada, Teppei; Otsubo, Kazuya; Makiura, Rie; Kitagawa, Hiroshi

    2013-08-21

    Coordination polymers (CPs) have large degrees of freedom in framework compositions and in the structures and environment of the inner pores. This review focuses on the recent significant progress achieved by controlling these degrees of freedom. Two breakthroughs are reviewed for constructing sophisticated structures of CP frameworks, especially in dimensional crossover regions. The first is the synthesis of quasi one-dimensional halogen-bridged coordinative tubes by applying state-of-the-art techniques of coordination chemistry. The electronic state of the coordinative tube was studied by structural, spectroscopic and theoretical methods and found to be distinct from conventional one-dimensional systems. The second breakthrough is the achievement of a quasi-two-dimensional architecture by combining Langmuir-Blodgett and layer-by-layer methods. Two-dimensional LB CP films were prepared on liquid; the films were stacked layer by layer, and a crystalline quasi-two-dimensional structure was constructed. This review also covers the design of the environment of the inner pore, where hydrogen bond networks with various acidic sites were modified. By appropriate design of the hydrogen bond network, proton-conductive CPs are invented, which are summarized in this review. Types of proton donor sites are discussed and classified, and superprotonic conductive CPs were achieved in these investigations. These results will provide new strategies for constructing functional materials for smart devices.

  5. Controlling the self-assembly of protein polymers via heterodimer-forming modules

    NARCIS (Netherlands)

    Domeradzka, Natalia Eliza

    2016-01-01

    Supramolecular assemblies formed by protein polymers are attractive candidates for future biomaterials. Ideally, one would like to be able to define the nanostructure, in which the protein polymers should self-assemble, and then design protein polymer sequences that assemble exactly into such nanost

  6. Pyridine coordination chemistry for molecular assemblies on surfaces.

    Science.gov (United States)

    de Ruiter, Graham; Lahav, Michal; van der Boom, Milko E

    2014-12-16

    CONSPECTUS: Since the first description of coordination complexes, many types of metal-ligand interactions have creatively been used in the chemical sciences. The rich coordination chemistry of pyridine-type ligands has contributed significantly to the incorporation of diverse metal ions into functional materials. Here we discuss molecular assemblies (MAs) formed with a variety of pyridine-type compounds and a metal containing cross-linker (e.g., PdCl2(PhCN2)). These MAs are formed using Layer-by-Layer (LbL) deposition from solution that allows for precise fitting of the assembly properties through molecular programming. The position of each component can be controlled by altering the assembly sequence, while the degree of intermolecular interactions can be varied by the level of π-conjugation and the availability of metal coordination sites. By setting the structural parameters (e.g., bond angles, number of coordination sites, geometry) of the ligand, control over MA structure was achieved, resulting in surface-confined metal-organic networks and oligomers. Unlike MAs that are constructed with organic ligands, MAs with polypyridyl complexes of ruthenium, osmium, and cobalt are active participants in their own formation and amplify the growth of the incoming molecular layer. Such a self-propagating behavior for molecular systems is rare, and the mechanism of their formation will be discussed. These exponentially growing MAs are capable of storing metal salts that can be used during the buildup of additional molecular layers. Various parameters influencing the film growth mechanism will be presented, including (i) the number of binding sites and geometry of the organic ligands, (ii) the metal and the structure of the polypyridyl complexes, (iii) the influence of the metal cross-linker (e.g., second or third row transition metals), and (iv) the deposition conditions. By systematic variation of these parameters, switching between linear and exponential growth could

  7. Hydrogen bonding and multiphonon structure in copper pyrazine coordination polymers.

    Science.gov (United States)

    Brown, S; Cao, J; Musfeldt, J L; Conner, M M; McConnell, A C; Southerland, H I; Manson, J L; Schlueter, J A; Phillips, M D; Turnbull, M M; Landee, C P

    2007-10-15

    We report a systematic investigation of the temperature-dependent infrared vibrational spectra of a family of chemically related coordination polymer magnets based upon bridging bifluoride (HF(2)-) and terminal fluoride (F-) ligands in copper pyrazine complexes including Cu(HF(2))(pyz)(2)BF(4), Cu(HF(2))(pyz)(2)ClO(4), and CuF(2)(H(2)O)(2)(pyz). We compare our results with several one- and two-dimensional prototype materials including Cu(pyz)(NO(3))(2) and Cu(pyz)(2)(ClO(4))(2). Unusual low-temperature hydrogen bonding, local structural transitions associated with stronger low-temperature hydrogen bonding, and striking multiphonon effects that derive from coupling of an infrared-active fundamental with strong Raman-active modes of the pyrazine building-block molecule are observed. On the basis of the spectroscopic evidence, these interactions are ubiquitous to this family of coordination polymers and may work to stabilize long-range magnetic ordering at low temperature. Similar interactions are likely to be present in other molecule-based magnets.

  8. Complex coacervate core micelles from iron-based coordination polymers.

    Science.gov (United States)

    Wang, Junyou; de Keizer, Arie; Fokkink, Remco; Yan, Yun; Cohen Stuart, Martien A; van der Gucht, Jasper

    2010-07-01

    Complex coacervate core micelles (C3Ms) from cationic poly(N-methyl-2-vinyl-pyridinium iodide)-b-poly(ethylene oxide) (P2MVP(41)-b-PEO(205)) and anionic iron coordination polymers are investigated in the present work. Micelle formation is studied by light scattering for both Fe(II)- and Fe(III)-containing C3Ms. At the stoichiometric charge ratio, both Fe(II)-C3Ms and Fe(III)-C3Ms are stable for at least 1 week at room temperature. Excess of iron coordination polymers has almost no effect on the formed Fe(II)-C3Ms and Fe(III)-C3Ms, whereas excess of P2MVP(41)-b-PEO(205) copolymers in the solution can dissociate the formed micelles. Upon increasing salt concentration, the scattering intensity decreases. This decrease is due to both a decrease in the number of micelles (or an increase in CMC) and a decrease in aggregation number. The salt dependence of the CMC and the aggregation number is explained using a scaling argument for C3M formation. Compared with Fe(II)-C3Ms, Fe(III)-C3Ms have a lower CMC and a higher stability against dissociation by added salt.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-15

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

  10. Metal selective co-ordinative self-assembly of -donors

    Indian Academy of Sciences (India)

    Ankit Jain; K Venkata Rao; Ankita Goswami; Subi J George

    2011-11-01

    Metal selective co-ordinative nanostructures were constructed by the supramolecular co-assembly of pyridine appended TTF (TTF-Py) and pyrene (PYR-Py) derivatives in appropriate solvent composition mixtures with metal ions.Microscopic analyses show that TTF-Py shows distinctive morphology with either of these metal ions, forming I-D tapes with 1:1 Pb2+ complex and 2-D sheets with 1:2 Zn2+ complex. A rationale has been provided from molecular level packing for such hierarchical changes. In case of Cu2+, we have observed an anomalous binding of metal ion to the core sulphur groups causing redox changes in the TTF core. PYR-Py on the other hand is shown to be a fluorescent sensor for Pb2+, Zn2+, Hg2+ and Ag+. With different fluorescent response for metal complexes, we essentially obtained similar 1-D assemblies suggesting similar binding modes for all of them. Supramolecular approach through which morphology of an electron donor moiety can be engineered by metal ions can be a new tool in nanoelectronics.

  11. Self-assembly through secondary interactions in formation of two-dimensional lead(II) supramolecular polymer with nanosheets morphology

    Science.gov (United States)

    Noori, Yasamin; Akhbari, Kamran; Phuruangrat, Anukorn; Costantino, Ferdinando

    2017-02-01

    In order to study the role of self-assembly through secondary interactions in formation of [Pb(3-AB)2]n (1), [3-ABbar = 3-aminobenzoate], we designed some experiments and synthesized two samples of 1 under ultrasonic irradiations. Nanosheets of 1 were synthesized under these conditions. Compound 1 is a one-dimensional coordination polymer. Self-assembly through hydrogen bonding and π-π stacking interactions between these chains results in formation of two-dimensional supramolecular polymer. It seems that self-assembly through secondary interactions between these chain structures is responsible for formation of 1 with nanosheet morphology. Formation nanoparticles of [Pb(2,6-DHB)2]n (2), [2,6-DHBbar = 2,6-dihydroxybenzoate], under the same condition applied for 1, which has three-dimensional coordination network in its crystalline structure, approved our hypotheses. These microstructures were characterized by IR spectroscopy, X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM).

  12. Aligned and Electrospun Piezoelectric Polymer Fiber Assembly and Scaffold

    Science.gov (United States)

    Scott-Carnell, Lisa A. (Inventor); Siochi, Emilie J. (Inventor); Holloway, Nancy M. (Inventor); Leong, Kam W. (Inventor); Kulangara, Karina (Inventor)

    2015-01-01

    A scaffold assembly and related methods of manufacturing and/or using the scaffold for stem cell culture and tissue engineering applications are disclosed which at least partially mimic a native biological environment by providing biochemical, topographical, mechanical and electrical cues by using an electroactive material. The assembly includes at least one layer of substantially aligned, electrospun polymer fiber having an operative connection for individual voltage application. A method of cell tissue engineering and/or stem cell differentiation uses the assembly seeded with a sample of cells suspended in cell culture media, incubates and applies voltage to one or more layers, and thus produces cells and/or a tissue construct. In another aspect, the invention provides a method of manufacturing the assembly including the steps of providing a first pre-electroded substrate surface; electrospinning a first substantially aligned polymer fiber layer onto the first surface; providing a second pre-electroded substrate surface; electrospinning a second substantially aligned polymer fiber layer onto the second surface; and, retaining together the layered surfaces with a clamp and/or an adhesive compound.

  13. Cationic zinc (II) dimers and one dimensional coordination polymer from ionic carboxylic acid

    Indian Academy of Sciences (India)

    Paladugu Suresh; Ganesan Prabusankar

    2014-09-01

    A rare example of chelating two tetra cationic paddle-wheel zinc dimers were synthesized from the reaction between flexible imidazolium carboxylate (LH2Br2) and corresponding zinc precursors. A zinc coordination polymer was synthesised by treating in situ generation of 2 in the presence of 4,4′-bipyridine. These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques. Zinc polymer is the first example of 1D coordination polymer constructed by tetra cationic zinc dimer as a secondary building unit in coordination polymer.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-12-15

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

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

    Science.gov (United States)

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

    2016-03-14

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

  16. Coordination-driven in situ self-assembly strategy for the preparation of metal-organic framework hybrid membranes.

    Science.gov (United States)

    Zhang, Rong; Ji, Shulan; Wang, Naixin; Wang, Lin; Zhang, Guojun; Li, Jian-Rong

    2014-09-08

    Metal-organic frameworks (MOFs) have emerged as porous solids of a superior type for the fabrication of membranes. However, it is still challenging to prepare a uniformly dispersed robust MOF hybrid membrane. Herein, we propose a simple and powerful strategy, namely, coordination-driven in situ self-assembly, for the fabrication of MOF hybrid membranes. On the basis of the coordination interactions between metal ions and ligands and/or the functional groups of the organic polymer, this method was confirmed to be feasible for the production of a stable membrane with greatly improved MOF-particle dispersion in and compatibility with the polymer, thus providing outstanding separation ability. As an experimental proof of concept, a high-quality ZIF-8/PSS membrane was fabricated that showed excellent performance in the nanofiltration and separation of dyes from water.

  17. Mediator coordinates PIC assembly with recruitment of CHD1.

    Science.gov (United States)

    Lin, Justin J; Lehmann, Lynn W; Bonora, Giancarlo; Sridharan, Rupa; Vashisht, Ajay A; Tran, Nancy; Plath, Kathrin; Wohlschlegel, James A; Carey, Michael

    2011-10-15

    Murine Chd1 (chromodomain helicase DNA-binding protein 1), a chromodomain-containing chromatin remodeling protein, is necessary for embryonic stem (ES) cell pluripotency. Chd1 binds to nucleosomes trimethylated at histone 3 Lys 4 (H3K4me3) near the beginning of active genes but not to bivalent domains also containing H3K27me3. To address the mechanism of this specificity, we reproduced H3K4me3- and CHD1-stimulated gene activation in HeLa extracts. Multidimensional protein identification technology (MuDPIT) and immunoblot analyses of purified preinitiation complexes (PICs) revealed the recruitment of CHD1 to naive chromatin but enhancement on H3K4me3 chromatin. Studies in depleted extracts showed that the Mediator coactivator complex, which controls PIC assembly, is also necessary for CHD1 recruitment. MuDPIT analyses of CHD1-associated proteins support the recruitment data and reveal numerous components of the PIC, including Mediator. In vivo, CHD1 and Mediator are recruited to an inducible gene, and genome-wide binding of the two proteins correlates well with active gene transcription in mouse ES cells. Finally, coimmunoprecipitation of CHD1 and Mediator from cell extracts can be ablated by shRNA knockdown of a specific Mediator subunit. Our data support a model in which the Mediator coordinates PIC assembly along with the recruitment of CHD1. The combined action of the PIC and H3K4me3 provides specificity in targeting CHD1 to active genes.

  18. Bringing an "old" biological buffer to coordination chemistry: new 1D and 3D coordination polymers with [Cu(4)(Hbes)(4)] cores for mild hydrocarboxylation of alkanes.

    Science.gov (United States)

    Kirillov, Alexander M; Coelho, Jaime A S; Kirillova, Marina V; da Silva, M Fátima C Guedes; Nesterov, Dmytro S; Gruenwald, Katrin R; Haukka, Matti; Pombeiro, Armando J L

    2010-07-19

    New water-soluble 1D and 3D Cu(II)/Na coordination polymers 1-3 bearing unprecedented [Cu(4)(Hbes)(4)] cores have been easily generated by aqueous-medium self-assembly and fully characterized, thus opening up the use of the common biological buffer H(3)bes, (HO(3)SCH(2)CH(2))N(CH(2)CH(2)OH)(2), in synthetic coordination chemistry. Apart from representing the first isolated and structurally characterized coordination compounds derived from H(3)bes, 1-3 show a remarkable promoting effect in the mild aqueous-medium hydrocarboxylation, by CO and H(2)O, of gaseous alkanes (C(3)H(8) and n-C(4)H(10)) to the corresponding carboxylic acids, which are obtained in up to 95% yields based on the alkane.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-03-17

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

  20. Coordination Polymers of Palladium Bridged by Carboxylate and Dimethylaminoalkylselenolate Ligands.

    Science.gov (United States)

    Paluru, Dilip K; Dey, Sandip; Wadawale, Amey P; Bhuvanesh, Nattamai; Grupp, Anita; Kaim, Wolfgang; Jain, Vimal K

    2016-02-04

    Coordination polymers of palladium stabilized by dimethylaminoalkylselenolate and carboxylate ligands are reported. The reaction of [PdCl(SeCH2 CH2 NMe2 )]3 with AgOTf followed by treatment with sodium acetate afforded [Pd(0) Pd(II) 4 (SeCH2 CH2 NMe2 )3 (OAc)3 ](OTf)2 (1) in which one of the Pd atoms is in the zero oxidation state. In the absence of NaOAc, a tetranuclear complex, [Pd(II) 4 (SeCH2 CH2 NMe2 )4 (OTf)](OTf)3 (2), is isolated from the same reaction. Subsequent treatment with NaO2 CR afforded [Pd4 (SeCH2 CH2 NMe2 )4 (O2 CR)4 ] (R=tBu (3) and Ph (4)). The reaction of [PdCl(SeCH2 CH2 CH2 NMe2 )]2 with AgOTf and NaOAc yielded an ionic binuclear complex, [Pd(II) 2 (SeCH2 CH2 CH2 NMe2 )2 (OAc)](OTf) (5). These complexes have been characterized by NMR spectroscopy, crystal structures, and in some cases by X-ray photoelectron spectroscopy, cyclic voltammetry and mass spectrometry. Complexes 1 and 5 are associated through secondary interactions and coordinate bonds, respectively, to generate polymeric structures in the solid state. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2010-04-20

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

  2. Two new coordination polymers, a trinuclear metal complex and their interconversion depending on the solvent.

    Science.gov (United States)

    Koike, Shiori; Hirakawa, Takeshi; Yamanishi, Katsunori; Kondo, Mitsuru

    2014-09-14

    Two new 1-D coordination polymers and a discrete trinuclear complex with a double-ring framework were synthesized and structurally characterized. The unique irreversible conversion from one of the 1-D coordination polymers to the trinuclear complex by contact with MeCN is described.

  3. Multi-functional particle assemblies in polymer nanocomposites

    Science.gov (United States)

    Jiao, Yang

    Self-assembly into ordered and equilibrium configurations underlie the microphase separation of block copolymers, protein folding and anisotropic aggregation of functionalized nanoparticles. In this project, we explored the assembly of polymer-grafted magnetic nanoparticles in solution and bulk states to combine various properties, such as ionic conductivity, mechanical reinforcement and responsiveness to external flows, within the same sample. The multi-functionality of iron oxide nanoparticles in polymer media is achieved using bottom-up approaches. Starting from the particle core synthesis, many layers of functionalities are added on magnetite (Fe3O4) nanoparticles by i) grafting polystyrene chains at different densities, lengths and elasticity; by ii) functionalizing particles with ionomers; and by iii) attaching charged diblock copolymers onto particles. In these three complex systems, particle nanostructures are investigated to explain the role of interactions between particle-particle, polymer-particle and polymer-polymer. We found that polystyrene-grafted Fe3O4 nanoparticles can form strings, spherical clusters and dispersed structures in polymer matrices by tuning the polymer graft density and grafted chain length. This structural transition has been explained through chain interactions and short-range dipolar interactions. We showed that chain conformation (radius of gyration) interestingly is not influenced within different dispersion states. Small-angle x-ray and neutron scattering results reveal that matrix chains do not govern the formation of strings, but have a significant impact on the size and internal structure of aggregated particles. Our findings showed that spherical aggregates of nanoparticles with low polymer graft densities are similar to interpenetrating networks in which free matrix chains bridge the fractals of particles and control the cluster density. Further, the mechanical properties of these different composite structures under

  4. Preparing high-density polymer brushes by mechanically assisted polymer assembly (MAPA)

    Science.gov (United States)

    Wu, Tao; Efimenko, Kirill; Genzer, Jan

    2001-03-01

    We introduce a novel method of modifying the surface properties of materials. This technique, called MAPA (="mechanically assisted polymer assembly"), is based on: 1) chemically attaching polymerization initiators to the surface of an elastomeric network that has been previously stretched by a certain length, Δx, and 2) growing end-anchored macromolecules using surface initiated ("grafting from") atom transfer living radical polymerization. After the polymerization, the strain is removed from the substrate, which returns to its original size causing the grafted macromolecules to stretch away from the substrate and form a dense polymer brush. We demonstrate the feasibility of the MAPA method by preparing high-density polymer brushes of poly(acryl amide), PAAm. We show that, as expected, the grafting density of the PAAm brushes can be increased by increasing Δx. We demonstrate that polymer brushes with extremely high grafting densities can be successfully prepared by MAPA.

  5. Syntheses, Structures and Photoluminescence of Two New Europium(Ⅲ) Coordination Polymers

    Institute of Scientific and Technical Information of China (English)

    ZHU Hai—Yun

    2012-01-01

    Two new europium (Ⅲ) coordination polymers formulated as Eu2(H2O)2(ox)4 ]· (C5H6N)2 ·2H 2 O(1) and Eu 2(ad)3(H2O)4 ]·0.25H2O (2) (H2ox = oxalic acid, H2ad = adipic acid) have been synthesized from the self-assembly of lanthanide ions Eu 3+ with flexible oxalic and adipic acid ligands, respectively. Structural analyses revealed that complex 1 exhibits three-dimensional metalorganic frameworks, and 2 has intricate two-dimensional interpenetrated metal-organic networks. In addition, the photoluminescent properties of complexes 1 and 2 were discussed in detail, which shows strong red emission, corresponding to 5 D0 → 7 F 2 transition of Eu3+ ions.

  6. Syntheses, Structures and Photoluminescence of Two New Europium(III) Coordination Polymers

    Institute of Scientific and Technical Information of China (English)

    LI Min; HUANG Qun-Zeng; FENG Yu-Quan; SHI Heng-Zhen

    2012-01-01

    Two new europium (Ⅲ) coordination polymers formulated as Eu2(H20)a(ox)4]· (CsH6N)2-2H20 (1) and Eu2(ad)3(H20)4]'0.25H20 (2) (H20x = oxalic acid, H2ad = adipic acid) have been synthesized from the self-assembly of lanthanide ions Eu^3+ with flexible oxalic and adipic acid ligands, respectively. Structural analyses revealed that complex 1 exhibits three-dimensional metalorganic frameworks, and 2 has intricate two-dimensional interpenetrated metal-organic networks. In addition, the photoluminescent properties of complexes 1 and 2 were discussed in detail, which shows strong red emission, corresponding to ^5Do →^7F? transition of Eu^3+ ions.

  7. Simulation Methods for Self-Assembled Polymers and Rings

    Science.gov (United States)

    Kindt, James T.

    2003-11-01

    New off-lattice grand canonical Monte Carlo simulation methods have been developed and used to model the equilibrium structure and phase diagrams of equilibrium polymers and rings. A scheme called Polydisperse Insertion, Removal, and Resizing (PDIRR) is used to accelerate the equilibration of the size distribution of self-assembled aggregates. This method allows the insertion or removal of aggregates (e.g., chains) containing an arbitrary number of monomers in a single Monte Carlo move, or the re-sizing of an existing aggregate. For the equilibrium polymer model under semi-dilute conditions, a several-fold increase in equilibration rate compared with single-monomer moves is observed, facilitating the study of the isotropic-nematic transition of semiflexible, self-assembled chains. Combined with the pivot-coupled GCMC method for ring simulation, the PDIRR approach also allows the phenomenological simulation of a polydisperse equilibrium phase of rings, 2-dimensional fluid domains, or flat self-assembled disks in three dimensions.

  8. Ultrasonic-assisted synthesis and structural characterization of two new nano-structured Hg(II) coordination polymers.

    Science.gov (United States)

    Ghasempour, Hosein; Azhdari Tehrani, Alireza; Morsali, Ali

    2015-11-01

    Two new Hg(II) coordination polymers containing N,N'-Bis-pyridin-3-ylmethylene-naphtalene-1,5-diamine ligand were synthesized by conventional and sonochemical methods, characterized by spectroscopic techniques (FT-IR and elemental analysis), and their X-ray crystallographic structures were determined. The crystal packing and supramolecular features of these coordination polymers were studied using geometrical analysis and Hirshfeld surface analysis. The crystal structure analysis revealed that H⋯H contacts, C-H⋯π and C-H⋯X (X = Cl for 1 and X = Br for 2) hydrogen bonding interactions are strong enough to govern the supramolecular architecture. The BFDH analysis helps us to compare the predicted morphology to that obtained under ultrasonication. This study may provide further insight into discovering the role of weak intermolecular interactions in the context of nano-supramolecular assembly.

  9. Coordination polymer based on (1,2-bis(2-picolinamido) phenyl)copper

    Institute of Scientific and Technical Information of China (English)

    YE Kaiqi; WU Ying; ZHANG Hongyu; YE Ling; YU Jingsheng; YANG Guangdi; WANG Yue

    2005-01-01

    (1,2-bis(2-pyridinecarboxamido)benzene copper Cu(bpb) was synthesized and employed as a building block to construct supramolecular coordination polymer based on intermolecular coordination and hydrogen bonding interactions. X-ray single-crystal diffraction characterization revealed that intermolecular coordination interactions lead to the formation of one-dimensional infinite molecular columns, which array along the same direction in the crystal resulting in the three-dimensional network. The molecular columns are linked together by hydrogen-bonding interactions, which infinitely extend in bc plane. The one-dimensional coordination bonding and two-dimensional hydrogen-bonding interactions result in the formation of supramolecular coordination polymer.

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

    OpenAIRE

    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 design 1 . 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 rela...

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

    Science.gov (United States)

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

    2013-03-01

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

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

    Science.gov (United States)

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

    2012-06-24

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

  13. Nanoscale coordination polymers for platinum-based anticancer drug delivery.

    Science.gov (United States)

    Rieter, William J; Pott, Kimberly M; Taylor, Kathryn M L; Lin, Wenbin

    2008-09-01

    Pt-containing nanoscale coordination polymer (NCP) particles with the formula of Tb2(DSCP)3(H2O)12 (where DSCP represents disuccinatocisplatin), NCP-1, were precipitated from an aqueous solution of Tb3+ ions and DSCP bridging ligands via the addition of a poor solvent. SEM and TEM images showed that as-synthesized NCP-1 exhibited a spherical morphology with a DLS diameter of 58.3 +/- 11.3 nm. NCP-1 particles were stabilized against rapid dissolution in water by encapsulation in shells of amorphous silica. The resulting silica-coated particles NCP-1' exhibited significantly longer half-lives for DSCP release from the particles (a t1/2 of 9 h for NCP-1' with 7 nm silica coating vs t1/2 of 1 h for as-synthesized NCP-1). In vitro cancer cell cytotoxicity assays with the human colon carcinoma cell line (HT-29) showed that internalized NCP-1' particles readily released the DSCP moieties which were presumably reduced to cytotoxic Pt(II) species to give the Pt-containing NCPs anticancer efficacy superior to the cisplatin standard. The generality of this degradable nanoparticle formulation should allow for the design of NCPs as effective delivery vehicles for a variety of biologically and medically important cargoes such as therapeutic and imaging agents.

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

    Science.gov (United States)

    1989-05-15

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

  15. Phosphorylcholine substituted polyolefins: New syntheses, solution assemblies, and polymer vesicles

    Science.gov (United States)

    Kratz, Katrina A.

    This thesis describes the synthesis and applications of a new series of amphiphilic homopolymers and copolymers consisting of hydrophobic polyolefin backbone and hydrophilic phosphorylcholine (PC) pendant groups. These polymers are synthesized by ring opening metathesis polymerization (ROMP) of a novel PC- cyclooctene monomer, and copolymerization of various functionalized cyclooctene comonomers. Incorporation of different comonomers into the PC-polyolefin backbone affords copolymers with different functionalities, including crosslinkers, fluorophores, and other reactive groups, that tune the range of applications of these polymers, and their hydrophobic/hydrophilic balance. The amphiphilic nature of PC-polyolefins was exploited in oil-water interfacial assembly, providing robust polymer capsules to encapsulate and deliver nanoparticles to damaged regions of a substrate in a project termed `repair-and-go.' In repair-and-go, a flexible microcapsule filled with a solution of nanoparticles probes an imperfection-riddled substrate as it rolls over the surface. The thin capsule wall allows the nanoparticles to escape the capsules and enter into the cracks, driven in part by favorable interactions between the nanoparticle ligands and the cracked surface (i.e., hydrophobic-hydrophobic interactions). The capsules then continue their transport along the surface, filling more cracks and depositing particles into them. The amphiphilic nature of PC-polyolefins was also exploited in aqueous assembly, forming novel polymer vesicles in water. PC-polyolefin vesicles ranged in size from 50 nm to 30 µm. The mechanical properties of PC-polyolefin vesicles were measured by micropipette aspiration techniques, and found to be more robust than conventional liposomes or polymersomes prepared from block copolymers. PC-polyolefin vesicles have potential use in drug delivery; it was found that the cancer drug doxorubicin could be encapsulated efficiently in PC-polyolefin vesicles. In

  16. Supply coordination based on bonus policy in assembly under uncertain delivery time

    Science.gov (United States)

    Li, Guo; Liu, Mengqi; Wang, Zhaohua; Peng, Bingzong

    2013-03-01

    The existing research of supply coordination under uncertain delivery time mainly focuses on the collaboration between the supplier and the manufacturer, which aim at minimizing the total cost of each side and finding comparative optimal solutions under decentralized decision. In the supply coordination, the collaboration between suppliers in assembly system is usually not considered. As a result, the manufacturer's production is often delayed due to mismatching delivery of components between suppliers. Therefore, to ensure supply coordination in assembly system, collaboration between suppliers should be taken into consideration. In this paper, an assembly system with two suppliers and one manufacturer under uncertain delivery time is considered. The model is established and optimal solution is given under decentralized decision. Furthermore, the cost functions of two suppliers are both convex, and a unique Nash equilibrium exists between two suppliers. Then the optimal decision under supply coordination is analyzed, which is regarded as a benchmark for supply coordination. Additionally, the total cost of the assembly system is jointly convex in agreed delivery time. To achieve supply coordination a bonus policy is explored in the assembly system under uncertain delivery time, and the total cost under bonus policy must be lower than under decentralized decision. Finally the numerical and sensitivity analysis shows the cost of assembly system under bonus policy equals that under supply coordination, and the cost of each side in assembly system under bonus policy is lower compared to that under decentralized decision. The proposed research minimizes the total cost of each side with bonus policy in assembly system, ensures the supply coordination between suppliers and the manufacturer, and improves the competiveness of the whole supply chain.

  17. Supramolecular Polymer Network-Mediated Self-Assembly of Semicrystalline Polymers with Excellent Crystalline Performance.

    Science.gov (United States)

    Cheng, Chih-Chia; Chuang, Wei-Tsung; Lee, Duu-Jong; Xin, Zhong; Chiu, Chih-Wei

    2017-03-01

    A novel application of supramolecular interactions within semicrystalline polymers, capable of self-assembling into supramolecular polymer networks via self-complementary multiple hydrogen-bonded complexes, is demonstrated for efficient construction of highly controlled self-organizing hierarchical structures to offer a direct, efficient nucleation pathway resulting in superior crystallization performance. Herein, a novel functionalized poly(ε-caprolactone) containing self-complementary sextuple hydrogen-bonded uracil-diamidopyridine (U-DPy) moieties is successfully developed and demonstrated excellent thermal and viscoelastic properties as well as high dynamic structural stability in the bulk state due to physical cross-linking created by reversible sextuple hydrogen bonding between U-DPy units. Due to the ability to vary the extent of the reversible network by tuning the U-DPy content, this newly developed material can be readily adjusted to obtain the desired crystalline products with specific characteristics. Importantly, incorporating only 0.1% U-DPy resulted in a polymer with a high crystallization rate constant, short crystallization half-time, and much more rapid crystallization kinetics than pristine PCL, indicating a low content of U-DPy moieties provides highly efficient nucleation sites that manipulate the nucleation and growth processes of polymer crystals to promote crystallization and chain alignment in bulk. This new system is suggested as a potential new route to substantially improve the performance of polymer crystallization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Observation of a large magnetocaloric effect in a 2D Gd(III)-based coordination polymer.

    Science.gov (United States)

    Biswas, Soumava; Adhikary, Amit; Goswami, Soumyabrata; Konar, Sanjit

    2013-10-07

    A new 2D Gd(III)-based coordination polymer has close to the highest cryogenic magnetocaloric effect of any MOF reported so far. The experimental results reveal its structural features and magnetic properties.

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

    Science.gov (United States)

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

    2016-07-01

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

  20. Rail-Guided Multi-Robot System for 3D Cellular Hydrogel Assembly with Coordinated Nanomanipulation

    Directory of Open Access Journals (Sweden)

    Huaping Wang

    2014-08-01

    Full Text Available The 3D assembly of micro-/nano-building blocks with multi-nanomanipulator coordinated manipulation is one of the central elements of nanomanipulation. A novel rail-guided nanomanipulation system was proposed for the assembly of a cellular vascular-like hydrogel microchannel. The system was equipped with three nanomanipulators and was restricted on the rail in order to realize the arbitrary change of the end-effectors during the assembly. It was set up with hybrid motors to achieve both a large operating space and a 30 nm positional resolution. The 2D components such as the assembly units were fabricated through the encapsulation of cells in the hydrogel. The coordinated manipulation strategies among the multi-nanomanipulators were designed with vision feedback and were demonstrated through the bottom-up assembly of the vascular-like microtube. As a result, the multi-layered microchannel was assembled through the cooperation of the nanomanipulation system.

  1. Rail-guided Multi-robot System for 3D Cellular Hydrogel Assembly with Coordinated Nanomanipulation

    Directory of Open Access Journals (Sweden)

    Huaping Wang

    2014-08-01

    Full Text Available The 3D assembly of micro-/nano-building blocks with multi-nanomanipulator coordinated manipulation is one of the central elements of nanomanipulation. A novel rail-guided nanomanipulation system was proposed for the assembly of a cellular vascular-like hydrogel microchannel. The system was equipped with three nanomanipulators and was restricted on the rail in order to realize the arbitrary change of the end-effectors during the assembly. It was set up with hybrid motors to achieve both a large operating space and a 30 nm positional resolution. The 2D components such as the assembly units were fabricated through the encapsulation of cells in the hydrogel. The coordinated manipulation strategies among the multi-nanomanipulators were designed with vision feedback and were demonstrated through the bottom-up assembly of the vascular-like microtube. As a result, the multi-layered microchannel was assembled through the cooperation of the nanomanipulation system.

  2. A one-dimensional barium(II) coordination polymer with a coordinated nitro group of 2-nitrobenzoate

    Indian Academy of Sciences (India)

    Bikshandarkoil R Srinivasan; Santosh Y Shetgaonkar; Pallepogu Raghavaiah

    2008-03-01

    The aqueous reaction of barium carbonate with 2-nitrobenzoic acid (2-nbaH) results in the formation of a one-dimensional coordination polymer, catena-poly[[hexa(aqua)dibarium(II)]bis[(2-2-nitrobenzoate-O,O,O-NO2)(2-2-nitrobenzoate-O,O,O')

  3. Soft porous crystal meets TCNQ: charge transfer-type porous coordination polymers

    OpenAIRE

    Shimomura, Satoru; Kitagawa, Susumu

    2011-01-01

    The significant progress of porous coordination polymers (or metal–organic frameworks) has been attracting the attention of a lot of scientists in various disciplines and encouraging their entry into this field. The synergy of diverse scientific senses brings further spread of the chemistry of porous coordination polymers. In this review, we introduced the recent developments in PCPs resulting from the hybridization with TCNQ chemistry. Electronic and structural diversities of TCNQ provide no...

  4. Linear rheology of water-soluble reversible neodymium (III) coordination polymers

    NARCIS (Netherlands)

    Vermonden, T.; Steenbergen, van M.J.; Besseling, N.A.M.; Marcelis, A.T.M.; Hennink, W.E.; Sudhölter, E.J.R.; Cohen Stuart, M.A.

    2004-01-01

    The rheology of reversible coordination polymer networks in aqueous solution is studied. The polymers are formed by neodymium(III) ions and bifunctional ligands, consisting of two pyridine-2,6-dicarboxylate groups connected at the 4-positions by an ethylene oxide spacer. Neodymium(III) ions can bind

  5. 柔性配体癸二酸构筑的镍多孔配位聚合物的合成和晶体结构%Self-assembly of Nickel(Ⅱ) Coordination Polymer Based on a Flexible Sebacic Acid Ligand

    Institute of Scientific and Technical Information of China (English)

    赵国良; 沈金杯; 咸会朵

    2011-01-01

    由硫酸镍和癸二酸(C10H18O4)合成了配合物:[Ni(C10H16O4)(H2O)4]·1.5H2O,并通过元素分析、红外光谱、热重分析对其进行表征,用单晶X-射线衍射方法测定了配合物的晶体结构.配合物属于正交晶系,空间群Cmca,晶胞参数:a=0.753820(10) nm,b=1.076 97(2)nm,c=4.130 42(8) nm,晶胞体积:V=3.353 25(10) nm3,晶胞内结构基元数Z=4,分子量Mr=358.02,电子数F(000)=1 528,密度Dc=1.418 9·cm-3,吸收系数μ(Mo Kα)=1.195mm-1.%A nickel(Ⅱ) complex [Ni(C10H16O4)(H2O)4]·1.5H2O (C10H18O4=sebacic acid), was synthesized and characterized by elemental analysis, Infrared radiation (IR) and thermogravimetry-derivative thermogravimetry (TG-DTG). Its crystal structure was determined by single crystal X-ray diffraction method. The complex, C10H27O93Ni, crystallizes in the orthorhombic system, space group Cmca,with cell parameters: a=0.753 820(10) nm, 6=1.07697(2) nm, c= 4.13042(8) nm, cell volume: F=3.353 25(10) nm3, number of molecules inside the cell: Z=A, relative molecular mass: Mr=358.02, numbers of electrons: F(000)=l 528, density calculated: DC=1.418 g·cm-3, absorptive parameter: μ(Mo Kα)=l.l95 mm-1. The coordination polymer was constructed by molecular self-assembly from hydrogen-bonding interactions. CCDC: 728231.

  6. Trigger sequence can influence final morphology in the self-assembly of asymmetric telechelic polymers

    NARCIS (Netherlands)

    Kumar, Aatish; Lowe, C.P.; Cohen Stuart, M.A.; Bolhuis, P.G.

    2016-01-01

    We report on a numerical study of polymer network formation of asymmetric biomimetic telechelic polymers with two reactive ends based on a self-assembling collagen, elastin or silk-like polypeptide sequence. The two reactive ends of the polymer can be activated independently using physicochemical

  7. Beyond molecules: mesoporous supramolecular frameworks self-assembled from coordination cages and inorganic anions.

    Science.gov (United States)

    Luo, Dong; Zhou, Xiao-Ping; Li, Dan

    2015-05-18

    Biological function arises by the assembly of individual biomolecular modules into large aggregations or highly complex architectures. A similar strategy is adopted in supramolecular chemistry to assemble complex and highly ordered structures with advanced functions from simple components. Here we report a series of diamond-like supramolecular frameworks featuring mesoporous cavities, which are assembled from metal-imidazolate coordination cages and various anions. Small components (metal ions, amines, aldehydes, and anions) are assembled into the hierarchical complex structures through multiple interactions including covalent bonds, dative bonds, and weak C-H⋅⋅⋅X (X=O, F, and π) hydrogen bonds. The mesoporous cavities are large enough to trap organic dye molecules, coordination cages, and vitamin B12. The study is expected to inspire new types of crystalline supramolecular framework materials based on coordination motifs and inorganic ions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Directed colloidal assembly and characterization of PZT-polymer composites

    Science.gov (United States)

    Smay, James Earl

    Lead zirconate titanate (PZT)-based layers and 3-D structures were directly assembled using two colloidal routes: (1) tape casting and (2) a layer-by-layer robotic deposition technique, known as robocasting. First, concentrated (φsolids > 0.45) suspensions of PZT-5H and a latex emulsion were tape cast with the aid of viscosifier and surfactant additions. Drying stress evolved to a maximum at φ PZT ˜ 0.49, followed by a reduction and a secondary stress rise attributed to latex coalescence. Dielectric and piezoelectric properties of sintered PZT multilayer laminates exhibited good agreement with those for isostatically pressed and sintered samples. Concentrated, weakly gelled suspensions of PZT 95/5 and poly(ethylene) (PE) latices, a fugitive species, were developed as inks for the robotic deposition of monolithic and tri-layered composite structures. Monoliths, with densities of 93.6% and 96.1%, and composites with a 96.1% dense layer between 93.6% regions were fabricated. The structures displayed equivalent electrical properties to cold isostatically pressed parts. The composites withstood repeated saturation polarization switching as well as a 500 MPa hydrostatic pressure-induced poled ferroelectric (FE) to antiferroelectric (AFE) phase transformation. Concentrated (φPZT = 0.47) PZT-5H gels were developed as inks for the robotic deposition of 3-D, mesoscale periodic structures with self-supporting features such as lattices of rod-like elements and v-shaped test structures. The gels exhibited pH dependent viscoelastic properties and Hershel-Bulkley flow behavior. The deflection of as-deposited spanning elements was measured using laser profilometry. Flow modeling and shape evolution data indicated a core-shell architecture as the ink exited the deposition nozzle, which simultaneously provided strength to form spanning elements and good bonding between layers. The core grew rapidly (˜1s) due to the quick recovery of gel structure in these inks. 3-X type PZT-polymer

  9. Engineering Metal Ion Coordination to Regulate Amyloid Fibril Assembly And Toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Dong, J.; Canfield, J.M.; Mehta, A.K.; Shokes, J.E.; Tian, B.; Childers, W.S.; Simmons, J.A.; Mao, Z.; Scott, R.A.; Warncke, K.; Lynn, D.G.

    2009-06-02

    Protein and peptide assembly into amyloid has been implicated in functions that range from beneficial epigenetic controls to pathological etiologies. However, the exact structures of the assemblies that regulate biological activity remain poorly defined. We have previously used Zn{sup 2+} to modulate the assembly kinetics and morphology of congeners of the amyloid {beta} peptide (A{beta}) associated with Alzheimer's disease. We now reveal a correlation among A{beta}-Cu{sup 2+} coordination, peptide self-assembly, and neuronal viability. By using the central segment of A{beta}, HHQKLVFFA or A{beta}(13-21), which contains residues H13 and H14 implicated in A{beta}-metal ion binding, we show that Cu{sup 2+} forms complexes with A{beta}(13-21) and its K16A mutant and that the complexes, which do not self-assemble into fibrils, have structures similar to those found for the human prion protein, PrP. N-terminal acetylation and H14A substitution, Ac-A{beta}(13-21)H14A, alters metal coordination, allowing Cu{sup 2+} to accelerate assembly into neurotoxic fibrils. These results establish that the N-terminal region of A{beta} can access different metal-ion-coordination environments and that different complexes can lead to profound changes in A{beta} self-assembly kinetics, morphology, and toxicity. Related metal-ion coordination may be critical to the etiology of other neurodegenerative diseases.

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

    Science.gov (United States)

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

    2014-01-28

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

  11. Anion-induced Ag(I) self-assemblies with electron deficient aromatic ligands: anion-π-system interactions as a driving force for templated coordination networks.

    Science.gov (United States)

    Safin, Damir A; Pialat, Amélie; Leitch, Alicea A; Tumanov, Nikolay A; Korobkov, Ilia; Filinchuk, Yaroslav; Brusso, Jaclyn L; Murugesu, Muralee

    2015-06-11

    Three novel 1D, 2D and 3D coordination polymers were successfully isolated using nitrogen based 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine (BPymTz) and 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) ligands with Ag(I) ions. The formation of these supramolecular assemblies was templated through anion-π-system interactions.

  12. Crystallization-driven assembly of conjugated-polymer-based nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Hayward, Ryan C. [Univ. of Massachusetts, Amherst, MA (United States). Polymer Science & Engineering

    2016-10-15

    The goal of this project has been to improve our ability to simultaneously control the organization, and therefore the opto-electronic properties, of conjugated-polymer based materials across three different length-scales: 1) the molecular scale, in the sense of controlling growth and functionalization of highly crystalline semiconducting organic materials capable of efficient charge transport, 2) the nanoscale, in terms of positioning n- and p-type materials with domain sizes comparable to exciton diffusion lengths (~ 10 nm) to facilitate charge separation, and 3) the colloidal scale, such that well-defined crystalline nanoscale building blocks can be hierarchically organized into device layers. As described in more detail below, the project was successful in generating powerful new approaches to, and improved fundamental understanding of, processing and self-assembly of organic and hybrid semiconducting materials across all three length-scales. Although the goals of the project were formulated with primarily photovoltaic architectures in mind, the outcomes of the project have significant implications for a variety of conjugated-polymer-based devices including field-effect-transistors for sensors and logic devices, as well as potentially thermoelectrics and battery electrode materials. The project has resulted in 10 peer-reviewed publications to date [1-10], with several additional manuscripts currently in preparation.

  13. A series of Ti(IV)/Ti(III) coordination polymers: structures and surface photoelectric properties.

    Science.gov (United States)

    Li, Lei; Zhang, Li; Liu, Dong-Wei; Jin, Jing; Chi, Yu-Xian; Niu, Shu-Yun

    2012-02-01

    Three titanium coordination polymers, {[Ti(SO(4))(2)(H(2)O)]·0.5bipy·2H(2)O}(n)1, {[Ti1(SO(4))(2)(H(2)O)]·[Ti2(SO(4))(2)(H(2)O)]·bipy·5H(2)O}(n)2 and [Ti(tea)](n)3 (bipy=4,4'-bipyridine, H(3)tea=triethanolamine) were synthesized and characterized by IR, UV-Vis absorption spectra, TG analysis, X-ray single crystal diffraction and surface photovoltage spectroscopy (SPS). The surface photoelectric properties of titanium coordination polymers were discussed emphatically by the SPS. The results of single crystal diffraction indicate that polymers 1 and 2 possess 1D infinite structure bridged by SO(4)(2-) groups and coordinated water molecules and further connected into supramolecular structures by hydrogen bonds. Polymer 3 possesses 2D infinite structure bridged by weak sub-coordinated Ti-O bonds. The results of SPS show that there are obvious photovoltage responses in the range of 300-500 nm, which indicates that they possess photoelectric conversion ability. The SPS of three titanium polymers were analyzed comparatively. It is found that the valence of central metal ions, coordination micro-environment and kinds of coordination atoms influence the results of the SPS. The SPS is associated with UV-Vis absorption spectra.

