Sample records for rigid nonlabile polyoxometalate

  1. Non-labile Soil Nitrogen Retention beneath Three Tree Species in a Tropical Plantation (United States)

    Jason P. Kaye; Dan Binkley; Xiaoming Zou; John A. Parrotta


    Soil organic matter is the largest sink for N additions to forests. Species composition may affect soilNretention by altering the amount or proportion of added N stored in non-labile organic pools. We measured 15N tracer retention in labile and non-labile pools of surface (0–20 cm) mineral soils, 7 yr after the tracer was applied to a 9 yr-old Puerto Rican tree...

  2. Non-labile Soil 15Nitrogen Retention beneath Three Tree Species in a Tropical Plantation (United States)

    Jason P. Kaye; Dan Binkley; Xiaoming Zou; John A. Parrotta


    Soil organic matter is the largest sink for N additions to forests.Species composition may affect soilNretention by altering the amount or proportion of added N stored in non-labile organic pools. We measured 15N tracer retention in labile and non-labile pools of surface (0–20 cm) mineral soils, 7 yr after the tracer was applied to a 9 yr-old Puerto Rican tree...

  3. Polyoxometalate-based Supramolecular Gel (United States)

    He, Peilei; Xu, Biao; Liu, Huiling; He, Su; Saleem, Faisal; Wang, Xun


    Self-assemblyings of surfactant-encapsulated Wells-Dawson polyoxometalates (SEPs) nanobuilding blocks in butanone and esters yielded supramolecular gels showing thermo and photo responsive properties. The gels can be further polymerized if unsaturated esters were used and subsequently electrospinned into nanowires and non-woven mats. The as-prepared non-woven mats have a Young's modulus as high as 542.55 MPa. It is believed that this supramolecular gel is a good platform for polyoxometalates processing.

  4. Synthesis of polyoxometalate-loaded epoxy composites (United States)

    Anderson, Benjamin J


    The synthesis of a polyoxometalate-loaded epoxy uses a one-step cure by applying an external stimulus to release the acid from the polyoxometalate and thereby catalyze the cure reaction of the epoxy resin. Such polyoxometalate-loaded epoxy composites afford the cured epoxy unique properties imparted by the intrinsic properties of the polyoxometalate. For example, polyoxometalate-loaded epoxy composites can be used as corrosion resistant epoxy coatings, for encapsulation of electronics with improved dielectric properties, and for structural applications with improved mechanical properties.

  5. Polymers incorporating covalently attached organoimido polyoxometalates (United States)

    Maatta, Eric A.; Moore, Aaron R.


    New polyoxometalate compounds and polymers comprising recurring monomers of those compounds are provided. The compounds are formed by replacing at least one oxide of the starting polyoxometalate with an organoimido (NR) group bonded to the polyoxometalate via a triple bond to the nitrogen atom. The R of the (NR) group comprises a reactive functional group which renders the compound readily polymerizable, alone or with other monomers (e.g., divinylbenzene), to form the inventive polymers. Additionally, a countercation (e.g., bis(tetra-n-butylammonium)) can be mixed with the polyoxometalate compounds in order to neutralize the negative charge thereof as well as to make those compounds more soluble in organic solvents.

  6. Catalytic Desulfurization of Benzothiophene Using Keggin Type Polyoxometalates as Catalyst

    Directory of Open Access Journals (Sweden)

    Aldes Lesbani


    Full Text Available Performance of catalytic desulfurization of benzothiophen (BT was studied using polyoxometalates as catalyst. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40], have different heteroatom in Keggin structure and catalytic activities. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] have high crystallinity with homogeneous distribution particles. Desulfurization of BT using polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] resulted % conversion up to 99% for 3 h reaction time and at temperature 40 oC. Application of polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] for crude oil desulfurization showed % conversion of 4-88%. The main functional groups of polyoxometalates still retained after catalytic desulfurization indicated the stability of polyoxometalate compounds

  7. Recent advances in polyoxometalate based delignification (United States)

    R. H. Atalla; L. A. Weinstock; R. S. Reiner; C. J. Houtman; S. Reichel; C. G. Hill; C. L. Hill


    A new delignification technology based on the use of polyoxometalates (POMs) as delignification agents is under development at the USDA Forest Service, Forest Products Labotatory (FPL), in Madison, Wisconsin. These reagents are chlorine free and can be used under conditions wherein they oxidize lignin and chromophores in wood pulp fibers while leaving the cellulose...

  8. Delignification of wood and kraft pulp with polyoxometalates (United States)

    Edward L. Springer; Richard S. Reiner; Ira A. Weinstock; Rajai H. Atalla; Michael W. Wemple; Elena M. G. Barbuzzi


    Finely divided aspen and spruce woods and a high lignin pine kraft pulp have been selectively delignified to low lignin levels using aqueous solutions of polyoxometalates under anaerobic conditions. The reduced polyoxometalates in the solutions can be reoxidized with oxygen and act as wet oxidation catalysts for the mineralization of the solubilized lignin and...

  9. Polyoxometalates: from inorganic chemistry to materials science. (United States)

    Casañ-Pastor, Nieves; Gómez-Romero, Pedro


    Polyoxometalates have been traditionally the subject of study of molecular inorganic chemistry. Yet, these polynuclear molecules, reminiscent of oxide clusters, present a wide range of structures and with them ideal frameworks for the deployment of a plethora of useful magnetic, electroionic, catalytic, bioactive and photochemical properties. With this in mind, a new trend towards the application of these remarkable species in materials science is beginning to develop. In this review we analyze this trend and discuss two main lines of thought for the application of polyoxometalates as materials. On the one hand, there is their use as clusters with inherently useful properties on themselves, a line which has produced fundamental studies of their magnetic, electronic or photoelectrochemical properties and has shown these clusters as models for quantum-sized oxides. On the other hand, the encapsulation or integration of polyoxometalates into organic, polymeric or inorganic matrices or substrates opens a whole new field within the area of hybrid materials for harnessing the multifunctional properties of these versatile species in a wide variety of applications, ranging from catalysis to energy storage to biomedicine.


    Energy Technology Data Exchange (ETDEWEB)



    The pairing of a Lindqvist or Keggin polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation, [R{sub 3}R{prime}P]{sup +}, has been shown to yield an original family of ionic liquids (POM-ILs), among them salts liquid at or near ambient temperature. The physicochemical properties of several such 'inorganic liquids', in particular their thermal properties, suggests the possible application of these compounds as robust, thermally-stable solvents for liquid-liquid extraction. A preliminary evaluation of the potential of POM-ILs in this application is presented.

  11. On affine rigidity

    Directory of Open Access Journals (Sweden)

    Steven J. Gortler


    Full Text Available We study the properties of affine rigidity of a hypergraph and prove a variety of fundamental results. First, we show that affine rigidity is a generic property (i.e., depends only on the hypergraph, not the particular embedding. Then we prove that a graph is generically neighborhood affinely rigid in d-dimensional space if it is (d+1-vertex-connected. We also show neighborhood affine rigidity of a graph implies universal rigidity of its squared graph.  Our results, and affine rigidity more generally, have natural applications in point registration and localization, as well as connections to manifold learning.

  12. Rigid particulate matter sensor (United States)

    Hall, Matthew [Austin, TX


    A sensor to detect particulate matter. The sensor includes a first rigid tube, a second rigid tube, a detection surface electrode, and a bias surface electrode. The second rigid tube is mounted substantially parallel to the first rigid tube. The detection surface electrode is disposed on an outer surface of the first rigid tube. The detection surface electrode is disposed to face the second rigid tube. The bias surface electrode is disposed on an outer surface of the second rigid tube. The bias surface electrode is disposed to face the detection surface electrode on the first rigid tube. An air gap exists between the detection surface electrode and the bias surface electrode to allow particulate matter within an exhaust stream to flow between the detection and bias surface electrodes.

  13. The wing-patterning network in the wingless castes of Myrmicine and Formicine ant species is a mix of evolutionarily labile and non-labile genes. (United States)

    Shbailat, Seba Jamal; Abouheif, Ehab


    Wing polyphenism in ants is the ability of a single genome to produce winged or wingless castes in a colony in response to environmental cues. Although wing polyphenism is a universal and homologous feature of ants, the gene network underlying wing polyphenism is conserved in the winged castes, but is labile in the wingless castes, that is, the network is interrupted at different points in the wingless castes of different ant species. Because the expression of all genes sampled so far in this network in the wingless castes is evolutionarily labile across species, an important question is whether all "interruption points" in the network are evolutionarily labile or are there interruption points that are evolutionarily non-labile. Here we show that in the wingless castes, the expression of the gene brinker (brk), which mediates growth, patterning, and apoptosis in the Drosophila wing disc, is non-labile; it is absent in vestigial wing discs of four ants species. In contrast, the expression of engrailed (en), a gene upstream of brk is labile; it is present in some species but absent in others. In the winged castes, both brk and en expression are conserved relative to their expression in Drosophila wing discs. The differential lability of genes in the network in wingless castes may be a general feature of networks underlying polyphenic traits. This raises the possibility that some genes, like brk, may be under stabilizing selection while most others, like en, may be evolving via directional selection or neutral drift. Copyright © 2012 Wiley Periodicals, Inc.

  14. Ionic liquid polyoxometalates as light emitting materials

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz-acosta, Denisse [Los Alamos National Laboratory; Del Sesto, Rico E [Los Alamos National Laboratory; Scott, Brian [Los Alamos National Laboratory; Bennett, Bryan L [Los Alamos National Laboratory; Purdy, Geraldine M [Los Alamos National Laboratory; Muenchausen, Ross E [Los Alamos National Laboratory; Mc Kigney, Edward [Los Alamos National Laboratory; Gilbertson, Robert [Los Alamos National Laboratory


    The low melting point, negligible vapor pressure, good solubility, and thermal and chemical stability make ionic liquids useful materials for a wide variety of applications. Polyoxometalates are early transition metal oxygen clusters that can be synthesized in many different sizes and with a variety of heterometals. The most attractive feature of POMs is that their physical properties, in particular electrical, magnetic, and optical properties, can be easily modified following known procedures. It has been shown that POMs can exhibit cooperative properties, as superconductivity and energy transfer. POM ionic liquids can be obtained by selecting the appropliate cation. Different alkyl ammonium and alkyl phosphonium salts are being used to produce new POM ionic liquids together with organic or inorganic luminescent centers to design light emitting materials. Ammonium and phosphonium cations with activated, polymerizable groups are being used to further polymerize the ionic liquid into transparent, solid materials with high metal density.

  15. Interaction between nanocluster polyoxometallates and low-molecular-weight organic compounds (United States)

    Ostroushko, A. A.; Adamova, L. V.; Eremina, E. V.; Grzhegorzhevskii, K. V.


    The equilibrium sorption of methanol and benzene vapors by spherical porous nanocluster polyoxometallates with keplerate structures of different compositions (Mo132 and Mo72Fe30) and polyoxometallate (Mo138) with a toroidal structure and patterns in the kinetics of these processes are studied. Changes in the chemical potentials of the sorbates and polyoxometallates, specific Gibbs energies of the interaction of the polyoxometallates with the indicated substances, and the partial molar entropy of the interaction of Mo132 with methanol are calculated. The stability of the polyoxometallate structure in the sorbate vapors is studied via IR and Raman spectroscopy.

  16. Polyoxometalates as mediators in the laccase catalyzed delignification


    Balakshin, M. Yu.; Evtuguin, D. V.; Neto, C. Pascoal; Paulo, Artur Cavaco


    The polyoxometalate (POM)-laccase catalytic system was applied for the first time to aerobic delignification of kraft pulps at moderate (40-60 degreesC) temperatures. Laccase was found to readily catalyze the re-oxidation of different kinds of polyoxometalates, including those, which cannot be re-oxidized by dioxygen even at high temperatures (PMo11V1, SiW11V1. etc.). This allows a sequence of catalytic redox cycles similar to that in the laccase-mediator system (LMS) where electrons are tran...

  17. Polyoxometallates as effective photocatalysts in water purification from pesticides


    Gkika, E.; P. Kormali; Antonaraki, S.; D. Dimoticali; E. Papaconstantinou; Hiskia, A.


    Polyoxometallates (POM), i.e., metal oxide clusters of mainly tungsten are effective homogeneous photocatalysts for the mineralization of organic pollutants. POM are, at least, as effective as the well studied TiO2. OH⋅radicals formed by the reaction of the photo-excited polyoxometallates with H2O, appear to play a key role in the process. In this study, the photocatalytic activity of POM have been tested on some diversified pesticides of interest such as lindane, bentazone and feni...

  18. Progress in the development and optimization of polyoxometalate delignification systems (United States)

    R.H. Atalla; I.A. Weinstock; J.S. Bond; R.S. Reiner; E.L. Springer; C.G. Hill; Yu. Geletii; V.A. Grigoriev; A.J. Bailey; L. Delannoy; C.L. Hill


    We have reported the use of polyoxometalates (POMs) as selective, regenerable delignification agents that are inherently thermodynamically stable, and self-buffering. The re-activation with oxygen is under conditions that mineralize the organic byproducts of the delignification process. Thus, the POMs provide the basis for a closed bleach plant wherein the consumable...

  19. Electrochemical delignification of wood pulp using polyoxometalate mediators (United States)

    R.S. Reiner; E.L. Springer; R.H. Atalla


    It has been found that polyoxometalates (POMs) can act as mediators in the electrochemical oxidation of lignin in pulps. An electrochemical cell, with a Nafion® membrane separating the anode and cathode compartments, was used in the delignification experiments. A softwood kraft pulp was placed in the anode compartment with a buffered 0.01M solution of the...

  20. Progress in the development and optimization of polyoxometalate delignification systems (United States)

    R.H. Atalla; I.A. Weinstock; R.S. Reiner; E.L. Springer; C.G. Hill


    We have reported the use of polyoxometalates (POMs) as selective, regenerable delignification agents that are inherently thermodynamically stable, and self-buffering. The re-activation with oxygen is under conditions that mineralize the organic byproducts of the delignification process. Thus, the POMs provide the basis for a closed bleach plant wherein the consumable...

  1. Europium polyoxometalates encapsulated in silica nanoparticles - characterization and photoluminescence studies

    Energy Technology Data Exchange (ETDEWEB)

    Neves, Cristina S.; Granadeiro, Carlos M.; Cunha-Silva, Luis; Eaton, Peter; Balula, Salete S.; Pereira, Eulalia [REQUIMTE/Departamento de Quimica e Bioquimica, Faculdade de Ciencias, Universidade do Porto (Portugal); Ananias, Duarte [CICECO, Departamento de Quimica, Universidade de Aveiro (Portugal); Gago, Sandra [REQUIMTE, Departamento de Quimica, Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, Monte de Caparica (Portugal); Feio, Gabriel [CENIMAT/I3N, Departamento de Ciencia dos Materiais, Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, Monte de Caparica (Portugal); Carvalho, Patricia A. [ICEMS/Departamento de Bioengenharia, Instituto Superior Tecnico, Lisboa (Portugal)


    The incorporation of europium polyoxometalates into silica nanoparticles can lead to a biocompatible nanomaterial with luminescent properties suitable for applications in biosensors, biological probes, and imaging. Keggin-type europium polyoxometalates Eu(PW{sub 11}){sub x} (x = 1 and 2) with different europium coordination environments were prepared by using simple methodologies and no expensive reactants. These luminescent compounds were then encapsulated into silica nanoparticles for the first time through the water-in-oil microemulsion methodology with a nonionic surfactant. The europium polyoxometalates and the nanoparticles were characterized by using several techniques [FTIR, FT-Raman, {sup 31}P magic angle spinning (MAS) NMR, and TEM/energy-dispersive X-ray spectroscopy (TEM-EDS), AFM, dynamic light scattering (DLS), and inductively coupled plasma MS (ICP-MS) analysis]. The stability of the material and the integrity of the europium compounds incorporated were also examined. Furthermore, the photoluminescence properties of the Eu(PW{sub 11}){sub x} rate at SiO{sub 2} nanomaterials were evaluated and compared with those of the free europium polyoxometalates. The silica surface of the most stable nanoparticles was successfully functionalized with appropriate organosilanes to enable the covalent binding of oligonucleotides. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Two hybrids based on Keggin polyoxometalates and dinuclear ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 10. Two hybrids based on Keggin polyoxometalates and dinuclear copper(II) complexes: syntheses, structures and electrocatalytic properties. YAN HOU YING NIU CHUNJING ZHANG HAIJUN PANG HUIYUAN MA. REGULAR ARTICLE Volume 129 Issue ...

  3. Oxidation catalysis by polyoxometalates fundamental electron-transfer phenomena (United States)

    Yurii V. Geletii; Rajai H. Atalla; Alan J. Bailey; Laurent Delannoy; Craig L. Hill; Ira A. Weinstock


    Early transition-metal oxygen-anion clusters (polyoxometalates, POMs) are a large and rapidly growing class of versatile and tunable oxidation catalysts. All key molecular properties of these clusters (composition, size, shape, charge density, reduction potential, solubility, etc.) can be systematically altered, and the clusters themselves can serve as tunable ligands...

  4. Functionalization of polyoxometalates by carboxylato and azido ligands: macromolecular complexes and extended compounds. (United States)

    Mialane, Pierre; Dolbecq, Anne; Sécheresse, Francis


    Polyoxometalate compounds continue to be widely studied due to their relevance in various fields such as catalysis or magnetochemistry. In this article, we will focus on two topics we recently developed, the functionalization of rare earth polyoxometalates by organic ligands, which has led to compounds ranging from magnetic macromolecular complexes to a 3D open-framework system, and the functionalization of first row transition metal substituted polyoxometalates by azido ligands, which has allowed the isolation of complexes exhibiting the largest ferromagnetic exchange couplings observed to date in polyoxometalate chemistry.

  5. Rigidity and symmetry

    CERN Document Server

    Weiss, Asia; Whiteley, Walter


    This book contains recent contributions to the fields of rigidity and symmetry with two primary focuses: to present the mathematically rigorous treatment of rigidity of structures, and to explore the interaction of geometry, algebra, and combinatorics. Overall, the book shows how researchers from diverse backgrounds explore connections among the various discrete structures with symmetry as the unifying theme.  Contributions present recent trends and advances in discrete geometry, particularly in the theory of polytopes. The rapid development of abstract polytope theory has resulted in a rich theory featuring an attractive interplay of methods and tools from discrete geometry, group theory, classical geometry, hyperbolic geometry and topology.  The volume will also be a valuable source as an introduction to the ideas of both combinatorial and geometric rigidity theory and its applications, incorporating the surprising impact of symmetry. It will appeal to students at both the advanced undergraduate and gradu...

  6. Towards polyoxometalate-cluster-based nano-electronics. (United States)

    Vilà-Nadal, Laia; Mitchell, Scott G; Markov, Stanislav; Busche, Christoph; Georgiev, Vihar; Asenov, Asen; Cronin, Leroy


    We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO2, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom-built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non-volatile molecular memories (NVMM) or flash-RAM. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The UV and IR Comparative Spectrophotometric Study of Some Saturated and Lacunary Polyoxometalates

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    Grama Lavinia


    Full Text Available Objectives: The polyoxometalates are a class of inorganic compounds with controllable shapes and sizes, and with excellent properties that make them attractive for various applications. This study is aimed at the comparative UV and IR spectra of Keggin type polyoxometalates.

  8. Rigid molecular foams

    Energy Technology Data Exchange (ETDEWEB)

    Steckle, W.P. Jr. [Los Alamos National Lab., NM (United States); Mitchell, M.A. [Chemidal Corp., Palatine, IL (United States); Aspen, P.G. [Simula Inc., Phoenix, AZ (United States)


    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Organic analogues to inorganic zeolites would be a significant step forward in engineered porous materials and would provide advantages in range, selectivity, tailorability, and processing. Rigid molecular foams or {open_quotes}organic zeolites{close_quotes} would not be crystalline materials and could be tailored over a broader range of pore sizes and volumes. A novel process for preparing hypercrosslinked polymeric foams has been developed via a Friedel-Crafts polycondensation reaction. A series of rigid hypercrosslinked foams have been prepared using simple rigid polyaromatic hydrocarbons including benzene, biphenyl, m-terphenyl, diphenylmethane, and polystyrene, with dichloroxylene (DCX) as the pore size. After drying the foams are robust and rigid. Densities of the resulting foams can range from 0.15 g/cc to 0.75 g/cc. Nitrogen adsorption studies have shown that by judiciously selecting monomers and the crosslinking agent along with the level of crosslinking and the cure time of the resulting gel, the pore size, pore size distribution, and the total surface area of the foam can be tailored. Surface areas range from 160 to 1,200 m{sup 2}/g with pore sizes ranging from 6 {angstrom} to 2,000 {angstrom}.

  9. Polyoxometalate catalyzed ozonation of chemical pulps in organic solvent media


    Shatalov, Anatoly A.; Pereira, Helena


    Polyoxometalate (POM) catalyzed ozonation of chemical pulps in organic solvent media was found to be particularly effective and selective environmentally benign bleaching approach providing a way for substantial increase in pulp brightness, viscosity and degree of delignification in comparison with other ozone-based bleaching techniques. A series of tested low-boiling polar aprotic and protic organic solvents showed awell-defined capacity for ozonation improvement in the presence ...

  10. Closed-mill delignification by design using polyoxometalates (United States)

    C. J. Houtman; R. S. Reiner; S. E. Reichel; M. J. Birchmeier; C. E. Sullivan; L. A. Weinstock; R. H. Atalla


    Polyoxometalates (POMs) are a class of delignification agents that promise to provide the basis for a new closed-mill bleaching technology. The results presented here are based on the use of Na6SiV2W10O40, which is effective in reducing the Kappa number of softwood Kraft pulp from 30 to below 10 with minimal loss in viscosity. A critical part of a viable POM process is...

  11. Catalytic application of two novel sandwich-type polyoxometalates ...

    Indian Academy of Sciences (India)

    on open-access literatures on the use of the sandwich- type polyoxometalates as catalyst in the synthesis of. 14-aryl or alkyl-14H-dibenzo[a, j]xanthenes. In this study, an attempt was made to explain a facile and efficient synthetic strategy for synthesis of 14-aryl or alkyl-14H-dibenzo[a, j]xanthenes using one-pot con-.

  12. Enumeration of non-labile oxygen atoms in dissolved organic matter by use of ¹⁶O/ ¹⁸O exchange and Fourier transform ion-cyclotron resonance mass spectrometry. (United States)

    Kostyukevich, Yury; Kononikhin, Alexey; Zherebker, Alexander; Popov, Igor; Perminova, Irina; Nikolaev, Eugene


    We report a simple approach for enumeration of non-labile oxygen atoms in individual molecules of dissolved organic matter (DOM), using acid-catalyzed (16)O/(18)O exchange and ultrahigh-resolution Fourier-transform ion-cyclotron-resonance mass spectrometry (FTICR-MS). We found that by dissolving DOM in H2 (18)O at 95 °C for 20 days it is possible to replace all oxygen atoms of DOM molecules (excluding oxygen from ether groups) with (18)O. The number of exchanges in each molecule can be determined using high-resolution FTICR. Using the proposed method we identified the number of non-labile oxygen atoms in 231 molecules composing DOM. Also, using a previously developed hydrogen-deuterium (H/D)-exchange approach we identified the number of labile hydrogen atoms in 450 individual molecular formulas. In addition, we observed that several backbone hydrogen atoms can be exchanged for deuterium under acidic conditions. The method can be used for structural and chemical characterization of individual DOM molecules, comparing different DOM samples, and investigation of biological pathways of DOM in the environment.

  13. Advanced Rigid Ablative TPS (United States)

    Gasch, Matthew J.


    NASA Exploration Systems Mission Directorate s (ESMD) Entry, Descent, and Landing (EDL) Technology Development Project (TDP) and the NASA Aeronautics Research Mission Directorate s (ARMD) Hypersonics Project are developing new advanced rigid ablators in an effort to substantially increase reliability, decrease mass, and reduce life cycle cost of rigid aeroshell-based entry systems for multiple missions. Advanced Rigid Ablators combine ablation resistant top layers capable of high heat flux entry and enable high-speed EDL with insulating mass-efficient bottom that, insulate the structure and lower the areal weight. These materials may benefit Commercial Orbital Transportation Services (COTS) vendors and may potentially enable new NASA missions for higher velocity returns (e.g. asteroid, Mars). The materials have been thermally tested to 400-450 W/sq cm at the Laser Hardened Materials Evaluation Lab (LHMEL), Hypersonics Materials Evaluation Test System (HyMETS) and in arcjet facilities. Tested materials exhibit much lower backface temperatures and reduced recession over the baseline materials (PICA). Although the EDL project is ending in FY11, NASA in-house development of advanced ablators will continue with a focus on varying resin systems and fiber/resin interactions.

  14. Rigid Bodies in Contact

    DEFF Research Database (Denmark)

    Niebe, Sarah Maria

    The topic of this thesis is the numerics of rigid body simulation, with focus on the contact force problem. Three contact force models are presented, followed by three contact point determination methods. To solve the contact force problem, six different numerical methods are presented, each......-Seidel (PGS), although computationally more expensive. The NNCG method has been implemented in the physics library Bullet, as of revision r2709, as an alternative to the PGS method. A subspace minimization method is developed to improve convergence of the PGS method, improving the results of large mass ratio...

  15. Eucalypt kraft pulp delignification with polyoxometalate assisted by fungal versatile peroxidase


    Marques, Gisela; Gamelas, José A. F.; Ruiz-Dueñas, F. J.; Río Andrade, José Carlos del; Evtuguin, Dmitry; Martínez, Ángel T.; Gutiérrez Suárez, Ana


    Polyoxometalates have been reported as alternative redox catalysts for pulp delignification in environmentally-friendly bleaching sequences. Enzymatic catalysis is a promising approach to regenerate polyoxometalates that are highly effective in delignification, but very difficult to be subsequently reoxidized by O2 and other oxidants. In this work, the oxidation of a manganese-substituted polyoxometalate (POM) [SiW11MnII(H2O)O39]6- (SiW11MnII) by Mn-oxidizing versatile peroxidase (VP) to give...

  16. Synthesis, Characterization and Applications in Catalysis of Polyoxometalate/Zeolite Composites

    Directory of Open Access Journals (Sweden)

    Frédéric Lefebvre


    Full Text Available An overview of the synthesis, characterization and catalytic applications of polyoxometalates/zeolites composites is given. The solids obtained by direct synthesis of the polyoxometalate in the presence of the zeolite are first described with their applications in catalysis. Those obtained by a direct mixing of the two components are then reviewed. In all cases, special care is taken in the localization of the polyoxometalate, inside the zeolite crystal, in mesopores or at the external surface of the crystals, as deduced from the characterization methods.

  17. Tetraalkylphosphonium polyoxometalate ionic liquids: novel, organic-inorganic hybrid materials. (United States)

    Rickert, Paul G; Antonio, Mark R; Firestone, Millicent A; Kubatko, Karrie-Ann; Szreder, Tomasz; Wishart, James F; Dietz, Mark L


    Pairing of a Keggin or Lindqvist polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation is shown to yield the first members of a new family of ionic liquids (ILs). Detailed characterization of one of them, an ambient-temperature "liquid POM" comprising the Lindqvist salt of the trihexyl(tetradecyl) phosphonium cation, by voltammetry, viscometry, conductimetry, and thermal analysis indicates that it exhibits conductivity and viscosity comparable to those of the one previously described inorganic-organic POM-IL hybrid but with substantially improved thermal stability.

  18. Tetraalkylphosphonium polyoxometalate ionic liquids : novel, organic-inorganic hybrid materials.

    Energy Technology Data Exchange (ETDEWEB)

    Rickert, P. G.; Antonio, M. P.; Firestone, M. A.; Kubatko, K.-A.; Szreder, T.; Wishart, J. F.; Dietz, M. L.; Chemistry; Univ. of Notre Dame; BNL


    Pairing of a Keggin or Lindqvist polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation is shown to yield the first members of a new family of ionic liquids (ILs). Detailed characterization of one of them, an ambient-temperature 'liquid POM' comprising the Lindqvist salt of the trihexyl(tetradecyl) phosphonium cation, by voltammetry, viscometry, conductimetry, and thermal analysis indicates that it exhibits conductivity and viscosity comparable to those of the one previously described inorganic-organic POM-IL hybrid but with substantially improved thermal stability.

  19. Rigid Motion and Adapted Frames (United States)

    Lyle, Stephen N.

    The aim here is to describe the rigid motion of a continuous medium in special and general relativity. Section 7.1 defines a rigid rod in special relativity, and Sect. 7.2 shows the link with the space coordinates of a certain kind of accelerating frame in flat spacetimes. Section 7.3 then sets up a notation for describing the arbitrary smooth motion of a continuous medium in general curved spacetimes, defining the proper metric of such a medium. Section 7.4 singles out rigid motions and shows that the rod in Sect. 7.1 undergoes rigid motion in the more generally defined sense. Section 7.5 defines a rate of strain tensor for a continuous medium in general relativity and reformulates the rigidity criterion. Section 7.6 aims to classify all possible rigid motions in special relativity, reemphasizing the link with semi-Euclidean frames adapted to accelerating observers in special relativity. Then, Sects. 7.7 and 7.8 describe rigid motion without rotation and rigid rotation, respectively. Along the way we introduce the notion of Fermi-Walker transport and discuss its relevance for rigid motions. Section 7.9 brings together all the above themes in an account of a recent generalization of the notion of uniform acceleration, thereby characterizing a wide class of rigid motions.

  20. Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing. (United States)

    Clemente-Juan, Juan M; Coronado, Eugenio; Gaita-Ariño, Alejandro


    In this review we discuss the relevance of polyoxometalate (POM) chemistry to provide model objects in molecular magnetism. We present several potential applications in nanomagnetism, in particular, in molecular spintronics and quantum computing.

  1. Synthesis and crystal structure of two supramolecular compounds constructed from amantadine and polyoxometalate (United States)

    Yang, Jing; Huang, Kunlin; Pu, Zhifa; Gong, Yun; Li, Hui; Hu, Changwen


    Two organic-inorganic hybrid compounds based on amantadines and polyoxometalates formulated as (C 10H 18N) 4(H 2V 10O 28)·2DMF·2H 2O ( 1) and (C 10H 18N) 3(PMo 12O 40) ( 2), were synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction analysis, IR, UV and TGA. Compounds 1 and 2 consist of protonated amantadines together with different polyoxometalates, [H 2V 10O 28] 4- and [PMo 12O 40] 3-, respectively. There are hydrogen bonding interactions and electrostatic attractions between polyoxometalates and amantadines in 1 and 2. Polyoxometalates are linked through amantadines into a two-dimensional network via hydrogen bonds in the two compounds. The two-dimensional framework is further extended into supramolecular network by hydrophobic interaction of amantadines between adjacent layers. The crystal packing patterns of the two compounds reveal various supramolecular framework.

  2. Polyoxometalate-mediated electron transfer-oxygen transfer oxidation of cellulose and hemicellulose to synthesis gas

    National Research Council Canada - National Science Library

    Sarma, Bidyut Bikash; Neumann, Ronny


    .... Here we show that by using a polyoxometalate as an electron transfer-oxygen transfer catalyst, carbon monoxide is formed by cleavage of all the carbon-carbon bonds through dehydration of initially formed formic acid...

  3. Torsional Rigidity of Minimal Submanifolds

    DEFF Research Database (Denmark)

    Markvorsen, Steen; Palmer, Vicente


    We prove explicit upper bounds for the torsional rigidity of extrinsic domains of minimal submanifolds $P^m$ in ambient Riemannian manifolds $N^n$ with a pole $p$. The upper bounds are given in terms of the torsional rigidities of corresponding Schwarz symmetrizations of the domains in warped...... for the torsional rigidity are actually attained and give conditions under which the geometric average of the stochastic mean exit time for Brownian motion at infinity is finite....

  4. Designing rigid carbon foams

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sora; Ahn, Jeung Sun; Kwon, Young-Kyun; Tomanek, David [Department of Physics and Research Institute for Basic Sciences, Kyung Hee University, Seoul, 130-701 (Korea, Republic of); Kittimanapun, Kritsada, E-mail:, E-mail: tomanek@pa.msu.ed [Physics and Astronomy Department, Michigan State University, East Lansing, MI 48824-2320 (United States)


    We use ab initio density functional calculations to study the stability, elastic properties and electronic structure of sp{sup 2} carbon minimal surfaces with negative Gaussian curvature, called schwarzites. We focus on two systems with cubic unit cells containing 152 and 200 carbon atoms, which are metallic and very rigid. The porous schwarzite structure allows for efficient and reversible doping by electron donors and acceptors, making it a promising candidate for the next generation of alkali ion batteries. We identify schwarzite structures that act as arrays of interconnected spin quantum dots or become magnetic when doped. We introduce two interpenetrating schwarzite structures that may find their use as the ultimate super-capacitor.

  5. After Rigid Interfaces

    DEFF Research Database (Denmark)

    Troiano, Giovanni Maria

    Deformable and shape-changing interfaces are rapidly emerging in the field of human-computer interaction (HCI). Deformable interfaces provide users with newer input possibilities such as bending, squeezing, or stretching, which were impossible to achieve with rigid interfaces. Shape...... sensors in the five preferred objects and programmed them for controlling sounds with computer software. Finally, we ran a performance study where six musicians performed music with deformable interfaces at their studios. Results from the performance study show that musicians systematically map......, Transformation, Adaptation and Physicalization. In synthesis, the work presented in this thesis shows (1) implications of usefulness for deformable interfaces and how their new input modalities can redefine the way users interact with computers, and (2) how a systematic understanding of conventional design...

  6. Multifunctional multilayer films containing polyoxometalates and bismuth oxide nanoparticles. (United States)

    Li, Chunxiang; O'Halloran, Kevin P; Ma, Huiyuan; Shi, Shilin


    Multifunctional multilayer films consisting of the Keggin-type polyoxometalate [SiW(9)V(3)O(40)](7-) (SiW(9)V(3)) and bismuth oxide nanoparticles (Bi(2)O(3)) were prepared by the layer-by-layer assembly method. For the first time, electrochromic and photochromic studies were done on a film containing both polyoxometalates and nanoparticles. The films were characterized by UV-vis absorption, emission spectra, and atomic force microscopy. Their electrochromic and photochromic properties were investigated by cyclic voltammetry and UV-vis spectroscopy. The results show that the reduction of SiW(9)V(3) is very reversible and tunable with the addition of Bi(2)O(3) layers into the film. The electrocatalytic activity of the films toward oxidation of l-cysteine hydrochloride hydrate (l-cysteine) and reduction of nitrite were studied with cyclic voltammetry. The results show that the incorporation of Bi(2)O(3) nanoparticles into the films changed the films' photoluminescence properties and electrocatalytic efficiency.

  7. Preparation of polyoxometalates in ionic liquids by ionothermal synthesis. (United States)

    Lin, Shiwei; Liu, Wenli; Li, Yangguang; Wu, Qiong; Wang, Enbo; Zhang, Zhiming


    Ionothermal synthesis was applied to the formation of polyoxometalates (POMs) and two new compounds [EMIM](8)Na(9)[WFe(9)(micro(3)-O)(3)(micro(2)-OH)(6)O(4)H(2)O(SiW(9)O(34))(3)].7H(2)O (, [EMIM](8)Na(9)[].7H(2)O, EMIM = 1-ethyl-3-methylimidazolium) and [EMIM](4)[SiMo(12)O(40)].12H(2)O (), have been successfully produced in the ionic liquid (IL) [EMIM](4)Br. They were characterized by single-crystal X-ray diffraction, elemental analysis, UV-vis, IR and TG analysis. Furthermore, the magnetic properties of and the electrochemical properties of were studied. is a high-nuclear transition metal substituted polyoxometalate (TMSP) and the unprecedented polyoxoanion of is composed of three [alpha-SiW(9)O(34)](10-) Keggin moieties connected by a {WFe(9)} cluster core. is a heteropolyoxometalate with the polyoxoanion of alpha-Keggin type.

  8. Quantum charged rigid membrane

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, Ruben [Departamento de Fisica, Escuela Superior de Fisica y Matematicas del I.P.N., Unidad Adolfo Lopez Mateos, Edificio 9, 07738 Mexico, D.F. (Mexico); Molgado, Alberto [Unidad Academica de Fisica, Universidad Autonoma de Zacatecas, Zacatecas Zac. (Mexico); Rojas, Efrain, E-mail:, E-mail:, E-mail: [Departamento de Fisica, Facultad de Fisica e Inteligencia Artificial, Universidad Veracruzana, 91000 Xalapa, Veracruz (Mexico)


    The early Dirac proposal to model the electron as a charged membrane is reviewed. A rigidity term, instead of the natural membrane tension, involving linearly the extrinsic curvature of the worldvolume swept out by the membrane is considered in the action modeling the bubble in the presence of an electromagnetic field. We set up this model as a genuine second-order derivative theory by considering a non-trivial boundary term which plays a relevant part in our formulation. The Lagrangian in question is linear in the bubble acceleration and by means of the Ostrogradski-Hamiltonian approach, we observed that the theory comprises the management of both first- and second-class constraints. We thus show that our second-order approach is robust allowing for a proper quantization. We found an effective quantum potential which permits us to compute bounded states for the system. We comment on the possibility of describing brane world universes by invoking this kind of second-order correction terms.

  9. Porphyrin-Sensitized Evolution of Hydrogen using Dawson and Keplerate Polyoxometalate Photocatalysts. (United States)

    Panagiotopoulos, Athanassios; Douvas, Antonios M; Argitis, Panagiotis; Coutsolelos, Athanassios G


    Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP(4+) ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P2 Mo18 O62(6-) and P2 W18 O62(6-) anions, and one Keplerate {Mo132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP(4+) sensitization in relation to the direct photoreduction of those compounds; (b) the P2 Mo18 O62(6-) anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P2 W18 O62(6-) anion; and (c) the high nuclearity Keplerate {Mo132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Polyoxometalates in Oxidative Delignification of Chemical Pulps: Effect on Lignin (United States)

    Bujanovic, Biljana; Ralph, Sally; Reiner, Richard; Hirth, Kolby; Atalla, Rajai


    Chemical pulps are produced by chemical delignification of lignocelluloses such as wood or annual non-woody plants. After pulping (e.g., kraft pulping), the remaining lignin is removed by bleaching to produce a high quality, bright paper. The goal of bleaching is to remove lignin from the pulp without a negative effect on the cellulose; for this reason, delignification should be performed in a highly selective manner. New environmentally-friendly alternatives to conventional chlorine-based bleaching technologies (e.g., oxygen, ozone, or peroxide bleaching) have been suggested or implemented. In an attempt to find inorganic agents that mimic the action of highly selective lignin-degrading enzymes and that can be applicable in industrial conditions, the researchers have focused on polyoxometalates (POMs), used either as regenerable redox reagents (in anaerobic conditions) or as catalysts (in aerobic conditions) of oxidative delignification. The aim of this paper is to review the basic concepts of POM delignification in these two processes.

  11. Heterogeneous Catalysis of Polyoxometalate Based Organic–Inorganic Hybrids (United States)

    Ren, Yuanhang; Wang, Meiyin; Chen, Xueying; Yue, Bin; He, Heyong


    Organic–inorganic hybrid polyoxometalate (POM) compounds are a subset of materials with unique structures and physical/chemical properties. The combination of metal-organic coordination complexes with classical POMs not only provides a powerful way to gain multifarious new compounds but also affords a new method to modify and functionalize POMs. In parallel with the many reports on the synthesis and structure of new hybrid POM compounds, the application of these compounds for heterogeneous catalysis has also attracted considerable attention. The hybrid POM compounds show noteworthy catalytic performance in acid, oxidation, and even in asymmetric catalytic reactions. This review summarizes the design and synthesis of organic–inorganic hybrid POM compounds and particularly highlights their recent progress in heterogeneous catalysis. PMID:28788017

  12. Heterogeneous Catalysis of Polyoxometalate Based Organic–Inorganic Hybrids

    Directory of Open Access Journals (Sweden)

    Yuanhang Ren


    Full Text Available Organic–inorganic hybrid polyoxometalate (POM compounds are a subset of materials with unique structures and physical/chemical properties. The combination of metal-organic coordination complexes with classical POMs not only provides a powerful way to gain multifarious new compounds but also affords a new method to modify and functionalize POMs. In parallel with the many reports on the synthesis and structure of new hybrid POM compounds, the application of these compounds for heterogeneous catalysis has also attracted considerable attention. The hybrid POM compounds show noteworthy catalytic performance in acid, oxidation, and even in asymmetric catalytic reactions. This review summarizes the design and synthesis of organic–inorganic hybrid POM compounds and particularly highlights their recent progress in heterogeneous catalysis.

  13. Heterogeneous Catalysis of Polyoxometalate Based Organic-Inorganic Hybrids. (United States)

    Ren, Yuanhang; Wang, Meiyin; Chen, Xueying; Yue, Bin; He, Heyong


    Organic-inorganic hybrid polyoxometalate (POM) compounds are a subset of materials with unique structures and physical/chemical properties. The combination of metal-organic coordination complexes with classical POMs not only provides a powerful way to gain multifarious new compounds but also affords a new method to modify and functionalize POMs. In parallel with the many reports on the synthesis and structure of new hybrid POM compounds, the application of these compounds for heterogeneous catalysis has also attracted considerable attention. The hybrid POM compounds show noteworthy catalytic performance in acid, oxidation, and even in asymmetric catalytic reactions. This review summarizes the design and synthesis of organic-inorganic hybrid POM compounds and particularly highlights their recent progress in heterogeneous catalysis.