  14. A series of Ti(IV)/Ti(III) coordination polymers: Structures and surface photoelectric properties

    Science.gov (United States)

    Li, Lei; Zhang, Li; Liu, Dong-Wei; Jin, Jing; Chi, Yu-Xian; Niu, Shu-Yun

    2012-02-01

    Three titanium coordination polymers, {[Ti(SO 4) 2(H 2O)]·0.5bipy·2H 2O} n1, {[Ti1(SO 4) 2(H 2O)]·[Ti2(SO 4) 2(H 2O)]·bipy·5H 2O} n2 and [Ti(tea)] n3 (bipy = 4,4'-bipyridine, H 3tea = triethanolamine) were synthesized and characterized by IR, UV-Vis absorption spectra, TG analysis, X-ray single crystal diffraction and surface photovoltage spectroscopy (SPS). The surface photoelectric properties of titanium coordination polymers were discussed emphatically by the SPS. The results of single crystal diffraction indicate that polymers 1 and 2 possess 1D infinite structure bridged by SO 42- groups and coordinated water molecules and further connected into supramolecular structures by hydrogen bonds. Polymer 3 possesses 2D infinite structure bridged by weak sub-coordinated Ti-O bonds. The results of SPS show that there are obvious photovoltage responses in the range of 300-500 nm, which indicates that they possess photoelectric conversion ability. The SPS of three titanium polymers were analyzed comparatively. It is found that the valence of central metal ions, coordination micro-environment and kinds of coordination atoms influence the results of the SPS. The SPS is associated with UV-Vis absorption spectra.

  15. Self-assembly of Nanopatterns on Shape Memory Polymer Substrates

    Science.gov (United States)

    Chen, Zhongbi

    Periodic surface nanostructures provide unique acoustic, electronic, optical and mechanical properties, with potential applications to metamaterials, sensors, catalysis, medicine, etc. However, assembling nanometer scale constituents into engineering scale components or devices poses tremendous challenges such as cost reduction and scalability. In this work, we will introduce a novel directed self-assembly method that has the potential to address these challenges by forming unidirectional micro- and nano-wrinkles on engineering scale polymer substrates. The approach utilizes a smart material, shape memory polymer (SMP), as the substrate in a bi-layer thin-film/substrate system. With a specially-designed programming scheme, the SMP substrate can retract in one direction while expand in the perpendicular direction in a heating process. Consequently, the thin film corrugates and the wrinkling patterns are aligned. A parametric study that investigates how the system parameters influence the surface topology will be presented. Besides wrinkles, surface defects that occurred concurrently were also observed. We will present a progressive damage scheme and a microdomain-based model to understand and possibly help preventing the formation of defects. In addition, this work will also address our efforts in shrinking the wrinkle feature size from several microns to the tens of nanometer range. Two methods, through which the minimum wrinkle wavelength was reduced from one micron to 300 nm and further down to 35 nm will be elaborated. Such aligned wrinkles whose wavelength spanning two orders of magnitude from as small as 35 nm to as large as 5 mum will open up avenues for numerous exciting applications. The application of using the self-assembled wrinkled surface as the back-reflector in solar cells to improve the power conversion efficiency will be discussed as a case study. The long-term stability of the wrinkle topology, which is essential to efficiency boost will be

  16. Bending nanofibers into nanospirals: coordination chemistry as a tool for shaping hydrophobic assemblies.

    Science.gov (United States)

    Kossoy, Elizaveta; Weissman, Haim; Rybtchinski, Boris

    2015-01-01

    In the current work, we demonstrate how coordination chemistry can be employed to direct self-assembly based on strong hydrophobic interactions. To investigate the influence of coordination sphere geometry on aqueous self-assembly, we synthesized complexes of the amphiphilic perylene diimide terpyridine ligand with the first-row transition-metal centers (zinc, cobalt, and nickel). In aqueous medium, aggregation of these complexes is induced by hydrophobic interactions between the ligands. However, the final shapes of the resulting assemblies depend on the preferred geometry of the coordination spheres typical for the particular metal center. The self-assembly process was characterized by UV/Vis spectroscopy, zeta potential measurements, and cryogenic transmission electron microscopy (cryo-TEM). Coordination of zinc(II) and cobalt(II) leads to the formation of unique nanospiral assemblies, whereas complexation of nickel(II) leads to the formation of straight nanofibers. Notably, coordination bonds are utilized not as connectors between elementary building blocks, but as directing interactions, enabling control over supramolecular geometry.

  17. Blood-clotting-inspired reversible polymer-colloid composite assembly in flow

    Science.gov (United States)

    Chen, Hsieh; Fallah, Mohammad A.; Huck, Volker; Angerer, Jennifer I.; Reininger, Armin J.; Schneider, Stefan W.; Schneider, Matthias F.; Alexander-Katz, Alfredo

    2013-01-01

    Blood clotting is a process by which a haemostatic plug is assembled at the site of injury. The formation of such a plug, which is essentially a (bio)polymer-colloid composite, is believed to be driven by shear flow in its initial phase, and contrary to our intuition, its assembly is enhanced under stronger flowing conditions. Here, inspired by blood clotting, we show that polymer-colloid composite assembly in shear flow is a universal process that can be tailored to obtain different types of aggregates including loose and dense aggregates, as well as hydrodynamically induced ‘log’-type aggregates. The process is highly controllable and reversible, depending mostly on the shear rate and the strength of the polymer-colloidbinding potential. Our results have important implications for the assembly of polymer-colloid composites, an important challenge of immense technological relevance. Furthermore, flow-driven reversible composite formation represents a new paradigm in non-equilibrium self-assembly.

  18. 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

    Science.gov (United States)

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

    2009-03-01

    Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H 2O) 2][Cd(Dpq)(1,8-NDC)]·2H 2O ( 1), [Cd(Dpq)(1,4-NDC)(H 2O)] ( 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 2NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H 2NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H 2NDC)]. 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 π- π 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 π- π 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.

  19. Self-assembly of conjugated oligomers and polymers at the interface: structure and properties.

    Science.gov (United States)

    Xu, Lirong; Yang, Liu; Lei, Shengbin

    2012-08-01

    In this review, we give a brief account on the recent scanning tunneling microscopy investigation of interfacial structures and properties of π-conjugated semiconducting oligomers and polymers, either at the solid-air (including solid-vacuum) or at the solid-liquid interface. The structural aspects of the self-assembly of both oligomers and polymers are highlighted. Conjugated oligomers can form well ordered supramolecular assemblies either at the air-solid or liquid-solid interface, thanks to the relatively high mobility and structural uniformity in comparison with polymers. The backbone structure, substitution of side chains and functional groups can affect the assembling behavior significantly, which offers the opportunity to tune the supramolecular structure of these conjugated oligomers at the interface. For conjugated polymers, the large molecular weight limits the mobility on the surface and the distribution in size also prevents the formation of long range ordered supramolecular assembly. The submolecular resolution obtained on the assembling monolayers enables a detailed investigation of the chain folding at the interface, both the structural details and the effect on electronic properties. Besides the ability in studying the assembling structures at the interfaces, STM also provides a reasonable way to evaluate the distribution of the molecular weight of conjugated polymers by statistic of the contour length of the adsorbed polymer chains. Both conjugated oligomers and polymers can form composite assemblies with other materials. The ordered assembly of oligomers can act as a template to controllably disperse other molecules such as coronene or fullerene. These investigations open a new avenue to fine tune the assembling structure at the interface and in turn the properties of the composite materials. To summarize scanning tunneling microscopy has demonstrated its surprising ability in the investigation of the assembling structures and properties of

  20. Synthesis, Structural Characterization, and Antitumor Activity of a Ca(II Coordination Polymer Based on 1,6-Naphthalenedisulfonate and 4,4′-Bipyridyl

    Directory of Open Access Journals (Sweden)

    Xishi Tai

    2013-08-01

    Full Text Available A novel Ca(II coordination polymer, [CaL(4,4′-bipyridyl(H2O4]n (L = 1,6-naphthalenedisulfonate, was synthesized by reaction of calcium perchlorate with 1,6-naphthalenedisulfonic acid disodium salt and 4,4′-bipyridyl in CH3CH2OH/H2O. It was characterized by elemental analysis, IR, molar conductivity and thermogravimetric analysis. X-ray crystallography reveals that the Ca(II coordination polymer belongs to the orthorhombic system, with space group P212121. The geometry of the Ca(II ion is a distorted CaNO6 pengonal bipyramid, arising from its coordination by four water molecules, one nitrogen atom of 4,4′-bipyridyl molecule, and two oxygen atoms from two L ligands. The complex molecules form a helical chain by self-assembly. The antitumor activity of 1,6-naphthalenedisulfonic acid disodium salt and the Ca(II coordination polymer against human hepatoma smmc-7721 cell line and human lung adenocarcinoma A549 cell line reveals that the Ca(II coordination polymer inhibits cell growth of human lung adenocarcinoma A549 cell line with IC50 value of 27 μg/mL, and is more resistive to human lung adenocarcinoma A549 cell line as compared to 1,6-naphthalenedisulfonic acid disodium salt.

  1. New 4-carboxylphthalhydrazidate-bridged Mn2+/In3+ coordination polymers

    Science.gov (United States)

    Jin, Juan; Yan, Wen-Fu; Yu, Xiao-Yang; Yang, Qing-Feng; Liu, Bing; Xu, Ji-Qing; Gao, Shan-Min; Li, Chuan-Zhao; Lin, Chen

    2017-04-01

    Based on the hydrothermal in situ acylation reaction of benzene-1,2,4-tricarboxylic acid (btca) with N2H4·H2O, two containing-4-carboxylphthalhydrazidate Mn2+/In3+ coordination polymers, [Mn(cpth)(phen)] 1 and [In(cpth)(ox)0.5(phen)]·H2O 2 (cpth = 4-carboxylphthalhydrazidate, phen = 1,10-phenanthroline, ox = oxalate), were obtained and characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. In compound 1, the cpth ligands exhibit a μ4-bridging mode, which link Mn(II) centers into a 2-D layer structure with ancillary phen molecules. In compound 2, the cpth ligands exhibit a μ2-bridging mode, which link In(III) centers into a binuclear unit. Ox ligands act as the second linkers, extending binuclear unit into a 1-D chain with ancillary phen molecules. Via Nsbnd H⋯O interactions, compound 2 self-assembles into a 2-D supramolecular layer. The magnetic analysis indicates that there exists antiferromagnetic interactions between magnetic centers in compound 1. The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution.

  2. Transcriptional mechanisms coordinating tight junction assembly during epithelial differentiation.

    Science.gov (United States)

    Boivin, Felix J; Schmidt-Ott, Kai M

    2017-06-01

    Epithelial tissues form a selective barrier via direct cell-cell interactions to separate and establish concentration gradients between the different compartments of the body. Proper function and formation of this barrier rely on the establishment of distinct intercellular junction complexes. These complexes include tight junctions, adherens junctions, desmosomes, and gap junctions. The tight junction is by far the most diverse junctional complex in the epithelial barrier. Its composition varies greatly across different epithelial tissues to confer various barrier properties. Thus, epithelial cells rely on tightly regulated transcriptional mechanisms to ensure proper formation of the epithelial barrier and to achieve tight junction diversity. Here, we review different transcriptional mechanisms utilized during embryogenesis and disease development to promote tight junction assembly and maintenance of intercellular barrier integrity. We focus particularly on the Grainyhead-like transcription factors and ligand-activated nuclear hormone receptors, two central families of proteins in epithelialization. © 2017 New York Academy of Sciences.

  3. Design of a multi-coordinating polymer as a platform for functionalizing metal, metal oxide and semiconductor nanocrystals

    Science.gov (United States)

    Wang, Wentao; Ji, Xin; Kapur, Anshika; Mattoussi, Hedi

    2016-03-01

    We introduce a new set of amphiphilic polymers as multifunctional, metal-coordinating ligands adapted to surfacefunctionalize quantum dots (QDs), iron oxide nanoparticles (IONPs) and gold nanoparticles/nanorods (AuNPs/AuNRs). The ligand design relies on the introduction of several anchoring groups, hydrophilic moieties and reactive functionalities into a polymer chain, via one-step nucleophilic addition reaction. Such synthetic scheme also allows the insertion of target biomolecules during the ligand synthesis. This functionalization strategy yields nanocrystals that exhibit long-term colloidal stability over a broad range of biological conditions, such as pH changes and when mixed with growth media. When zwitterion groups are used as hydrophilic motifs, this provides compact nanocrystals that are compatible with conjugation to proteins via metal-polyhistidine self-assembly. In addition, we show that QDs ligated with these polymers can engage in energy or charge transfer interactions. Furthermore, nanocrystals coated with folic acid-modified polymers could promote the delivery of nanoparticle-conjugates into cancer cells via folate receptormediated endocytosis.

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

    Science.gov (United States)

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

    2016-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-15

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

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

    Science.gov (United States)

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

    2016-10-03

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

  7. Nanohelices from planar polymer self-assembled in carbon nanotubes

    Science.gov (United States)

    Fu, Hongjin; Xu, Shuqiong; Li, Yunfang

    2016-07-01

    The polymer possessing with planar structure can be activated and guided to encapsulate the inner space of SWNT and form a helix through van der Waals interaction and the π-π stacking effect between the polymer and the inner surface of SWNT. The SWNT size, the nanostructure and flexibility of polymer chain are all determine the final structures. The basic interaction between the polymer and the nanotubes is investigated, and the condition and mechanism of the helix-forming are explained particularly. Hybrid polymers improve the ability of the helix formation. This study provides scientific basis for fabricating helical polymers encapsulated in SWNTs and eventually on their applications in various areas.

  8. Polymeric microtubules that breathe: CO2 -driven polymer controlled-self-assembly and shape transformation.

    Science.gov (United States)

    Yan, Qiang; Zhao, Yue

    2013-09-16

    Tubular breathing motion: Polymer tubules self-assembled from a gas-sensitive triblock copolymer can undergo shape evolution. A sequence from microtubes through submicroscopic vesicles to nanosized spherical micelles is modulated by CO2 stimulation levels.

  9. Dynamics of nanoparticle assembly from disjointed images of nanoparticle-polymer composites

    Science.gov (United States)

    Murthy, Chaitanya R.; Gao, Bo; Tao, Andrea R.; Arya, Gaurav

    2016-02-01

    Understanding how nanoparticles (NPs) diffuse, stick, and assemble into larger structures within polymers is key to the design and fabrication of NP-polymer composites. Here we describe an approach for inferring the dynamic parameters of NP assembly from spatially and temporally disjointed images of composites. The approach involves iterative adjustment of the parameters of a kinetic model of assembly until the computed size statistics of NP clusters match those obtained from high-throughput analysis of the experimental images. Application of this approach to the assembly of shaped, metal NPs in polymer films suggests that NP structures grow via a cluster-cluster aggregation mechanism, where NPs and their clusters diffuse with approximately Stokes-Einstein diffusivity and stick to other NPs or clusters with a probability that depends strongly on the size and shape of the NPs and the molecular weight of the polymer.

  10. Blood-clotting-inspired reversible polymer-colloid composite assembly in flow

    National Research Council Canada - National Science Library

    Chen, Hsieh; Fallah, Mohammad A; Huck, Volker; Angerer, Jennifer I; Reininger, Armin J; Schneider, Stefan W; Schneider, Matthias F; Alexander-Katz, Alfredo

    2013-01-01

    .... The formation of such a plug, which is essentially a (bio)polymer-colloid composite, is believed to be driven by shear flow in its initial phase, and contrary to our intuition, its assembly is enhanced under stronger flowing conditions...

  11. Artificial tongue based on metal-biomolecule coordination polymer nanoparticles.

    Science.gov (United States)

    Pu, Fang; Ran, Xiang; Ren, Jinsong; Qu, Xiaogang

    2016-02-25

    We construct an array-based recognition system (the so-called artificial tongue) through the self-assembly of nucleotides, dyes and lanthanide ions. Metal ions are selected as model analytes for verifying its discrimination ability. The work provides valuable insights into the application and development of biomolecule-based materials.

  12. Nucleobase assemblies supported by uranyl cation coordination and other non-covalent interactions

    Indian Academy of Sciences (India)

    Jitendra Kumar; Sandeep Verma

    2011-11-01

    We describe synthesis and solid state structural description of uranyl complexes of carboxylate functionalized adenine and uracil derivatives. The metal coordination through carboxylate pendant leads to the formation of dimeric assemblies, whereas the directional nature of hydrogen bonding interaction supported by nucleobases and aqua ligands, result in the generation of complex 3-D architectures containing embedded nucleobase ribbons.

  13. Self-assembly of supramolecularly engineered polymers and their biomedical applications.

    Science.gov (United States)

    Wang, Dali; Tong, Gangsheng; Dong, Ruijiao; Zhou, Yongfeng; Shen, Jian; Zhu, Xinyuan

    2014-10-18

    Noncovalent interactions provide a flexible method of engineering various chemical entities with tailored properties. Specific noncovalent interactions between functionalized small molecules, macromolecules or both of them bearing complementary binding sites can be used to engineer supramolecular complexes that display unique structure and properties of polymers, which can be defined as supramolecularly engineered polymers. Due to their dynamic tunable structures and interesting physical/chemical properties, supramolecularly engineered polymers have recently received more and more attention from both academia and industry. In this feature article, we summarize the recent progress in the self-assembly of supramolecularly engineered polymers as well as their biomedical applications. In view of different molecular building units, the supramolecularly engineered polymers can be classified into the following three major types: supramolecularly engineered polymers built by small molecules, supramolecularly engineered polymers built by small molecules and macromolecules, and supramolecularly engineered polymers built by macromolecules, which possess distinct morphologies, definite architectures and specific functions. Owing to the reversible nature of the noncovalent interactions, the supramolecularly engineered polymers have exhibited unique features or advantages in molecular self-assembly, for example, facile preparation and functionalization, controllable morphologies and structures, dynamic self-assembly processes, adjustable performance, and so on. Furthermore, the self-assembled supramolecular structures hold great potential as promising candidates in various biomedical fields, including bioimaging, drug delivery, gene transfection, protein delivery, regenerative medicine and tissue engineering. Such developments in the self-assembly of supramolecularly engineered polymers and their biomedical applications greatly promote the interdiscipline research among

  14. Directed assembly of conducting polymers on sub-micron templates by electrical fields

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Jia; Wei, Ming [National Science Foundation (NSF) Nanoscale Science and Engineering Center for High-Rate Nanomanufacturing, University of Massachusetts Lowell, Lowell, MA 01854 (United States); Busnaina, Ahmed [National Science Foundation (NSF) Nanoscale Science and Engineering Center for High-Rate Nanomanufacturing, Northeastern University, Boston, MA 02115 (United States); Barry, Carol [National Science Foundation (NSF) Nanoscale Science and Engineering Center for High-Rate Nanomanufacturing, University of Massachusetts Lowell, Lowell, MA 01854 (United States); Mead, Joey, E-mail: Joey_Mead@uml.edu [National Science Foundation (NSF) Nanoscale Science and Engineering Center for High-Rate Nanomanufacturing, University of Massachusetts Lowell, Lowell, MA 01854 (United States)

    2013-02-20

    Highlights: Black-Right-Pointing-Pointer Nanoscale patterns with dimensions of assembled PANi down to 100 nm were fabricated. Black-Right-Pointing-Pointer We use electrophoretic and dielectrophoretic assembly to deposit PANi. Black-Right-Pointing-Pointer Electrophoretic and dielectrophoretic assembly of PANi finished in less than 1 min. Black-Right-Pointing-Pointer Effect of process parameters on assembly of PANi onto nanoscale pattern was studied. Black-Right-Pointing-Pointer The assembled PANi can be transferred to other flexible substrates. - Abstract: Patterning of conducting polymer into sub-micron patterns over large areas at high rate and low cost is significant for commercial manufacturing of novel devices. Electrophoretic and dielectrophoretic assembly provide an easily scaled approach with high fabrication rates. In this work, electrophoretic and dielectrophoretic assembly were used to assemble polyaniline (PANi) into multiscale sub-micron size patterns in less than 1 min. The process was controlled by assembly time, amplitude, and frequency of the electric field. Dielectrophoretic assembly is preferable for manufacturing as it reduces damage to the templates used to control the assembly. Using this method, sub-micron patterns with dimensions of the assembled PANi down to 100 nm were fabricated over large areas in short times. The assembled PANi was further transferred to other flexible polymer substrates by a thermoforming process, providing a fast, easily controlled and promising approach for fabrication of nanoscale devices.

  15. Molecular design, self-assembly, and material properties of silk-like protein polymers

    NARCIS (Netherlands)

    Beun, L.H.

    2015-01-01

    Summary In this thesis we present the design and characterization of bio-inspired hybrid protein polymers. All polymers are composed of two distinct types of building blocks. The first type is a silk-inspired block that is pH-responsive and can fold and self-assemble into highly ordered structures.

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

    Science.gov (United States)

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

    2013-05-01

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

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

    Science.gov (United States)

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

    2013-01-01

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz)2(H2O)]n (1), [Cd1Cd2(btec)(H2O)6]n (2), [Cd(3,4-pdc) (H2O)]n (3), [Zn(2,5-pdc)(H2O)4]·2H2O (4) and {[Zn(2,5-pdc)(H2O)2]·H2O}n (5) (H2bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H4btec=1,2,4,5-benzenetetracarboxylic acid, H2pdc=pyridine-dicarboxylic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, surface photovoltage spectroscopy, XRD, TG analysis, IR and UV-vis spectra and elemental analysis. Structural analyses show that complexes 1-3 are 1D, 2D and 3D Cd(II) coordination polymers, respectively. Complex 4 is a mononuclear Zn(II) complex. Complex 5 is a 3D Zn(II) coordination polymer. The surface photoelectric properties of complexes were investigated by SPS. The results indicate that all complexes exhibit photoelectric responses in the range of 300-600 nm, which reveals that they all possess certain photoelectric conversion properties. By the comparative analyses, it can be found that the species and coordination micro-environment of central metal ion, the species and property of ligands affect the intensity and scope of photoelectric response.

  18. Polyelectrolytes: Influence on Evaporative Self-Assembly of Particles and Assembly of Multilayers with Polymers, Nanoparticles and Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Tatiana Bukreeva

    2010-12-01

    Full Text Available Assembling polyelectrolyte multilayers in a bottom-up approach is reported for polymers, particles, nanoparticles, and carbon nanotubes. Effects of polyelectrolyte multilayers on evaporative self-assembly of particles, which are of interest to a number of applications including photonic crystals, films and substrates, are investigated. Polyelectrolyte multilayer coatings bring multifunctionality to spherical particles and planar films. Studying the construction of polyelectrolyte assemblies is convenient in the planar layout: it is reported here for incorporation of gold and magnetic nanoparticles as well as of carbon nanotubes. Gold nanoparticles concentration is controlled within the films. Potential applications of both spherical structures and planar films are highlighted.

  19. Aromatic N-oxides in construction of different carboxylate coordination polymers of zinc(II), cadmium(II) and mercury(II)

    Science.gov (United States)

    Sarma, Rupam; Baruah, Jubaraj B.

    2011-09-01

    The coordination polymers [Zn(C 6H 5COO) 2(PNO)] n ( 1), [Zn 2(C 6H 5COO) 4(4,4'-BPNO)] n ( 2), [Zn 4(C 6H 4C 2O 4) 4(4,4'-BPNO) 2(H 2O) 5] n· nH 2O ( 3), [Cd(C 6H 5COO) 2(PNO)] n ( 4), [Cd 3(C 6H 5COO) 6(4,4'-BPNO) 2] n·2 nH 2O ( 5), [Cd(C 6H 4C 2O 4)(4,4'-BPNO)(H 2O)] n ( 6) and [Hg(C 6H 5COO) 2(4,4'-BPNO) 2] n ( 7), (where PNO = pyridine N-oxide, 4,4'-BPNO = 4,4'-bipyridyl- N,N'-dioxide) are synthesized and structurally characterized. The structures of these coordination polymers exhibit mononuclear to trinuclear nodes built by ligation of carboxylate to metal ions connected by N-oxide ligands. Pyridine N-oxide interconnects metal nodes by acting as μ 2-bridging ligand in complexes 1, and 4. In the linear coordination polymer 2, the paddle wheel structure of zinc(II) benzoate units are interconnected by 4,4'-bipyridyl- N,N'-dioxide which acts as a bidentate spacer ligand adopting a trans μ 2-η 1 : η 1 coordination mode. The polymeric structure of 3 formed by terephthalate and 4,4'-bipyridyl- N,N'-dioxide with zinc(II) contains self-assembled dinuclear Zn 2O 2 type of carboxylate cores, with 4,4'-bipyridyl- N,N'-dioxide coordinating through cis μ 2-η 1 : η 1 coordination mode. The cadmium coordination polymer 5, comprising of 4,4'-bipyridyl- N,N'-dioxide and benzoate, has trinuclear cadmium benzoate cores wherein the terminal cadmium ions are interconnected by monodentate 4,4'-bipyridyl- N,N'-dioxide bridges. The coordination polymer 6 comprises of mononuclear cadmium nodes independently bridged by terephthalate and 4,4'-bipyridyl- N,N'-dioxide thereby leading to a 3-fold interpenetrated three dimensional network. Double helical polymeric structure is observed in the coordination polymer 7 derived from mononuclear mercury(II) benzoate nodes bridged by 4,4'-bipyridyl- N,N'-dioxide with cis μ 2-η 1 : η 1 coordination mode.

  20. Self-Assembly and Crystal Structure of a Novel Inorganic-Organic Hybrid Coordination Polymer:[Zn(N3)2(bpp)] n [bpp = 1,3-bis(4-pyridyl)-propane]%一种新的有机-无机混配配位聚合物[Zn(N3)2(bpp)]n的自组装及晶体结构(bpp=1,3-二吡啶丙烷)

    Institute of Scientific and Technical Information of China (English)

    陈丙义; 孟祥茹; 李林科; 侯红卫

    2003-01-01

    A novel coordination polymer [Zn(N3)2(bpp) ] n [bpp = 1, 3-bis(4-pyridyl)-propane] was synthesized at room temperature and structurally characterized by means of X-ray single crystal diffraction. The results show that the polymer exhibits a linear chain structure; the Zn-Zn distance is 12. 235A. Each Zn (Ⅱ) ion is coordinated by two nitrogen atoms from bpp ligands and two nitrogen atoms from azido (N3-) groups, the coordination geometry of Zn (Ⅱ) ion is a slightly distorted tetrahedron, the angles around Zn (Ⅱ) ions are from 103.27° to 121.37°. In the solid-state structure of the polymer, the linear chains are stacked with parallel mode along a direction. Moreover, between adjacent chains, there are π-π interactions between pyridine rings, which are arranged in face-to-face fashion with interplanar distances of av. 3. 821A. CCDC: 189591.

  1. Wormlike aggregates from a supramolecular coordination polymer and a diblock copolymer

    NARCIS (Netherlands)

    Yan, Y.; Besseling, N.A.M.; Keizer, de A.; Drechsler, M.; Fokkink, R.G.; Cohen Stuart, M.A.

    2007-01-01

    The formation of wormlike micelles in mixed systems of a supramolecular coordination polymer Zn-L2EO4 and a diblock copolymer P2MVP41-b-PEO205 is investigated by light scattering and Cryo-TEM. By direct mixing at a stoichiometric charge ratio, the above mixtures proved to be capable of formation of

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

    Science.gov (United States)

    Boeckmann, Jan; Näther, Christian

    2011-07-07

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Sezer, Güneş Günay [Vocational School of Health Services, Bartın University, Bartın (Turkey); Department of Chemistry, Eskişehir Osmangazi University, Eskişehir (Turkey); Yeşilel, Okan Zafer; Erer, Hakan [Department of Chemistry, Eskişehir Osmangazi University, Eskişehir (Turkey); Şahin, Onur [Scientific and Technological Research Application Center, Sinop University, Sinop (Turkey)

    2016-01-15

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

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

    NARCIS (Netherlands)

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

    2015-01-01

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

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

    NARCIS (Netherlands)

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

    2015-01-01

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

  6. Seawater-Assisted Self-Healing of Catechol Polymers via Hydrogen Bonding and Coordination Interactions.

    Science.gov (United States)

    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%).

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

    Science.gov (United States)

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

    2013-03-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil [Ajou University, Suwon (Korea, Republic of)

    2012-04-15

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

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

    Science.gov (United States)

    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.

  10. Synthesis and Structural Characterization of a New 2D Coordination Polymer [Cu(pzta)2]n

    Institute of Scientific and Technical Information of China (English)

    HU,Xin; LIU,Cong; WANG,Yongjiang; GUO,Jixi

    2009-01-01

    A new copper(Ⅱ)tetrazolate coordination polymer[Cu(pzta)2]n (1)(pzta=5-pyrazinyltetrazolate)was prepared from the hydrothermal reaction of Cu(OAc)2,·H2O with NaN3 and pyrazinecarbonitrile(pzCN)in the presence of ethanol,and characterized by elemental analysis,IR,TGA and X-ray crystallography.The X-ray diffraction analysis of 1 shows that the compound crystallizes in the monoclinic system with space group P2(1)/c and Cu(Ⅱ)ion center is six-coordinated by four different pzta ligands.The complex 1 features a 2D tetrazole coordination polymer.The thermal analysis of 1 shows that the decomposition of the complex OCCURS in two regions.

  11. Synthesis, Structure and Properties of Three-dimensional Gd(Ⅲ), Eu(Ⅲ) Coordination Polymers via in situ Decarboxylation

    Institute of Scientific and Technical Information of China (English)

    WANG Chuan-sheng; GU Xiao-fu; SUN Ya-guang; GAO En-jun; ZHANG Wan-zhong

    2009-01-01

    Two three-dimensional lanthanide(Ⅲ) coordination polymers with the formula [Ln(PYDC)(NA)(H_2O)]n [Ln=Gd(l), Eu(2), H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The NA came from in situ decarboxylation of the part of PYDC. X-ray single crystal structural analyses reveal that complexes 1 and 2 are iso-morphous, they possess the 4~3·6~3 topology assembled by Gd~(3+)/Eu~(3+) and two different multidentate carboxylate ligands. Magnetic measurements show that antiferromagnetic coupling exists between adjacent Gd~(3+) ions in complex 1. The complex 2 exhibits the corresponding characteristic luminescence in the visible region under an excitation at 305 nm.

  12. Lanthanide contraction effect on crystal structures of lanthanide coordination polymers with cyclohexanocucurbit[6]uril ligand

    Science.gov (United States)

    Zheng, Li-Mei; Liu, Jing-Xin

    2017-01-01

    A series of compounds based on the macrocyclic ligand cyclohexanocucurbit[6]uril (Cy6Q[6]) with formulas {Ln(H2O)6Cy6Q[6]}·2(CdCl4)·H3O·xH2O [isomorphous with Ln=La (1), Ce (2), Pr (3) and Nd (4), x=11 (1), 11 (2), 10 (3) and 11 (4)], {Sm(H2O)5Cy6Q[6]}·2(CdCl4)·H3O·10H2O (5) and {Ln(H2O)5(NO3)@Cy6Q[6]}·2(CdCl4)·2H3O·xH2O [isomorphous with Ln=Gd (6), Tb (7) and Dy (8), x=8 (6), 6 (7) and 6 (8)], have been successfully synthesized by the self-assembly of Cy6Q[6] with the corresponding lanthanide nitrate under hydrochloric acid aqueous solution in the presence of CdCl2. Single-crystal X-ray diffraction analyses revealed that compounds 1-8 all crystallize in monoclinic space group P21/c, and display 1D coordination polymer structures. The lanthanide contraction effect on the structures of 1-8 has also been investigated and discussed in detail. In contrast, the reaction of Cy6Q[6] with the Ho(NO)3, Tm(NO)3, Yb(NO)3 under the same conditions resulted in the compounds 9-11 with formulas Cy6Q[6]·2(CdCl4)·2H3O·xH2O [isomorphous with x=10 (9), 10 (10), and 9 (11)], in which no lanthanide cations are observed. The structural difference of these compounds indicates that the Cy6Q[6] may be used in the separation of lanthanide cations.

  13. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    Science.gov (United States)

    Paxton, Walter F.; Bouxsein, Nathan F.; Henderson, Ian M.; Gomez, Andrew; Bachand, George D.

    2015-06-01

    We describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4-5 h for corresponding lipid networks). The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.We describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4-5 h for corresponding lipid networks). The transport of materials in and on

  14. Bio-Inspired Composite Interfaces: Controlling Hydrogel Mechanics via Polymer-Nanoparticle Coordination Bond Dynamics

    Science.gov (United States)

    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.

  15. Formation and properties of surface-anchored polymer assemblies with tunable physico-chemical characteristics

    Science.gov (United States)

    Wu, Tao

    We describe two new methodologies leading to the formation of novel surface-anchored polymer assemblies on solid substrates. While the main goal is to understand the fundamentals pertaining to the preparation and properties of the surface-bound polymer assemblies (including neutral and chargeable polymers), several examples also are mentioned throughout the Thesis that point out to practical applications of such structures. The first method is based on generating assemblies comprising anchored polymers with a gradual variation of grafting densities on solid substrates. These structures are prepared by first covering the substrate with a molecular gradient of the polymerization initiator, followed by polymerization from these substrate-bound initiator centers ("grafting from"). We apply this technique to prepare grafting density gradients of poly(acryl amide) (PAAm) and poly(acrylic acid) (PAA) on silica-covered substrates. We show that using the grafting density gradient geometry, the characteristics of surface-anchored polymers in both the low grafting density ("mushroom") regime as well as the high grafting density ("brush") regime can be accessed conveniently on a single sample. We use a battery of experimental methods, including Fourier transform infrared spectroscopy (FTIR), Near-edge absorption fine structure spectroscopy (NEXAFS), contact angle, ellipsometry, to study the characteristics of the surface-bound polymer layers. We also probe the scaling laws of neutral polymer as a function of grafting density, and for weak polyelectrolyte, in addition to the grafting density, we study the affect of solution ionic strength and pH values. In the second novel method, which we coined as "mechanically assisted polymer assembly" (MAPA), we form surface anchored polymers by "grafting from" polymerization initiators deposited on elastic surfaces that have been previously extended uniaxially by a certain length increment, Deltax. Upon releasing the strain in the

  16. "Dual-template" synthesis of one-dimensional conductive nanoparticle superstructures from coordination metal-peptide polymer crystals.

    Science.gov (United States)

    Rubio-Martínez, Marta; Puigmartí-Luis, Josep; Imaz, Inhar; Dittrich, Petra S; Maspoch, Daniel

    2013-12-20

    Bottom-up fabrication of self-assembled structures made of nanoparticles may lead to new materials, arrays and devices with great promise for myriad applications. Here a new class of metal-peptide scaffolds is reported: coordination polymer Ag(I)-DLL belt-like crystals, which enable the dual-template synthesis of more sophisticated nanoparticle superstructures. In these biorelated scaffolds, the self-assembly and recognition capacities of peptides and the selective reduction of Ag(I) ions to Ag are simultaneously exploited to control the growth and assembly of inorganic nanoparticles: first on their surfaces, and then inside the structures themselves. The templated internal Ag nanoparticles are well confined and closely packed, conditions that favour electrical conductivity in the superstructures. It is anticipated that these Ag(I)-DLL belts could be applied to create long (>100 μm) conductive Ag@Ag nanoparticle superstructures and polymetallic, multifunctional Fe3 O4 @Ag nanoparticle composites that marry the magnetic and conductive properties of the two nanoparticle types.

  17. Surface-confined assemblies and polymers for molecular logic.

    Science.gov (United States)

    de Ruiter, Graham; van der Boom, Milko E

    2011-08-16

    Stimuli responsive materials are capable of mimicking the operation characteristics of logic gates such as AND, OR, NOR, and even flip-flops. Since the development of molecular sensors and the introduction of the first AND gate in solution by de Silva in 1993, Molecular (Boolean) Logic and Computing (MBLC) has become increasingly popular. In this Account, we present recent research activities that focus on MBLC with electrochromic polymers and metal polypyridyl complexes on a solid support. Metal polypyridyl complexes act as useful sensors to a variety of analytes in solution (i.e., H(2)O, Fe(2+/3+), Cr(6+), NO(+)) and in the gas phase (NO(x) in air). This information transfer, whether the analyte is present, is based on the reversible redox chemistry of the metal complexes, which are stable up to 200 °C in air. The concurrent changes in the optical properties are nondestructive and fast. In such a setup, the input is directly related to the output and, therefore, can be represented by one-input logic gates. These input-output relationships are extendable for mimicking the diverse functions of essential molecular logic gates and circuits within a set of Boolean algebraic operations. Such a molecular approach towards Boolean logic has yielded a series of proof-of-concept devices: logic gates, multiplexers, half-adders, and flip-flop logic circuits. MBLC is a versatile and, potentially, a parallel approach to silicon circuits: assemblies of these molecular gates can perform a wide variety of logic tasks through reconfiguration of their inputs. Although these developments do not require a semiconductor blueprint, similar guidelines such as signal propagation, gate-to-gate communication, propagation delay, and combinatorial and sequential logic will play a critical role in allowing this field to mature. For instance, gate-to-gate communication by chemical wiring of the gates with metal ions as electron carriers results in the integration of stand-alone systems: the

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

    Science.gov (United States)

    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

  19. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    Energy Technology Data Exchange (ETDEWEB)

    Vlassa, Mihaela, E-mail: mihaela_cecilia@yahoo.com [' ' Babes-Bolyai' ' University, Raluca Ripan Institute of Research in Chemistry, 30 Fantanele Str., 400294 Cluj-Napoca (Romania); Bende, Attila, E-mail: bende@itim-cj.ro [Molecular and Biomolecular Physics Department, National Institute for Research and Development of Isotopic and Molecular Technologies, Str. Donat 67-103, Cluj Napoca RO-400293 (Romania)

    2015-08-18

    Highlights: • Ni(II)- and Zn(II)-coordinated cyclam–azorubine complexes are described using DFT. • Ni(II) coordinated system shows a reasonably small singlet–triplet energy gap. • Intersystem crossing gives high barrier between singlet and triplet geometries. • For the Zn(II) case only the singlet state is energetically favorable. • The stability of a longer polymer (oligomer) chain was described using DFTB. - Abstract: Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet–triplet transition was studied in details and the corresponding spin–orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-15

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

  1. A Co(Ⅱ) 3,5-Diaminobenzoate Coordination Polymer

    Institute of Scientific and Technical Information of China (English)

    DAI Yu-Mei; TANG En; LI Zhao-Ji; WANG Xiao-Qin; YIN Pei-Xiu; YAO Yuan-Gen

    2006-01-01

    The title compound, [Co(C7N2H7O2)2]n·nH2O 1, was synthesized via the hydrothermal reaction of Co(Oac)2 with 3,5-diaminobenzoic acid and characterized by elemental analysis and infrared spectra. The crystal crystallizes in the monoclinic system, space group P21/c with a =7.456(3), b = 9.972(3), c = 10.391 (3) (A), β= 106.435(2)°, V = 741.0(4) (A)3, Z = 2, C14H16CoN4O5, Mr = 379.24, Dc = 1.700 g/cm3, F(000) = 390 and μ(MoKa) = 1.194 mm-1. The final R = 0.0324 and wR = 0.0886 for 1516 observed reflections with I>2σ(I) and R = 0.0337 and wR = 0.0899 for all data. X-ray diffraction studies reveal that the title compound has an interesting 3D microporous architecture with guest water molecules inside the channel. Each Co atom, adopting a distorted octahedral geometry, is coordinated by two O atoms from two 3,5-diaminobenzoate ligands and four N atoms from four symmetry-related 3,5-diaminobenzoate ligands.

  2. Nanoparticle Self-Assembly in a Polymer Matrix and Its Impact on Phase Separation

    Science.gov (United States)

    Douglas, Jack

    2011-03-01

    The ubiquitous clustering of nanoparticles (NPs) in solutions and polymer melts depends sensitively on the strength and directionality of the effective NP-NP interactions, as well as on the molecular geometry and interactions of the dispersing fluid. Surface functionalization apparently can also lead to emergent anisotropic interactions that can influence NP dispersion. Since NP clustering can strongly influence the properties of polymer nanocomposites and NP solutions, we investigate the reversible self-assembly of model NPs into clusters under equilibrium conditions through a combination of simulation and analytic methods. First, we performed molecular dynamics simulations of polyhedral NPs in a coarse-grained dense bead--spring polymer melt and find a transition from a dispersed to clustered NP state, consistent with the thermodynamic models of equilibrium particle association such as equilibrium polymerization. We also describe the competition between self-assembly and phase separation in an analytic lattice model of a mixture of polymers and NPs. We then focus on the particularly interesting situation where the associating ``monomeric'' NP species form high molecular mass dynamic polymeric clusters and where the assembly process then transforms the phase boundary from a form typical of a polymer solution to one that more resembles a polymer blend with increasing association near the critical point for phase separation. The model calculations elucidate basic physical principles governing the coupling of self-assembly and phase behavior in these complex mixtures.

  3. Understanding Molecular Interactions within Chemically Selective Layered Polymer Assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Gary J. Blanchard

    2009-06-30

    This work focuses on two broad issues. These are (1) the molecular origin of the chemical selectivity achieved with ultrathin polymer multilayers, and (2) how the viscoelastic properties of the polymer layers are affected by exposure to solvent and analytes. These issues are inter-related, and to understand them we need to design experiments that probe both the energetic and kinetic aspects of interfacial adsorption processes. This project focuses on controling the chemical structure, thickness, morphology and sequential ordering of polymer layers bound to interfaces using maleimide-vinyl ether and closely related alternating copolymerization chemistry and efficient covalent cross-linking reactions that allow for layer-by-layer polymer deposition. This chemistry has been developed during the funding cycle of this Grant. We have measure the equilibrium constants for interactions between specific layers within the polymer interfaces and size-controlled, surface-functionalized gold nanoparticles. The ability to control both size and functionality of gold nanoparticle model analytes allows us to evaluate the average “pore size” that characterizes our polymer films. We have measured the “bulk” viscosity and shear modulus of the ultrathin polymer films as a function of solvent overlayer identity using quartz crystal microbalance complex impedance measurements. We have measured microscopic viscosity at specific locations within the layered polymer interfaces with time-resolved fluorescence lifetime and depolarization techniques. We combine polymer, cross-linking and nanoparticle synthetic expertise with a host of characterization techniques, including QCM gravimetry and complex impedance analysis, steady state and time-resolved spectroscopies.

  4. Five 8-hydroxyquinolinate-based coordination polymers with tunable structures and photoluminescent properties for sensing nitroaromatics.

    Science.gov (United States)

    Zhang, Liyan; Sun, Liying; Li, Xinyuan; Tian, Yulan; Yuan, Guozan

    2015-01-01

    Using two 8-hydroxyquinolinate ligands (L1-MOM and L2-MOM) containing 3-pyridyl or 4-pyridyl groups, five novel coordination polymers, namely, [Zn3(L1)6] (1), [Zn(L1)2]·2MeOH (2), [Zn(L2)2] (3), [Cd(L2)2] (4), and [Cd4(L1)6]·13H2O (5), were synthesized and characterized by a variety of techniques. Single-crystal X-ray structures have revealed that these coordination polymers exhibit a structural diversification due to the different choices of metal salts and the effect of pyridyl nitrogen position. Compounds 1-5 exhibited different fluorescence emissions and lifetimes upon excitation in the solid state. The sensing behavior of these polymers was also investigated upon exposure to vapors of various nitroaromatic molecules (analytes). The results show that all five polymers are capable of sensing these nitroaromatic molecules in the vapor phase through fluorescence quenching. Interestingly, 3 exhibits superior sensitivity to the analytes in comparison with other polymers. 2-Nitrotoluene quenches the emission of 3 by as much as 96%.

  5. Performance of polymer nano composite membrane electrode assembly using Alginate as a dopant in polymer electrolyte membrane fuel cell

    Science.gov (United States)

    Mulijani, S.

    2017-01-01

    Polymer membrane and composite polymer for membrane electrode assembly (MEAs) are synthesized and studied for usage in direct methanol fuel cell (DMFC). In this study, we prepared 3 type of MEAs, polystyrene (PS), sulfonated polystyrene (SPS) and composite polymer SPS-alginat membrane via catalyst hot pressed method. The performance and properties of prepared MEAs were evaluated and analyzed by impedance spectrometry and scanning electron microscopy (SEM). The result showed that, water up take of MEA composite polymer SPS-alginate was obtained higher than that in SPS and PS. The proton conductivity of MEA-SPS-alginate was also higher than that PS and PSS. SEM characterization revealed that the intimate contact between the carbon catalyst layers (CL) and the membranes, and the uniformly porous structure correlate positively with the MEAs prepared by hot pressed method, exhibiting high performances for DMFC.

  6. Performance of polymer nano composite membrane electrode assembly using Alginate as a dopant in polymer electrolyte membrane fuel cell

    Science.gov (United States)

    Mulijani, S.

    2016-11-01

    Polymer membrane and composite polymer for membrane electrode assembly (MEAs) are synthesized and studied for usage in direct methanol fuel cell (DMFC). In this study, we prepared 3 type of MEAs, polystyrene (PS), sulfonated polystyrene (SPS) and composite polymer SPS-alginat membrane via catalyst hot pressed method. The performance and properties of prepared MEAs were evaluated and analyzed by impedance spectrometry and scanning electron microscopy (SEM). The result showed that, water up take of MEA composite polymer SPS-alginate was obtained higher than that in SPS and PS. The proton conductivity of MEA-SPS-alginate was also higher than that PS and PSS. SEM characterization revealed that the intimate contact between the carbon catalyst layers (CL) and the membranes, and the uniformly porous structure correlate positively with the MEAs prepared by hot pressed method, exhibiting high performances for DMFC.

  7. Thermally Induced Charge Reversal of Layer-by-Layer Assembled Single-Component Polymer Films.

    Science.gov (United States)

    Richardson, Joseph J; Tardy, Blaise L; Ejima, Hirotaka; Guo, Junling; Cui, Jiwei; Liang, Kang; Choi, Gwan H; Yoo, Pil J; De Geest, Bruno G; Caruso, Frank

    2016-03-23

    Temperature can be harnessed to engineer unique properties for materials useful in various contexts and has been shown to affect the layer-by-layer (LbL) assembly of polymer thin films and cause physical changes in preassembled polymer thin films. Herein we demonstrate that exposure to relatively low temperatures (≤ 100 °C) can induce physicochemical changes in cationic polymer thin films. The surface charge of polymer films containing primary and secondary amines reverses after heating (from positive to negative), and different characterization techniques are used to show that the change in surface charge is related to oxidation of the polymer that specifically occurs in the thin film state. This charge reversal allows for single-polymer LbL assembly to be performed with poly(allylamine) hydrochloride (PAH) through alternating heat/deposition steps. Furthermore, the negative charge induced by heating reduces the fouling and cell-association of PAH-coated planar and particulate substrates, respectively. This study highlights a unique property of thin films which is relevant to LbL assembly and biofouling and is of interest for the future development of thin polymer films for biomedical systems.

  8. A strategy for tuning achiral main-chain polymers into helical assemblies and chiral memory systems.

    Science.gov (United States)

    Yang, Dong; Zhao, Yin; Lv, Kai; Wang, Xiufeng; Zhang, Wei; Zhang, Li; Liu, Minghua

    2016-01-28

    A general strategy to tune the achiral main chain polymers into helical nanoassemblies was proposed based on the co-gelation approach. As an example, two achiral main chain polymers, PCz8 and PSi8, were selected, and their co-assembly with an amphiphilic l- or d-glutamide gelator was investigated. Although the polymers could not form gels individually, they could form co-gels with the gelator and the resultant gels exhibited macroscopic supramolecular chirality, which could be confirmed by CD spectra and SEM observations. Moreover, the supramolecular chirality can be memorized even after the gelator molecules were removed. Remarkably, either the gelator-containing or gelator-free chiral polymer assemblies showed circularly polarized luminescence (CPL), which is usually inherent to intrinsic chiral polymers. It was suggested that during the co-gelation, the chirality of the gelator was transferred to and memorized by the achiral polymers. The approach seems to be general and we provided the first example to tune the achiral polymers into helical assemblies through the co-gelation.

  9. Self-assembly of metal--polymer analogues of amphiphilic triblock copolymers

    Science.gov (United States)

    Nie, Zhihong; Fava, Daniele; Kumacheva, Eugenia; Zou, Shan; Walker, Gilbert; Rubinstein, Michael

    2008-03-01

    We proposed a block copolymer approach to the self-assembly of inorganic nanrods terminated with polymer molecules at both ends. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tetheredwith hydrophobic polymer chains at both ends. The self-assembly was tunable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. The distance between adjacent nanorods along chains can be tuned by varying the composition of mixture solvents or the molecular weight of polymer blocks, which allows us precisely control the plasmonic band of self-assembled structures. A systematic study of the self-assembly as a function of solvent composition and the molecular weight of the polymer blocks allowed us to construct a diagram that maps the assembled structures. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers.

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

    Science.gov (United States)

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

    2017-05-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Jin Jing; Han Xiao; Meng Qin; Li Dan; Chi Yuxian [School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029 (China); Niu Shuyun, E-mail: syniu@sohu.com [School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029 (China)

    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

  12. Temperature-controlled Hydrothermal Synthesis of Copper(Ⅰ or Ⅱ) Coordination Polymers via a Variety of Copper Coordination Modes

    Institute of Scientific and Technical Information of China (English)

    QU Xue-jian; WANG Shuang; ZHANG Dao-jun; JING Xue-min; ZHANG Li-rong; LI Guang-hua; HUO Qi-sheng; LIU Yun-ling

    2012-01-01

    Two 1D coordination polymers Cu2Ⅰ(C6N3H4)2(1) and CuⅡ(C6N3H4)2·H2O(2) based on benzotriazole(Bta)were hydrothermally synthesized by controlling the crystallization temperature.Single-crystal X-ray diffraction (XRD) analyses reveal that compound 1 is a 1D tubular structure constructed from two types of 1D chains {—Cu—N=N—N—}n,where the Cu(Ⅰ) ions adopt linear,triangular,and tetrahedral coordination modes to connect two types of Bta ligands via π-π interaction inside the tubular-like chain.For compound 2,the Cu(Ⅱ) ions assume a quadrilateral coordination mode linking to the Bta ligands to give 1D straight chains,which stacks through π-π interactions to construct a 2D layer structure.Further characterizations including elemental analyses,infrared IR spectra,thermogravimetric(TG) analyses and luminescence properties have been done.

  13. A 3d-4f complex constructed by the assembly of a cationic template, [Cu(en){sub 2}]{sup 2+}, and a 3D anionic coordination polymer, [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}(C{sub 5}O{sub 5})(H{sub 2}O){sub 2}]{sup 2-}

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Szu-Yu; Yeh, Chang-Tsung; Wang, Chih-Chieh [Department of Chemistry, Soochow University, Taipei, Taiwan (China); Lee, Gene-Hsiang [Instrumentation Center, National Taiwan University, Taipei, Taiwan (China); Sheu, Hwo-Shuenn [National Synchrotron Radiation Research Center, Hsinchu, Taiwan (China)

    2017-05-18

    A three-dimensional (3D) 3d-4f complex, [Cu(en){sub 2}][Sm{sub 2}(C{sub 5}O{sub 5})(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 2}].8H{sub 2}O (1) (en = ethylenediamine, C{sub 5}O{sub 5}{sup 2-} = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), were prepared via the in-situ ring-opening oxidation reaction of croconate in the presence of the template-directed complex, [Cu(en){sub 2}]{sup 2+} cation. The structural characterization determined by X-ray diffraction determination reveals that the 3D anionic coordination polymer of [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}(C{sub 5}O{sub 5})(H{sub 2}O){sub 2}]{sup 2-} in 1 can be describe in terms of in-plane 2D honeycomb-like [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}] layered frameworks bridged by oxalate with bis-chelating mode, being mutually interlinked via the bridge of μ{sub 1,2,3,4}-croconate ligands with bis-chelating coordination mode to complete the 3D open framework, which gives rise to 1D channels with pore size of 14.023 x 11.893 Aa (longest atom-atom contact distances) along the b axis. The structure-directing complex, [Cu(en){sub 2}]{sup 2+}, and solvated water molecules are resided into these honeycomb-type hexagonal channels. The thermal stability of 1 was further studied by TGA and in-situ powder X-ray diffraction measurement. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Synthesis, characterisation and thermal degradation behaviour of some coordination polymers by using TG–DTG and DTA techniques

    Directory of Open Access Journals (Sweden)

    Ratiram Gomaji Chaudhary

    2015-07-01

    Full Text Available The four chelate polymer complexes commonly called as coordination polymers of Mn(II, Co(II, Ni(II and Cu(II ions with fbpmpc (fbpmpc = fumaroyl bis (paramethoxyphenylcarbamide were synthesized and characterised by elemental analyses, infrared spectroscopy, diffuse reflectance, magnetic moment susceptibility, thermal analysis, X-ray diffraction, electrical conductivity and scanning electron microscopy technique (SEM. SEM investigations of coordination polymers were found in different shapes and sizes, though they are synthesized from a single ligand. Each metal ion is coordinated by a bis (bidentate manner through oxygen atom of the carboxylato group and the nitrogen atom of an amide group of ligand and two aqua ligands by coordinated bond which formed 6-member heterocyclic ring. In the present article, the main aim of research study is to find out the comparative studies of coordination polymers such as thermogravimetry (TG, derivative thermogravimetry (DTG, differential thermal analysis (DTA, electrical conductivity and morphology behaviour. Furthermore, the electrical conductivities of chelating ligand and coordination polymers were determined in the solid state powder form. The electrical conductivities measurements of undoped and doped ligand, coordination polymers were carried out at room temperature by the four probe technique using an electrometer. Thermal degradation studies of the coordination polymers have been carried out from a non-isothermal condition under nitrogen atmosphere at a heating rate of 10 °C min−1. The decomposition steps and thermal stabilities of these complexes were confirmed by thermal analysis techniques (TG/DTG/DTA. The thermal studies inferred the presence of crystallized water in all coordination polymers, whereas coordinated water was found in Ni(II and Cu(II ions.

  15. Stabilization of 2D assemblies of silver nanoparticles by spin-coating polymers

    Science.gov (United States)

    Hu, Longyu; Pfirman, Aubrie; Chumanov, George

    2015-12-01

    Silver nanoparticles self-assembled on poly(4-vinylpyridine) modified surfaces were spin-coated with poly(methyl methacrylate), poly(butyl methacrylate) and polystyrene from anisole and toluene solutions. The polymers filled the space between the particles thereby providing stabilization of the assemblies against particle aggregation when dried or chemically modified. The polymers did not coat the top surface of the nanoparticles offering the chemical accessibility to the metal surface. This was confirmed by converting the stabilized nanoparticles into silver sulfide and gold clusters. Etching the nanoparticles resulted in crater-like polymeric structures with the cavities extending down to the underlying substrate. Electrochemical reduction of silver inside the craters was performed. The approach can be extended to other nanoparticle assemblies and polymers.

  16. Application of a silver-olefin coordination polymer as a catalytic curing agent for self-healing epoxy polymers

    Science.gov (United States)

    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.

  17. Study of (Cyclic Peptide)-Polymer Conjugate Assemblies by Small-Angle Neutron Scattering.

    Science.gov (United States)

    Koh, Ming Liang; FitzGerald, Paul A; Warr, Gregory G; Jolliffe, Katrina A; Perrier, Sébastien

    2016-12-19

    We present a fundamental study into the self-assembly of (cyclic peptide)-polymer conjugates as a versatile supramolecular motif to engineer nanotubes with defined structure and dimensions, as characterised in solution using small-angle neutron scattering (SANS). This work demonstrates the ability of the grafted polymer to stabilise and/or promote the formation of unaggregated nanotubes by the direct comparison to the unconjugated cyclic peptide precursor. This ideal case permitted a further study into the growth mechanism of self-assembling cyclic peptides, allowing an estimation of the cooperativity. Furthermore, we show the dependency of the nanostructure on the polymer and peptide chemical functionality in solvent mixtures that vary in the ability to compete with the intermolecular associations between cyclic peptides and ability to solvate the polymer shell.

  18. Leveraging symmetry to predict self-assembly of multiple polymers

    Science.gov (United States)

    Lin, Milo M.

    2017-09-01

    Protein self-assembly is fundamental to biological function and disease. Experimentally, the atomic-level structure is difficult to obtain and the assembly mechanism is poorly understood. The large number of possible states accessible to such systems limits computational prediction. Here, I introduce a new computational approach that enforces conformational symmetry, whereby all chains in the system adopt the same conformation. Using this approach on a 2D lattice, a designed multi-chain conformation is found more than four orders of magnitude faster than existing approaches. Furthermore, the free energy landscape can be efficiently computed, showing potential for enabling atomistic prediction of protein self-assembly.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2017-03-01

    One dimensional coordination polymer Gd[(SO4)(NO3)(C2H6SO)2] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO42- ions to generate a 1-D chain, and all oxygen atoms in SO42- groups are connected to three nearest Gd atoms in μ3:η1:η1:η2 fashion. Gd, S and N from SO42- and NO3- are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with -ΔSm=28.8 J Kg-1 K-1 for ΔH=7 T.

  2. Synthesis, structure and masnetic properties of two new coordination polymers with carboxylate-substituted benzoimidazole lisands

    Institute of Scientific and Technical Information of China (English)

    HU BoWen; ZHAO JiongPeng; YANG Qian; ZHANG XiaoFeng; BU XianHe

    2009-01-01

    This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands:[Mn(L)-(HCO2)]n (1) and [Co(L)·(HCO2)]n (2) (L = benzoimidazol-1-yl-acetate).Complexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing interesting magnetic properties:spin canted antiferromagnetism for Mn11 complex 1,but simple antiferromagnetic coupling for CoⅡ complex 2.

  3. Picogram sensing of trinitrophenol in aqueous medium through a water stable nanoscale coordination polymer.

    Science.gov (United States)

    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.

  4. Novel Zn(II) ladder-like coordination polymer constructed from designed ferrocenyl ligand

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Reaction of Zn(NO3)2.6H2O with 3-(4-carboxylphenylamino)-1-ferrocenyl-2-butylen-1-one (HL) and 4,4'-bipyridine (4,4'-bipy) in methanol solution resulted in a novel ladder-like coordination polymer {[Zn2L2(μ2-L)2(4,4'-bipy)2].MeOH}n (1). Its crystal structure, thermal and electrochemical properties axe presented.

  5. A Perylene-Based Microporous Coordination Polymer Interacts Selectively with Electron-Poor Aromatics.

    Science.gov (United States)

    Tran, Ly D; Ma, Jialiu; Wong-Foy, Antek G; Matzger, Adam J

    2016-04-11

    The design, synthesis, and properties of the new microporous coordination polymer UMCM-310 are described. The unique electronic character of the perylene-based linker enables selective interaction with electron-poor aromatics leading to efficient separation of nitroaromatics. UMCM-310 possesses high surface area and large pore size and thus permits the separation of large organic molecules based on adsorption rather than size exclusion.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-15

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

  7. A 2D [Fe-II-bistetrazole] coordination polymer exhibiting spin-crossover properties

    NARCIS (Netherlands)

    Quesada, Manuel; Prins, Ferry; Roubeau, Olivier; Gamez, Patrick; Teat, Simon J.; van Koningsbruggen, Petra J.; Haasnoot, Jaap G.; Reedijk, Jan

    2007-01-01

    The reaction of 1,3-bis(tetrazol-1-yl)-2-propanol (btzpol) with Fe(BF4)(2) center dot 6H(2)O in acetonitrile yields the remarkable 2D coordination polymer [Fe-II(btzpol)(1.8)(btzpol-OBF3)(1.2)](BF4)(0.8) center dot (H2O)(0.8)(CH3CN) (1). This compound has been structurally characterized using an X-r

  8. Synthesis, structure and magnetic properties of two new coordination polymers with carboxylate-substituted benzoimidazole ligands

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands: [Mn(L)·(HCO2)]n (1) and [Co(L)·(HCO2)]n (2) (L = benzoimidazol-1-yl-acetate). Com-plexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing inter-esting magnetic properties: spin canted antiferromagnetism for MnⅡ complex 1, but simple antiferro-magnetic coupling for CoⅡ complex 2.

  9. Drug conjugation to cyclic peptide-polymer self-assembling nanotubes.

    Science.gov (United States)

    Blunden, Bianca M; Chapman, Robert; Danial, Maarten; Lu, Hongxu; Jolliffe, Katrina A; Perrier, Sébastien; Stenzel, Martina H

    2014-09-26

    We show for the first time how polymeric nanotubes (NTs) based on self-assembled conjugates of polymers and cyclic peptides can be used as an efficient drug carrier. RAPTA-C, a ruthenium-based anticancer drug, was conjugated to a statistical co-polymer based on poly(2-hydroxyethyl acrylate) (pHEA) and poly(2-chloroethyl methacrylate) (pCEMA), which formed the shell of the NTs. Self-assembly into nanotubes (length 200-500 nm) led to structures exhibiting high activity against cancer cells.

  10. Molecular Recognition Directed Self-Assembly of Supramolecular Polymers

    Science.gov (United States)

    1994-06-30

    demonstrated that various substituted gallic acid derivatives can be used to constmict exo-receptors with a tapered shape. "Tihis paper will review...understood self-assembled biological system [3ab.5]. Therefore, we believe it provides an ideal model to be used for the understanding of the principles...governing the self-assembly of synthetic supraimolecular architectures. Synthetic Strategy Used In The Design Of TMV-Like Supramolecular Architectures fl

  11. A Heterobimetallic Anionic 3,6-Connected 2D Coordination Polymer Based on Nitranilate as Ligand

    Directory of Open Access Journals (Sweden)

    Samia Benmansour

    2016-03-01

    Full Text Available In order to synthesize new coordination polymers with original architectures and interesting magnetic properties, we used the nitranilate ligand (C6O4(NO222− = C6N2O82−, derived from the dianionic ligand dhbq2− (2,5-dihydroxy-1,4-benzoquinone = H2C6O42−. The use of this bis-bidentate bridging ligand led to [(DAMS2{FeNa(C6N2O83}·CH3CN]n (1 (DAMS+ = C16H17N2+ = 4-[4-(dimethylamino-α-styryl]-1-methylpyridinium, a 2D heterometallic coordination polymer presenting an unprecedented structure for any anilato-based compound. This structural type is a 3,6-connected 2D coordination polymer derived from the well-known honeycomb hexagonal structure, where Fe(III ions alternate with Na+ dimers (as Na2O12 units in the vertices of the hexagons and with an additional [Fe(C6N2O83]3− anion located in the center of the hexagons connecting the three Na+ dimers. The magnetic properties of compound 1 show the presence of paramagnetic isolated high spin Fe(III complexes with a zero field splitting, |D| = 8.5 cm−1.

  12. Passive micro-assembly of modular, hot embossed, polymer microfluidic devices using exact constraint design

    Science.gov (United States)

    You, Byoung Hee; Chen, Pin-Chuan; Park, Daniel S.; Park, Sunggook; Nikitopoulos, Dimitris E.; Soper, Steven A.; Murphy, Michael C.

    2009-12-01

    Low-cost microfluidic platforms have the potential to change accepted practices in many fields, including biology and medicine, in the near future. Micro-assembly of molded polymer microfluidic devices is one approach to cost-effective mass production of modular, microfluidic instruments. Polymer, passive alignment structures were used to precisely assemble molded polymer components to prevent infinitesimal motions and minimize the misalignment between assembled components and devices. The motion and constraint of the assemblies were analyzed using screw theory to identify combinations of passive alignment structures that would provide exact constraint of all degrees of freedom of the two mating parts without over-constraint. One option identified by kinematic analysis was a set of three v-groove and hemisphere-tipped pin joints, which are well known from precision engineering and suitable for microfabrication. To validate the passive alignment scheme, brass mold inserts containing alignment structures were micro-milled and used to hot emboss components in polycarbonate (PC). Dimensional and location variations of prototype alignment structures were measured to quantify the difference between the as-designed and actual dimensions and the locations of the alignment structures. The dimensional variation was 0.2-3% less than the designed dimensions and the location variation was 0.7% less. The alignment accuracy of an assembly was characterized by measuring the mismatch and vertical variation between molded alignment standards embossed on each pair of mating plates. With molded, polymer alignment structures the mean mismatch and mean vertical variation were as low as 13 ± 3 µm in the lateral plane along the x- and y-axes and -6 ± 15 µm with respect to the nominal value of 107 µm. This micro-assembly technology is applicable to the integration of all microsystems including the interconnection of microfluidic devices, the assembly of hybrid microsystems and the

  13. Virus-Assembled Flexible Electrode-Electrolyte Interfaces for Enhanced Polymer-Based Battery Applications

    OpenAIRE

    Ayan Ghosh; Juchen Guo; Brown, Adam D.; Elizabeth Royston; Chunsheng Wang; Peter Kofinas; James N. Culver

    2012-01-01

    High-aspect-ratio cobalt-oxide-coated Tobacco mosaic virus (TMV-) assembled polytetrafluoroethylene (PTFE) nonstick surfaces were integrated with a solvent-free polymer electrolyte to create an anode-electrolyte interface for use in lithium-ion batteries. The virus-assembled PTFE surfaces consisted primarily of cobalt oxide and were readily intercalated with a low-molecular-weight poly (ethylene oxide) (PEO) based diblock copolymer electrolyte to produce a solid anode-electrolyte system. The ...

  14. Correction: Coordination-directed self-assembly of a simple benzothiadiazole-fused tetrathiafulvalene to low-bandgap metallogels.

    Science.gov (United States)

    Amacher, Anneliese M; Puigmartí-Luis, Josep; Geng, Yan; Lebedev, Victor; Laukhin, Vladimir; Krämer, Karl; Hauser, Jürg; Amabilino, David B; Decurtins, Silvio; Liu, Shi-Xia

    2015-11-25

    Correction for 'Coordination-directed self-assembly of a simple benzothiadiazole-fused tetrathiafulvalene to low-bandgap metallogels' by Anneliese M. Amacher et al., Chem. Commun., 2015, 51, 15063-15066.

  15. Multiscale modeling of drug-polymer nanoparticle assembly identifies parameters influencing drug encapsulation efficiency.

    Science.gov (United States)

    Mackenzie, R; Booth, J; Alexander, C; Garnett, M C; Laughton, C A

    2015-06-09

    Using a multiscale (dual resolution) approach combining an atomistic (GROMOS96) and coarse-grain (MARTINI) force field, we have been able to simulate the process of drug-polymer nanoparticle assembly by nanoprecipitation from mixed solvents. Here, we present the development and application of this method to the interaction of three poly(glycerol adipate) polymer variants with the anticancer drug dexamethasone phosphate. Differences in encapsulation efficiency and drug loading between the polymers are in agreement with the experimental trend. Reference atomistic simulations at key points along the predicted aggregation pathway support the accuracy of the much more computationally efficient multiscale methodology.

  16. Monolithic and assembled polymer-ceramic composites for bone regeneration

    NARCIS (Netherlands)

    Nandakumar, A.; Cruz, C.; Mentink-Leusink, Anouk; Tahmasebi Birgani, Zeinab; Moroni, Lorenzo; van Blitterswijk, Clemens; Habibovic, Pamela

    2013-01-01

    The rationale for the use of polymer - ceramic composites for bone regeneration stems from the natural composition of bone, with collagen type I and biological apatite as main organic and inorganic constituents, respectively. In the present study, composite materials of PolyActive™ (PA), a poly

  17. One-Dimensional Coordination Polymers of Lanthanide Cations to Cucurbit[7]uril Built Using a Range of Tetrachloride Transition-Metal Dianion Structure Inducers

    Directory of Open Access Journals (Sweden)

    Sai-Feng Xue

    2013-05-01

    Full Text Available A number of linear coordination polymers have been assembled from lanthanide cations (Ln3+ and cucurbit[7]uril (Q[7] in the presence of [CuCl4]2−or [CoCl4]2− anions acting as inorganic structure inducers in HCl solution. X-ray diffraction analysis has revealed that they form three groups of isomorphous structures. Generally, the complexes of Q[7] with light lanthanide cations (those with atomic number below that of neodymium (Nd3+ are in one group. The other two groups, in which the lanthanide cation has atomic number greater than that of europium (Eu3+, seem to follow no obvious rule. For example, the complexes of Q[7] with Eu3+ and Gd3+cations are in the second group in the presence of [CuCl4]2− anions, while they are in the third group in the presence of [CoCl4]2− anions. However, whatever group a given complex belongs to, they all show a common honeycomb-patterned supramolecular assembly, in which [CuCl4]2−or [CoCl4]2− anions form a honeycomb structure. The Ln3+ cations then coordinate to neighboring Q[7] molecules to form 1D coordination polymers that are inserted into the channels of the honeycomb framework, such that each individual coordination polymer is surrounded by [CuCl4]2−or [CoCl4]2− anions.

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

    Science.gov (United States)

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

    2016-09-01

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

  19. Two-dimensional coordination polymers constructed using, simultaneously, linear and angular spacers and cobalt(II) nodes. New examples of networks of single-ion magnets.

    Science.gov (United States)

    Ion, Adrian E; Nica, Simona; Madalan, Augustin M; Shova, Sergiu; Vallejo, Julia; Julve, Miguel; Lloret, Francesc; Andruh, Marius

    2015-01-01

    Two novel bidimensional coordination polymers, [Co(azbbpy)(4,4'-bipy)0.5(DMF)(NCS)2]·MeOH (1) and [Co(azbbpy)(bpe)0.5(DMF)(NCS)2]·0.25H2O (2), resulted from the assembling of cobalt(II) ions by 1,3-bis(4-pyridyl)azulene, using either 4,4'-bipyridyl or 1,2-bis(4-pyridyl)ethylene as neutral spacers. The cobalt(II) nodes in 1 and 2 act as single-ion magnets (SIMs).

  20. Single-ion-magnet behavior in a two-dimensional coordination polymer constructed from Co(II) nodes and a pyridylhydrazone derivative.

    Science.gov (United States)

    Liu, Xiangyu; Sun, Lin; Zhou, Huiliang; Cen, Peipei; Jin, Xiaoyong; Xie, Gang; Chen, Sanping; Hu, Qilin

    2015-09-21

    A novel two-dimensional (2D) coordination polymer, [Co(ppad)2]n (1), resulted from the assembly of Co(II) ions based on a versatile ligand termed N(3)-(3-pyridoyl)-3-pyridinecarboxamidrazone. Alternating/direct-current magnetic studies of compound 1 indicate that the spatially separated high-spin Co(II) ions act as single-ion magnets (SIMs). The present work represents the first case of a 2D Co(II)-based SIM composed of a monocomponent organic spacer.

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

    Energy Technology Data Exchange (ETDEWEB)

    Barros, Bráulio Silva, E-mail: brauliobarros@ect.ufrn.br [School of Science and Technology, Federal University of Rio Grande do Norte (UFRN), Campus Universitário Lagoa Nova, 59078-970 Natal, RN (Brazil); Chojnacki, Jaroslaw [Department of Inorganic Chemistry, Chemical Faculty, Gdansk University of Technology, G. Narutowicza 11/12, 80-233 Gdansk (Poland); Macêdo Soares, Antonia Alice; Kulesza, Joanna; Lourenço da Luz, Leonis; Júnior, Severino Alves [Department of Fundamental Chemistry, Federal University of Pernambuco (UFPE), Av. Prof. Moraes Rego, 1235 – Cidade Universitária, 50670-901 Recife, PE (Brazil)

    2015-07-15

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

  2. Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)2M](2+) nodes (M = Ni, Zn and Cd) (H2L = salen-type di-Schiff base) and dicyanamide spacers.

    Science.gov (United States)

    Das, Lakshmi Kanta; Gómez-García, Carlos J; Ghosh, Ashutosh

    2015-01-21

    Three new 2D coordination polymers (CPs) (2)∞[(NiL)2Ni(μ1,5-N(CN)2)2]n (), (2)∞[(NiL)2Cd(μ1,5-N(CN)2)2]n () and (2)∞[(NiL)2Zn(μ1,5-N(CN)2)2]n () have been synthesized by reacting a [NiL] "metalloligand" (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) with three different metal(ii) (Ni, Cd and Zn) perchlorates and sodium dicyanamide, with identical molar ratios of the reactants. All three products have been characterized by IR and UV-Vis spectroscopies, elemental analyses, powder and single crystal X-ray diffraction and variable temperature magnetic measurements. The isomorphous compounds and consist of similar [(NiL)2M(μ1,5-N(CN)2)] (M = Ni for and Cd for ) angular trinuclear units in which two terminal "metalloligands" [NiL] coordinate to the central nickel(ii) (in ) or cadmium(ii) (in ) ion through phenoxido oxygen atoms. The μ1,5-bridging dicyanamido spacers connect the central Ni(ii) or Cd(ii) of one node to terminal Ni(ii) of two different nodes giving rise to 2D CPs. Compound also contains trinuclear units with the same formula as those of and : [(NiL)2M(μ1,5-N(CN)2)] (M = Zn in ). The main differences are that these units are linear in and the dicyanamide spacers link only the nickel atoms of neighbouring nodes. As in and , these trinuclear units are connected to four other units via four μ1,5-bridging dicyanamido ligands, giving rise to 2D CP with a similar topology: a uninodal 4-connected underlying net with the sql (Shubnikov tetragonal plane net) topology and (4(4)·6(2)) point symbol. The magnetic properties show the presence of moderate intra-trimer antiferromagnetic interactions in (J = -12.9 cm(-1)) and weak antiferromagnetic interactions between the terminal Ni(ii) ions in (J = -2.4 cm(-1)). In the Ni(ii) ions are well isolated by the central Zn(ii) ion and accordingly, only a very weak antiferromagnetic interaction through the single μ1,5-bridging dicyanamido ligands is observed (J = -0.44 cm(-1), D = -3.9 cm(-1)).

  3. Assembly of optical fibers for the connection of polymer-based waveguide

    Science.gov (United States)

    Ansel, Yannick; Grau, Daniel; Holzki, Markus; Kraus, Silvio; Neumann, Frank; Reinhard, Carsten; Schmitz, Felix

    2003-03-01

    This paper describes the realization of polymer-based optical structures and the assembly and packaging strategy to connect optical fiber ribbons to the waveguides. For that a low cost fabrication process using the SU-8TM thick photo-resist is presented. This process consists in the deposition of two photo-structurized resist layers filled up with epoxy glue realising the core waveguide. For the assembly, a new modular vacuum gripper was realised and installed on an automatic pick and place assembly robot to mount precisely and efficiently the optical fibers in the optical structures. First results have shown acceptable optical propagation loss for the complete test structure.

  4. Synthesis, crystal structure and Thermogravimetry of ortho-phthalic acid bridged coordination polymer of Copper(II)

    Indian Academy of Sciences (India)

    BABITA SARMA; SAURAV BHARALI; DIGANTA KUMAR DAS

    2016-06-01

    Coordination polymer of Cu(II) bridged by o-phthalic acid alone is not known. The reaction of$CuCl_{2}.2H_{2}O$ with (2-butoxycarbonyl)benzoic acid yielded three dimensional coordination polymer bridged byo-phthalic acid. X-ray crystal structure shows structure with monoclinic P21/c space group. o-Phthalic acidmolecules act as bridge between two Cu(II), one carboxylate binds to one Cu(II) as bidentate while the othercarboxylate binds to another Cu(II) as monodentate. The four planar co-ordination positions of Cu(II) aresatisfied by two chelated carboxylates while fifth and sixth co-ordination positions are satisfied by monodentatecarboxylates. EPR and TGA of the coordination polymer are also reported.

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

    Science.gov (United States)

    Robson, R

    2008-10-14

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

  6. Polymer self-assembling of light converting microlenses arrays

    Science.gov (United States)

    Coppola, S.; Mandracchia, B.; Nasti, G.; Vespini, V.; Pareo, P.; Carbone, L.; Manca, M.; Gigli, G.; Ferraro, P.

    2014-05-01

    In the case of light emitting semiconducting polymers, different techniques have been used for the fabrication of electroluminescent devices. Experiments and characterizations have been carried out at different operating voltages and for voltage dependent emission color also combining the processability of organic materials with efficient luminescence displayed by inorganic nanocrystals (NCs). In fact, the experimental perspective to disperse emitting colloidal NCs into polymers has allowed to further engineer hybrid organic-inorganic materials introducing innovative functionalities as for instance photoluminescence conversion capabilities. This has proved of great interest for novel applications such as the fabrication of photonic crystals and, notably, of innovative solar cells showing enhanced efficiency. Here we report on the fabrication of novel active micro-optical elements made by a mixture of rod-shaped inorganic NCs dispersed into poly-dimethylsiloxane.

  7. Structural and chemical control in assembly of multicomponent metal-organic coordination networks on a surface.

    Science.gov (United States)

    Shi, Ziliang; Lin, Nian

    2010-08-11

    Surface-supported supramolecular self-assembly has been used to generate multicomponent two-dimensional metal-organic coordination networks on a Au(111) surface. The networks consist of linker ligands of 4',4''''-(1,4-phenylene)bis(2,2':6',2''-terpyridine) and nodal ligands of 5,10,15,20-tetra(4-pyridyl)porphyrin that are connected by pyridine-Fe-terpyridine motifs. Scanning tunneling microscopy revealed the coexistence of two polymorphic types of network structures (rhombus and Kagome). Through control of the dosage of the constituent ligands, homogeneous structural phases were obtained selectively. In particular, the rhombus structure could be converted into the more complex and more open Kagome structure by inclusion of guest molecules. Finally, coordination networks providing structural and chemical homogeneity were realized by judiciously choosing the dosages of the constituent ligands and the chemical substitution of the porphyrin ligands.

  8. Order-disorder transitions in self-assembled polymers : A positron annihilation study

    NARCIS (Netherlands)

    Ramani, Ramasubbu; Valkama, Sami; Kilpeläinen, Simo; Tumisto, Filip; Brinke, Gerrit ten; Ruokolainen, Janne; Alam, Sarfaraz; Ikkala, Olli

    2009-01-01

    We report here the first results of order-disorder transition (ODT) in a self-assembled comb-like polymer-amphiphile supramolecular system as identified from the change in positron lifetime parameters. We have used poly(4-vinyl pyridine) hydrogen bonded with 3-pentadecyl phenol, which upon heating s

  9. Self-assembly in a polymer matrix and its impact on phase separation.

    Science.gov (United States)

    Dudowicz, Jacek; Douglas, Jack F; Freed, Karl F

    2009-03-26

    Molecular self-assembly often occurs in the presence of long chain polymers, and we develop a theory to describe the competition between self-assembly and phase separation that generally occurs in these complex fluid mixtures. The theory includes a description of the particularly interesting situation where the associating "monomeric" species form high molecular mass polymeric structures and where the assembly process transforms the phase boundary from a form typical of a polymer solution to one that more resembles a polymer blend. We consider both self-assembly upon cooling and upon heating, but the van der Waals interactions are chosen so that phase separation occurs only upon cooling in the absence of association. Systems that associate upon heating prove to be particularly rich, and closed loop and ordinary (upper solution critical) phase boundaries are found to coexist over a wide range of interaction parameter values. Each critical temperature in the limit of a large polymerization index for the matrix polymers approaches its respective theta temperature. The calculations elucidate basic physical principles governing the phase behavior of these complex mixtures.

  10. Mcm10 coordinates the timely assembly and activation of the replication fork helicase

    Science.gov (United States)

    Perez-Arnaiz, Patricia; Bruck, Irina; Kaplan, Daniel L.

    2016-01-01

    Mcm10 is an essential replication factor that is required for DNA replication in eukaryotes. Two key steps in the initiation of DNA replication are the assembly and activation of Cdc45–Mcm2–7-GINS (CMG) replicative helicase. However, it is not known what coordinates helicase assembly with helicase activation. We show in this manuscript, using purified proteins from budding yeast, that Mcm10 directly interacts with the Mcm2–7 complex and Cdc45. In fact, Mcm10 recruits Cdc45 to Mcm2–7 complex in vitro. To study the role of Mcm10 in more detail in vivo we used an auxin inducible degron in which Mcm10 is degraded upon addition of auxin. We show in this manuscript that Mcm10 is required for the timely recruitment of Cdc45 and GINS recruitment to the Mcm2–7 complex in vivo during early S phase. We also found that Mcm10 stimulates Mcm2 phosphorylation by DDK in vivo and in vitro. These findings indicate that Mcm10 plays a critical role in coupling replicative helicase assembly with helicase activation. Mcm10 is first involved in the recruitment of Cdc45 to the Mcm2–7 complex. After Cdc45–Mcm2–7 complex assembly, Mcm10 promotes origin melting by stimulating DDK phosphorylation of Mcm2, which thereby leads to GINS attachment to Mcm2–7. PMID:26582917

  11. Facile fabrication and adsorption property of a nano/microporous coordination polymer with controllable size and morphology.

    Science.gov (United States)

    Liu, Qing; Jin, Li-Na; Sun, Wei-Yin

    2012-09-11

    A porous coordination polymer [Cu(3)(btc)(2)] with controllable size and morphology from nanocube to microoctahedron was readily synthesized in an ethanol-water mixture at room temperature by adjusting the concentration of the surfactant and the polymer shows size- and morphology-dependent sorption properties.

  12. Synthesis, spectral characterization and thermal aspects of coordination polymers of some transition metal ions with adipoyl bis(isonicotinoylhydrazone)

    Science.gov (United States)

    Haque, Mahejabeen Azizul; Paliwal, L. J.

    2017-04-01

    A series of metal coordination polymers of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), obtained by the reaction of metal acetate with newly synthesized adipoyl bis(isonicotinoylhydrazone) (ADBI) have been investigated. The ligand has been characterized by 1H NMR, 13C NMR, FTIR, and ESI mass spectra. Structural and spectroscopic characterization of the coordination polymers have been carried out using elemental analysis, XRD, SEM, infrared and diffused reflectance spectra, magnetic susceptibility measurements and thermogravimetric analytical techniques. Each metal ion is coordinated to the ligand through oxygen of carbonyl group and the nitrogen of azomethine group of ligand forming a stable 5-membered heterocyclic ring. The synthesized ligand coordinates in an octadentate manner. Magnetic and diffused reflectance spectral studies reveal octahedral geometry of Co(II), Cu(II), Fe(II) and Ni(II) coordination polymers and tetrahedral geometry of Mn(II) and Zn(II) coordination polymers. The thermal stability and decomposition steps of all coordination polymers have been studied using TG, DTG and DTA techniques. Moreover, the kinetic parameters such as activation energy (Ea*), order of reaction (n), Arrhenius factor (A), change in entropy (ΔS*), change in enthalpy (ΔH*) and free energy change (ΔG*) were evaluated at each stage of decomposition curve using Coats-Redfern method.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-15

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

  14. In-process assembly of micro metal inserts in a polymer matrix

    DEFF Research Database (Denmark)

    Tosello, Guido; Hansen, Hans Nørgaard

    2006-01-01

    New functionalities and smaller dimensions of micro products can be achieved by means of a higher degree of integration of both materials and components. Smart micro assembly techniques (such as on-the-machine assembly) together with hybrid structures (as metal inserts in polymer matrix......) are suitable solutions to manufacture new micro products with several integrated functionalities, reduced number of components and assembly phases, as well as the possibility to be replicated in a high number of specimens. Innovative manufacturing systems, as well as new design rules and testing methodologies......, have to be established in order to be able to develop new and more integrated micro products. In this paper a method for testing the bonding between micro thickened metal inserts and the polymer matrix they are moulded in is presented. A specific demonstrator has been manufactured by means of a hot...

  15. Chiral molecular assemblies from a novel achiral amphiphilic 2-(heptadecyl) naphtha[2,3]imidazole through interfacial coordination.

    Science.gov (United States)

    Yuan, Jing; Liu, Minghua

    2003-04-30

    A novel amphiphilic compound 2-(heptadecyl) naphtha[2,3]imidazole (NpImC17) was synthesized, and its coordination with AgNO(3) in situ in the monolayer at the air/water interface and ex situ in the Langmuir-Blodgett (LB) film on solid substrate has been investigated. It has been found that interfacial coordination between NpImC17 and Ag(I) ion occurred both in the monolayer and in the LB film. It is interesting to note that the Ag(I)-coordinated ultrathin film became chiral although the ligand itself is achiral. It was suggested that the chirality of the Ag(I)-coordinated LB film was developed due to the formation of a helical coordination polymer through the interfacial coordination. To the best of our knowledge, this is the first report on the formation of chiral monolayer and LB films from an achiral molecule through interfacial coordination.

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

    Energy Technology Data Exchange (ETDEWEB)

    He, Tian [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhao, Yi-xing; Chen, San-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn [Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, College of Chemical Engineering and Modern Materials, Shangluo University, Shangluo 726000 (China); Yan, Ni [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China)

    2016-07-15

    Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC

  17. Synthesis and Crystal Structure of a New Cadmium(Ⅱ) Coordination Polymer with Ethylenediaminetetraacetic Acid

    Institute of Scientific and Technical Information of China (English)

    ZHENG Jian-Mei; WU Mei-Feng; ZHENG Fa-Kun; LIU Hua

    2012-01-01

    A new cadmium(Ⅱ) coordination polymer,namely,[KCd2(edta)I]n(1,H4edta = ethylenediaminetetraacetic acid),has been prepared and structurally characterized by single-crystal X-ray diffraction.Crystallographic data for 1:C10H12Cd2IKN2O8,Mr = 679.02,monoclinic,space group P21/n,a = 9.870(5),b = 8.989(4),c = 19.082(10) ,β = 104.581(10)o,V = 1638.5(13) 3,Z = 4,Dc = 2.753 g/cm3,μ = 4.776 mm-1,F(000) = 1272,the final R = 0.0473 and wR = 0.1311 for 2846 observed reflections with I 〉 2σ(I).Polymer 1 features a 2-D layered structure,in which each edta4-ligand chelates/bridges five adjacent six-/seven-coordinated Cd(Ⅱ) centers with all ten donors(eight oxygen and two nitrogen) involved with coordination.Additional iodide I-ions as counterions are bound to the Cd(Ⅱ) centers in a terminal mode and the potassium K+ ions are located in the layers and surrounded by O and I atoms from neighboring environment.The thermal stability of 1 has been discussed.

  18. Micro-assembly of a Vascular-like Micro-channel with Railed Micro-robot Team-coordinated Manipulation

    Directory of Open Access Journals (Sweden)

    Huaping Wang

    2014-07-01

    strategies were evaluated based on the assembly of micro-donuts. Through the novel, designed, concentric movement of the multi-manipulators along the rail, arbitrary change of the approaching angle and the coordination posture was achieved to improve the micro-assembly’s flexibility. The operation range for every micromanipulator in different coordinated manipulation modes was analysed to avoid the breakdown of the assembled 3D structure. The image processing for the target location and end-effector identification was conducted to improve assembly efficiency in the micro-robot-team system. Finally, the assembly of the cellular vascular-like micro-channel was achieved with coordinated manipulation in the rail- guided micro-robot-team system.

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

    Science.gov (United States)

    Garai, Mousumi; Biradha, Kumar

    2017-01-05

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

  20. Desymmetrization of an Octahedral Coordination Complex Inside a Self-Assembled Exoskeleton.

    Science.gov (United States)

    Johnstone, Mark D; Schwarze, Eike K; Ahrens, Jennifer; Schwarzer, Dirk; Holstein, Julian J; Dittrich, Birger; Pfeffer, Frederick M; Clever, Guido H

    2016-07-25

    The synthesis of a centrally functionalized, ribbon-shaped [6]polynorbornane ligand L that self-assembles with Pd(II) cations into a {Pd2 L4 } coordination cage is reported. The shape-persistent {Pd2 L4 } cage contains two axial cationic centers and an array of four equatorial H-bond donors pointing directly towards the center of the cavity. This precisely defined supramolecular environment is complementary to the geometry of classic octahedral complexes [M(XY)6 ] with six diatomic ligands. Very strong binding of [Pt(CN)6 ](2-) to the cage was observed, with the structure of the host-guest complex {[Pt(CN)6 ]@Pd2 L4 } supported by NMR spectroscopy, MS, and X-ray data. The self-assembled shell imprints its geometry on the encapsulated guest, and desymmetrization of the octahedral platinum species by the influence of the D4h -symmetric second coordination sphere was evidenced by IR spectroscopy. [Fe(CN)6 ](3-) and square-planar [Pt(CN)4 ](2-) were strongly bound. Smaller octahedral anions such as [SiF6 ](2-) , neutral carbonyl complexes ([M(CO)6 ]; M=Cr, Mo, W) and the linear [Ag(CN)2 ](-) anion were only weakly bound, showing that both size and charge match are key factors for high-affinity binding.