  14. The structure of rigid functions (United States)

    Balka, Richárd; Elekes, Márton


    A function is called vertically rigid if graph(cf) is isometric to graph(f) for all c[not equal to]0. We prove Jankovic's conjecture by showing that a continuous function is vertically rigid if and only if it is of the form a+bx or a+bekx (). We answer the question of Cain, Clark and Rose by showing that there exists a Borel measurable vertically rigid function which is not of the above form. We discuss the Lebesgue and Baire measurable case, consider functions bounded on some interval and functions with at least one point of continuity. We also introduce horizontally rigid functions, and show that a certain structure theorem can be proved without assuming any regularity.

  15. Two polyoxometallate-based supramolecular compounds influenced by the ratio between the polyoxometallate anion and organic cation. (United States)

    Zhang, Qian; Liu, Jie; Lu, Jing; Gong, Shu-Wen


    Two polyoxometallate-based compounds, tris[1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium)] bis[tetracosa-μ2-oxido-dodecaoxido-μ12-phosphato-dodecamolybdenum(VI)], (C10H16N4)3[PMo12O40]2, (I), and 1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium) 1-[4-(1H-imidazol-1-yl)butyl]-1H-imidazol-3-ium tetracosa-μ2-oxido-dodecaoxido-μ12-phosphato-dodecamolybdenum(VI) dihydrate, (C10H16N4)(C10H15N4)[PMo12O40]·2H2O, (II), were synthesized by hydrothermal techniques at different pH values. The stoichiometric ratio between the polyoxometallate (POM) anions and organic cations is 2:3 in (I), with one of the cations lying on an inversion centre. The doubly protonated 1,1'-(butane-1,4-diyl)diimidazole (BIM) cations are linked to the [PMo12O40](3-) anions by hydrogen bonds to form a three-dimensional supramolecular network. The stoichiometric ratio of POM anions and organic cations is 1:2 in (II), and the anion is located about a centre of inversion. The partly protonated BIM cations and solvent water molecules form hydrogen bonds with the [PMo12O40](3-) anions, yielding a two-dimensional supramolecular layer. The different lattice architectures of (I) and (II) may be governed by the ratio between the POM anions and organic cations, which, in turn, is determined by the pH value.

  16. Delignification of eucalypt kraft pulp with manganese-substituted polyoxometalate assisted by fungal versatile peroxidase. (United States)

    Marques, Gisela; Gamelas, José A F; Ruiz-Dueñas, Francisco J; del Rio, José C; Evtuguin, Dmitry V; Martínez, Angel T; Gutiérrez, Ana


    Oxidation of the manganese-substituted polyoxometalate [SiW(11)Mn(II)(H(2)O)O(39)](6-) (SiW(11)Mn(II)) to [SiW(11)Mn(III)(H(2)O)O(39)](5-) (SiW(11)Mn(III)), one of the most selective polyoxometalates for the kraft pulp delignification, by versatile peroxidase (VP) was studied. First, SiW(11)Mn(II) was demonstrated to be quickly oxidized by VP at room temperature in the presence of H(2)O(2) (K(m)=6.4+/-0.7 mM and k(cat)=47+/-2s(-1)). Second, the filtrate from eucalypt pulp delignification containing reduced polyoxometalate was treated with VP/H(2)O(2), and 95-100% reoxidation was attained. In this way, it was possible to reuse the liquor from a first SiW(11)Mn(III) stage for further delignification, in a sequence constituted by two polyoxometalate stages, and a short intermediate step consisting of the addition of VP/H(2)O(2) to the filtrate for SiW(11)Mn(II) reoxidation. When the first ClO(2) stage of a conventional bleaching sequence was substituted by the two-stage delignification with polyoxometalate (assisted by VP) a 50% saving in ClO(2) was obtained for similar mechanical strength of the final pulp. (c) 2010 Elsevier Ltd. All rights reserved.

  17. Rigid therapies, rigid minds: italian professionals' perspectives on autism interventions. (United States)

    Cascio, M Ariel


    Many therapies, interventions, and programs seek to improve outcomes and quality of life for people diagnosed with autism spectrum conditions. This paper addresses Italian professionals' perspectives on a variety of such interventions, including TEACCH, ABA, Defeat Autism Now!, and Doman-Delacato. Drawing on participant-observation and interviews collected in 2012-2013 in a northern region of Italy, it highlights the theme of "rigidity" that appears in professionals' discourses about both the characteristics of people with autism and the potential risks of adhering too strictly to any particular treatment protocol. The co-occurrence of the theme of rigidity across different domains demonstrates a way in which diagnostic characteristics become metaphors for medical practice. This paper proposes that such discursive moves may help bridge the gap between people with autism and people who work with them because a key attribute of people with autism-thinking and/or acting rigidly-is also a potential pitfall for people without autism.

  18. The dynamical rigid body with memory


    Albu, Ion Doru; Neamtu, Mihaela; Opris, Dumitru


    In the present paper we describe the dynamics of the revised rigid body, the dynamics of the rigid body with distributed delays and the dynamics of the fractional rigid body. We analyze the stationary states for given values of the rigid body's parameters.

  19. First examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands

    Energy Technology Data Exchange (ETDEWEB)

    Wang Lamei; Fan Yong; Wang Yan; Xiao Lina; Hu Yangyang; Peng Yu; Wang Tiegang; Gao Zhongmin; Zheng Dafang [College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun 130023 (China); Cui Xiaobing, E-mail: [College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun 130023 (China); Xu Jiqing, E-mail: [College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun 130023 (China)


    Two new organic-inorganic compounds based on polyoxometalates, metal halide clusters and organic ligands: [BW{sub 12}O{sub 40}]{sub 2}[Cu{sub 2}(Phen){sub 4}Cl](H{sub 2}4, 4 Prime -bpy){sub 4}{center_dot}H{sub 3}O{center_dot}5H{sub 2}O (1) and [HPW{sub 12}O{sub 40}][Cd{sub 2}(Phen){sub 4}Cl{sub 2}](4, 4 Prime -bpy) (2) (Phen=1, 10-phenanthroline, bpy=bipyridine), have been prepared and characterized by IR, UV-vis, XPS, XRD and single crystal X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 is constructed from [BW{sub 12}O{sub 40}]{sup 5-}, metal halide clusters [Cu{sub 2}(Phen){sub 4}Cl]{sup +}and 4, 4 Prime -bpy ligands, while compound 2 is constructed from [PW{sub 12}O{sub 40}]{sup 3-}, metal halide cluster [Cd{sub 2}(Phen){sub 4}Cl{sub 2}]{sup 2+} and 4, 4 Prime -bpy ligands. Compound 1 and compound 2 are not common hybrids based on polyoxometalates and metal halide clusters, they also contain dissociated organic ligands, therefore, compound 1 and 2 are the first examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. - Graphical Abstract: Two new compounds have been synthesized and characterized. Structure analyses revealed that the two compounds are the first examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. Highlights: Black-Right-Pointing-Pointer First examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. Black-Right-Pointing-Pointer Two different kinds of metal halide clusters. Black-Right-Pointing-Pointer Supramolecular structures based on polyoxometalates, metal halide clusters and organic ligands. Black-Right-Pointing-Pointer Hybridization of three different of building blocks.

  20. Chiral Dawson-Type Hybrid Polyoxometalate Catalyzes Enantioselective Diels-Alder Reactions. (United States)

    Xuan, Wen-Jing; Botuha, Candice; Hasenknopf, Bernold; Thorimbert, Serge


    Can achiral organocatalysts linked to chiral polyanionic metal oxide clusters provide good selectivity in enantioselective C-C bond formations? The answer to this question is investigated by developing a new active hybrid polyoxometalate-based catalyst for asymmetric Diels-Alder reaction. Chirality transfer from the chiral anionic polyoxometalate to the covalently linked achiral imidazolidinone allows Diels-Alder cycloaddition products to be obtained with good yields and high enantioselectivities when using cyclopentadiene and acrylaldehydes as partners. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. New synthetic routes to polyoxometalate containing ionic liquids an investigation of their properties

    CERN Document Server

    Herrmann, Sven


    In his Master project Sven Herrmann for the first time carried out fundamental investigations into the development of polyoxometalate based ionic liquids (POM-ILs). The POM-ILs were obtained by charge balancing inorganic polyoxometalate (POM) anions with sterically demanding tetraalkylammonium or tetraalkylphosphonium cations. By functionalization of lacunary Keggin clusters with 3d-transition metals and charge balancing with tetraalkylammonium cations of differing chain length, a model system for the correlation of the molecular structure with macroscopic materials properties was obtained. In

  2. Rigidly foldable origami gadgets and tessellations. (United States)

    Evans, Thomas A; Lang, Robert J; Magleby, Spencer P; Howell, Larry L


    Rigidly foldable origami allows for motion where all deflection occurs at the crease lines and facilitates the application of origami in materials other than paper. In this paper, we use a recently discovered method for determining rigid foldability to identify existing flat-foldable rigidly foldable tessellations, which are also categorized. We introduce rigidly foldable origami gadgets which may be used to modify existing tessellations or to create new tessellations. Several modified and new rigidly foldable tessellations are presented.

  3. On flexible and rigid nouns

    DEFF Research Database (Denmark)

    Rijkhoff, Jan


    This article argues that in addition to the major flexible lexical categories in Hengeveld’s classification of parts of speech systems (Contentive, Non-Verb, Modifier), there are also flexible word classes within the rigid lexical category Noun (Set Noun, Sort Noun, General Noun). Members...... classes. Finally this article wants to claim that the distinction between rigid and flexible noun categories (a) adds a new dimension to current classifications of parts of speech systems, (b) correlates with certain grammatical phenomena (e.g. so-called number discord), and (c) helps to explain the parts...

  4. Polyoxometalate-stabilized Pt nanoparticles and their electrocatalytic activities. (United States)

    Hsu-Yao, Thomas; Browne, Kevin P; Honesty, Nicole; Tong, YuYe J


    The synthesis of long-term stable polyoxometalate (POM)-stabilized Pt nanoparticles (NPs) is described here. By means of controlled bulk electrolysis, the reduced POM anions, SiW(12)O(40)(4-) (or SiW(12)) and H(2)W(12)O(40)(6-) (or H(2)W(12)), respectively, served the dual role of reductant and protecting/stabilizing ligand for the Pt NPs. Transmission electron microscopy (TEM) images confirmed the formation of 3 to 4 nm sized Pt NPs, which coincidently was in the same size range of the commercial Pt black that was used as a reference. Elemental XPS analyses showed W/Pt ratios of 0.12 for the SiW(12)- and 0.18 for the H(2)W(12)-stabilized Pt NPs, but found no evidence of the presence of Cl(-) anion in the samples. Controlled electrochemical (EC), UV-Vis, and IR data provided unambiguous evidence for the structural integrity of the POM anions on the Pt NP surface. CO stripping, methanol oxidation reaction (MOR), and oxygen reduction reaction (ORR) were used to assess their electrocatalytic activities. It was found that both SiW(12)- and H(2)W(12)-stabilized Pt NPs showed enhanced activities in MOR and ORR as compared to that of Pt black, with the latter having higher enhancement. These observations clearly demonstrated that the stabilizing POM anions have a profound influence on the electrocatalytic activity of the underlying Pt NPs.

  5. Novel Polyoxometalate Containing Membranes for PEM Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Mason K. Harrup; Frederick F. Stewart; Thomas A Luther; Tammy Trowbridge


    Current proton exchange membrane (PEM) technologies are inadequate to address the projected needs for fuel cell performance above 80 ºC. Continuing research into traditional ion carriers in novel membrane materials offers the promise of marginal improvement, representing only an evolutionary increase in performance. This conclusion is supported by the role of water in conduction. Thus, the key to better PEMs is not to eliminate water, but to change the role of water by developing ion carriers that will bind water more tightly than traditional sulfur or phosphorus based carriers resulting in materials that will conduct at higher temperatures. This change entails having a carrier structure that interacts more intimately with water and by increasing the ion carrier anionic charge to result in more tightly held inner shell protonated waters of hydration. Both of these factors synergistically act to maintain a critical water concentration at the carrier necessary for conduction. In this work, polyoxometalate (POM) clusters were selected to serve as these different proton carriers.

  6. A mixed valent Keggin polyoxometallate involving molybdenum and tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Leclaire, A.; Borel, M.M.; Chardon, J.; Raveau, B. [Universite de Caen (France). Laboratoire CRISMAT


    A new mixed valent ``Mo-W`` polyoxometallate K{sub 6}Mo{sub 3}W{sub 9}PO{sub 40}{center_dot}13H{sub 2}O has been synthesized in the form of single crystals. The structure determination of this cubic phase (a = 21.381 {angstrom}) shows that it is isotypic to K{sub 5.5}Na{sub 1.5}PW{sub 10}Cu{sub 2}(H{sub 2}O){sub 2}O{sub 38{center_dot}}13H{sub 2}O. The two structures differ by the nature of the ligands that form the Keggin units ``PMo{sub 3}W{sub 9}O{sub 40}`` and ``PW{sub 10}Cu{sub 2}(H{sub 2}O){sub 2}O{sub 38},`` respectively, and by the stoichiometry and distribution of the alkaline cations located outside the Keggin units.

  7. Polyoxometalates in Oxidative Delignification of Chemical Pulps: Effect on Lignin

    Directory of Open Access Journals (Sweden)

    Kolby Hirth


    Full Text Available Chemical pulps are produced by chemical delignification of lignocelluloses such as wood or annual non-woody plants. After pulping (e.g., kraft pulping, the remaining lignin is removed by bleaching to produce a high quality, bright paper. The goal of bleaching is to remove lignin from the pulp without a negative effect on the cellulose; for this reason, delignification should be performed in a highly selective manner. New environmentally-friendly alternatives to conventional chlorine-based bleaching technologies (e.g., oxygen, ozone, or peroxide bleaching have been suggested or implemented. In an attempt to find inorganic agents that mimic the action of highly selective lignin-degrading enzymes and that can be applicable in industrial conditions, the researchers have focused on polyoxometalates (POMs, used either as regenerable redox reagents (in anaerobic conditions or as catalysts (in aerobic conditions of oxidative delignification. The aim of this paper is to review the basic concepts of POM delignification in these two processes.

  8. Polyoxometalate delignification of birch kraft pulp and effect on residual lignin (United States)

    Biljana Bujanovic; Richard S. Reiner; Sally A. Ralph; Rajai H. Atalla


    To advance the understanding of delignification with polyoxometalates (POMs) that have been explored for use in bleaching of chemical pulps, the transformation of lignin during anaerobic treatment of birch kraft pulp with an equilibrated POM mixture composed of Na5(+2)[SiV1(-0.1)MoW10(+0.1)O

  9. Structural changes of residual lignin of softwood and hardwood kraft pulp upon oxidative treatment with polyoxometalates (United States)

    Biljana Bujanovic; Richard S. Reiner; Sally A. Ralph; Umesh P. Agarwal; Rajai H. Atalla


    Structural transformation of lignin in pulps bleached with polyoxometalates (POMs) should be explored in order to gain insight into the lignin reactions leading to its solubilization during POM treatment of kraft pulp. Our studies include characterization of residual lignin isolated from softwood commercial and birch laboratory kraft pulps delignified with POMs....

  10. Studies of lignin transformation in polyoxometalate (POM) bleaching of kraft pulp (United States)

    Biljana Bujanovic; Richard S. Reiner; Kolby C. Hirth; Sally A. Ralph; Rajai H. Atalla


    In order to elucidate changes occurring in lignin during polyoxometalate delignification of kraft pulp, residual lignins of a series of POM- delignified kraft pulps of decreasing kappa number were isolated and characterized. Oxidative treatment of commercial unbleached kraft pulp was performed using complex POM solutions containing the active [SiVW11O40]anion. For...

  11. Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films

    NARCIS (Netherlands)

    Lunkenbein, T.; Kamperman, M.M.G.; Li, Z.; Bojer, C.; Drechsler, M.; Forster, S.; Wiesner, U.; Muller, A.; Breu, J.


    Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are

  12. Bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au: Study on luminescence and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail:; Fan, Shaohua; Zhao, Weiqian; Lu, Xuelian; Li, Wuke


    In this paper, the synthesis and properties of composite silica microspheres grafted with gold nanoparticles and lanthanide-polyoxometalates are described. This synthesis employs polyethyleneimine as the crosslink polymer to immobilize the Au nanoparticles and lanthanide-polyoxometalates on silica spheres, which results in the formation of bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au. The composite material was found to be catalytically active in the oxidation of styrene, and benzaldehyde and styrene oxide were the main products. Catalyzed oxidation of styrene demonstrates the size-dependent activity of catalysts and the smaller catalyst shows the higher selectivity. Moreover, the composite particles show bright red luminescence under UV light, which could be seen by naked eyes. The luminescence properties of composite material and the effect of Au nanoparticles on the luminescence of Eu ion were investigated, and energy could be more effectively transferred from ligand to lanthanide ion when Au nanoparticles were grafted on silica spheres. The integration of luminescent components and Au particles makes it possible to label catalyst and monitor the catalyzed reactions. - Highlights: • The bifunctional composite microspheres were fabricated. • Both polyoxometalates and Au nanoparticles could be grafted on silica spheres. • The composite particles exhibit the excellent luminescence and catalytic activity. • The Au nanoparticles affect the luminescence properties of Eu{sup 3+} ions.

  13. Fabrication of network films of conducting polymer-linked polyoxometallate-stabilized carbon nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Kulesza, Pawel J.; Skunik, Magdalena; Baranowska, Beata; Miecznikowski, Krzysztof; Chojak, Malgorzata; Karnicka, Katarzyna; Starobrzynska, Barbara; Ernst, Andrzej [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Frackowiak, Elzbieta [ICTE, Poznan University of Technology, Piotrowo 3, PL-60-965 Poznan (Poland); Beguin, Francois [CRMD, CNRS-University, 1B, rue de la Ferollerie, F-45071 Orleans Cedex 02 (France); Kuhn, Alexander [Laboratoire d' Analyse Chimique par Reconnaissance Moleculaire Ecole Nationale Superieure de Chimie et de Physique de Bordeaux, 16 avenue Pey Berland, 33607 Pessac (France); Delville, Marie-Helene [Institut de Chimie de la Matiere Condensee de Bordeaux, 87 Avenue du Dr. Schweitzer, 33608 Pessac Cedex (France)


    The ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo{sub 12}O{sub 40}{sup 3-}), to form stable anionic monolayers on carbon nanoparticles and multi-wall nanotubes is explored here to produce stable colloidal solutions of polyoxometallate covered carbon nanostructures and to disperse them within conducting polymer, poly(3,4-ethylenedioxythiophene), i.e. PEDOT, or polyaniline multilayer films. By repeated alternate treatments in the colloidal suspension of PMo{sub 12}O{sub 40}{sup 3-}-protected carbon nanoparticles or nanotubes, and in the acid solution of a monomer (3,4-ethylenedioxythiophene or aniline), the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional organized arrangements (networks) of interconnected organic and inorganic layers on electrode (e.g. glassy carbon) surfaces. In hybrid films, the negatively charged polyoxometallate-covered carbon nanostructures interact electrostatically with positively charged conducting polymer ultra-thin layers. Consequently, the attractive electrochemical charging properties of conducting polymers, reversible redox behavior of polyoxometallate, as well as the mechanical and electrical properties of carbon nanoparticles or nanotubes can be combined. The films are characterized by fast dynamics of charge transport, and they are of potential importance to electrocatalysis and charge storage in redox capacitors. (author)

  14. A multifunctional lanthanide metal-organic framework supported by Keggin type polyoxometalates. (United States)

    Zhu, Wen-Hua; Zeng, Min; Wang, Juan; Li, Chen-Yang; Tian, Li-Hong; Yin, Jia-Cheng; Liu, Yu-Kun


    A neodymium metal-organic framework with 1D nanotubular channels incorporating Keggin type [SiWWO38](3-) has been synthesized by utilizing pyridine-2,5-dicarboxylic acid as an organic ligand. It represents an unusual polyoxometalate-templated framework with the multifunctionality of magnetism, near-infrared luminescence and the selective adsorption of Rhodamine B dye molecules.

  15. Polyoxometalate grafting onto silica: stability diagrams of H3PMo12O40 on {001}, {101}, and {111} β-cristobalite surfaces analyzed by DFT

    KAUST Repository

    Rozanska, Xavier


    The process of grafting H3PMo12O40 onto silica surfaces is studied using periodic density functional theory methods. For surfaces with a high hydroxyl coverage, the hydroxyl groups are consumed by the polyoxometalate protons, resulting in water formation and the creation of a covalent bond between the polyoxometalate and the surface, and mostly no remaining acidic proton on the polyoxometalate. When the surfaces are partially dehydroxylated and more hydrophobic, after temperature pretreatment, less covalent and hydrogen bonds are formed and the polyoxometalate tends to retain surface hydroxyl groups, while at least one acidic proton remains. Hence the hydroxylation of the surface has a great impact on the chemical properties of the grafted polyoxometalate. In return, the polyoxometalate species affects the compared stability of the partially hydroxylated silica surfaces in comparison with the bare silica case. © 2011 the Owner Societies.

  16. A new environmentally benign technology and approach to bleaching kraft pulp. Polyoxometalates for selective delignification and waste mineralization

    Energy Technology Data Exchange (ETDEWEB)

    Weinstock, I.A.; Atalla, R.H.; Reiner, R.S.; Moen, M.A.; Hammel, K.E. [Forest Products Lab., Madison, WI (United States); Houtman, C.J. [Wisconsin Univ., Madison, WI (United States). Dept. of Chemical Engineering; Hill, C.L. [Emory Univ., Atlanta, GA (United States)


    A new technology based on polyoxometalates for bleaching and processing wood pulp in conjunction with paper manufacture is presented. In four Unit Operations not only is kraft pulp selectively delignified by polyoxometalates in an anaerobic process, but also all organic waste from the bleaching step is mineralized to CO{sub 2} and H{sub 2}O by polyoxometalates in a complex aerobic process. The sum of the Unit Operations is the selective conversion of kraft pulp into a bleached pulp with attractive papermaking profiles (strength indices, mechanical properties, etc.), plus CO{sub 2} and H{sub 2}O. Studies using dimeric lignin models link lignin fragmentation during anaerobic polyoxometalate delignification to a combination of oxidative and hydrolytic steps. (Author). 37 refs., 7 figs.

  17. Rigid body dynamics of mechanisms

    CERN Document Server

    Hahn, Hubert


    The second volume of Rigid Body Dynamics of Mechanisms covers applications via a systematic method for deriving model equations of planar and spatial mechanisms. The necessary theoretical foundations have been laid in the first volume that introduces the theoretical mechanical aspects of mechatronic systems. Here the focus is on the application of the modeling methodology to various examples of rigid-body mechanisms, simple planar ones as well as more challenging spatial problems. A rich variety of joint models, active constraints, plus active and passive force elements is treated. The book is intended for self-study by working engineers and students concerned with the control of mechanical systems, i.e. robotics, mechatronics, vehicles, and machine tools. The examples included are a likely source from which to choose models for university lectures.

  18. Elasticity of Relativistic Rigid Bodies? (United States)

    Smarandache, Florentin


    In the classical Twin Paradox, according to the Special Theory of Relativity, when the traveling twin blasts off from the Earth to a relative velocity v =√{/3 } 2 c with respect to the Earth, his measuring stick and other physical objects in the direction of relative motion shrink to half their lengths. How is that possible in the real physical world to have let's say a rigid rocket shrinking to half and then later elongated back to normal as an elastic material when it stops? What is the explanation for the traveler's measuring stick and other physical objects, in effect, return to the same length to their original length in the Stay-At-Home, but there is no record of their having shrunk? If it's a rigid (not elastic) object, how can it shrink and then elongate back to normal? It might get broken in such situation.

  19. On flexible and rigid nouns

    DEFF Research Database (Denmark)

    Rijkhoff, Jan


    Studies in Language 32-3 (2008), 727-752. Special issue: Parts of Speech: Descriptive tools, theoretical constructs Jan Rijkhoff - On flexible and rigid nouns This article argues that in addition to the flexible lexical categories in Hengeveld’s classification of parts-of-speech systems (Contentive...... classifications of parts-of-speech systems, (b) correlates with certain grammatical phenomena (e.g. so called number discord), and (c) helps to explain the parts-of-speech hierarchy....

  20. Nanostructured polyoxometalate arrays with unprecedented properties and functions.

    Energy Technology Data Exchange (ETDEWEB)

    Dunphy, Darren Robert; Brinker, C. Jeffrey; Singh, Seema; Nyman, May Devan


    Polyoxometalates (POMs) are ionic (usually anionic) metal -oxo clusters that are both functional entities for a variety of applications, as well as structural units that can be used as building blocks if reacted under appropriate conditions. This is a powerful combination in that functionality can be built into materials, or doped into matrices. Additionally, by assembling functional POMs in ordered materials, new collective behaviors may be realized. Further, the vast variety of POM geometries, compositions and charges that are achievable gives this system a high degree of tunability. Processing conditions to link together POMs to build materials offer another vector of control, thus providing infinite possibilities of materials that can he nano-engineered through POM building blocks. POM applications that can be built into POM-based materials include catalysis, electro-optic and electro-chromic, anti-viral, metal binding, and protein binding. We have begun to explore three approaches in developing this field of functional, nano-engineered POM-based materials; and this report summarizes the work carried out for these approaches to date. The three strategies are: (1) doping POMs into silica matrices using sol-gel science, (2) forming POM-surfactant arrays and metal-POM-surfactant arrays, (3) using aerosol-spray pyrolysis of the POM-surfactant arrays to superimpose hierarchical architecture by self-assembly during aerosol-processing. Doping POMs into silica matrices was successful, but the POMs were partially degraded upon attempts to remove the structure-directing templates. The POM-surfactant and metal-POM-surfactant arrays approach was highly successful and holds much promise as a novel approach to nano-engineering new materials from structural and functional POM building blocks, as well as forming metastable or unusual POM geometries that may not be obtained by other synthetic methods. The aerosol-assisted self assembly approach is in very preliminary state of

  1. Kinetic analysis of polyoxometalate (POM) oxidation of non-phenolic lignin model compound (United States)

    Tomoya Yokoyama; Hou-min Chang; Ira A. Weinstock; Richard S. Reiner; John F. Kadla


    Kinetic and reaction mechanism of non-phenolic lignin model compounds under anaerobic polyoxometalate (POM), Na5(+1.9)[SiV1(-0.1)MoW10(+0.1) 40], bleaching conditions were examined. Analyses using a syringyl type model, 1-(3,4,5-trimethoxyphenyl)ethanol (1), a guaiacyl type, 1-(3,4- imethoxyphenyl)ethanol (2), and 1- (4-ethoxy-3,5-dimethoxyphenyl)ethanol (3) suggest...

  2. Lignin modification in the initial phase of softwood kraft pulp delignification with polyoxometalates (POMs) (United States)

    Biljana Bujanovic; Sally A. Ralph; Richard S. Reiner; Rajai H. Atalla


    Commercial softwood kraft pulp with kappa number 30.5 (KP30.5) was delignified with polyoxometalates (POM, Na5(+2)[SiV1(-0.1)MoW10(+0.1)O40]), and POM-treated kraft pulp of kappa number 23.6 was obtained (KPPOM,23.6). Residual lignin from pulps was isolated by mild acid hydrolysis and characterized by analytical and spectral methods to gain insight into lignin...

  3. Photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Craig L.; Gueletii, Iourii V.; Song, Jie; Lv, Hongjin; Musaev, Djamaladdin; Luo, Zhen


    This disclosure relates to photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts. In certain embodiments, the disclosure relates to compositions comprising water, a complex of a tetra-metal oxide cluster and VW.sub.9O.sub.34 ligands, and a photosensitizer. Typically, the metal oxide cluster is Co. In certain embodiments, the disclosure relates to electrodes and other devices comprising water oxidation catalysts disclosed herein and uses in generating fuels and electrical power from solar energy.

  4. Polyoxometalates for radioactive waste treatment. Annual progress report, June 15, 1996--September 30, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Pope, M.T.


    'Four areas of research have been investigated during the first year of this project: (1) Selective separations of Ln{sup 3+} and An{sup 4+}; (2) Very large tungstate complexes of Ln{sup 3+}; (3) U{sup 4+} and UO{sub 2}{sup 2+} polytungstate complexes; (4) Rhenium (technetium) polyoxometalates. Progress in each of these areas is summarized.'

  5. A New Approach for the Modification of Paper Surface Properties Using Polyoxometalates (United States)

    Saraiva, Mikhail S.; Gamelas, José A. F.; Mendes de Sousa, António P.; Reis, Bruno M.; Amaral, José L.; Ferreira, Paulo J.


    A new approach for the chemical modification of the surface of paper based on the application of colloidal mixtures containing cationic starch and polyoxometalates on uncoated base paper is presented. Polyoxometalates with the Keggin-type structure and physical properties similar to those presented by coating pigments, namely H3PW12O40·23H2O, H4SiW12O40·24H2O, and K7PW11O39·9H2O, have been used in order to improve the quality of inkjet printing. The analysis of the different samples by FTIR-ATR spectroscopy showed the presence of the polyoxometalates (and the cationic starch) on the top surface of the paper. In addition, the determination of surface energy parameters, namely the polar component (σsp) and the dispersive component (σsd) of the surface energy, by contact angle measurements revealed that, for the new samples, the polar component level was much higher than that of the uncoated base paper. The quality of inkjet printing, evaluated by parameters such as the gamut area and the optical density, was considerably improved by these surface treatments.

  6. Tosylation of alcohols: an effective strategy for the functional group transformation of organic derivatives of polyoxometalates. (United States)

    Jia, Hongli; Li, Qi; Bayaguud, Aruuhan; She, Shan; Huang, Yichao; Chen, Kun; Wei, Yongge


    Recently, the organic functionalization of polyoxometalates (POMs) has drawn increasing interest, and an easy and effective route to achieve organic derivatives is of great importance. Herein, the first reported synthesis of a tosyl ester derivative of the polyoxometalate (Bu4N)2[V6O13{(OCH2)3CCH2SO3C7H4}2]·2.5CH3CN (compound 1) was performed by using DMAP as an activating reagent and triethylamine as an HCl scavenger. The tosyl ester was transformed into an azide or halide group by using sodium azide or sodium bromide, respectively, as the nucleophilic agent. Two derivatives of POMs, (Bu4N)2[V6O13{(OCH2)3CCH2N3}2]·4CH3CN (compound 2) and (Bu4N)2[V6O13{(OCH2)3CCH2Br}2] (compound 3), were easily obtained. All the compounds were structurally and compositionally characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, NMR spectroscopy, ESI-MS, UV-Vis spectroscopy and TGA. This work provides a new route for the functional group transformation of organic derivatives of polyoxometalates.

  7. Polyoxometalates for Radioactive Waste Treatment - Final Report - 06/15/1996 - 09/14/2000

    Energy Technology Data Exchange (ETDEWEB)

    Pope, Michael T.


    The research was directed primarily towards the use of polyoxometalate complexes for separation of lanthanide, actinide, and technetium species from aqueous waste solutions, such as the Hanford Tank Wastes. Selective binding of these species responsible for much of the high level waste (HWL) activity, can reduce the volume of material to be subsequently vitrified or otherwise converted for long-term storage. A secondary objective was to explore the direct conversion of the polyoxometalate complexes into possible waste forms, oxide bronzes, thereby avoiding additional handling and energy-intensive vitrification procedures. Although the advantages of polyoxometalate anions (POMs) lie in their high thermal and radiolytical stabilities, that has been no attempt to exploit the remarkable variety of these complexes beyond the use of the two anions mentioned above. Our broad knowledge of POM chemistry has allowed us to address and rectify this omission. The innovative aspects of the project are: (a) the selective sequestration of lanthanide and actinide cations by a POM system in the presence of excess alkali and transition metal cations; (b) the formation of the first examples of POM complexes of UO2-2+ and their extraction into nonaqueous solvents; (c) the thermal conversion of ammonium salts of lanthanide and actinide POM complexes into inert oxide bronzes at relatively low temperatures; and (d) the direct formation of highly thermally-robust niobate and tantalate complexes of Re (surrogate for Tc) in highly basic solutions.

  8. Electroreduction of oxygen at polyoxometallate-modified glassy carbon-supported Pt nanoparticles (United States)

    Wlodarczyk, Renata; Chojak, Malgorzata; Miecznikowski, Krzysztof; Kolary, Aneta; Kulesza, Pawel J.; Marassi, Roberto

    Platinum nanoparticles of ca. 8 nm diameter (that had been first deposited on glassy carbon) were subsequently modified with ultra-thin films of polyoxometallates through their spontaneous adsorption on solid (platinum and carbon) surfaces. The following polyoxometallates (Keggin type heteropolyacids), H 3SiW 12O 40, H 3SiMo 12O 40, H 3PW 12O 40 and H 3PMo 12O 40, were considered as potential activating agents. Rotating disk voltammetry was used to probe the electroreduction of dioxygen in 0.5 mol dm -3 H 2SO 4 at 25 °C. For the same loading and the approximately identical distribution of platinum nanoparticles on glassy carbon, the statistically higher (in comparison to bare Pt) electrocatalytic currents for the oxygen reduction were observed upon introduction of monolayers of heteropolyanions. Out of polyoxometallates considered, the system modified with heteropolytungstate (H 3PW 12O 40) seemed to be the most effective in electrocatalysis. Although the possibility of structural changes cannot be excluded, the synergistic effect originated presumably from the bifunctional activity of the electrocatalyst. While Pt retained its usual reactivity towards the oxygen reduction, H 3PW 12O 40 could act as both effective mediator (e.g. for the reduction of the hydrogen peroxide intermediate) and the source of mobile protons at the electrocatalytic interface.

  9. Hybrid organic-inorganic materials based on poly(o-phenylenediamine) and polyoxometallate functionalized carbon nanotubes (United States)

    Baibarac, M.; Baltog, I.; Smaranda, I.; Scocioreanu, M.; Lefrant, S.


    The chemical polymerization of o-phenylenediamine (OPD) on single-walled carbon nanotubes (SWCNTs) in the presence of phosphomolybdic acid (H 3PMo 12O 40xH 2O) has been studied by surface enhanced resonant Raman scattering (SERRS) spectroscopy. One demonstrates that an organic-inorganic hybrid composite of the type poly(o-phenylenediamine)/polyoxometallate-functionalized SWCNTs is produced by the chemical interaction between polyoxometallate-functionalized SWCNTs and poly(o-phenylenediamine) (POPD) doped with [H 2PMo 12O 40] - ions. According to TEM investigations, a result of the chemical interaction of SWCNT with H 3PMo 12O 40xH 2O is the formation into the composite mass of tube fragments of shorter length, which behave like closed shell fullerenes since Raman fingerprint is given by lines situated at 240-275 and 1450-1472 cm -1. The chemical polymerization of OPD on SWCNTs achieved in the absence of H 3PMo 12O 40xH 2O leads to a covalent functionalization of the wall side of the tubes, which is revealed in Raman spectra, recorded at the excitation wavelength of 514 nm, by an enhancement of the lines associated with the tangential vibrational modes of SWCNTs. Using FTIR spectroscopy, significant hindrance steric effects are evidenced in the POPD/polyoxometallate-functionalized SWCNT composite.

  10. Rigidizing Inflatable Deployable Dwelling (RIDD) Project (United States)

    National Aeronautics and Space Administration — By combining thin thermoplastic films, woven Vectran reinforcements, and heat a reliable, deployable, rigidizing space habitat can be created. Although much research...

  11. Polyoxometallates as inorganic templates for electrocatalytic network films of ultra-thin conducting polymers and platinum nanoparticles. (United States)

    Karnicka, Katarzyna; Chojak, Malgorzata; Miecznikowski, Krzysztof; Skunik, Magdalena; Baranowska, Beata; Kolary, Aneta; Piranska, Aleksandra; Palys, Barbara; Adamczyk, Lidia; Kulesza, Pawel J


    We develop a concept of fabrication of the multilayer network films on electrodes by exploring the ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo(12)O(40)(3-)), to form stable anionic monolayers (templates) on carbon and metals including platinum. By repeated alternate treatments in the solution of PMo(12)O(40)(3-) (or in the colloidal suspension of polyoxometallate-protected Pt-nanoparticles) and in the solution of monomer (e.g. anilinium) cations, the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional assemblies on electrode (e.g. glassy carbon) surfaces. In the resulting hybrid (organic-inorganic) films, the layers of negatively charged polyoxometallate, or polyoxometallate-protected (stabilized) Pt-nanoparticles, are linked or electrostatically attracted by ultra-thin layers of such positively charged conducting polymers as polyaniline (PANI), polypyrrole (PPy) or poly(3,4-ethylenedioxythiophene), PEDOT. Consequently, the attractive physicochemical properties of polymers and reactivity of polyoxometallate or noble metal particles are combined. The films are functionalized and show electrocatalytic properties towards reduction of nitrite, bromate, hydrogen peroxide or oxygen. They are of importance to the chemical and biochemical sensing as well as to the biochemical and medical applications.

  12. Rigidity in Mentally Retarded and Nonretarded Children. (United States)

    Kreitler, Shulamith; And Others


    Seven rigidity tests varying in difficulty were administered to 45 retarded subjects, with a mean age of 10, and 45 mental age-matched nonretarded subjects. Subjects did not differ on 3 easy tests, but retarded children were more rigid on 4 difficult tests. (Author/JDD)

  13. Preparation and application of multiple-component-doped keggin polyoxometalate microtubes--towards a component-tunable hollow structure. (United States)

    Shen, Yan; Peng, Jun; Pang, Haijun; Zhang, Pengpeng; Chen, Dan; Chen, Changyun; Zhang, Huanqiu; Meng, Cuili; Su, Zhongmin


    In this paper, the preparation of ascorbic acid (AA)-doped polyoxometalate (SiW(12)-AA) microtubes is described. The SiW(12)-AA microtubes convert to heteropoly blue microtubes upon exposure to ammonia gas, which is an ammonia-triggered solid-solid redox reaction between AA molecules and polyoxometalates, and can possibly be applied to a chemical sensor for detecting ammonia and volatile organic amines. Furthermore, the SiW(12)-AA microtubes have been applied to the in situ synthesis of Ag nanoparticles (NPs) through the redox reaction between the AA component and Ag(+) ions occurring on the surfaces of the SiW(12)-AA microtubes to give silver NPs immobilized on polyoxometalate microtubes (Ag@SiW(12)). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Structural instability of shell-like assemblies of a keplerate-type polyoxometalate induced by ionic strength. (United States)

    Veen, Sandra J; Kegel, Willem K


    We demonstrate a new structural instability of shell-like assemblies of polyoxometalates. Besides the colloidal instability, that is, the formation of aggregates that consist of many single layered POM-shells, these systems also display an instability on a structural scale within the shell-like assemblies. This instability occurs at significantly lower ionic strength than the colloidal stability limit and only becomes evident after a relatively long time. For the polyoxometalate, abbreviated as {Mo(72)Fe(30)}, it is shown that the structural stability limit of POM-shells lies between a NaCl concentration of 1.00 and 5.00 mM in aqueous solution.

  15. Semiclassical Theory of Spectral Rigidity (United States)

    Berry, M. V.


    The spectral rigidity Δ(L) of a set of quantal energy levels is the mean square deviation of the spectral staircase from the straight line that best fits it over a range of L mean level spacings. In the semiclassical limit (hslash-> 0), formulae are obtained giving Δ(L) as a sum over classical periodic orbits. When L ~= Lmax, where Lmax ~ hslash-(N-1) for a system of N freedoms, Δ(L) is shown to display the following universal behaviour as a result of properties of very long classical orbits: if the system is classically integrable (all periodic orbits filling tori), Δ(L) = 1/15L (as in an uncorrelated (Poisson) eigenvalue sequence); if the system is classically chaotic (all periodic orbits isolated and unstable) and has no symmetry, Δ(L) = ln L/2π^2 + D if 1 ~= L ~= Lmax (as in the gaussian unitary ensemble of random-matrix theory); if the system is chaotic and has time-reversal symmetry, Δ(L) = ln L/π^2 + E if 1 ~= L ~= Lmax (as in the gaussian orthogonal ensemble). When L >> Lmax, Δ(L) saturates non-universally at a value, determined by short classical orbits, of order hslash-(N-1) for integrable systems and ln (hslash-1) for chaotic systems. These results are obtained by using the periodic-orbit expansion for the spectral density, together with classical sum rules for the intensities of long orbits and a semiclassical sum rule restricting the manner in which their contributions interfere. For two examples Δ(L) is studied in detail: the rectangular billiard (integrable), and the Riemann zeta function (assuming its zeros to be the eigenvalues of an unknown quantum system whose unknown classical limit is chaotic).