  1. Tuning the sphere-to-rod transition in the self-assembly of thermoresponsive polymer hybrids.

    Science.gov (United States)

    Lee, Jangwook; Park, Honghyun; Jeong, Eun Ju; Kwark, Young-Je; Lee, Kuen Yong

    2015-12-01

    Nano-scale drug delivery systems have undergone extensive development, and control of size and structure is critical for regulation of their biological responses and therapeutic efficacy. Amphiphilic polymers that form self-assembled structures in aqueous media have been investigated and used for the diagnosis and therapy of various diseases, including cancer. Here, we report the design and fabrication of thermoresponsive polymeric micelles from alginate conjugated with poly(N-isopropylacrylamide) (PNIPAAm). Alginate-PNIPAAm hybrids formed self-aggregated structures in response to temperature changes near body temperature. A structural transition from micellar spheres to rods of alginate-PNIPAAm hybrids was observed depending on the molecular weight of PNIPAAm and the polymer concentration. Additionally, hydrogels with nanofibrous structures were formed by simply increasing the polymer concentration. This approach to controlling the structure of polymer micelles from nanoparticles to fibrous hydrogels may be useful in applications in drug delivery and tissue engineering.

  2. Solid structures of the stepwise self-assembled copillar[5]arene-based supramolecular polymers

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yeon Sil; Hwang, Seong Min; Shin, Jae Yeon; Paek, Kyung Soo [Dept. of Chemistry, Soongsil University, Seoul (Korea, Republic of)

    2016-10-15

    Development of supramolecular polymer has attracted much interest because of their interesting properties such as stimuli-responsiveness, recycling, self-healing and degradability, and their consequential applications. The essential feature of this class of polymers is the self-assembly of discrete monomeric subunits via non-covalent interactions or dynamic covalent bonds. Among the many monomeric subunits, pillar[n]arenes have been ideal building blocks for the fabrication of polymeric supramolecules because of their intrinsic characteristics. The ring-shaped morphologies in supramolecular polymer P are probably due to the tendency of the end-to-end connection in the solid state of long flexible supramolecular chains. The size increase of nano-rings as the stepwise addition increases might be due to the fact that the linear supramolecular polymer P in solution seems to be maintained until the nano-ring formation by solidification.

  3. Resolving Properties of Polymers and Nanoparticle Assembly through Coarse-Grained Computational Studies.

    Energy Technology Data Exchange (ETDEWEB)

    Grest, Gary S.

    2017-09-01

    Coupled length and time scales determine the dynamic behavior of polymers and polymer nanocomposites and underlie their unique properties. To resolve the properties over large time and length scales it is imperative to develop coarse grained models which retain the atomistic specificity. Here we probe the degree of coarse graining required to simultaneously retain significant atomistic details a nd access large length and time scales. The degree of coarse graining in turn sets the minimum length scale instrumental in defining polymer properties and dynamics. Using polyethylene as a model system, we probe how the coarse - graining scale affects the measured dynamics with different number methylene group s per coarse - grained beads. Using these models we simulate polyethylene melts for times over 500 ms to study the viscoelastic properties of well - entangled polymer melts and large nanoparticle assembly as the nanoparticles are driven close enough to form nanostructures.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-15

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

  6. Self-Organizing Circuit Assembly through Spatiotemporally Coordinated Neuronal Migration within Geometric Constraints

    Science.gov (United States)

    Sun, Yi; Huang, Zhuo; Yang, Kaixuan; Liu, Wenwen; Xie, Yunyan; Yuan, Bo; Zhang, Wei; Jiang, Xingyu

    2011-01-01

    Background Neurons are dynamically coupled with each other through neurite-mediated adhesion during development. Understanding the collective behavior of neurons in circuits is important for understanding neural development. While a number of genetic and activity-dependent factors regulating neuronal migration have been discovered on single cell level, systematic study of collective neuronal migration has been lacking. Various biological systems are shown to be self-organized, and it is not known if neural circuit assembly is self-organized. Besides, many of the molecular factors take effect through spatial patterns, and coupled biological systems exhibit emergent property in response to geometric constraints. How geometric constraints of the patterns regulate neuronal migration and circuit assembly of neurons within the patterns remains unexplored. Methodology/Principal Findings We established a two-dimensional model for studying collective neuronal migration of a circuit, with hippocampal neurons from embryonic rats on Matrigel-coated self-assembled monolayers (SAMs). When the neural circuit is subject to geometric constraints of a critical scale, we found that the collective behavior of neuronal migration is spatiotemporally coordinated. Neuronal somata that are evenly distributed upon adhesion tend to aggregate at the geometric center of the circuit, forming mono-clusters. Clustering formation is geometry-dependent, within a critical scale from 200 µm to approximately 500 µm. Finally, somata clustering is neuron-type specific, and glutamatergic and GABAergic neurons tend to aggregate homo-philically. Conclusions/Significance We demonstrate self-organization of neural circuits in response to geometric constraints through spatiotemporally coordinated neuronal migration, possibly via mechanical coupling. We found that such collective neuronal migration leads to somata clustering, and mono-cluster appears when the geometric constraints fall within a critical

  7. Selective Adsorption of CO2 from Light Gas Mixtures Using a Structurally Dynamic Porous Coordination Polymer**

    Energy Technology Data Exchange (ETDEWEB)

    Kristi L. Kauffman, Jeffrey T. Culp, Andrew J. Allen, Laura Espinal, Winnie Wong-Ng, Thomas D.

    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.

  8. Beyond Single-Wavelength SHG Measurements: Spectrally-Resolved SHG Studies of Tetraphosphonate Ester Coordination Polymers.

    Science.gov (United States)

    Zaręba, Jan K; Białek, Michał J; Janczak, Jan; Nyk, Marcin; Zoń, Jerzy; Samoć, Marek

    2015-11-16

    Powder second-harmonic generation (SHG) efficiencies are usually measured at single wavelengths. In the present work, we provide a proof of concept of spectrally resolved powder SHG measured for a newly obtained series of three non-centrosymmetric coordination polymers (CPs). CPs are constructed from tetrahedral linker-tetraphenylmethane-based tetraphosphonate octaethyl ester and cobalt(II) ions of mixed, octahedral (Oh), and tetrahedral (Td), geometries and different sets of donors (CoO6 vs CoX3O). Isostructurality of the obtained materials allowed for the determination of anion-dependent tunability of SHG optical spectra and their relationship with solid-state absorption spectra.

  9. Efficient fixation of CO2 by a zinc-coordinated conjugated microporous polymer.

    Science.gov (United States)

    Xie, Yong; Wang, Ting-Ting; Yang, Rui-Xia; Huang, Nian-Yu; Zou, Kun; Deng, Wei-Qiao

    2014-08-01

    Zinc-coordinated conjugated microporous polymers (Zn-CMPs), prepared by linking salen zinc and 1,3,5-triethynylbenzene, exhibit extraordinary activities (turnover frequencies of up to 11600 h(-1) ), broad substrate scope, and group tolerance for the synthesis of functional organic carbonates by coupling epoxides with CO2 at 120 °C and 3.0 MPa without the use of additional solvents. The catalytic activity of Zn-CMP is comparable to those of homogeneous catalysts and superior to those of other heterogeneous catalysts. This catalyst could be reused more than ten times without a significant decrease in performance.

  10. A New 3D Coordination Polymer of Bismuth with Nicotinic Acid N-Oxide

    Directory of Open Access Journals (Sweden)

    Farzin Marandi

    2013-01-01

    Full Text Available The new three-dimensional coordination polymer {[Bi(NNO2(NO3]·1.5H2O}n (1, NNO− = nicotinate N-oxide was synthesized and characterized by elemental analysis, IR and 1H-NMR spectroscopy, as well as single-crystal X-ray diffraction analysis. 1 crystallizes in the monoclinic space group C2/c. The crystal structure consists of a rectangular-shaped grid constructed with NNO linkers. Cavities of a diameter of 7.9–8.3 Å2 are filled with disordered water molecules. The thermal stability of the compound was evaluated by thermogravimetric analysis.

  11. Counter anion dependent gradual spin transition in a 1D cobalt(ii) coordination polymer.

    Science.gov (United States)

    Roy, Subhasis; Choubey, Somnath; Bhar, Kishalay; Sikdar, Nivedita; Costa, José Sánchez; Mitra, Partha; Ghosh, Barindra Kumar

    2015-05-07

    One Co(ii) SCO coordination polymer [Co(enbzpy)(μ1,5-dca)]n(PF6)n (·PF6) has been isolated and characterised structurally and magnetostructurally. The properties of ·PF6 are compared with the reported perchlorate analogue [Co(enbzpy)(μ1,5-dca)]n(ClO4)n (·ClO4). The gradual spin transition in ·PF6 in contrast to an abrupt spin transition with a hysteresis loop in ·ClO4 has been analysed in terms of structural factors.

  12. Synthesis and characterization of 1D iron(II) spin crossover coordination polymers with hysteresis.

    Science.gov (United States)

    Bauer, Wolfgang; Lochenie, Charles; Weber, Birgit

    2014-02-07

    Purposeful ligand design was used for the synthesis of eight new 1D iron(II) spin crossover coordination polymers aiming for cooperative spin transitions with hysteresis. The results from magnetic measurements and X-ray structure analysis show that the combination of rigid linkers and a hydrogen bond network between the 1D chains is a promising tool to reach this goal. Five of the eight new samples show a cooperative spin transition with hysteresis with up to 43 K wide hysteresis loops.

  13. A self-assembling polymer-bound rotaxane under thermodynamic control.

    Science.gov (United States)

    Johnstone, Ken D; Bampos, Nick; Sanders, Jeremy K M; Gunter, Maxwell J

    2003-06-21

    The thermodynamically controlled self-assembly of a neutral donor-acceptor rotaxane, stoppered via porphyrin coordination and bound to polystyrene beads is described, and the dynamic equilibrium between solid and solution phases has been examined by HR MAS nmr spectroscopy.

  14. π-Conjugated polymer anisotropic organogel nanofibrous assemblies for thermoresponsive photonic switches.

    Science.gov (United States)

    Narasimha, Karnati; Jayakannan, Manickam

    2014-11-12

    The present work demonstrates one of the first examples of π-conjugated photonic switches (or photonic wave plates) based on the tailor-made π-conjugated polymer anisotropic organogel. New semicrystalline segmented π-conjugated polymers are designed with rigid aromatic oligophenylenevinylene π-core and flexible alkyl chain along the polymer backbone. These polymers are found to be self-assembled as semicrystalline or amorphous with respect to the number of carbon atoms in the alkyl units. These semicrystalline polymers produce organogels having nanofibrous morphology of 20 nm thickness with length up to 5 μm. The polymer organogel is aligned in a narrow glass capillary, and this anisotropic gel device is further demonstrated as photonic switches. The glass capillary device behaves as typical λ/4 photonic wave plates upon the illumination of the plane polarized light. The λ/4 photonic switching ability is found to be maximum at θ = 45° angle under the cross polarizers. The orthogonal arrangements of the gel capillaries produce dark and bright spots as on-and-off optical switches. Thermoreversibility of the polymer organogel (also its xerogel) was exploited to construct thermoresponsive photonic switches for the temperature window starting from 25 to 160 °C. The organic photonic switch concept can be adapted to large number of other π-conjugated materials for optical communication and storage.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-01

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

  16. A Novel 3D Zn-La Heterometallic Coordination Polymer Involving in situ Glycinate Ligand Synthesis

    Institute of Scientific and Technical Information of China (English)

    SONG Wen-Donga; LI Shi-Jie; GUO Jian; TONG Shao-Wei; JI Li-Li; MIAO Dong-Liang; AN Jing-Bo; NG Seik Weng

    2012-01-01

    One novel 3D 3d-4f coordination polymer, [LaZn(glc)(ox)2(H20)2]n (1, glc = glycinate, ox = oxalate), was obtained by the in situ synthesis of glycinate from the reaction of tetrazole-l-acetic acid, sodium oxalate, zinc nitrate and lanthanide oxide in the presence of a trace quantity of nitric acid under hydrothermal conditions. Compound 1 is of monoclinic, space group P21/n with a = 0.99601(9), b = 1.14592(10), c = 1.19107(10) nm and β = 108.7150(10)°. 1 exhibits an unusual 3D heterometallic coordination framework constructed by heterometallic dinuclear LaZn subunits and mixed ox and glc linkers with a uninodal 6-connected vine {33.43.58.6} net.

  17. Hysteretic Spin Crossover in Two-Dimensional (2D) Hofmann-Type Coordination Polymers.

    Science.gov (United States)

    Liu, Wei; Wang, Lu; Su, Yu-Jun; Chen, Yan-Cong; Tucek, Jiri; Zboril, Radek; Ni, Zhao-Ping; Tong, Ming-Liang

    2015-09-08

    Three new two-dimensional (2D) Hofmann-type coordination polymers with general formula [Fe(3-NH2py)2M(CN)4] (3-NH2py = 3-aminopyridine, M = Ni (1), Pd (2), Pt (3)) have been synthesized. Magnetic susceptibility measurements show that they exhibited cooperative spin crossover (SCO) with remarkable hysteretic behaviors. Their hysteresis widths are 25, 37, and 30 K for 1-3, respectively. The single-crystal structure of 1 suggest that the pseudo-octahedral Fe sites are equatorially bridged by [M(CN)4](2-) to form 2D grids and axially coordinated by 3-NH2py ligands. The intermolecular interactions between layers (the offset face-to-face π···π interactions, hydrogen bonds, and weak N(amino)···Ni(II) contacts) together with the covalent bonds bridged by [M(CN)4](2-) units are responsible to the significant cooperativity.

  18. Polymer-mediated nanorod self-assembly predicted by dissipative particle dynamics simulations.

    Science.gov (United States)

    Khani, Shaghayegh; Jamali, Safa; Boromand, Arman; Hore, Michael J A; Maia, Joao

    2015-09-14

    Self-assembly of nanoparticles in polymer matrices is an interesting and growing subject in the field of nanoscience and technology. We report herein on modelling studies of the self-assembly and phase behavior of nanorods in a homopolymer matrix, with the specific goal of evaluating the role of deterministic entropic and enthalpic factors that control the aggregation/dispersion in such systems. Grafting polymer brushes from the nanorods is one approach to control/impact their self-assembly capabilities within a polymer matrix. From an energetic point of view, miscible interactions between the brush and the matrix are required for achieving a better dispersibility; however, grafting density and brush length are the two important parameters in dictating the morphology. Unlike in previous computational studies, the present Dissipative Particle Dynamics (DPD) simulation framework is able to both predict dispersion or aggregation of nanorods and determine the self-assembled structure, allowing for the determination of a phase diagram, which takes all of these factors into account. Three types of morphologies are predicted: dispersion, aggregation and partial aggregation. Moreover, favorable enthalpic interactions between the brush and the matrix are found to be essential for expanding the window for achieving a well-dispersed morphology. A three-dimensional phase diagram is mapped on which all the afore-mentioned parameters are taken into account. Additionally, in the case of immiscibility between brushes and the matrix, simulations predict the formation of some new and tunable structures.

  19. 1D coordination polymers with polychalcogenides as linkers between metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Kysliak, Oleksandr; Beck, Johannes, E-mail: j.beck@uni-bonn.de

    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

  20. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    Science.gov (United States)

    Vlassa, Mihaela; Bende, Attila

    2015-08-01

    Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet-triplet transition was studied in details and the corresponding spin-orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  1. Hybrid Materials Prepared from Polymers and Self-assembled Systems by Physical Processes

    Institute of Scientific and Technical Information of China (English)

    Jean-Michel; Guenet

    2007-01-01

    1 Results A new type of hybrid materails prepared from ternary systems polymer/bicopper organic complex/solvent is presented.Each binary system displays differing types of behaviour: The polymer solutions produce thermoreversible gels while the bicopper organic complex (designated as CuS8) forms randomly-dispersed,self-assembling threads in organic solvents (See Fig.1(a),(b)).Fig.1 The CuS8 and ips thermoreversible gels Thermoreversible gels possess a fibrillar morphology with a typical mesh size ra...

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yong Hong [Huaibei Normal Univ., Huaibei (China)

    2013-04-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Aslani, Alireza, E-mail: a.aslani110@yahoo.com [Nanobiotechnology Research Center, Baqiyatallah University Medical of Science, PO BOX 1994x81, Tehran (Iran, Islamic Republic of); Department of Chemistry, University of Lorestan, Lorestan-Khoramabad 68135-465 (Iran, Islamic Republic of); Musevi, Seyid Javad, E-mail: Erkin_musevi@hotmail.com [Department of Chemistry, Shahid Beheshti Technical and Vocational University, Urmia (Iran, Islamic Republic of); Şahin, Ertan, E-mail: Ertan@atauni.edu.tr [Department of Chemistry, Faculty of Science, Ataturk University, Erzurum 25240 (Turkey); Yilmaz, Veysel T., E-mail: vtyilmaz@uludag.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Uludag University, 16059 Bursa (Turkey)

    2014-11-01

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

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

    Science.gov (United States)

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

    2014-07-14

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

  5. Electrical bistability around room temperature in an unprecedented one-dimensional coordination magnetic polymer.

    Science.gov (United States)

    Amo-Ochoa, Pilar; Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martin, Avelino; Zamora, Félix

    2013-05-20

    The synthesis, crystal structure, and physical properties of an unprecedented one-dimensional (1D) coordination polymer containing [Fe2(S2C6H2Cl2)4](2-) entities bridged by dicationic [K2(μ-H2O)2(THF)4](2+) units are described. The magnetic properties show that the title compound presents pairwise Fe-Fe antiferromagnetic interactions that can be well reproduced with a S = 1/2 dimer model with an exchange coupling, J = -23 cm(-1). The electrical conductivity measurements show that the title compound is a semiconductor with an activation energy of about 290 meV and two different transitions, both with large hysteresis of about 60 and 30 K at 260-320 K and 350-380 K, respectively. These two transitions are assumed to be due to slight structural changes in the cation-anion interactions. Differential Scanning Calorimetry confirms the presence of both transitions. This compound represents the first sample of a coordination polymer showing electrical bistability.

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

    Directory of Open Access Journals (Sweden)

    Yann Garcia

    2011-10-01

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

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

    Science.gov (United States)

    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.

  8. One-dimensional coordination polymers of [Co3(dpa)4]2+ and [MF6]2- (M = ReIV, ZrIV and SnIV)

    DEFF Research Database (Denmark)

    Bulicanu, Vladimir; Pedersen, Kasper Steen; Rouzières, Mathieu;

    2015-01-01

    One-dimensional coordination polymers of alternating metal-metal bonded trinuclear [Co3(dpa)4]2+ (dpa = the anion of 2,2'-dipyridylamine) building blocks and [ReF6]2- (1), [ZrF6]2- (2) or [SnF6]2- (3) linkers have been self-assembled and crystallographically characterized. Magnetic measurements...

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen Jianshan; Sheng Tianlu; Hu Shengmin; Xiang Shengchang; Fu Ruibiao; Zhu Qilong [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Wu Xintao, E-mail: wxt@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2012-08-15

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

  10. Exploiting Fluorescent Polymers To Probe the Self-Assembly of Virus-like Particles

    DEFF Research Database (Denmark)

    Caden-Nava, Ruben D.; Hu, Yufang; Garmann, Rees F.

    2011-01-01

    The inside surfaces of the protein shells of many viruses are positively charged, thereby enhancing the self-assembly of capsid proteins around their (oppositely charged) RNA genome. These proteins have been shown to organize similarly around a variety of nonbiological, negatively charged, polymers......), and that the total charge on the PSS exceeds that of the capsid protein by as much as a factor of 9. Here, we extend studies of this kind to PSS molecules that are sufficiently small that two or more can be packaged into VLPs. The use of 38 kDa PSS polymers that have been fluorescently labeled with Rhodamine B...... than that of the capsid protein by as much as a factor of 2. VLPs of this kind provide a versatile model system for determining the principles underlying self-assembly of controlled numbers of cargo molecules in nanocontainers of increasing size....

  11. Virus-Assembled Flexible Electrode-Electrolyte Interfaces for Enhanced Polymer-Based Battery Applications

    Directory of Open Access Journals (Sweden)

    Ayan Ghosh

    2012-01-01

    Full Text Available High-aspect-ratio cobalt-oxide-coated Tobacco mosaic virus (TMV- assembled polytetrafluoroethylene (PTFE nonstick surfaces were integrated with a solvent-free polymer electrolyte to create an anode-electrolyte interface for use in lithium-ion batteries. The virus-assembled PTFE surfaces consisted primarily of cobalt oxide and were readily intercalated with a low-molecular-weight poly (ethylene oxide (PEO based diblock copolymer electrolyte to produce a solid anode-electrolyte system. The resulting polymer-coated virus-based system was then peeled from the PTFE backing to produce a flexible electrode-electrolyte component. Electrochemical studies indicated the virus-structured metal-oxide PEO-based interface was stable and displayed robust charge transfer kinetics. Combined, these studies demonstrate the development of a novel solid-state electrode architecture with a unique peelable and flexible processing attribute.

  12. Water-Soluble Conjugated Polymers: Self-Assembly and Biosensor Applications

    Science.gov (United States)

    Bazan, Guillermo

    2005-03-01

    Homogeneous assays can be designed which take advantage of the optical amplification of conjugated polymers and the self-assembly characteristic of aqueous polyelectrolytes. For example, a ssDNA sequence sensor comprises an aqueous solution containing a cationic water soluble conjugated polymer such as poly(9,9-bis(trimethylammonium)-hexyl)-fluorene phenylene) with a peptide nucleic acid (PNA) labeled with a dye (PNA-C*). Signal transduction is controlled by hybridization of the neutral PNA-C* probe and the negative ssDNA target, resulting in favorable electrostatic interactions between the hybrid complex and the cationic polymer. Distance requirements for Förster energy transfer are thus met only when ssDNA of complementary sequence to the PNA-C* probe is present. Signal amplification by the conjugated polymer provides fluorescein emission >25 times higher than that of the directly excited dye. Transduction by electrostatic interactions followed by energy transfer is a general strategy. Examples involving other biomolecular recognition events, such as DNA/DNA, RNA/protein and RNA/RNA, will also be provided. The mechanism of biosensing will be discussed, with special attention to the varying contributions of hydrophobic and electrostatic forces, polymer conformation, charge density, local concentration of C*s and tailored defect sites for aggregation-induced optical changes. Finally, the water solubility of these conjugated polymers opens possibilities for spin casting onto organic materials, without dissolving the underlying layers. This property is useful for fabricating multilayer organic optoelectronic devices by simple solution techniques.

  13. Ratiometric fluorescence detection of superoxide anion based on AuNPs-BSA@Tb/GMP nanoscale coordination polymers.

    Science.gov (United States)

    Liu, Nan; Hao, Juan; Cai, Keying; Zeng, Mulan; Huang, Zhenzhong; Chen, Lili; Peng, Bingxian; Li, Ping; Wang, Li; Song, Yonghai

    2017-08-03

    A novel ratiometric fluorescence nanosensor for superoxide anion (O2(•-) ) detection was designed with gold nanoparticles-bovine serum albumin (AuNPs-BSA)@terbium/guanosine monophosphate disodium (Tb/GMP) nanoscale coordination polymers (NCPs) (AuNPs-BSA@Tb/GMP NCPs). The abundant hydroxyl and amino groups of AuNPs-BSA acted as binding points for the self-assembly of Tb(3+) and GMP to form core-shell AuNPs-BSA@Tb/GMP NCP nanosensors. The obtained probe exhibited the characteristic fluorescence emission of both AuNPs-BSA and Tb/GMP NCPs. The AuNPs-BSA not only acted as a template to accelerate the growth of Tb/GMP NCPs, but also could be used as the reference fluorescence for the detection of O2(•-) . The resulting AuNPs-BSA@Tb/GMP NCP ratiometric fluorescence nanosensor for the detection of O2(•-) demonstrated high sensitivity and selectivity with a wide linear response range (14 nM-10 μM) and a low detection limit (4.7 nM). Copyright © 2017 John Wiley & Sons, Ltd.

  14. New oxalate-propagated layered Mn2+/Fe2+-4,4‧-sulfoyldiphthalhydrazidate coordination polymers

    Science.gov (United States)

    Jin, Juan; Yan, Wen-Fu; Yang, Qing-Feng; Yu, Xiao-Yang; Sun, Li-Xiang; Xu, Ji-Qing; Chen, Zi-Ao; Li, Chuan-Zhao

    2017-01-01

    Based on the hydrothermal in situ acylation reaction of 4,4‧-sulfoyldiphthalic anhydride (sdpha) with N2H4ṡH2O, two isostructural oxalate-propagated Mn2+/Fe2+-diacylhydrazidate coordination polymers, [M3(sdpth)2(ox)(H2O)2]ṡ2H2O (M2+ = Mn2+1, Fe2+2; sdpth = 4,4‧-sulfoyldiphthalhydrazidate, ox = oxalate), were obtained and characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. In both compounds, ox ligands act as the second linkers, extending the metal-diacylhydrazidate chains into a 2-D layer. Via Nsbnd H⋯O interactions, compounds 1 and 2 self-assemble into 3-D supramolecular networks. The magnetic analyses indicate that there are antiferromagnetic interactions between magnetic centers in compounds 1 and 2. The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution.

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

    Directory of Open Access Journals (Sweden)

    Takeshi Kawasaki

    2016-08-01

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

  16. Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim; Yager, Kevin G.; Yuan, Guangcui; Satija, Sushil K.; Durstock, Michael F.; Raghavan, Dharmaraj; Karim, Alamgir

    2016-03-04

    Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (EBD) and dielectric permittivity (εr) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher EBD over that of component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS-b-PMMA system show ~50% enhancement in EBD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in EBD is attributed to the “barrier effect”, where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in EBD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. This approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.

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

    Science.gov (United States)

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

    2016-10-01

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

  18. Engineering Functionalization in a Supramolecular Polymer: Hierarchical Self-Organization of Triply Orthogonal Non-covalent Interactions on a Supramolecular Coordination Complex Platform.

    Science.gov (United States)

    Zhou, Zhixuan; Yan, Xuzhou; Cook, Timothy R; Saha, Manik Lal; Stang, Peter J

    2016-01-27

    Here we present a method for the construction of functionalizable supramolecular polymers by controlling three orthogonal interactions within a single system: (i) coordination-driven self-assembly; (ii) H-bonding; and (iii) host-guest interactions between crown ether and dialkylammonium substrates. Three unique molecules constitute the supramolecular construct, including a 2-ureido-4-pyrimidinone (UPy)-functionalized rigid dipyridyl donor and a complementary organoplatinum(II) acceptor decorated with a crown ether moiety that provide the basis for self-assembly and polymerization. The final host-guest interaction is demonstrated by using one of two dialkylammonium molecules containing fluorophores that bind to the benzo-21-crown-7 (B21C7) groups of the acceptors, providing a spectroscopic handle to evaluate the functionalization. An initial coordination-driven self-assembly yields hexagonal metallacycles with alternating UPy and B21C7 groups at their vertices. The assembly does not interfere with H-bonding between the UPy groups, which link the discrete metallacycles into a supramolecular network, leaving the B21C7 groups free for functionalization via host-guest chemistry. The resultant network results in a cavity-cored metallogel at high concentrations or upon solvent swelling. The light-emitting properties of the dialkylammonium substrates were transferred to the network upon host-guest binding. This method is compatible with any dialkylammonium substrate that does not disrupt coordination nor H-bonding, and thus, the unification of these three orthogonal interactions represents a simple yet highly efficient strategy to obtain supramolecular polymeric materials with desirable functionality.

  19. Self-assembly of octapod-shaped colloidal nanocrystals into a hexagonal ballerina network embedded in a thin polymer film

    NARCIS (Netherlands)

    Arciniegas, Milena P.; Kim, Mee R.; De Graaf, Joost|info:eu-repo/dai/nl/314838961; Brescia, Rosaria; Marras, Sergio; Miszta, Karol; Dijkstra, Marjolein|info:eu-repo/dai/nl/123538807; Van Roij, René|info:eu-repo/dai/nl/152978984; Manna, Liberato

    2014-01-01

    Nanoparticles with unconventional shapes may exhibit different types of assembly architectures that depend critically on the environmental conditions under which they are formed. Here, we demonstrate how the presence of polymer (polymethyl methacrylate, PMMA) molecules in a solution, in which

  20. Polymer-Carbon Nanotube Composite Films at the Oil/Water Interface: Assembly and Properties

    Science.gov (United States)

    Hoagland, David; Feng, Tao; Russell, Thomas P.

    2015-03-01

    Efficient carbon nanotube assembly at the oil/water interface was achieved by dissolving cationic polymers in the oil phase and oxidized nanotubes in the water phase, the two components spontaneously forming salt bridges to produce a composite interfacial film of nanoscopic thickness. As seen by pendant drop tensiometry, parameters such as carbon nanotube and polymer concentration, pH, polymer molecular weight, and degree of nanotube oxidation all affect assembly strongly, with measured trends to be described and explained. The frequency-dependent elastic and viscous moduli of films in dilation were characterized by interfacial pendant drop rheology. Structural (fast, minutes) and adsorption/desorption (slow, tens of minutes) relaxations were both noted, and at frequencies intermediate to the two, almost insensitive to assembly parameters, the films displayed expected behaviors for 2D critical gels, i.e., at the crossover between fluid and solid. Tan(delta) was frequency-independent over one to two decades of frequency, and the modulus of linear stress relaxation was a power law in time. Films wrinkled by larger (nonlinear) strains recovered over the structural relaxation time. Support: NSF-sponsored UMass MRSEC and the US DoE Office of Basic Energy Science through Contract DE-FG02-04ER46126.

  1. Enhanced performance of blue polymer light-emitting diodes by a self-assembled thin interlayer.

    Science.gov (United States)

    Kim, Yun Ho; Lee, Wonjoo; Cai, Gangri; Baek, Su Jin; Han, Sung-Hwan; Lee, Soo-Hyoung

    2008-09-01

    High efficiency and long lifetime, blue polymer light-emitting diodes were obtained by adding a thin interlayer, which was fabricated by a layer-by-layer self-assembly technique between poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) hole transporting and emissive polymer layers in the device configuration of indium tin oxide (ITO)/PEDOT:PSS (65 nm)/interlayer (10-30 nm)/emissive polymer (70 nm)/BaF2 (2 nm)/Ca (50 nm)/Al (300 nm). The interlayer, (PPV/PSS)n, consisted of self-assembled multilayers of the conjugated polymer, poly (p-phenylenevinylene) (PPV), and the polyelectrolyte, poly (styrene sulfonic acid) (PSS). Electroluminescence (EL) characteristics such as luminescence and current efficiency of the devices were enhanced by the addition of the interlayer. Furthermore, the devices with interlayer showed longer lifetime than those without interlayer. The maximum device performance was obtained from the device with (PPV/PSS)3 interlayer.

  2. Anisotropic Self-Assembly of Supramolecular Polymers and Plasmonic Nanoparticles at the Liquid-Liquid Interface.

    Science.gov (United States)

    Armao Iv, Joseph J; Nyrkova, Irina; Fuks, Gad; Osypenko, Artem; Maaloum, Mounir; Moulin, Emilie; Arenal, Raul; Gavat, Odile; Semenov, Alexander; Giuseppone, Nicolas

    2017-02-15

    The study of supramolecular polymers in the bulk, in diluted solution, and at the solid-liquid interface has recently become a major topic of interest, going from fundamental aspects to applications in materials science. However, examples of supramolecular polymers at the liquid-liquid interface are mostly unexplored. Here, we describe the supramolecular polymerization of triarylamine molecules and their light-triggered organization at a chloroform-water interface. The resulting interfacial nematic layer of these 1D supramolecular polymers is further used as a template for the precise alignment of spherical gold nanoparticles coming from the water phase. These hybrid thin films are spontaneously formed in a single process, without chemical prefunctionalization of the metallic nanoparticles, and their ordering is improved by centrifugation. The resulting polymer chains and strings of nanoparticles can be co-aligned with high anisotropy over very large distances. By using a combination of experimental and theoretical investigations, we decipher the full sequence of this oriented self-assembly process. In such a highly anisotropic configuration, electron energy loss spectroscopy reveals that the self-assembled nanoparticles behave as plasmonic waveguides.

  3. Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates

    KAUST Repository

    Zhao, Kui

    2016-07-13

    We demonstrate that local and long range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the dielectric surface with solution-state disentanglement and pre-aggregation of P3HT in a theta solvent, leading to a very significant enhancement of the field effect carrier mobility. The pre-aggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of pre-aggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of pre-aggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to un-aggregated polymer chains. Additional investigations reveal the combined pre-aggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known pre-aggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

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

    Science.gov (United States)

    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.

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

    KAUST Repository

    Mugnaini, Verónica

    2013-01-01

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

  6. HTP-1 coordinates synaptonemal complex assembly with homolog alignment during meiosis in C. elegans.

    Science.gov (United States)

    Couteau, Florence; Zetka, Monique

    2005-11-15

    During meiosis, the mechanisms responsible for homolog alignment, synapsis, and recombination are precisely coordinated to culminate in the formation of crossovers capable of directing accurate chromosome segregation. An outstanding question is how the cell ensures that the structural hallmark of meiosis, the synaptonemal complex (SC), forms only between aligned pairs of homologous chromosomes. In the present study, we find that two closely related members of the him-3 gene family in Caenorhabditis elegans function as regulators of synapsis. HTP-1 functionally couples homolog alignment to its stabilization by synapsis by preventing the association of SC components with unaligned and immature chromosome axes; in the absence of the protein, nonhomologous contacts between chromosomes are inappropriately stabilized, resulting in extensive nonhomologous synapsis and a drastic decline in chiasma formation. In the absence of both HTP-1 and HTP-2, synapsis is abrogated per se and the early association of SC components with chromosomes observed in htp-1 mutants does not occur, suggesting a function for the proteins in licensing SC assembly. Furthermore, our results suggest that early steps of recombination occur in a narrow window of opportunity in early prophase that ends with SC assembly, resulting in a mechanistic coupling of the two processes to promote crossing over.

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

    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.

  9. Metal-Organic Coordination Network Thin Film by Surface-Induced Assembly.

    Science.gov (United States)

    Laokroekkiat, Salinthip; Hara, Mitsuo; Nagano, Shusaku; Nagao, Yuki

    2016-07-01

    The growth of metal-organic coordination network thin films on surfaces has been pursued extensively and intensively to manipulate the molecular arrangement. For this study, the oriented multilayer thin films based on porphyrinic nanoarchitecture were synthesized toward metal-organic coordination networks using surface-induced assembly (SIA). Nanoscale molecular thin films were prepared at room temperature using cobalt(II) ion and porphyrin building blocks as precursors. Stepwise growth with a highly uniform layer was characterized using UV-vis, AFM, IR, and XPS studies. The grazing incidence small-angle X-ray scattering and X-ray reflectivity results remarkably suggested a periodic structure in in-plane direction with constant and high mass density (ca. 1.5 g/cm(3)) throughout the multilayer formation. We propose that orientation of the porphyrin macrocycle plane with a hexagonal packed model by single anchoring mode was tilted approximately 60° with respect to the surface substrate. It is noteworthy that the well-organized structure of porphyrin-based macrocyclic framework on the amine-terminated surface substrate can be achieved efficiently using a simple SIA approach under mild synthetic conditions. The synthesized thin film provides a different structure from that obtained using bulk synthesis. This result suggests that the SIA technique can control not only the film thickness but also the structural arrangement on the surface. This report of our research provides insight into the ordered porphyrin-based metal-organic coordination network thin films, which opens up opportunities for exploration of unique thin film materials for diverse applications.

  10. Fabrication of composite polymer foam films at the liquid/liquid interface through emulsion-directed assembly and adsorption processes.

    Science.gov (United States)

    Geng, Yuanyuan; Liu, Mei; Tong, Kun; Xu, Jian; Lee, Yong-Ill; Hao, Jingcheng; Liu, Hong-Guo

    2014-03-04

    The foam films of polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-b-PAA-b-PS) doped with Cd(II) or Pb(II) species were fabricated at the planar liquid/liquid interfaces between a DMF/chloroform (v/v: 1/1) solution of the polymer and aqueous solutions containing cadmium acetate or lead acetate at ambient temperature. Optical microscopic observation shows the thin film is uniform on a larger length scale. Transmission electron microscopic (TEM) investigations reveal that the foam films are made up of microcapsules with the size of several hundreds of nanometers to micrometers. The walls of the microcapsules have a layered structure decorating with nanofibers and hollow nanospheres, where numerous inorganic fine nanoparticles are dispersed homogeneously. The film formation is a result of emulsion droplet-templated assembly and adsorption of the formed microcapsules at the planar liquid/liquid interface. Because of the miscibility of DMF with chloroform and water, DMF migrates to the aqueous phase while water migrates to the organic phase across the interface, resulting in the formation of a W/O emulsion, as revealed by optical microscopic observation, freeze fracture transmission electron microscopic (FF-TEM) observation, and dynamic laser scattering (DLS) investigation. The triblock copolymer molecules and the inorganic species adsorb and self-assemble around the emulsion drops, leading to the formation of the composite microcapsules. X-ray photoelectron spectroscopic (XPS) and FTIR spectroscopic results indicate that two kinds of Cd(II) or Pb(II) species, metal oxide or hydroxide, resulting from the hydrolysis of the metal ions and the coordinated metal ions to the carboxyl groups coexist in the formed thin films, which transform to metal sulfide completely after treating with hydrogen sulfide to get metal sulfide nanoparticle-doped polymer thin films.

  11. A new three-dimensional manganese(II) coordination polymer based on the 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene ligand.

    Science.gov (United States)

    Lu, Xin Hua; Zhong, Kai Long

    2016-11-01

    The self-assembly of coordination polymers and the crystal engineering of metal-organic coordination frameworks have attracted great interest, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic-organic hybrid materials through metal-ligand coordination and hydrogen-bonding interactions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional Mn(II) coordination polymer based on 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene, namely poly[(ethane-1,2-diol-κO)(μ-sulfato-κ(2)O:O'){μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ(3)N:N':N''}manganese(II)], [Mn(SO4)(C18H18N6)(C2H6O2)]n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent Mn(II) centres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring Mn(II) centres to generate a two-dimensional layered structure running parallel to the ab plane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with 3,4,6-c topology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol molecules, and further decomposition occurred at 648 K.

  12. Thermosensitive Polymer Nanocontainers Prepared by Self-Assembly of Block Copolymers

    Institute of Scientific and Technical Information of China (English)

    Chen Xiangrong; Ding Xiaobing; Zheng Zhaohui; Peng Yuxing

    2004-01-01

    In recent years, considerable effort has been devoted to the preparation of polymer nanocontainers because of their unique advantages. Compared to polymer microspheres or micelles,polymer nanocontainers are hollow-sphere structures and can encapsulate large quantities of guest molecules or large-sized guests within the "empty" core domain. Compared to polymer vesicles,polymer nanocontainers have enough mechanical stability to prevent them from structure changes due to covalent or ionic interactions responsible for their formation. Therefore, polymer nanocontainers have many potential applications such as confined reaction vesicles, drug carriers,protective shells for cells or enzymes, artificial cells and so on. However, most of polymer nanocontainers reported by now, load and release guest molecules from their interior only through diffuse mechanism. It is rather difficult to control intelligently the process based on demands. In order to solve this problem, one promising strategy is to design intelligent polymer nanocontainers.They can undergo reversible structural transitions from a closed to an open state with the help of external stimuli.In this paper, we report on our preliminary study of the thermosensitive polymer nanocontainers formed by self-assembly of the block copolymers PCEMA-b-PNIPAM and sequent photo-crosslinking of PCEMA shells.Block copolymers PCEMA-b-PNIPAM were prepared by reacting PHEMA-b-PNIPAM with excess cinnamoyl chloride in pyridine at room temperature, where PHEMA-b-PNIPAM was prepared by reacting succinimidyl ester of PHEMA-COOH with PNIPAAm-NH2, similar to the method of the literature. The block copolymers were characterized by FTIR and 1H-NMR and GPC.To obtain polymer vesicles, deionized water, as a precipitant, was added at a rate of 0.3wt%/10s with vigorous stirring to the PCEMA-b-PNIPAM solution in THE After the formation of polymer vesicles, more water was added until the water content reached ca.50wt%. The hollow structure of the

  13. Self-assembling semiconducting polymers--rods and gels from electronic materials.

    Science.gov (United States)

    Clark, Andrew P-Z; Shi, Chenjun; Ng, Benny C; Wilking, James N; Ayzner, Alexander L; Stieg, Adam Z; Schwartz, Benjamin J; Mason, Thomas G; Rubin, Yves; Tolbert, Sarah H

    2013-02-26

    In an effort to favor the formation of straight polymer chains without crystalline grain boundaries, we have synthesized an amphiphilic conjugated polyelectrolyte, poly(fluorene-alt-thiophene) (PFT), which self-assembles in aqueous solutions to form cylindrical micelles. In contrast to many diblock copolymer assemblies, the semiconducting backbone runs parallel, not perpendicular, to the long axis of the cylindrical micelle. Solution-phase micelle formation is observed by X-ray and visible light scattering. The micelles can be cast as thin films, and the cylindrical morphology is preserved in the solid state. The effects of self-assembly are also observed through spectral shifts in optical absorption and photoluminescence. Solutions of higher-molecular-weight PFT micelles form gel networks at sufficiently high aqueous concentrations. Rheological characterization of the PFT gels reveals solid-like behavior and strain hardening below the yield point, properties similar to those found in entangled gels formed from surfactant-based micelles. Finally, electrical measurements on diode test structures indicate that, despite a complete lack of crystallinity in these self-assembled polymers, they effectively conduct electricity.

  14. Influence of coupling agent's self-assembly upon performance of polymer coated FBG pressure sensors

    Institute of Scientific and Technical Information of China (English)

    ZHOU Hong; QIAO Xue-guang; SHAO-Jun; WANG Hong-liang; FENG De-quan

    2006-01-01

    @@ Based on super-molecule self-assembly and entropy-driven self-assembly mechanisms,the coupling agent was evolved into colloid spheres with average diameter of 2-2.3 μm on the fiber Bragg grating (FBG) with silicon substrate,and the coupling mechanism among polymer,coupling agent and FBG was analyzed.The polymer coated FBG pressure sensors was capsulated by uniform coupling mode and self-assembly coupling mode of the coupling agent respectively,and their performance parameters were tested.It was shown,adopting the self-assembly coating of coupling agent and with the same other capsulated technologies,that the measuring range of the sensor expanded from 0.6 MPa to 1.6 MPa,the repeated times for coupling failure increased from 54 to 125 times and the pressure sensitivity coefficient enhanced from 1.09 to 2.98.By controlling the diameter of the spheres and the line density,the measuring range and the sensitivity of the FBG pressure sensors can be obviously improved.

  15. The new one-dimensional coordination polymer catena-poly[[diaquasodium(I)]-μ-oxalato-[diaquairon(III)]-μ-oxalato].

    Science.gov (United States)

    Benhacine, Mohamed Al Amine; Hamadène, Malika; Bouacida, Sofiane; Merazig, Hocine

    2016-03-01

    The oxalate dianion is one of the most studied ligands and is capable of bridging two or more metal centres and creating inorganic polymers based on the assembly of metal polyhedra with a wide variety of one-, two- or three-dimensional extended structures. Yellow single crystals of a new mixed-metal oxalate, namely catena-poly[[diaquasodium(I)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')-[diaquairon(III)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')], [NaFe(C2O4)2(H2O)4]n, have been synthesized and the crystal structure elucidated by X-ray diffraction analysis. The compound crystallizes in the noncentrosymmetric space group I41 (Z = 4). The asymmetric unit contains one Na(I) and one Fe(III) atom lying on a fourfold symmetry axis, one μ2-bridging oxalate ligand and two aqua ligands. Each metal atom is surrounded by two chelating oxalate ligands and two equivalent water molecules. The structure consists of infinite one-dimensional chains of alternating FeO4(H2OW1)2 and NaO4(H2OW2)2 octahedra, bridged by oxalate ligands, parallel to the [100] and [010] directions, respectively. Because of the cis configuration and the μ2-coordination mode of the oxalate ligands, the chains run in a zigzag manner. This arrangement facilitates the formation of hydrogen bonds between neighbouring chains involving the H2O and oxalate ligands, leading to a two-dimensional framework. The structure of this new one-dimensional coordination polymer is shown to be unique among the A(I)M(III)(C2O4)2(H2O)n series. In addition, the absorption bands in the IR and UV-Visible regions and their assignments are in good agreement with the local symmetry of the oxalate ligand and the irregular environment of iron(III). The final product of the thermal decomposition of this precursor is the well-known ternary oxide NaFeO2.

  16. Leucine zipper motif inspiration: a two-dimensional leucine Velcro-like array in peptide coordination polymers generates hydrophobicity.

    Science.gov (United States)

    Rodríguez-Hermida, Sabina; Evangelio, Emi; Rubio-Martínez, Marta; Imaz, Inhar; Verdaguer, Albert; Juanhuix, Jordi; Maspoch, Daniel

    2017-08-29

    Here, we show that the well-known hydrophobic leucine (Leu) zipper motif (also known as the coiled-coil or Leu scissors motif), typically found in proteins, can be used as a source of inspiration in coordination polymers built from Leu-containing dipeptides or tripeptides. We demonstrate that this motif can be extended to form Velcro-like layers of Leu, and that the hydrophobicity of these layers is transferred to coordination polymers, thereby enabling the development of a new type of hydrophobic materials.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-15

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

  18. Morphological Studies on Sn-O Coordination Driving Self-assembly of Well-defined Organotin-containing Block Copolymers

    Institute of Scientific and Technical Information of China (English)

    Jian Jiang; Wei Yan; Ling-yan Liu; Wei-xing Chang; Jing Li

    2014-01-01

    A tin-oxygen coordination driving self-assembly was developed in the block copolymers containing organotin,which were prepared by the radical addition-fraction transfer (RAFT) method and characterized by the gel-permeation chromatography (GPC) and 1H-NMR.And the self-assemblies of these block copolymers with various chain length ratios in the different concenaations in CHCl3 were stable according to the results of DLS and TEM.Additionally,it was also given an insight investigation on the regulation of self-assembly of the block copolymers by adding dibutyltin dichloride and a possible mechanism was proposed.

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

    Directory of Open Access Journals (Sweden)

    Eon S. Burkett

    2014-12-01

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

  20. Coordination polymer core/shell structures: Preparation and up/down-conversion luminescence.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-05

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

  3. Trapping of a spatial transient state during the framework transformation of a porous coordination polymer.

    Science.gov (United States)

    Kondo, Mio; Furukawa, Shuhei; Hirai, Kenji; Tsuruoka, Takaaki; Reboul, Julien; Uehara, Hiromitsu; Diring, Stéphane; Sakata, Yoko; Sakata, Osami; Kitagawa, Susumu

    2014-04-01

    Structural transformability accompanied by molecular accommodation is a distinguished feature of porous coordination polymers (PCPs) among porous materials. Conventional X-ray crystallography allows for the determination of each structural phase emerged during transformation. However, the propagation mechanism of transformation through an entire crystal still remains in question. Here we elucidate the structural nature of the spatial transient state, in which two different but correlated framework structures, an original phase and a deformed phase, simultaneously exist in one crystal. The deformed phase is distinctively generated only at the crystal surface region by introducing large guest molecules, while the remaining part of crystal containing small molecules maintains the original phase. By means of grazing incidence diffraction techniques we determine that the framework is sheared with sharing one edge of the original primitive cubic structure, leading to the formation of crystal domains with four mirror image relationships.

  4. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    Science.gov (United States)

    Rood, Jeffrey A; Huttenstine, Ashley L; Schmidt, Zachery A; White, Michael R; Oliver, Allen G

    2014-06-01

    Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF is N,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT-IR and (1)H NMR spectroscopy and elemental analyses.

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

    Science.gov (United States)

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

    2017-01-01

    We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu2+ coordination polymers with different dimensionality, namely, 1D [Cu2(5-tza)2(1,10-phenanthroline)2(NO3)2] (1), 2D [Cu(5-tza)2(MeOH)2] (2), and 3D [Cu(5-tza)2]·H2O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza)2]·1.5H2O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air.

  6. Synthesis and Characterization of Metal-B-diketonate Coordination Complexes and Polymers

    Directory of Open Access Journals (Sweden)

    Mohammed A. Al-Anber

    2013-10-01

    Full Text Available A mononuclear [M(tba2(H2O2] (3: M = Mn, 4: M = Ni, 5: M = Zn; tba = deprotonated of 1 complexes have been prepared by the reaction of 3-benzoyl-1.1.1-trifluoro-acetone (H-tba: 1 with M(OAc2.nH2O (M = Mn, Ni, Zn; OAc = O2CMe in a 2:1 molar ratio. Complexes 3 - 5 can be extended to form a coordination polymers of general formula [M(tba2(4,4'-bipy]n (6: M = Mn, 7: M = Ni, 8: M = Zn; tba = 3-benzoyl-1.1.1-trifluoro-acetone; 4,4'-bipy = 4,4’-bipyridine by bridging the central metal atom with 4,4’-bipyridine (4,4'-bipy. The reaction progress was controlled via FTIR, UV-Vis spectroscopy and elemental analysis.

  7. Flexible Two-Dimensional Square-Grid Coordination Polymers: Structures and Functions

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    Cătălin M. Jureschi

    2015-01-01

    Full Text Available We have investigated the suitability of using the 1D spin crossover coordination polymer [Fe(4-(2’-hydroxyethyl-1,2,4-triazole3]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.

  9. Flexible Two-Dimensional Square-Grid Coordination Polymers: Structures and Functions

    Directory of Open Access Journals (Sweden)

    Hiroshi Kajiro

    2010-09-01

    Full Text Available 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.

  10. Extended structures of two coordination polymers based on 1,10-phenanthroline derivatives:Preparation, structural characterization and properties

    Indian Academy of Sciences (India)

    Yan-Ju Huang; Ya-Ru Pan; Gang Du; Yi-Xin Cao

    2016-03-01

    In this paper,we report two coordination polymers, [Cd(Medpq)(SO4) (H2O)2]n (1)and {[Mn(Medpq)(QUI)H2O]·H2O}n (2) (H2QUI=2,3-pyridinedicarboxylic acid,Medpq=2-methyldipyrido[3,2-f:2,3-h]quinoxaline) by hydrothermal processing and structural characterization by elemental analysis,thermogravimetric analysis and single-crystal X-ray diffraction. The coordination polymers and 2 have 1D chains formed via coordination bonds, and unique two-dimensional supramolecular structures are further formed due to π-π stacking interactions. The results reveal that the coordination preferences ofmetal ions play a critical role in the framework construction of the two coordination polymers. Meanwhile,natural bond orbital (NBO) analysis was performed by the PBE0/LANL2DZ method in Gaussian 09 program.The calculated results show the obvious covalent interaction between the coordinated atoms and metal ions.

  11. Carboxyl group (-CO2 H) functionalized coordination polymer nanoparticles as efficient platforms for drug delivery.

    Science.gov (United States)

    Novio, Fernando; Lorenzo, Julia; Nador, Fabiana; Wnuk, Karolina; Ruiz-Molina, Daniel

    2014-11-17

    Functionalization of nanoparticles can significantly influence their properties and potential applications. Although researchers can now functionalize metal, metal oxide, and organic polymer nanoparticles with a high degree of precision, controlled surface functionalization of nanoscale coordination polymer particles (CPPs) has remained a significant challenge. The lack of methodology is perhaps one of the greatest roadblocks to the advancement of CPPs into high added-value drug delivery applications. Here, we report having achieved this goal through a stepwise formation and functionalization protocol. We fabricated robust nanoparticles with enhanced thermal and colloidal stabilities by incorporation of carboxyl groups and these surface carboxyl groups could be subsequently functionalized through well-known peptide coupling reactions. The set of chemistries that we employed as proof-of-concept enabled a plethora of new functional improvements for the application of CPPs as drug delivery carriers, including enhanced colloidal stabilities and the incorporation of additional functional groups such as polyethylene glycol (PEG) or fluorescent dyes that enabled tracking of their cellular uptake. Finally, we ascertained the cytotoxicity of the new CPP nanoparticles loaded with camptothecin to human breast adenocarcinoma (MCF-7). Efflux measurements show that the encapsulation of camptothecin enhances the potency of the drug 6.5-fold and increases the drug retention within the cell.

  12. Structure and magnetic properties of heterometallic coordination carboxylate polymers with cobalt and lithium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Evstifeev, I. E.; Kiskin, M. A., E-mail: mkiskin@igic.ras.ru [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation); Bogomyakov, A. S. [Russian Academy of Sciences, International Tomography Center, Siberian Branch (Russian Federation); Sidorov, A. A.; Novotortsev, V. M.; Eremenko, I. L. [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation)

    2011-09-15

    Reactions between lithium pivalate and cobalt coordination polymers [Co{sub 5}(OH{sub 2})(OH)(Piv){sub 9})L{sup 1}){sub 4}]{sub n} (I) and [Co{sub 2}(OH{sub 2})(Piv){sub 4}(L{sup 2}){sub 2}]{sub n} (II), where Piv-is the pivalate anion, L{sup 1} is pyrazine, and L{sup 2} is pyrimidine, result in new heterometallic polymers {l_brace}[Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 1}){sub 2}]{sub 2}MeCN{r_brace}{sub n} (III), {l_brace}[Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 2})]{sub 0.5}MeCN{r_brace}{sub n} (IV), and [Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 2}){sub 2}]{sub n} (V). The resulting compounds contain tetra-nuclear {l_brace}Li{sub 2}Co{sub 2}(Piv){sub 6}{r_brace} fragments connected by neutral bridging ligands (pyrazine or pyrimidine) into layer structures. Crystal structures III-V are determined, and the magnetic properties of III and IV are studied.

  13. Synthesis and characterization of two one-dimensional lanthanide coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Yin Mingcai; Sun Jutang

    2004-11-03

    Two lanthanide coordination polymers [Eu(H{sub 2}sal)(Hsal)(sal){center_dot}H{sub 2}O]{sub n} (1) and {l_brace}[Tb(FUR){sub 3}(H{sub 2}O){sub 2}]{center_dot}DMF{r_brace}{sub n} (2) (H{sub 2}sal, salicylic acid; Hsal{sup -}, o-HOC{sub 6}H{sub 4}CO{sub 2}{sup -}; HFUR, {alpha}-furancarboxylic acid; DMF, N,N-dimethylformamide) were synthesized and characterized by elemental analysis, TG, IR, and luminescence spectra. The crystal structures were determined by X-ray single crystal analysis. Both complexes are one-dimensional polymers. Probably the luminescence quenching of complex 1 is assigned to its special one-dimensional ribbon structure. The vibration energy level caused by the one-dimensional ribbon and located between {sup 5}D{sub 0} and {sup 7}F{sub j} maybe is the main reason. Complex 2 displays intense green luminescence under the excitation of UV light. The emission bands at 486, 541, 584, and 618 nm are attributed to the characteristic {sup 5}D{sub 4}{yields}{sup 7}F{sub j} (j = 6, 5, 4, 3) transitions of Tb(III) ions, respectively.

  14. Solvent-dependent self-assembly and ordering in slow-drying semi-crystalline conjugated polymer solutions

    KAUST Repository

    Zhao, Kui

    2015-09-07

    The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport and optoelectronic properties. Yet, to date the vast majority of studies have focused on the fast solution process itself, with studies of slower intrinsic molecular self-assembly in formulations lagging behind. Here we have investigated molecular self-assembly during spontaneous organization and uncovered how changes in formulation influence the microstructure, morphology and transport properties of conjugated polymer thin films. Our results suggest that the polymer-solvent interaction is the key factor for the molecular self-assembly and changes in macroscopic charge transport, which is in contrast with most solution processes, such as spin-coating and blade coating, where solvent drying kinetics dominates the aggregation and crystallization processes. Energetically favourable interactions between the polymer and its solvent are shown to cause chain expansion, resulting in a large hydrodynamic volume and few chain entanglements in solution. This provides molecular freedom for self-assembly and is shown to greatly enhance the local and long range order of the polymer, intra-chain backbone planarity and crystallite size. These improvements, in turn, are shown to endow the conjugated polymer with high carrier transport, as demonstrated by organic thin film transistors.

  15. The influence of self-assembly behavior of nanoparticles on the dielectric polymer composites

    Directory of Open Access Journals (Sweden)

    Xin Lu

    2013-11-01

    Full Text Available To clearify the influence of the distribution of the conductive nanoparticles on the dielectric properties of the corresponding polymer composites, the microstructure and dielectric character of the composites based on the oleic acid modified ferroferric oxide and polyvinylidene fluoride (PVDF polymer have been studied experimentally. It is found that these composites exhibit a normal percolative phase transition over the filler content from insulator to conductor, consistent with the classical percolation theory. However, when the percentage of fillers is at a certain value which is below the percolation threshold, these nanoparticles can assemble into a special porous structure in the PVDF matrix, associated with the enhancement of dielectric constant at low frequency. In addition, the controllable dispersion of conducting nanoparticles in a polymer matrix can prevent premature agglomeration at low filling fractions and avoid the appearance of anomalously early percolation. Therefore, the self-assembly behavior of nanoparticles can be beneficial to preparation of the high dielectric constant and low loss composites for the application of electric energy storage.

  16. The influence of self-assembly behavior of nanoparticles on the dielectric polymer composites

    Science.gov (United States)

    Lu, Xin; Li, Weiping; Wang, Tingting; Jiang, Long; Luo, Laihui; Hua, Dayin; Zhu, Yuejin

    2013-11-01

    To clearify the influence of the distribution of the conductive nanoparticles on the dielectric properties of the corresponding polymer composites, the microstructure and dielectric character of the composites based on the oleic acid modified ferroferric oxide and polyvinylidene fluoride (PVDF) polymer have been studied experimentally. It is found that these composites exhibit a normal percolative phase transition over the filler content from insulator to conductor, consistent with the classical percolation theory. However, when the percentage of fillers is at a certain value which is below the percolation threshold, these nanoparticles can assemble into a special porous structure in the PVDF matrix, associated with the enhancement of dielectric constant at low frequency. In addition, the controllable dispersion of conducting nanoparticles in a polymer matrix can prevent premature agglomeration at low filling fractions and avoid the appearance of anomalously early percolation. Therefore, the self-assembly behavior of nanoparticles can be beneficial to preparation of the high dielectric constant and low loss composites for the application of electric energy storage.

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

    Science.gov (United States)

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

    2016-01-04

    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.

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

    Science.gov (United States)

    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.

  19. Hydrothermal Synthesis, Crystal Structure, Spectrum and Electrochemical Analysis of the Copper(Ⅱ) Coordination Polymer

    Institute of Scientific and Technical Information of China (English)

    LI Chang-Hong; LI Wei; LI Yu-Lin; KUANG Yun-Fei

    2012-01-01

    The three-dimensional framework copper(Ⅱ) coordination polymer with basic copper carbonate and 3-(pyridin-2-yl)-1,2,4-triazole has been hydrothermally synthesized. It crystallizes in monoclinic space group P21/c, with a = 1.20860(3), b = 1.29581(2), c = 1.67863(3) nm, β = 116.0280(2)°, C21H12Cu3N12, Mr = 623.05, V = 2.36230(9) nm3, Dc = 1.752 g/cm3, Z = 4, F(000) = 1236, GOOF = 1.037, the final R = 0.0408 and wR = 0.1141. Every unit cell contains three copper atoms and three 3-(pyridin-2-yl)-1,2,4-triazole ligands. Every central Cu(Ⅱ) ion is coordinated by four nitrogen atoms of the 3-(pyridin-2-yl)-1,2,4-triazole ligands, forming a distorted tetrahedron. The title complex exhibits an intense photoluminescence at room temperature with the maximum emission at 392 nm. The cyclic voltametric behavior of the complex shows that the electron transfer in electrolysis reaction is irreversible.

  20. Drying-Mediated Self-Assembly of Highly Ordered Complex Structures: From Polymers to Nanoparticles

    Science.gov (United States)

    Lin, Zhiqun

    2009-03-01

    Drying of a sessile drop containing nonvolatile solutes readily self-assembles into a number of concentric ``coffee rings'' by repetitive ``stick-slip'' motion of the three-phase contact line. However, due mainly to lack of control over the evaporation process of the drop, the challenge remains to use evaporative self-assembly to rationally ``synthesize'' ``coffee rings'' of different shapes and sizes of high regularity and fidelity. Here, we report a facile, robust, and one-step evaporation method for producing in a precisely controllable manner versatile microstructures possessing high regularity, dispensing with the need for lithographic techniques and externally applied fields. Polymer or nanocrystal solutions are confined in a simple geometry comprised of a curved surface placed upon a flat substrate. By changing the shape of the upper surface of the imposed geometry, the controlled, evaporative self-assembly of polymer or nanocrystal solutions yields a variety of complex, intriguing, and well-ordered structures over large areas. As such, this method represents a significant advance in creating regularly organized, complex structures with potential applications in microelectronics, optoelectronics, and biotechnology, among other areas.

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

    KAUST Repository

    Chen, Xia

    2012-05-02

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

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-05

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

  4. Hg(II Coordination Polymers Based on N,N’-bis(pyridine-4-ylformamidine

    Directory of Open Access Journals (Sweden)

    Wayne Hsu

    2016-04-01

    Full Text Available Reactions of N,N’-bis(pyridine-4-ylformamidine (4-Hpyf with HgX2 (X = Cl, Br, and I afforded the formamidinate complex {[Hg(4-pyf2]·(THF}n, 1, and the formamidine complexes {[HgX2(4-Hpyf]·(MeCN}n (X = Br, 2; I, 3, which have been structurally characterized by X-ray crystallography. Complex 1 is a 2D layer with the {44·62}-sql topology and complexes 2 and 3 are helical chains. While the helical chains of 2 are linked through N–H···Br hydrogen bonds, those of 3 are linked through self-complementary double N–H···N hydrogen bonds, resulting in 2D supramolecular structures. The 4-pyf- ligands of 1 coordinate to the Hg(II ions through one pyridyl and one adjacent amine nitrogen atoms and the 4-Hpyf ligands of 2 and 3 coordinate to the Hg(II ions through two pyridyl nitrogen atoms, resulting in new bidentate binding modes. Complexes 1–3 provide a unique opportunity to envisage the effect of the halide anions of the starting Hg(II salts on folding and unfolding the Hg(II coordination polymers. Density function theory (DFT calculation indicates that the emission of 1 is due to intraligand π→π * charge transfer between two different 4-pyf- ligands, whereas those of 2 and 3 can be ascribed to the charge transfer from non-bonding p-type orbitals of the halide anions to π * orbitals of the 4-pyf- ligands (n→π *. The gas sorption properties of the desolvated product of 1 are compared with the Cu analogues to show that the nature of the counteranion and the solvent-accessible volume are important in determining their adsorption capability.

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

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Fausthon Fred da; Fernandes de Oliveira, Carlos Alberto; Lago Falcão, Eduardo Henrique [Laboratório de Terras Raras, Departamento de Química Fundamental, Universidade Federal de Pernambuco (DQF-UFPE), 50590-470 Recife, PE (Brazil); Gatto, Claudia Cristina [Laboratório de Síntese Inorgânica e Cristalografia, Instituto de Química, Universidade de Brasília (IQ-UnB), 70904-970 Brasilia, DF (Brazil); Bezerra da Costa, Nivan; Oliveira Freire, Ricardo [Pople Computational Chemistry Laboratory, Departamento de Química, Universidade Federal de Sergipe, São Cristóvão-SE 49100-000 (Brazil); Chojnacki, Jarosław [Department of Inorganic Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Alves Júnior, Severino, E-mail: salvesjr@ufpe.br [Laboratório de Terras Raras, Departamento de Química Fundamental, Universidade Federal de Pernambuco (DQF-UFPE), 50590-470 Recife, PE (Brazil)

    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

  6. Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films

    Science.gov (United States)

    Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei; Qu, Ge; Zhang, Fengjiao; Zhao, Xikang; Mei, Jianguo; Zuo, Jian-Min; Shukla, Diwakar; Diao, Ying

    2017-07-01

    Solution processable semiconducting polymers have been under intense investigations due to their diverse applications from printed electronics to biomedical devices. However, controlling the macromolecular assembly across length scales during solution coating remains a key challenge, largely due to the disparity in timescales of polymer assembly and high-throughput printing/coating. Herein we propose the concept of dynamic templating to expedite polymer nucleation and the ensuing assembly process, inspired by biomineralization templates capable of surface reconfiguration. Molecular dynamic simulations reveal that surface reconfigurability is key to promoting template-polymer interactions, thereby lowering polymer nucleation barrier. Employing ionic-liquid-based dynamic template during meniscus-guided coating results in highly aligned, highly crystalline donor-acceptor polymer thin films over large area (>1 cm2) and promoted charge transport along both the polymer backbone and the π-π stacking direction in field-effect transistors. We further demonstrate that the charge transport anisotropy can be reversed by tuning the degree of polymer backbone alignment.

  7. Ion conductivity and transport by porous coordination polymers and metal-organic frameworks.

    Science.gov (United States)

    Horike, Satoshi; Umeyama, Daiki; Kitagawa, Susumu

    2013-11-19

    Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have been recognized for their easy design and the dynamic behavior of the ionic components in the structures. These PCP/MOFs consist of metal ions (or clusters) and organic ligands structured via coordination bonds. They could have highly concentrated mobile ions with dynamic behavior, and their characteristics have inspired the design of a new class of ion conductors and transporters. In this Account, we describe the state-of-the-art of studies of ion conductivity by PCP/MOFs and nonporous coordination polymers (CPs) and offer future perspectives. PCP/MOF structures tend to have high hydrophilicity and guest-accessible voids, and scientists have reported many water-mediated proton (H(+)) conductivities. Chemical modification of organic ligands can change the hydrated H(+) conductivity over a wide range. On the other hand, the designable structures also permit water-free (anhydrous) H(+) conductivity. The incorporation of protic guests such as imidazole and 1,2,4-triazole into the microchannels of PCP/MOFs promotes the dynamic motion of guest molecules, resulting in high H(+) conduction without water. Not only the host-guest systems, but the embedding of protic organic groups on CPs also results in inherent H(+) conductivity. We have observed high H(+) conductivities under anhydrous conditions and in the intermediate temperature region of organic and inorganic conductors. The keys to successful construction are highly mobile ionic species and appropriate intervals of ion-hopping sites in the structures. Lithium (Li

  8. Effect of Charge Patterning on the Phase Behavior of Polymer Coacervates for Charge Driven Self Assembly

    Science.gov (United States)

    Radhakrishna, Mithun; Sing, Charles E.

    Oppositely charged polymers can undergo associative liquid-liquid phase separation when mixed under suitable conditions of ionic strength, temperature and pH to form what are known as `polymeric complex coacervates'. Polymer coacervates find use in diverse array of applications like microencapsulation, drug delivery, membrane filtration and underwater adhesives. The similarity between complex coacervate environments and those in biological systems has also found relevance in areas of bio-mimicry. Our previous works have demonstrated how local charge correlations and molecular connectivity can drastically affect the phase behavior of coacervates. The precise location of charges along the chain therefore dramatically influences the local charge correlations, which consequently influences the phase behavior of coacervates. We investigate the effect of charge patterning along the polymer chain on the phase behavior of coacervates in the framework of the Restricted Primitive Model using Gibbs Ensemble Monte Carlo simulations. Our results show that charge patterning dramatically changes the phase behavior of polymer coacervates, which contrasts with the predictions of the classical Voorn-Overbeek theory. This provides the basis for designing new materials through charge driven self assembly by controlling the positioning of the charged monomers along the chain.

  9. Nonvolatile Transistor Memory with Self-Assembled Semiconducting Polymer Nanodomain Floating Gates.

    Science.gov (United States)

    Wang, Wei; Kim, Kang Lib; Cho, Suk Man; Lee, Ju Han; Park, Cheolmin

    2016-12-14

    Organic field effect transistor based nonvolatile memory (OFET-NVM) with semiconducting nanofloating gates offers additional benefits over OFET-NVMs with conventional metallic floating gates due to the facile controllability of charge storage based on the energetic structure of the floating gate. In particular, an all-in-one tunneling and floating-gate layer in which the semiconducting polymer nanodomains are self-assembled in the dielectric tunneling layer is promising. In this study, we utilize crystals of a p-type semiconducting polymer in which the crystalline lamellae of the polymer are spontaneously developed and embedded in the tunneling matrix as the nanofloating gate. The widths and lengths of the polymer nanodomains are approximately 20 nm and a few hundred nanometers, respectively. An OFET-NVM containing the crystalline nanofloating gates exhibits memory performance with a large memory window of 10 V, programming/erasing switching endurance for over 500 cycles, and a long retention time of 5000 s. Moreover, the device performance is improved by comixing with an n-type semiconductor; thus, the solution-processed p- and n-type double floating gates capable of storing both holes and electrons allow for the multilevel operation of our OFET-NVM. Four highly reliable levels (two bits per cell) of charge trapping and detrapping are achieved using this OFET-NVM by accurately choosing the programming/erasing voltages.

  10. Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

    Science.gov (United States)

    Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto; Barker, Thomas H.

    2017-01-01

    In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels.

  11. Assembly of poly(dopamine) films mixed with a nonionic polymer.

    Science.gov (United States)

    Zhang, Yan; Thingholm, Bo; Goldie, Kenneth N; Ogaki, Ryosuke; Städler, Brigitte

    2012-12-21

    Poly(dopamine) (PDA) coatings have recently attracted considerable interest for a variety of applications. Here, we investigate the film deposition of dopamine mixed with a nonionic polymer (i.e., poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA), and poly(N-vinyl pyrrolidone) (PVP)) onto silica substrates using X-ray photoelectron spectroscopy and quartz crystal microbalance. Furthermore, we assess the possibility of coating silica colloids to yield polymer capsules and liposomes with these mixtures. We found that mixed PDA/PEG and PDA/PVA films are deposited without the need for a covalent linker such as an amine or thiol. We also discovered the first material, namely, PVP, that can suppress PDA film assembly. These fundamental findings give further insight into PDA film properties and contribute to establish PDA as a widely applicable coating.

  12. Self-assembly of azobenzene based side-chain liquid crystalline polymer and -alkyloxybenzoic acids

    Indian Academy of Sciences (India)

    Kumarasamy Gayathri; Subramanian Balamurugan; Palaninathan Kannan

    2011-05-01

    Liquid crystalline pendant polymeric complexes have been obtained by supramolecular assembly of two mesogenic components namely, poly[4-(10-acryloyloxydecyloxy)-4'- phenylazobenzonitrile] (P10) and 4-alkyloxybenzoic acids (A7-A12). Hydrogen bond formed between carboxylic acid and cyano moiety served as molecular bridge. The polymeric complexes acquitted as undivided liquid crystalline properties exhibited stable and enantiotropic mesophases. The precursor, monomer and polymer were analysed by 1H-NMR and 13C-NMR spectroscopy. The hydrogen bonding interaction in polymer complexes (P10-A7 to P10-A12) was investigated by FT-IR spectroscopy. The thermal behaviours and textural analysis were studied by differential scanning calorimetry and polarized optical microscopy respectively.

  13. [Synthesis and structure of silver(I) coordination polymers with bis(pyridyl) ligands linked by an aromatic sulfonamide].

    Science.gov (United States)

    Katagiri, Kosuke

    2014-01-01

    Aromatic sulfonamides exist in a synclinal conformation with the twisted structure arising from rotation around the S-N bond in both the solid state and in solution. Simple bidentate ligands containing the sulfonamide moiety can be extended to form elongated ligands, and optically active components can be added to form a versatile building block for the construction of coordination polymers with many structures. Mixing the simple ligands 1 and 2 and the elongated ligands 3 and 4 with different Ag(I) salts yielded the corresponding complexes [Ag(1)OTf]n (1a), [Ag(2)]n•nOTf(2a), [Ag(3)OTf]n (3a), [Ag(3)]n•nBF₄ (3b), [Ag(4)CH₃CN]n•nBF₄•nCHCl₃ (4b), and [Ag(4)]n•nSbF₆•nCH₄O (4c). Straight chains and racemic helical polymers were observed in the crystal structure of complexes 1a and 2a, respectively. In the crystal structures of complexes 3a and 4b, infinite 1D straight chains containing a T-shaped coordination geometry about the Ag(I) centers were formed by the reaction of ligands 3 or 4 with Ag(I) salts in CH₃CN/CHCl₃. A continuous 1D coordination polymer containing a racemic mixture of left- and right-handed helices formed in the crystal structure of complex 3b. Furthermore, a layered coordination polymer consisting of a racemic mixture of left- and right-handed polymers was observed from the crystal structure of complex 4c. The construction of optically pure left- or right-handed 1D helical polymers via the introduction of chiral functional groups on the nitrogen atom of the sulfonamide ligand is currently under investigation in our laboratory.

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

    Directory of Open Access Journals (Sweden)

    James S. Wright

    2015-03-01

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

  15. Synthesis and structural characterization of a calcium coordination polymer based on a 3-bridging tetradentate binding mode of glycine

    Indian Academy of Sciences (India)

    Subramanian Natarajan; Bikshandarkoil R Srinivasan; J Kalyana Sundar; K Ravikumar; R V Krishnakumar; J Suresh

    2012-07-01

    A new coordination polymer namely [[Ca6(H-gly)12(H2O)18]Cl12·6H2O] (1) (H-gly = glycine) has been isolated from the calcium chloride-glycine-water system and structurally characterized. Each Ca(II) in 1 is eight-coordinated and is bonded to eight oxygen atoms three of which are from terminal water molecules and five oxygen atoms from four symmetry related zwitterionic glycine ligands. The H-gly ligands exhibit two different binding modes viz. a monodentate carboxylate ligation and a 3-tetradentate bridging carboxylate binding mode, which results in the formation of a one-dimensional coordination polymer. In the infinite chain the Ca(II) atoms are organized in a zigzag fashion. A comparative study reveals a rich and diverse structural chemistry of calcium halide-glycine compounds.

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

    Science.gov (United States)

    Hussain, Navid; Bhardwaj, Vimal K

    2016-05-04

    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.

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

    Science.gov (United States)

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

    2017-02-01

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

  18. Polymer/hemoglobin assemblies: biodegradable oxygen carriers for artificial red blood cells.

    Science.gov (United States)

    Li, Taihang; Jing, Xiabin; Huang, Yubin

    2011-07-07

    In routine clinical procedures, blood transfusion is now suffering from the defects of the blood products, like cross-matching, short storage time and virus infection. Various blood substitutes have been designed by researchers through continual efforts. With recent progress in nanotechnology, new types of artificial red blood cells with cellular structure are available. This article aims to describe some artificial red blood cells which encapsulate or conjugate hemoglobin molecules through various approaches, especially the nanoscale self-assembly technique, to mitigate the adverse effects of free hemoglobin molecules. These types of artificial red blood cell systems, which make use of biodegradable polymers as matrix materials, show advantages over the traditional types.

  19. Polymer solution, fiber mat, and nanofiber membrane-electrode-assembly therewith, and method of fabricating same

    DEFF Research Database (Denmark)

    2016-01-01

    In one aspect of the present invention, a fiber mat is provided. The fiber mat includes at least one type of fibers, which includes one or more polymers. The fiber mat may be a single fiber mat which includes one type of fibers, or may be a dual or multi fiber mat which includes multiple types...... of fibers. The fibers may further include particles of a catalyst. The fiber mat may be used to form an electrode or a membrane. In a further aspect, a fuel cell membrane-electrode-assembly has an anode electrode, a cathode electrode, and a membrane disposed between the anode electrode and the cathode...

  20. Smart assembly of polymer fibers: lessons from major ampullate spider silk

    Science.gov (United States)

    Viney, Christopher

    1996-02-01

    Studies of major ampullate silk (MAS), especially the secretions and fibers produced by the spider Nephila clavipes (golden orb weaver), have yielded several results of potential value to the materials scientist/engineer. There are lessons to be learned about synthesis, processing and microstructural design of high-tensile polymer fibers. The 'smart' aspect of silk production in nature concerns the ability of the spider to rapidly process a concentrated, viscous aqueous solution of silk protein (stored in the gland) into water-insoluble fiber on demand. This process centers on the assembly of a shear-sensitive supramolecular liquid crystalline phase by aggregation of the solubilized globular protein molecules.

  1. Self-assembly of DNA-polymer complexes using template polymerization.

    Science.gov (United States)

    Trubetskoy, V S; Budker, V G; Hanson, L J; Slattum, P M; Wolff, J A; Hagstrom, J E

    1998-09-15

    The self-assembly of supramolecular complexes of nucleic acids and polymers is of relevance to several biological processes including viral and chromatin formation as well as gene therapy vector design. We now show that template polymerization facilitates condensation of DNA into particles that are <150 nm in diameter. Inclusion of a poly(ethylene glycol)-containing monomer prevents aggregation of these particles. The DNA within the particles remains biologically active and can express foreign genes in cells. The formation or breakage of covalent bonds has until now not been employed to compact DNA into artificial particles.

  2. Synthesis and Crystal Structure of 1D Coordination Polymer of N,N'-Bis(3-pyridylmethyl)-1,4-benzenedicarboxamide and Cobalt(II) Nitrate

    Institute of Scientific and Technical Information of China (English)

    GE,Chun-Hua(葛春华); ZHANG,Xiang-Dong(张向东); TONG,Jian(佟健); ZHANG,Peng(张鹏); GUO,Fang(郭放); LIU,Qi-Tao(刘祁涛)

    2004-01-01

    A noval cobalt(II)coordination polymer,{[Co(bpmb)(H2O)2(C2H5OH)2]·(NO3)2}∞(1),where bpmb=N,N'-bis(3-pyridylmethyl)-1,4-benzenedicarboxamide,was synthesized by self-assembly of the two topic ligands with cobalt nitrate in ethanol solution,and characterized structurally by X-ray crystallography analysis.The crystal data belong to triclinic,space group Pwith cell parameters a=0.8911(3)nm,b=0.9042(3)nm,c=1.0068(3)nm,α=73.083(5)°,β=81.069(5)°,γ=76.210(5)°,R1=0.0518,wR2=0.0947.The results of structure analysis indicate that each bpmb ligand coordinates two Co(II)atoms and each metal atom is in octahedral coordination geometry with four oxygen atoms of two ethanol and two water molecules,two nitrogen atoms from two different bpmb ligands in trans position forming an infinite 1D chain-like structure.There are hydrogen bonding and π-π stacking interaction among these chains,leading to supramolecular formation with 3D net structure.

  3. o-, m-, and p-Pyridyl isomer effects on construction of 1D loop-and-chains: Silver(I) coordination polymers with Y-type tridentate ligands

    Science.gov (United States)

    Kim, Jeong Gyun; Cho, Yoonjung; Lee, Haeri; Lee, Young-A.; Jung, Ok-Sang

    2016-10-01

    Self-assembly of silver(I) hexafluorophosphate with unique Y-type tridentate ligands (2,6-bis[(2-picolinoyloxy-5-methylphenyl)methyl]-p-tolylpicolinate (o-L), 2-nicotinoyloxy- (m-L), and 2-isonicotinoyloxy- (p-L)) produces single crystals consisting of 1D loop-and-chain coordination polymers of [Ag(o-L)](PF6)·Me2CO·CHCl3, [Ag(m-L)](PF6)·Me2CO, and [Ag3(p-L)2](PF6)3·2H2O·2C2H5OH·4CH2Cl2 with quite different trigonal prismatic, trigonal, and linear silver(I) coordination geometry, respectively. Coordinating ability of the three ligands for AgPF6 is in the order of p-L > o-L > m-L. The solvate molecules of [Ag(o-L)](PF6)·Me2CO·CHCl3 can be removed, and be replaced reversibly in the order of acetone ≫ chloroform ≈ dichloromethane ≫ benzene, without destruction of its skeleton.

  4. Polymer blend lithography: A versatile method to fabricate nanopatterned self-assembled monolayers

    Directory of Open Access Journals (Sweden)

    Cheng Huang

    2012-09-01

    Full Text Available A rapid and cost-effective lithographic method, polymer blend lithography (PBL, is reported to produce patterned self-assembled monolayers (SAM on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity, the molar mass of the polystyrene (PS and poly(methyl methacrylate (PMMA, and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix can be reproducibly induced. Either of the formed phases (PS or PMMA can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This “monolayer copy” of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS and (3-aminopropyltriethoxysilane (APTES, and at the same time featuring regions of bare SiOx. The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures.

  5. Performance of dielectric nanocomposites: matrix-free, hairy nanoparticle assemblies and amorphous polymer-nanoparticle blends.

    Science.gov (United States)

    Grabowski, Christopher A; Koerner, Hilmar; Meth, Jeffrey S; Dang, Alei; Hui, Chin Ming; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Durstock, Michael F; Vaia, Richard A

    2014-12-10

    Demands to increase the stored energy density of electrostatic capacitors have spurred the development of materials with enhanced dielectric breakdown, improved permittivity, and reduced dielectric loss. Polymer nanocomposites (PNCs), consisting of a blend of amorphous polymer and dielectric nanofillers, have been studied intensely to satisfy these goals; however, nanoparticle aggregates, field localization due to dielectric mismatch between particle and matrix, and the poorly understood role of interface compatibilization have challenged progress. To expand the understanding of the inter-relation between these factors and, thus, enable rational optimization of low and high contrast PNC dielectrics, we compare the dielectric performance of matrix-free hairy nanoparticle assemblies (aHNPs) to blended PNCs in the regime of low dielectric contrast to establish how morphology and interface impact energy storage and breakdown across different polymer matrices (polystyrene, PS, and poly(methyl methacrylate), PMMA) and nanoparticle loadings (0-50% (v/v) silica). The findings indicate that the route (aHNP versus blending) to well-dispersed morphology has, at most, a minor impact on breakdown strength trends with nanoparticle volume fraction; the only exception being at intermediate loadings of silica in PMMA (15% (v/v)). Conversely, aHNPs show substantial improvements in reducing dielectric loss and maintaining charge/discharge efficiency. For example, low-frequency dielectric loss (1 Hz-1 kHz) of PS and PMMA aHNP films was essentially unchanged up to a silica content of 50% (v/v), whereas traditional blends showed a monotonically increasing loss with silica loading. Similar benefits are seen via high-field polarization loop measurements where energy storage for ∼15% (v/v) silica loaded PMMA and PS aHNPs were 50% and 200% greater than respective comparable PNC blends. Overall, these findings on low dielectric contrast PNCs clearly point to the performance benefits of

  6. Interfacial self-assembly of metal-mediated viologen-like coordination polyelectrolyte hybrids of the bisterpyridine ligand and their optical, electrochemical, and electrochromic properties.

    Science.gov (United States)

    Zhang, Chao-Feng; Liu, An; Chen, Meng; Nakamura, Chikashi; Miyake, Jun; Qian, Dong-Jin

    2009-06-01

    Metal-mediated coordination polyelectrolyte multilayers with a bisterpyridine ligand (Bisterpy) have been self-assembled at air-water interfaces via coordination reactions of the bidentate ligand Bisterpy with inorganic salts in the subphases. To avoid dissolution of the viologen-like coordination polyelectrolyte monolayers, anionic poly(styrenesulfonic acid-o-maleic) (PSS) acid was added in the subphases as a supporting layer. The average molecular area of the ligand Bisterpy could reach 1.2-1.5 nm(2) on the surfaces of the subphases containing mixtures of inorganic salts (M) and PSS, although the ligand was unable to form a stable monolayer on the pure water surface. The Langmuir-Blodgett (LB) method was used to deposit the Bisterpy/PSS and M-Bisterpy/PSS hybrid multilayers on the substrate surfaces, which were characterized by using absorption and fluorescence spectroscopy as well as electrochemical analysis. Quasi-reversible redox waves were recorded and centered at about -0.68 and -0.92 V (vs Ag/AgCl), respectively, corresponding to the two-electron process of the ligand, Bisterpy2+ Bisterpy(*+) Bisterpy(0), which were slightly shifted to lower potentials in the LB films of metal-mediated coordination polymers. The film compositions were determined by using X-ray photoelectron spectroscopy. The as-prepared LB films showed strong stability and good electrochromic response upon the applied potential of -1.1 V vs Ag/AgCl and thus could act as potential materials in the development of redox-based molecular switches and display devices.

  7. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes

    NARCIS (Netherlands)

    Wang, J.; Groeneveld, A.; Oikonomou, M.E.; Prusova, A.; As, van H.; Lent, van J.W.M.; Velders, A.H.

    2016-01-01

    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and

  8. An unusual double T5(2) water tape trapped in silver(I) coordination polymer hosts: influence of the solvent on the assembly of Ag(I)-4,4'-bipyridine chains with trans-cyclohexanedicarboxylate and their luminescent properties.

    Science.gov (United States)

    Li, Ting; Huang, Xi-He; Zhao, Ya-Feng; Li, Hao-Hong; Wu, Shu-Ting; Huang, Chang-Cang

    2012-11-07

    In this paper, four silver(I) compounds, namely, {[Ag(4)(bipy)(4)(chda)]·2NO(3)·10H(2)O}(n) (1), {[Ag(2)(bipy)(2)(chda)]·14H(2)O}(n) (2), {[Ag(2)(bipy)(2)(chda)]·3EG·2H(2)O}(n) (3) and {[Ag(2)(bipy)(2)(chda)]·H(2)chda}(n) (4) (where bipy = 4,4'-bipyridine, H(2)chda = trans-cyclohexane-dicarboxylate and EG = ethylene glycol), have been synthesized and characterized by single-crystal X-ray diffraction analyses. In all of these compounds, the Ag(I) centers are linked by bipy ligands to form 1D Ag(I)-bipy chain structures. The chda(2-) anions of compound 1 adopt a μ(4)-coordination mode to connect the Ag(I)-bipy chains, forming a H-beam-like chain. In 2, the chda(2-) anions adopt a μ(2)-coordination mode to connect the Ag(I)-bipy chains resulting in two distinct 2D brick wall-like layers. These layers are further stacked in an ···ABAB··· fashion through interlayer π···π stacking interactions giving rise to a 3D framework consisting of quasi-rectangular channels, in which an unusual double T5(2) water tape is trapped. For 3 and 4, the chda(2-) anions show a similar μ(4)-coordination mode to that of 1 and connect the Ag(I)-bipy chains to form 2D grid layers with identical compositions and connective topologies. The experimental studies show that the final structures are greatly influenced by the molar ratio of the components and the solvents, which can be rationally interpreted by the existence of various supramolecular interactions between the host and guest molecules within these compounds through a systematic structural comparison. Additionally, the thermal stability and luminescent properties of these compounds were also studied.

  9. Cd(II) and Co(II) coordination polymers constructed from benzene-1,4-dicarboxylic acid and 2-(pyridin-3-yl)-1H-benzimidazole ligands.

    Science.gov (United States)

    Chen, Xiao-Hua; Huang, Hua; Yang, Ming-Xing; Chen, Li-Juan; Lin, Shen

    2014-05-01

    In poly[aqua(μ3-benzene-1,4-dicarboxylato-κ(5)O(1),O(1'):O(1):O(4),O(4'))[2-(pyridin-3-yl-κN)-1H-benzimidazole]cadmium(II)], [Cd(C8H4O4)(C12H9N3)(H2O)]n, (I), each Cd(II) ion is seven-coordinated by the pyridine N atom from a 2-(pyridin-3-yl)benzimidazole (3-PyBIm) ligand, five O atoms from three benzene-1,4-dicarboxylate (1,4-bdc) ligands and one O atom from a coordinated water molecule. The complex forms an extended two-dimensional carboxylate layer structure, which is further extended into a three-dimensional network by hydrogen-bonding interactions. In catena-poly[[diaquabis[2-(pyridin-3-yl-κN)-1H-benzimidazole]cobalt(II)]-μ2-benzene-1,4-dicarboxylato-κ(2)O(1):O(4)], [Co(C8H4O4)(C12H9N3)2(H2O)2]n, (II), each Co(II) ion is six-coordinated by two pyridine N atoms from two 3-PyBIm ligands, two O atoms from two 1,4-bdc ligands and two O atoms from two coordinated water molecules. The complex forms a one-dimensional chain-like coordination polymer and is further assembled by hydrogen-bonding interactions to form a three-dimensional network.