  16. Inertial rotation of a rigid body (United States)

    Butikov, Eugene


    A simple approach to the important problem of torque-free rotation of a symmetrical rigid body is suggested which is appropriate for teaching introductory mechanics and general physics to undergraduate students and is free from the difficulties of traditional treatment of the problem. A small simulation program (Java-applet) is developed that visualizes the investigated motion and illustrates its principal features. The program facilitates understanding of concepts behind rigid body dynamics. Simultaneously with simulating the rigid body motion, the program presents a clear geometrical interpretation of the inertial rotation.

  17. Electroreduction of oxygen at polyoxometallate-modified glassy carbon-supported Pt nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Wlodarczyk, Renata; Kolary, Aneta; Marassi, Roberto [Department of Chemistry, University of Camerino, S. Agostino 1, I-62032 Camerino (Italy); Chojak, Malgorzata; Miecznikowski, Krzysztof; Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)


    Platinum nanoparticles of ca. 8nm diameter (that had been first deposited on glassy carbon) were subsequently modified with ultra-thin films of polyoxometallates through their spontaneous adsorption on solid (platinum and carbon) surfaces. The following polyoxometallates (Keggin type heteropolyacids), H{sub 3}SiW{sub 12}O{sub 40}, H{sub 3}SiMo{sub 12}O{sub 40}, H{sub 3}PW{sub 12}O{sub 40} and H{sub 3}PMo{sub 12}O{sub 40}, were considered as potential activating agents. Rotating disk voltammetry was used to probe the electroreduction of dioxygen in 0.5moldm{sup -3} H{sub 2}SO{sub 4} at 25{sup o}C. For the same loading and the approximately identical distribution of platinum nanoparticles on glassy carbon, the statistically higher (in comparison to bare Pt) electrocatalytic currents for the oxygen reduction were observed upon introduction of monolayers of heteropolyanions. Out of polyoxometallates considered, the system modified with heteropolytungstate (H{sub 3}PW{sub 12}O{sub 40}) seemed to be the most effective in electrocatalysis. Although the possibility of structural changes cannot be excluded, the synergistic effect originated presumably from the bifunctional activity of the electrocatalyst. While Pt retained its usual reactivity towards the oxygen reduction, H{sub 3}PW{sub 12}O{sub 40} could act as both effective mediator (e.g. for the reduction of the hydrogen peroxide intermediate) and the source of mobile protons at the electrocatalytic interface. (author)

  18. Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Racimor, D


    The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

  19. Polyoxometalate (POM)-aided modification of lignin from wheat straw biorefinery


    Dizhbite, Tatiana; Jashina, Lilija; Dobele, Galina; Andersone, Anna; Evtuguin, Dmitry; Bikovens, Oskar; Telysheva, Galina


    The oxidative modification of Biolignin (BL) has been investigated to make it more suitable as an adsorbent for transition/heavy metals. BL is a by-product of a wheat straw organosolv process for the production of pulp, ethanol, and pentoses (CIMV S.A. pilot plant, Levallois Perret, France). It was subjected to oxidation by a polyoxometalate (POM) H-3[PMo12O40], aiming at the increment of oxygen-containing adsorption-active sites. The POM oxidation of BL was performed under moderate condition...

  20. Analysis of Switched-Rigid Floating Oscillator

    Directory of Open Access Journals (Sweden)

    Prabhakar R. Marur


    Full Text Available In explicit finite element simulations, a technique called deformable-to-rigid (D2R switching is used routinely to reduce the computation time. Using the D2R option, the deformable parts in the model can be switched to rigid and reverted back to deformable when needed during the analysis. The time of activation of D2R however influences the overall dynamics of the system being analyzed. In this paper, a theoretical basis for the selection of time of rigid switching based on system energy is established. A floating oscillator problem is investigated for this purpose and closed-form analytical expressions are derived for different phases in rigid switching. The analytical expressions are validated by comparing the theoretical results with numerical computations.

  1. Rigid bronchoscope dilatation of postintubation tracheal stenosis

    African Journals Online (AJOL)

    The management modalities that have been employed for the management of. PITS include stenting, surgical resection and reconstruction, percutaneous dilatation, rigid bronchoscopic dilatation, fibreoptic assisted balloon dilatation and Nd: YAG. (neodyiniumrvttritiurn-aluniinuni garnet) laser therapy with or without stenting.

  2. An Immersed Boundary Method for Rigid Bodies (United States)

    Bhalla, Amneet Pal Singh; Kallemov, Bakytzhan; Donev, Aleksandar; Griffith, Boyce


    The traditional immersed boundary (IB) method is a very flexible method for coupling elastic structures to fluid flow. When rigid bodies are modeled using an IB approach, a penalty method is usually employed to approximately enforce the rigidity of the body; this requires small time step sizes and leads to difficult-to-control errors in the solution. We develop a method that exactly enforces a rigidity constraint by solving a linear system coupling a standard semi-implicit discretization of the fluid equations with a rigidity constraint. We develop a preconditioned iterative solver that combines an approximate multigrid solver for the fluid problem with an approximate direct solver for the Schur complement system. We demonstrate the efficiency and study the accuracy of the method on several test problems for both zero and finite Reynolds numbers.

  3. Consumers' Imperfect Information and Price Rigidities


    Jean-Paul L'Huillier


    This paper develops a model of price rigidities and information diffusion in decentralized markets with private information. First, I provide a strategic microfoundation for price rigidities, by showing that firms are better off delaying the adjustment of prices when they face a high number of uninformed consumers. Second, in an environment where consumers learn from firms' prices, the diffusion of information follows a Bernoulli differential equation. Therefore, learning follows nonlinear dy...

  4. Photogeneration of two reduction-active charge-separated states in a hybrid crystal of polyoxometalates and naphthalene diimides. (United States)

    Liu, Jian-Jun; Wang, Yao; Lin, Mei-Jin; Huang, Chang-Cang; Dai, Wen-Xin


    The combination of naphthalene diimide tectons with zinc cations in the presence of polyanions, Mo6O19(2-), leads to a hybrid crystal composed of two-dimensional porous coordination networks and polyoxometalates, which can generate two kinds of long-lived charge-separated states for the reduction reactions upon irradiation.

  5. Structural instability of shell-like assemblies of a keplerate-type polyoxometalate induced by ionic strength

    NARCIS (Netherlands)

    Veen, S.J.; Kegel, W.K.


    We demonstrate a new structural instability of shell-like assemblies of polyoxometalates. Besides the colloidal instability, that is, the formation of aggregates that consist of many single layered POM-shells, these systems also display an instability on a structural scale within the shell-like

  6. Recovery of homogeneous polyoxometallate catalysts from aqueous and organic media by a mesoporous ceramic membrane without loss of catalytic activity

    NARCIS (Netherlands)

    Roy Chowdhury, S.; Roy Chowdhury, Sankhanilay; Witte, Peter T.; Blank, David H.A.; Alsters, Paul L.; ten Elshof, Johan E.


    The recovery of homogeneous polyoxometallate (POM) oxidation catalysts from aqueous and non-aqueous media by a nanofiltration process using mesoporous γ-alumina membranes is reported. The recovery of Q12[WZn3(ZnW9O34)2] (Q=[MeN(n-C8H17)3]+) from toluene-based media was quantitative within

  7. Tetrahedral connection of ε-Keggin-type polyoxometalates to form an all-inorganic octahedral molecular sieve with an intrinsic 3D pore system. (United States)

    Zhang, Zhenxin; Sadakane, Masahiro; Murayama, Toru; Izumi, Shoko; Yasuda, Nobuhiro; Sakaguchi, Norihito; Ueda, Wataru


    A new type of polyoxometalate-based porous material was successfully synthesized. The new material is the first fully inorganic Keggin-type polyoxometalate-based microporous material with intrinsically ordered open micropores and is the third member of the small family of octahedral molecular sieves (OMSs). Twelve MoO6 or VO6 octahedra surround a central VO4 tetrahedron to form ε-Keggin polyoxometalate building blocks (ε-VMo9.4V2.6O40) that are linked by Bi(III) ions to form crystalline Mo-V-Bi oxide with a diamondoid topology. The presence of a tetrahedral shape of the ε-Keggin polyoxometalate building block results in arrangement of microporosity in a tetrahedral fashion which is new in OMSs. Owing to its microporosity, this Mo-V-Bi oxide shows zeolitic-like properties such as ion-exchange and molecule adsorption.

  8. Metrology of Non-Rigid Objects

    Energy Technology Data Exchange (ETDEWEB)

    Blaedel, K L; Smith, D W; Claudet, A A; Kasper, E P; Patterson, S R


    Dimensional characterization of non-rigid parts presents many challenges. For example, when a non-rigid part is mounted in an inspection apparatus the effects of fixturing constraints cause significant deformation of the part. If the part is not used in normal service with the same load conditions as during inspection, the dimensional characteristics in service will deviate from the reported values during inspection. Further, the solution of designing specialized fixturing to duplicate ''as-installed'' conditions does not fully resolve the problem because each inspection requires its own methodology. The goal of this project is to formulate the research problem and propose a method of assessing the dimensional characteristics of non-rigid parts. The measured dimension of a rigid component is traceable at some level of confidence to a single source (NIST in the USA). Hence the measurement of one component of an assembly can be related to the measurement of another component of that assembly. There is no generalized analog to this pedigreed process for dimensionally characterizing non-rigid bodies. For example, a measurement made on a sheet-metal automobile fender is heavily influenced by how it is held during the measurement making it difficult to determine how well that fender will assemble to the rest of the (non-rigid) car body. This problem is often overcome for specific manufacturing problems by constructing rigid fixtures that over-constrain the non-rigid parts to be assembled and then performing the dimensional measurement of the contour of each component to check whether each meets specification. Note that such inspection measurements will yield only an approximation to the assembled shape, which is a function of both the geometry and the compliance of the component parts of the assembly. As a result, non-rigid components are more difficult to specify and inspect and therefore are more difficult to purchase from outside vendors compared

  9. Metrology of Non-Rigid Objects

    Energy Technology Data Exchange (ETDEWEB)

    Blaedel, K; Swift, D; Claudet, A; Kasper, E; Patterson, S


    Dimensional characterization of non-rigid parts presents many challenges. For example, when a non-rigid part is mounted in an inspection apparatus the effects of fixturing constraints are significant. If the part is not used in normal service with the same load conditions as during inspection, the dimensional characteristics will deviate from reported values. Further, the solution of designing specialized fixturing to duplicate ''as-installed'' conditions does not fully resolve the problem because each inspection requires its own methodology. The goal of this project is to formulate the research problem and propose a method of assessing the dimensional characteristics of non-rigid parts. The measured dimension of a rigid component is traceable at some level of confidence to a single source (NIST in the USA). Hence the measurement of one component of an assembly can be related to the measurement of another component of that assembly. There is no generalized analog to this pedigreed process for dimensionally characterizing non-rigid bodies. For example, a measurement made on a sheet-metal automobile fender is heavily influenced by how it is held during the measurement making it difficult to determine how well that fender will assemble to the rest of the (non-rigid) car body. This problem is often overcome for specific manufacturing problems by constructing rigid fixtures that over-constrain the non-rigid parts to be assembled and then performing the dimensional measurement of the contour of each component to check whether each meets specification. Note that such inspection measurements will yield only an approximation to the assembled shape, which is a function of both the geometry and the compliance of the component parts of the assembly. As a result, non-rigid components are more difficult to specify and inspect and therefore are more difficult to purchase from outside vendors compared to rigid components. The problems are compounded as the

  10. Effects of europium polyoxometalate encapsulated in silica nanoparticles (nanocarriers) in soil invertebrates (United States)

    Bicho, Rita C.; Soares, Amadeu M. V. M.; Nogueira, Helena I. S.; Amorim, Mónica J. B.


    Polyoxometalates (POMs) are metal oxo clusters that have been investigated for several applications in material sciences, catalysis, and biomedicine; these gained increasing interest in the field of nanotechnology as nanocarriers for drug delivery. Associated to the increasing applications, there is the need for information regarding the effects on the environment of these compounds, which is completely absent in the literature. In the present study, the effects of europium polyoxometalates encapsulated into silica nanoparticles (Eu-POM/SiO2 NPs) were assessed on the soil representative Enchytraeus crypticus. The individual materials were also assessed (Eu-POMs and SiO2 NPs). Toxicity was evaluated in various test media with increasing complexity: water, soil/water extracts, and soil. Toxicity was only observed for Eu-POM/SiO2 NPs and in the presence of soil components. Despite the fact that effects were observed for concentrations higher than current predicted environmental concentration (PEC), attention should be given to the growing use of these compounds. The present study shows the importance of assessing the effects in soil media, also compared to water. Moreover, results of "no effect" are critically needed and often unpublished. The present study can contribute to the improvement of the OECD guidelines for safety of manufactured nanomaterials on environmental toxicity in the soil compartment providing an improved test alternative.

  11. Oxidative Polyoxometalates Modified Graphitic Carbon Nitride for Visible-Light CO2 Reduction. (United States)

    Zhou, Jie; Chen, Weichao; Sun, Chunyi; Han, Lu; Qin, Chao; Chen, Mengmeng; Wang, Xinlong; Wang, Enbo; Su, Zhongmin


    Developing a photocatalysis system for converting CO2 to valuable fuels or chemicals is a promising strategy to address global warming and fossil fuel consumption. Exploring photocatalysts with high-performance and low-cost has been two ultimate goals toward photoreduction of CO2. Herein, noble-metal-free polyoxometalates (Co4) with oxidative ability was first introduced into g-C3N4 resulted in inexpensive hybrid materials (Co4@g-C3N4) with staggered band alignment. The staggered composited materials show a higher activity of CO2 reduction than bare g-C3N4. An optimized Co4@g-C3N4 hybrid sample exhibited a high yield (107 μmol g(-1) h(-1)) under visible-light irradiation (λ ≥ 420 nm), meanwhile maintaining high selectivity for CO production (94%). After 10 h of irradiation, the production of CO reached 896 μmol g(-1). Mechanistic studies revealed the introduction of Co4 not only facilitate the charge transfer of g-C3N4 but greatly increased the surface catalytic oxidative ability. This work creatively combined g-C3N4 with oxidative polyoxometalates which provide novel insights into the design of low-cost photocatalytic materials for CO2 reduction.

  12. Effects of europium polyoxometalate encapsulated in silica nanoparticles (nanocarriers) in soil invertebrates

    Energy Technology Data Exchange (ETDEWEB)

    Bicho, Rita C., E-mail:; Soares, Amadeu M.V.M. [Universidade de Aveiro, Departamento de Biologia & CESAM (Portugal); Nogueira, Helena I.S. [Universidade de Aveiro, Departamento de Química & CICECO (Portugal); Amorim, Mónica J.B. [Universidade de Aveiro, Departamento de Biologia & CESAM (Portugal)


    Polyoxometalates (POMs) are metal oxo clusters that have been investigated for several applications in material sciences, catalysis, and biomedicine; these gained increasing interest in the field of nanotechnology as nanocarriers for drug delivery. Associated to the increasing applications, there is the need for information regarding the effects on the environment of these compounds, which is completely absent in the literature. In the present study, the effects of europium polyoxometalates encapsulated into silica nanoparticles (Eu-POM/SiO{sub 2} NPs) were assessed on the soil representative Enchytraeus crypticus. The individual materials were also assessed (Eu-POMs and SiO{sub 2} NPs). Toxicity was evaluated in various test media with increasing complexity: water, soil/water extracts, and soil. Toxicity was only observed for Eu-POM/SiO{sub 2} NPs and in the presence of soil components. Despite the fact that effects were observed for concentrations higher than current predicted environmental concentration (PEC), attention should be given to the growing use of these compounds. The present study shows the importance of assessing the effects in soil media, also compared to water. Moreover, results of “no effect” are critically needed and often unpublished. The present study can contribute to the improvement of the OECD guidelines for safety of manufactured nanomaterials on environmental toxicity in the soil compartment providing an improved test alternative.

  13. Polyoxometalate ionic liquids as self-repairing acid-resistant corrosion protection. (United States)

    Herrmann, Sven; Kostrzewa, Monika; Wierschem, Andreas; Streb, Carsten


    Corrosion is a global problem for any metallic structure or material. Herein we show how metals can easily be protected against acid corrosion using hydrophobic polyoxometalate-based ionic liquids (POM-ILs). Copper metal disks were coated with room-temperature POM-ILs composed of transition-metal functionalized Keggin anions [SiW11 O39 TM(H2 O)](n-) (TM=Cu(II) , Fe(III) ) and quaternary alkylammonium cations (Cn H2 n+1 )4 N(+) (n=7-8). The corrosion resistance against acetic acid vapors and simulated "acid rain" was significantly improved compared with commercial ionic liquids or solid polyoxometalate coatings. Mechanical damage to the POM-IL coating is self-repaired in less than one minute with full retention of the acid protection properties. The coating can easily be removed and recovered by rinsing with organic solvents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Desulfurization of 4-methyl dibenzothiophene using titanium supported Keggin type polyoxometalate (United States)

    Lesbani, Aldes; Anggraini, Ana; Mohadi, Risfidian; Rohendi, Dedi; Said, Muhammad


    Titanium supported Keggin type polyoxometalate H5PV2Mo10O40.nH2O has been prepared using tetra isopropyl orthotitanate by sol-gel method and microemulsion to form H5PV2Mo10O40/TiO2. Compound H5PV2Mo10O40.nH2O/TiO2 was characterized using FTTR spectroscopy, X-Ray analysis, and acidity measurement. FTTR spectrum showed that all vibration of titanium and polyoxometalate were appeared in H5PV2Mo10O40.nH2O/TiO2 with decreasing crystallinity. The acidity of H5PV2Mo10O40.nH2O/TiO2 was higher than H5PV2Mo10O40.nH2O. Desulfurization of 4-methyl dibenzothiophene (4-MDBT) using H5PV2Mo10O40.nH2O/TiO2 as catalyst resulted conversion of 4-MDBT was 99% and higher than desulfurization using H5PV2Mo10O40.nH2O under mild conditions.

  15. Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

    Directory of Open Access Journals (Sweden)

    Takeru Ito


    Full Text Available Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC1, were successfully hybridized with heteropolyanions of [PW12O40]3− (PW12 to form inorganic-organic hybrid monomers of MAImC1-PW12. The synthetic procedure of MAImC1-PW12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC1-PW12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC1-PW12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10−4 S·cm−1 order under humidified conditions at 313 K.

  16. 21 CFR 876.3630 - Penile rigidity implant. (United States)


    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Penile rigidity implant. 876.3630 Section 876.3630...) MEDICAL DEVICES GASTROENTEROLOGY-UROLOGY DEVICES Prosthetic Devices § 876.3630 Penile rigidity implant. (a) Identification. A penile rigidity implant is a device that consists of a pair of semi-rigid rods implanted in the...

  17. Algorithms for Graph Rigidity and Scene Analysis

    DEFF Research Database (Denmark)

    Berg, Alex Rune; Jordán, Tibor


    We investigate algorithmic questions and structural problems concerning graph families defined by `edge-counts'. Motivated by recent developments in the unique realization problem of graphs, we give an efficient algorithm to compute the rigid, redundantly rigid, M-connected, and globally rigid...... components of a graph. Our algorithm is based on (and also extends and simplifies) the idea of Hendrickson and Jacobs, as it uses orientations as the main algorithmic tool. We also consider families of bipartite graphs which occur in parallel drawings and scene analysis. We verify a conjecture of Whiteley...... by showing that 2d-connected bipartite graphs are d-tight. We give a new algorithm for finding a maximal d-sharp subgraph. We also answer a question of Imai and show that finding a maximum size d-sharp subgraph is NP-hard....

  18. Measuring the Acceleration of a Rigid Body

    Directory of Open Access Journals (Sweden)

    Peter G. Martin


    Full Text Available Two methods to measure the six-degree-of-freedom acceleration of a point on a rigid body are presented. The first, referred to as the periphery scheme, makes use of three clusters of accelerometers mounted orthogonal to each other and coincident with the axes of the point. One of the clusters consists of the three accelerometers attached to a cube-shaped triaxial angular rate sensor (ARS. The second method, called the compact cube scheme, uses a single 3-accelerometer/ARS cluster that may be mounted anywhere on the rigid body. During impact tests with an instrumented rigid body, both methods produced measurements that were highly correlated near the time of peak acceleration. Whereas the compact cube scheme was more economical and easier to implement, the periphery scheme produced results that were less disrupted by instrument signal errors and noisy environments.

  19. Torsional rigidity of submanifolds with controlled geometry

    DEFF Research Database (Denmark)

    Hurtado, Ana; Markvorsen, Steen; Palmer, Vicente


    We prove explicit upper and lower bounds for the torsional rigidity of extrinsic domains of submanifolds ^m$ with controlled radial mean curvature in ambient Riemannian manifolds ^n$ with a pole $ and with sectional curvatures bounded from above and from below, respectively. These bounds are given...... in terms of the torsional rigidities of corresponding Schwarz symmetrizations of the domains in warped product model spaces. Our main results are obtained using methods from previously established isoperimetric inequalities, as found in e.g. [MP4] and [MP5]. As in [MP4] we also characterize the geometry...... of those situations in which the bounds for the torsional rigidity are actually attained and study the behavior at infinity of the so-called geometric average of the mean exit time for Brownian motion....

  20. Quantum mechanics of a generalised rigid body (United States)

    Gripaios, Ben; Sutherland, Dave


    We consider the quantum version of Arnold’s generalisation of a rigid body in classical mechanics. Thus, we quantise the motion on an arbitrary Lie group manifold of a particle whose classical trajectories correspond to the geodesics of any one-sided-invariant metric. We show how the derivation of the spectrum of energy eigenstates can be simplified by making use of automorphisms of the Lie algebra and (for groups of type I) by methods of harmonic analysis. We show how the method can be extended to cosets, generalising the linear rigid rotor. As examples, we consider all connected and simply connected Lie groups up to dimension 3. This includes the universal cover of the archetypical rigid body, along with a number of new exactly solvable models. We also discuss a possible application to the topical problem of quantising a perfect fluid.

  1. On Saturnian cosmic ray cutoff rigidities (United States)

    Sauer, H. H.


    It has been determined that Saturn possesses a relatively pure dipolar magnetic field through magnetometer measurements made by Ness et al. (1979, private comm.) and Smith et al. (1979). The paper briefly outlines the dipole geomagnetic cutoff theory and demonstrates the scaling required for its applicability to energetic particle measurements in the vicinity of Saturn. Since the cutoff rigidity is a function of viewing direction, the effective cutoff rigidity must be determined as an integration over the finite viewing angle of a physical detector.

  2. Evaluating a method for automated rigid registration

    DEFF Research Database (Denmark)

    Darkner, Sune; Vester-Christensen, Martin; Larsen, Rasmus


    , the influence of different norms and sampling point densities is evaluated. The performance of the two methods has been evaluated on data consisting of 178 scanned ear impressions taken from the right ear. To quantify the difference of the two methods we calculate the registration cost and the mean point......We evaluate a novel method for fully automated rigid registration of 2D manifolds in 3D space based on distance maps, the Gibbs sampler and Iterated Conditional Modes (ICM). The method is tested against the ICP considered as the gold standard for automated rigid registration. Furthermore...

  3. Rigid origami vertices: conditions and forcing sets

    Directory of Open Access Journals (Sweden)

    Zachary Abel


    Full Text Available We develop an intrinsic necessary and sufficient condition for single-vertex origami crease patterns to be able to fold rigidly.  We classify such patterns in the case where the creases are pre-assigned to be mountains and valleys as well as in the unassigned case.  We also illustrate the utility of this result by applying it to the new concept of minimal forcing sets for rigid origami models, which are the smallest collection of creases that, when folded, will force all the other creases to fold in a prescribed way.

  4. Rigidity analysis of HIV-1 protease (United States)

    Heal, J. W.; Wells, S. A.; Jimenez-Roldan, E.; Freedman, R. F.; Römer, R. A.


    We present a rigidity analysis on a large number of X-ray crystal structures of the enzyme HIV-1 protease using the 'pebble game' algorithm of the software FIRST. We find that although the rigidity profile remains similar across a comprehensive set of high resolution structures, the profile changes significantly in the presence of an inhibitor. Our study shows that the action of the inhibitors is to restrict the flexibility of the β-hairpin flaps which allow access to the active site. The results are discussed in the context of full molecular dynamics simulations as well as data from NMR experiments.

  5. The 'twin paradox' in relativistic rigid motion


    Ben-Ya'acov, Uri


    Relativistic rigid motion suggests a new version for the so-called `twin paradox', comparing the ages of two astronauts on a very long spaceship. Although there is always an instantaneous inertial frame in which the whole spaceship, being rigid, is simultaneously at rest, the twins' ages, measured as the proper-times along their individual world lines, are different when they are located at remote parts of the spaceship. The age, or proper-time, difference depends on the distance at rest betw...

  6. Synthesis and characterization of two polyoxometalates consisting of different Cu-ligand hydrogen phosphate units

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Jinshuang; Zhao, Xiaofang; Huang, Jiao; Gong, Kaining; Han, Zhangang, E-mail:; Zhai, Xueliang, E-mail:


    Two polyoxometalates [(Cu-mbpy){sub 4}(HPO{sub 4}){sub 2}(H{sub 2}O){sub 2}][PMo{sub 12}O{sub 40}]·H{sub 2}O (1) and [(Cu-mbpy){sub 6}(HPO{sub 4}){sub 4}][PW{sub 12}O{sub 40}]·4H{sub 2}O (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl in 1; 5,5″-dimethyl-2,2'-dipyridyl in 2) have been synthesized and characterized by IR, X-ray powder diffraction, TG analysis and electrochemical property. The structural features of 1–2 are in their cationic moieties consisting of different linkages of [Cu-mbpy]{sup 2+} and HPO{sub 4}{sup 2−} groups. In 1 four Cu-mbpy bridged by two HPO{sub 4}{sup 2−} ions form a discrete cluster with an interesting octahedron of (Cu{sub 4}P{sub 2}), while in 2 Cu-mbpy fragments are bridged by HPO{sub 4}{sup 2−} ions into 1D structure consisting of trigonal bipyramidal polyhedra of (Cu{sub 3}P{sub 2}). Photocatalytic experiments indicate that compounds 1 and 2 are actively photocatalytic for degradation of methyl orange in the presence of H{sub 2}O{sub 2} under UV light irradiation. -- Graphical abstract: Two polyoxometalate-based supramolecular compounds consisting of different linkages based on Cu-ligand and HPO{sub 4}{sup 2−} groups have been synthesized and characterized. The photocatalytic activity are studied. Highlights: • Two polyoxometalate-based supramolecular compounds consisting of different linkages based on Cu-ligand and HPO{sub 4}{sup 2−} groups have been synthesized. • Hydrogen bonding and π…π interactions play important roles in constructing crystal supramolecular frameworks. • Two compounds represent a high photocatalytic activity in the degradation of methyl orange.

  7. Rigid polyurethane and kenaf core composite foams (United States)

    Rigid polyurethane foams are valuable in many construction applications. Kenaf is a bast fiber plant where the surface stem skin provides bast fibers whose strength-to-weight ratio competes with glass fiber. The higher volume product of the kenaf core is an under-investigated area in composite appli...

  8. Settling dynamics of asymmetric rigid fibers (United States)

    E.J. Tozzi; C Tim Scott; David Vahey; D.J. Klingenberg


    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with...

  9. Geometric integrators for stochastic rigid body dynamics

    KAUST Repository

    Tretyakov, Mikhail


    Geometric integrators play an important role in simulating dynamical systems on long time intervals with high accuracy. We will illustrate geometric integration ideas within the stochastic context, mostly on examples of stochastic thermostats for rigid body dynamics. The talk will be mainly based on joint recent work with Rusland Davidchak and Tom Ouldridge.

  10. Secondary structure and rigidity in model proteins. (United States)

    Perticaroli, Stefania; Nickels, Jonathan D; Ehlers, Georg; O'Neill, Hugh; Zhang, Qui; Sokolov, Alexei P


    There is tremendous interest in understanding the role that secondary structure plays in the rigidity and dynamics of proteins. In this work we analyze nanomechanical properties of proteins chosen to represent different secondary structures: α-helices (myoglobin and bovine serum albumin), β-barrels (green fluorescent protein), and α + β + loop structures (lysozyme). Our experimental results show that in these model proteins, the β motif is a stiffer structural unit than the α-helix in both dry and hydrated states. This difference appears not only in the rigidity of the protein, but also in the amplitude of fast picosecond fluctuations. Moreover, we show that for these examples the secondary structure correlates with the temperature- and hydration-induced changes in the protein dynamics and rigidity. Analysis also suggests a connection between the length of the secondary structure (α-helices) and the low-frequency vibrational mode, the so-called boson peak. The presented results suggest an intimate connection of dynamics and rigidity with the protein secondary structure.

  11. Analysis and Modeling of Rigid Microswimmers (United States)

    Meshkati, Farshad

    In this thesis, we investigate magnetically actuated rigid microswimmers based on analytical and numerical schemes. These swimming micro-robots have medical applications such as drug delivery and in vivo diagnostics. Our model employs the method of regularized Stokeslets to faithfully incorporate the low-Reynolds-number hydrodynamics of arbitrary rigid geometries. We show how these magnetized swimmers can be actuated and controlled by externally rotating uniform magnetic fields. Our model predicts the swimming characteristics such as speed and direction. We show how to determine the dynamic stability of steadily rotating microswimmers. First, we address what is the simplest geometry capable of swimming. We illustrate that, despite the common belief that rigid microswimmers need to be chiral to be able to cause propulsion, a simple achiral 3-bead geometry can exhibit appreciable propulsion and controllability. We generalize this to explain the minimum geometric requirements for rigid rotating propulsion based on a symmetry analysis. Next, we investigate the implications of the stability analysis on the control of the 3-bead swimmer. We show that by adjusting the angle between the magnetic field and its rotation, one can control the existence of multiple stable rotation modes, leading to control of swimming direction and speed.

  12. On the combinatorics of infinitesimally rigid frameworks

    NARCIS (Netherlands)

    Laman, G.


    Starting from a short survey of minimal infinitesimally rigid frameworks it is shown by an example that and why a two-dimensional characterization of them cannot be extended to higher dimensions just like that. The findings of a closer inspection of the interdependence of the rows of the relevant

  13. A relativistic generalisation of rigid motions (United States)

    Llosa, J.; Molina, A.; Soler, D.


    A weaker substitute for the too restrictive class of Born-rigid motions is proposed, which we call radar-holonomic motions. The definition is expressed as a set of differential equations. Integrability conditions and Cauchy problem are studied. We finally obtain an example of a radar-holonomic congruence containing a given worldline with a given value of the rotation on this line.

  14. Reference frames and rigid motions in relativity (United States)

    Llosa, J.; Soler, D.


    A reference frame consists of a reference space, a time scale and a spatial metric. The geometric structure induced by these objects in spacetime is developed. The existence of a class of spatial metrics which are rigid, have free mobility and can be derived as a slight deformation of the radar metric, is demonstrated.

  15. Cracking of open traffic rigid pavement

    Directory of Open Access Journals (Sweden)

    Niken Chatarina


    Full Text Available The research is done by observing the growth of real structure cracking in Natar, Lampung, Indonesia compared to C. Niken’s et al research and literature study. The rigid pavement was done with open traffic system. There are two main crack types on Natar rigid pavement: cracks cross the road, and cracks spreads on rigid pavement surface. The observation of cracks was analyzed by analyzing material, casting, curing, loading and shrinkage mechanism. The relationship between these analysis and shrinkage mechanism was studied in concrete micro structure. Open traffic make hydration process occur under vibration; therefore, fresh concrete was compressed and tensioned alternately since beginning. High temperature together with compression, cement dissociation, the growth of Ca2+ at very early age leads abnormal swelling. No prevention from outside water movement leads hydration process occur with limited water which caused spreads fine cracks. Limited water improves shrinkage and plastic phase becomes shorter; therefore, rigid pavement can’t accommodate the abnormal swelling and shrinking alternately and creates the spread of cracks. Discontinuing casting the concrete makes both mix under different condition, the first is shrink and the second is swell and creates weak line on the border; so, the cracks appear as cracks across the road.

  16. The two-body problem of a pseudo-rigid body and a rigid sphere

    DEFF Research Database (Denmark)

    Kristiansen, Kristian Uldall; Vereshchagin, M.; Gózdziewski, K.


    n this paper we consider the two-body problem of a spherical pseudo-rigid body and a rigid sphere. Due to the rotational and "re-labelling" symmetries, the system is shown to possess conservation of angular momentum and circulation. We follow a reduction procedure similar to that undertaken...... in the study of the two-body problem of a rigid body and a sphere so that the computed reduced non-canonical Hamiltonian takes a similar form. We then consider relative equilibria and show that the notions of locally central and planar equilibria coincide. Finally, we show that Riemann's theorem on pseudo...

  17. Rigid Spine Syndrome among Children in Oman

    Directory of Open Access Journals (Sweden)

    Roshan Koul


    Full Text Available Objectives: Rigidity of the spine is common in adults but is rarely observed in children. The aim of this study was to report on rigid spine syndrome (RSS among children in Oman. Methods: Data on children diagnosed with RSS were collected consecutively at presentation between 1996 and 2014 at the Sultan Qaboos University Hospital (SQUH in Muscat, Oman. A diagnosis of RSS was based on the patient’s history, clinical examination, biochemical investigations, electrophysiological findings, neuro-imaging and muscle biopsy. Atrophy of the paraspinal muscles, particularly the erector spinae, was the diagnostic feature; this was noted using magnetic resonance imaging of the spine. Children with disease onset in the paraspinal muscles were labelled as having primary RSS or rigid spinal muscular dystrophy. Secondary RSS was classified as RSS due to the late involvement of other muscle diseases. Results: Over the 18-year period, 12 children were included in the study, with a maleto- female ratio of 9:3. A total of 10 children were found to have primary RSS or rigid spinal muscular dystrophy syndrome while two had secondary RSS. Onset of the disease ranged from birth to 18 months of age. A family history was noted, with two siblings from one family and three siblings from another (n = 5. On examination, children with primary RSS had typical features of severe spine rigidity at onset, with the rest of the neurological examination being normal. Conclusion: RSS is a rare disease with only 12 reported cases found at SQUH during the study period. Cases of primary RSS should be differentiated from the secondary type.

  18. Three-dimensional films of photoluminescent polyoxometalates fabricated by a colloidal crystal template

    Energy Technology Data Exchange (ETDEWEB)

    Chai Fang [Key Lab of Polyoxometalate Science of Minister of Education, Northeast Normal University, 130024, Changchun (China); Department of Chemistry, Harbin Normal University, 150500, Harbin (China); Li Dongliu; Zhang Xia [Key Lab of Polyoxometalate Science of Minister of Education, Northeast Normal University, 130024, Changchun (China); Wang Xiaohong, E-mail: [Key Lab of Polyoxometalate Science of Minister of Education, Northeast Normal University, 130024, Changchun (China)


    Three-dimensional ordered thin films based on 12-phosphotungstic acid (PW{sub 12}O{sub 40}/SiO{sub 2}) and lanthanide-substituted phosphotungstate (Eu(PW{sub 11}O{sub 39}){sub 2}/SiO{sub 2}, Gd(PW{sub 11}O{sub 39}){sub 2}/SiO{sub 2} and Eu(P{sub 2}W{sub 17}O{sub 61}){sub 2}/SiO{sub 2}) were constructed by an inverse opal method, using polystyrene colloidal crystal as a template. The samples were characterized by elemental analysis, XRD, IR spectra, UV-vis diffuse reflectance spectra (DR-UV-Vis) and SEM techniques. These thin films show well-defined lamellar array with inverse opal structure, and lanthanide polyoxometalate thin films exhibit photoluminescent properties.

  19. Photoreduction of graphene oxide with polyoxometalate clusters and its enhanced saturable absorption. (United States)

    Li, Haolong; Gupta, Jyotsana; Wang, Shan; Zhang, Na; Bubeck, Christoph


    We investigated the photocatalytic abilities of three Keggin-type polyoxometalate (POM) clusters, H3PW12O40 (PW), H4SiW12O40 (SiW), and H3PMo12O40 (PMo) to reduce graphene oxide (GO) under UV-irradiation in water. UV-vis absorption and X-ray photoelectron spectroscopy were performed and show that PW and SiW can photoreduce GO effectively, in contrast to PMo. We conclude that the LUMO levels of POMs should be located energetically above the work function of GO to enable electron transfer from POM to GO. We also investigated the saturable absorption of GO and reduced GO by means of z-scan experiments at 532 nm. The POM-assisted photoreduction of GO can greatly enhance the saturable absorber properties of GO, which appears useful for modelocking in ultrafast laser systems. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. Photochemical reduction of carbon dioxide catalyzed by a ruthenium-substituted polyoxometalate. (United States)

    Khenkin, Alexander M; Efremenko, Irena; Weiner, Lev; Martin, Jan M L; Neumann, Ronny


    A polyoxometalate of the Keggin structure substituted with Ru(III), (6)Q(5)[Ru(III)(H(2)O)SiW(11)O(39)] in which (6)Q=(C(6)H(13))(4)N(+), catalyzed the photoreduction of CO(2) to CO with tertiary amines, preferentially Et(3)N, as reducing agents. A study of the coordination of CO(2) to (6)Q(5)[Ru(III)(H(2)O)SiW(11)O(39)] showed that 1) upon addition of CO(2) the UV/Vis spectrum changed, 2) a rhombic signal was obtained in the EPR spectrum (g(x)=2.146, g(y)=2.100, and g(z)=1.935), and 3) the (13)C NMR spectrum had a broadened peak of bound CO(2) at 105.78 ppm (Delta(1/2)=122 Hz). It was concluded that CO(2) coordinates to the Ru(III) active site in both the presence and absence of Et(3)N to yield (6)Q(5)[Ru(III)(CO(2))SiW(11)O(39)]. Electrochemical measurements showed the reduction of Ru(III) to Ru(II) in (6)Q(5)[Ru(III)(CO(2))SiW(11)O(39)] at -0.31 V versus SCE, but no such reduction was observed for (6)Q(5)[Ru(III)(H(2)O)SiW(11)O(39)]. DFT-calculated geometries optimized at the M06/PC1//PBE/AUG-PC1//PBE/PC1-DF level of theory showed that CO(2) is preferably coordinated in a side-on manner to Ru(III) in the polyoxometalate through formation of a Ru-O bond, further stabilized by the interaction of the electrophilic carbon atom of CO(2) to an oxygen atom of the polyoxometalate. The end-on CO(2) bonding to Ru(III) is energetically less favorable but CO(2) is considerably bent, thus favoring nucleophilic attack at the carbon atom and thereby stabilizing the carbon sp(2) hybridization state. Formation of a O(2)C-NMe(3) zwitterion, in turn, causes bending of CO(2) and enhances the carbon sp(2) hybridization. The synergetic effect of these two interactions stabilizes both Ru-O and C-N interactions and probably determines the promotional effect of an amine on the activation of CO(2) by [Ru(III)(H(2)O)SiW(11)O(39)](5-). Electronic structure analysis showed that the polyoxometalate takes part in the activation of both CO(2) and Et(3)N. A mechanistic pathway for

  1. Photocatalytic degradation of textile dye X-3B using polyoxometalate-TiO2 hybrid materials. (United States)

    Jin, Hongxiao; Wu, Qingyin; Pang, Wenqin


    Titanium dioxide functionalized with Keggin type polyoxometalate (POMs) [X(n+)W(12)O(40)]((8-n)-) (XW(12); X(n+)=P(5+), Si(4+), Ge(4+)) were prepared by sol-gel method. The Keggin structure and dispersion state of POMs were monitored by FT-IR and XRD. The composites showed higher photocatalytic activity than pure TiO(2), pure POMs or mechanical mixture of TiO(2) and POMs for X-3B degradation. Among the three POMs-TiO(2) hybrid materials, the reactivity was: PW(12)>SiW(12)>GeW(12). With different loading weights for the same POMs, the reactivity followed the order: 30wt.%>15wt.%>45wt.%.

  2. Decisive Interactions between the Heterocyclic Moiety and the Cluster Observed in Polyoxometalate-Surfactant Hybrid Crystals

    Directory of Open Access Journals (Sweden)

    Saki Otobe


    Full Text Available Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda and dodecylpyridinium (C12py surfactants. The decatungstate (W10 anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10, the heterocyclic moiety directly interacted with W10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C12py (C12py-W10 had similar crystal packing and molecular arrangement to those in the W10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions.

  3. A new Keggin-type polyoxometalate catalyst for degradation of aqueous organic contaminants (United States)

    Olgun, Asim; Çolak, Alper Tolga; Gübbük, İ. Hilal; Şahin, Onur; Kanar, Ebru


    In this study, a new polyoxometalate, K16[Ni(H2O)6]2[BW12O40]4·48H2O (1) was synthesized at room temperature and characterized by X-ray single crystal diffractions, elemental analyses, IR spectra, and thermo gravimetric analyses (TGA). Crystal structure analysis reveals that compound 1 exhibits a supramolecular structure containing one Keggin-type [BW12O40]4 heteropoly anion. The catalytic properties of this molecule for the degradation of Methyl red (MR), Rhodamine B (RhB), Methyl orange (MO) and Congo red (CR) were investigated. The results show that the compound 1 is a promising catalyst candidate for dye degradation.