  10. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes.

    Science.gov (United States)

    Wang, Junyou; Groeneveld, Andrea; Oikonomou, Maria; Prusova, Alena; Van As, Henk; van Lent, Jan W M; Velders, Aldrik H

    2016-01-07

    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and magnetic relaxation enhancement). Micelles are prepared by charge-driven self-assembly of a polycationic-neutral diblock copolymer and anionic coordination complexes formed by Ln(III) ions and the bis-ligand L2EO4, which contains two dipicolinic acid (DPA) ligand groups (L) connected by a tetra-ethylene oxide spacer (EO4). By varying the DPA/Ln ratio, micelles are obtained with similar size but with different stability, different aggregation numbers and different oligomeric and polymeric lanthanide(III) coordination structures in the core. Electron microscopy, light scattering, luminescence spectroscopy and magnetic resonance relaxation experiments provide an unprecedented detailed insight into the core structures of such micelles. Concomitantly, the self-assembly is controlled such that tunable luminescence or magnetic relaxation with Eu-C3Ms, respectively, Gd-C3Ms is achieved, showing potential for applications, e.g. as contrast agents in (pre)clinical imaging. Considering the various lanthanide(III) ions have unique electron configurations with specific physical chemical properties, yet very similar coordination chemistry, the generality of the current coordination-structure based micellar design shows great promise for development of new materials such as, e.g., hypermodal agents.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lun, Huijie [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004 (China); Li, Yamin, E-mail: liyamin@henu.edu.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Zhang, Xudong [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Yang, Jing-He; Xiao, Changyu [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004 (China); Xu, Yanqing [School of Chemistry, Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Institute of Technology, Beijing 100081 (China); Li, Junrui [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004 (China)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-08-15

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

  14. Polymer-virus core-shell structures prepared via co-assembly and template synthesis methods

    Institute of Scientific and Technical Information of China (English)

    SUTHIWANGCHAROEN; Nisaraporn; PREVELIGE; Peter; E.Jr

    2010-01-01

    Bionanoparticles(BNPs),consisting of virus and virus-like assemblies,have attracted much attention in the biomedical field for their applications such as imaging and targeted drug delivery,owing to their well-defined structures and well-controlled chemistries.BNPs-based core-shell structures provide a unique system for the investigation of biological interactions such as protein-protein and protein-carbohydrate interactions.However,it is still a challenge to prepare the BNPs-based core-shell structures.Herein,we describe(i) co-assembly method and(ii) template synthesis method in the development of polymer-BNPs core-shell structures.These two methods can be divided into three different systems.In system A,different polymers including poly(2-vinylpyridine)(P2VP),poly(4-vinylpyridine)(P4VP) and poly(ε-caprolactone)-block-poly(2-vinylpyridine)(PCL-b-P2VP) can form a raspberry-like structure with BNPs.In system B,polystyrene(PS) spheres end capped with free amine and BNPs can form a core-shell structure.In System C,layer-by-layer(LBL) method is used to prepare positive charged PS particles,which can be used as a template to form the core-shell structures with BNPs.These two methods may open a new way for preparing novel protein-based functional materials for potential applications in the biomedical field.

  15. RAFT Synthesis and Self-Assembly of Free-Base Porphyrin Cored Star Polymers

    Directory of Open Access Journals (Sweden)

    Lin Wu

    2011-01-01

    Full Text Available Reversible addition fragmentation chain transfer (RAFT synthesis and self-assembly of free-base porphyrin cored star polymers are reported. The polymerization, in the presence of a free-base porphyrin cored chain transfer agent (CTA-FBP, produced porphyrin star polymers with controlled molecular weights and narrow polydispersities for a number of monomers including N, N-dimethylacrylamide (DMA and styrene (St. Well-defined amphiphilic star block copolymers, P-(PS-PDMA4 and P-(PDMA-PS4 (P: porphyrin, were also prepared and used for self-assembly studies. In methanol, a selective solvent for PDMA, spherical micelles were observed for both block copolymers as characterized by TEM. UV-vis studies suggested star-like micelles were formed from P-(PS-PDMA4, while P-(PDMA-PS4 aggregated into flower-like micelles. Spectrophotometric titrations indicated that the optical response of these two micelles to external ions was a function of micellar structures. These structure-related properties will be used for micelle studies and functional material development in the future.

  16. Cluster computing as an assembly process: coordination with S-Net

    NARCIS (Netherlands)

    Grelck, C.; Julku, J.; Penczek, F.; Shafarenko, A.; Parashar, M.; Buyya, R.

    2010-01-01

    This poster will present a coordination language for distributed computing and will discuss its application to cluster computing. It will introduce a programming technique of cluster computing whereby application components are completely dissociated from the communication/coordination infrastructur

  17. Cluster computing as an assembly process: coordination with S-Net

    NARCIS (Netherlands)

    Grelck, C.; Julku, J.; Penczek, F.; Shafarenko, A.; Parashar, M.; Buyya, R.

    2010-01-01

    This poster will present a coordination language for distributed computing and will discuss its application to cluster computing. It will introduce a programming technique of cluster computing whereby application components are completely dissociated from the communication/coordination

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

    Science.gov (United States)

    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.

  19. A series of Zn-4f heterometallic coordination polymers and a zinc complex containing a flexible mixed donor dicarboxylate ligand.

    Science.gov (United States)

    Feng, Xun; Feng, Yu-Quan; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Ng, Seik-Weng

    2013-06-01

    A new zinc compound, together with a corresponding series of Zn-4f heterometallic coordination polymers, namely, [Zn(H2PBDA)(PBDA)]n (1), {[Ln2(PBDA)2·2H2O] [Zn2(PBDA)2Cl2]}n [H2PBDA = 3-(pyridin-3-yl-oxy) benzene-1,2-dicarboxylic acid, and Ln = Pr(2), Nd(3), Eu(4), Gd(5), Dy(6), Ho(7), Er(8)] have been hydrothermally synthesized and characterized systematically. Polymers 2-8 feature two-dimensional (2D) 4,4 networks, containing the original 1D heterometallic double stranded chains composed of [Ln2Zn2(PBDA)2] entities. The extensive hydrogen bonding and π-π stacking interactions were observed to stabilize the extended architectures. The luminescence emission spectra of the polymers vary depending on the lanthanide(III) ion present. Informative magnetic susceptibility measurements show that the same carboxylate bridging fashion of the PBDA ligand results in the different magnetic properties occurring within the heterometallic coordination polymers. In addition, polymer 6 exhibits an interesting slow magnetic relaxation behavior at lower temperatures.

  20. Cis-and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper(II) and Silver(I)

    Institute of Scientific and Technical Information of China (English)

    TAN Di; TAN Gui-ping; HUANG Xiao-chun; TONG Shan-ling; YANG Ke-er; YAN Yan

    2008-01-01

    After the preparation of 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene(bdib),a nitrogen heterocycle with potential coordination manners of both cis-and tram-configuration forms,three complexes,including successfully self-assembled.Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with P1 space group.

  1. Invertible micellar polymer assemblies for delivery of poorly water-soluble drugs.

    Science.gov (United States)

    Hevus, Ivan; Modgil, Amit; Daniels, Justin; Kohut, Ananiy; Sun, Chengwen; Stafslien, Shane; Voronov, Andriy

    2012-08-13

    Strategically designed amphiphilic invertible polymers (AIPs) are capable of (i) self-assembling into invertible micellar assemblies (IMAs) in response to changes in polarity of environment, polymer concentration, and structure, (ii) accommodating (solubilizing) substances that are otherwise insoluble in water, and (iii) inverting their molecular conformation in response to changes in the polarity of the local environment. The unique ability of AIPs to invert the molecular conformation depending on the polarity of the environment can be a decisive factor in establishing the novel stimuli-responsive mechanism of solubilized drug release that is induced just in response to a change in the polarity of the environment. The IMA capability to solubilize lipophilic drugs and deliver and release the cargo molecules by conformational inversion of polymer macromolecules in response to a change of the polarity of the environment was demonstrated by loading IMA with a phytochemical drug, curcumin. It was demonstrated that four sets of micellar vehicles based on different AIPs were capable of delivering the curcumin from water to an organic medium (1-octanol) by means of unique mechanism: AIP conformational inversion in response to changing polarity from polar to nonpolar. The IMAs are shown to be nontoxic against human cells up to a concentration of 10 mg/L. On the other hand, the curcumin-loaded IMAs are cytotoxic to breast carcinoma cells at this concentration, which confirms the potential of IMA-based vehicles in controlled delivery of poorly water-soluble drug candidates and release by means of this novel stimuli-responsive mechanism.

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

    Science.gov (United States)

    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.

  3. Coordination chemistry of mercury(ii) with 2-pyridylnitrones: monomers to polymers.

    Science.gov (United States)

    Azizpoor Fard, Mahmood; Behnia, Ava; Puddephatt, Richard J

    2017-03-14

    The coordination chemistry of mercury(ii) halides, HgX2, X = Cl, Br, I, with N-methyl-α-(2-pyridyl)nitrone, L1, and N-t-butyl-α-(2-pyridyl)nitrone, L2, is reported. The structures of 1 : 1 complexes [HgX2L], X = Cl, L = L1; X = Br, L = L2, 2 : 1 complexes [(HgX2)2L], X = Br or I, L = L1; X = Cl or I, L = L2, and a unique compound [(HgBr2)5(L2)3] have been determined. In the 1 : 1 and 1 : 2 complexes, the ligand L1 adopts the anti conformation, and is either monodentate or bridging, while the ligand L2 adopts the syn conformation and acts as a chelate ligand. In the compound [(HgBr2)5(L2)3] the ligand L2 is present in both syn-chelate and anti-bridging bonding modes. Secondary intermolecular bonding, involving OHg or XHg interactions, can lead to association of the molecular compounds to form polymers of several kinds. In solution, the complexes are labile and the crystalline products do not necessarily reflect the reaction stoichiometry.

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

    Science.gov (United States)

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

    2015-01-01

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

  5. Synthesis and Characterization of Nanosized Uranyl Coordination Polymers derived from Terephthalic acid and Azoles

    Directory of Open Access Journals (Sweden)

    Maged S.Al-Fakeh

    2016-05-01

    Full Text Available The structure of the complexes [UO2(TPA(Azole(H2O].xH2O, TPA = 1,4-benzenedicarboxylic acid and azoles = 2-aminobenzothiazole, 2-aminothiazole, 2-amino-4-methylthiazole and 2-mercaptobenzothiazole has been prepared and characterized. The structure of the complexes has been assigned based on elemental analysis, IR, electronic spectral studies, magnetic measurement, molar conductance, Scanning electron microscope (S.E.M, X-ray powder diffraction techniques investigations and thermogravimetric analysis complete the characterization of the compound. Thermogravimetry(TG, derivative thermogravimetry (DTG and differential thermal analysis (DTA have been used to study the thermal decomposition of the complexes. The kinetic parameters have been calculated making use of the Coats-Redfern and Horowitz-Metzger. The scanning electron microscope SEM photographs and particle size calculations from the powder XRD data indicate the average size of the prepared UO2(II (28-56 nm supramolecular coordination polymers in the nanoscale range. The biological screening of the compounds was also tested.

  6. Syntheses, structures, and properties of multidimensional lithium coordination polymers based on aliphatic carboxylic acids.

    Science.gov (United States)

    Cheng, Pei-Chi; Lin, Wei-Cheng; Tseng, Feng-Shuen; Kao, Ching-Che; Chang, Ting-Guang; Senthil Raja, Duraisamy; Liu, Wei-Ren; Lin, Chia-Her

    2013-02-28

    Three lithium coordination polymers, [Li4(H2O)2(EDTA)] (1), [Li4(H2O)4(BTCA)] (2), and (H2NMe2)2[Li2(H2O)2(BTCA)] (3) (H4EDTA = ethylenediaminetetraacetic acid, H4BTCA = 1,2,3,4-butane tetracarboxylic acid, H2NMe2 = dimethyl amine), have been synthesized by reacting lithium salts with aliphatic carboxylic acids using a solvothermal method. The structures of all the three complexes have been determined by single crystal X-ray diffraction studies. The single crystal structure analysis revealed that complex 1 has a three-dimensional framework, whereas complex 2 has 2D sheets and complex 3 has 1D chains. In addition, these lithium complexes contain various inorganic motifs with a tetramer in 1 and 2, and discrete tetrahedra in 3 and have further been connected through organic ligands to construct multidimensional structures. Further, the electrochemical properties of complexes 1–3 have been studied to evaluate these compounds as electrode materials for lithium ion batteries with discharge capacities of around 100 mA h g(-1) in the first thirty cycles.

  7. Natural gas purification using a porous coordination polymer with water and chemical stability.

    Science.gov (United States)

    Duan, Jingui; Jin, Wanqin; Krishna, Rajamani

    2015-05-04

    Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we demonstrate a new PCP, [(Cu4Cl)(BTBA)8·(CH3)2NH2)·(H2O)12]·xGuest (PCP-33⊃guest), which shows high potential for purification of natural gas, separation of C2H2/CO2 mixtures, and selective removal of C2H2 from C2H2/C2H4 mixtures at ambient temperature. The lower binding energy of the framework toward these light hydrocarbons indicates the reduced net costs for material regeneration, and meanwhile, the good water and chemical stability of it, in particular at pH = 2 and 60 °C, shows high potential usage under some harsh conditions. In addition, the adsorption process and effective site for separation was unravelled by in situ infrared spectroscopy studies.

  8. Self-assembled lamellar MoS2, SnS2 and SiO2 semiconducting polymer nanocomposites.

    Science.gov (United States)

    Kirmayer, Saar; Aharon, Eyal; Dovgolevsky, Ekaterina; Kalina, Michael; Frey, Gitti L

    2007-06-15

    Lamellar nanocomposites based on semiconducting polymers incorporated into layered inorganic matrices are prepared by the co-assembly of organic and inorganic precursors. Semiconducting polymer-incorporated silica is prepared by introducing the semiconducting polymers into a tetrahydrofuran (THF)/water homogeneous sol solution containing silica precursor species and a surface-active agent. Semiconducting polymer-incorporated MoS(2) and SnS(2) are prepared by Li intercalation into the inorganic compound, exfoliation and restack in the presence of the semiconducting polymer. All lamellar nanocomposite films are organized in domains aligned parallel to the substrate surface plane. The incorporated polymers maintain their semiconducting properties, as evident from their optical absorption and photoluminescence spectra. The optoelectronic properties of the nanocomposites depend on the properties of both the inorganic host and the incorporated guest polymer as demonstrated by integrating the nanocomposite films into light-emitting diodes. Devices based on polymer-incorporated silica and polymer-incorporated MoS(2) show no diode behaviour and no light emission due to the insulating and metallic properties of the silica and MoS(2) hosts. In contrast, diode performance and electroluminescence are obtained from devices based on semiconducting polymer-incorporated semiconducting SnS(2), demonstrating that judicious selection of the composite components in combination with the optimization of material synthesis conditions allows new hierarchical structures to be tailored for electronic and optoelectronic applications.

  9. Synthesis, Crystal Structure and Thermal Stability of 1D Linear Silver(I Coordination Polymers with 1,1,2,2-Tetra(pyrazol-1-ylethane

    Directory of Open Access Journals (Sweden)

    Evgeny Semitut

    2016-10-01

    Full Text Available Two new linear silver(I nitrate coordination polymers with bitopic ligand 1,1,2,2-tetra(pyrazol-1-ylethane were synthesized. Synthesized compounds were characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction and thermal analysis. Silver coordination polymers demonstrated a yellow emission near 500 nm upon excitation at 360 nm. Crystal structures of coordination polymers were determined and structural peculiarities are discussed. In both of the structures, silver ions are connected via bridging ligand molecules to form polymeric chains with a five-atomic environment. The coordination environment of the central atom corresponds to a distorted trigonal bipyramid with two N atoms of different ligands in apical positions. The Ag–N bond distances vary in a wide range of 2.31–2.62 Å, giving strongly distorted metallacycles. Thermolysis of coordination polymers in reductive atmosphere (H2/He leads to the formation of silver nanoparticles with a narrow size distribution.

  10. Arf6 coordinates actin assembly through the WAVE complex, a mechanism usurped by Salmonella to invade host cells

    Science.gov (United States)

    Humphreys, Daniel; Davidson, Anthony C.; Hume, Peter J.; Makin, Laura E.; Koronakis, Vassilis

    2013-01-01

    ADP ribosylation factor (Arf) 6 anchors to the plasma membrane, where it coordinates membrane trafficking and cytoskeleton remodelling, but how it assembles actin filaments is unknown. By reconstituting membrane-associated actin assembly mediated by the WASP family veroprolin homolog (WAVE) regulatory complex (WRC), we recapitulated an Arf6-driven actin polymerization pathway. We show that Arf6 is divergent from other Arf members, as it was incapable of directly recruiting WRC. We demonstrate that Arf6 triggers actin assembly at the membrane indirectly by recruiting the Arf guanine nucleotide exchange factor (GEF) ARNO that activates Arf1 to enable WRC-dependent actin assembly. The pathogen Salmonella usurped Arf6 for host cell invasion by recruiting its canonical GEFs EFA6 and BRAG2. Arf6 and its GEFs facilitated membrane ruffling and pathogen invasion via ARNO, and triggered actin assembly by generating an Arf1–WRC signaling hub at the membrane in vitro and in cells. This study reconstitutes Arf6-dependent actin assembly to reveal a mechanism by which related Arf GTPases orchestrate distinct steps in the WRC cytoskeleton remodelling pathway. PMID:24085844

  11. Self-Assembly of Octapod-Shaped Colloidal Nanocrystals into a Hexagonal Ballerina Network Embedded in a Thin Polymer Film

    OpenAIRE

    Arciniegas, Milena P.; Kim, Mee R.; de Graaf, Joost; Brescia, Rosaria; Marras, Sergio; Miszta, Karol; Dijkstra, Marjolein; Van Roij, René; Manna, Liberato

    2014-01-01

    Nanoparticles with unconventional shapes may exhibit different types of assembly architectures that depend critically on the environmental conditions under which they are formed. Here, we demonstrate how the presence of polymer (polymethyl methacrylate, PMMA) molecules in a solution, in which CdSe(core)/CdS(pods) octapods are initially dispersed, affects the octapod-polymer organization upon solvent evaporation. We show that a fast drop-drying process can induce a remarkable two-dimensional (...

  12. Structural aspects, thermal behavior, and stability of a self-assembled supramolecular polymer derived from flunixin-meglumine supramolecular adducts

    Energy Technology Data Exchange (ETDEWEB)

    Cassimiro, Douglas L.; Kobelnik, Marcelo [Institute of Chemistry, Paulista State University, Av. Prof. Francisco Degni, s/n, 14800-900 Araraquara, Sao Paulo (Brazil); Ribeiro, Clovis A., E-mail: ribeiroc@iq.unesp.br [Institute of Chemistry, Paulista State University, Av. Prof. Francisco Degni, s/n, 14800-900 Araraquara, Sao Paulo (Brazil); Crespi, Marisa S.; Boralle, Nivaldo [Institute of Chemistry, Paulista State University, Av. Prof. Francisco Degni, s/n, 14800-900 Araraquara, Sao Paulo (Brazil)

    2012-02-10

    Highlights: Black-Right-Pointing-Pointer The thermal behavior of flunixin-meglumine, a potent NSAID, was investigated. Black-Right-Pointing-Pointer This supramolecular adduct self-assembled resulting in a polymer-like material. Black-Right-Pointing-Pointer The supramolecular polymer showed a high molecular weight around 290 {+-} 88 MDa. Black-Right-Pointing-Pointer NMR and FT-IR showed that hydrogen bonding can be responsible for the self-assembly. Black-Right-Pointing-Pointer The stability of the supramolecular polymer was also studied and presented here. - Abstract: Flunixin-meglumine, a potent non-steroidal anti-inflammatory drug (NSAID) and a cyclo-oxygenase inhibitor for Veterinary use, is a hydrogen-bonded supramolecular adduct. Two monotropically related crystalline modifications (Forms I and II) were observed for a flunixin-meglumine sample. During the melt of form I, flunixin-meglumine adducts self-assembled by hydrogen bonds involving the hydroxyl groups from meglumine, resulting in an amorphous rigid glassy supramolecular polymer, which showed a high molecular weight around 290 {+-} 88 MDa and a glass transition around 49.5 Degree-Sign C. Both the adduct and the resulting supramolecular polymer were characterized by differential scanning calorimetry (DSC), nuclear magnetic resonance spectroscopy (NMR), Fourier transform-infrared spectroscopy (FT-IR), and weight-average molecular weight determination by light scattering. The chemical stability and morphological changes of the depolymerization process were also investigated for the supramolecular polymer, by DSC and scanning electron microscopy (SEM), respectively.

  13. Solution-processed low dimensional nanomaterials with self-assembled polymers for flexible photo-electronic devices (Presentation Recording)

    Science.gov (United States)

    Park, Cheolmin

    2015-09-01

    Self assembly driven by complicated but systematic hierarchical interactions offers a qualified alternative for fabricating functional micron or nanometer scale pattern structures that have been potentially useful for various organic and nanotechnological devices. Self assembled nanostructures generated from synthetic polymer systems such as controlled polymer blends, semi-crystalline polymers and block copolymers have gained a great attention not only because of the variety of nanostructures they can evolve but also because of the controllability of these structures by external stimuli. In this presentation, various novel photo-electronic materials and devices are introduced based on the solution-processed low dimensional nanomaterials such as networked carbon nanotubes (CNTs), reduced graphene oxides (rGOs) and 2 dimensional transition metal dichalcogenides (TMDs) with self assembled polymers including field effect transistor, electroluminescent device, non-volatile memory and photodetector. For instance, a nanocomposite of networked CNTs and a fluorescent polymer turned out an efficient field induced electroluminescent layer under alternating current (AC) as a potential candidate for next generation displays and lightings. Furthermore, scalable and simple strategies employed for fabricating rGO as well as TMD nanohybrid films allowed for high performance and mechanically flexible non-volatile resistive polymer memory devices and broad band photo-detectors, respectively.

  14. Supramolecular Engineering of Hierarchically Self-Assembled, Bioinspired, Cholesteric Nanocomposites Formed by Cellulose Nanocrystals and Polymers.

    Science.gov (United States)

    Zhu, Baolei; Merindol, Remi; Benitez, Alejandro J; Wang, Baochun; Walther, Andreas

    2016-05-04

    Natural composites are hierarchically structured by combination of ordered colloidal and molecular length scales. They inspire future, biomimetic, and lightweight nanocomposites, in which extraordinary mechanical properties are in reach by understanding and mastering hierarchical structure formation as tools to engineer multiscale deformation mechanisms. Here we describe a hierarchically self-assembled, cholesteric nanocomposite with well-defined colloid-based helical structure and supramolecular hydrogen bonds engineered on the molecular level in the polymer matrix. We use reversible addition-fragmentation transfer polymerization to synthesize well-defined hydrophilic, nonionic polymers with a varying functionalization density of 4-fold hydrogen-bonding ureidopyrimidinone (UPy) motifs. We show that these copolymers can be coassembled with cellulose nanocrystals (CNC), a sustainable, stiff, rod-like reinforcement, to give ordered cholesteric phases with characteristic photonic stop bands. The dimensions of the helical pitch are controlled by the ratio of polymer/CNC, confirming a smooth integration into the colloidal structure. With respect to the effect of the supramolecular motifs, we demonstrate that those regulate the swelling when exposing the biomimetic hybrids to water, and they allow engineering the photonic response. Moreover, the amount of hydrogen bonds and the polymer fraction are decisive in defining the mechanical properties. An Ashby plot comparing previous ordered CNC-based nanocomposites with our new hierarchical ones reveals that molecular engineering allows us to span an unprecedented mechanical property range from highest inelastic deformation (strain up to ∼13%) to highest stiffness (E ∼ 15 GPa) and combinations of both. We envisage that further rational design of the molecular interactions will provide efficient tools for enhancing the multifunctional property profiles of such bioinspired nanocomposites.

  15. Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy

    Science.gov (United States)

    Lin, Tao

    Organic molecules are envisioned as the building blocks for design and fabrication of functional devices in future, owing to their versatility, low cost and flexibility. Although some devices such as organic light-emitting diode (OLED) have been already applied in our daily lives, the field is still in its infancy and numerous challenges still remain. In particular, fundamental understanding of the process of organic material fabrication at a molecular level is highly desirable. This thesis focuses on the design and fabrication of supramolecular and macromolecular nanostructures on a Au(111) surface through self-assembly, polymerization and a combination of two. We used scanning tunneling microscopy (STM) as an experimental tool and Monte Carlo (MC) and kinetic Monte Carlo (KMC) simulations as theoretical tools to characterize the structures of these systems and to investigate the mechanisms of the self-assembly and polymerization processes at a single-molecular level. The results of this thesis consist of four parts as below: Part I addresses the mechanisms of two-dimensional multicomponent supramolecular self-assembly via pyridyl-Fe-terpyridyl coordination. Firstly, we studied four types of self-assembled metal-organic systems exhibiting different dimensionalities using specifically-designed molecular building blocks. We found that the two-dimensional system is under thermodynamic controls while the systems of lower dimension are under kinetic controls. Secondly, we studied the self-assembly of a series of cyclic supramolecular polygons. Our results indicate that the yield of on-surface cyclic polygon structures is very low independent of temperature and concentration and this phenomenon can be attributed to a subtle competition between kinetic and thermodynamic controls. These results shed light on thermodynamic and kinetic controls in on-surface coordination self-assembly. Part II addresses the two-dimensional supramolecular self-assembly of porphyrin

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

    Science.gov (United States)

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

    2016-11-05

    An innovative approach is proposed for the recycling of metals from a simulant lithium-ion battery (LIBs) waste aqueous solution. Phosphonate organic linkers are introduced as precipitating agents to selectively react with the metals to form coordination polymers from an aqueous solution containing Ni, Mn and Co in a hydrothermal process. The supernatant is analyzed by ICP-AES to quantify the efficiency and the selectivity of the precipitation and the materials are characterized by Scanning Electron Microscopy (SEM), Powder X-Ray Diffraction (PXRD), Thermogravimetric Analyses (TGA) and nitrogen gas sorption (BET). Conditions have been achieved to selectively precipitate Manganese or Manganese/Cobalt from this solution with a high efficiency. This work describes a novel method to obtain potentially valuable coordination polymers from a waste metal solution that can be generalized on any waste solution. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2009-03-01

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

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

    Science.gov (United States)

    Marandi, Farzin

    2014-02-01

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

  19. Conformational assembly and biological properties of collagen mimetic peptides and their thermally responsive polymer conjugates

    Science.gov (United States)

    Krishna, Ohm Divyam

    2011-12-01

    Collagens are one of the most abundant proteins found in body tissues and organs, endowing structural integrity, mechanical strength, and multiple biological functions. Destabilized collagen inside human body leads to various degenerative diseases (ex. osteoarthritis) and ageing. This has continued to motivate the design of synthetic peptides and bio-synthetic polypeptides to closely mimic the native collagens in terms of triple helix structure and stability, potential for higher order assembly, and biological properties. However, the widespread application of de novo collagens has been limited in part by the need for hydroxylated proline in the formation of stable triple helical structures. To address this continued need, a hydroxyproline-free, thermally stable collagen-mimetic peptide (CLP-Cys) was rationally designed via the incorporation of electrostatically stabilized amino acid triplets. CLP-Cys was synthesized via solid phase peptide synthesis. The formation and stability of the triple helical structure were indicated via circular dichroism (CD) experiments and confirmed via differential scanning calorimetry (DSC) results. CLP-Cys also self-assembled into nano-rods and micro-fibrils, as evidenced via a combination of dynamic light scattering and transmission electron microscopy. Given the high thermal stability and its propensity for higher-order assembly, CLP-Cys was further functionalized at both the ends with a thermally responsive polymer, poly(diethylene glycol methyl ether methacrylate), (PDEGMEMA) to synthesize a biohybrid triblock copolymer. The CD results indicated that the triple helical form is retained, the thermal unfolding is sustained and helix to coil transition is reversible in the triblock hybrid context. The LCST of PDEGMEMA homopolymer (26 °C) is increased (to 35 °C) upon conjugation to the hydrophilic collagen peptide domain. Further, a combination of static light scattering, Cryo-SEM, TEM and confocal microscopy elucidated that the

  20. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui

    2013-06-26

    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  1. Designing Functionalized Nanoparticles for Controlled Assembly in Polymer Matrix: Self consistent PRISM Theory and Monte Carlo simulation Study

    Science.gov (United States)

    Jayaraman, Arthi; Nair, Nitish

    2011-03-01

    Significant interest has grown around the ability to create hybrid materials with controlled spatial arrangement of nanoparticles mediated by a polymer matrix. By functionalizing or grafting polymers on to nanoparticle surfaces and systematically tuning the composition, chemistry, molecular weight and grafting density of the grafted polymers one can tailor the inter-particle interactions and control the assembly/dispersion of the particles in the polymer matrix. In our recent work using self-consistent Polymer Reference Interaction Site Model (PRISM) theory- Monte Carlo simulations we have shown that tailoring the monomer sequences in the grafted copolymers provides a novel route to tuning the effective inter-particle interactions between the functionalized nanoparticles in a polymer matrix. In this talk I will present how monomer sequence and molecular weights (with and without polydispersity) of the grafted polymers, compatibility of the graft and matrix polymers, and nanoparticle size affect the chain conformations of the grafted polymers and the potential of mean force between the grafted nanoparticles in the matrix.

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

    Science.gov (United States)

    Zhang, Xiaoxing; Tan, Jipeng; Xu, Xinxin; Shi, Fanian; Li, Guanglu; Yang, Yiqiao

    2017-09-01

    A composite material has been obtained successfully through the loading of nanoscale coordination polymer on magnetic Fe3O4@SiO2 core-shell particle. In this composite material, coordination polymer nanoparticles distribute uniformly on Fe3O4@SiO2 and these two components are ;tied; together firmly with chemical bonds. Adsorption experiments suggest this composite material exhibits very excellent selectivity to hemoglobin. But under the same condition, its adsorption to bovine serum albumin can almost be ignored. This selectivity can be attributed to the existence of hydrophobic interactions between coordination polymer nanoparticle and hemoglobin. For composite material, the hemoglobin adsorption process follows Langmuir model perfectly with high speed. The adsorbed hemoglobin can be eluted easily by sodium dodecyl sulfate stripping reagent with structure and biological activity of hemoglobin keeps well. The composite material was also employed to separate hemoglobin from human whole blood, which receives a very satisfactory result. Furthermore, magnetic measurement reveals ferromagnetic character of this composite material with magnetization saturation 3.56 emu g-1 and this guarantees its excellent magnetic separation performance from the treated solution.

  3. In-Situ Composition and Luminescence of Europium and Terbium Coordination Polymers/PEMA Hybrid Thick Films

    Institute of Scientific and Technical Information of China (English)

    YAN Bing; WANG Qianming

    2005-01-01

    Europium and terbium coordination polymers of pyridine- 3-carboxylic acid were in-situ composed with ethyl methacrylate ( EMA ). With the polymerization of EMA monomer and the formation of europium and terbium coordination polymers of pyridine- 3-carboxylic acid, the transparent hybrid thick films composed of [Eu( NIC)3 ]n ( [ Tb( NIC)3 ]n ) and poly ethyl methacrylate ( PEMA ) have been prepared. The luminescence properties and energy transfer of these polymeric composites were studied with absorption spectra, fluorescent excitation and emission spectra in detail. All the hybrid thick films composed of terbium coordination polymer show the characteristic strong green emission of terbium ions, which implies the same energy transfer mechanism as the pure complex and the hybrid composite film is a suitable substrate for the luminescence of terbium ions. In the range of composing concentration of luminescent species (0.01,0.025,0.05,0.1 mmol/15 mL EMA ) , emission intensities increase with the increasing of corresponding composing concentration and the concentration quenching effect does not take place.

  4. Structure Variation from One-Dimensional Chain to Three-Dimensional Architecture: Effect of Ligand on Construction of Lanthanide Coordination Polymers

    Indian Academy of Sciences (India)

    LEI WANG; WEN-XUAN LI; XIAO-MIN GU; WEN-LI ZHANG; LIANG NI

    2017-02-01

    Four lanthanide coordination polymers were constructed from mixed ligands of phenanthroline derivative and flexible polydentate ligands, [Gd2 (1,3-BDC)3(MOPIP) 2]n•nH2O (1), [Gd(1,4-BDC)1.5(MOPIP)] n• (2), [Yb(1,4-BDC)1.5(MOPIP)] n• (3) and [Sm(1,4-BDC)1.5(MOPIP)] n• (4), (MOPIP = 2-(4-methoxyphenyl)-1Himidazo[ 4,5-f ][1,10]phenanthroline, 1,3-BDC = benzene-1,3- dicarboxylic acid, 1,4-BDC = benzene-1, 4-dicarboxylic acid). The polymers have been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction analysis. Compound 1 possesses one-dimensional chain structure,and expands into the three-dimensional supramolecular architecture by π • • • π stacking and hydrogen-bonding interactions. Meanwhile, compounds 2–4 exhibit three-dimensional frameworks with pcu topology (412•63). The structural differences among such compounds show that the steric hindrances of benzene dicarboxylicacid ligands play a key role in the assembly and the structures of the title compounds. Compounds 1 and 2 act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde in high yields, due to the strong Lewisacidity

  5. Stereochemically Distinct Cyclotetrasiloxanes Containing 3-Pyridyl Moieties and Their Functional Coordination Polymers.

    Science.gov (United States)

    Deshmukh, Mahesh S; Vijayakanth, Thangavel; Boomishankar, Ramamoorthy

    2016-03-21

    Synthesis of new cyclotetrasiloxane scaffolds containing peripherally functionalized 3-pyridyl moieties, [MeSiO(CH═CH(3)Py)]4 (L(1)) and [MeSiO(CH2CH2(3)Py)]4 (L(2)), and their reactivity studies with certain d(10) metal ions are reported. The ligand L(1) is obtained by the Heck-coupling reaction of tetramethyl tetravinyl tetrasiloxane (D4(vi)) and 3-bromopyridine in the presence of the Pd(0) catalysts. The as-synthesized ligand L(1) shows the presence of three stereoisomers, cis-trans-cis (L(1A)), cis-cis-trans (L(1B)), and all-trans (L(1C)), which are quantitatively separated by column chromatography. Subsequent reduction of L(1A), L(1B), and L(1C) with triethylsilane in the presence of catalytic amounts of Pd/C leads to the formation of the ligands L(2A), L(2B), and L(2C) with retention of stereochemistry due to the precursor moieties. Treatment of ZnI2 with L(1A) gives a one-dimensional coordination framework [(L(1A))4(ZnI2)2]∞, 1. These 1D-chains are further connected by π-π stacking interactions between the pyridyl groups of the adjacent chains leading to the formation of a three-dimensional network with the topology of a PtS net. The reaction of silver nitrate with ligand L(1B) gives a chain like one-dimensional cationic coordination polymer {[(L(1B))4Ag2]·2NO3·H2O·CH3OH }∞, 2, consisting of two different kinds of 32-membered macrocycles. Treatment of the all-trans ligand L(2C) with copper(I) iodide salt results in the formation of a cubane-type Cu4I4 cluster MOF [(L(2C))4Cu4I4]∞, 3, in a two-dimensional 4-connected uninodal sql/Shubnikov tetragonal plane net topology represented by the Schläfli symbol {4(4).6(2)}. This MOF displays a thermochromic luminescence behavior due to Cu4I4 clusters showing an orange emission at 298 K and a blue emission at 77 K.

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

    Science.gov (United States)

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

    2012-09-17

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

  7. Synthesis of nanostructured materials by using metal-cyanide coordination polymers and their lithium storage properties.

    Science.gov (United States)

    Nie, Ping; Shen, Laifa; Luo, Haifeng; Li, Hongsen; Xu, Guiyin; Zhang, Xiaogang

    2013-11-21

    Herein, we demonstrate a novel and simple two-step process for preparing LiCoO2 nanocrystals by using a Prussian blue analogue Co3[Co(CN)6]2 as a precursor. The resultant LiCoO2 nanoparticles possess single crystalline nature and good uniformity with an average size of ca. 360 nm. The unique nanostructure of LiCoO2 provides relatively shorter Li(+) diffusion pathways, thus facilitating the fast kinetics of electrochemical reactions. As a consequence, high reversible capacity, excellent cycling stability and rate capability are achieved with these nanocrystals as cathodes for lithium storage. The LiCoO2 nanocrystals deliver specific capacities of 154.5, 135.8, 119, and 100.3 mA h g(-1) at 0.2, 0.4, 1, and 2 C rates, respectively. Even at a high current density of 4 C, a reversible capacity of 87 mA h g(-1) could be maintained. Importantly, a capacity retention of 83.4% after 100 cycles is achieved at a constant discharge rate of 1 C. Furthermore, owing to facile control of the morphology and size of Prussian blue analogues by varying process parameters, as well as the tailored design of multi-component metal-cyanide hybrid coordination polymers, with which we have successfully prepared porous Fe2O3@NixCo3-xO4 nanocubes, one of the potential anode materials for lithium-ion batteries, such a simple and scalable approach could also be applied to the synthesis of other nanomaterials for energy storage devices.

  8. Syntheses,Structures and Properties of Lanthanide Coordination Polymers Constructed from Mixed Acid

    Institute of Scientific and Technical Information of China (English)

    孙长艳; 吕琼; 张慧燕; 李文军; 常志东; 郑向军

    2012-01-01

    Two new coordination polymers,[Ln(oba)(ox)0.5(H2O)2]n(Ln = Ho(1),Eu(2);H2oba = 4,4?-oxybis(benzoic acid),H2ox = oxalic acid) have been synthesized under hydrothermal conditions.According to single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P21/c with a = 13.783(2),b =10.0120(15),c = 12.1974(18) ,β = 105.217(2)°,V = 1624.2(4) 3,C15H12O9Ho,Mr = 501.18,Z = 4,Dc = 2.050 g/cm3,F(000) = 964,μ = 4.919 mm-1,λ(MoKα) = 0.71073 ?,GOOF = 1.124,the final R = 0.0239 and wR = 0.0570 for 3310 independent reflections with Rint = 0.0298.Complexes 2 and 1 are isostructural.Oba and ox ligands bridge the Ln(III) ions into 2D layers with(4,4) topology,which are further interlinked into a 3D supramolecular network by hydrogen bonds.TG curves of the two complexes are studied to examine their thermal stabilities.Additionally,complex 2 shows red fluorescence in the solid state at room temperature.

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

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Qing-Jun; Zheng, Yue-Qing, E-mail: yqzhengmc@163.com; 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.

  10. Thermodynamically metastable thiocyanato coordination polymer that shows slow relaxations of the magnetization.

    Science.gov (United States)

    Werner, Julia; Rams, Michał; Tomkowicz, Zbigniew; Runčevski, Tomče; Dinnebier, Robert E; Suckert, Stefan; Näther, Christian

    2015-03-16

    Reaction of cobalt thiocyanate with 4-acetylpyridine leads to the formation of [Co(NCS)2(4-acetylpyridine)2]n (3/I). In its crystal structure the Co cations are connected by pairs of μ-1,3-bridging thiocyanato ligands into dimers that are further connected into layers by single anionic ligands. DTA-TG measurements of Co(NCS)2(4-acetyl-pyridine)4 (1) led to the formation of 3/I. In contrast, when the hydrate Co(NCS)2(4-acetyl-pyridine)2(H2O)2 (2) is decomposed, a mixture of 3/I and a thermodynamically metastable form 3/II is obtained. Further investigations reveal that thermal annealing of 2 leads to the formation of 3/II, that contains only traces of the stable form 3/I. DSC and temperature dependent X-ray powder diffraction (XRPD) measurements prove that 3/II transforms into 3/I on heating. The crystal structure of 3/II was determined ab initio from XRPD data. In its crystal structure the Co cations are linked by pairs of bridging thiocyanato anions into a 1D coordination polymer, and thus, 3/II is an isomer of 3/I. Magnetic measurements disclose that the stable form 3/I only shows paramagnetism without any magnetic anomaly down to 2 K. In contrast, the metastable form 3/II shows ferromagnetic behavior. The phase transition into ordered state at Tc = 3.8 K was confirmed by specific heat measurements. Alternating current susceptibility measurements show frequency dependent maxima in χ' and χ″, which is indicative for a slow relaxation of the magnetization.

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

    Science.gov (United States)

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

    2017-01-01

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

  12. Syntheses, Structures, and Properties of Five Coordination Polymers Involving Phthalic Acid

    Institute of Scientific and Technical Information of China (English)

    WU Li-li; HE Rong; WEI Zhen; SONG Hui-hua

    2011-01-01

    Five new coordination polymers Cu(phen)(H2O)(phth)·CH3OH(1),[Cu(2,2'-bipy)(H2O)](phth).3.5H2O(2),Zn(phen)(phth)(H2O).1.125H2O(3) and [M(4,4'-bipy)(H2O)2](phth).2H2O[M=Zn(4),Mn(5)](H2phth=phthalic acid,bipy=bipyridine,phen=l,10-phenanthroline) have been synthesized from the amino acid derivatives(phthalyl-I-valine,H2L) and structurally characterized.H2L was hydrolyzed into phth2- group during the reaction,but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature,revealing that H2L played an important role in composing the novel compounds.Compounds 1,2 and 3 are all 1D chains,but the differences are that compound 1 is further hydrogen-bonded into 2D networks,and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions.However,compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking.Compounds 4 and 5 are isostructural and exhibit the same 2D layers,which are further connected by hydrogen-bonding interactions to form 3D supramolecular network.Antiferromagnetic superexchange was observed for compounds 1,2 and 5.

  13. Structures and properties of porous coordination polymers based on lanthanide carboxylate building units.

    Science.gov (United States)

    Han, Yinfeng; Li, Xiaoyan; Li, Liqing; Ma, Chunlin; Shen, Zhen; Song, You; You, Xiaozeng

    2010-12-06

    A series of 3-D lanthanide porous coordination polymers, [Ln(6)(BDC)(9)(DMF)(6)(H(2)O)(3)·3DMF](n) [Ln = La, 1; Ce, 2; Nd, 3], [Ln(2)(BDC)(3)(DMF)(2)(H(2)O)(2)](n) [Ln = Y, 4; Dy, 5; Eu, 6], [Ln(2)(ADB)(3)(DMSO)(4)·6DMSO·8H(2)O](n) [Ln = Ce, 7; Sm, 8; Eu, 9; Gd, 10], {[Ce(3)(ADB)(3)(HADB)(3)]·30DMSO·29H(2)O}(n) (11), and [Ce(2)(ADB)(3)(H(2)O)(3)](n) (12) (H(2)BDC = benzene-1,4-dicarboxylic acid and H(2)ADB = 4,4'-azodibenzoic acid), have been synthesized and characterized. In 1-3, the adjacent Ln(III) ions are intraconnected to form 1-D metal-carboxylate oxygen chain-shaped building units, [Ln(4)(CO(2))(12)](n), that constructed a 3-D framework with 4 × 7 Å rhombic channels. In 4-6, the dimeric Ln(III) ions are interlinked to yield scaffolds with 3-D interconnecting tunnels. Compounds 7-10 are all 3-D interpenetrating structures with the CaB6-type topology structure. Compound 11 is constructed by ADB spacers and trinulcear Ce nodes with a NaCl-type topology structure and a 1.9-nm open channel system. In 12, the adjacent Ce(III) ions are intraconnected to form 1-D metal-carboxylate oxygen chain-shaped building units, [Ln(4)(CO(2))(12)](n), and give rise to a 3-D framework. Moreover, 6 exhibits characteristic red luminescence properties of Eu(III) complexes. The magnetic susceptibilities, over a temperature range of 1.8-300 K, of 3, 6, and 7 have also been investigated; the results show paramagnetic properties.

  14. Tunable Gas Permeability of Polymer-Clay Nano Brick Wall Thin Film Assemblies

    Science.gov (United States)

    Gamboa, Daniel; Priolo, Morgan; Grunlan, Jaime

    2010-03-01

    Thin films of anionic natural montmorrilonite (MMT) clay and cationic polyethylenimine (PEI) have been produced by alternately dipping a plastic substrate into dilute aqueous mixtures containing each ingredient. After 40 polymer-clay layers have been deposited, the resulting transparent film exhibits an oxygen transmission rate (OTR) below 0.35 cm^3/m^2 . day when the pH of PEI solution is 10. This low permeability is due to a brick wall nanostructure comprised of completely exfoliated clay bricks in polymeric mortar. This brick wall creates an extremely tortuous path at thicknesses below 250 nm and clay concentration above 80 wt%. A 70-bilayer PEI-MMT assembly has an undetectable OTR (packaging and foil replacement for food.

  15. Cadmium coordination polymers based on flexible bis(imidazole) ligands: A rare example for doublet of doublet cadmium polyhedron arrangements

    Science.gov (United States)

    Babu, Chatla Naga; Suresh, Paladugu; Sampath, Natarajan; Prabusankar, Ganesan

    2014-10-01

    Two one-dimensional (1D) coordination polymers, [{LCd(O2NO)2(DMF)2}2{(LCd(O2NO)2(DMF))(DMF)}2]n (1) and [L‧Cd(O2NO)(ONO2)(DMF)2]n (2), having an aryl chromophoric unit and a flexible bis(imidazole) tail, 9,10-bis{(benzimidazol)methyl}anthracene (L) and 1,4-bis{(imidazol)methyl}benzene (L‧), with various coordination modes have been obtained. Molecule 1 represents the first structurally characterized one dimensional coordination polymer consisting of both hepta- and octa-coordinated cadmium centers. In 1, two distorted pentagonal bipyramidal Cd(II) centers and two distorted triangular dodecahedral Cd(II) centers are alternately arranged via bridging bidentate N,N-chelating ligand, L. Whereas, a distorted pentagonal bipyramidal Cd(II) center is formed in 2 where the sterically less crowded L‧ serves as a bridging bidentate N,N-chelating ligand. Furthermore, 1 and 2 have been characterized by elemental analysis, FT-IR, 1H NMR, UV-vis and fluorescent techniques.

  16. SYNTHESIS, CHARACTERIZATION AND ANTITUMOR ACTIVITY OF A Ca (II COORDINATION POLYMER BASED ON 3-AMINO-2-PYRAZINECARBOXYLIC ACID

    Directory of Open Access Journals (Sweden)

    XI-SHI TAI

    2015-10-01

    Full Text Available A new Ca(II coordination polymer has been obtained by reaction of Ca(ClO42·H2O with 3-amino-2-pyrazinecarboxylic acid in CH3CH2OH/H2O. It was characterized by IR, 1HNMR, thermal analysis and X-ray single crystal diffraction analysis. X-ray analysis reveals that each Ca(II center is seven-coordination with a N2O5 distorted pentagonal bipyramidal coordination environment. The Ca(II ions are linked through the O atoms of 3-amino-2-pyrazinecarboxylic acid ligands to form 1D chain structure. And then a 3D network structure is constructed by hydrogen bonds and π-π stacking. The antitumor activity of 3-amino-2-pyrazinecarboxylic acid ligand and its Ca(II coordination polymer against human intestinal adenocarcinoma HCT-8 cells, lung adenocarcinoma HCT-116 cells and human lung adenocarcinoma A549 cells line have been investigated.

  17. Synthesis, characterization and magnetic property of a succinate bridged 1D coordination polymer of cobalt(II) containing benzidine as end-capping ligand

    Science.gov (United States)

    Roy, Subhasis; Choubey, Somnath; Khan, Sumitava; Bhar, Kishalay; Ribas, Joan; Ghosh, Barindra Kumar

    2014-03-01

    A new bis(monodentate) succinate bridged 1D coordination polymer [Co(bnzd)2(μ-suc)(OH2)2]nṡ(H2O)n (1) (bnzd = benzidine; suc = succinate dianion) has been isolated using a one-pot reaction of the building components, and characterized structurally and magneto-structurally. Single crystal X-ray diffraction measurement reveals that each cobalt(II) center adopts an octahedral geometry with a CoN2O4 chromophore coordinated by two N atoms of two bnzd ligands, two O atoms of two water molecules and two O atoms of two suc units. In crystalline state, individual units of 1 self-assemble through cooperative N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds and C-H⋯π interactions affording a 3D network structure. Variable-temperature magnetic susceptibility measurement of 1 in the 2-300 K temperature range shows weak antiferromagnetic coupling among the adjacent cobalt(II) centers presumably due to long bridging arm of the dicarboxylate.

  18. Synthesis and Crystal Structure of a One-Dimensional Coordination Polymer Containing Unusual Na2Cu2 Tetrametallacyclic Units

    Institute of Scientific and Technical Information of China (English)

    GAO,En-Qing(高恩庆); SUN,Hai-Ying(孙海英); LIAO,Dai-Zheng(廖代正); JIANG,Zong-Hui(姜宗慧); YAN Shi-Ping(阎世平)

    2002-01-01

    A unique coordination polymer, {[CuLNa(ClO4)]@ H2O}n (1), was isolated from the solution containing sodium perchlorate and the neutral macrocyclic oxamidocopper(Ⅱ) complex [CuL] (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(ethoxycarbonyl)-1, 4, 8, 11-tetraazacyclotetradeca-7, 11-diene). The complex is composed of [Na2Cu2] tetrametallavycles bridged by perchlorate ions to form infinite one-dimensional chains which are stacked via π-π interactions and weak coordination bonds to result in a two-dimensional supramolecular network. The perclorate ions were found to coordinate to sodium atoms in the unusual bridging chelating tridentate mode of μ2-(O:O′,O").

  19. Self-assembly of octapod-shaped colloidal nanocrystals into a hexagonal ballerina network embedded in a thin polymer film

    NARCIS (Netherlands)

    Arciniegas, Milena P.; Kim, Mee R.; De Graaf, Joost|info:eu-repo/dai/nl/314838961; Brescia, Rosaria; Marras, Sergio; Miszta, Karol; Dijkstra, Marjolein|info:eu-repo/dai/nl/123538807; Van Roij, René|info:eu-repo/dai/nl/152978984; Manna, Liberato

    2014-01-01

    Nanoparticles with unconventional shapes may exhibit different types of assembly architectures that depend critically on the environmental conditions under which they are formed. Here, we demonstrate how the presence of polymer (polymethyl methacrylate, PMMA) molecules in a solution, in which CdSe(c

  20. Heparin as a Bundler in a Self-Assembled Fibrous Network of Functionalized Protein-Based Polymers

    NARCIS (Netherlands)

    Wlodarczyk-Biegun, Gosia; Slingerland, Cornelis J.; Werten, Marc W.T.; Hees, van Ilse A.; Wolf, de Frits A.; Vries, de Renko; Cohen Stuart, Martien; Kamperman, Marleen

    2016-01-01

    Nature shows excellent control over the mechanics of fibrous hydrogels by assembling protein fibers into bundles of well-defined dimensions. Yet, obtaining artificial materials displaying controlled bundling remains a challenge. Here, we developed genetically engineered protein-based polymers

  1. Self-assembly of octapod-shaped colloidal nanocrystals into a hexagonal ballerina network embedded in a thin polymer film

    NARCIS (Netherlands)

    Arciniegas, Milena P.; Kim, Mee R.; De Graaf, Joost; Brescia, Rosaria; Marras, Sergio; Miszta, Karol; Dijkstra, Marjolein; Van Roij, René; Manna, Liberato

    2014-01-01

    Nanoparticles with unconventional shapes may exhibit different types of assembly architectures that depend critically on the environmental conditions under which they are formed. Here, we demonstrate how the presence of polymer (polymethyl methacrylate, PMMA) molecules in a solution, in which CdSe(c

  2. Ion current behaviors of mesoporous zeolite-polymer composite nanochannels prepared by water-assisted self-assembly.

    Science.gov (United States)

    Zhang, Wenjuan; Meng, Zheyi; Zhai, Jin; Heng, Liping

    2014-04-07

    Inspired by the asymmetry of biological ion channels in structure and composition, we designed a novel type of artificial asymmetric nanochannels based on mesoporous zeolite (MCM-41) and polyimide (PI) by water-assisted self-assembly. Meanwhile, we studied ionic current behaviors and rectifying characteristics of the mesoporous zeolite-polymer composite nanochannels.

  3. Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid

    Science.gov (United States)

    Zhan, Honglei; Liang, Jun F.

    2016-12-01

    Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 boric acid will have wide biomedical applications especially in biomaterials and drug delivery field.

  4. Hepatic trans-Golgi action coordinated by the GTPase ARFRP1 is crucial for lipoprotein lipidation and assembly[S

    Science.gov (United States)

    Hesse, Deike; Radloff, Katrin; Jaschke, Alexander; Lagerpusch, Merit; Chung, Bomee; Tailleux, Anne; Staels, Bart; Schürmann, Annette

    2014-01-01

    The liver is a major organ in whole body lipid metabolism and malfunctioning can lead to various diseases including dyslipidemia, fatty liver disease, and type 2 diabetes. Triglycerides and cholesteryl esters are packed in the liver as very low density lipoproteins (VLDLs). Generation of these lipoproteins is initiated in the endoplasmic reticulum and further maturation likely occurs in the Golgi. ADP-ribosylation factor-related protein 1 (ARFRP1) is a small trans-Golgi-associated guanosine triphosphatase (GTPase) that regulates protein sorting and is required for chylomicron lipidation and assembly in the intestine. Here we show that the hepatocyte-specific deletion of Arfrp1 (Arfrp1liv−/−) results in impaired VLDL lipidation leading to reduced plasma triglyceride levels in the fasted state as well as after inhibition of lipoprotein lipase activity by Triton WR-1339. In addition, the concentration of ApoC3 that comprises 40% of protein mass of secreted VLDLs is markedly reduced in the plasma of Arfrp1liv−/− mice but accumulates in the liver accompanied by elevated triglycerides. Fractionation of Arfrp1liv−/− liver homogenates reveals more ApoB48 and a lower concentration of triglycerides in the Golgi compartments than in the corresponding fractions from control livers. In conclusion, ARFRP1 and the Golgi apparatus play an important role in lipoprotein maturation in the liver by influencing lipidation and assembly of proteins to the lipid particles. PMID:24186947

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

    Science.gov (United States)

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

    2016-09-01

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

  6. Transition metal coordination polymers based on tetrabromoterephthalic and bis(imidazole) ligands: Syntheses, structures, topological analysis and photoluminescence properties

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Hiroyuki Kawaguchi

    2010-08-01

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

  8. A TEMPERATURE AND pH DOUBLE SENSITIVE CHOLESTERIC POLYMER FILM FROM A PHOTOPOLYMERIZABLE CHIRAL HYDROGEN-BONDED ASSEMBLY

    Institute of Scientific and Technical Information of China (English)

    Feng-jin Chen; Jin-bao Guo; Ou-yu Jin; Jie Wei

    2013-01-01

    In this study,a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated.The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal (Ch-LC) monomers mixture containing a photopolymerizable chiral H-bonded assembly (PCHA).The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased,which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film.Additionally,the selective reflection band (SRB) of the cholesteric polymer film in solution with pH > 7showed an obvious red shift with increasing pH values.While the SRB of the cholesteric polymer film in solutions with pH =7 and pH < 7 hardly changed.This pH sensitivity in solutions with pH > 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by-OFF and-K+ ions in the alkaline solution.In contrast,it couldn't happen in the neutral and acidic solutions.The cholesteric polymer film in this study can be used as optical/photonic papers,optical sensors and LCs displays,etc.

  9. Exploiting Supramolecular Interactions for the Intramolecular Folding of Side-Chain Functionalized Polymers and Assembly of Anisotropic Colloids

    Science.gov (United States)

    Romulus, Joy

    The overarching goal presented in this thesis is the self-assembly of synthetic systems into higher ordered structures utilizing supramolecular chemistry. Noncovalent interactions including charge-transfer and hydrogen bonding as well as DNA hybridization are exploited to induce the assembly of polymers and colloids into well-defined architectures. This strategy provides a tunable handle on materials bulk properties that can be adjusted by simply changing variables such as temperature and solvent. A brief overview of design principles for the supramolecular assembly of side-chain functionalized polymers is presented. The polymerization technique selected was living ring-opening metathesis polymerization (ROMP), thus affording control over molecular weight and molecular weight distributions. ROMP also allowed for the incorporation of functional groups that were used to assemble the polymers into ordered structures. Charge-transfer motifs were exploited and shown to drive the assembly of random and alternating copolymers via intramolecular side-chain interactions. Incorporation of complementary hydrogen bonding motifs was shown to guide the single-chain folding of a multifunctional triblock copolymer into sheet-like structures. Precision over the size, shape, and monomer sequence were identified as key elements for efficient self-assembly. The self-assembly of colloids using DNA hybridization was also investigated. Previously, the majority of colloid-based research relied upon the self-assembly of spherical isotropic particles into closed-packed arrangements. In contrast, anisotropic particles may allow for the realization of open structures. By expanding upon a method to permanently cross-link DNA strands incubated on a colloidal surface, a new strategy to engineer patchy particles is described. These functional DNA-coated patches are demonstrated to direct particle assembly. The self-assembly of polymer and colloidal systems utilizing noncovalent interactions

  10. Preparation of surface-tethered polymer layer on inorganic substrates by photoreactive self-assembled monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seong-Ho; Ohtsuka, Hanae [Tokyo University of Agriculture and Technology, Department of Organic and Polymer Materials Chemistry, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588 (Japan); Tria, Maria Celeste R. [University of Houston, Department of Chemistry, 136 Fleming Building, Houston, TX 77204-5008 (United States); Tanaka, Kuniaki [Tokyo University of Agriculture and Technology, Department of Organic and Polymer Materials Chemistry, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588 (Japan); Advincula, Rigoberto C. [Case Western Reserve University, Department of Macromolecular Science and Engineering, 2100 Adelbert Road, Cleveland, OH 44106 (United States); Usui, Hiroaki, E-mail: h_usui@cc.tuat.ac.jp [Tokyo University of Agriculture and Technology, Department of Organic and Polymer Materials Chemistry, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588 (Japan)

    2014-03-03

    A self-assembled monolayer (SAM) that has benzophenone (BP) terminal group was prepared on Si and indium–tin oxide (ITO) substrates, on which poly(9-vinyl carbazol) (PVK) was spin-coated and then irradiated with ultraviolet (UV) light. Upon UV irradiation, the BP unit reacted with the PVK backbone, yielding a crosslinked PVK layer that was covalently tethered to the substrate surface. Using this procedure, a patterned thin film of PVK was obtained by irradiating UV light through a photomask and then rinsing in chloroform. When polystylene (PSt) was spin-coated on the BP-SAM, only a thin interfacial layer was tethered by UV irradiation because PSt does not crosslink upon UV irradiation. The BP-SAM improved the adhesion strength between the PVK layer and ITO substrate without reducing the carrier injection from ITO to PVK. The photoreactive BP-SAM appeared to be an effective method to improve the interface between an inorganic electrode and a polymer layer deposited on its surface. - Highlights: • Polyvinylcarbazole (PVK) was tethered to substrate by self-assembled monolayer (SAM). • The photoreactive SAM was effective in improving adhesion strength of the films. • This process was applied for photopatterning of PVK layer. • The photoreactive SAM did not impede carrier injection from electrode to PVK.

  11. Coordination Polymers towards Advanced Functions%向高功能发展的配位聚合物

    Institute of Scientific and Technical Information of China (English)

    杜淼; 卜显和

    2009-01-01

    The rational design and preparation of metal-organic coordination polymers with specific network structures and physicochemical properties by using the experience and method of crystal engineering has currently been a hot research topic in coordination chemistry, supramolecular chemistry, material chemistry and other related areas. As a new type of molecular-based crystalline material, coordination polymers (especially microporous coordination polymers) have displayed potential applications in many aspects such as guest exchange/separation, gas storage, chiral resolution, drug release, electroluminescence, selective catalysis, molecular recognition, and microporous devices. In this paper, the recent progress of such advanced multifunctional crystalline materials and their applications in adsorption, catalysis as well as optics, electrics, and magnetism are briefly reviewed.%运用晶体工程的经验和方法合理设计和制备具有特定网络结构和理化性能的配位聚合物是当前配位化学、超分子化学、材料化学及相关领域的研究热点之一.作为一类新型分子基晶体材料,配位聚合物(尤其是多孔配位聚合物)在客体交换与分离、气体储存、手性拆分、药物缓释、电致发光、选择性催化、分子识别及微孔器件等诸多方面均显示出潜在的应用前景.本文简要介绍了此类化合物作为具有复合性能的多功能晶体材料在吸附、催化及光、电、磁等方面应用的最新研究进展.

  12. Towards surface-supported supramolecular architectures: tailored coordination assembly of 1,4-benzenedicarboxylate and Fe on Cu(100).

    Science.gov (United States)

    Lingenfelder, Magalí A; Spillmann, Hannes; Dmitriev, Alexandre; Stepanow, Sebastian; Lin, Nian; Barth, Johannes V; Kern, Klaus

    2004-04-19

    We present a comprehensive investigation of the modular assembly of surface-supported metal-organic coordination systems with specific topologies and high structural stability formed by vapor deposition of 1,4-benzenedicarboxylic acid molecules and iron atoms on a Cu(100) surface under ultra-high vacuum conditions. By making use of the two carboxylate moieties available for lateral linkage to Fe atoms, we succeeded in the fabrication of distinct Fe-carboxylate coordination architectures at the surface by carefully adjusting the ligand and metal concentration ratio and the temperature of the post-deposition annealing treatment. The mononuclear, 1D-polymeric and fully 2D-reticulated metallosupramolecular arrangements obtained were characterized in situ at the single-molecule level by scanning tunneling microscopy.

  13. Lanthanide-directed synthesis of luminescent self-assembly supramolecular structures and mechanically bonded systems from acyclic coordinating organic ligands.

    Science.gov (United States)

    Barry, Dawn E; Caffrey, David F; Gunnlaugsson, Thorfinnur

    2016-06-01

    Herein some examples of the use of lanthanide ions (f-metal ions) to direct the synthesis of luminescent self-assembly systems (architectures) will be discussed. This area of lanthanide supramolecular chemistry is fast growing, thanks to the unique physical (magnetic and luminescent) and coordination properties of the lanthanides, which are often transferred to the resulting supermolecule. The emphasis herein will be on systems that are luminescent, and hence, generated by using either visibly emitting ions (such as Eu(III), Tb(III) and Sm(III)) or near infrared emitting ions (like Nd(III), Yb(III) and Er(III)), formed through the use of templating chemistry, by employing structurally simple ligands, possessing oxygen and nitrogen coordinating moieties. As the lanthanides have high coordination requirements, their use often allows for the formation of coordination compounds and supramolecular systems such as bundles, grids, helicates and interlocked molecules that are not synthetically accessible through the use of other commonly used templating ions such as transition metal ions. Hence, the use of the rare-earth metal ions can lead to the formation of unique and stable species in both solution and in the solid state, as well as functional and responsive structures.

  14. A new two-dimensional manganese(II) coordination polymer based on thiophene-3,4-dicarboxylic acid.

    Science.gov (United States)

    Wang, Gui-Xia; Shang, Li-Li; Li, Zhao-Hao; Zhao, Bang-Tun

    2014-07-01

    A novel manganese coordination polymer, poly[(μ5-thiophene-3,4-dicarboxylato)manganese(II)], [Mn(C6H2O4S)]n, was synthesized hydrothermally using 3,4-thiophenedicarboxylate (3,4-tdc(2-)) as the organic linker. The asymmetric unit of the complex contains an Mn(2+) cation and one half of a deprotonated 3,4-tdc(2-) anion, both residing on a twofold axis. Each Mn(2+) centre is six-coordinated by O atoms of bridging/chelating carboxylate groups from five 3,4-tdc(2-) anions, forming a slightly distorted octahedron. The Mn(2+) centres are bridged by 3,4-tdc(2-) anions to give an infinite two-dimensional layer which incorporates one-dimensional Mn-O gridlike chains, and in which the 3,4-tdc(2-) anion adopts a novel hexadentate chelating and μ5-bridging coordination mode. The fully deprotonated 3,4-tdc(2-) anion exhibits unexpected efficiency as a ligand towards the Mn(2+) centres, which it coordinates through all of its carboxylate O atoms to provide the novel coordination mode. The IR spectrum of the complex is also reported.

  15. Hydrogen-bonded porous coordination polymers: structural transformation, sorption properties, and particle size from kinetic studies.

    Science.gov (United States)

    Uemura, Kazuhiro; Saito, Kazuya; Kitagawa, Susumu; Kita, Hidetoshi

    2006-12-20

    Three new coordination polymers, [CoCl2(4-pmna)2]n (1), {[Co(NCS)2(4-pmna)2].2Me2CO}n (2 superset 2Me2CO), and {[Co(4-pmna)2(H2O)2](NO3)2.2CH3OH}n (3 superset 2H2O.2MeOH) (4-pmna = N-(pyridin-4-ylmethyl)nicotinamide), have been synthesized and characterized using single-crystal X-ray diffraction. The cobalt(II) atoms are bridged by 4-pmna ligands in all three compounds to form double-stranded one-dimensional "repeated rhomboid-type" chains with rectangular-shaped cavities. In 1, each chain slips and obstructs the neighboring cavities so that there are no guest-incorporated pores. Both 2 superset 2Me2CO and 3 superset 2H2O.2MeOH do not have such a staggered arrangement and have pores that can be filled with a guest molecule. Compound 3 superset 2H2O.2MeOH traps guest molecules with multiple hydrogen bonds and shows a reversible structural rearrangement during adsorption and desorption. The new crystalline compound, 3, is stabilized by forming hydrogen bonds with the amide moieties of the 4-pmna ligands and was characterized using infrared spectroscopy. The clathration enthalpy of the reaction 3 + 2H2O(l) + 2MeOH(l) 3 superset 2H2O.2MeOH (approximately 35 kJ/mol) was estimated from differential scanning calorimetry data by considering the vaporization enthalpies of H2O and MeOH. The desorption process of 3 superset 2H2O.2MeOH --> 3 follows a single zero-order reaction mechanism under isothermal conditions. The activation energy of ca. 100 kJ/mol was obtained by plotting the logarithm of the reaction time for the same reacted fraction versus the reciprocal of the temperature. Moreover, the distribution of the one-dimensional channels in 3 superset 2H2O.2MeOH was estimated using the observation that the reaction rate is directly proportional to the total sectional area.

  16. Proton dynamics of two-dimensional oxalate-bridged coordination polymers.

    Science.gov (United States)

    Miyatsu, Satoshi; Kofu, Maiko; Nagoe, Atsushi; Yamada, Takeshi; Sadakiyo, Masaaki; Yamada, Teppei; Kitagawa, Hiroshi; Tyagi, Madhusudan; García Sakai, Victoria; Yamamuro, Osamu

    2014-08-28

    A two-dimensional porous coordination polymer (NH4)2{HOOC(CH2)4COOH}[Zn2(C2O4)3] (abbreviated as (NH4)2(adp)[Zn2(ox)3] (adp = adipic acid, ox = oxalate)), which accommodates water molecules between the [Zn2(ox)3] layers, is highly remarked as a new type of crystalline proton conductor. In order to investigate its phase behavior and the proton conducting mechanism, we have performed adiabatic calorimetry, neutron diffraction, and quasi-elastic neutron scattering experiments on a fully hydrated sample (NH4)2(adp)[Zn2(ox)3]·3H2O with the highest proton conductivity (8 × 10(-3) S cm(-1), 25 °C, 98% RH). Its isostructural derivative K2(adp)[Zn2(ox)3]·3H2O was also measured to investigate the role of ammonium ions. (NH4)2(adp)[Zn2(ox)3]·3H2O and K2(adp)[Zn2(ox)3]·3H2O exhibit higher order transitions at 86 K and 138 K, respectively. From the magnitude of the transition entropy, the former is of an order-disorder type while the latter is of a displacive type. (NH4)2(adp)[Zn2(ox)3]·3H2O has four Debye-type relaxations and K2(adp)[Zn2(ox)3]·3H2O has two similar relaxations above each transition temperature. The two relaxations of (NH4)2(adp)[Zn2(ox)3]·3H2O with very small activation energies (ΔEa < 5 kJ mol(-1)) are due to the rotational motions of ammonium ions and play important roles in the proton conduction mechanism. It was also found that the protons in (NH4)2(adp)[Zn2(ox)3]·3H2O are carried through a Grotthuss mechanism. We present a discussion on the proton conducting mechanism based on the present structural and dynamical information.

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

    Science.gov (United States)

    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.

  18. Functional tetrametallic linker modules for coordination polymers and metal-organic frameworks.

    Science.gov (United States)

    Johansson, Frank B; Bond, Andrew D; McKenzie, Christine J

    2007-03-19

    potential construction of 1-D and 2-D coordination polymers/metal-organic frameworks (MOFs) capable of reversible O2 binding.

  19. Self-assembly of metal-organic coordination structures on surfaces

    Science.gov (United States)

    Dong, Lei; Gao, Zi'Ang; Lin, Nian

    2016-08-01

    Metal-organic coordination structures are materials comprising reticular metal centers and organic linkers in which the two constituents bind with each other via metal-ligand coordination interaction. The underlying chemistry is more than a century old but has attracted tremendous attention in the last two decades owing to the rapidly development of metal-organic (or porous coordination) frameworks. These metal-coordination materials exhibit extraordinarily versatile topologies and many potential applications. Since 2002, this traditionally three-dimensional chemistry has been extended to two-dimensional space, that is, to synthesize metal-organic coordination structures directly on solid surfaces. This endeavor has made possible a wide range of so-called surface-confined metal-organic networks (SMONs) whose topology, composition, property and function can be tailored by applying the principle of rational design. The coordination chemistry manifests unique characteristics at the surfaces, and in turn the surfaces provide additional control for design structures and properties that are inaccessible in three-dimensional space. In this review, our goal is to comprehensively cover the progress made in the last 15 years in this rapidly developing field. The review summarizes (1) the experimental and theoretical techniques used in this field including scanning tunneling microscopy and spectroscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, density functional theory, and Monte Carlo and kinetic Monte Carlo simulation; (2) molecular ligands, metal atoms, substrates, and coordination motifs utilized for synthesizing SMON; (3) representative SMON structures with different topologies ranging from finite-size discrete clusters to one-dimensional chains, two-dimensional periodical frameworks and random networks; and (4) the properties and potential applications of SMONs. We conclude the review with some perspectives.

  20. Solvothermal Synthesis, Crystal Structure and Luminescent Property of a Dy(Ⅲ) Coordination Polymer Constructed by 1,2,4,5-Benzenetetracarboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    BAI Wei-Wei; ZHU Ning; HAN Li-Min; tONG Hai-Long; GAOYuan-Yuan; SUO Quan-Ling

    2012-01-01

    A three-dimensional coordination polymer {[Dy(H2btec)2/4(btec)3/6(H2O)]·2H2O} n has been synthesized through the reaction of DyCl3·6H2O and 1,2,4,5-benzenetetracarboxylic acid by solvothermal technique, and the crystal structure was determined by X-ray diffraction. The Dy(Ⅲ) coordination polymer crystallizes in monoclinic, space group P21/n with a=10.7063(1), b=7.1491(1), c=17.1197(3), α=90, β=97.10, γ=90°, V=1300.31(3)3 , C10H9DyO11 , Dc=2.389g/cm3 , Z=4, F(000)=892, the final R=0.0165 and wR=0.0448 for I 〉 2σ(I). The title coordination polymer possesses a three-dimensional framework consisting of nine-coordinate Dy(Ⅲ) centers and two kinds of coordination modes for the 1,2,4,5-benzenetetracarboxylic acid ligands. Every btec4- ligand (deprotonated four protons from 1,2,4,5-benzenetetracarboxylic acid) in the title coordination polymer can clamp three Dy atoms like forceps, which could make the Dy atoms closer in the area of metal-metal interaction. The 3-D framework of the coordination polymer has many channels occupied by the free guest water molecules, and the hydrogen bonds between the coordinated carboxylic groups and guest water molecules could stabilize the crystal structure of the title coordination polymer. In addition, the luminescence properties were also studied.

  1. Thermo-reversible morphology and conductivity of a conjugated polymer network embedded in polymeric self-assembly

    Science.gov (United States)

    Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; Li, Yunchao; Hong, Kunlun; Sumpter, Bobby G.; Ohl, Michael; Paranthaman, Mariappan Parans; Smith, Gregory S.; Do, Changwoo

    Self-assembly of block copolymers provides opportunities to create nano hybrid materials, utilizing self-assembled micro-domains with a variety of morphology and periodic architectures as templates for functional nano-fillers. Here we report new progress towards the fabrication of a thermally responsive conducting polymer self-assembly made from a water-soluble poly(thiophene) derivative with short PEO side chains and Pluronic L62 solution in water. The structural and electrical properties of conjugated polymer-embedded nanostructures were investigated by combining SANS, SAXS, CGMD simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. The conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. The research was sponsored by the Scientific User Facilities Division, Office of BES, U.S. DOE and Laboratory Directed Research and Development Program of ORNL, managed by UT-Battelle, LLC.

  2. Tris(bipyridineMetal(II-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

    Directory of Open Access Journals (Sweden)

    Alla Dikhtiarenko

    2016-02-01

    Full Text Available A series of 3D oxalate-bridged ruthenium-based coordination polymers with the formula of {[ZII(bpy3][MIRu(C2O43]}n (ZII = Zn2+ (1, Cu2+ (3, 4, Ru2+ (5, 6, Os2+ (7, 8; MI = Li+, Na+; bpy = 2,2’-bipyridine and {[ZnII(bpy3](H2O[LiRu(C2O43]}n (2 has been synthesized at room temperature through a self-assembly reaction in aqueous media and characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared and diffuse reflectance UV–Vis spectroscopy and thermogravimetric analysis. The crystal structures of all compounds comprise chiral 3D honeycomb-like polymeric nets of the srs-type, which possess triangular anionic cages where [ZII(bpy3]2+ cationic templates are selectively embedded. Structural analysis reveals that the electronic configuration of the cationic guests is affected by electrostatic interaction with the anionic framework. Moreover, the MLCT bands gaps values for 1–8 can be tuned in a rational way by judicious choice of [ZII(bpy3]2+ guests. The 3D host-guest polymeric architectures can be used as self-supported heterogeneous photocatalysts for the reductive splitting of water, exhibiting photocatalytic activity for the evolution of H2 under UV light irradiation.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Wen-Yu; Zhuang, Guo-Yong; Huang, Zuo-Long; Cheng, Hong-Jian; Zhou, Li; Ma, Man-Hong; Wang, Hao; Tang, Xiao-Yan, E-mail: xytang@cslg.edu.cn; Ma, Yun-Sheng; Yuan, Rong-Xin, E-mail: yuanrx@cslg.edu.cn

    2016-03-15

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

  4. Self-assembled M2L4 coordination cages : Synthesis and potential applications

    NARCIS (Netherlands)

    Schmidt, Andrea; Casini, Angela; Kuehn, Fritz E.

    2014-01-01

    Metal-mediated self-assemblies of the general formula MxLy (M = metal ion, L = ligand) have emerged as a promising research area of supramolecular chemistry because of their applicability in various fields such as molecular recognition, catalysis and drug delivery. The focus of this review is on dis

  5. Self-assembled M2L4 coordination cages : Synthesis and potential applications

    NARCIS (Netherlands)

    Schmidt, Andrea; Casini, Angela; Kuehn, Fritz E.

    2014-01-01

    Metal-mediated self-assemblies of the general formula MxLy (M = metal ion, L = ligand) have emerged as a promising research area of supramolecular chemistry because of their applicability in various fields such as molecular recognition, catalysis and drug delivery. The focus of this review is on

  6. Fe-nitrilotriacetic acid coordination polymer nanowires: an effective sensing platform for fluorescence-enhanced nucleic acid detection

    Science.gov (United States)

    Zhou, Yunchun; Liu, Qian; Sun, Xuping; Kong, Rongmei

    2017-02-01

    The determination of specific nucleic acid sequences is key in identifying disease-causing pathogens and genetic diseases. In this paper we report the utilization of Fe-nitrilotriacetic acid coordination polymer nanowires as an effective nanoquencher for fluorescence-enhanced nucleic acid detection. The detection is fast and the whole process can be completed within 15 min. This nanosensor shows a low detection limit of 0.2 nM with selectivity down to single-base mismatch. This work provides us with an attractive sensing platform for applications.

  7. Interpenetrating 2D Manganese(Ⅱ) Coordination Polymer Supported by 4,4'-Bis(dimethoxyphosphorylmethyl)-biphenyl Ligands

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiangdong; GE Chunhua; YIN Jing; ZHAO Yang; HE Cui

    2009-01-01

    A novel coordination polymer [Mn(bdpbp)2(NO3)2] n (1), where bdpbp=4,4'-bis(dimethoxyphosphoryl-methyl)biphenyl, was prepared under mild condition. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, luminescent property and thermo-gravimetric analyses. Structure of 1 exhibits infinite grid frameworks and forms two fold interpenetrating nets.Weak C--H…O hydrogen bonds ensure the formation and stability of a three dimensional supramolecular network.

  8. Design and synthesis of chiral Ti-1,1'-bi-2-naphthol coordination polymers for heterogeneous catalytic asymmetric oxidation of sulfides

    Institute of Scientific and Technical Information of China (English)

    YUAN Xiao-ya; WANG Xiao-tian

    2008-01-01

    Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1'-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti(OiPr)4 under mild conditions. The prepared polymers exhibited good activity and excellent enantioselectivity (over 99%ee) in catalyzing the asymmetric oxidation of sulfides. The bridge linker in the polymer and the reaction solvent noticeably affected the enantioselectivity. The chiral coordination polymer was very stable and easy to separate from catalyzed reaction systems, with no significant loss of activity or enantioselectivity after reuse for at least ten times. These findings suggest a promising type of catalysts for synthesizing the widely used sulfoxides by asymmetrically oxidizing sulfides.

  9. Syntheses,crystal structures and properties of three novel coordination polymers with tripodal imidazole-containing ligands and benzenetetracarboxylate

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Three novel coordination polymers, [Ni2(tib)2(btec)]·2H2O (1), [Co2(tib)2(btec)]·2H2O (2) and [Zn4(tib)2(btec)Cl4]·2H2O (3), have been synthesized by using mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under hydrothermal conditions. Complexes 1 and 2 have the same structure and are rare three-dimensional (3D) self-penetrating (3,4,5)-connected nets, while complex 3 is an unprecedented (3,4)-connected 3D net. The different structures of 1 (2) and 3 are ascribed to the distinct coordination geometry of the metal centers. The thermal stability and photoluminescence property of the complexes were investigated.

  10. Two Gd(III) coordination polymers based on a flexible tricarboxylate: Syntheses, structures, luminescence and catalytic properties

    Science.gov (United States)

    Zhu, Yu; Zhu, Min; Liu, Pan; Xia, Li; Wu, Yunlong; Xie, Jimin

    2017-02-01

    Two Gadolinium coordination polymers {[Gd·(TTTA)·(H2O)2]·2H2O}n (1) and [Gd·(TTTA)·DMF]n (2) have been synthesized based on Gd(NO3)3·6H2O and the flexible tripodal ligand 2,2‧,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H3TTTA) under hydrothermal conditions. In the structure of 1, the tridentate TTTA3- ligands connect the dimeric metal centers into an infinite one dimensional chain. While 2 shows a two dimensional network with tridentate TTTA3- ligands. The two complexes all quench the emission spectra after coordinated to the Gd3+ ions. The catalytic results indicate that two complexes show excellent activities for the cyanosilylation of benzaldehyde and its derivatives. Besides, 2 is better than 1 in the catalytic reactions due to more possibility of metal open sites.

  11. Synthesis, structure, thermostability and luminescence properties of Zn(II) and Cd(II) coordination polymers based on dimethysuccinate and flexible 1,4-bis(imidazol-1-ylmethyl)benzene ligands.

    Science.gov (United States)

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

    2016-09-01

    The design and synthesis of functional coordination polymers is motivated not only by their structural beauty but also by their potential applications. Zn(II) and Cd(II) coordination polymers are promising candidates for producing photoactive materials because these d(10) metal ions not only possess a variety of coordination numbers and geometries, but also exhibit luminescence properties when bound to functional ligands. It is difficult to predict the final structure of such polymers because the assembly process is influenced by many subtle factors. Bis(imidazol-1-yl)-substituted alkane/benzene molecules are good bridging ligands because their flexibility allows them to bend and rotate when they coordinate to metal centres. Two new Zn(II) and Cd(II) coordination polymers based on mixed ligands, namely, poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ(2)N(3):N(3')]bis(μ3-2,2-dimethylbutanoato-κ(3)O(1):O(4):O(4'))dizinc(II)], [Zn2(C6H8O4)2(C14H14N4)]n, and poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ(2)N(3):N(3')]bis(μ3-2,2-dimethylbutanoato-κ(5)O(1),O(1'):O(4),O(4'):O(4))dicadmium(II)], [Cd2(C6H8O4)2(C14H14N4)]n, have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Both complexes crystallize in the monoclinic space group C2/c with similar unit-cell parameters and feature two-dimensional structures formed by the interconnection of S-shaped Zn(Cd)-2,2-dimethylsuccinate chains with 1,4-bis(imidazol-1-ylmethyl)benzene bridges. However, the Cd(II) and Zn(II) centres have different coordination numbers and the 2,2-dimethylsuccinate ligands display different coordination modes. Both complexes exhibit a blue photoluminescence in the solid state at room temperature.

  12. Effect of Coordinate Bond in Molecular Recognition of Enrofloxacin with Imprinted Polymers

    Institute of Scientific and Technical Information of China (English)

    Recilas-mota; J; Jesús; Gracia-mora; Jesús; Bernad-bernad; Josefa

    2007-01-01

    1 Results Molecular imprinting is a technique for the preparation of functional materials with molecular recognition properties.Molecular imprinted polymers (MIPs) have become an increasingly active field of study for the construction of new material capable of molecular recognition.In general,MIPs are synthesized by polymerization of cross-linking complexes of template molecules and functional monomers.After removing the template molecules from de polymers,binding sites are formed by functional monomer...

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

    Science.gov (United States)

    Paul, Mithun; Dastidar, Parthasarathi

    2016-01-18

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

  14. Synthesis, crystal structure, and luminescent properties of two coordination polymers based on 1,4-phenylenediacetic acid

    Science.gov (United States)

    Zhang, Meili; Ren, Yixia; Ma, Zhenzhen; Qiao, Lei

    2017-06-01

    Two coordination polymers, [Zn(pda)(bib)]n (1) and [Cd(pda)0.5(bib)Cl]n (2)]. (H2pda = 1,4-phenylenediacetic acid, bib = 1,2-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(II)/Cd(II) salts with two flexible ligands pda and bib under hydrothermal conditions. Their structures have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD) analysis. Due to the coordination geometry around the metal ions and the diverse coordination modes of the flexible ligands, the obtained complex show diverse structures. In the structure of 1, a pair of bib ligands connect two Zn(II) atoms give rise a 22-membered ring, which is further extended by pda ligands in bidentate coordination mode leading a ring-containing 2D layer. In 2, bib ligands join [Cd2Cl2]2+ dimmers generate 1D polymeric ribbon, the pda ligands further extend such ribbon forming a 2D layer network containing rectangular windows, which discovers the effect of the central metal ions on the formation of metal-organic frameworks. In additional, luminescent properties of two complexes have also been studied, they could be potential fluorescence materials.

  15. Metal coordination polymers of 2,3-bis(benzimidazol-1-ylmethyl)quinoxaline: Syntheses, crystal structures and luminescent properties

    Science.gov (United States)

    Du, Jian-Long; Wei, Zi-Zhang; Hu, Tong-Liang

    2011-06-01

    Two new metal-organic frameworks, {[Cu LI]·CHCl 3} ∞( 1) and {[Hg L(Br) 2] 4·2CH 2Cl 2} ∞ ( 2) have been prepared by reacting CuI and HgBr 2 with the new flexible ligand L [ L = 2,3-Bis(benzimidazol-1-ylmethyl)quinoxaline]. Both complexes have been characterized by elemental analysis, IR, TGA, XRPD, and single crystal X-ray diffraction determination. In 1, the Cu(I) ion takes tetrahedral coordination geometry, and the flexible ligands bridge dinuclear units (Cu 2I 2) to form a one dimensional (1D) double chain structure. While in 2, the Hg(II) coordinates to two bromine ions and two nitrogen donors of L to form a 1D coordination polymer. The structure differences of the two complexes mainly depend on the geometry of the metal ions and the influence of anions. The coordination features of the ligand have also been primarily investigated by density functional theory (DFT) calculations. In addition, the fluorescent properties of the complexes and free ligand L have been investigated in the solid state at room temperature.

  16. Synthesis of Lanthanide Coordination Polymers with Benzophenone-4,4'-dicarboxylate:Effect of Lanthanide Contraction on Structures

    Institute of Scientific and Technical Information of China (English)

    WANG, Yi-Bo(王轶博); JIN, Lin-Pei(金林培)

    2004-01-01

    Four lanthanide coordination polymers with benzophenone-4,4'-dicarboxylic acid (H2bpndc) and 1,10-phenanthroline(phen),[Ln2(bpndc)3(phen)](Ln=La(1),Pr(2) and Tb(3)),[Yb(bpndc)1.5(phen)]·0.5H2O(4) were obtained through solvothermal synthesis. The crystallographic data show that 1, 2, and 3 are isostructural, the Ln(Ⅲ)ions in 1, 2 and 3 are all eight- and ten-coordinated, respectively, and thus the Ln(Ⅲ) ions are connected by bpndc ligands, resulting in an interpenetrating 3D structure. While in 4, the Yb(Ⅲ) ions are eight-coordinated and connected by bpndc ligands into a 3D structure with 1D rhombic channels, which result from the effect of lanthanide contraction from La(Ⅲ) to Yb(Ⅲ) ions, and the bpndc ligands in 1, 2, 3, and 4 display three types of coordination modes.

  17. A two-dimensional yttrium phthalate coordination polymer, [Y4(H2O)2(C8H4O4)6]∞, exhibiting different coordination geometries

    Indian Academy of Sciences (India)

    A Thirumurugan; Srinivasan Natarajan

    2003-10-01

    A hydrothermal reaction of a mixture of Y(NO3)3, 1,2-benzenedicarboxylic acid (1,2-BDC) and NaOH gives rise to a new yttrium phthalate coordination polymer, [Y4(H2O)2(C8H4O4)6]∞, I. The Y ions in I are present in four different coordination environments with respect to the oxygen atoms (CN6 = octahedral, CN7 = pentagonal bipyramid, CN8 = dodecahedron and CN9 =capped square antiprism). The oxygen atoms of the 1,2-BDC are fully deprotonated, and show variations in their connectivity with Y atoms. The Y atoms themselves are connected through their vertices forming infinite Y-O-Y one-dimensional chains. The Y-O-Y chains are cross-linked by the 1,2-BDC anions forming a corrugated layer structure. The layers are supported by favourable $\\ldots$ interactions between the benzene rings of the 1,2-BDC anions. The variations in the coordination environment of the Y atoms and the presence of Y-O-Y interactions along with the favourable $\\ldots$ interactions between the benzene rings from different layers are noteworthy structural features. Crystal data: triclinic, space group = -1 (no. 2), = 12.6669 (2), = 13.8538 (2), = 16.0289 Å, = 75.20 (1), = 69.012 (1), = 65.529 (1)°, = 2371.28 (7) Å3, calc = 1.922 g cm-1, (MoK) = 4.943 mm-1. A total of 9745 reflections collected and merged to give 6566 unique reflections (int = 0.0292) of which 5252 with > 2() were considered to be observed. Final 2 = 0.0339, 2 = 0.0724 and =1.036 were obtained for 704 parameters.