  4. Polyoxometallate-stabilized platinum catalysts on multi-walled carbon nanotubes for fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Z.P.; Liu, H.K. [School of Mechanical, Materials and Mechatronic Engineering, University of Wollongong, NSW 2522 (Australia); Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Han, D.M. [School of Mechanical, Materials and Mechatronic Engineering, University of Wollongong, NSW 2522 (Australia); State Key Laboratory of Optoelectronic Materials and Technologies, Institute of Optoelectronic and Functional Composite Materials,Sun Yat-Sen University, Guangzhou 510275 (China); Wexler, D.; Zeng, R. [School of Mechanical, Materials and Mechatronic Engineering, University of Wollongong, NSW 2522 (Australia)


    A novel catalyst, Pt-PMo{sub 12}-CNT, with well-dispersed Pt nanoparticles and monolayer PMo{sub 12} on multi-walled carbon nanotubes (CNTs) is reported. A polyoxometallate (PMo{sub 12}) was chemically adsorbed on the surface of Pt nanoparticles and on outer walls of CNTs. These effectively prevented the agglomeration of Pt nanoparticles and CNTs due to the electrostatic repulsive interactions between negatively charged PMo{sub 12} monolayers. The as-prepared Pt-PMo{sub 12}-CNT materials show higher electrocatalytic activity, higher cycle stability, and better tolerance to poisoning species in methanol oxidation than do Pt-CNT catalysts prepared by the same method. The reasons for the improved catalytic performance of the Pt-PMo{sub 12}-CNT catalysts are discussed. (author)

  5. Electrostatic immobilization of polyoxometallates on silicon: X-ray Photoelectron Spectroscopy and electrochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Fleury, Benoit [INAC/LCIB/RICC (UMR E3 CEA-UJF, FRE CNRS 3200), CEA-Grenoble 17 rue des martyrs, 38054 Grenoble cedex 9 (France); Billon, Martial [INAC/SPrAM/CREAB (UMR 5819 CEA-CNRS-UJF), CEA-Grenoble 17 rue des martyrs, 38054 Grenoble cedex 9 (France); Duclairoir, Florence, E-mail: florence.duclairoir@cea.f [INAC/LCIB/RICC (UMR E3 CEA-UJF, FRE CNRS 3200), CEA-Grenoble 17 rue des martyrs, 38054 Grenoble cedex 9 (France); Dubois, Lionel [INAC/LCIB/RICC (UMR E3 CEA-UJF, FRE CNRS 3200), CEA-Grenoble 17 rue des martyrs, 38054 Grenoble cedex 9 (France); Fanton, Aurelien [LETI/DPTS/SCPIO/LCPO, CEA-Grenoble 17 rue des martyrs, 38054 Grenoble cedex 9 (France); Bidan, Gerard [INAC/DIR, CEA-Grenoble 17 rue des martyrs, 38054 Grenoble cedex 9 (France)


    Keggin-type dodecatungstosilicates polyoxometallates (POMs) ([SiW{sub 12}O{sub 40}]{sup 4-}) were immobilized in a straightforward manner by electrostatic interactions on ammonium layers covalently grafted on silicon. This method does not require any POM modification synthetical steps. The presence of [SiW{sub 12}O{sub 40}]{sup 4-} on the surface is demonstrated by X-ray Photoelectron Spectroscopy from a specific modification of the tungsten 4f{sub 7/2} signal. Moreover the surface coverage of [SiW{sub 12}O{sub 40}]{sup 4-} has been improved by 35% upon changing the nature of the anchoring ammonium groups from protonated to methylated amino groups. The organic-inorganic composite films have also been characterized by cyclic voltammetry showing that POMs have a specific behavior on silicon surfaces. In addition the use of a polyallylamine capping layer proved to stabilize efficiently the POM electrochemical response.

  6. A nanosized {Ag@Ag12} "molecular windmill" templated by polyoxometalates anions. (United States)

    Wang, Lei; Yang, Weiting; Zhu, Wei; Guan, Xingang; Xie, Zhigang; Sun, Zhong-Ming


    Reaction of multidentate 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (L) ligand with Ag(I) ions in the existence of H3PW12O40 as anionic template under hydrothermal conditions results in tridecanuclear silver cluster-polyoxometalates hybrid: {Ag13L12}{PW12O40}4·30H2O (1). X-ray single crystal diffraction analysis indicates that the main structural feature of 1 is a nanosized molecular windmill-shaped polynuclear Ag cluster with intriguing {M@M12}-type cuboctahedral topology. The as-synthesized compound exhibits effective photocatalytic activity in the photodegradation of Rhodamine-B (RhB) and antibacterial activity against Escherichia coli, respectively.

  7. Breaking the Gordian Knot in the Structural Chemistry of Polyoxometalates: Copper(II)-Oxo/Hydroxo Clusters. (United States)

    Kondinski, Aleksandar; Monakhov, Kirill Yu


    This Concept article provides insights into the molecular design and construction aspects of polyoxocuprates (POCus), an emerging class of polyoxometalate (POM)-like architectures featuring low-to-high nuclearity copper(II)-oxo/hydroxo skeletons. POCus have been identified to adopt the structural principles of classical POMs consisting of early transition metals. Their potential to afford motifs of the noble-metal-based POMs is exploited. "Cross-structural topological transformation" is introduced to generalize skeletal relationships between POCus and POMs. The study opens up strategies toward the brand-new structural chemistry of POCus with relevance to homogeneous photocatalysis, medicinal chemistry, molecular magnetism, and quantum computing. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Production of Adipic Acid from Mixtures of Cyclohexanol-Cyclohexanone using Polyoxometalate Catalysts

    Directory of Open Access Journals (Sweden)

    Aldes Lesbani


    Full Text Available Adipic acid production through catalytic conversion of cyclohexanol-cyclohexanone using polyoxometalate H5[a-BW12O40] and H4[a-SiW12O40] as catalysts was carried out systematically. Polyoxometalates H5[a-BW12O40] and H4[a-SiW12O40] were synthesized using an inorganic synthesis method and were characterized using Fourier transform infrared spectroscopy (FTIR. Adipic acid was formed from conversion of cyclohexanol-cyclohexanone and was characterized by using melting point measurement, identification of functional group using FTIR spectrophotometer, analysis of gas chromatography-mass spectrometry (GC-MS, and 1H and 13C NMR (nuclear magnetic resonance spectrophotometer. This research investigated the influence of reaction time and temperature on the conversion. The results showed that adipic acid was formed successfully with a yield of 68% by using H5[a-BW12O40] as the catalyst with a melting point of 150-152 °C after optimization. In contrast, using H4[a-SiW12O40] as the catalyst, the formation was only 3.7%. Investigation of time and temperature showed 9 h as the optimum reaction time and 90 °C as the optimum temperature for conversion of up to 68%. Identification using FTIR, 1H, and 13C NMR showed that the adipic acid from conversion of cyclohexanol-cyclohexanone was in agreement with the standard adipic acid data in the literatures. GC-MS analysis indicated that several by-products were formed in conversion of cyclohexanol-cyclohexanone using H5[a-BW12O40] and H4[a-SiW12O40] as the catalysts.

  9. Multisensor system for determination of polyoxometalates containing vanadium at its different oxidation states. (United States)

    Rudnitskaya, Alisa; Evtuguin, Dmitry V; Gamelas, Jose A F; Legin, Andrey


    The electronic tongue (ET) multisensor system has been employed for the detection of metal-oxygen cluster anions (polyoxometalates) containing vanadium (IV/V) atoms. Sensitivity of a variety of potentiometric chemical sensors with plasticized polyvinyl chloride and chalcogenide glass membranes was evaluated with respect to vanadyl/vanadate ions, decavanadate and a series of Keggin-type polyoxometalates (POM) such as alpha-[SiW(11)V(IV)O(40)](6-), alpha-[SiW(11)V(V)O(40)](5-), alpha-[BW(11)V(IV)O(40)](7-), alpha-[BW(11)V(V)O(40)](6-), alpha-[PW(11)V(IV)O(40)](5-) and alpha-[PW(12-n)V(n)(V)O(40)]((3+n)-) (n=1, 2, 3). Sensor's responses to vanadium complexes were evaluated in the pH range of 2.4-6.5 and a set of sensors appropriate for detecting a variety of vanadium species was selected. Such sensor array was able to distinguish different vanadium complexes allowing their simultaneous quantification in binary (V(IV)/V(V)) mixtures. The vanillyl alcohol oxidation with alpha-[SiW(11)V(V)O(40)](5-) was monitored using ET to evaluate the capacity of proposed analytic system to detect simultaneously V(IV)/V(V) in POM under dynamic equilibrium. ET was demonstrated to be a promising tool for the discrimination and quantification of vanadium-containing POMs at different oxidation states. In particular, such a system could represent a significant interest for the mechanistic studies of redox reactions with POMs.

  10. Polyoxometalate catalysts: toward the development of green H2O2-based epoxidation systems. (United States)

    Mizuno, Noritaka; Yamaguchi, Kazuya


    This paper describes the development of green, efficient H(2)O(2)-based epoxidation systems with three kinds of polyoxometalates: (i) a dinuclear peroxotungstate [W(2)O(3)(O(2))(4)(H(2)O)(2)](2-) (I), (ii) a divacant lacunary polyoxotungstate [gamma-SiW(10)O(34)(H(2)O)(2)]4 (II), (iii) and a divanadium-substituted polyoxotungstate [gamma-1,2-H(2)SiV(2)W(10)O(40)](4-) (III). The highly chemo-, regio-, and diastereoselective epoxidation of various allylic alcohols with only 1 equiv H(2)O(2) in water can be efficiently catalyzed by potassium salt of I (K-I). The catalyst K-I can be recycled with the retention of the catalytic performance. Protonation of a divacant lacunary polyoxotungstate [gamma-SiW(10)O(36)](8-) gives [gamma-SiW(10)O(34)(H(2)O)(2)](4-) (II) with two aquo ligands. The tetra-n-butylammonium salt of II (TBA-II) catalyzes epoxidation of common olefins including propylene with >or=99% selectivity to epoxide and >or=99% efficiency of H(2)O(2) utilization. The bis(mu-hydroxo)bridged dioxovanadium site in [gamma-1,2-H(2)SiV(2)W(10)O(40)](4-) (III) can also efficiently catalyze epoxidation of a variety of olefins with 1 equiv H(2)O(2). Notably, the system with III shows unique stereospecificity, diastereoselectivity, and regioselectivity for the epoxidation of cis/trans olefins, 3-substituted cyclohexenes, and nonconjugated dienes, respectively, which are quite different from those reported for epoxidation systems up to now. Furthermore, the heterogenization of the mentioned polyoxometalates can be achieved by using ionic liquid-modified SiO(2) as a support without loss of catalytic performance. (c) 2006 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

  11. Tubular solids of lanthanide-doped polyoxometalates in micrometer-scale: synthesis and NIR-luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xia [Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China); Analytical and Testing Center, Beihua University, Jilin, 132013 (China); Peng, Jun, E-mail: [Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China); Shi, Zhenyu; Shen, Yan; Zhang, Zheyu; Li, Guangzhe [Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China)


    A series of lanthanide-doped polyoxometalate microtubes, Ln-SiW{sub 12} (Ln=Nd, Dy and Yb), have been synthesized, and characterized by X-ray diffraction, elemental analysis and thermogravimetric analysis. In the microtubes, the lanthanide cations combine with polyanions through electrostatic interaction. Furthermore, the lanthanide-doped microtubes were chelated with 8-hydroxyquinoline (HQ) in a post-synthesis step (designed as LnQ-SiW{sub 12}). The LnQ-SiW{sub 12} show characteristic near-infrared (NIR) luminescence, corresponding to Ln{sup 3+} ions due to efficient energy transfer from Q to the Ln{sup 3+} ions through antenna effect. - Highlights: • A series of lanthanide-doped polyoxometalate microtubes have been firstly synthesized. • The Ln-SiW{sub 12} microtubes were chelated with HQ in a post-synthesis step. • The LnQ-SiW{sub 12} microtubes show characteristic NIR luminescence through antenna effect.

  12. Selective oxidation of lignocellulosic biomass to formic acid and high-grade cellulose using tailor-made polyoxometalate catalysts. (United States)

    Albert, Jakob


    The main goal of this project was to identify and optimize tailor-made polyoxometalate catalysts for a fractionated oxidation of lignocellulosic biomass (i.e. wood and residues from sugar or paper industries) to produce formic acid (FA) and high-grade cellulose for further processing e.g. in white biotechnology to provide bio-ethanol. Homogeneous vanadium precursors like sodium metavanadate and vanadyl sulfate as well as Keggin-type polyoxometalates (POMs) and more exotic structures like Anderson-, Wells-Dawson- and Lindqvist-type POMs were screened for the desired catalytic performance. The most promising behaviour was found using the Lindqvist-type POM K5V3W3O19, showing for the first time in the literature a selective oxidation of only hemicellulose and lignin to formic acid, while the cellulose fraction was untrapped. However, this can only be a first step towards the project goal as low product yields were obtained.

  13. Silver nanocrystal-decorated polyoxometalate single-walled nanotubes as nanoreactors for desulfurization catalysis at room temperature. (United States)

    Zhang, Hao; Xu, Xiaobin; Lin, Haifeng; Ud Din, Muhammad Aizaz; Wang, Haiqing; Wang, Xun


    Ultrathin nanocrystals generally provide a remarkable catalytic performance due to their high specific surface area and exposure of certain active sites. However, deactivation caused by growth and gathering limits the catalytic application of ultrathin nanocrystals. Here we report Ag nanocrystal-decorated polyoxometalate (Ag-POM) single-walled nanotubes assembled via a concise, surfactant-free soaking method as a new kind of well-defined core-sheath nanoreactor. The diameter of Ag nanocrystals inside polyoxometalate nanotubes can be controlled via simply adjusting the reactant concentration. Ag-POM provided outstanding oxidative desulfurization (ODS) catalytic performance for aromatic sulfocompounds at room temperature. It was suggested that Ag nanocrystals decorated on the inner surface played a key role in adjusting the electronic distribution and enhancing the catalytic activity. The as-prepared Ag-POM nanotubes are promising candidate catalysts with enhanced performance for practical catalytic applications in the gasoline desulfurization industry.

  14. Polyoxometalate oxidation of non-phenolic lignin subunits in water : effect of substrate structure on reaction kinetics (United States)

    Tomoya Yokoyama; Hou-min Chang; Richard S. Reiner; Raja H. Atalla; Ira A. Weinstock; John F. Kadla


    The effect of lignin-biopolymer structure on the mechanism of its oxidative depolymerization by polyoxometalates (POMs) was investigated by reacting an equilibrated POM ensemble with a series of ring-substituted benzyl alcohols. Under anaerobic conditions in mixed water/methanol, observed pseudo-first order reaction rates (150°C) of 8.96 x 10–3 and 4.89 x 10–3 sec–1...

  15. Synthetic considerations in the self-assembly of coordination polymers of pyridine-functionalised hybrid Mn-Anderson polyoxometalates


    Yazigi, Francois-Joseph; Wilson, Claire; Long, De-Liang; Forgan, Ross S.


    The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal-organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilised, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups t...

  16. Two nanoscale Nb containing polyoxometalates based on {P2W15Nb3O62} clusters and chromium cations. (United States)

    Huang, Peng; Wang, Xin-Long; He, De-Qing; Wu, Hai-Yang; Qin, Chao; Du, Meng; Lai, Chao; Su, Zhong-Min


    Two novel mixed-addenda Nb/W polyoxometalates are successfully fabricated, and investigated as anode materials for lithium-ion batteries. For the Cs5K4{Cr3(H2O)12[P2W15Nb3O62]2}·60H2O sample, a reversible capacity (466.6 mA h g(-1)) and stable cycle performance are obtained.

  17. Rigid cohomology over Laurent series fields

    CERN Document Server

    Lazda, Christopher


    In this monograph, the authors develop a new theory of p-adic cohomology for varieties over Laurent series fields in positive characteristic, based on Berthelot's theory of rigid cohomology. Many major fundamental properties of these cohomology groups are proven, such as finite dimensionality and cohomological descent, as well as interpretations in terms of Monsky-Washnitzer cohomology and Le Stum's overconvergent site. Applications of this new theory to arithmetic questions, such as l-independence and the weight monodromy conjecture, are also discussed. The construction of these cohomology groups, analogous to the Galois representations associated to varieties over local fields in mixed characteristic, fills a major gap in the study of arithmetic cohomology theories over function fields. By extending the scope of existing methods, the results presented here also serve as a first step towards a more general theory of p-adic cohomology over non-perfect ground fields. Rigid Cohomology over Laurent Series Fields...

  18. Financial Constraints and Nominal Price Rigidities

    DEFF Research Database (Denmark)

    Menno, Dominik Francesco; Balleer, Almut; Hristov, Nikolay

    This paper investigates how financial market imperfections and the frequency of price adjustment interact. Based on new firm-level evidence for Germany, we document that financially constrained firms adjust prices more often than their unconstrained counterparts, both upwards and downwards. We show...... that these empirical patterns are consistent with a partial equilibrium menu-cost model with a working capital constraint. We then use the model to show how the presence of financial frictions changes profits and the price distribution of firms compared to a model without financial frictions. Our results suggest...... that tighter financial constraints are associated with higher nominal rigidities, higher prices and lower output. Moreover, in response to aggregate shocks, aggregate price rigidity moves substantially, the response of inflation is dampened, while output reacts more in the presence of financial frictions...

  19. Lectures on formal and rigid geometry

    CERN Document Server

    Bosch, Siegfried


    A first version of this work appeared in 2005 as a Preprint of the Collaborative Research Center "Geometrical Structures in Mathematics" at the University of Münster. Its aim was to offer a concise and self-contained 'lecture-style' introduction to the theory of classical rigid geometry established by John Tate, together with the formal algebraic geometry approach launched by Michel Raynaud. These Lectures are now viewed commonly as an ideal means of learning advanced rigid geometry, regardless of the reader's level of background. Despite its parsimonious style, the presentation illustrates a number of key facts even more extensively than any other previous work. This Lecture Notes Volume is a revised and slightly expanded version of the original preprint and has been published at the suggestion of several experts in the field.

  20. Rigidity of the magic pentagram game (United States)

    Kalev, Amir; Miller, Carl A.


    A game is rigid if a near-optimal score guarantees, under the sole assumption of the validity of quantum mechanics, that the players are using an approximately unique quantum strategy. Rigidity has a vital role in quantum cryptography as it permits a strictly classical user to trust behavior in the quantum realm. This property can be traced back as far as 1998 (Mayers and Yao) and has been proved for multiple classes of games. In this paper we prove ridigity for the magic pentagram game, a simple binary constraint satisfaction game involving two players, five clauses and ten variables. We show that all near-optimal strategies for the pentagram game are approximately equivalent to a unique strategy involving real Pauli measurements on three maximally-entangled qubit pairs.

  1. Rigidity of the magic pentagram game (United States)

    Kalev, Amir; Miller, Carl A.


    A game is rigid if a near-optimal score guarantees, under the sole assumption of the validity of quantum mechanics, that the players are using an approximately unique quantum strategy. Rigidity has a vital role in quantum cryptography as it permits a strictly classical user to trust behavior in the quantum realm. This property can be traced back as far as 1998 (Mayers and Yao) and has been proved for multiple classes of games. In this paper we prove ridigity for the magic pentagram game, a simple binary constraint satisfaction game involving two players, five clauses and ten variables. We show that all near-optimal strategies for the pentagram game are approximately equivalent to a unique strategy involving real Pauli measurements on three maximally-entangled qubit pairs.

  2. Rigid aleph_epsilon-saturated models of superstable theories


    Shami, Ziv; Shelah, Saharon


    In a countable superstable NDOP theory, the existence of a rigid aleph_epsilon-saturated model implies the existence of 2^lambda rigid aleph_epsilon-saturated models of power lambda for every lambda>2^{aleph_0}.

  3. Rank rigidity for CAT(0) cube complexes


    Caprace, Pierre-Emmanuel; Sageev, Michah


    We prove that any group acting essentially without a fixed point at infinity on an irreducible finite-dimensional CAT(0) cube complex contains a rank one isometry. This implies that the Rank Rigidity Conjecture holds for CAT(0) cube complexes. We derive a number of other consequences for CAT(0) cube complexes, including a purely geometric proof of the Tits Alternative, an existence result for regular elements in (possibly non-uniform) lattices acting on cube complexes, and a characterization ...

  4. Balancing of Rigid and Flexible Rotors (United States)


    IA14 nf~VO1lS t’ , f,~ riabtiB SVM-12 Balancing of Rigid and Flexible Rotors Neville F. Rieger Stress Technology, Inc. 1986 The Shock end Vibration...a bearing or other Atructural components by fatigue . Unbalance is therefore recognized as an important potential cause of machinery failure. A number...runout on slow rotation, stress relaxation with time often heavy vibration during rota- "tion Section of blade or vane broken Visually observable; bearing

  5. Stability for the Lens Rigidity Problem (United States)

    Bao, Gang; Zhang, Hai


    Let g be a Riemannian metric for R^d ({d ≥q 3}) which differs from the Euclidean metric only in a smooth and strictly convex bounded domain M. The lens rigidity problem is concerned with recovering the metric g inside M from the corresponding lens relation on the boundary {partial M}. In this paper, the stability of the lens rigidity problem is investigated for metrics which are a priori close to a given non-trapping metric satisfying the "strong fold-regular" condition. A metric g is called strong fold-regular if for each point {x\\in M}, there exists a set of geodesics passing through x whose conormal bundle covers {T^*xM}. Moreover, these geodesics contain either no conjugate points or only fold conjugate points with a non-degeneracy condition. Examples of strong fold-regular metrics are constructed. Our main result gives the first stability result for the lens rigidity problem in the case of anisotropic metrics which allow conjugate points. The approach is based on the study of the linearized inverse problem of recovering a metric from its induced geodesic flow, which is a weighted geodesic X-ray transform problem for symmetric 2-tensor fields. A key ingredient is to show that the kernel of the X-ray transform on symmetric solenoidal 2-tensor fields is of finite dimension. It remains open whether the kernel space is trivial or not.

  6. Rigid internal fixation of infected mandibular fractures. (United States)

    Mehra, Pushkar; Van Heukelom, Emily; Cottrell, David A


    To evaluate the treatment outcomes of rigid internal fixation for the management of infected mandible fractures. A retrospective chart review of infected mandible fractures managed by a single oral and maxillofacial surgeon at a level I trauma center during a 7-year period was accomplished by independent examiners. All patients were treated with incision and drainage, culture and sensitivity testing, extraction of nonsalvageable teeth, placement of maxillomandibular fixation when possible, fracture reduction with bone debridement and decortication, rigid internal fixation of the mandible by an extraoral approach, and antibiotic therapy. The medical and social history was contributory in most patients. The analysis was stratified by the differentiation of the fractures into 2 groups: those with soft tissue infections in the fracture region versus those with hard tissue-infected fractures (biopsy-proven osteomyelitis). A total of 44 patients were included in this study, with an average follow-up of 18.2 months from the date of surgery (range 3 to 48). The treatment protocol was successful in all 18 patients (100%) with soft tissue infected mandibular fractures and 24 (92%) of 26 patients with hard tissue-infected fractures. A protocol consisting of concomitant incision and drainage, mandibular debridement, fracture reduction, and stabilization with rigid internal fixation can be effectively used for single-stage management of infected mandible fractures.

  7. 21 CFR 886.5916 - Rigid gas permeable contact lens. (United States)


    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Rigid gas permeable contact lens. 886.5916 Section 886.5916 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Therapeutic Devices § 886.5916 Rigid gas permeable contact lens. (a) Identification. A rigid gas permeable...

  8. Influence of flock coating on bending rigidity of woven fabrics (United States)

    Ozdemir, O.; Kesimci, M. O.


    This work presents the preliminary results of our efforts that focused on the effect of the flock coating on the bending rigidity of woven fabrics. For this objective, a laboratory scale flocking unit is designed and flocked samples of controlled flock density are produced. Bending rigidity of the samples with different flock densities are measured on both flocked and unflocked sides. It is shown that the bending rigidity depends on both flock density and whether the side to be measured is flocked or not. Adhesive layer thickness on the bending rigidity is shown to be dramatic. And at higher basis weights, flock density gets less effective on bending rigidity.

  9. Effects of support on bifunctional methanol oxidation pathways catalyzed by polyoxometallate keggin clusters

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Haichao; Iglesia, Enrique


    H5PV2Mo10O40 polyoxometallate Keggin clusters supported on ZrO2, TiO2, SiO2, and Al2O3 are effective catalysts for CH3OH oxidation reactions to form HCHO, methyl formate (MF), and dimethoxymethane (DMM). Rates and selectivities and the structure of supported clusters depend on the surface properties of the oxide supports. Raman spectroscopy showed that Keggin structures remained essentially intact on ZrO2, TiO2, and SiO2 after treatment in air at 553 K, but decomposed to MoOx and VOx oligomers on Al2O3. Accessible protons per Keggin unit (KU) were measured during CH3OH oxidation by titration with 2,6-di-tert-butyl pyridine. For similar KU surface densities (0.28 0.37 KU/nm2), the number of accessible protons was larger on SiO2 than on ZrO2 and TiO2 and much smaller on Al2O3 supports, even though residual dimethyl ether (DME) synthesis rates after titrant saturation indicated that the fractional dispersion of KU was similar on the first three supports. These effects of support on structure and on H+ accessibility reflect varying extents of interaction between polyoxometallate clusters and supports. Rates of CH3OH oxidative dehydrogenation per KU were higher on ZrO2 and TiO2 than on SiO2 at similar KU surface densities (0.28 0.37 KU/nm2) and dispersion, indicating that redox properties of Keggin clusters depend on the identity of the support used to disperse them. ZrO2 and TiO2 supports appear to enhance the reducibility of anchored polyoxometallate clusters. Rates were much lower on Al2O3, because structural degradation led to less reactive MoOx and VOx domains. CH3OH reactions involve primary oxidation to form HCHO and subsequent secondary reactions to form DMM and MF. These reactions involve HCHO CH3OH acetalization steps leading to methoxymethanol (CH3OCH2OH) or hemiacetal intermediates, which condense with CH3OH on acid sites to form DMM or dehydrogenate to form MF. COx formation rates are much lower than those of other reactions, and DME forms in parallel

  10. Keggin type polyoxometalate H4[αSiW12O40].nH2O as intercalant for hydrotalcite

    Directory of Open Access Journals (Sweden)

    Neza Rahayu Palapa


    Full Text Available The synthesis of hydrotalcite and polyoxometalate H4[αSiW12O40].nH2O with the ratio (2:1, (1:1, (1:2 and (1:3 has been done. The product of intercalation was characterized using FT-IR spectrophotometer, XRD, and TG-DTA. Polyoxometalate H4[αSiW12O40].nH2O intercalated layered double hydroxide was optimised to use as adsorbent Congo red dye. Characterization using FT-IR was not showing the optimal insertion process. The result using XRD characterization was showed successful of polyoxometalate H4[αSiW12O40].nH2O inserted layered double hydroxide with a ratio (1:1 which the basal spacing was expanded from 7,8 Ȧ to 9,81 Ȧ. Furthermore, the thermal analysis was performed using TG-DTA. The result show that the decomposition of polyoxometalate H4[αSiW12O40].nH2O intercalated  hydrotalcite with ratio (1:1 was occured at 80oC to 400oC with a loss of OH in the layer at 150oC to 220oC, and then the decomposition of the compound polyoxometalate H4[αSiW12O40].nH2O at 350oC to 420oC. Keywords: Hydrotalcite, Layered Double Hydroxide, Polyoxometalate, Intercalation

  11. Understanding geological processes: Visualization of rigid and non-rigid transformations (United States)

    Shipley, T. F.; Atit, K.; Manduca, C. A.; Ormand, C. J.; Resnick, I.; Tikoff, B.


    Visualizations are used in the geological sciences to support reasoning about structures and events. Research in cognitive sciences offers insights into the range of skills of different users, and ultimately how visualizations might support different users. To understand the range of skills needed to reason about earth processes we have developed a program of research that is grounded in the geosciences' careful description of the spatial and spatiotemporal patterns associated with earth processes. In particular, we are pursuing a research program that identifies specific spatial skills and investigates whether and how they are related to each other. For this study, we focus on a specific question: Is there an important distinction in the geosciences between rigid and non-rigid deformation? To study a general spatial thinking skill we employed displays with non-geological objects that had been altered by rigid change (rotation), and two types of non-rigid change ("brittle" (or discontinuous) and "ductile" (or continuous) deformation). Disciplinary scientists (geosciences and chemistry faculty), and novices (non-science faculty and undergraduate psychology students) answered questions that required them to visualize the appearance of the object before the change. In one study, geologists and chemists were found to be superior to non-science faculty in reasoning about rigid rotations (e.g., what an object would look like from a different perspective). Geologists were superior to chemists in reasoning about brittle deformations (e.g., what an object looked like before it was broken - here the object was a word cut into many fragments displaced in different directions). This finding is consistent with two hypotheses: 1) Experts are good at visualizing the types of changes required for their domain; and 2) Visualization of rigid and non-rigid changes are not the same skill. An additional important finding is that there was a broad range of skill in both rigid and non-rigid

  12. Brownian dynamics of confined rigid bodies

    Energy Technology Data Exchange (ETDEWEB)

    Delong, Steven; Balboa Usabiaga, Florencio; Donev, Aleksandar, E-mail: [Courant Institute of Mathematical Sciences, New York University, New York, New York 10012 (United States)


    We introduce numerical methods for simulating the diffusive motion of rigid bodies of arbitrary shape immersed in a viscous fluid. We parameterize the orientation of the bodies using normalized quaternions, which are numerically robust, space efficient, and easy to accumulate. We construct a system of overdamped Langevin equations in the quaternion representation that accounts for hydrodynamic effects, preserves the unit-norm constraint on the quaternion, and is time reversible with respect to the Gibbs-Boltzmann distribution at equilibrium. We introduce two schemes for temporal integration of the overdamped Langevin equations of motion, one based on the Fixman midpoint method and the other based on a random finite difference approach, both of which ensure that the correct stochastic drift term is captured in a computationally efficient way. We study several examples of rigid colloidal particles diffusing near a no-slip boundary and demonstrate the importance of the choice of tracking point on the measured translational mean square displacement (MSD). We examine the average short-time as well as the long-time quasi-two-dimensional diffusion coefficient of a rigid particle sedimented near a bottom wall due to gravity. For several particle shapes, we find a choice of tracking point that makes the MSD essentially linear with time, allowing us to estimate the long-time diffusion coefficient efficiently using a Monte Carlo method. However, in general, such a special choice of tracking point does not exist, and numerical techniques for simulating long trajectories, such as the ones we introduce here, are necessary to study diffusion on long time scales.

  13. Polynuclear complexes of main group and transition metals with polyaminopolycarboxylate and polyoxometalate. (United States)

    Zhang, Chun-Hua; Chen, Ya-Guang; Tang, Qun; Liu, Shu-Xia


    Six supramolecular compounds constructed by main group and transition metals, polyoxotungstates (SiW(12)O(40)(4-)) and trans-N,N,N',N'-1,2-cyclohexanediaminotetraacetic acid (H(4)CyDTA), (NH(4))(3)[Ni(4)Na(H(2)O)(10)(CyDTA)(2)][SiW(12)O(40)]·10H(2)O (1) (NH(4))(2)[Cu(3)Na(2)(HCyDTA)(2)(H(2)O)(13)][SiW(12)O(40)]·5H(2)O (2), (NH(4))(2)[Zn(5)(CyDTA)(2)(H(2)O)(16)][SiW(12)O(40)]·8H(2)O (3), (NH(4))(4)[Cd(4)(CyDTA)(2)(H(2)O)(8)][SiW(12)O(40)]·6H(2)O (4), (NH(4))(4)[Sr(3)(HCyDTA)(2)(H(2)O)(14)][SiW(12)O(40)]·2H(2)O (5) and [Ca(4)(H(2)CyDTA)(2)(H(2)O)(22)][SiW(12)O(40)]·8H(2)O (6), were synthesized in aqueous solution and characterized by IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction techniques. Single-crystal structure analyses indicate they are constructed by the complexes with different nuclearity and polyoxometalates. In the sequence of Ni, Cu, Zn the nuclearity of the homometallic complex units increases from 2 to 5. Cadmium ions gives a tetranuclear complex with a compact structure. In 5 and 6 the main group metal ions and CyDTA form polymeric chains. CyDTA exhibits rather different coordination patterns to main group metal ions and transition metal ions due to their ionic radii and electronic configuration. The complex units and polyoxometalates arrange in different patterns due to the different shapes of the complex units. The compounds exhibit different thermal decomposition processes and the formation of compounds 3 and 4 quenches ligand-centered emissions and gives a ligand-to-metal emission. The study on various temperature susceptibilities of 1 and 2 shows that there is an antiferromagnetic coupling in the two compounds but coupling patterns are different.

  14. Rigid gas permeable lenses and patient management. (United States)

    Terry, R; Schnider, C; Holden, B A


    The introduction of new rigid gas permeable (RGP) contact lens materials provides the practitioner with a number of alternatives for patient management. But whatever the lens materials used, problems related to the lenses, care and maintenance solutions, and patients may arise. This paper examines concerns such as parameter instability, durability of lenses, compatibility of materials and solutions, patient education and compliance, 3 and 9 o'clock staining, corneal distortion, and lid changes. Suggestions are made on ways to avoid or minimize problems related to RGP lens wear.

  15. Mechanical Characterization of Rigid Polyurethane Foams

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Wei-Yang [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Mechanics of Materials


    Foam materials are used to protect sensitive components from impact loading. In order to predict and simulate the foam performance under various loading conditions, a validated foam model is needed and the mechanical properties of foams need to be characterized. Uniaxial compression and tension tests were conducted for different densities of foams under various temperatures and loading rates. Crush stress, tensile strength, and elastic modulus were obtained. A newly developed confined compression experiment provided data for investigating the foam flow direction. A biaxial tension experiment was also developed to explore the damage surface of a rigid polyurethane foam.

  16. Gabapentin for decerebrate rigidity: a case report. (United States)

    Kao, Chuen-Der; Chen, Jen-Tse; Lai, Kuan-Lin; Chang, Jiun-Bin; Wu, Zin-An; Liao, Kwong-Kum


    A 48-year-old woman suddenly lost consciousness as a result of a right rostral pontine tegmentum haemorrhage. The patient presented with decerebrate rigidity (DR) and regained full consciousness 5 days after the initial onset. The patient was given gabapentin 1200 mg/day nasogastrically and her DR significantly improved, although other antiepileptic drugs such as phenytoin and carbamazepine were given in larger dosages to decrease muscle hypertonicity. The patients' preserved consciousness and motor-evoked potentials to transcranial magnetic stimulation indicated a derangement of the extrapyramidal tracts with preservation of the pyramidal tracts. This case report discusses the possible mechanisms of action of gabapentin in DR.

  17. Vertebral Column Resection for Rigid Spinal Deformity. (United States)

    Saifi, Comron; Laratta, Joseph L; Petridis, Petros; Shillingford, Jamal N; Lehman, Ronald A; Lenke, Lawrence G


    Broad narrative review. To review the evolution, operative technique, outcomes, and complications associated with posterior vertebral column resection. A literature review of posterior vertebral column resection was performed. The authors' surgical technique is outlined in detail. The authors' experience and the literature regarding vertebral column resection are discussed at length. Treatment of severe, rigid coronal and/or sagittal malalignment with posterior vertebral column resection results in approximately 50-70% correction depending on the type of deformity. Surgical site infection rates range from 2.9% to 9.7%. Transient and permanent neurologic injury rates range from 0% to 13.8% and 0% to 6.3%, respectively. Although there are significant variations in EBL throughout the literature, it can be minimized by utilizing tranexamic acid intraoperatively. The ability to correct a rigid deformity in the spine relies on osteotomies. Each osteotomy is associated with a particular magnitude of correction at a single level. Posterior vertebral column resection is the most powerful posterior osteotomy method providing a successful correction of fixed complex deformities. Despite meticulous surgical technique and precision, this robust osteotomy technique can be associated with significant morbidity even in the most experienced hands.

  18. Public policies targeting labour market rigidities

    Directory of Open Access Journals (Sweden)

    Andreea Claudia ŞERBAN


    Full Text Available Labour market rigidity becomes an issue of increasing importance under conditions of shocks associated with the economic crisis due to the need to increase the adaptability and responsiveness to them. Thus, labour market policies must be directed towards mitigating rigidities caused by institutional or demographic factors or certain mismatch between demand and supply of education qualifications. This paper highlights the major role of the active labour market policies targeting the increase of labour flexibility, stressing the importance and impact on the ability to adapt quickly and effectively to macroeconomic shocks. Located on a declining trend in the years preceding the crisis, spending on labour market policies increased in 2009 in all the Member States of the European Union. Spending differences are significant between countries, Romania being at the lowest end of the European Union. This requires special attention because the increased adaptability of workers through training, as active measure, is of major importance considering the increased speed of changes in the labour market.

  19. EGFR and HER2 activate rigidity sensing only on rigid matrices (United States)

    Saxena, Mayur; Liu, Shuaimin; Yang, Bo; Hajal, Cynthia; Changede, Rishita; Hu, Junqiang; Wolfenson, Haguy; Hone, James; Sheetz, Michael P.


    Epidermal growth factor receptor (EGFR) interacts with integrins during cell spreading and motility, but little is known about the role of EGFR in these mechanosensing processes. Here we show, using two different cell lines, that in serum- and EGF-free conditions, EGFR or HER2 activity increase spreading and rigidity-sensing contractions on rigid, but not soft, substrates. Contractions peak after 15-20 min, but diminish by tenfold after 4 h. Addition of EGF at that point increases spreading and contractions, but this can be blocked by myosin-II inhibition. We further show that EGFR and HER2 are activated through phosphorylation by Src family kinases (SFK). On soft surfaces, neither EGFR inhibition nor EGF stimulation have any effect on cell motility. Thus, EGFR or HER2 can catalyse rigidity sensing after associating with nascent adhesions under rigidity-dependent tension downstream of SFK activity. This has broad implications for the roles of EGFR and HER2 in the absence of EGF both for normal and cancerous growth.

  20. Parkinson's disease rigidity: relation to brain connectivity and motor performance

    Directory of Open Access Journals (Sweden)

    Nazanin eBaradaran


    Full Text Available Objective: 1 To determine the brain connectivity pattern associated with clinical rigidity scores in Parkinson's disease (PD and 2 to determine the relation between clinically-assessed rigidity and quantitative metrics of motor performance.Background: Rigidity, the resistance to passive movement, is exacerbated in PD by asking the subject to move the contralateral limb, implying that rigidity involves a distributed brain network. Rigidity mainly affects subjects when they attempt to move; yet the relation between clinical rigidity scores and quantitative aspects of motor performance are unknown.Methods: Ten clinically diagnosed PD patients (off medication and ten controls were recruited to perform an fMRI squeeze-bulb tracking task that included both visually guided and internally guided features. The direct functional connectivity between anatomically defined regions of interest was assessed with Dynamic Bayesian Networks (DBNs. Tracking performance was assessed by fitting Linear Dynamical System (LDS models to the motor performance, and was compared to the clinical rigidity scores. A cross-validated Least Absolute Shrinkage and Selection Operator (LASSO regression method was used to determine the brain connectivity network that best predicted clinical rigidity scores.Results: The damping ratio of the LDS models significantly correlated with clinical rigidity scores (p < 10-4. An fMRI connectivity network in subcortical and primary and premotor cortical regions accurately predicted clinical rigidity scores (p < 10-5. Conclusions: A widely distributed cortical/subcortical network is associated with rigidity observed in PD patients, which reinforces the importance of altered functional connectivity in the pathophysiology of PD. PD subjects with higher rigidity scores tend to have less overshoot in their tracking performance, and damping ratio may represent a robust, quantitative marker of the motoric effects of increasing rigidity.

  1. Use of polyoxometalate catalysts in ionic liquids to enhance the dissolution and delignification of woody biomass. (United States)

    Sun, Ning; Jiang, Xinyu; Maxim, Mirela L; Metlen, Andreas; Rogers, Robin D


    A well-known polyoxometalate, [PV₂Mo₁₀O₄₀]⁵⁻, in both acidic (acidic POM, H₅[PV₂Mo₁₀O₄₀]) and ionic liquid-compatible form ([C₂mim]POM, [1-ethyl-3-methylimidazolium]₄H[PV₂Mo₁₀O₄₀]), has been studied as a catalyst for the dissolution and delignification of wood in the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C(2) mim]OAc). Differences were observed with variables such as the form of POM, POM loading, and reaction conditions. Generally, the addition of POM leads to a faster dissolution, a lower lignin content in the recovered cellulose-rich materials (isolated pulp), and a lower isolated yield of lignin due to its oxidation. Acidic POM decreases the lignin content of the pulp without compromising the yield of the pulp. [C₂mim]POM in the IL facilitates greater delignification (lower lignin content in pulp) than the IL with acidic POM; however, the overall pulp yield is also lower indicating some degradation of the carbohydrates. The POM can be recovered with [C₂mim]OAc after evaporation of the reconstitution solvent (e.g., acetone/water) and can be reused, albeit with some loss of POM and loss of POM activity under the current conditions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Design and synthesis of polyoxometalate-framework materials from cluster precursors (United States)

    Vilà-Nadal, Laia; Cronin, Leroy


    Inorganic oxide materials are used in semiconductor electronics, ion exchange, catalysis, coatings, gas sensors and as separation materials. Although their synthesis is well understood, the scope for new materials is reduced because of the stability limits imposed by high-temperature processing and top-down synthetic approaches. In this Review, we describe the derivatization of polyoxometalate (POM) clusters, which enables their assembly into a range of frameworks by use of organic or inorganic linkers. Additionally, bottom-up synthetic approaches can be used to make metal oxide framework materials, and the features of the molecular POM precursors are retained in these structures. Highly robust all-inorganic frameworks can be made using metal-ion linkers, which combine molecular synthetic control without the need for organic components. The resulting frameworks have high stability, and high catalytic, photochemical and electrochemical activity. Conceptually, these inorganic oxide materials bridge the gap between zeolites and metal-organic frameworks (MOFs) and establish a new class of all-inorganic POM frameworks that can be designed using topological and reactivity principles similar to MOFs.

  3. Incorporation of cationic electron donor of Ni-pyridyltetrathiafulvalene with anionic electron acceptor of polyoxometalate. (United States)

    Tsunashima, Ryo; Matsumoto, Takumi; Hoshino, Norihisa; Niiho, Wataru; Kimura, Mizuki; Kondo, Kei; Suyama, Yoshihiko; Nishioka, Yukihiro; Kawamata, Jun; Noro, Shin-ichiro; Nakamura, Takayoshi; Akutagawa, Tomoyuki; Ishiguro, Katsuya


    A new salt-[Ni(II)(DMSO)(5)(TTFPy)](2)[α-SiW(12)O(40)] (1)-based on polyoxometalates was prepared by coordinating a cationic electron donor of pyridyltetrathiafulvalene (TTFPy) with Ni(II). Although the TTFPy molecule did not form a salt with the anionic α-[SiW(VI)(12)O(40)](4-) because of the weak charge-transfer (CT) interaction, the coordination of Ni with the pyridyl moiety permitted salt formation driven by electrostatic interaction, giving a single crystal of 1. Crystallographic analysis, UV-vis and IR spectroscopy and electrochemical characterization revealed that the fully oxidized α-[SiW(VI)(12)O(40)](4-) was crystallized with the neutral TTFPy moiety from the acetonitrile solution because of the low electron-withdrawing ability of α-[SiW(VI)(12)O(40)](4-), forming a brown-orange crystal. The crystal colour quickly turned to black by immersing in methanol, due to CT from TTF moiety to α-[SiW(VI)(12)O(40)](4-), which was caused by the solvent effect. Increase in the solvent acceptor number from 18.9 for acetonitrile to 41.3 for methanol resulted in the enhancement of the electron withdrawing ability of α-[SiW(VI)(12)O(40)](4-) by 0.317 V in methanol.

  4. pH-responsive controlled release of antitumour-active polyoxometalate from mesoporous silica materials. (United States)

    Sun, Guoying; Chang, Yaping; Li, Siheng; Li, Qiuyu; Xu, Rui; Gu, Jianmin; Wang, Enbo


    Two efficient pH-responsive oral delivery systems have been fabricated through a dative bonding between the amino-functionalized mesoporous silica materials, including MCM-41-type mesoporous silica nanospheres (MMSNs) and bimodal mesoporous silica microspheres (BMSMs), and an antitumour-active polyoxometalate K(8)H(2)[Ti(H(2)O)](3)SiW(9)O(34) (Ti(3)SiW(9)). The Ti(3)SiW(9) loaded in the pores of MMSNs and BMSMs are up to 23.72 wt% and 28.69 wt% at pH 6.5, respectively. Both delivery systems reveal an increase of Ti(3)SiW(9) release under mildly alkaline conditions, while zero premature release is observed under acidic and neutral conditions, making them ideal for use as a new class of colon-specific oral delivery systems. Importantly, these systems provide very promising possibilities for many medical applications that require an increase or decrease in the rate of drug release, depending on disease evolution. Upon incorporation into mesoporous silica materials, the antitumour activity of Ti(3)SiW(9) against Ls-174-T was improved from 0.8 mg mL(-1) to 0.186 and 0.102 mg mL(-1) for Ti(3)SiW(9)@MMSN-NH(2) and Ti(3)SiW(9)@BMSM-NH(2), respectively.

  5. Self-assembled multilayer films based on a Keggin-type polyoxometalate and polyaniline. (United States)

    Wang, Yonghui; Guo, Caixin; Chen, Yanwei; Hu, Changwen; Yu, Wenhua


    Multilayer ultrathin films were fabricated from partially doped polyaniline (PAN) and a Keggin-type polyoxometalate [alpha-SiW(12)O(40)](4-) (alpha-SiW(12)) in aqueous solution via the layer-by-layer self-assembly technique and characterized by UV-vis, FTIR, and X-ray photoelectron spectra (XPS), ellipsometry, scanning electron microscopy (SEM), and atomic force microscopy (AFM). UV-vis spectroscopy shows that the absorbance values at characteristic wavelengths of the multilayer films increase almost linearly with the number of PAN/alpha-SiW(12) bilayers, suggesting that the deposition process is regular and highly reproducible from layer to layer. FTIR and XPS spectra confirm the incorporation of alpha-SiW(12) and PAN into the films. Ellipsometric measurements show that the PAN/alpha-SiW(12) bilayer thickness increases with the increasing PAN solution concentration. SEM and AFM images indicate that the film surface is relatively uniform and smooth. In addition, the electrical conductivities of the multilayer films doped with hydrochloric acid were also measured.

  6. Hexameric polyoxometalates decorated by six 3d-4f heterometallic clusters. (United States)

    Zhang, Zhi-Ming; Li, Yang-Guang; Yao, Shuang; Wang, En-Bo


    Two nanosized hexameric polyoxometalate-based solid state assemblies (H(2)en)(6)Na(15)K(9)[Dy(6)Fe(6)(H(2)O)(12)(SiW(10)O(38))(6)]·34H(2)O (1) and K(13)Na(17)[H(2)en](3)[Tb(6)Fe(6)(H(2)O)(12)(SiW(10)O(38))(6)]·40H(2)O (2) (en = 1,2-ethylenediamine), decorated by six [Ln-(μ(3)-O)(3)-Fe] 3d-4f heterometallic clusters, have been synthesized by the hydrothermal method, and characterized by IR, element analysis, magnetic studies and the single-crystal X-ray analyses. The detailed study of the synthetic conditions reveals that the use of the organic ligands, pH value and the reaction temperature all play important roles in the synthesis of the 3d-4f heterometallic POMs. Magnetic study suggests the presence of antiferromagnetic interactions in these two compounds. This journal is © The Royal Society of Chemistry 2011

  7. Polyoxometalate/laccase-mediated oxidative polymerization of catechol for textile dyeing. (United States)

    Kim, Suyeon; Silva, Carla; Evtuguin, Dmitry V; Gamelas, José A F; Cavaco-Paulo, Artur


    The synergistic effect between polyoxometalates (POMs), namely K(5)[SiW(11)V(V)O(40)]·11H(2)O and H(5)[PMo(10)V(V) (2)O(40)]·13H(2)O and laccase from ascomycete Myceliophthora thermophila has been employed for the first time in oxidative polymerization of catechol. Such a laccase-mediator system allowed the formation of a relatively high molecular weight polycatechol as confirmed by size exclusion chromatography and electrospray ionization mass spectrometry (ESI-MS) (3990 Da when using K(5)[SiW(11)V(V)O(40)]·11H(2)O and 3600 Da with H(5)[PMo(10)V(V) (2)O(40)]·13H(2)O). The synthesized polymers were applied as dyes for the dyeing of flax fabrics. The color intensity of flax fabrics colored with polymer solutions was evaluated by diffuse reflectance spectrophotometry via k/s measurements (+10% of fixation ratio). A new synthetic process allowed a dyeing polymer, provided upon flax coloration, better color fixation and color resistance when compared to that obtained by conventional synthesis with laccase solely or with addition of organic mediator (1-hydroxybenzotriazole).

  8. Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties (United States)

    Tang, Qun; Liu, Shu-Xia; Liang, Da-Dong; Ma, Feng-Ji; Ren, Guo-Jian; Wei, Feng; Yang, Yuan; Li, Cong-Cong


    A series of lanthanide-organic complexes based on polyoxometalates (POMs) [Ln2(DNBA)4(DMF)8][W6O19] (Ln=La(1), Ce(2), Sm(3), Eu(4), Gd(5); DNBA=3,5-dinitrobenzoate; DMF=N,N-dimethylformamide) has been synthesized. These complexes consist of [W6O19]2- and dimeric [Ln2(DNBA)4(DMF)8]2+ cations. The luminescence properties of 4 are measured in solid state and different solutions, respectively. Notably, the emission intensity increases gradually with the increase of solvent permittivity, and this solvent effect can be directly observed by electrospray mass spectrometry (ESI-MS). The analyses of ESI-MS show that the eight coordinated solvent DMF units of dimeric cation are active. They can move away from dimeric cations and exchange with solvent molecules. Although the POM anions escape from 3D supramolecular network, the dimeric state structure of [Ln2(DNBA)4]2+ remains unchanged in solution. The conservation of red luminescence is attributed to the maintenance of the aggregated state structures of dimeric cations.

  9. Human versus Robots in the Discovery and Crystallization of Gigantic Polyoxometalates. (United States)

    Duros, Vasilios; Grizou, Jonathan; Xuan, Weimin; Hosni, Zied; Long, De-Liang; Miras, Haralampos N; Cronin, Leroy


    The discovery of new gigantic molecules formed by self-assembly and crystal growth is challenging as it combines two contingent events; first is the formation of a new molecule, and second its crystallization. Herein, we construct a workflow that can be followed manually or by a robot to probe the envelope of both events and employ it for a new polyoxometalate cluster, Na6 [Mo120 Ce6 O366 H12 (H2 O)78 ]⋅200 H2 O (1) which has a trigonal-ring type architecture (yield 4.3 % based on Mo). Its synthesis and crystallization was probed using an active machine-learning algorithm developed by us to explore the crystallization space, the algorithm results were compared with those obtained by human experimenters. The algorithm-based search is able to cover ca. 9 times more crystallization space than a random search and ca. 6 times more than humans and increases the crystallization prediction accuracy to 82.4±0.7 % over 77.1±0.9 % from human experimenters. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  10. Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media (United States)

    Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.


    Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

  11. New trends in polyoxometalate photoredox chemistry: from photosensitisation to water oxidation catalysis. (United States)

    Streb, Carsten


    Molecular metal oxide clusters, so-called polyoxometalates (POM) have been extensively used as homogeneous photocatalysts in various photoredox reactions such as the oxidation of alkanes, alkenes and alcohols as well as the light-induced mineralisation of various organic and inorganic pollutants. The more general application of POMs as photoactive compounds, in particular in solar energy harnessing, has been hampered as the clusters typically absorb light in the UV-region only. Over the past decade, concepts have been put forward on how the reactivity of this class of compounds can be optimised to improve their overall photoactivity, and a particular focus has been on the design of photocatalytic processes which allow the conversion of solar light into useful chemical reactivity. This perspective gives a brief overview of general aspects of POM photochemistry and critically discusses the advantages and challenges of a range of POM-based systems for photooxidations and photoreductions with a focus on the development of sustainable solar light conversion systems.

  12. Challenges in polyoxometalate-mediated aerobic oxidation catalysis: catalyst development meets reactor design. (United States)

    Lechner, Manuel; Güttel, Robert; Streb, Carsten


    Selective catalytic oxidation is one of the most widely used chemical processes. Ideally, highly active and selective catalysts are used in combination with molecular oxygen as oxidant, leading to clean, environmentally friendly process conditions. For homogeneous oxidation catalysis, molecular metal oxide anions, so-called polyoxometalates (POMs) are ideal prototypes which combine high reactivity and stability with chemical tunability on the molecular level. Typically, POM-mediated aerobic oxidations are biphasic, using gaseous O2 and liquid reaction mixtures. Therefore, the overall efficiency of the reaction is not only dependent on the chemical components, but requires chemical engineering insight to design reactors with optimized productivity. This Perspective shows that POM-mediated aerobic liquid-phase oxidations are ideal reactions to be carried out in microstructured flow reactors as they enable facile mass and energy transfer, provide large gas-liquid interfaces and can be easily upscaled. Recent advances in POM-mediated aerobic catalytic oxidations are therefore summarized with a focus on technological importance and mechanistic insight. The principles of reactor design are discussed from a chemical engineering point of view with a focus on homogeneous oxidation catalysis using O2 in microfluidic systems. Further, current limitations to catalytic activity are identified and future directions based on combined chemistry and chemical engineering approaches are discussed to show that this approach could lead to sustainable production methods in industrial chemistry based on alternative energy sources and chemical feedstocks.

  13. Theoretical simulation of CO2 capture in organic cage impregnated with polyoxometalates. (United States)

    Gao, Jingyuan; Li, Wenliang; Zhang, Jingping


    To explore the adsorption and separation properties of CO2 in a novel material consisting of a series of polyoxometalates (POMs) impregnated within supramolecular porous catenane (shorted as SPC), grand canonical Monte Carlo (GCMC) simulations and ab initio calculations were used. GCMC simulations showed this impregnation can enhance CO2 /CH4 (or CO2 /N2 ) selectivity almost 30 times compared to the bare SPC due to the strong interaction of CO2 with the nPOMs@SPC structures. And, the loading of CO2 inhibits the adsorption of CH4 (or N2 ) as CO2 occupying the preferred adsorption sites. Furthermore, the effect of number, mass, and volume of POMs inserted in SPC on CO2 /CH4 (or CO2 /N2 ) selectivity over large pressure range was investigated in detail. Additionally, the accurate ab initio calculations further confirmed our GCMC simulations. As a result, the proposed nPOMs@SPC structures are promising candidates for CO2 /N2 and CO2 /CH4 separations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  14. A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization. (United States)

    Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo


    A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Synthesis of diamondoid lanthanide-polyoxometalate solids as tunable photoluminescent materials. (United States)

    Zhao, Wen-Feng; Zou, Chao; Shi, Lian-Xu; Yu, Jian-Can; Qian, Guo-Dong; Wu, Chuan-De


    The reaction between polyoxometalate (POM) [TBA](12)[WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] (TBA = tetrabutyl ammonium) and lanthanide (Ln) nitrate (Ln = La, Eu and Tb) in a mixed solvent of CH(3)CN and DMF yielded three noncentrosymmetric diamondoid Ln-POM solid materials, {[Ln(2)(DMF)(8)(H(2)O)(6)][ZnW(12)O(40)]}·4DMF (Ln-POM; Ln = La, Eu and Tb). In these compounds, the {ZnW(12)O(40)} unit, transferred from the metastable [WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] cluster, acts as a tetradentate ligand to connect with four Ln nodes, while the Ln ion links up two {ZnW(12)O(40)} units. These compounds generated interesting luminescence emissions that are dependent on the Ln ions and their ratios. White light emission was obtained by a doped approach with a rational ratio of the Eu(3+) and Tb(3+) ions.

  16. Functionalization and post-functionalization: a step towards polyoxometalate-based materials. (United States)

    Proust, Anna; Matt, Benjamin; Villanneau, Richard; Guillemot, Geoffroy; Gouzerh, Pierre; Izzet, Guillaume


    Polyoxometalates (POMs) have remarkable properties and a great deal of potential to meet contemporary societal demands regarding health, environment, energy and information technologies. However, implementation of POMs in various functional architectures, devices or materials requires a processing step. Most developments have considered the exchange of POM counterions in an electrostatically driven approach: immobilization of POMs on electrodes and other surfaces including oxides, embedding in polymers, incorporation into Layer-by-Layer assemblies or Langmuir-Blodgett films and hierarchical self-assembly of surfactant-encapsulated POMs have thus been thoroughly investigated. Meanwhile, the field of organic-inorganic POM hybrids has expanded and offers the opportunity to explore the covalent approach for the organization or immobilization of POMs. In this critical review, we focus on the use of POM hybrids in selected fields of applications such as catalysis, energy conversion and molecular nanosciences and we endeavor to discuss the impact of the covalent approach compared to the electrostatic one. The synthesis of organic-inorganic POM hybrids starting from bare POMs, that is the direct functionalization of POMs, is well documented and reliable and efficient synthetic procedures are available. However, as the complexity of the targeted functional system increases a multi-step strategy relying on the post-functionalization of preformed hybrid POM platforms could prove more appealing. In the second part of this review, we thus survey the synthetic methodologies of post-functionalization of POMs and critically discuss the opportunities it offers compared to direct functionalization.

  17. Heterogeneous oxidative desulfurization of diesel fuel catalyzed by mesoporous polyoxometallate-based polymeric hybrid. (United States)

    Yang, Huawei; Jiang, Bin; Sun, Yongli; Zhang, Luhong; Huang, Zhaohe; Sun, Zhaoning; Yang, Na


    In this work, the simple preparation of novel polymer supported polyoxometallates (POMs) catalysts has been reported. Soluble task-specific cross-linked poly (ionic liquid) (PIL) was prepared with N,​N-​dimethyl-​dodecyl-​(4-​vinylbenzyl) ammonium chloride and divinylbenzene as co-monomers. The as-prepared cationic PILs were assembled with different commercial POMs to form the interlinked mesoporous catalysts, and the formation mechanism was provided. The catalytic oxidation activities of the catalysts were closely related to the formation pathway of their corresponding peroxide active species. The catalyst with H2W12O4210- as counterion, which exhibited the best activity in the oxidation of benzothiophene (BT) and dibenzothiophene (DBT) to sulfones in model oil with hydrogen peroxide (H2O2, 30wt%) as oxidant, was characterized by different techniques and systematically studied for its sulfur removal performance. As for the oxidative desulfurization of a real diesel, it was observed that almost all of the original sulfur compounds could be completely converted, and the catalyst could be reused for at least eight cycles without noticeable changes in both catalytic activity and chemical structure. In the end, a catalytic mechanism was put forward with the assistant of Raman analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Polyoxometallate-based layered composite films on electrodes; Preparation through alternate immersions in modification solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ingersoll, D.; Kulesza, P.J.; Faulkner, L.R. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry and Materials Research Lab.


    An approach for the modification of electrode surfaces with thin films composed of polyoxometallate anions and large water-soluble cationic species is described. In the procedure, a ca. monolayer of the iso- or heteropolyanion is first adsorbed onto the electrode surface. By immersing the resulting system into a solution containing a large monovalent, multivalent, or polyvalent cation, a composite layer is formed due to the interaction between the adsorbed polyanion and the solution cation. After rinsing, this electrode is reimmersed into the solution of the polyanion, and immobilization of an additional quantity of the polyanion takes place. By the repeated and alternate immersions into the anionic and cationic modification solutions, the amount of material on the electrode can be increased systematically in a controlled fashion leading to stable three-dimensional multilayered molecular assemblies. The immobilized polyanions (isopolymolybdate, phosphotungstate, or silicotungstate) have redox characteristics similar to those of their solution counterparts. The precipitate-forming cationic species include tetrabutylammonium and tris(1,10-phenanthroline)-iron(II) ions, as well as protonated poly(4-vinylpyridine). Composite films of heteropoly-12-tungstate anions with protonated poly(4-vinylpyridine) are the most robust. The approach permits introduction of multiple redox centers into the thin films on electrodes, formation of bilayer-type systems, and, in some cases, even insulating coatings. Details of the preparation and physicochemical, particularly electrochemical, properties of the produced systems are described.

  19. Solid-state electroanalytical characterization of the nonaqueous proton-conducting redox gel containing polyoxometallates

    Energy Technology Data Exchange (ETDEWEB)

    Lewera, Adam [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Zukowska, Grazyna [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Chojak, Malgorzata [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Wieczorek, Wladyslaw [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)]. E-mail:


    A novel polymetacrylate-based redox-conducting polymeric gel, into which Keggin-type polyoxometallate, phosphododecatungstic acid (H{sub 3}PW{sub 12}O{sub 40}), had been incorporated, was electrochemically characterized in the absence of external liquid supporting electrolyte using an ultramicrodisk-working electrode. The phosphotungstate component (15 wt.% of the gel block) was entrapped as the polar organic solvent solution within pores of the polymer matrix. H{sub 3}PW{sub 12}O{sub 40} plays bifunctional role: it provides well-behaved redox centers and serves as strong acid (source of mobile protons). The solid-state voltammetric properties of the system are defined by the reversible one-electron transfers between phosphotungstate redox centers. The following parameters have been determined from the combination of potential step experiments performed in two limiting (radial and linear) diffusional regimes: the concentration of heteropolytungstate redox centers, 6 x 10{sup -2} mol dm{sup -3}, and the apparent diffusion coefficient, 5 x 10{sup -7} cm{sup 2} s{sup -1}. The room temperature ionic (protonic) conductivity of the bulk gel was equal to 1.6 x 10{sup -3} S cm{sup -1}. The charge propagation mechanism was found to be primarily controlled by physical diffusion of heteropolytungstate units within the gel pores rather than by electron hopping (self-exchange) between mixed-valence sites.

  20. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. (United States)

    Voitl, Tobias; Rudolf von Rohr, Philipp


    A novel approach has been developed in order to use Kraft lignin as a renewable resource for the production of chemicals. The concept is based on the use of polyoxometalates as reversible oxidants and on the use of radical scavengers, which prevent lignin fragments from repolymerizing. The oxidation of Kraft lignin, which is a potential source of functionalized phenols, by H3PMo12O40 in water yields a relatively small amount of monomeric species detected by GC-MS. The addition of methanol to the reaction resulted in an increase in the yield of monomeric products by a factor of up to 15. Vanillin and methyl vanillate are the main products obtained, in a maximum yield of 5 wt % based on dry Kraft lignin. Methanol plays a decisive role in the prevention of repolymerization by reducing lignin-lignin condensation reactions. Furthermore, it is proposed that methanol generates small amounts of .CH3 and CH3O. radicals through the acid-catalyzed formation of dimethyl ether which couple with lignin fragments.

  1. Electrochemistry and electrocatalysis of polyoxometalate-ordered mesoporous carbon modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Zhou Ming [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Guo Liping [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China)]. E-mail:; Lin Fanyun [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Liu Haixia [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China)


    In this work, we have developed a convenient and efficient method for the functionalization of ordered mesoporous carbon (OMC) using polyoxometalate H{sub 6}P{sub 2}Mo{sub 18}O{sub 62}.xH{sub 2}O (P{sub 2}Mo{sub 18}). By the method, glassy carbon (GC) electrode modified with P{sub 2}Mo{sub 18} which was immobilized on the channel surface of OMC was prepared and characterized for the first time. The large specific surface area and porous structure of the modified OMC particles result in high heteropolyacid loading, and the P{sub 2}Mo{sub 18} entrapped in this order matrix is stable. Fourier transform infrared spectroscopy (FTIR), nitrogen adsorption-desorption isotherm and X-ray diffraction (XRD) were employed to give insight into the intermolecular interaction between OMC and P{sub 2}Mo{sub 18}. The electrochemical behavior of the modified electrode was studied in detail, including pH-dependence, stability and so on. The cyclic voltammetry (CV) and amperometry studies demonstrated that P{sub 2}Mo{sub 18}/OMC/GC electrode has high stability, fast response and good electrocatalytic activity for the reduction of nitrite, bromate, idonate, and hydrogen peroxide. The mechanism of catalysis on P{sub 2}Mo{sub 18}/OMC/GC electrode was discussed. Moreover, the development of our approach for OMC functionalization suggests the potential applications in catalysis, molecular electronics and sensors.

  2. Crystal Engineering in Supramolecular Polyoxometalate Hybrids through pH Controlled in Situ Ligand Hydrolysis. (United States)

    Roy, Soumyabrata; Mumbaraddi, Dundappa; Jain, Ankit; George, Subi J; Peter, Sebastian C


    A family of five different three-dimensional polyoxometalate (POM) based supramolecular hybrids were synthesized by a hydrothermal route under different pH using a hydrolyzable naphthalene diimide ligand. The mechanism of crystallographic phase variation of the POM-amino pyridine hybrids under different pH was studied through controlled experiments where the final hydrolyzed products were analyzed through NMR and single crystal X-ray diffraction. Different pH conditions led to variation in the extent of protonation and hydrolyzation of the ligand, yielding different phases. All of these were identified, and the structures of the supramolecular hybrids were characterized extensively. Mechanistic study proved that only the reaction conditions are responsible for the hydrolysis of the ligand and the in situ generated POM species do not have any role in it. Magnetic measurements confirmed the hexavalent oxidation states of the transition metal center (Mo) in the POM. Optical band gap measurements revealed that these hybrids are semiconducting in nature. Two of the compounds were studied for hydrogen peroxide mediated selective oxidation catalysis of small organic molecules and found to exhibit very good activity with high percentage of selectivity for the desired products of industrial importance.

  3. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution (United States)

    Rustad, James R.; Casey, William H.


    Reactions involving minerals and glasses in water are slow and difficult to probe spectroscopically but are fundamental to the performance of oxide materials in green technologies such as automotive thermoelectric power generation, CO2 capture and storage and water-oxidation catalysis; these must be made from geochemically common elements and operate in hydrous environments. Polyoxometalate ions (POMs) have structures similar to condensed oxide phases and can be used as molecular models of the oxide/water interface. Oxygen atoms in POM exchange isotopes at different rates, but, at present, there is no basis for predicting how the coordination environment and metal substitution influences rates and mechanisms. Here we identify low-energy metastable configurations that form from the breaking of weak bonds between metals and underlying highly coordinated oxygen atoms, followed by facile hydroxide, hydronium or water addition. The mediation of oxygen exchange by these stuffed structures suggests a new view of the relationship between structure and reactivity at the oxide/solution interface.

  4. Discrete covalent organic-inorganic hybrids: terpyridine functionalized polyoxometalates obtained by a modular strategy and their metal complexation. (United States)

    Santoni, Marie-Pierre; Pal, Amlan K; Hanan, Garry S; Proust, Anna; Hasenknopf, Bernold


    The rational design and synthesis of organic-inorganic hybrids as functional molecular materials relies on both the careful conception of building-blocks and the strategy for their assembly. Three families of trialkoxo polyoxometalates (Lindqvist 2, Anderson 3, Dawson 4) grafted with remote terpyridine coordination sites have been synthesized to extend the available building-blocks. These new units can be combined with metal complexes that play a role as (i) chromophores toward charge-separated systems in light-harvesting devices and (ii) coordination motifs for metal-directed self-assembly toward multifunctional molecular hybrid materials. The X-ray crystal structures of polyoxometalate-terpyridine hybrids indicate distances of 21 Å and 19 Å between the two terpyridyl coordination sites in 2 and 3, respectively, with angles between the coordination vectors of 180° and 177.4°, respectively. Lindqvist 2 displays a reduction at -0.52 V vs SCE while Anderson 3 exhibits one reversible oxidation attributed to Mn(III)/Mn(IV) (+0.75 V vs SCE) and a broad wave at -1.28 V vs SCE assigned to the Mn(III)/Mn(II) reduction. Dawson 4 displays several processes on a wide range of potentials (+0.5 to -2.0 V vs SCE) centered on V(V), W(VI) and the organic ligand in order of decreasing potentials. The grafted terpyridine ligands in Anderson 3 and Dawson 4 were successfully coordinated to {PdCl}(+) and {RuCl(3)} moieties, respectively. The polyoxometalates and transition metal complexes retain their intrinsic properties in the final assemblies.

  5. Polyoxometalates as artificial nucleases: hydrolytic cleavage of DNA promoted by a highly negatively charged Zr(IV)-substituted Keggin polyanion. (United States)

    Luong, T K N; Govaerts, I; Robben, J; Shestakova, P; Parac-Vogt, T N


    A highly negatively charged binuclear Zr(IV)-substituted Keggin polyoxometalate [{α-PW11O39Zr(μ-OH)(H2O)}2](8-) (ZrK 2 : 2) has been shown to promote the hydrolytic cleavage of phosphoester bonds in the supercoiled plasmid pUC19 DNA under physiological pH and temperature, giving relaxed and linear forms of pUC19 as hydrolysis products. The interaction between ZrK 2 : 2 and DNA was experimentally proven by circular dichroism (CD) spectroscopy and (31)P diffusion ordered NMR spectroscopy.

  6. Synthesis of gold nanosheets at a liquid/liquid interface using an amphiphilic polyoxometallate/surfactant hybrid photocatalyst. (United States)

    Kida, Tetsuya


    Control of the morphology of gold nanoparticles has received considerable attention because the physical and chemical properties of gold depend significantly on its size and shape. A novel route for obtaining 2-D gold nanostructures has been developed in which chloroaurate ions (AuCl (4)(-)) are reduced at the 2-D interface between water and chloroform using an amphiphilic polyoxometallate (SiW (12)O (40)(4-))/surfactant (dimethyldioctadecylammonium; DODA) hybrid photocatalyst under UV irradiation at room temperature in air. This simple method can readily produce large single-crystalline gold nanosheets (lateral size, ca. 20 microm; thickness, ca. 150 nm).

  7. Polyoxometalate clusters integrated into peptide chains and as inorganic amino acids: solution- and solid-phase approaches. (United States)

    Yvon, Carine; Surman, Andrew J; Hutin, Marie; Alex, Jennifer; Smith, Brian O; Long, De-Liang; Cronin, Leroy


    General synthetic methods for the grafting of peptide chains onto polyoxometalate clusters by the use of general activated precursors have been developed. Using a solution-phase approach, pre-synthesized peptides can be grafted to a metal oxide cluster to produce hybrids of unprecedented scale (up to 30 residues). An adapted solid-phase method allows the incorporation of these clusters, which may be regarded as novel hybrid unnatural amino acids, during the peptide synthesis itself. These methods may open the way for the automated synthesis of peptides and perhaps even proteins that contain "inorganic" amino acids. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. MR findings of decerebrate rigidity with preservation of consciousness. (United States)

    Kao, C-D; Guo, W-Y; Chen, J-T; Wu, Z-A; Liao, K-K


    We describe a case of decerebrate rigidity, with preservation of consciousness, caused by a discrete pontine tegmentum lesion identified on MR imaging. Lesions within a certain brain stem region are responsible for decerebrate rigidity in animal studies, but there has been a lack of MR imaging evidence in humans. This report also implies that a discrete lesion was responsible for the decerebrate rigidity, while consciousness was preserved.

  9. Observational properties of rigidly rotating dust configurations

    CERN Document Server

    Ilyas, Batyr; Yang, Jinye


    We study the observational properties of a class of exact solutions of Einstein's field equations describing stationary, axially symmetric, rigidly rotating dust. We ask the question whether such solutions can describe astrophysical rotating dark matter clouds and we probe the possibility that they may constitute an alternative to supermassive black holes at the center of galaxies. We show that light emission from accretion disks in this space-time has several differences with respect to the emission of light from accretion disks around black holes. The shape of the iron K{\\alpha} line in the reflection spectrum of accretion disks can potentially distinguish this class of solution from the Kerr metric, but this may not be possible with current X-ray missions.

  10. Settling dynamics of asymmetric rigid fibers (United States)

    Tozzi, E. J.; Scott, C. T.; Vahey, D.; Klingenberg, D. J.


    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with its center of mass following a helical trajectory. Numerical and analytical methods were used to predict translational and angular velocities as well as the evolution of the fiber orientation as a function of time. A comparison of calculated and measured values shows that it is possible to quantitatively predict complex motions of particles that have highly asymmetric shape. The relations between particle shape and settling trajectory have potential applications for hydrodynamic characterization of fiber shapes and fiber separation.

  11. Suspension of rigid spheres in shear flows (United States)

    Rahmani, Mona; Esteghamatian, Amir; Wachs, Anthony


    Suspension of rigid spheres in a plane Couette flow is studied using three-dimensional particle resolved numerical simulations. We use a fixed mesh that resolves each particle diameter using 24 points and a Distributed Lagrange Multi- plier/Fictitious Domain (DLM/FD) method. The effects of particle volume fraction and particle Reynolds number on the macrcoscopic and microscopic stresses in the suspension are examined. The kinematics of particle are also studied for a range of dilute to dense suspensions and Stokes to inertial flows. For dense suspensions and also for higher particle Reynolds numbers the particle/particle and particle/wall contacts are enhanced. For such cases, lubrication forces need to be taken into account. We compare simulations with and without the lubrication forces to conclude for what range of parameters lubrication should be incorporated into the simulations.

  12. On real structures on rigid surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kulikov, Vik S [Steklov Mathematical Institute, Russian Academy of Sciences (Russian Federation); Kharlamov, V M [Institut de Recherche Matematique Avanee Universite Louis Pasteur et CNRS 7 rue Rene Descartes (France)


    We construct examples of rigid surfaces (that is, surfaces whose deformation class consists of a unique surface) with a particular behaviour with respect to real structures. In one example the surface has no real structure. In another it has a unique real structure, which is not maximal with respect to the Smith-Thom inequality. These examples give negative answers to the following problems: the existence of real surfaces in each deformation class of complex surfaces, and the existence of maximal real surfaces in every complex deformation class that contains real surfaces. Moreover, we prove that there are no real surfaces among surfaces of general type with p{sub g}=q=0 and K{sup 2}=9. These surfaces also provide new counterexamples to the 'Dif = Def' problem.

  13. Advanced Rigid Ablative Thermal Protection Systems (United States)

    Feldman, J. D.; Gasch, M. J.; Poteet, C. C.; Szalai, Christine


    With the gradual increase in robotic rover sophistication and the desire for humans to explore the solar system, the need for reentry systems to deliver large payloads into planetary atmospheres is looming. Heritage ablative Thermal Protection Systems (TPS) using Viking or Pathfinder era materials are at or near their performance limits and will be inadequate for many future missions. Significant advances in TPS materials technology are needed in order to enable susequent human exploration missions. This paper summarizes some recent progress at NASA in developing families of advanced rigid ablative TPS that could be used for thermal protection in planetary entry missions. In particular, the effort focuses on technologies required to land heavy masses on Mars to facilitate exploration.

  14. Observational properties of rigidly rotating dust configurations

    Energy Technology Data Exchange (ETDEWEB)

    Ilyas, Batyr; Malafarina, Daniele [Nazarbayev University, Department of Physics, Astana (Kazakhstan); Yang, Jinye [Fudan University, Center for Field Theory and Particle Physics and Department of Physics, Shanghai (China); Bambi, Cosimo [Fudan University, Center for Field Theory and Particle Physics and Department of Physics, Shanghai (China); Eberhard-Karls Universitaet Tuebingen, Theoretical Astrophysics, Tuebingen (Germany)


    We study the observational properties of a class of exact solutions of Einstein's field equations describing stationary, axially symmetric, rigidly rotating dust (i.e. non-interacting particles). We ask the question whether such solutions can describe astrophysical rotating dark matter clouds near the center of galaxies and we probe the possibility that they may constitute an alternative to supermassive black holes at the center of galaxies. We show that light emission from accretion disks made of ordinary baryonic matter in this space-time has several differences with respect to the emission of light from similar accretion disks around black holes. The shape of the iron Kα line in the reflection spectrum of accretion disks can potentially distinguish this class of solutions from the Kerr metric, but this may not be possible with current X-ray missions. (orig.)

  15. Magnetic adsorbent constructed from the loading of amino functionalized Fe3O4 on coordination complex modified polyoxometalates nanoparticle and its tetracycline adsorption removal property study (United States)

    Ou, Jinzhao; Mei, Mingliang; Xu, Xinxin


    A magnetic polyoxometalates based adsorbent has been synthesized successfully through the loading of amino functionalized Fe3O4 (NH2-Fe3O4) on nanoparticle of a coordination complex modified polyoxometalates (CC/POMNP). FTIR illustrate there exist intense hydrogen bonds between NH2-Fe3O4 and CC/POMNP, which keep the stability of this adsorbent. At room temperature, this adsorbent exhibits ferromagnetic character with saturation magnetization of 8.19 emu g-1, which provides prerequisite for fast magnetic separation. Water treatment experiment illustrates this POM based magnetic adsorbent exhibits high adsorption capacity on tetracycline. The adsorption process can be described well with Temkin model, which illustrates the interaction between adsorbent and tetracycline plays the dominated role in tetracycline removal. The rapid, high efficient tetracycline adsorption ability suggests this POM based magnetic adsorbent exhibits promising prospect in medical and agriculture waste water purification. A magnetic polyoxometalates based adsorbent, which exhibits excellent tetracycline adsorption removal property has been synthesized through the loading of NH2-Fe3O4 on coordination complex modified polyoxometalates

  16. Iontophoretic transport of associates based on porous Keplerate-type cluster polyoxometalate Mo72Fe30 and containing biologically active substances (United States)

    Ostroushko, A. A.; Gagarin, I. D.; Tonkushina, M. O.; Grzhegorzhevskii, K. V.; Danilova, I. G.; Gette, I. F.; Kim, G. A.


    The possibility of iontophoretic transport through the native membranes of biologically active substances (vitamin B1 and insulin) associated with porous clusters Mo72Fe30 polyoxometalate of the Keplerate type is demonstrated for the first time in an experimental setup. The diffusion coefficient is estimated. The possibility of transferring Keplerate ions with a protective coating of biocompatible polymer polyvinylpyrrolidone is also shown.

  17. Rigid-only versus combined rigid and flexible percutaneous nephrolithotomy: a systematic review. (United States)

    Cracco, Cecilia M; Knoll, Thomas; Liatsikos, Evangelos N; Osther, Palle J; Smith, Arthur D; Scarpa, Roberto M; Scoffone, Cesare M


    Percutaneous nephrolithotomy (PNL) is usually performed worldwide with a rigid-only antegrade approach. Daily practice suggests that adding flexible nephroscopy and/or ureteroscopy to conventional rigid PNL might improve its efficacy and safety, but available evidence is weak. Appraisal of reliable outcomes of such PNL techniques would better guide intraoperative choices and optimize surgical results. Therefore, our objective was to systematically review relevant literature comparing the outcomes of rigid-only PNL and combined flexible PNLs (adding flexible nephroscopy and/or flexible ureteroscopy) for the treatment of large and/or complex upper urinary tract calculi, with regard to efficacy and safety. Ovid MedLine, PubMed, Scopus and Web of Science databases were searched in August 2016 to identify relevant studies. Article selection was performed according to the Preferred Reporting Items for Systematic Review and Meta-analysis criteria. Six articles reporting on 666 patients were included: two randomized controlled trials, two retrospective comparative studies and two case series ≥50 patients (one prospective and one retrospective). A narrative synthesis of minor evidences was also prepared. The adjunct of flexible nephroscopy and/or ureteroscopy provided better stone-free rates (range 86.7-96.97%), through a single percutaneous access most of the times and in any position, reducing the need for second-look procedures. Safety of the combined flexible procedures was improved to a variable degree, with a consensual reduction of the mean hospital stay (range 5.1-7 days). The current evidence suggests that patients with large and/or complex urolithiasis might benefit from the adjunct of flexible nephroscopy and/or ureteroscopy to rigid PNL.

  18. Precursor salt assisted syntheses of high-index faceted concave hexagon and nanorod-like polyoxometalates (United States)

    Pal, Jaya; Ganguly, Mainak; Mondal, Chanchal; Negishi, Yuichi; Pal, Tarasankar


    This paper describes an effective method for a precursor salt assisted fabrication and reshaping of two different polyoxometalates [(NH4)2Cu(MoO4)2 (ACM) and Cu3(MoO4)2(OH)2 (CMOH)] into five distinctive shapes through straightforward and indirect routes. Explicit regulation of the structural arrangements of ACM and CMOH has been studied in detail with altered precursor salt concentration employing our laboratory developed modified hydrothermal (MHT) method. Morphologically different ACM 3D architectures are evolved with higher molybdate concentration, whereas 1D growth of CMOH is observed with increased copper concentration. Interesting morphological transformation of the products has been accomplished employing one precursor salt at a time without using any other foreign reagent. It has been proven that large ACMs become labile in the presence of incoming Cu(ii) and NH4+ ions of the precursor salts. A new strategy for the conversion of faceted ACMs (hexagonal plate, circular plate and hollow flower) to exclusive CMOH nanorods through a Cu(ii) assisted reaction has been adopted. According to thermodynamic consideration, the synthesis of rare concave nanostructures with high index facet is still challenging due to their higher reactivity. In this study, concave hexagonal ACM with high index facet {hkl} has been successfully prepared for the first time from hexagonal ACM through simple etching with ammonium heptamolybdate (AHM), which is another precursor salt. Hexagonal ACM corrugates to a concave hexagon because of the higher reactivity of the {001} crystal plane than that of the {010} plane. It has been shown that high index facet exposed concave hexagonal ACM serves as a better catalyst for the photodegradation of dye than the other microstructures enclosed by low index facets.This paper describes an effective method for a precursor salt assisted fabrication and reshaping of two different polyoxometalates [(NH4)2Cu(MoO4)2 (ACM) and Cu3(MoO4)2(OH)2 (CMOH)] into

  19. Self-assembly, aggregates morphology and ionic liquid crystal of polyoxometalate-based hybrid molecule: From vesicles to layered structure (United States)

    Tan, Chunxia


    Polyoxometalate anions [SiW12O40]4- were encapsulated by four 1, 3-dioctadecylimidazolium cations (labeled as L+) driven by electrostatic interaction to obtain hybrid molecule L4[SiW12O40]. The composition and ingredients of L4[SiW12O40] were confirmed by infrared spectroscopy (IR) and elemental analysis. In mixedsolvent (chloroform/methanol volume of 4:1), the self-assembled aggregates of L4[SiW12O40] appear at multilamllar vesicles under optical microscopy and the micron-size bulky flower-like aggregates in scanning electron microscopy (SEM). However, Transmission electron microscopy (TEM) images and small-angle X-ray diffraction (XRD) of L4[SiW12O40] demonstrate that spherical aggregations in mixed-solvent are densely packed by flakes, which can self-assembly into ordered one dimension layered structure. In addition, L4[SiW12O40] shows typical thermotropic liquid crystal behavior similar to imidazole cations. The ordered self-assembly hybrid molecule materials based on organic-polyoxometalate ionic liquids would be exciting branch of nanostructure functional materials.