  18. Two Zn(II) coordination complexes assembled by trithiocyanuric acid and two different N-donor auxiliary ligands.

    Science.gov (United States)

    He, Xiao Xiao; Guo, Ya Mei

    2014-08-01

    The dipyridyl-type building blocks 4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole (3-bpt) and 4,4'-bipyridine (bpy) have been used to assemble with Zn(II) in the presence of trithiocyanuric acid (ttcH3) to afford two coordination compounds, namely bis[4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole-κN(3)]bis(trithiocyanurato-κ(2)N,S)zinc(II), [Zn(C3H2N3S3)2(C12H10N6)2]·2H2O, (1), and catena-poly[[[bis(trithiocyanurato-κ(2)N,S)zinc(II)]-μ-4,4'-bipyridine-κ(2)N:N'] 4,4'-bipyridine monosolvate], {[Zn2(C3H2N3S3)4(C10H8N2)3]·C10H8N2}n, (2). Single-crystal X-ray analysis indicates that complex (1) is a mononuclear structure, while complex (2) presents a one-dimensional chain coordination motif. In both complexes, the central Zn(II) cation adopts an octahedral geometry, coordinated by four N- and two S-donor atoms. Notably, trithiocyanurate (ttcH2(-)) adopts the same bidentate chelating coordination mode in each complex and exists in the thione tautomeric form. The 3-bpt co-ligand in (1) adopts a monodentate coordination mode and serves as a terminal pendant ligand, whereas the 4,4'-bipyridine (bpy) ligand in (2) adopts a bidentate-bridging coordination mode. The different coordination characters of the different N-donor auxiliary ligands lead to structural diversity for complexes (1) and (2). Further analysis indicates that the resultant three-dimensional supramolecular networks for (1) and (2) arise through intermolecular N-H...S and N-H...N hydrogen bonds. Both complexes have been further characterized by FT-IR spectroscopy and elemental analyses.

  19. Self-assembly of Ru4 and Ru8 assemblies by coordination using organometallic Ru(II2 precursors: Synthesis, characterization and properties

    Directory of Open Access Journals (Sweden)

    Sankarasekaran Shanmugaraju

    2012-02-01

    Full Text Available Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II complexes [Ru2(μ-η4-C2O4(MeOH2(η6-p-cymene2](O3SCF32 (1a or [Ru2(μ-η4-N,N'-diphenyloxamidato(MeOH2(η6-p-cymene2](O3SCF32 (1b separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq bridged binuclear complex [Ru2(μ-η4-C6H2O4(MeOH2(η6-p-cymene2](O3SCF32 (1c in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a–2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (1H, 13C and 19F NMR, infrared (IR and electrospray ionization mass spectrometry (ESIMS. In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 Å × 12.39 Å. Furthermore, the photo- and electrochemical properties of these newly synthesized assemblies have been studied by using UV–vis absorption and cyclic voltammetry analysis.

  20. Chemically crosslinked nanogels of PEGylated poly ethyleneimine (L-histidine substituted) synthesized via metal ion coordinated self-assembly for delivery of methotrexate: Cytocompatibility, cellular delivery and antitumor activity in resistant cells

    Energy Technology Data Exchange (ETDEWEB)

    Abolmaali, Samira Sadat, E-mail: s.abolmaali@gmail.com [Pharmaceutical Nanotechnology Department, Shiraz University of Medical Sciences, Shiraz 71345 (Iran, Islamic Republic of); Tamaddon, Ali Mohammad, E-mail: amtamadon@gmail.com [Center for Nanotechnology in Drug Delivery, Shiraz University of Medical Sciences, Shiraz 71345 (Iran, Islamic Republic of); Mohammadi, Samaneh, E-mail: samaneh.mohammadi1986@gmail.com [Center for Nanotechnology in Drug Delivery, Shiraz University of Medical Sciences, Shiraz 71345 (Iran, Islamic Republic of); Amoozgar, Zohreh, E-mail: zohreh_amoozgar@dfci.harvard.edu [Department of Cancer Immunology and Aids, Dana-Farber Cancer Institute and Harvard Medical School, Boston, MA 02115 (United States); Dinarvand, Rasoul, E-mail: dinarvand@tums.ac.ir [Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran 14174 (Iran, Islamic Republic of)

    2016-05-01

    Self-assembled nanogels were engineered by forming Zn{sup 2+}-coordinated micellar templates of PEGylated poly ethyleneimine (PEG-g-PEI), chemical crosslinking and subsequent removal of the metal ion. Creation of stable micellar templates is a crucial step for preparing the nanogels. To this aim, imidazole moieties were introduced to the polymer by Fmoc-L-histidine using carbodiimide chemistry. It was hypothesized the nanogels loaded with methotrexate (MTX), a chemotherapeutic agent, circumvent impaired carrier activity in HepG2 cells (MTX-resistant hepatocellular carcinoma). So, the nanogels were post-loaded with MTX and characterized by {sup 1}H-NMR, FTIR, dynamic light scattering-zeta potential, atomic force microscopy, and drug release experiments. Cellular uptake and the antitumor activity of MTX-loaded nanogels were investigated by flow cytometry and MTT assay. Discrete, spherical and uniform nanogels, with sizes about 77–83 nm and a relatively high drug loading (54 ± 4% w/w), showed a low polydispersity and neutral surface charges. The MTX-loaded nanogels, unlike empty nanogels, lowered viability of HepG2 cells; the nanogels demonstrated cell-cycle arrest and apoptosis comparably higher than MTX as free drug that was shown to be through i) cellular uptake of the nanogels by clathrin-mediated transport and ii) endosomolytic activity of the nanogels in HepG2 cells. These findings indicate the potential antitumor application of this preparation, which has to be investigated in-vivo. - Highlights: • Nanogel synthesis through chemical crosslinking of the transition metal ion coordinated polymer self-assembly • An enhanced cytocompatibility if compared to unmodified polymer • A noticeable endocytic cellular internalization and endosomolytic activity • A specific antitumor cytotoxicity, cell cycle arrest and apoptosis in resistant tumor cells.

  1. Kinetic Effects on Self-Assembly and Function of Protein-Polymer Bioconjugates in Thin Films Prepared by Flow Coating

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Dongsook [Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave Cambridge MA 02142 USA; Huang, Aaron [Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave Cambridge MA 02142 USA; Olsen, Bradley D. [Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave Cambridge MA 02142 USA

    2016-11-04

    The self-assembly of nanostructured globular protein arrays in thin films is demonstrated using protein–polymer block copolymers based on a model protein mCherry and the polymer poly(oligoethylene glycol acrylate) (POEGA). Conjugates are flow coated into thin films on a poly(ethylene oxide) grafted Si surface, forming self-assembled cylindrical nanostructures with POEGA domains selectively segregating to the air–film interface. Long-range order and preferential arrangement of parallel cylinders templated by selective surfaces are demonstrated by controlling relative humidity. Long-range order increases with coating speed when the film thicknesses are kept constant, due to reduced nucleation per unit area of drying film. Fluorescence emission spectra of mCherry in films prepared at <25% relative humidity shows a small shift suggesting that proteins are more perturbed at low humidity than high humidity or the solution state.

  2. Self-assembly of monodisperse polymer microspheres from PPQ-b-PEG rod-coil block copolymers in selective solvents

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xueao; CHEN Ke; XIE Kai; LONG Yongfu

    2005-01-01

    Poly(phenylquinoline)-block-poly(ethylene glycol)(PPQ-b-PEG) rod-coil block copolymers possess the self-assembly behavior in selective solvents. The copolymers in the mixed solvents of V(trifluoroacetic acid, TFA):V(dichloromethane, DCM)=1:1 can self-assemble into polymer hollow microspheres with diameters of a few micrometers. The polymer hollow microspheres are monodisperse, and the diameters of them increase with an increased polymerization degree of the PPQ rigid-rod block. The solution concentration has no effect on the microsphere diameter, but spherical surface shows burrs when the solution concentration is too low. It has been found that the obtained dilute solution has the strongest absorption peak at 376 nm and strongest emission peak at 604 nm by the spectroscopy analysis.

  3. Probing the self-assembled nanostructures of functional polymers with synchrotron grazing incidence X-ray scattering.

    Science.gov (United States)

    Ree, Moonhor

    2014-05-01

    For advanced functional polymers such as biopolymers, biomimic polymers, brush polymers, star polymers, dendritic polymers, and block copolymers, information about their surface structures, morphologies, and atomic structures is essential for understanding their properties and investigating their potential applications. Grazing incidence X-ray scattering (GIXS) is established for the last 15 years as the most powerful, versatile, and nondestructive tool for determining these structural details when performed with the aid of an advanced third-generation synchrotron radiation source with high flux, high energy resolution, energy tunability, and small beam size. One particular merit of this technique is that GIXS data can be obtained facilely for material specimens of any size, type, or shape. However, GIXS data analysis requires an understanding of GIXS theory and of refraction and reflection effects, and for any given material specimen, the best methods for extracting the form factor and the structure factor from the data need to be established. GIXS theory is reviewed here from the perspective of practical GIXS measurements and quantitative data analysis. In addition, schemes are discussed for the detailed analysis of GIXS data for the various self-assembled nanostructures of functional homopolymers, brush, star, and dendritic polymers, and block copolymers. Moreover, enhancements to the GIXS technique are discussed that can significantly improve its structure analysis by using the new synchrotron radiation sources such as third-generation X-ray sources with picosecond pulses and partial coherence and fourth-generation X-ray laser sources with femtosecond pulses and full coherence.

  4. Responsive Hydrogels and Ion Gels by Self-Assembly of ABA and ABC Triblock Polymers

    Science.gov (United States)

    Lodge, Timothy

    2014-03-01

    Gels - polymeric networks swollen with a substantial amount of solvent - represent a fascinating class of soft materials, with wide-ranging applications in fields as diverse as biomedicine, pharmaceutics, personal care products, foods, sensors, actuators, flexible electronics, oil recovery, and adhesives. Physical gels are held together by non-covalent interactions, which may be as specific as hydrogen bonds, or as general as solvophobic association of insoluble blocks. Among the attractive features of physical gels are reversibility, stimuli-responsiveness, and tunability of macroscopic properties. In this talk two classes of physical gels will be highlighted. In one, the ability of ABC block terpolymers to form novel structures will be demonstrated, where blocks A and C are mutually immiscible and solvophobic, while B is solvophilic. In particular, the formation of gels by sequential association (first A, then C) leads to a remarkably sharp gelation transition, at a relatively low polymer concentration, compared to analogous gels formed from ABA systems. In the second class, gels formed by self-assembly of a variety of ABA systems in ionic liquids will be described, and in particular how gelation can be controlled through factors such as block chemistry, temperature, choice of ionic liquid, and application of light.

  5. Water-Based Assembly of Polymer-Metal Organic Framework (MOF) Functional Coatings

    Energy Technology Data Exchange (ETDEWEB)

    De, Souvik [Artie McFerrin Department of Chemical Engineering, Texas A& M University, 77843-3122 TAMU College Station TX 77843-3122 USA; Nandasiri, Manjula I. [Environmental Molecular Sciences Laboratory (EMSL), Pacific Northwest National Laboratory, Richland WA 99352 USA; Schaef, Herbert T. [Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; McGrail, Benard Peter [Energy & Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99352 USA; Nune, Satish K. [Energy & Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99352 USA; Lutkenhaus, Jodie L. [Artie McFerrin Department of Chemical Engineering, Texas A& M University, 77843-3122 TAMU College Station TX 77843-3122 USA; Department of Materials Science & Engineering, Texas A& M University, 3122 TAMU College Station TX 77843-3122 USA

    2016-12-27

    Metal organic frameworks (MOFs) have gained tremendous attention for their porosity, size selectivity, and structural diversity. There is a need for MOF-based coatings, particularly in applications such as separations, electronics and energy; yet forming thin, functional, conformal coatings is prohibitive because MOFs exist as a powder. Layer-by- layer assembly, a versatile thin film coating approach, offers a unique solution to this problem, but this approach requires MOFs that are water-dispersible and bear a surface charge. Here, we address these issues by examining water-based dispersions of MIL-101(Cr) that facilitate the formation of robust polymer-MOF hybrid coatings. Specifically, the substrate to be coated is alternately exposed to an aqueous solution of poly(styrene sulfonate) and dispersion MIL-101(Cr), yielding linear film growth and coatings with a MOF content as high as 77 wt%.This approach is surface-agnostic, in which the coating is successfully applied to silicon, glass, flexible plastic, and even cotton fabric, conformally coating individual fibers. In contrast, prior attempts at forming MOF-coatings were severely limited to a handful of surfaces, required harsh chemical treatment, and were not conformal. The approach presented here unambiguously confirms that MOFs can be conformally coated onto complex and unusual surfaces, opening the door for a wide variety of applications.

  6. Facile hierarchical assembly of gold particle decorated conductive polymer nanofibers for electrochemical sensing

    Science.gov (United States)

    Dai, Minhui; Chen, Juhong; Goddard, Julie M.; Nugen, Sam R.

    2017-02-01

    In this study, we successfully applied vapor-phase polymerization towards the synthesis of PEDOT nanofibers which were subsequently functionalized with gold particles and used as electrodes for electrochemical sensing. Two methods were used to synthesize the PEDOT nanofibers including (1) electrospinning followed by vapor-phase polymerization (EVP), and (2) one-step vapor-phase polymerization (OSVP). The average diameter of EVP fibers was approximately 350 nm, and OSVP was approximately 200 nm. Gold particles (∼500 nm) were synthesized by an oxidation-reduction reaction between gold precursors and residue EDOT monomers on the surface of the PEDOT nanofibers. In order to investigate the electrochemical performance of these electrodes, ascorbic acid was chosen as an analyte model. Our results indicated that PEDOT nanofiber electrodes showed an enhanced response with respect to bare gold electrodes. Furthermore, the OSVP PEDOT nanofibers with gold particles demonstrated the highest sensitivity at low ascorbic acid concentrations. These hierarchically assembled, gold particle-decorated, conductive polymer nanofibers were further fabricated into flexible electrodes, demonstrating a potential in advanced applications such as wearable electronics.

  7. Multi-colored fibers by self-assembly of DNA, histone proteins, and cationic conjugated polymers.

    Science.gov (United States)

    Wang, Fengyan; Liu, Zhang; Wang, Bing; Feng, Liheng; Liu, Libing; Lv, Fengting; Wang, Yilin; Wang, Shu

    2014-01-01

    The development of biomolecular fiber materials with imaging ability has become more and more useful for biological applications. In this work, cationic conjugated polymers (CCPs) were used to construct inherent fluorescent microfibers with natural biological macromolecules (DNA and histone proteins) through the interfacial polyelectrolyte complexation (IPC) procedure. Isothermal titration microcalorimetry results show that the driving forces for fiber formation are electrostatic and hydrophobic interactions, as well as the release of counterions and bound water molecules. Color-encoded IPC fibers were also obtained based on the co-assembly of DNA, histone proteins, and blue-, green-, or red- (RGB-) emissive CCPs by tuning the fluorescence resonance energy-transfer among the CCPs at a single excitation wavelength. The fibers could encapsulate GFP-coded Escherichia coli BL21, and the expression of GFP proteins was successfully regulated by the external environment of the fibers. These multi-colored fibers show a great potential in biomedical applications, such as biosensor, delivery, and release of biological molecules and tissue engineering.

  8. Expanded experimental parameter space of semiflexible polymer assemblies through programmable nanomaterials

    Science.gov (United States)

    Smith, David; Schuldt, Carsten; Lorenz, Jessica; Tschirner, Teresa; Moebius-Winkler, Maximilian; Kaes, Josef; Glaser, Martin; Haendler, Tina; Schnauss, Joerg

    2015-03-01

    Biologically evolved materials are often used as inspiration in the development of new materials as well as examinations into the underlying physical principles governing their behavior. For instance, the biopolymer constituents of the highly dynamic cellular cytoskeleton such as actin have inspired a deep understanding of soft polymer-based materials. However, the molecular toolbox provided by biological systems has been evolutionarily optimized to carry out the necessary functions of cells, and the inability modify basic properties such as biopolymer stiffness hinders a meticulous examination of parameter space. Using actin as inspiration, we circumvent these limitations using model systems assembled from programmable materials such as DNA. Nanorods with comparable, but controllable dimensions and mechanical properties as actin can be constructed from small sets of specially designed DNA strands. In entangled gels, these allow us to systematically determine the dependence of network mechanical properties on parameters such as persistence length and crosslink strength. At higher concentrations in the presence of local attractive forces, we see a transition to highly-ordered bundled and ``aster'' phases similar to those previously characterized in systems of actin or microtubules.

  9. Oxygen reduction electrocatalysts in solid polymer fuel cell membrane electrode assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Ralph, T.R.; Keating, J.E.; Collis, N.J.; Hyde, T.I.

    1997-07-01

    The feasibility of using platinum/base metal alloy electrodes in the cathode to improve the performance of a 50 mV solid polymer fuel cell (SPFC) under typical operating conditions was investigated. A range of alloys of platinum with iron, manganese, titanium, chromium, copper and nickel were prepared at a nominal 50:50 platinum to base metal ratio and supported on Vulcan Xc72R carbon black. The catalysts were fired in an inert atmosphere at temperatures between 650{sup o}C and 930{sup o}C to create the alloy catalysts, which were then incorporated into Nafion coated cathodes. Cell performance was assessed using a standard anode structure in membrane-based electrode assembles (MEAs). A clear electrokinetic benefit for some alloys (eg Pt/Fe, Pt/Mn and Pt/Cr over the range of alloying temperatures and Pt/Ti at 930{sup o}C) was found. This benefit was found to be due to improved rates of oxygen reduction with the alloys.

  10. Composite thin film by hydrogen-bonding assembly of polymer brush and poly(vinylpyrrolidone).

    Science.gov (United States)

    Yang, Shuguang; Zhang, Yongjun; Wang, Li; Hong, Song; Xu, Jian; Chen, Yongming; Li, Chengming

    2006-01-03

    Based on hydrogen-bonding layer-by-layer (LBL) assembly in aqueous solution, poly(vinylpyrrolidone) (PVPON) and a spherical polymer brush with a poly(methylsilsesquioxane) (PSQ) core and poly(acrylic acid) (PAA) hair chains were used to fabricate composite multilayer thin films. Hydrogen bonding as the driving force was confirmed by FT-IR spectrometry. A simple method (Filmetric F20) was introduced to determine the thickness and refractive index of the films. The film thickness was found to be a linear function of the number of bilayers. The average increase in thickness per bilayer is 28.3 nm. The film morphology was characterized with scanning electron microscopy and atomic force microscopy. The images obtained from the two instruments show a great resemblance. The films were further calcined to get an inorganic film by removing the organic components, or treated with tetrabutylammonium fluoride (TBAF) to remove the PSQ core and get an organic film. The optical properties and morphological changes induced by these treatments were also studied.

  11. Assembly of Two Transgenes in an Artificial Chromatin Domain Gives Highly Coordinated Expression in Tobacco

    OpenAIRE

    2002-01-01

    The chromatin loop model predicts that genes within the same chromatin domain exhibit coordinated regulation. We here present the first direct experimental support for this model in plants. Two reporter genes, the E. coli beta-glucuronidase gene and the firefly luciferase gene, driven by different promoters, were placed between copies of the chicken lysozyme A element, a member of the matrix-associated region (MAR) group of chromatin boundary elements, and introduced in tobacco (Nicotiana tab...

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

    Directory of Open Access Journals (Sweden)

    Adrián Angulo-Ibáñez

    2016-01-01

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

  13. 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

    Science.gov (United States)

    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.

  14. Modulation of the Structure and Properties of Uranyl Ion Coordination Polymers Derived from 1,3,5-Benzenetriacetate by Incorporation of Ag(I) or Pb(II).

    Science.gov (United States)

    Thuéry, Pierre; Harrowfield, Jack

    2016-07-05

    Reaction of uranyl nitrate with 1,3,5-benzenetriacetic acid (H3BTA) in the presence of additional species, either organic bases or their conjugate acids or metal cations, has provided 12 new crystalline complexes, all but one obtained under solvo-hydrothermal conditions. The complexes [C(NH2)3][UO2(BTA)]·H2O (1) and [H2NMe2][UO2(BTA)] (2) crystallize as one- or two-dimensional (1D or 2D) assemblies, respectively, both with uranyl tris-chelation by carboxylate groups and hydrogen-bonded counterions but different ligand conformations. One of the bound carboxylate units is replaced by chelating 1,10-phenanthroline (phen) or 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4phen) in the complexes [(UO2)3(BTA)2(phen)3]·4H2O (3) and [(UO2)3(BTA)2(Me4phen)3]·NMP·3H2O (4) (NMP = N-methyl-2-pyrrolidone), which are a 2D network with honeycomb topology and a 1D polymer, respectively. With silver(I) cations, [UO2Ag(BTA)] (5), a three-dimensional (3D) framework in which the ligand assumes various chelating/bridging coordination modes, and the aromatic ring is involved in Ag(I) bonding, is obtained. A series of seven heterometallic complexes results when lead(II) cations and N-chelating molecules are both present. The complexes [UO2Pb(BTA)(NO3)(bipy)] (6) and [UO2Pb2(BTA)2(bipy)2]·3H2O (7), where bipy is 2,2'-bipyridine, crystallize from the one solution, as 1D and 2D assemblies, respectively. The two 1D coordination polymers [UO2Pb(BTA)(HCOO)(phen)] (8 and 9), again obtained from the one synthesis, provide an example of coordination isomerism, with the formate anion bound either to lead(II) or to uranyl cations. Another 2D architecture is found in [(UO2)2Pb2(BTA)2(HBTA)(H2O)2(phen)2]·2H2O (10), which provides a possible example of a Pb-oxo(uranyl) "cation-cation" interaction. While [UO2Pb(BTA)(HCOO)0.5(NO3)0.5(Me2phen)] (11), where Me2phen is 5,6-dimethyl-1,10-phenanthroline, is a 1D assembly close to those in 6 and 8, [UO2Pb2(BTA)2(Me4phen)2] (12), obtained together with

  15. Two new hexacoordinated coordination polymers of cadmium(II) containing bridging units only: Syntheses, structures and molecular properties

    Indian Academy of Sciences (India)

    DIPU SUTRADHAR; HABIBAR CHOWDHURY; SUSHOVAN KONER; SUBHASIS ROY; BARINDRA KUMAR GHOSH

    2016-09-01

    The syntheses, characterizations and structures of a neutral 2D coordination polymer [Cd(bnzd)(NCS)₂]n (1) and a polycationic 3D coordination polymer isolated as perchlorate salt [Cd(bnzd)₃]n(ClO₄)₂n (2) (bnzd = benzidine) are described. X-ray structural analyses reveal that each hexacoordinated cadmium(II) center in 1 adopts a distorted octahedral geometry with a CdN₄S₂ chromophore bound by two N atoms of two different bnzd units and two N and two S atoms of symmetric doubly bridged end-toend NCS− units extended in a 2D sheet. Six N atoms of six different bridged bnzd units are bonded to each cadmium(II) in 2 in a non-ended fashion affording a 3D network structure. In the crystalline state, each 2D sheet structure in 1 is further stabilized by π· · ·π interaction which in turn affords a 3D network structure through multiple intermolecular N-H· · · S hydrogen bonds. On the other hand, the 3D network structure in 2 is stabilized by weak intermolecular N-H· · ·O hydrogen bonds and C-H· · ·π interactions. Bnzd, 1 and 2 display intraligand 1(π-π*) fluorescence in DMF solution at room temperature.

  16. A luminescent lanthanide coordination polymer based on energy transfer from metal to metal for hydrogen peroxide detection.

    Science.gov (United States)

    Zeng, Hui-Hui; Zhang, Li; Rong, Lian-Qing; Liang, Ru-Ping; Qiu, Jian-Ding

    2017-03-15

    A bimetal lanthanide coordination polymer nanoparticle (ATP-Ce/Tb-Tris CPNs) with good biocompatibility was synthesized in Tris-HCl buffer using adenosine triphosphate (ATP) molecules as the bridge ligands. The large absorption cross section and suitable emission energy of Ce(3+) matching to the adsorption energy of Tb(3+)((4)fn) results in the efficient energy transfer from Ce(3+) to Tb(3+), thus the synthesized ATP-Ce/Tb-Tris CPNs exhibit the characteristic green emission of Tb(3+). Such energy transfer from metal to metal in fluorescent lanthanide coordination polymer nanoparticles (Ln-CPNs) has been demonstrated. It is found that the oxidation of Ce(3+) in ATP-Ce/Tb-Tris CNPs to Ce(4+) would interrupt the energy transfer from Ce(3+) to Tb(3+), leading to fluorescence quenching of Tb(3+). On the basis of this quenching mechanism, ATP-Ce/Tb-Tris CPNs has been successfully used to detect reactive oxygen H2O2 with detection limit as low as 2nM. If glucose oxidase is present in the system, glucose can be determined using the ATP-Ce/Tb-Tris CNPs nanosensor.

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

    Science.gov (United States)

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

    2017-08-01

    Careful choice of the organic ligands is one of the most important parameters in the rational design and synthesis of coordination polymers. Aromatic polycarboxylates have been widely used in the preparation of metal-organic polymers since they can utilize various coordination modes to form diverse structures and can act as hydrogen-bond acceptors and donors in the assembly of supramolecular structures. Nitrogen-heterocyclic organic compounds have also been used extensively as ligands for the construction of polymers with interesting structures. In the polymers catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN(3)}cobalt(II)]-μ2-benzene-1,4-dicarboxylato-κ(2)O(1):O(4)] dihydrate], {[Co(C8H4O4)(C12H11N4)2(H2O)2]·2H2O}n, (I), and catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN(3)}nickel(II)]-μ2-benzene-1,4-dicarboxylato-κ(2)O(1):O(4)] dihydrate], {[Ni(C8H4O4)(C12H11N4)2(H2O)2]·2H2O}n, (II), the Co(II) or Ni(II) ion lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry, coordinated by two N atoms from two imidazole rings and four O atoms from two monodentate carboxylate groups and two water molecules. The dicarboxylate ligands bridge metal ions forming a polymeric chain. The 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole ligands coordinate to the Co(II) or Ni(II) centres in monodentate modes through an imidazole N atom and are pendant on opposite sides of the main chain. The two structures are isomorphous. In the crystal, the one-dimensional chains are further connected through O-H...O, O-H...N and N-H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviours and fluorescence properties of both polymers have been investigated.

  18. Self-Assembled ROS-Sensitive Polymer-Peptide Therapeutics Incorporating Built-in Reporters for Evaluation of Treatment Efficacy.

    Science.gov (United States)

    Qiao, Zeng-Ying; Zhao, Wen-Jing; Cong, Yong; Zhang, Di; Hu, Zhiyuan; Duan, Zhong-Yu; Wang, Hao

    2016-05-09

    One of the major challenges in current cancer therapy is to maximize therapeutic effect and evaluate tumor progression under the scheduled treatment protocol. To address these challenges, we synthesized the cytotoxic peptide (KLAKLAK)2 (named KLAK) conjugated amphiphilic poly(β-thioester)s copolymers (H-P-K) composed of reactive oxygen species (ROS) sensitive backbones and hydrophilic polyethylene glycol (PEG) side chains. H-P-K could self-assemble into micelle-like nanoparticles by hydrophobic interaction with copolymer backbones as cores and PEG and KLAK as shells. The assembled polymer-peptide nanoparticles remarkably improved cellular internalization and accumulation of therapeutic KLAK in cells. Compared to free KLAK peptide, the antitumor activity of H-P-K was significantly enhanced up to ∼400 times, suggesting the effectiveness of the nanoscaled polymer-peptide conjugation as biopharmaceuticals. The higher antitumor activity of nanoparticles was attributed to the efficient disruption of mitochondrial membranes and subsequent excessive ROS production in cells. To realize the ROS monitoring and treatment evaluation, we encapsulated squaraine (SQ) dyes as built-in reporters in ROS-sensitive H-P-K micelles. The overgenerated ROS around mitochondria stimulated the swelling of nanoparticles and subsequent release of SQ, which formed H-aggregates and significantly increased the photoacoustic (PA) signal. We believed that this self-assembled polymer-peptide nanotherapeutics incorporating built-in reporters has great potential for high antitumor performance and in situ treatment evaluation.

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

    Science.gov (United States)

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

    2017-04-01

    Five functional coordination polymers (formic-based CPs) namely: {[Cu2(CHOO)3(bibp)2]·CHOO}n (1), {[Co2(CHOO)3(bibp)2]·NO3·H2O}n (2), {[Ni2(CHOO)3(bibp)2]·NO3·H2O}n (3) [Co(CHOO)2(bbibp)]n (4) and [Zn(CHOO)2(bbibp)]n (5) (bibp=4,4‧-bis(imidazolyl)biphenyl, bbibp=4,4‧-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N‧-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1-3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member between the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C-H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.

  20. Single-step microfluidic synthesis of various nonspherical polymer nanoparticles via in situ assembling: dominating role of polyelectrolytes molecules.

    Science.gov (United States)

    Visaveliya, Nikunjkumar; Köhler, J Michael

    2014-07-23

    In this paper, a microfluidic approach has been used for the synthesis of ellipsoidal, dumbbell, rodlike, and necklacelike polymer nanoparticles. High yields of special types of nonspherical nanoparticles have been achieved by the implementation of an emulsion polymerization into microfluidic arrangement with a micro hole-plate reactor for the formation of monomer droplets. Here, in particular, the formation of nonspherical polymer nanoparticles is dependent on the presence of polyelectrolyte surface active molecules such as poly(4-styrenesulfonic acid-co-maleic acid) sodium salt (PSS-co-PM), poly(sodium-p-styrenesulfonate) (PSSS), and polyanetholesulfonic acid sodium salt (PAES). The shapes and sizes of the interparticle nanoassemblies are precisely controlled by adjusting the concentration of polyelectrolytes in the aqueous phase, and by choosing suitable flow rate ratios (aqueous to monomer phase), respectively. The formation of polymer nanoparticles with different morphologies can be explained by a spontaneous in situ assembling under partial electrostatic repulsive control in the single step synthesis. The effect of particle charge and the competition between thermal motion of particles and electrostatic repulsion on the spontaneous assembling under the condition of a limited polarizability are discussed here as an important factor for the formation process of nonspherical polymer nanoparticles.

  1. Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence.

    Science.gov (United States)

    Zhou, Xiaoyan; Guo, Yanling; Shi, Zhaohua; Song, Xueqin; Tang, Xiaoliang; Hu, Xiong; Zhu, Zhentong; Li, Pengxuan; Liu, Weisheng

    2012-02-14

    Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2 : 3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.

  2. Structural variability, Hirshfeld surface analysis and properties of three Zn(II) coordination polymers based on flexible bis(thiabendazole) and aromatic dicarboxylate co-ligands

    Science.gov (United States)

    Chang, Hai-Ning; Liu, Ce; Hao, Zeng-Chuan; Cui, Guang-Hua

    2017-02-01

    Three zinc(II) coordination polymers (CPs), {[Zn(L)0.5(tbta)]·0.5 L·2.5H2O}n (1), {[Zn(L)0.5(mip)]·H2O}n (2) and {[Zn(L)0.5(npht)(H2O)]·0.5H2O}n (3) (L = 1,4-bis(thiabendazole)butane, H2tbta = tetrabromoterephthalic acid, H2mip = 5-methylisophthalic acid, H2npht = 3-nitrophthalic acid) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that CP 1 shows a 2D honeycomb-like (6, 3) network. CP 2 displays a hybrid helical chain, and further assembled into a 2D supramolecular layer via weak Csbnd H⋯O hydrogen bonding interactions, whereas CP 3 is a right-handed helical chain and finally extended into a 3D supramolecular structure by classical Osbnd H⋯O hydrogen bonds and π-π stacking interactions. Further, the Hirshfeld surfaces, fingerprint plots, fluorescence properties and catalytic performances of three CPs for the degradation of methyl orange dye in a Fenton-like process have been investigated.

  3. Solid-state synthesis of ordered mesoporous carbon catalysts via a mechanochemical assembly through coordination cross-linking

    Science.gov (United States)

    Zhang, Pengfei; Wang, Li; Yang, Shize; Schott, Jennifer A.; Liu, Xiaofei; Mahurin, Shannon M.; Huang, Caili; Zhang, Yu; Fulvio, Pasquale F.; Chisholm, Matthew F.; Dai, Sheng

    2017-04-01

    Ordered mesoporous carbons (OMCs) have demonstrated great potential in catalysis, and as supercapacitors and adsorbents. Since the introduction of the organic-organic self-assembly approach in 2004/2005 until now, the direct synthesis of OMCs is still limited to the wet processing of phenol-formaldehyde polycondensation, which involves soluble toxic precursors, and acid or alkali catalysts, and requires multiple synthesis steps, thus restricting the widespread application of OMCs. Herein, we report a simple, general, scalable and sustainable solid-state synthesis of OMCs and nickel OMCs with uniform and tunable mesopores (~4-10 nm), large pore volumes (up to 0.96 cm3 g-1) and high-surface areas exceeding 1,000 m2 g-1, based on a mechanochemical assembly between polyphenol-metal complexes and triblock co-polymers. Nickel nanoparticles (~5.40 nm) confined in the cylindrical nanochannels show great thermal stability at 600 °C. Moreover, the nickel OMCs offer exceptional activity in the hydrogenation of bulky molecules (~2 nm).

  4. Coordination-directed one-dimensional coordination polymers generated from a new oxadiazole bridging ligand and HgX2 (X=Cl, Br and I).

    Science.gov (United States)

    Yang, Rui; Ma, Jian Ping; Huang, Ru Qi; Dong, Yu Bin

    2011-06-01

    A new 1,3,4-oxadiazole bridging bent organic ligand, 2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole, C(28)H(24)N(4)O(3), L, has been used to create three novel one-dimensional isomorphic coordination polymers, viz. catena-poly[[[dichloridomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgCl(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n), catena-poly[[[dibromidomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgBr(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n), and catena-poly[[[diiodidomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgI(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n). The free L ligand itself adopts a cis conformation, with the two terminal pyridine rings and the central oxadiazole ring almost coplanar [dihedral angles = 5.994 (7) and 9.560 (6)°]. In the Hg(II) complexes, however, one of the flexible pyridylmethyl arms of ligand L is markedly bent and helical chains are obtained. The Hg(II) atom lies in a distorted tetrahedral geometry defined by two pyridine N-atom donors from two L ligands and two halide ligands. The helical chains stack together via interchain π-π interactions that expand the dimensionality of the structure from one to two. The methanol solvent molecules link to the complex polymers through O-H···N and O-H···O hydrogen bonds. © 2011 International Union of Crystallography

  5. Selective Synthesis of Molecular Borromean Rings: Engineering of Supramolecular Topology via Coordination-Driven Self-Assembly.

    Science.gov (United States)

    Kim, Taegeun; Singh, Nem; Oh, Jihun; Kim, Eun-Hee; Jung, Jaehoon; Kim, Hyunuk; Chi, Ki-Whan

    2016-07-13

    Molecular Borromean rings (BRs) is one of the rare topology among interlocked molecules. Template-free synthesis of BRs via coordination-driven self-assembly of tetracene-based Ru(II) acceptor and ditopic pyridyl donors is reported. NMR and single-crystal XRD analysis observed sequential transformation of a fully characterized monomeric rectangle to molecular BRs and vice versa. Crystal structure of BRs revealed that the particular topology was enforced by the appropriate geometry of the metallacycle and multiple parallel-displaced π-π interactions between the donor and tetracene moiety of the acceptor. Computational studies based on density functional theory also supported the formation of BRs through dispersive intermolecular interactions in solution.

  6. Fabrication of Ag/CPs composite material, an effective strategy to improve the photocatalytic performance of coordination polymers under visible irradiation.

    Science.gov (United States)

    Xu, Xinxin; Cui, Zhongping; Qi, Ji; Liu, Xiaoxia

    2013-10-01

    To enhance the photocatalytic property of coordination polymers (CPs) in the visible light region, Ag loaded coordination polymer composite materials (Ag/CPs) were synthesized successfully through a photoreduction reaction of Ag(+) on the surface of CPs. Photoluminescence (PL) was used to investigate the separation of photogenerated electron-hole pairs and the results illustrated Ag/CPs display higher quantum yields than CPs. This can be attributed to the strong interactions between Ag nanorods and coordination polymers, which lead to electron-hole pair separation between Ag nanorods and CPs. The degradation of Rhodamine B (RhB) was investigated to study the photocatalytic activities. Ag/CPs exhibited excellent photocatalytic activity in the UV and visible light region, while CPs can only decompose RhB under the irradiation of UV light. Furthermore, Ag/CPs showed outstanding stability during degradation of RhB.

  7. Robust Photocatalytic H2O2 Production by Octahedral Cd3(C3N3S3)2 Coordination Polymer under Visible Light

    Science.gov (United States)

    Zhuang, Huaqiang; Yang, Lifang; Xu, Jie; Li, Fuying; Zhang, Zizhong; Lin, Huaxiang; Long, Jinlin; Wang, Xuxu

    2015-11-01

    Herein, we reported a octahedral Cd3(C3N3S3)2 coordination polymer as a new noble metal-free photocatalyst for robust photocatalytic H2O2 production from methanol/water solution. The coordination polymer can give an unprecedented H2O2 yield of ca. 110.0 mmol • L-1 • g-1 at pH = 2.8 under visible light illumination. The characterization results clearly revealed that the photocatalytic H2O2 production proceeds by a pathway of two-electron reduction of O2 on the catalyst surface. This work showed the potential perspective of Mx(C3N3S3)y (M = transitional metals) coordination polymers as a series of new materials for solar energy storage and conversion.

  8. Synthesis, Crystal Structure, Luminescence and Magnetism of Three Novel Coordination Polymers Based on Flexible Multicarboxylate Zwitterionic Ligand

    Directory of Open Access Journals (Sweden)

    Yulu Ma

    2017-01-01

    Full Text Available Three novel zwitterionic coordination polymers, namely, {[Zn(HCbdcp2]·H2O} (1, {[Mn(Cbdcp]·3H2O} (2 and {[Cu2(Cbdcp(HCbdcpCl·H2O]·2H2O} (3, Cbdcp = 3,5-dicarboxy-1-(4-carboxybenzylpyridin-1-ium, have been prepared by a hydrothermal method and characterized by X-ray single crystal diffraction analysis, powder X-ray diffraction analysis, IR spectroscopy, and thermogravimetric analysis. With the changing of metal centers, these complexes show distinct structures: a mononuclear 2D 44-sql network for 1, a 3D 6,6-connected-type topology for 2 and a novel dinuclear 2D layer for 3. These diverse architectures prove that coordination geometry of metal ions, coordination modes of carboxylate groups and the rotationally flexible CH2 linker played significant roles in the construction of CPs; moreover, they also indicated that H3CbdcpCl is an ideal organic candidate for the building of novel structures. The solid-state luminescent properties of complexes 1–3 were investigated, respectively. In addition, the magnetic properties of 2 and 3 were studied and both of them exhibit antiferromagnetic behaviors.

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

    Science.gov (United States)

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

    2014-05-01

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

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

    Science.gov (United States)

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

    2014-02-01

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

  11. Tellurium rings as electron pair donors in cluster compounds and coordination polymers; Tellurringe als Elektronenpaardonoren in Clusterverbindungen und Koordinationspolymeren

    Energy Technology Data Exchange (ETDEWEB)

    Guenther, Anja

    2011-11-08

    In this dissertation novel and already known molecular tellurium rings are presented in cluster compounds and quasi-one-dimensional coordination polymers. The cyclic, homonuclear units are always stabilized by coordination to electron-rich transition metal atoms, with the coordinating tellurium atoms acting as two-electron donors. As a synthesis route, the solid-state reaction in quartz glass vials was used uniformly. In addition to structural determination, the focus was on the characterization of the resulting compounds. For this purpose, resistance measurements were carried out on selected compounds, the magnetic behavior and the thermal degradation reactions were investigated and accompanying quantum chemical calculations were carried out. [German] In dieser Dissertation werden neuartige sowie bereits bekannte molekulare Tellurringe in Clusterverbindungen und quasi-eindimensionalen Koordinationspolymeren vorgestellt. Die Stabilisierung der zyklischen, homonuklearen Einheiten erfolgt dabei stets durch die Koordination an elektronenreiche Uebergangsmetallatome, wobei die koordinierenden Telluratome gegenueber diesen als Zwei-Elektronendonoren fungieren. Als Syntheseroute wurde dabei einheitlich auf die Festkoerperreaktion in Quarzglasampullen zurueckgegriffen. Neben der Strukturaufklaerung stand die Charakterisierung der erhaltenden Verbindungen im Fokus der Arbeit. Dazu wurden an ausgewaehlten Verbindungen Widerstandsmessungen durchgefuehrt, das magnetische Verhalten sowie die thermischen Abbaureaktionen untersucht und begleitende quantenchemische Rechnungen durchgefuehrt.

  12. Crystal Structure and Fluorescent Property of a 2D Coordination Polymer: [Eu(PCPA)3(H2O)]n

    Institute of Scientific and Technical Information of China (English)

    SUN Rui-Qing; ZHANG Han-Hui; CAO Yan-Ning; CHEN Yi-Ping; WANG Zhen; YANG Qi-Yu

    2006-01-01

    The title coordination polymer [Eu(PCPA)3(H2O)]n (PCPA = p-chlorophenoxyacetate) has been synthesized under hydrothermal condition, determined by single-crystal X-ray diffraction and characterized by FT-IR, UV-VIS and fluorescent spectra. The crystal belongs to triclinic system, space group P1 with a = 7.8036(1), b = 12.7458(4), c = 14.0208(3) (A), α =81.610(8), β = 79.406(8), γ = 77.567(7)°, V = 1330.40(5) (A)3, C24H20Cl3EuO10, Mr = 726.71, Z = 2,F(000) = 716, Dc= 1.814 g/cm3, λ(MoKα) = 0.71073 (A), μ(MoKα) = 2.713 mm-1, the final R =0.0284 and wR = 0.0678 for 5529 observed reflections with 1 > 2σ(Ⅰ). The europium ions are located in a nine-coordinate environment. PCPA ions with two different coordination modes connect the metal ions to form 1D zigzag chains which are arranged to generate 2D supramolecular layers by intermolecular hydrogen bonds. The luminescence properties of the rare-earth ions are studied in this paper.

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

    Science.gov (United States)

    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.

  14. Dye-sensitized solar cells assembled with composite gel polymer electrolytes containing nanosized Al2O3 particles.

    Science.gov (United States)

    Jeon, Nawon; Kim, Dong-Won

    2013-12-01

    Polymeric ionic liquid, poly(1-methyl 3-(2-acryloyloxy propyl) imidazolium iodide) (PMAPII) containing iodide ions is synthesized and used as a matrix polymer for preparing the composite polymer electrolytes. The composite gel polymer electrolytes are prepared by utilizing PMAPII, organic solvent containing redox couple and aluminum oxide nanoparticle for application in dye-sensitized solar cells (DSSCs). PMAPII is highly compatible with organic solvents and thus there is no phase separation between the PMAPII and organic solvents. This makes it be possible to directly solidify the liquid electrolyte in the cell and maintain good interfacial contacts between the electrolyte and electrodes. The addition of 10 wt.% Al2O3 nanoparticle to gel polymer electrolyte provides the most desirable environment for ionic transport, resulting in the improvement of the photovoltaic performance of DSSC. The quasi-solid-state DSSC assembled with optimized composite gel polymer electrolyte containing 10 wt.% Al2O3 nanoparticle exhibits a relatively high conversion efficiency of 6.51% under AM 1.5 illumination at 100 mA cm(-2) and better stability than DSSC with liquid electrolyte.

  15. Synthesis of Biocompatible Nanoparticulate Coordination Polymers for Diagnostic and Therapeutic Applications

    Science.gov (United States)

    Kandanapitiye, Murthi S.

    The combination of nanotechnology with medicinal chemistry has developed into a burgeoning research area. Nanomaterials (NMs) could be seamlessly interfaced with various facets in biology, biochemistry, medicinal chemistry and environmental chemistry that may not be available to the same material in the bulk scale. This dissertation research has focused on the development of nanoparticulate coordination polymers for diagnostic and therapeutic applications. Modern imaging techniques include X-ray computed tomography (CT), magnetic resonance imaging (MRI), single photon emission computed tomography (SPECT) and positron emission tomography (PET). We have successfully developed several types of nanoparticulate diagnostics and therapeutics that have some potential usefulness in biomedicine. Synthesis and characterization of nanoparticulate based PET (Positron emission tomography)/SPECT (Single photon emission computed tomography) are discussed in chapter 3. In chapter 4, preparation and potential utility of non-gadolinium based MRI contrast agent are reported for T1-weighted application. As far as the solely effectiveness of relaxation is concerned, Gd-based T 1-weighted MRI contrast agents have excellent enhancement of image contrast but they have risks of biological toxicity. Consequently, the search for T 1-weighted CAs with high efficacy and low toxicity has gained attention toward the Mn(II) and Fe(III). Fe(II