  20. Assembly and luminescence properties of lanthanide-polyoxometalates/polyethyleneimine/SiO{sub 2} particles with core–shell structure

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail:; Fan, Shaohua; Zhao, Weiqian; Zhang, Hongyan


    In this paper, two lanthanide-polyoxometalate (LnW{sub 10}) complexes were bonded on the surface of the polyethyleneimine (PEI)-modified silica nanoparticles with different sizes, resulting in the formation of LnW{sub 10}/PEI/SiO{sub 2} particles. The hybrid core–shell particles were characterized by infrared, luminescent spectra, scanning electronic microscope, and transmission electronic microscope. The particles obtained exhibit the fine spherical core–shell structure and the excellent luminescence properties. The luminescence spectra studies revealed that the formation of LnW{sub 10}/PEI/SiO{sub 2} particles and the size of particle have an influence on the luminescence properties of lanthanide ions. - Highlights: ► SiO{sub 2}/polyethyleneimine (PEI) shows the chemisorption for Ln-polyoxometalates (LnW{sub 10}). ► The core-shell LnW{sub 10}/PEI/SiO{sub 2} nanoparticles with different sizes were fabricated. ► The hybrid particles exhibit the excellent luminescence properties. ► The sizes of particles affect the luminescence properties of lanthanide ions.

  1. Modification of Pt nanoparticles with polyoxometallate monolayers: Competition between activation and blocking of reactive sites for the electrocatalytic oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Chojak, Malgorzata [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Kolary-Zurowska, Aneta [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw, (Poland); Department of Chemistry, University of Camerino, S. Agostino 1, I-62032 Camerino (Italy); Wlodarczyk, Renata [Department of Chemistry, University of Camerino, S. Agostino 1, I-62032 Camerino (Italy); Division of Chemistry, Department of Materials and Process Engineering and Applied Physics, Czestochowa University of Technology, Al. Armii Krajowej 16, PL 42-200 Czestochowa (Poland); Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Karnicka, Katarzyna [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Palys, Barbara [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Marassi, Roberto [Department of Chemistry, University of Camerino, S. Agostino 1, I-62032 Camerino (Italy)]. E-mail:; Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)]. E-mail:


    Surfaces of bulk platinum and unsupported (Vulcan-free) Pt nanoparticles, that are modified and stabilized with such Keggin type heteropolyacids of molybdenum and tungsten as H{sub 3}PMo{sub 12}O{sub 40} and H{sub 3}PW{sub 12}O{sub 40}, have been characterized using cyclic voltammetry, FTIR (by reflectance), as well as transmission and scanning electron microscopies. The presence of the polyoxometallate monolayer on platinum results in the partial suppression of the interfacial formation of PtOH/PtO oxides. Both molybdates and tungstates seem to interact with Pt surface via their corner oxygen atoms. The existence of spacious, largely hydrated, polyoxometallate monolayers on platinum does not block access of reactant (oxygen) to the catalytic Pt sites. The electrocatalytic properties of H{sub 3}PMo{sub 12}O{sub 40} and H{sub 3}PW{sub 12}O{sub 40} modified Pt nanoparticles towards reduction of oxygen in acid medium have been examined and compared using rotating ring-disk voltammetry. Reactivity of Pt-free H{sub 3}PMo{sub 12}O{sub 40} and H{sub 3}PW{sub 12}O{sub 40} with respect to reduction of hydrogen peroxide has also been considered. Our results clearly show that modification of Pt nanoparticles with PW{sub 12} (but not with PMo{sub 12}) results in the enhancement of the electrocatalytic reduction of oxygen.

  2. Development of a polyoxometallate-based photocatalyst assembled with cucurbit[6]uril via hydrogen bonds for azo dyes degradation

    Energy Technology Data Exchange (ETDEWEB)

    Cao Minna [Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, the Chinese Academy of Science, Fuzhou 350002 (China); Lin Jingxiang; Lue Jian; You Yanglijun; Liu Tianfu [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou 350002 (China); Cao Rong, E-mail: [Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou 350002 (China)


    Graphical abstract: A novel photocatalyst assembled from {alpha}-Keggin type polyoxometallate and macrocycle cucurbit[6]uril via hydrogen bonding has been synthesized and exhibits good photocatalytic activity towards azo dyes degradation. - Abstract: A water insoluble cucurbit[6]uril-polyoxometallates (CB[6]-POMs) composite assembled from {alpha}-Keggin type polysilicontungstate anions and macrocycle cucurbit[6]uril (CB[6]) via hydrogen bonding has been synthesized as visible light active photocatalyst. The physical and photocatalytic properties of such photocatalyst have been fully characterized by PXRD, FTIR, TG, XPS, and UV/vis diffuse reflectance spectra. The catalyst shows a good photocatalytic activity towards the degradation of methyl orange (MO) under visible light irradiation and displays good reproducibility of photocatalytic degradation by a simple recycled procedure without obvious loss in catalytic activity, which is of great significance for practical use of the photocatalyst. In the photodegradation process, the {l_brace}Ni-CB[6]{r_brace}{sub n} chain of the photocatalyst acts as sensitizer and can be induced by visible light, meanwhile the POMs chain of the photocatalyst acts as electron acceptor and deposits the electron in its LUMO. The effects of various experimental parameters and the proposed mechanisms are discussed in detail.

  3. Polyoxometalate-modified TiO2 nanotube arrays photoanode materials for enhanced dye-sensitized solar cells (United States)

    Liu, Ran; Sun, Zhixia; Zhang, Yuzhuo; Xu, Lin; Li, Na


    In this work, we prepared for the first time the TiO2 nanotube arrays (TNAs) photoanode with polyoxometalate(POMs)-modified TiO2 electron-transport layer for improving the performance of zinc phthalocyanine(ZnPc)-sensitized solar cells. The as-prepared POMs/TNAs/ZnPc composite photoanode exhibited higher photovoltaic performances than the TNAs/ZnPc photoanode, so that the power conversion efficiency of the solar cell device based on the POMs/TNAs/ZnPc photoanode displayed a notable improvement of 45%. These results indicated that the POMs play a key role in reducing charge recombination in phthalocyanine-sensitized solar cells, together with TiO2 nanotube arrays being helpful for electron transport. The mechanism of the performance improvement was demonstrated by the measurements of electrochemical impedance spectra and open-circuit voltage decay curves. Although the resulting performance is still below that of the state-of-the-art dye-sensitized solar cells, this study presents a new insight into improving the power conversion efficiency of phthalocyanine-sensitized solar cells via polyoxometalate-modified TiO2 nanotube arrays photoanode.

  4. Polyoxometalate incorporated polymer monolith microextraction for highly selective extraction of antidepressants in undiluted urine. (United States)

    Cai, Jiao; Zhu, Gang-Tian; He, Xiao-Mei; Zhang, Zheng; Wang, Ren-Qi; Feng, Yu-Qi


    In this work, a polyoxometalate (POM) incorporated polymer monolith microextraction (PMME) was successfully proposed and employed in the selective extraction of basic antidepressants in undiluted urine sample. This hybrid monolith exhibited strong cation-exchange interaction (SCX) with positively charged antidepressants when pH was 3.0, because of the multiple ionizable moieties on polyanionic POM. As such, antidepressants in complex sample matrices were efficiently extracted by the monolith, and the matrix effect was significantly reduced. In addition, due to the high amount of anionic POM, the monolith exhibited remarkable extraction capacities for target antidepressants ranging from 4.7 to 5.8mg/g. Further, the POM incorporated PMME was coupled with high-performance liquid chromatography-ultraviolet (HPLC-UV). Thus, antidepressants in undiluted urine sample was efficiently extracted under optimized extraction conditions online. The limits of detection (LODs) for the target antidepressants ranged from 0.7 to 1.4ng/mL, and the linear range was 5-1000ng/mL with determination coefficients (R2) higher than 0.9960. The recoveries ranged from 86.8% to 104.0% with relative standard deviations (RSDs) of 0.4-10.1%. The proposed procedure was successfully applied to determine antidepressant in human urine. Taken together, the developed method presented a new strategy for the analysis of basic drugs in undiluted urine sample, which could be used for monitoring medicines in pharmacokinetic analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics. (United States)

    Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy


    Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H3 PMo12 O40 /TiO2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Electronic and relativistic contributions to ion-pairing in polyoxometalate model systems. (United States)

    Sures, Dylan J; Serapian, Stefano A; Kozma, Károly; Molina, Pedro I; Bo, Carles; Nyman, May


    Ion pairs and solubility related to ion-pairing in water influence many processes in nature and in synthesis including efficient drug delivery, contaminant transport in the environment, and self-assembly of materials in water. Ion pairs are difficult to observe spectroscopically because they generally do not persist unless extreme solution conditions are applied. Here we demonstrate two advanced techniques coupled with computational studies that quantify the persistence of ion pairs in simple solutions and offer explanations for observed solubility trends. The system of study, ([(CH3)4N]+,Cs)8[M6O19] (M = Nb,Ta), is a set of unique polyoxometalate salts whose water solubility increases with increasing ion-pairing, contrary to most ionic salts. The techniques employed to characterize Cs+ association with [M6O19]8- and related clusters in simple aqueous media are 133Cs NMR (nuclear magnetic resonance) quadrupolar relaxation rate and PDF (pair distribution function) from X-ray scattering. The NMR measurements consistently showed more extensive ion-pairing of Cs+ with the Ta-analogue than the Nb-analogue, although the electrostatics of the ions should be identical. Computational studies also ascertained more persistent Cs+-[Ta6O19] ion pairs than Cs+-[Nb6O19] ion pairs, and bond energy decomposition analyses determined relativistic effects to be the differentiating factor between the two. These distinctions are likely responsible for many of the unexplained differences between aqueous Nb and Ta chemistry, while they are so similar in the solid state. The X-ray scattering studies show atomic level detail of this ion association that has not been prior observed, enabling confidence in our structures for calculations of Cs-cluster association energies. Moreover, detailed NMR studies allow quantification of the number of Cs+ associated with a single [Nb6O19]8- or [Ta6O19]8- anion which agrees with the PDF analyses.

  7. Assemblies of copper bis(triazole) coordination polymers using the same keggin polyoxometalate template. (United States)

    Tian, Ai-xiang; Ying, Jun; Peng, Jun; Sha, Jing-quan; Pang, Hai-jun; Zhang, Peng-peng; Chen, Yuan; Zhu, Min; Su, Zhong-min


    Four inorganic-organic hybrid compounds, [Cu(I)(4)(bte)(4)(SiW(12)O(40))] (1), [Cu(II)(2)(bte)(4)(SiW(12)O(40))].4H(2)O (2) [bte = 1,2-bis(1,2,4-triazol-1-yl)ethane], [Cu(I)(4)(btb)(2)(SiW(12)O(40))].2H(2)O (3), and [Cu(II)(2)(btb)(4)(SiW(12)O(40))].2H(2)O (4) [btb = 1,4-bis(1,2,4-triazol-1-yl)butane], were hydrothermally synthesized through use of the same Keggin polyoxometalate as the template and tuning the molar ratio of the bis(triazole) ligand to the Cu(II) ion. The ratio of the bis(triazole) ligand to Cu(II) has a crucial influence on the structures of this series. Single-crystal X-ray diffraction analyses indicate that compound 1 is constructed by tetranuclear ring-connecting chains and polymerized [Cu(bte)](+) chains, between which SiW(12) anions are inserted to form a three-dimensional (3D) structure. Compound 2 shows a (4(4).6(2)) two-dimensional grid sheet. The discrete SiW(12) anions are sandwiched by the sheets, just like "hamburgers". Compound 3 presents channel-like [Cu(2)(btb)](2+) polymerized chains, which are further connected by SiW(12) anions to construct a 3D framework. Compound 4 exhibits a (6(6)) 3D Cu-btb framework with hexagonal channels, into which the tetradentate SiW(12) anions are incorporated. The thermal stabilities of the compounds are discussed.

  8. Asymmetric Supercapacitors Based on Reduced Graphene Oxide with Different Polyoxometalates as Positive and Negative Electrodes. (United States)

    Dubal, Deepak P; Chodankar, Nilesh R; Vinu, Ajayan; Kim, Do-Heyoung; Gomez-Romero, Pedro


    Nanofabrication using a "bottom-up" approach of hybrid electrode materials into a well-defined architecture is essential for next-generation miniaturized energy storage devices. This paper describes the design and fabrication of reduced graphene oxide (rGO)/polyoxometalate (POM)-based hybrid electrode materials and their successful exploitation for asymmetric supercapacitors. First, redox active nanoclusters of POMs [phosphomolybdic acid (PMo12 ) and phosphotungstic acid (PW12 )] were uniformly decorated on the surface of rGO nanosheets to take full advantage of both charge-storing mechanisms (faradaic from POMs and electric double layer from rGO). The as-synthesized rGO-PMo12 and rGO-PW12 hybrid electrodes exhibited impressive electrochemical performances with specific capacitances of 299 (269 mF cm-2 ) and 370 F g-1 (369 mF cm-2 ) in 1 m H2 SO4 as electrolyte at 5 mA cm-2 . An asymmetric supercapacitor was then fabricated using rGO-PMo12 as the positive and rGO-PW12 as the negative electrode. This rGO-PMo12 ∥rGO-PW12 asymmetric cell could be successfully cycled in a wide voltage window up to 1.6 V and hence exhibited an excellent energy density of 39 Wh kg-1 (1.3 mWh cm-3 ) at a power density of 658 W kg-1 (23 mW cm-3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Influence of rigid boundary on the propagation of torsional surface ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Earth System Science; Volume 124; Issue 1. Influence of rigid boundary on the propagation of torsional ... rigid boundary, whereas it does at the free boundary. Graphical user interface (GUI) software has been developed using MATLAB 7.5 to generalize the effect of various parameter discussed.

  10. Anti-synchronization of the rigid body exhibiting chaotic dynamics ...

    African Journals Online (AJOL)

    Anti-synchronization of the rigid body exhibiting chaotic dynamics. ... Journal of the Nigerian Association of Mathematical Physics ... Global asymptotic stability and convergence of the sum of the dynamical variables representing the Eulerian state space of the two rigid bodies was verified by numerical simulations. JONAMP ...

  11. effects of flexural rigidity of reinforcement bars on the fundamental ...

    African Journals Online (AJOL)



    Sep 2, 2009 ... numerical method, and the results show that the flexural rigidity of the bars has significant effect on the fundamental natural frequency of heavily reinforced concrete sections. KEYWORDS: Fundamental Natural Frequency, Reinforced Concrete Slab, Flexural Rigidity,. Reinforcement Bars. INTRODUCTION.

  12. Conflict and creativity: Threat-rigidity or motivated focus

    NARCIS (Netherlands)

    de Dreu, C.K.W.; Nijstad, B.A.


    According to the traditional threat-rigidity reasoning, people in social conflict will be less flexible, less creative, more narrow-minded, and more rigid in their thinking when they adopt a conflict rather than a cooperation mental set. The authors propose and test an alternative, motivated focus

  13. Non-rigid registration by geometry-constrained diffusion

    DEFF Research Database (Denmark)

    Andresen, Per Rønsholt; Nielsen, Mads


    Assume that only partial knowledge about a non-rigid registration is given: certain points, curves, or surfaces in one 3D image are known to map to certain points, curves, or surfaces in another 3D image. In trying to identify the non-rigid registration field, we face a generalized aperture problem...

  14. The relationship between torsional rigidity and bending strength ...

    African Journals Online (AJOL)

    The modulus of rigidity, G, and bending moment of elasticity, MOE, of SA pine are evaluated from a direct torsion test and bending tests. Specimens were subjected to a series of tests with the view to determining direct torsional rigidity, apparent bending modulus of elasticity and pure bending modulus of elasticity. Torsional ...

  15. Tautochrone and Brachistochrone Shape Solutions for Rocking Rigid Bodies

    CERN Document Server

    Glaschke, Patrick


    Rocking rigid bodies appear in several shapes in everyday life: As furniture like rocking chairs and rocking cradles or as toys like rocking horses or tilting dolls. The familiar rocking motion of these objects, a non-linear combination of a rigid rotation and a translation of the center of mass, gives rise to a number of interesting dynamical properties. However, their study has received little attention in the literature. This work presents a comprehensive introduction to the dynamics of rocking rigid bodies, including a concise derivation of the equations of motion as well as a general inversion procedure to construct rocking rigid body shapes with specified dynamical properties. Moreover, two novel rigid body shapes are derived - the tautochrone shape and the brachistochrone shape - which represent an intriguing generalization of the well-know tautochrone and brachistochrone curves. In particular, tautochrone shapes offer an alternative construction of a tautochrone pendulum, in addition to Huygens' cyclo...

  16. The theory of pseudo-rigid bodies

    CERN Document Server

    Cohen, Harley


    This monograph concerns the development, analysis, and application of the theory of pseudo-rigid bodies. It collects together our work on that subject over the last five years. While some results have appeared else­ where, much of the work is new. Our objective in writing this mono­ graph has been to present a new theory of the deformation of bodies, one that has not only a firm theoretical basis, but also the simplicity to serve as an effective tool in practical problems. Consequently, the main body of the treatise is a multifaceted development of the theory, from foundations to explicit solutions to linearizations to methods of approximation. The fact that this variety of aspects, each examined in considerable detail, can be collected together in a single, unified treat­ ment gives this theory an elegance that we feel sets it apart from many others. While our goal has always been to give a complete treatment of the theory as it now stands, the work here is not meant to be definitive. Theories are not ent...

  17. Spontaneous droplet trampolining on rigid superhydrophobic surfaces (United States)

    Schutzius, Thomas M.; Jung, Stefan; Maitra, Tanmoy; Graeber, Gustav; Köhme, Moritz; Poulikakos, Dimos


    Spontaneous removal of condensed matter from surfaces is exploited in nature and in a broad range of technologies to achieve self-cleaning, anti-icing and condensation control. But despite much progress, our understanding of the phenomena leading to such behaviour remains incomplete, which makes it challenging to rationally design surfaces that benefit from its manifestation. Here we show that water droplets resting on superhydrophobic textured surfaces in a low-pressure environment can self-remove through sudden spontaneous levitation and subsequent trampoline-like bouncing behaviour, in which sequential collisions with the surface accelerate the droplets. These collisions have restitution coefficients (ratios of relative speeds after and before collision) greater than unity despite complete rigidity of the surface, and thus seemingly violate the second law of thermodynamics. However, these restitution coefficients result from an overpressure beneath the droplet produced by fast droplet vaporization while substrate adhesion and surface texture restrict vapour flow. We also show that the high vaporization rates experienced by the droplets and the associated cooling can result in freezing from a supercooled state that triggers a sudden increase in vaporization, which in turn boosts the levitation process. This effect can spontaneously remove surface icing by lifting away icy drops the moment they freeze. Although these observations are relevant only to systems in a low-pressure environment, they show how surface texturing can produce droplet-surface interactions that prohibit liquid and freezing water-droplet retention on surfaces.


    Directory of Open Access Journals (Sweden)

    K. E. BULLEN


    Full Text Available The purpose of this paper is to examine and assess, in the
    light of recent evidence, the theory lliat the Earth's inner core has
    a significant rigidity.
    The presenee of an inner core in the Earth is revealed from
    observations of the seismie pliase PKP in the « sliadow zone » for
    which the epicentral distance A lies in the range 105" < A < 143".
    Miss I. Lehmann (r in 1936, followed by Gutenberg and Richter (2
    in 1938, atlrihuted these observations to tlie presence of an inner
    core; and Jeffreys (3 in 1939 applied Airy's theory of diffraetion
    near a caustic to sliow that the alternative theory of diffraetion
    round the outer boundary of the centrai core was not capable of
    explaining tlie observations in the shadow zone. The existence of the
    inner core has been fairly generallv accepted sinee tliis ealculation
    of Jeffreys.

  19. Molecular rigidity and enthalpy-entropy compensation in DNA melting. (United States)

    Vargas-Lara, Fernando; Starr, Francis W; Douglas, Jack F


    Enthalpy-entropy compensation (EEC) is observed in diverse molecular binding processes of importance to living systems and manufacturing applications, but this widely occurring phenomenon is not sufficiently understood from a molecular physics standpoint. To gain insight into this fundamental problem, we focus on the melting of double-stranded DNA (dsDNA) since measurements exhibiting EEC are extensive for nucleic acid complexes and existing coarse-grained models of DNA allow us to explore the influence of changes in molecular parameters on the energetic parameters by using molecular dynamics simulations. Previous experimental and computational studies have indicated a correlation between EEC and changes in molecular rigidity in certain binding-unbinding processes, and, correspondingly, we estimate measures of DNA molecular rigidity under a wide range of conditions, along with resultant changes in the enthalpy and entropy of binding. In particular, we consider variations in dsDNA rigidity that arise from changes of intrinsic molecular rigidity such as varying the associative interaction strength between the DNA bases, the length of the DNA chains, and the bending stiffness of the individual DNA chains. We also consider extrinsic changes of molecular rigidity arising from the addition of polymer additives and geometrical confinement of DNA between parallel plates. All our computations confirm EEC and indicate that this phenomenon is indeed highly correlated with changes in molecular rigidity. However, two distinct patterns relating to how DNA rigidity influences the entropy of association emerge from our analysis. Increasing the intrinsic DNA rigidity increases the entropy of binding, but increases in molecular rigidity from external constraints decreases the entropy of binding. EEC arises in numerous synthetic and biological binding processes and we suggest that changes in molecular rigidity might provide a common origin of this ubiquitous phenomenon in the mutual

  20. Hamiltonian theory for the non-rigid Earth: Semidiurnal terms (United States)

    Getino, J.; Ferrándiz, J. M.; Escapa, A.


    The purpose of this paper is to determine the contributions to the nutation series arising from the triaxiality of a non-rigid Earth model composed of a rigid mantle and a liquid core. With this aim, the canonical formulation of the rotation of the non-rigid Earth developed by Getino and Ferrándiz is applied in order to study the semidiurnal terms arising from the C22 and S22 geopotential coefficients. Once the corresponding generating function is calculated, analytical expressions of the Andoyer and figure planes are derived. We also provide numerical nutation series based on the analytical formulae.

  1. Observations on the Partial Breaking of $N=2$ Rigid Supersymmetry

    CERN Document Server

    Andrianopoli, Laura; Ferrara, Sergio; Trigiante, Mario


    We study the partial breaking of $N=2$ rigid supersymmetry for a generic rigid special geometry of $n$ abelian vector multiplets in the presence of Fayet-Iliopoulos terms induced by the Hyper-K\\"ahler momentum map. By exhibiting the symplectic structure of the problem we give invariant conditions for the breaking to occur, which rely on a quartic invariant of the Fayet-Iliopoulos charges as well as on a modification of the $N=2$ rigid symmetry algebra by a vector central charge.

  2. Near field acoustic holography with microphones on a rigid sphere

    DEFF Research Database (Denmark)

    Jacobsen, Finn; Moreno-Pescador, Guillermo; Fernandez Grande, Efren


    Spherical near field acoustic holography (spherical NAH) is a technique that makes it possible to reconstruct the sound field inside and just outside a spherical surface on which the sound pressure is measured with an array of microphones. This is potentially very useful for source identification....... The sphere can be acoustically transparent or it can be rigid. A rigid sphere is somewhat more practical than an open sphere. However, spherical NAH based on a rigid sphere is only valid if it can be assumed that the sphere has a negligible influence on the incident sound field, and this is not necessarily...

  3. Observations on the partial breaking of N=2 rigid supersymmetry

    Directory of Open Access Journals (Sweden)

    Laura Andrianopoli


    Full Text Available We study the partial breaking of N=2 rigid supersymmetry for a generic rigid special geometry of n abelian vector multiplets in the presence of Fayet–Iliopoulos terms induced by the hyper-Kähler momentum map. By exhibiting the symplectic structure of the problem we give invariant conditions for the breaking to occur, which rely on a quartic invariant of the Fayet–Iliopoulos charges as well as on a modification of the N=2 rigid symmetry algebra by a vector central charge.

  4. Multi-iron silicotungstates: synthesis, characterization, and stability studies of polyoxometalate dimers. (United States)

    Anderson, Travis M; Neiwert, Wade A; Hardcastle, Kenneth I; Hill, Craig L


    The reaction of Fe(III) with Na(+) and K(+) salts of the trivacant [alpha-SiW(9)O(34)](10)(-) ligand have been investigated at pH 6 and pH 1. A new dimer, [(alpha-SiFe(3)W(9)(OH)(3)O(34))(2)(OH)(3)](11-) (1), is synthesized by reacting Na(7)H(3)[alpha-SiW(9)O(34)] or K(10)[alpha-SiW(9)O(34)] with exactly 3 equiv of Fe(III) in a 0.5 M sodium acetate solution (pH 6). The structure of 1, determined by single-crystal X-ray diffraction (a = 22.454(2) A, b = 12.387(2) A, c = 37.421(2), beta = 100.107(8) degrees , monoclinic, C2/c, Z = 4, R(1) = 5.11% based on 12739 independent reflections), consists of two [alpha-SiFe(3)W(9)(OH)(3)O(34)](4-) units linked by three Fe-mu-OH-Fe bonds. Reaction of K(10)[alpha-SiW(9)O(34)] with 3 equiv of Fe(III) in water (pH 1) yields [(alpha-Si(FeOH(2))(2)FeW(9)(OH)(3)O(34))(2)](8)(-2). The structure of 2 was also determined by single-crystal X-ray diffraction (a = 36.903(2) A, b = 13.9868(9) A, c = 21.7839(13) A, beta = 122.709(1) degrees , monoclinic, C2/c, Z = 4, R(1) = 4.57% based on 11787 independent reflections). It consists of two [alpha-Si(FeOH(2))(2)FeW(9)(OH)(3)O(34)](4-) Keggin units linked by a single edge. The terminal ligand on Fe1 in each trisubstituted Keggin unit becomes a mu(2) oxo ligand bridging to a [WO(6)](2-) moiety. The UV-vis spectra of both complexes show the characteristic oxygen-to-metal-charge-transfer bands of polyoxometalates as well as an Fe(III)-centered band at 436 nm (epsilon = 146 M(-1) cm(-1)) and 456 nm (epsilon = 104 M(-1) cm(-1)) for complexes 1 and 2, respectively. Differential scanning calorimetry data show that complex 1 decomposes between 575 and 600 degrees C whereas no decomposition is observed for complex 2 up to temperatures of 600 degrees C.

  5. Polyoxometalate-based Catalysts for Toxic Compound Decontamination and Solar Energy Conversion (United States)

    Guo, Weiwei

    Polyoxometalates (POMs) have been attracting interest from researchers in the fields of Inorganic Chemistry, Physical Chemistry, Biomolecular Chemistry, etc. Their unique structures and properties render them versatile and facilitate applications in medicine, magnetism, electrochemistry, photochemistry and catalysis. In particular, toxic compound (chemical warfare agents (CWAs) and toxic industrial compounds (TICs)) decontamination and solar energy conversion by POM-based materials have becoming promising and important research areas that deserve much attention. The focus of this thesis is to explore the structural features of POMs, to develop POM-based materials and to investigate their applications in toxic compound decontamination and solar energy conversion. The first part of this thesis gives a general introduction on the history, structures, properties and applications of POMs. The second part reports the synthesis, structures, and reactivity of different types of POMs in the destruction of TICs and CWAs. Three tetra-n-butylammonium (TBA) salts of polyvanadotungstates, [n-Bu4N]6[ PW9V3], [n-Bu4N] 5H2PW8V4O40 (PW 8V4), [n-Bu4N]4H 5PW6V6O40· 20H2O (PW6V6) are discussed in detail. These vanadium-substituted Keggin type POMs show effective activity for the aerobic oxidation of formaldehyde (a major TIC and human-environment carcingen) to formic acid under ambient conditions. Moreover, two types of POMs have also been developed for the removal of CWAs and/or their simulants. Specifically, a layered manganese(IV)-containing heteropolyvanadate with a 1:14 Stoichiometry, K4Li2[MnV14O40]˙21H2 O has been prepared. Its catalytic activity for oxidative removal of 2-chloroethyl ethyl sulfide (a mustard simulant) is discussed. The second type of POM developed for decontamination of CWAs and their simulants is the new one-dimensional polymeric polyniobate (P-PONb), K12[Ti 2O2][GeNb12O40]˙19H2O (KGeNb). The complex has been applied to the decontamination of a wide range

  6. Sound propagation over rigid porous layers (United States)

    Howorth, Craig

    Two related topics are discussed: (1) the measurement of the acoustical characteristics of rigid porous materials, that is the impedance and propagation constant; and (2) the propagation of sound over the surface of a hard backed layer of such a material. A review of impedance measurement leads to the selection of an indirect method which is employed successfully on a wide range of surfaces. A numerical comparison of impedance models follows including a one-parameter semi-empirical model, a phenomenological model, and a microstructural model which relates several physical parameters of a material to the acoustical properties of a surface. The models differ in their prediction of the acoustical properties of a low porosity material. A numerical comparison of the solutions of point source propagation in the presence of a porous media indicates that the 'extended' Weyl van der Pol approximation is reliable over short source receiver distances. The study is extended to examine the phenomenon of the acoustical surface wave. Three experimental techniques are used to produce new evidence for the existence of such a wave which shows good agreement with the theoretical predictions. The indirect method is used to obtain impedances and model parameters for a wide variety of surfaces varying from soils to fiberglass and which are compared with the results of an impedance technique and with standing wave tube measurements. The indirect method of impedance is employed together with the microstructural model and the propagation model examined earlier in studies of the acoustical properties of porous road surfaces. It proves possible to use the indirect method both to determine the microstructural parameters and to classify the acoustical properties of such a previous surface when the sound source is either a loudspeaker point source or a vehicle. The results of the parameter determination are validated by a series of non-acoustical measurements. With regard only to the excess

  7. Solar-induced direct biomass-to-electricity hybrid fuel cell using polyoxometalates as photocatalyst and charge carrier. (United States)

    Liu, Wei; Mu, Wei; Liu, Mengjie; Zhang, Xiaodan; Cai, Hongli; Deng, Yulin


    The current polymer-exchange membrane fuel cell technology cannot directly use biomass as fuel. Here we present a solar-induced hybrid fuel cell that is directly powered with natural polymeric biomasses, such as starch, cellulose, lignin, and even switchgrass and wood powders. The fuel cell uses polyoxometalates as the photocatalyst and charge carrier to generate electricity at low temperature. This solar-induced hybrid fuel cell combines some features of solar cells, fuel cells and redox flow batteries. The power density of the solar-induced hybrid fuel cell powered by cellulose reaches 0.72 mW cm(-2), which is almost 100 times higher than cellulose-based microbial fuel cells and is close to that of the best microbial fuel cells reported in literature. Unlike most cell technologies that are sensitive to impurities, the cell reported in this study is inert to most organic and inorganic contaminants present in the fuels.

  8. Fine-tuning the antimicrobial profile of biocompatible gold nanoparticles by sequential surface functionalization using polyoxometalates and lysine.

    Directory of Open Access Journals (Sweden)

    Hemant K Daima

    Full Text Available Antimicrobial action of nanomaterials is typically assigned to the nanomaterial composition, size and/or shape, whereas influence of complex corona stabilizing the nanoparticle surface is often neglected. We demonstrate sequential surface functionalization of tyrosine-reduced gold nanoparticles (AuNPs(Tyr with polyoxometalates (POMs and lysine to explore controlled chemical functionality-driven antimicrobial activity. Our investigations reveal that highly biocompatible gold nanoparticles can be tuned to be a strong antibacterial agent by fine-tuning their surface properties in a controllable manner. The observation from the antimicrobial studies on a gram negative bacterium Escherichia coli were further validated by investigating the anticancer properties of these step-wise surface-controlled materials against A549 human lung carcinoma cells, which showed a similar toxicity pattern. These studies highlight that the nanomaterial toxicity and biological applicability are strongly governed by their surface corona.

  9. Inorganic-organic hybrid polyoxometalate containing supramolecular helical chains: Preparation, characterization and application in chemically bulk-modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Han Zhangang [Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China); Zhao Yulong [Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China); Peng Jun [Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China)]. E-mail:; Liu Qun [Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China); Wang Enbo [Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024 (China)


    An inorganic-organic hybrid polyoxometalate (POM) (Hbpy){sub 4}[SiMo{sub 12}O{sub 40}] (1) (bpy = 2,4-bipyridine), has been prepared and characterized. X-ray diffraction study reveals that compound 1 contains interesting organic double helical chains. The hybrid nanoparticles was used as a solid bulkmodifier to fabricate a three-dimensional chemically modified carbon paste electrode (1-CPE) by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE has been studied in detail. The results indicate that 1-CPE has a good electrocatalytic activity toward the reduction of nitrite in 1 M H{sub 2}SO{sub 4} aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the interactions existed between POM anions and organic double helical bpy chains, which are very important for practical applications in electrode modification.

  10. Solar-induced direct biomass-to-electricity hybrid fuel cell using polyoxometalates as photocatalyst and charge carrier (United States)

    Liu, Wei; Mu, Wei; Liu, Mengjie; Zhang, Xiaodan; Cai, Hongli; Deng, Yulin


    The current polymer-exchange membrane fuel cell technology cannot directly use biomass as fuel. Here we present a solar-induced hybrid fuel cell that is directly powered with natural polymeric biomasses, such as starch, cellulose, lignin, and even switchgrass and wood powders. The fuel cell uses polyoxometalates as the photocatalyst and charge carrier to generate electricity at low temperature. This solar-induced hybrid fuel cell combines some features of solar cells, fuel cells and redox flow batteries. The power density of the solar-induced hybrid fuel cell powered by cellulose reaches 0.72 mW cm-2, which is almost 100 times higher than cellulose-based microbial fuel cells and is close to that of the best microbial fuel cells reported in literature. Unlike most cell technologies that are sensitive to impurities, the cell reported in this study is inert to most organic and inorganic contaminants present in the fuels.

  11. Glass fiber and silica reinforced rigid polyurethane foams

    National Research Council Canada - National Science Library

    M W Kim; S H Kwon; H Park; B K Kim


    Ternary composites of rigid polyurethane foam (RPUF)/glass fiber/silica as well as RPUF/glass fiber have been fabricated from glass fiber, silica, polymeric 4,4'-di-phenylmethane diisocyanate (PMDI...

  12. Stabilization of Rigid Body Dynamics by Internal and External Torques

    National Research Council Canada - National Science Library

    Bloch, A. M; Krishnaprasad, P. S; Marsden, J. E; Sanchez de Alvarez, G


    ...] with quadratic feedback torques for internal rotors. We show that with such torques, the equations for the rigid body with momentum wheels are Hamiltonian with respect to a Lie-Poisson bracket structure. Further...

  13. Resin Infusion Rigidized Inflatable Concept Development and Demonstration Project (United States)

    National Aeronautics and Space Administration — Utilizing resin infusion to rigidize an inflatable structure and form fiber-reinforced composites on-orbit is a novel concept that builds on current NASA technology...

  14. A Concise Introduction to Mechanics of Rigid Bodies Multidisciplinary Engineering

    CERN Document Server

    Huang, L


    A Concise Introduction to Mechanics of Rigid Bodies: Multidisciplinary Engineering presents concise, key concepts of kinematics and dynamics of rigid bodies. This compact volume bridges the steep gap between  introductory texts on engineering mechanics, which focus on one and two dimensional motions of particles and rigid bodies, and advanced texts on multi-body dynamics in high dimension spaces  found in multidisciplinary areas like mechatronics, robotics and biomechanics. In the book, rigid body motions in the spaces with different dimensions are described in addition to studies in a uniform framework supported by vector and matrix operations. Rigorous mathematic tools and explanations are provided to clarify the most complex concepts. This book also: Provides practical examples from different engineering areas, offering a link between theoretical fundamentals and everyday applications Offers simplified mathematical equations to clearly present essential theories in robotics and mechanics Presents statics...

  15. [Arterial rigidity in patients with chronic obstructive pulmonary disease]. (United States)

    Karoli, N A; Dolishniaia, G R; Rebrov, A P


    The aim of this open study was to estimate arterial rigidity in patients with chronic obstructive pulmonary disease (COPD). It included 105 patients above 40 years of age. Exclusion criteria were clinical signs of CHD, peripheral atherosclerosis, and other severe chronic diseases in the exacerbation phase. The control group was comprised of 27 practically healthy volunteers. The arterial fluid was detected using a Tensioclinic arteriograph (Tensiomed, Hungary). Arterial rigidity was estimated in patients of two age groups (below and above 60 years) with COPD of different severity The results suggest the development of arterial wall lesions in proportion to the patients' age and COPD severity. It was shown that excessive arterial rigidity and accelerated pulse wave reflection (increased speed of pulse wave propagation and augmentation index) exert significant influence on the elevation of central arterial pressure. Enhanced rigidity of the arterial wall being a cardiovascular risk factor further prospective studies are needed.

  16. Dynamic Simulation of Rigid Guide Structure Based on ANSYS

    National Research Council Canada - National Science Library

    Zhang Xin; Wang Zhe


    ... commonly used calculation model of rigid guide and bunton by ANSYS. Simulation of the horizontal force through a section of the guide evenly, and the deflection curves of each model are obtained...

  17. Electronic properties of polyoxometalates: electron and proton affinity of mixed-addenda Keggin and Wells-Dawson anions. (United States)

    López, Xavier; Bo, Carles; Poblet, Josep M


    A series of systematic DFT calculations were conducted on Keggin [SiW(9)M(3)O(40)](n-), M = Mo, V, and Nb; and Wells-Dawson anions [P(2)M(18)O(62)],(6-) M = W and Mo; [P(2)M(15)M(3)'O(62)](m-), M = W and Mo, M' = W, Mo, and V to analyze the redox properties and the basicity of the external oxygen sites in polyoxometalates with nonequivalent addenda metals. The energy and composition of the lowest unoccupied orbitals, formally delocalized over the addenda atoms, determine the redox properties of a polyoxometalate. When a Mo(6+) substitutes one W(6+) in the 1:12 tungstate, the energy of the LUMO decreases and the cluster is more easily reduced. The tungstoniobates behave differently because the niobium orbitals insert into the tungsten band and the reduction of [SiW(9)Nb(3)O(40)](7-) yields the blue species SiW(9)Nb(3) 1e and not the cluster SiW(9)Nb(2)Nb(IV). In Wells-Dawson structures, the polar and equatorial sites have different electron affinities and the reduction preferentially occurs in the equatorial sites. Inserting ions with larger electron affinities into the polar sites can modify this traditional conduct. Hence, the trisubstituted [P(2)W(15)V(3)O(62)](9-) anion is reduced in the vanadium polar sites. By means of molecular electrostatic potential maps and the relative energy of the various protonated forms of [SiW(9)V(3)O(40)](7-) and [SiW(9)Mo(3)O(40)](4-), we established the basicity scale: OV(2) > OMo(2) > OW(2) > OV > OW > OMo. Finally, a continuum model for the solvent enabled us to compare anions with different total charges.

  18. Crystalline polyoxometalate (POM)–polyethylene glycol (PEG) composites aimed as non-humidified intermediate-temperature proton conductors

    Energy Technology Data Exchange (ETDEWEB)

    Tsuboi, Masaki [Department of Basic Sciences, School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902 (Japan); Hibino, Mitsuhiro; Mizuno, Noritaka [Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Uchida, Sayaka, E-mail: [Department of Basic Sciences, School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902 (Japan); JST-PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan)


    Crystalline polyoxometalate (POM)–polyethylene glycol (PEG) composites aimed as non-humidified intermediate-temperature proton conductors were synthesized and characterized by single crystal and powder XRD, solid state MASNMR, and TG-DTA measurements. Among the POM–PEG composites, Cs{sub 2.7}H{sub 0.3}[PW{sub 12}O{sub 40}]·1.2PEG1000 (CsHPW-PEG1000) possessed one-dimensional channels with diameters of ca. 6 and 8 Å, where PEG probably resided, and showed the best performance as a proton conductor (1.2×10{sup −5} S cm{sup −1} at 443 K). Proton conductivities of POM–PEG composites decreased by the increase in molecular weights of PEG (CsHPW-PEG12,000) or anion charges (CsHSiW-PEG1000). Variable contact time {sup 13}C-CP (cross polarization) MASNMR revealed that local mobility (i.e., segmental motion) of PEG is related to the trends in proton conductivities. These results show that amount of acidic protons (H{sup +}) is not the primary factor in proton conduction and that segmental motion of PEG assists the proton hopping among POMs in the crystal lattice of POM–PEG composites. - Graphical abstract: Non-humidified intermediate-temperature proton conduction in crystalline polyoxometalate (POM)–polyethylene (PEG) composites are assisted by the segmental motion of PEG. - Highlights: • Crystalline polyoxometalate–polyethlene glycol (PEG) composites were synthesized. • CsHPW-PEG1000 possessed one-dimensional channels and showed the highest proton conductivity. • {sup 13}C CPMASNMR revealed that segmental motion of PEG is related to the proton conduction.

  19. Synthesis and energy band characterization of hybrid molecular materials based on organic–polyoxometalate charge-transfer salts

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Chunxia [Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou City, Gansu Province (China); Traditional Chinese Medicine College of Gansu, Gansu (China); Bu, Weifeng, E-mail: [Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou City, Gansu Province (China)


    A cationic amphiphilic molecule was synthesized and employed to encapsulate Lindqvist ([M{sub 6}O{sub 19}]{sup 2−}) and Keggin polyoxometalates ([SiM{sub 12}O{sub 40}]{sup 4−}, M=Mo, W) to form hybrid molecules through electrostatic interaction. The X-ray diffraction results illustrate that the former hybrids possess lamellar nanostructures in their solid states, while the latter hybrids show a cubic Im3m packing model with low intensities and poor long-range order. These hybrids have clear charge-transfer characters as shown in their deeper colors and UV–vis diffuse reflectance spectra. According to the reported reduction potentials of the POM acceptors and the band gaps deduced from their diffuse reflectance spectra, we have calculated the theoretical values of the lowest unoccupied molecular orbital (LUMO) position similar to the electron affinity (E{sub A}) of solid materials. Such energy level parameters are comparable to those of electroluminescence and electron-transport materials commonly used in organic electroluminescence devices. These organic–polyoxometalate charge-transfer salts have more advantages, such as higher decomposition temperatures, easier film fabrication and better electron affinities, which presumably would be used for electron-transport materials in the area of the electroluminescence. - Graphical abstract: Hybrid molecular materials with charge-transfer characters formed by a positively charged donor L and acceptors of the Lindqvist-type and Keggin-type POMs have lamellar and cubic structures in their solid state. - Highlights: • Charge-transfer salts are obtained by self-assembling POMs with an anthracene cation. • Their energy parameters are comparable to those of optoelectronic materials in OLEDs. • These POM-based hybrids could be applied in the area of optoelectronic devices.

  20. Invariant scrambled sets, uniform rigidity and weak mixing


    Foryś, Magdalena; Huang, Wen; Li, Jian; Oprocha, Piotr


    We show that for a non-trivial transitive dynamical system, it has a dense Mycielski invariant strongly scrambled set if and only if it has a fixed point, and it has a dense Mycielski invariant $\\delta$-scrambled set for some $\\delta>0$ if and only if it has a fixed point and not uniformly rigid. We also provide two methods for the construction of completely scrambled systems which are weakly mixing, proximal and uniformly rigid.

  1. Observability/Identifiability of Rigid Motion under Perspective Projection


    Soatto, Stefano


    The "visual motion estimation" problem concerns the reconstruction of the motion of an object viewed under projection. This paper addresses the feasibility of such a problem when the object is represented as a "rigid" set of point-features in the Euclidean 3D space. We represent rigid motion as a point on the so-called "essential manifold" and show that it is globally observable from perspective projections under some general position conditions. Such conditions hold when the path of the view...

  2. On the inertial motions of liquid-filled rigid bodies (United States)

    Mazzone, Giusy; Galdi, Giovanni; Zunino, Paolo


    We consider a rigid body with a cavity completely filled by a viscous liquid and study the inertial motions of the system liquid-filled rigid body S . The equations governing the motion of this coupled system are given by the Navier-Stokes equations and the equations of the balance of the total angular momentum of S in absence of external forces and torques. Given any initial motion to the coupled system, characterized by an initial relative velocity of the fluid and an initial total angular momentum, we give a complete description of the behavior that the system liquid-filled rigid body will show at large times. From both analytical and numerical viewpoints, we are able to prove a longstanding conjecture stated by Zhukovskii, namely that S will eventually reach a steady state which is a rigid body permanent rotation. In other words, the liquid goes to rest with respect to the rigid body and the coupled system will rotate as a whole rigid body, with a constant angular velocity that is directed along one of the principal axes of inertia of the system.

  3. Synergistic effect of polyoxometalate solution and TiO2 under UV irradiation to catalyze formic acid degradation and their application in the fuel cell and hydrogen evolution

    Directory of Open Access Journals (Sweden)

    Congmin Liu


    Full Text Available The synergistic effect of H3PMo12O40 or H3PW12O40 polyoxometalate solution (POM and TiO2 to catalyze formic acid oxidation was investigated. Under UV irradiation, hole and electron were photogenerated by TiO2. Formic acid was oxided by the photogenerated hole and photogenerated electron was transferred to reduce polyoxometalate. With this design, formic acid can be converted into electricity in the fuel cell and hydrogen can be generated in the electrolysis cell without noble metal catalyst. Unlike other noble metal catalysts applied in the fuel cells and electrolysis cell, POM and TiO2 are stable and low cost. The maximum output power density of liquid formic acid fuel cell after 12 h UV irradiation is 5.21 mW/cm2 for phosphmolybdic acid and 22.81 mW/cm2 for phosphotungstic acid respectively. The applied potential for the hydrogen evolution is as low as 0.8 V for phosphmolybdic acid and 0.6 V for phosphotungstic acid. Keywords: TiO2, UV, Polyoxometalate solution (POM, Fuel cell, Hydrogen evolution

  4. Rigidity analysis of protein biological assemblies and periodic crystal structures (United States)


    Background We initiate in silico rigidity-theoretical studies of biological assemblies and small crystals for protein structures. The goal is to determine if, and how, the interactions among neighboring cells and subchains affect the flexibility of a molecule in its crystallized state. We use experimental X-ray crystallography data from the Protein Data Bank (PDB). The analysis relies on an effcient graph-based algorithm. Computational experiments were performed using new protein rigidity analysis tools available in the new release of our KINARI-Web server Results We provide two types of results: on biological assemblies and on crystals. We found that when only isolated subchains are considered, structural and functional information may be missed. Indeed, the rigidity of biological assemblies is sometimes dependent on the count and placement of hydrogen bonds and other interactions among the individual subchains of the biological unit. Similarly, the rigidity of small crystals may be affected by the interactions between atoms belonging to different unit cells. We have analyzed a dataset of approximately 300 proteins, from which we generated 982 crystals (some of which are biological assemblies). We identified two types of behaviors. (a) Some crystals and/or biological assemblies will aggregate into rigid bodies that span multiple unit cells/asymmetric units. Some of them create substantially larger rigid cluster in the crystal/biological assembly form, while in other cases, the aggregation has a smaller effect just at the interface between the units. (b) In other cases, the rigidity properties of the asymmetric units are retained, because the rigid bodies did not combine. We also identified two interesting cases where rigidity analysis may be correlated with the functional behavior of the protein. This type of information, identified here for the first time, depends critically on the ability to create crystals and biological assemblies

  5. General terms and rigidity: another solution to the trivialization problem

    Directory of Open Access Journals (Sweden)

    Eleonora Orlando


    Full Text Available In this paper I am concerned with the problem of applying the notion of rigidity to general terms. In Naming and Necessity, Kripke has clearly suggested that we should include some general terms among the rigid ones, namely, those common nouns semantically correlated with natural substances, species and phenomena, in general, natural kinds -'water', 'tiger', 'heat'- and some adjectives -'red', 'hot', 'loud'. However, the notion of rigidity has been defined for singular terms; after all, the notion that Kripke has provided us with is the notion of a rigid designator. But general terms do not designate single individuals: rather, they apply to many of them. In sum, the original concept of rigidity cannot be straightforwardly applied to general terms: it has to be somehow redefined in order to make it cover them. As is known, two main positions have been put forward to accomplish that task: the identity of designation conception, according to which a rigid general term is one that designates the same property or kind in all possible worlds, and the essentialist conception, which conceives of a rigid general term as an essentialist one, namely, a term that expresses an essential property of an object. My purpose in the present paper is to defend a particular version of the identity of designation conception: on the proposed approach, a rigid general term will be one that expresses the same property in all possible worlds and names the property it expresses. In my opinion, the position can be established on the basis of an inference to the best explanation of our intuitive interpretation and evaluation, relative to counterfactual circumstances, of statements containing different kinds of general terms, which is strictly analogous to our intuitive interpretation and evaluation, relative to such circumstances, of statements containing different kinds of singular ones. I will argue that it is possible to offer a new solution to the trivialization

  6. Unified Creep Plasticity Damage (UCPD) Model for Rigid Polyurethane Foams.

    Energy Technology Data Exchange (ETDEWEB)

    Neilsen, Michael K. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lu, Wei-Yang [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Scherzinger, William M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Hinnerichs, Terry D. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lo, Chi S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)


    Numerous experiments were performed to characterize the mechanical response of several different rigid polyurethane foams (FR3712, PMDI10, PMDI20, and TufFoam35) to large deformation. In these experiments, the effects of load path, loading rate, and temperature were investigated. Results from these experiments indicated that rigid polyurethane foams exhibit significant volumetric and deviatoric plasticity when they are compressed. Rigid polyurethane foams were also found to be very strain-rate and temperature dependent. These foams are also rather brittle and crack when loaded to small strains in tension or to larger strains in compression. Thus, a new Unified Creep Plasticity Damage (UCPD) model was developed and implemented into SIERRA with the name Foam Damage to describe the mechanical response of these foams to large deformation at a variety of temperatures and strain rates. This report includes a description of recent experiments and experimental findings. Next, development of a UCPD model for rigid, polyurethane foams is described. Selection of material parameters for a variety of rigid polyurethane foams is then discussed and finite element simulations with the new UCPD model are compared with experimental results to show behavior that can be captured with this model.

  7. Non-rigid, but not rigid, motion interferes with the processing of structural face information in developmental prosopagnosia. (United States)

    Maguinness, Corrina; Newell, Fiona N


    There is growing evidence to suggest that facial motion is an important cue for face recognition. However, it is poorly understood whether motion is integrated with facial form information or whether it provides an independent cue to identity. To provide further insight into this issue, we compared the effect of motion on face perception in two developmental prosopagnosics and age-matched controls. Participants first learned faces presented dynamically (video), or in a sequence of static images, in which rigid (viewpoint) or non-rigid (expression) changes occurred. Immediately following learning, participants were required to match a static face image to the learned face. Test face images varied by viewpoint (Experiment 1) or expression (Experiment 2) and were learned or novel face images. We found similar performance across prosopagnosics and controls in matching facial identity across changes in viewpoint when the learned face was shown moving in a rigid manner. However, non-rigid motion interfered with face matching across changes in expression in both individuals with prosopagnosia compared to the performance of control participants. In contrast, non-rigid motion did not differentially affect the matching of facial expressions across changes in identity for either prosopagnosics (Experiment 3). Our results suggest that whilst the processing of rigid motion information of a face may be preserved in developmental prosopagnosia, non-rigid motion can specifically interfere with the representation of structural face information. Taken together, these results suggest that both form and motion cues are important in face perception and that these cues are likely integrated in the representation of facial identity. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Efficient computation of root mean square deviations under rigid transformations. (United States)

    Hildebrandt, Anna K; Dietzen, Matthias; Lengauer, Thomas; Lenhof, Hans-Peter; Althaus, Ernst; Hildebrandt, Andreas


    The computation of root mean square deviations (RMSD) is an important step in many bioinformatics applications. If approached naively, each RMSD computation takes time linear in the number of atoms. In addition, a careful implementation is required to achieve numerical stability, which further increases runtimes. In practice, the structural variations under consideration are often induced by rigid transformations of the protein, or are at least dominated by a rigid component. In this work, we show how RMSD values resulting from rigid transformations can be computed in constant time from the protein's covariance matrix, which can be precomputed in linear time. As a typical application scenario is protein clustering, we will also show how the Ward-distance which is popular in this field can be reduced to RMSD evaluations, yielding a constant time approach for their computation. Copyright © 2014 Wiley Periodicals, Inc.

  9. Correlated rigidity percolation and gelation of colloidal particles (United States)

    Zhang, Shang; Zhang, Leyou; Rocklin, D. Zeb; Mao, Xiaoming

    Rigidity percolation on a lattice with sites or bonds randomly diluted is controlled by the isostatic point, where the degrees of freedom and constraints balance, and the system is at the verge of mechanical instability. In the case of triangular lattice rigidity percolation occurs very close to p = 2 / 3 as predicted from isostaticity. Interestingly, we found that when the site dilution is correlated, this transition occurs at a lower p, meaning that less material is needed for rigidity in the disordered structure. This correlation may be seen as a consequence of short range attraction between the particles which makes them cluster. We characterized critical scaling associated with the site correlation parameter, and will discuss implication to understand experimental systems such as gelation of colloidal particles.

  10. Interaction of the rigid journal with Newtonian fluid (United States)

    Michal, Havlásek; František, Pochylý


    This paper deals with the problem of identification of added effects of incompressible Newtonian fluid that impacts on the rigid journal performing translational motion. It considers two degrees of freedom. The axial motion of the rigid journal was neglected. It assumes small oscillations and linear model. The task was solved for two geometrical configurations of the computational domain. In the first variant of geometry, there is no flow between the bases of journal and stator. The second variant of geometry also allows liquid to flow in space between the bases of journal and stator. The introduction describes the mathematical model for the identification of added mass, damping and stiffness matrices. On the basis of the mathematical model and computational modeling of velocity and pressure fields using CFD, the force components are determined. From there, the mentioned matrices are determined depending on the eccentricity of the rigid journal.

  11. A concise introduction to mechanics of rigid bodies multidisciplinary engineering

    CERN Document Server

    Huang, L


    This updated second edition broadens the explanation of rotational kinematics and dynamics — the most important aspect of rigid body motion in three-dimensional space and a topic of much greater complexity than linear motion. It expands treatment of vector and matrix, and includes quaternion operations to describe and analyze rigid body motion which are found in robot control, trajectory planning, 3D vision system calibration, and hand-eye coordination of robots in assembly work, etc. It features updated treatments of concepts in all chapters and case studies. The textbook retains its comprehensiveness in coverage and compactness in size, which make it easily accessible to the readers from multidisciplinary areas who want to grasp the key concepts of rigid body mechanics which are usually scattered in multiple volumes of traditional textbooks. Theoretical concepts are explained through examples taken from across engineering disciplines and links to applications and more advanced courses (e.g. industrial rob...

  12. Friction effects on lateral loading behavior of rigid piles

    DEFF Research Database (Denmark)

    Zania, Varvara; Hededal, Ole


    The adequacy of the p -y curves used in the current practice for the design of rigid pile foundations with large diameter, like in the case of monopile foundations of offshore wind turbines, has been widely questioned. The current study aims at analyzing the lateral behavior of rigid piles, while...... taking into account the shear frictional resistance along the pile. For this purpose efficient three dimensional finite element models of different diameter have been developed. The increase of the side friction and of the diameter of the pile is shown to alter the failure pattern and increase...... the lateral capacity of the pile. The obtained p - y curves demonstrate the importance of the aforementioned parameters in the design of rigid piles, as the reduction of friction along the interface reduces not only the ultimate load but also the stiffness of the soil-pile response. Read More: http...

  13. Toxicity evaluation and hazard review for Rigid Foam

    Energy Technology Data Exchange (ETDEWEB)

    Archuleta, M.M.; Stocum, W.E.


    Rigid Foam is a chemical delay foam used to completely encapsulate an object or to block access to an area. Prior studies have indicated that the final foam product is essentially non-toxic. The purpose of this study was to evaluate and summarize the current chemical and toxicological data available on the components of Rigid Foam and to update the information available on the toxicity of the final Rigid Foam product. Since the possibility exists for a partial deployment of Rigid Foam where only one of the components is released, this study also examined the toxicity of its chemical constituents. Rigid Foam is composed of an {open_quotes}A{close_quotes} and {open_quotes}B{close_quotes} Component. The {open_quotes}A{close_quotes} component is primarily a polymeric isocyanate and the {open_quotes}B{close_quotes} component is a mixture of polyols. In addition to the primary constituents, dichlorodifluoromethane and trichlorofluoromethane are present as blowing agents along with catalysts and silicone surfactants necessary for foaming. The pre-deployed {open_quotes}A{close_quotes} and {open_quotes}B{close_quotes} components are stored in separate vessels and are brought together in static mixing nozzles for dispersal. The results of this evaluation indicate that a completely deployed Rigid Foam under normal conditions is essentially non-toxic as determined previously. However, in the event of a partial deployment or deployment of an individual component directly at an unprotected individual, the degree of hazard is increased due to the toxic and corrosive nature of the individual constituents. The health hazard would depend on the properties of the material to which the person was exposed.

  14. Topology-Preserving Rigid Transformation of 2D Digital Images. (United States)

    Ngo, Phuc; Passat, Nicolas; Kenmochi, Yukiko; Talbot, Hugues


    We provide conditions under which 2D digital images preserve their topological properties under rigid transformations. We consider the two most common digital topology models, namely dual adjacency and well-composedness. This paper leads to the proposal of optimal preprocessing strategies that ensure the topological invariance of images under arbitrary rigid transformations. These results and methods are proved to be valid for various kinds of images (binary, gray-level, label), thus providing generic and efficient tools, which can be used in particular in the context of image registration and warping.

  15. Shear-induced rigidity in spider silk glands (United States)

    Koski, Kristie J.; McKiernan, Keri; Akhenblit, Paul; Yarger, Jeffery L.


    We measure the elastic stiffnesses of the concentrated viscous protein solution of the dehydrated Nephila clavipes major ampullate gland with Brillouin light scattering. The glandular material shows no rigidity but possesses a tensile stiffness similar to that of spider silk. We show, however, that with application of a simple static shear, the mechanical properties of the spider gland protein mixture can be altered irreversibly, lowering symmetry and enabling shear waves to be supported, thus, giving rise to rigidity and yielding elastic properties similar to those of the naturally spun (i.e., dynamically sheared) silk.

  16. Quadratic Twists of Rigid Calabi–Yau Threefolds Over

    DEFF Research Database (Denmark)

    Gouvêa, Fernando Q.; Kiming, Ian; Yui, Noriko


    We consider rigid Calabi–Yau threefolds defined over Q and the question of whether they admit quadratic twists. We give a precise geometric definition of the notion of a quadratic twists in this setting. Every rigid Calabi–Yau threefold over Q is modular so there is attached to it a certain newform...... of weight 4 on some Γ 0(N). We show that quadratic twisting of a threefold corresponds to twisting the attached newform by quadratic characters and illustrate with a number of obvious and not so obvious examples. The question is motivated by the deeper question of which newforms of weight 4 on some Γ 0(N...

  17. Non-rigid image registration using bone growth model

    DEFF Research Database (Denmark)

    Bro-Nielsen, Morten; Gramkow, Claus; Kreiborg, Sven


    Non-rigid registration has traditionally used physical models like elasticity and fluids. These models are very seldom valid models of the difference between the registered images. This paper presents a non-rigid registration algorithm, which uses a model of bone growth as a model of the change...... between time sequence images of the human mandible. By being able to register the images, this paper at the same time contributes to the validation of the growth model, which is based on the currently available medical theories and knowledge...

  18. Reference Frames and Rigid Motions in Relativity: Applications (United States)

    Soler, D.


    The concept of rigid reference frame and of constricted spatial metric, given in the previous work [\\emph{Class. Quantum Grav.} {\\bf 21}, 3067,(2004)] are here applied to some specific space-times: In particular, the rigid rotating disc with constant angular velocity in Minkowski space-time is analyzed, a new approach to the Ehrenfest paradox is given as well as a new explanation of the Sagnac effect. Finally the anisotropy of the speed of light and its measurable consequences in a reference frame co-moving with the Earth are discussed.

  19. Rigid 4D N=2 supersymmetric backgrounds and actions

    Energy Technology Data Exchange (ETDEWEB)

    Butter, Daniel; Inverso, Gianluca; Lodato, Ivano [Nikhef Theory Group,Science Park 105, 1098 XG Amsterdam (Netherlands)


    We classify all N=2 rigid supersymmetric backgrounds in four dimensions with both Lorentzian and Euclidean signature that preserve eight real supercharges, up to discrete identifications. Among the backgrounds we find specific warpings of S{sup 3}×ℝ and AdS{sub 3}×ℝ, AdS{sub 2}×S{sup 2} and H{sup 2}×S{sup 2} with generic radii, and some more exotic geometries. We provide the generic two-derivative rigid vector and hypermultiplet actions and analyze the conditions imposed on the special Kähler and hyperkähler target spaces.

  20. Magnetic adsorbent constructed from the loading of amino functionalized Fe{sub 3}O{sub 4} on coordination complex modified polyoxometalates nanoparticle and its tetracycline adsorption removal property study

    Energy Technology Data Exchange (ETDEWEB)

    Ou, Jinzhao; Mei, Mingliang; Xu, Xinxin, E-mail:


    A magnetic polyoxometalates based adsorbent has been synthesized successfully through the loading of amino functionalized Fe{sub 3}O{sub 4} (NH{sub 2}-Fe{sub 3}O{sub 4}) on nanoparticle of a coordination complex modified polyoxometalates (CC/POMNP). FTIR illustrate there exist intense hydrogen bonds between NH{sub 2}-Fe{sub 3}O{sub 4} and CC/POMNP, which keep the stability of this adsorbent. At room temperature, this adsorbent exhibits ferromagnetic character with saturation magnetization of 8.19 emu g{sup −1}, which provides prerequisite for fast magnetic separation. Water treatment experiment illustrates this POM based magnetic adsorbent exhibits high adsorption capacity on tetracycline. The adsorption process can be described well with Temkin model, which illustrates the interaction between adsorbent and tetracycline plays the dominated role in tetracycline removal. The rapid, high efficient tetracycline adsorption ability suggests this POM based magnetic adsorbent exhibits promising prospect in medical and agriculture waste water purification. A magnetic polyoxometalates based adsorbent, which exhibits excellent tetracycline adsorption removal property has been synthesized through the loading of NH{sub 2}-Fe{sub 3}O{sub 4} on coordination complex modified polyoxometalates - Graphical abstract: A magnetic polyoxometalates based adsorbent, which exhibits excellent tetracycline adsorption removal property has been synthesized through the loading of NH{sub 2}-Fe{sub 3}O{sub 4} on coordination complex modified polyoxometalate. Display Omitted - Highlights: • A POM based magnetic adsorbent was fabricated through the loading of NH{sub 2}-Fe{sub 3}O{sub 4} on POM nanoparticle. • This adsorbent possesses excellent tetracycline adsorption property. • Saturation magnetization value of this adsorbent is 8.19 emug−1, which is enough for magnetic separation.

  1. High Resolution Quantification of Cellular Forces for Rigidity Sensing (United States)

    Liu, Shuaimin

    This thesis describes a comprehensive study of understanding the mechanism of rigidity sensing by quantitative analysis using submicron pillar array substrates. From mechanobiology perspective, we explore and study molecular pathways involved in rigidity and force sensing at cell-matrix adhesions with regard to cancer, regeneration, and development by quantification methods. In Chapter 2 and 3, we developed fabrication and imaging techniques to enhance the performance of a submicron pillar device in terms of spatial and temporal measurement ability, and we discovered a correlation of rigidity sensing forces and corresponding proteins involved in the early rigidity sensing events. In Chapter 2, we introduced optical effect arising from submicron structure imaging, and we described a technique to identify the correct focal plane of pillar tip by fabricating a substrate with designed-offset pillars. From calibration result, we identified the correct focal plane that was previously overlooked, and verified our findings by other imaging techniques. In Chapter 3, we described several techniques to selectively functionalize elastomeric pillars top and compared these techniques in terms of purposes and fabrication complexity. Techniques introduced in this chapter included direct labeling, such as stamping of fluorescent substances (organic dye, nano-diamond, q-dot) to pillars top, as well as indirect labeling that selectively modify the surface of molds with either metal or fluorescent substances. In Chapter 4, we examined the characteristics of local contractility forces and identified the components formed a sarcomere like contractile unit (CU) that cells use to sense rigidity. CUs were found to be assembled at cell edge, contain myosin II, alpha-actinin, tropomodulin and tropomyosin (Tm), and resemble sarcomeres in size (˜2 mum) and function. Then we performed quantitative analysis of CUs to evaluate rigidity sensing activity over ˜8 hours time course and found that

  2. Polyoxometalate-based metal organic frameworks (POMOFs): structural trends, energetics, and high electrocatalytic efficiency for hydrogen evolution reaction. (United States)

    Nohra, Brigitte; El Moll, Hani; Rodriguez Albelo, L Marleny; Mialane, Pierre; Marrot, Jérôme; Mellot-Draznieks, Caroline; O'Keeffe, Michael; Ngo Biboum, Rosa; Lemaire, Joël; Keita, Bineta; Nadjo, Louis; Dolbecq, Anne


    The grafting of the triangular 1,3,5-benzene tricarboxylate linkers (denoted trim) on tetrahedral ε-Keggin polyoxometalates (POMs) capped by Zn(II) ions, formed in situ under hydrothermal conditions, has generated three novel POM-based metal organic frameworks (POMOFs). (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)][C(6)H(3)(COO)(3)](4/3)·6H(2)O (ε(trim)(4/3)) is a 3D open-framework built of molecular Keggin units connected by trim linkers, with channels occupied by tetrabutylammonium (TBA) counterions. ε(trim)(4/3) is a novel (3,4)-connected net, named ofp for open-framework polyoxometalate, and computer simulations have been used to evaluate its relative stability in comparison with ctn- and bor-like polymorphs, showing the stability of this novel phase directly related to its greatest density. A computational study was also undertaken with the aim of locating TBA molecules, the positions of which could not be deduced from single crystal X-ray diffraction, and further rationalizes their structure directing role. In (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)] (ε(2)(trim)(2)), the building unit is not the molecular Keggin but a dimerized form of this POM. Their connection via trim linkers generates a 3D framework with channels filled by TBA cations. In (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)]·8H(2)O ([ε(trim)](∞)), zigzag chains are connected via the organic linkers, forming 2D grids. Modified electrodes were fabricated by direct adsorption of the POMOFs on glassy carbon or entrapment in carbon paste (CPE). A remarkable electrocatalytic hydrogen evolution reaction (HER) was detected with a yield greater than 95%, and a turnover number as high as 1.2 × 10(5) was obtained after 5 h. The reported POMOF-based electrodes are more active than platinum, with a roughly 260 mV anodic shift. Finally, the electrocatalytic activities of ε(trim)(4/3)/CPE electrodes in various XCl (X = Li, Na, K, Cs) media have been studied

  3. Accuracy limit of rigid 3-point water models (United States)

    Izadi, Saeed


    Classical 3-point rigid water models are most widely used due to their computational efficiency. Recently, we introduced a new approach to constructing classical rigid water models [S. Izadi et al., J. Phys. Chem. Lett. 5, 3863 (2014)], which permits a virtually exhaustive search for globally optimal model parameters in the sub-space that is most relevant to the electrostatic properties of the water molecule in liquid phase. Here we apply the approach to develop a 3-point Optimal Point Charge (OPC3) water model. OPC3 is significantly more accurate than the commonly used water models of same class (TIP3P and SPCE) in reproducing a comprehensive set of liquid bulk properties, over a wide range of temperatures. Beyond bulk properties, we show that OPC3 predicts the intrinsic charge hydration asymmetry (CHA) of water — a characteristic dependence of hydration free energy on the sign of the solute charge — in very close agreement with experiment. Two other recent 3-point rigid water models, TIP3PFB and H2ODC, each developed by its own, completely different optimization method, approach the global accuracy optimum represented by OPC3 in both the parameter space and accuracy of bulk properties. Thus, we argue that an accuracy limit of practical 3-point rigid non-polarizable models has effectively been reached; remaining accuracy issues are discussed. PMID:27544113

  4. Buffers Affect the Bending Rigidity of Model Lipid Membranes

    DEFF Research Database (Denmark)

    Bouvrais, H.; Duelund, L.; Ipsen, J. H.


    vesicles, of a more complex behavior, where the buffering molecules may considerably affect the bending rigidity of phosphatidylcholine bilayers. Furthermore, a synergistic effect on the bending modulus is observed in the presence of both salt and buffer molecules, which serves as a warning...

  5. Flexibility versus rigidity in the practice of Islamic Family law

    NARCIS (Netherlands)

    N.Y. Shehada (Nahda)


    textabstractThe last decades have witnessed a sustained critique of the mainstream Orientalist notion that classical Islamic family law was rigid, inflexible, and homogeneous. Many historians have used innovative methods to demonstrate that jurists and judges in precodification times enjoyed the

  6. Rigidity of unilateral external fixators - A biomechanical study

    NARCIS (Netherlands)

    P.T.P.W. Burgers (Paul); M.P.J.M. Riel (Marcel); L.M.M. Vogels (Lucas); R.W. Stam (Ronald); P. Patka (Peter); E.M.M. van Lieshout (Esther)


    textabstractIntroduction: External fixation is the primary choice of temporary fracture stabilisation for specific polytrauma patients. Adequate initial fracture healing requires sufficient stability at the fracture site. The purpose of this study was to compare the rigidity of the Dynafix

  7. Behaviour and Modelling of Semi-rigid Structural Frame Systems ...

    African Journals Online (AJOL)

    A computational finite element model is developed to predict the load-deflection characteristic of portal frames with semi-rigid welded and bolted joints. Plate components of frame ... The modelling of friction effect between the contact surfaces of bolted joints is verified to be the most important factor. The comparative analysis ...

  8. Dielectric relaxation phenomena of rigid polar liquid molecules ...

    Indian Academy of Sciences (India)

    The dielectric relaxation phenomena of rigid polar liquid molecules chloral and ethyltrichloroacetate () in benzene, -hexane and -heptane () under 4.2, 9.8 and 24.6 GHz electric fields at 30°C are studied to show the possible existence of double relaxation times 2 and 1 for rotations of the whole and the flexible ...

  9. Rigid Biobased Building Blocks: Current Developments and Outlook

    NARCIS (Netherlands)

    Es, van D.S.


    In this perspectives paper we will look at the state-of-the-art in rigid renewable building blocks for biobased materials, with a focus on two types of carbohydrate-based difunctional monomers, i.e.,isohexides and furan-2,5-dicarboxylic acid (FDCA).

  10. Wrist rigidity assessment during Deep Brain Stimulation surgery. (United States)

    Costa, Pedro; Rosas, Maria José; Vaz, Rui; Cunha, João Paulo


    Parkinson's Disease (PD) patients often need Deep Brain Stimulation (DBS) surgery when they become intolerant to drugs or these lose efficiency. A stimulation electrode is implanted in the basal ganglia to promote the functional control of the deregulated dopaminergic motor pathways. The stimulation target is defined by medical imaging, followed by electrophysiological inspection for fine electrode position trimming and electrical stimulation tuning. Intra-operative stimulation of the target and the evaluation of wrist rigidity allows to choose the stimulation parameters which best alleviate PD symptoms without side effects. Neurologists impose a passive wrist flexion movement and qualitatively describe the perceived decrease in rigidity under different voltages, based on its experience and with subjectivity. We designed a novel, comfortable and wireless wearable motion sensor to classify the wrist rigidity by deriving a robust signal descriptor from angular speed values and a polynomial mathematical model to classify signals using a quantitative continuous scale. The descriptor significantly (pwrist rigidity, improving upon the inherent subjective clinical evaluation while using small, simple and easy to use motion sensor.

  11. A mixed elastoplastic/rigid-plastic material model

    NARCIS (Netherlands)

    Huetink, Han; van den Boogaard, Antonius H.; Rietman, Bert; Lof, J.; Meinders, Vincent T.


    In forming process simulations, the rigid-plastic material model is widely used because of its numerically robust behaviour. The model yields accurate results, as long as the strain increments are large compared to the elastic limit strain. In cases where the strain increments are small e.g. in dead

  12. The rigid pendulum - an antique but evergreen physical model (United States)

    Butikov, Eugene I.


    Various kinds of motion of a rigid pendulum (including swinging with arbitrarily large amplitudes and complete revolutions) are investigated both analytically and with the help of computerized simulations. The simulation experiments reveal many interesting peculiarities of this famous physical model and complement the analytical study of the subject in a manner that is mutually reinforcing.

  13. Substructural Identification of Flexural Rigidity for Beam-Like Structures

    Directory of Open Access Journals (Sweden)

    Ki-Young Koo


    Full Text Available This study proposes a novel substructural identification method based on the Bernoulli-Euler beam theory with a single variable optimization scheme to estimate the flexural rigidity of a beam-like structure such as a bridge deck, which is one of the major structural integrity indices of a structure. In ordinary bridges, the boundary condition of a superstructure can be significantly altered by aging and environmental variations, and the actual boundary conditions are generally unknown or difficult to be estimated correctly. To efficiently bypass the problems related to boundary conditions, a substructural identification method is proposed to evaluate the flexural rigidity regardless of the actual boundary conditions by isolating an identification region within the internal substructure. The proposed method is very simple and effective as it utilizes the single variable optimization based on the transfer function formulated utilizing Bernoulli Euler beam theory for the inverse analysis to obtain the flexural rigidity. This novel method is also rigorously investigated by applying it for estimating the flexural rigidity of a simply supported beam model with different boundary conditions, a concrete plate-girder bridge model with different length of an internal substructure, a cantilever-type wind turbine tower structure with different type of excitation, and a steel box-girder bridge model with internal structural damages.

  14. Numerical rigid plastic modelling of shear capacity of keyed joints

    DEFF Research Database (Denmark)

    Herfelt, Morten Andersen; Poulsen, Peter Noe; Hoang, Linh Cao


    Keyed shear joints are currently designed using simple and conservative design formulas, yet these formulas do not take the local mechanisms in the concrete core of the joint into account. To investigate this phenomenon a rigid, perfectly plastic finite element model of keyed joints is used. The ...

  15. Impulsive and rigid temperament subtypes and executive functioning

    African Journals Online (AJOL)

    The results indicate that the rigid temperament subtype reacted slower to both complex (executive functioning) and less complex tasks (attention and working memory) than the impulsive temperament subtype. ... Significant differences were maintained with analyses of intelligence and parental education as covariates.

  16. Rigid rod spaced fullerene as building block for nanoclusters

    Indian Academy of Sciences (India)

    By using phenylacetylene based rigid-rod linkers (PhA), we have successfully synthesized two fullerene derivatives, C60-PhA and C60-PhA-C60. The absorption spectral features of C60, as well as that of the phenylacetylene moiety are retained in the monomeric forms of these fullerene derivatives, ruling out the possibility ...

  17. On the mechanism of gas transport in rigid polymer membranes

    NARCIS (Netherlands)

    Hensema, E.R.; Hensema, E.R.; Mulder, M.H.V.; Smolders, C.A.; Smolders, C.A.


    Conventional polymers are compared as gas separation membrane materials with tailormade polymers. The increased permeability of the latter are due to their higher free volume available for gas transport. The increased free volume is associated with the rigidity polymer backbone. Free volume is

  18. Assessment of Lumped-Parameter Models for Rigid Footings

    DEFF Research Database (Denmark)

    Andersen, Lars


    The quality of consistent lumped-parameter models of rigid footings is examined. Emphasis is put on the maximum response during excitation and the geometrical damping related to free vibrations. The optimal order of a lumped-parameter model is determined for each degree of freedom, i.e. horizontal...

  19. Design of the new rigid endoscope distortion measurement system (United States)

    Zhai, Xiaohao; Liu, Xiaohua; Liu, Ming; Hui, Mei; Dong, Liquan; Zhao, Yuejin; Wang, Yakun; Li, Yonghui; Zhou, Peng


    Endoscopic imaging quality affects industrial safety and medical security. Rigid endoscope distortion is of great signification as one of optical parameters to evaluate the imaging quality. This paper introduces a new method of rigid endoscope distortion measurement, which is different from the common methods with low accuracy and fussy operation. It contains a Liquid Crystal Display (LCD) to display the target, a CCD to obtain the images with distortion, and a computer to process the images. The LCD is employed instead of common white screen. The autonomous control system of LCD makes it showing the test target designed for distortion, and its parameter is known. LCD control system can change the test target to satisfy the different demand for accuracy, which avoids replacing target frequently. The test system also contains a CCD to acquire images in the exit pupil position of rigid endoscope. Rigid endoscope distortion is regarded as centrosymmetric, and the MATLAB software automatically measures it by processing the images from CCD. The MATLAB software compares target images with that without distortion on LCD and calculates the results. Relative distortion is obtained at different field of view (FOV) radius. The computer plots the curve of relative distortion, abscissa means radius of FOV, ordinate means relative distortion. The industry standard shows that, the distortion at 70% field of view is pointed on the curve, which can be taken as an evaluation standard. This new measuring method achieves advantages of high precision, high degree of intelligence, excellent repeatability and gets calculation results quickly.

  20. Patient satisfaction related to rigid external distraction osteogenesis

    NARCIS (Netherlands)

    van Eggermont, Bas; Jansma, J.; Bierman, M. W. J.; Stegenga, B.


    The aim of this study was to evaluate satisfaction with treatment among cleft lip and palate patients who underwent maxillary advancement using a rigid external distraction (RED) device. Nine patients (four boys, five girls), mean age 17.7 years (SD 4.0), were included in the study. Outcome measures

  1. Nonlinear optical properties of rigid-rod polymers (United States)

    Trimmer, Mark S.; Wang, Ying


    The purpose of this research project was to integrate enhanced third order nonlinear optical (NLO) properties, especially high x(exp (3)) (greater than 10(exp -8) esu), into Maxdem's novel conjugated rigid-rod polymers while retaining their desirable processing, mechanical, and thermal properties. This work primarily involved synthetic approaches to optimized materials.

  2. Rigidly connected magnetic lines: twisting and winding of magnetic lines (United States)

    Prasad, G.


    The dynamical process of magnetic flux variation in a fluid's stream tube is described by constructing 1+1+ (2) decomposition of the gradient of fluid's 4-velocity. The necessary and sufficient conditions are obtained for a spacelike congruence to be a congruence of rigidly connected spacelike curves. The evolution of magnetic flux in a magnetic tube is explored under the assumptions that magnetic lines are rigidly connected and the chemical potential of the fluid is constant along a magnetic tube. The interplay between magnetic and stream tubes is demonstrated. It is shown that the growth of magnetic energy in a magnetic tube cannot exceed to that of a stream tube. It is found that the proper time variation of twist of magnetic lines is caused by gravitation inside a neutron star if magnetic lines are rigidly connected and charge neutrality condition holds. Helmholtz-like magnetic vorticity flux conservation in a magnetic tube constituted by rigidly connected geodetic magnetic lines is derived under the assumption that the charge neutrality condition holds. It is shown that the winding of frozen-in poloidal magnetic field due to differential rotation requires meridional circulation in an axisymmetric stationary hydromagnetic configuration.

  3. Rigid-plastic seismic design of reinforced concrete structures

    DEFF Research Database (Denmark)

    Costa, Joao Domingues; Bento, R.; Levtchitch, V.


    In this paper a new seismic design procedure for Reinforced Concrete (R/C) structures is proposed-the Rigid-Plastic Seismic Design (RPSD) method. This is a design procedure based on Non-Linear Time-History Analysis (NLTHA) for systems expected to perform in the non-linear range during a lifetime ...

  4. Behaviour and Modelling of Semi-rigid Structural Frame Systems ...

    African Journals Online (AJOL)

    A computational finite element model is developed to predict the load-deflection characteristic of portal frames with semi-rigid welded and bolted joints. Plate components of frame members and joints are modelled by thin shell finite elements while bolt connectors by springs with the force-deformation characteristic ...

  5. Influence of rigid boundary on the propagation of torsional surface ...

    Indian Academy of Sciences (India)

    The present work illustrates a theoretical study on the effect of rigid boundary for the propagation of torsional surface wave in an inhomogeneous crustal layer over an inhomogeneous half space. It is believed that the inhomogeneity in the half space arises due to hyperbolic variation in shear modulus and density whereas ...

  6. Connect-disconnect coupling for preadjusted rigid shafts (United States)

    Bajkowski, F. W.; Holmberg, A.


    Coupling device enables a rigid shaft to be connected to or disconnected from a fixed base without disturbing the point of adjustment of the shaft in a socket or causing the shaft to rotate. The coupling consists of an externally threaded, internally slotted boss extending from the fixed base.

  7. Importance of axial penile rigidity in objective evaluation of erection quality in patients with erectile dysfunction--comparison with radial rigidity. (United States)

    Mizuno, Ichiro; Komiya, Akira; Watanabe, Akihiko; Fuse, Hideki


    The aim of this prospective study was to evaluate the usefulness of measurement of axial penile rigidity, compared with radial penile rigidity. Twenty-two patients, aged 21-75 years old (a mean of 50), with erectile dysfunction underwent axial penile rigidity measurements by the digital inflection rigidometer (DIR) as well as radial penile rigidity measurements by the RigiScan Plus during intracavernous pharmacological erection testing. A significant correlation was recognized between axial rigidity, and radial rigidity at the tip (p = 0.0024) and base (p = 0.0098) of the penis. In 10 patients, the DIR revealed axial rigidity of 550 g or more, and they also had radial rigidity of 60% or more at the tip and base. In 14 and 17 subjects, radial rigidity of 60% or more was observed at the tip and base, respectively. Four of the former 14 and 7 of the latter 17 had axial rigidity <550 g. A RigiScan results of radial rigidity of 60% or more should be interpreted cautiously and not necessarily regarded as normal. Copyright (c) 2010 S. Karger AG, Basel.

  8. Initial Development of an Electronic Testis Rigidity Tester

    Directory of Open Access Journals (Sweden)

    Petros Mirilas


    Full Text Available We aimed to develop our previously presented mechanical device, the Testis Rigidity Tester (TRT, into an electronic system (Electronic Testis Rigidity Tester, ETRT by applying tactile imaging, which has been used successfully with other solid organs. A measuring device, located at the front end of the ETRT incorporates a tactile sensor comprising an array of microsensors. By application of a predetermined deformation of 2 mm, increased pressure alters linearly the resistance of each microsensor, producing changes of voltage. These signals were amplified, filtered, and digitized, and then processed by an electronic collector system, which presented them as a color-filled contour plot of the area of the testis coming into contact with the sensor. Testis models of different rigidity served for initial evaluation of ETRT; their evacuated central spaces contained different, increasing glue masses. An independent method of rigidity measurement, using an electric weight scale and a micrometer, showed that the more the glue injected, the greater the force needed for a 2-mm deformation. In a preliminary test, a single sensor connected to a multimeter showed similar force measurement for the same deformation in these phantoms. For each of the testis models compressed in the same manner, the ETRT system offered a map of pressures, represented by a color scale within the contour plot of the contact area with the sensor. ETRT found certain differences in rigidity between models that had escaped detection by a blind observer. ETRT is easy to use and provides a color-coded “insight“ of the testis internal structure. After experimental testing, it could be valuable in intraoperative evaluation of testes, so that the surgeon can decide about orchectomy or orcheopexy.

  9. Deformable registration of multi-modal data including rigid structures

    Energy Technology Data Exchange (ETDEWEB)

    Huesman, Ronald H.; Klein, Gregory J.; Kimdon, Joey A.; Kuo, Chaincy; Majumdar, Sharmila


    Multi-modality imaging studies are becoming more widely utilized in the analysis of medical data. Anatomical data from CT and MRI are useful for analyzing or further processing functional data from techniques such as PET and SPECT. When data are not acquired simultaneously, even when these data are acquired on a dual-imaging device using the same bed, motion can occur that requires registration between the reconstructed image volumes. As the human torso can allow non-rigid motion, this type of motion should be estimated and corrected. We report a deformation registration technique that utilizes rigid registration for bony structures, while allowing elastic transformation of soft tissue to more accurately register the entire image volume. The technique is applied to the registration of CT and MR images of the lumbar spine. First a global rigid registration is performed to approximately align features. Bony structures are then segmented from the CT data using semi-automated process, and bounding boxes for each vertebra are established. Each CT subvolume is then individually registered to the MRI data using a piece-wise rigid registration algorithm and a mutual information image similarity measure. The resulting set of rigid transformations allows for accurate registration of the parts of the CT and MRI data representing the vertebrae, but not the adjacent soft tissue. To align the soft tissue, a smoothly-varying deformation is computed using a thin platespline(TPS) algorithm. The TPS technique requires a sparse set of landmarks that are to be brought into correspondence. These landmarks are automatically obtained from the segmented data using simple edge-detection techniques and random sampling from the edge candidates. A smoothness parameter is also included in the TPS formulation for characterization of the stiffness of the soft tissue. Estimation of an appropriate stiffness factor is obtained iteratively by using the mutual information cost function on the result

  10. Reversibilidade de fósforo não-lábil em solos submetidos à redução microbiana e química: II - extrações sucessivas do fósforo pela resina de troca aniônica Reversibility of non-labile phosphorus in soils under microbial and chemical reduction: II - successive anion exchange resin extraction of phosphorus

    Directory of Open Access Journals (Sweden)

    Iván Ernesto Fernández R.


    alteração para o grupo dos solos menos oxídicos, com menor CMAP. Todavia, nos solos mais oxídicos, com maior CMAP, o efeito prévio da sacarose foi o aumenta do P-rem (diminuição da CMAP 10 vezes em relação aos solos para o tratamento sem redução. Entretanto, a redução gerada pela sacarose não alterou a dessorção do P anteriormente adsorvido. A expectativa de que ocorreria significativa reversibilidade de P não-lábil com a redução microbiana ou química dos solos não se concretizou, demonstrando a grande estabilidade dessas formas.The formation of non-labile from labile P forms, adsorbed onto Fe and Al oxyhydroxides, is the reason for low residual of phosphate fertilization in tropical soils. The reversibility of non-labile P to labile forms in these soils may be favored by the reduction of Fe3+ and, or,by the reduced activity of Fe and Al oxyhydroxides. This study aimed to evaluate P adsorption and desorption, the transformation into non-labile forms and reversibility of these forms in soil samples from environments of microbial or chemical reduction. Samples of 11 soils were homogenized with 300 mg kg-1 P (NaH2PO4 in solution and incubated for 30 days. P was extracted in 10 successive extractions with anion-exchange resin (AER (treatment without reduction. In a second experiment, the soil samples were treated with 0.1 mol L-1 sucrose solution to create a reduction enrviroment and subsequent application of P dose (300 mg kg-1 and 10 successive P extractions (treatment microbial reduction. In a third experiment, the samples were complexed/reduced with ammonium oxalate (Ox or with citrate-dithionite-bicarbonate (CDB. The soils/residues were treated with the above P dose, incubated for 30 days and subjected to successive extractions with AER (chemical reduction. It was observed that maximum P adsorption capacity (MPAC of the soils was closer related with goethite, (which accounted for 70.8 % of the value, than gibbsite (with a contribution of 29

  11. Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers

    Directory of Open Access Journals (Sweden)

    Simone Piccinin


    Full Text Available Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main structural and electronic molecular properties. In particular, we compare the thermodynamics of the water oxidation cycle for single-site Ru-POM and multiple-site Ru4-POM complexes. For the Ru-POM case, we also investigate the reaction free energy as a function of the Ru oxidation state. We find that the overpotential of these molecular catalysts is primarily determined by the oxidation state of the metal center and is minimum for Ru(IV. In solution, the number of active sites is shown to play a minor role on the reaction energetics. The results are rationalized and discussed in terms of the local structure around the active sites and of the electrostatic screening due to the molecular structure or the solvent.

  12. Can Electron-Rich Oxygen (O2-) Withdraw Electrons from Metal Centers? A DFT Study on Oxoanion-Caged Polyoxometalates. (United States)

    Takazaki, Aki; Eda, Kazuo; Osakai, Toshiyuki; Nakajima, Takahito


    The answer to the question "Can electron-rich oxygen (O2-) withdraw electrons from metal centers?" is seemingly simple, but how the electron population on the M atom behaves when the O-M distance changes is a matter of controversy. A case study has been conducted for Keggin-type polyoxometalate (POM) complexes, and the first-principles electronic structure calculations were carried out not only for real POM species but also for "hypothetical" ones whose heteroatom was replaced with a point charge. From the results of natural population analysis, it was proven that even an electron-rich O2-, owing to its larger electronegativity as a neutral atom, withdraws electrons when electron redistribution occurs by the change of the bond length. In the case where O2- coexists with a cation having a large positive charge (e.g., P5+(O2-)4 = [PO4]3-), the gross electron population (GEP) on the M atom seemingly increases as the O atom comes closer, but this increment in GEP is not due to the role of the O atom but due to a Coulombic effect of the positive charge located on the cation. Furthermore, it was suggested that not GEP but net electron population (NEP) should be responsible for the redox properties.

  13. Two polyoxometalate-directed 3D metal-organic frameworks with multinuclear silver-ptz cycle/belts as subunits. (United States)

    Wang, Xiuli; Li, Na; Tian, Aixiang; Ying, Jun; Liu, Guocheng; Lin, Hongyan; Zhang, Juwen; Yang, Yang


    Two new polyoxometalate (POM)-based metal-organic frameworks (MOFs) constructed from multinuclear silver-ptz cycle/belts, namely [Ag7(ptz)4(NO3)(H2O)][H4P2W18O62]·5H2O () and [Ag6(ptz)4(H2O)2][HPMo12O40]·3H2O () (ptzH = 5-(3-pyridyl)-1H-tetrazole), have been successfully synthesized under hydrothermal conditions via changing the polyoxoanions and adjusting the pH. Compound exhibits a 3D framework constructed from the Wells-Dawson [P2W18O62](6-) anion and a 2D layer based on two types of multinuclear Ag-ptz cycles. In compound , the 1D infinite multinuclear Ag-ptz belts consisting of repeated tetranuclear subunits [(Ag1)2(Ag2)2(ptz)4] are connected by Ag3 ions to form a 2D layer. The adjacent 2D layers are further linked by tetra-dentate Keggin [PMo12O40](3-) anions to construct a 3D framework. The structural analyses reveal that the different polyoxoanions have a great influence on the Ag(I)-ptz multinuclear cycle/belts and the whole structures. The influences of the pH and molar ratio of initial reactants in the hydrothermal process were also discussed. The electrochemical and photocatalytic properties of the title compounds have been studied in detail.

  14. Low Work Function Lacunary Polyoxometalates as Electron Transport Interlayers for Inverted Polymer Solar Cells of Improved Efficiency and Stability. (United States)

    Tountas, Marinos; Topal, Yasemin; Polydorou, Ermioni; Soultati, Anastasia; Verykios, Apostolis; Kaltzoglou, Andreas; Papadopoulos, Theodoros A; Auras, Florian; Seintis, Kostas; Fakis, Mihalis; Palilis, Leonidas C; Tsikritzis, Dimitris; Kennou, Stella; Koutsoureli, Matroni; Papaioannou, George; Ersöz, Mustafa; Kus, Mahmut; Falaras, Polycarpos; Davazoglou, Dimitris; Argitis, Panagiotis; Vasilopoulou, Maria


    Effective interface engineering has been shown to play a vital role in facilitating efficient charge-carrier transport, thus boosting the performance of organic photovoltaic devices. Herein, we employ water-soluble lacunary polyoxometalates (POMs) as multifunctional interlayers between the titanium dioxide (TiO2) electron extraction/transport layer and the organic photoactive film to simultaneously enhance the efficiency, lifetime, and photostability of polymer solar cells (PSCs). A significant reduction in the work function (WF) of TiO2 upon POM utilization was observed, with the magnitude being controlled by the negative charge of the anion and the selection of the addenda atom (W or Mo). By inserting a POM interlayer with ∼10 nm thickness into the device structure, a significant improvement in the power conversion efficiency was obtained; the optimized POM-modified poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2- 33 ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl

  15. Highly Dispersed Polyoxometalate-Doped Porous Co3 O4 Water Oxidation Photocatalysts Derived from POM@MOF Crystalline Materials. (United States)

    Lan, Qing; Zhang, Zhi-Ming; Qin, Chao; Wang, Xin-Long; Li, Yang-Guang; Tan, Hua-Qiao; Wang, En-Bo


    Rational design of earth-abundant photocatalysts is an important issue for solar energy conversion and storage. Polyoxometalate (POM)@Co3 O4 composites doped with highly dispersive molecular metal-oxo clusters, synthesized by loading a single Keggin-type POM cluster into each confined space of a metal-organic framework (MOF), exhibit significantly improved photocatalytic activity in water oxidation compared to the pure MOF-derived nanostructure. The systematic synthesis of these composite nanocrystals allows the conditions to be tuned, and their respective water oxidation catalytic performance can be efficiently adjusted by varying the thermal treatment temperature and the feeding amount of the POM. This work not only provides a modular and tunable synthetic strategy for preparing molecular cluster@TM oxide (TM=transition metal) nanostructures, but also showcases a universal strategy that is applicable to design and construct multifunctional nanoporous metal oxide composite materials. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Highly Efficient, Near-Infrared and Visible Light Modulated Electrochromic Devices Based on Polyoxometalates and W18O49 Nanowires. (United States)

    Gu, Hongxi; Guo, Chongshen; Zhang, Shouhao; Bi, Lihua; Li, Tianchan; Sun, Tiedong; Liu, Shaoqin


    Over the past years the performance of electrochromic smart windows with the promising potential for significant energy savings has been progressively improved; however, the electrochromic windows have not yet to come into use at scale mainly because the electrochromic materials suffer from some significant drawbacks such as low coloration efficiency, slow switching time, bad durability and poor functionality. Herein, we fabricate the optically modulated electrochromic smart devices through sequential deposition of the crown-type polyoxometalates, K28Li5H7P8W48O184·92H2O (P8W48), and W18O49 nanowires. Unlike most reported electrochromic smart devices, the resulting P8W48 and W18O49 nanocomposites allow active and selective manipulation of the transmittance of near-infrared (750-1360 nm) and visible light (400-750 nm) by varying the applied potential. Furthermore, thanks to the stable nature of both P8W48 and W18O49 and precise structural control over the nanocomposites, the prepared electrochromic smart devices exhibit high efficiency, quick response and excellent stability.

  17. Deep desulfurization by amphiphilic lanthanide-containing polyoxometalates in ionic-liquid emulsion systems under mild conditions. (United States)

    Xu, Junhua; Zhao, Shen; Ji, Yuanchun; Song, Yu-Fei


    Amphiphilic lanthanide-containing polyoxometalates (POMs) were prepared by surfactant encapsulation. Investigation of these lanthanide-containing POMs in oxidative desulfurization (ODS) showed that highly efficient deep desulfurization could be achieved in only 14 min with 100% conversion of dibenzothiophene under mild conditions by using (DDA)(9)LaW(10)/[omim]PF(6) (DDA=dimethyldioctadecylammonium, omim=1-octyl-3-methyl-imidazolium) in the presence of H(2) O(2) . Furthermore, deep desulfurization proceeds smoothly in model oil with an S content as low as 50 ppm. A scaled-up experiment in which the volume of model oil was increased from 5 to 1000 mL with S content of 1000 ppm indicated that about 99% sulfur removal can be achieved in 40 mins in an ionic-liquid emulsion system. To the best of our knowledge, the (DDA)(9)LaW(10)/[omim]PF(6) catalyst system with H(2)O(2) as oxidant is one of the most efficient desulfurization systems reported so far. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Development of a polyoxometallate-based photocatalyst assembled with cucurbit[6]uril via hydrogen bonds for azo dyes degradation. (United States)

    Cao, Minna; Lin, Jingxiang; Lü, Jian; You, Yanglijun; Liu, Tianfu; Cao, Rong


    A water insoluble cucurbit[6]uril-polyoxometallates (CB[6]-POMs) composite assembled from α-Keggin type polysilicontungstate anions and macrocycle cucurbit[6]uril (CB[6]) via hydrogen bonding has been synthesized as visible light active photocatalyst. The physical and photocatalytic properties of such photocatalyst have been fully characterized by PXRD, FTIR, TG, XPS, and UV/vis diffuse reflectance spectra. The catalyst shows a good photocatalytic activity towards the degradation of methyl orange (MO) under visible light irradiation and displays good reproducibility of photocatalytic degradation by a simple recycled procedure without obvious loss in catalytic activity, which is of great significance for practical use of the photocatalyst. In the photodegradation process, the {Ni-CB[6]}(n) chain of the photocatalyst acts as sensitizer and can be induced by visible light, meanwhile the POMs chain of the photocatalyst acts as electron acceptor and deposits the electron in its LUMO. The effects of various experimental parameters and the proposed mechanisms are discussed in detail. Copyright © 2010 Elsevier B.V. All rights reserved.

  19. Recovery of homogeneous polyoxometallate catalysts from aqueous and organic media by a mesoporous ceramic membrane without loss of catalytic activity. (United States)

    Roy Chowdhury, Sankhanilay; Witte, Peter T; Blank, Dave H A; Alsters, Paul L; Ten Elshof, Johan E


    The recovery of homogeneous polyoxometallate (POM) oxidation catalysts from aqueous and non-aqueous media by a nanofiltration process using mesoporous gamma-alumina membranes is reported. The recovery of Q(12)[WZn(3)(ZnW(9)O(34))(2)] (Q=[MeN(n-C(8)H(17))(3)](+)) from toluene-based media was quantitative within experimental error, while up to 97 % of Na(12)[WZn(3)(ZnW(9)O(34))(2)] could be recovered from water. The toluene-soluble POM catalyst was used repeatedly in the conversion of cyclooctene to cyclooctene oxide and separated from the product mixture after each reaction. The catalytic activity increased steadily with the number of times that the catalyst had been recycled, which was attributed to partial removal of the excess QCl that is known to have a negative influence on the catalytic activity. Differences in the permeability of the membrane for different liquid media can be attributed to viscosity differences and/or capillary condensation effects. The influence of membrane pore radius on permeability and recovery is discussed.

  20. Efficient Conversion of Lignin to Electricity Using a Novel Direct Biomass Fuel Cell Mediated by Polyoxometalates at Low Temperatures. (United States)

    Zhao, Xuebing; Zhu, J Y


    A novel polyoxometalates (POMs) mediated direct biomass fuel cell (DBFC) was used in this study to directly convert lignin to electricity at low temperatures with high power output and Faradaic efficiency. When phosphomolybdic acid H3 PMo12 O40 (PMo12) was used as the electron and proton carrier in the anode solution with a carbon electrode, and O2 was directly used as the final electron acceptor under the catalysis of Pt, the peak power density reached 0.96 mW cm(-2), 560 times higher than that of phenol-fueled microbial fuel cells (MFCs). When the cathode reaction was catalyzed by PMo12, the power density could be greatly enhanced to 5 mW cm(-2). Continuous operation demonstrated that this novel fuel cell was promising as a stable electrochemical power source. Structure analysis of the lignin indicated that the hydroxyl group content was reduced whereas the carbonyl group content increased. Both condensation and depolymerization takes place during the PMo12 oxidation of lignin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A multiunit catalyst with synergistic stability and reactivity: a polyoxometalate-metal organic framework for aerobic decontamination. (United States)

    Song, Jie; Luo, Zhen; Britt, David K; Furukawa, Hiroyasu; Yaghi, Omar M; Hardcastle, Kenneth I; Hill, Craig L


    A combination of polyanion size and charge allows the Keggin-type polyoxometalate (POM), [CuPW(11)O(39)](5-), a catalyst for some air-based organic oxidations, to fit snuggly in the pores of MOF-199 (HKUST-1), a metal-organic framework (MOF) with the POM countercations residing in alternative pores. This close matching of POM diameter and MOF pore size in this POM-MOF material, [Cu(3)(C(9)H(3)O(6))(2)](4)[{(CH(3))(4)N}(4)CuPW(11)O(39)H] (1), results in a substantial synergistic stabilization of both the MOF and the POM. In addition, this heretofore undocumented POM-MOF interaction results in a dramatic increase in the catalytic turnover rate of the POM for air-based oxidations. While 1 catalyzes the rapid chemo- and shape-selective oxidation of thiols to disulfides and, more significantly, the rapid and sustained removal of toxic H(2)S via H(2)S + 1/2 O(2) → 1/8 S(8) + H(2)O (4000 turnovers in MOF alone is catalytically slow or inactive. Three arguments are consistent with the catalytic reactions taking place inside the pores. POM activation by encapsulation in the MOF likely involves electrostatic interactions between the two components resulting in a higher reduction potential of the POM.

  2. Sonochemical synthesis of polyoxometalate based of ionic crystal nanostructure: A photocatalyst for degradation of 2,4-dichlorophenol. (United States)

    Shahrnoy, Abdolghafar Abolhosseini; Mahjoub, Ali Reza; Morsali, Ali; Dusek, Michal; Eigner, Vaclav


    Single crystals of new polyoxometalate based ionic crystal [Fe(phen)3]2[SiW12O40]·3DMF (IC-Fe), (phen=1,10-phenanthroline, DMF=N,N-dimethylformamide) and their nanoparticles (IC-Fe-NPs) have been synthesized via self-assembly of constituent ions and sonochemical reaction, respectively. All materials have been characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), thermal gravimetric (TG), powder X-ray diffraction (PXRD), FT-IR spectroscopy and elemental analyses. Effect of sonication conditions on size and morphology of IC-Fe was investigated including time, concentrations of initial reagents and power of irradiation. Further studies have shown that IC-Fe is not only active in photocatalytic degradation of 2,4-dichlorophenol under visible light irradiation, but also is very stable in the various solvents and it can be easily separated and reused for cycles of reaction. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Towards accurate modeling of noncovalent interactions for protein rigidity analysis. (United States)

    Fox, Naomi; Streinu, Ileana


    Protein rigidity analysis is an efficient computational method for extracting flexibility information from static, X-ray crystallography protein data. Atoms and bonds are modeled as a mechanical structure and analyzed with a fast graph-based algorithm, producing a decomposition of the flexible molecule into interconnected rigid clusters. The result depends critically on noncovalent atomic interactions, primarily on how hydrogen bonds and hydrophobic interactions are computed and modeled. Ongoing research points to the stringent need for benchmarking rigidity analysis software systems, towards the goal of increasing their accuracy and validating their results, either against each other and against biologically relevant (functional) parameters. We propose two new methods for modeling hydrogen bonds and hydrophobic interactions that more accurately reflect a mechanical model, without being computationally more intensive. We evaluate them using a novel scoring method, based on the B-cubed score from the information retrieval literature, which measures how well two cluster decompositions match. To evaluate the modeling accuracy of KINARI, our pebble-game rigidity analysis system, we use a benchmark data set of 20 proteins, each with multiple distinct conformations deposited in the Protein Data Bank. Cluster decompositions for them were previously determined with the RigidFinder method from Gerstein's lab and validated against experimental data. When KINARI's default tuning parameters are used, an improvement of the B-cubed score over a crude baseline is observed in 30% of this data. With our new modeling options, improvements were observed in over 70% of the proteins in this data set. We investigate the sensitivity of the cluster decomposition score with case studies on pyruvate phosphate dikinase and calmodulin. To substantially improve the accuracy of protein rigidity analysis systems, thorough benchmarking must be performed on all current systems and future

  4. Role of cation size in the energy of electron transfer to 1:1 polyoxometalate ion pairs {(M+)(Xn+VW11O40)}(8–n)–(M=Li, Na, K) (United States)

    Vladimir A. Grigoriev; Craig L. Hill; Ira A. Weinstock


    The use of soluble salts of polyoxometalates (d0-early-transition metal oxygen-anion clusters or POMs) as selective oxidation or electron-transfer catalysts, as probes in physical-organic and biological chemistry, and in the study of electron-and energy-transfer phenomena constitutes a substantial and rapidly growing literature. While rarely addressed, however, POM...

  5. The ‘twin paradox’ in relativistic rigid motion (United States)

    Ben-Ya'acov, Uri


    Relativistic rigid motion suggests a new version for the so-called ‘twin paradox’, comparing the ages of two astronauts on a very long spaceship. Although there is always an instantaneous inertial frame in which the whole spaceship, being rigid, is simultaneously at rest, the twins’ ages, measured as the proper-times along their individual world lines, are different when they are located at remote parts of the spaceship. The age, or proper-time, difference depends on the distance at rest between the astronauts and the rapidity difference between start to end. The relation of the age difference with the relative Doppler shift of light signals transmitted between the astronauts and implications for the possibility to assign a common age (proper-time) to complex, spatially extended, relativistic systems are also discussed.

  6. A density-independent rigidity transition in biological tissues (United States)

    Bi, Dapeng; Lopez, J. H.; Schwarz, J. M.; Manning, M. Lisa


    Cell migration is important in many biological processes, including embryonic development, cancer metastasis and wound healing. In these tissues, a cell’s motion is often strongly constrained by its neighbours, leading to glassy dynamics. Although self-propelled particle models exhibit a density-driven glass transition, this does not explain liquid-to-solid transitions in confluent tissues, where there are no gaps between cells and therefore the density is constant. Here we demonstrate the existence of a new type of rigidity transition that occurs in the well-studied vertex model for confluent tissue monolayers at constant density. We find that the onset of rigidity is governed by a model parameter that encodes single-cell properties such as cell-cell adhesion and cortical tension, providing an explanation for liquid-to-solid transitions in confluent tissues and making testable predictions about how these transitions differ from those in particulate matter.

  7. Rigid or flexible sigmoidoscopy in colorectal clinics? Appraisal through a systematic review and meta-analysis.

    LENUS (Irish Health Repository)

    Ahmad, Nasir Zaheer


    Rigid sigmoidoscopy is sometimes performed at first presentation in colorectal clinics. We assessed the feasibility of flexible sigmoidoscopy in similar situations by comparing it with rigid sigmoidoscopy as a first investigative tool.

  8. On Polya's inequality for torsional rigidity and first Dirichlet eigenvalue


    Berg, M. van den; Ferone, V.; Nitsch, C.; Trombetti, C.


    Let $\\Omega$ be an open set in Euclidean space with finite Lebesgue measure $|\\Omega|$. We obtain some properties of the set function $F:\\Omega\\mapsto \\R^+$ defined by $$ F(\\Omega)=\\frac{T(\\Omega)\\lambda_1(\\Omega)}{|\\Omega|} ,$$ where $T(\\Omega)$ and $\\lambda_1(\\Omega)$ are the torsional rigidity and the first eigenvalue of the Dirichlet Laplacian respectively. We improve the classical P\\'olya bound $F(\\Omega)\\le 1,$ and show that $$F(\\Omega)\\le 1- \

  9. NOLB: Nonlinear Rigid Block Normal Mode Analysis Method


    Hoffmann, Alexandre; Grudinin, Sergei


    International audience; We present a new conceptually simple and computationally efficient method for non-linear normal mode analysis called NOLB. It relies on the rotations-translations of blocks (RTB) theoretical basis developed by Y.-H. Sanejouand and colleagues. We demonstrate how to physically interpret the eigenvalues computed in the RTB basis in terms of angular and linear velocities applied to the rigid blocks and how to construct a non-linear extrapolation of motion out of these velo...

  10. Alternative Material Dowel Bars for Rigid Pavement Joints


    ECT Team, Purdue


    Over the last thirty to forty years, dowel support of the joint in Rigid Joint Pavement (RJP) has been widely used. The problem of deterioration of concrete pavement joints has resulted in the search for alternate solutions. Fiber-reinforced polymer (FRP) and stainless steel represent corrosion resistant alternatives to conventional galvanized steel in this application. The recently study by the FHWA of Alternative Materials for Highway Construction demonstrated that even with extended wet-dr...

  11. Nonlinear dynamics mathematical models for rigid bodies with a liquid

    CERN Document Server

    Lukovsky, Ivan A


    This book is devoted to analytically approximate methods in the nonlinear dynamics of a rigid body with cavities partly filled by liquid. It combines several methods and compares the results with experimental data. It is useful for experienced and early-stage readers interested in analytical approaches to fluid-structure interaction problems, the fundamental mathematical background and modeling the dynamics of such complex mechanical systems.

  12. Stability characterizations of fixtured rigid bodies with Coulomb friction

    Energy Technology Data Exchange (ETDEWEB)



    This paper formally introduces several stability characterizations of fixtured three-dimensional rigid bodies initially at rest and in unilateral contact with Coulomb friction. These characterizations, weak stability and strong stability, arise naturally from the dynamic model of the system, formulated as a complementarity problem. Using the tools of complementarity theory, these characterizations are studied in detail to understand their properties and to develop techniques to identify the stability classifications of general systems subjected to known external loads.

  13. Oscillation of a rigid rod in the special relativity

    CERN Document Server

    Paiva, F M


    In the special relativity, a rigid rod slides upon itself, with one extremity oscillating harmonically. We discovered restrictions in the amplitude of the motion and in the length of the rod, essential to eliminate unphysical solutions. ------- Cxe la speciala relativeco, rigida stango movigxas sur si mem, kun unu fino oscilante harmonie. Ni malkovris limigajn kondicxojn pri la amplitudo de movado kaj pri la longo de stango, necesegaj por elimini ne-fizikajn solvojn.

  14. Theory of the rotation of the rigid earth (United States)

    Kinoshita, H.


    Equations of motion for a triaxial rigid earth are derived in Andoyer variables. The reference plane is the ecliptic of date which is moving as a result of planetary perturbations. By using this noninertial system, the development of the disturbing function for the sun and moon is simplified, with an additional term appearing in the Hamiltonian which, however, contributes only to precessional motion. The nutation terms derived are compared with those of Woolard.

  15. As-Rigid-As-Possible molecular interpolation paths (United States)

    Nguyen, Minh Khoa; Jaillet, Léonard; Redon, Stéphane


    This paper proposes a new method to generate interpolation paths between two given molecular conformations. It relies on the As-Rigid-As-Possible (ARAP) paradigm used in Computer Graphics to manipulate complex meshes while preserving their essential structural characteristics. The adaptation of ARAP approaches to the case of molecular systems is presented in this contribution. Experiments conducted on a large set of benchmarks show how such a strategy can efficiently compute relevant interpolation paths with large conformational rearrangements.

  16. Rigid bronchoscOpic dilatation of postintubation tracheal stenosis

    African Journals Online (AJOL)

    trice, dilatation percutanée, dilatation bronchospique rigide, dilatation de la technologie des fibres optiques de la bulle ct. Nd;YAG (neodymium yttritium - aluminium garnet) la théra- pie laser avec ou sans le stenting. Méthodes: Trois malade du sexe féminins avec une histoire des périodes diverscs d'intubation endotrachée ...

  17. Rigidity theorem for Willmore surfaces in a sphere

    Indian Academy of Sciences (India)

    compact non-minimal flat Willmore surfaces in S3, and Castro and Urbano [2] constructed many compact non-minimal Willmore surfaces in S4. In [6], Li obtained the following rigidity theorem for Willmore surfaces in a unit sphere. Theorem A. Let M be a compact Willmore surface in S2+p. Then. ∫M ρ2 (2 − 2B ρ2) dv ≤ 0,.

  18. A model of the soft tissue artefact rigid component. (United States)

    Camomilla, V; Bonci, T; Dumas, R; Chèze, L; Cappozzo, A


    When using stereophotogrammetry and skin-markers, the reconstruction of skeletal movement is affected by soft-tissue artefact (STA). This may be described by considering a marker-cluster as a deformable shape undergoing a geometric transformation formed by a non-rigid (change in size and shape) and a rigid component (translation and rotation displacements). A modal decomposition of the STA, relative to an appropriately identified basis, allows the separation of these components. This study proposes a mathematical model of the STA that embeds only its rigid component and estimates the relevant six mode amplitudes as linear functions of selected proximal and distal joint rotations during the analysed task. This model was successfully calibrated for thigh and shank using simultaneously recorded pin- and skin-marker data of running volunteers. The root mean square difference between measured and model-estimated STA rigid component was 1.1(0.8)mm (median (inter-quartile range) over 3 subjects × 5 trials × 33 markers coordinates), and it was mostly due to the wobbling not included in the model. Knee joint kinematics was estimated using reference pin-marker data and skin-marker data, both raw and compensated with the model-estimated STA. STA compensation decreased inaccuracy on average from 6% to 1% for flexion/extension, from 43% to 18% for the other two rotations, and from 69% to 25% for the linear displacements. Thus, the proposed mathematical model provides an STA estimate which can be effectively used within optimal bone pose and joint kinematics estimators for artefact compensation, and for simulations aimed at their comparative assessments. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Crack identification for rigid pavements using unmanned aerial vehicles (United States)

    Bahaddin Ersoz, Ahmet; Pekcan, Onur; Teke, Turker


    Pavement condition assessment is an essential piece of modern pavement management systems as rehabilitation strategies are planned based upon its outcomes. For proper evaluation of existing pavements, they must be continuously and effectively monitored using practical means. Conventionally, truck-based pavement monitoring systems have been in-use in assessing the remaining life of in-service pavements. Although such systems produce accurate results, their use can be expensive and data processing can be time consuming, which make them infeasible considering the demand for quick pavement evaluation. To overcome such problems, Unmanned Aerial Vehicles (UAVs) can be used as an alternative as they are relatively cheaper and easier-to-use. In this study, we propose a UAV based pavement crack identification system for monitoring rigid pavements’ existing conditions. The system consists of recently introduced image processing algorithms used together with conventional machine learning techniques, both of which are used to perform detection of cracks on rigid pavements’ surface and their classification. Through image processing, the distinct features of labelled crack bodies are first obtained from the UAV based images and then used for training of a Support Vector Machine (SVM) model. The performance of the developed SVM model was assessed with a field study performed along a rigid pavement exposed to low traffic and serious temperature changes. Available cracks were classified using the UAV based system and obtained results indicate it ensures a good alternative solution for pavement monitoring applications.

  20. A Convertible Spinal Orthosis for Controlled Torso Rigidity

    Directory of Open Access Journals (Sweden)

    Nicole I. Kern


    Full Text Available A traditional spinal orthosis in conjunction with a hip-knee-ankle-foot orthosis (HKAFO improves posture in persons with paraplegia during standing and walking. It also limits the wearer's range of motion when worn during other activities, such as vehicle transfer or sitting and reaching for objects. In order to regain full torso flexibility the user would need to remove the spinal orthosis which can be arduous and time consuming. A Convertible Spinal Orthosis (CSO that allows the user to switch between Locked rigid torso support and Unlocked free motion has been designed, fabricated and tested. It shows promise for increasing functionality, wear time and subject comfort. Analysis of movement has been performed with an able-bodied and a paraplegic subject wearing a rigid spinal orthosis, the CSO in both states, and without any bracing. Configuration state had the most impact on lateral bending. Mean values for the paraplegic subject of 27°, 38°, 48°, and 48° and for the able-bodied subject of 22°, 26°, 48°, and 45° were found for lateral bending of the upper torso relative to the thighs in the Rigid, Locked, Unlocked, and No-Brace states, respectively.

  1. Symmetrical Parameterization of Rigid Body Transformations for Biomolecular Structures. (United States)

    Kim, Jin Seob; Chirikjian, Gregory S


    Assessing preferred relative rigid body position and orientation is important in the description of biomolecular structures (such as proteins) and their interactions. In this article, we extend and apply the "symmetrical parameterization," which we recently introduced in the kinematics community, to address problems in structural biology. We also review parameterization methods that are widely used in structural biology to describe relative rigid body motions (in particular, orientations) as a basis for comparison. The new symmetrical parameterization is useful in describing the relative biomolecular rigid body motions, where the parameters are symmetrical in the sense that the subunits of a complex biomolecular structure are described in the same way for the corresponding motion and its inverse. The properties of this new parameterization, singularity analysis, and inverse kinematics are also investigated in more detail. Finally, parameterization is applied to real biomolecular structures and a potential application to structure modeling of symmetric macromolecules to show the efficacy of the symmetrical parameterization in the field of computational structural biology.

  2. Chiral Orientation of Skeletal Muscle Cells Requires Rigid Substrate

    Directory of Open Access Journals (Sweden)

    Ninghao Zhu


    Full Text Available Reconstitution of tissue morphology with inherent left–right (LR asymmetry is essential for tissue/organ functions. For skeletal muscle, the largest tissue in mammalian organisms, successful myogenesis requires the regulation of the LR asymmetry to form the appropriate muscle alignment. However, the key factor for reproducing the LR asymmetry of skeletal tissues in a controllable, engineering context remains largely unknown. Recent reports indicate that cell chirality may underlie the LR development in tissue morphogenesis. Here, we report that a rigid substrate is required for the chirality of skeletal muscle cells. By using alternating micropatterned cell-adherent and cell-repellent stripes on a rigid substrate, we found that C2C12 skeletal muscle myoblasts exhibited a unidirectional tilted orientation with respect to the stripe boundary. Importantly, such chiral orientation was reduced when soft substrates were used instead. In addition, we demonstrated the key role of actin stress fibers in the formation of the chiral orientation. This study reveals that a rigid substrate is required for the chiral pattern of myoblasts, paving the way for reconstructing damaged muscle tissue with inherent LR asymmetry in the future.

  3. Green waste cooking oil-based rigid polyurethane foam (United States)

    Enderus, N. F.; Tahir, S. M.


    Polyurethane is a versatile polymer traditionally prepared using petroleum-based raw material. Petroleum, however, is a non-renewable material and polyurethane produced was found to be non-biodegradable. In quest for a more environmentally friendly alternative, wastecooking oil, a highly abundant domestic waste with easily derivatized structure, is a viable candidate to replace petroleum. In this study,an investigation to determine physical and chemical properties of rigid polyurethane (PU) foam from waste cooking oil (WCO) was carried out. WCO was first adsorbed by using coconut husk activated carbon adsorbent prior to be used for polyol synthesis. The purified WCO was then used to synthesize polyol via transesterification reaction to yield alcohol groups in the WCO chains structure. Finally, the WCO-based polyol was used to prepare rigid PU foam. The optimum formulation for PU formation was found to be 90 polyol: 60 glycerol: 54 water: 40 diethanolamine: 23 diisocyanate. The rigid PU foam has density of 208.4 kg/m3 with maximum compressive strength and capability to receive load at 0.03 MPa and 0.09 kN, respectively. WCO-based PU can potentially be used to replace petroleum-based PU as house construction materials such as insulation panels.

  4. Coarse-grained rigid blob model for soft matter simulations. (United States)

    Chao, Sheng D; Kress, Joel D; Redondo, Antonio


    We have developed a coarse-grained multiscale molecular simulation method for soft matter systems that directly incorporates stereochemical information. We divide the material into disjoint groups of atoms or particles that move as separate rigid bodies; we call these groups "rigid blobs," hence the name coarse-grained rigid blob model. The method is enabled by the construction of transferable interblob potentials that approximate the net intermolecular interactions, as obtained from ab initio electronic structure calculations, other all-atom empirical potentials, experimental data, or any combination of the above. We utilize a multipolar expansion to obtain the interblob potential-energy functions. The series, which contains controllable approximations that allow us to estimate the errors, approaches the original intermolecular potential as the number of terms increases. Using a novel numerical algorithm, we can calculate the interblob potentials very efficiently in terms of a few interaction moment tensors. This reduces the labor well beyond what is required in standard molecular-dynamics calculations and allows large-scale simulations for temporal scales commensurate with characteristic times of nano- and mesoscale systems. A detailed derivation of the formulas is presented, followed by illustrative applications to several systems showing that the method can effectively capture realistic microscopic details and can easily extend to large-scale simulations.

  5. Operator Algebras in Rigid C*-Tensor Categories (United States)

    Jones, Corey; Penneys, David


    In this article, we define operator algebras internal to a rigid C*-tensor category C. A C*/W*-algebra object in C is an algebra object A in ind-C whose category of free modules {FreeMod_C(A)} is a C-module C*/W*-category respectively. When C= Hilb_fd, the category of finite dimensional Hilbert spaces, we recover the usual notions of operator algebras. We generalize basic representation theoretic results, such as the Gelfand-Naimark and von Neumann bicommutant theorems, along with the GNS construction. We define the notion of completely positive morphisms between C*-algebra objects in C and prove the analog of the Stinespring dilation theorem. As an application, we discuss approximation and rigidity properties, including amenability, the Haagerup property, and property (T) for a connected W*-algebra M in C. Our definitions simultaneously unify the definitions of analytic properties for discrete quantum groups and rigid C*-tensor categories.

  6. Integrable Problems of the Dynamics of Coupled Rigid Bodies (United States)

    Bogoyavlenskiĭ, O. I.


    Several classical problems of dynamics are shown to be integrable for the special systems of coupled rigid bodies introduced in this paper and called Ck-central configurations. It is proved that the dynamics of an arbitrary Ck-central configuration in the Newtonian gravitational field with an arbitrary quadratic potential is integrable in the Liouville sense and in theta-functions of Riemann surfaces. A hidden symmetry of the inertial dynamics of these configurations is found, and reductions of the corresponding Lagrange equations to the Euler equations on the direct sums of Lie coalgebras SO(3) are obtained. Reductions and integrable cases of the equations for the rotation of a heavy Ck-central configuration about a fixed point are indicated. Separation of rotations of a space station type orbiting system, which is a Ck-central configuration of rigid bodies, is proved. This result leads to the possibility of independent stabilization of rotations of the rigid bodies in such orbiting configurations. Integrability of the inertial dynamics of CRn-central configurations of coupled gyrostats is proved.

  7. Predicting Protein Hinge Motions and Allostery Using Rigidity Theory (United States)

    Sljoka, Adnan; Bezginov, Alexandr


    Understanding how a 3D structure of a protein functions depends on predicting which regions are rigid, and which are flexible. One recent approach models molecules as a structure of fixed units (atoms with their bond angles as rigid units, bonds as hinges) plus biochemical constraints coming from the local geometry. This generates a `molecular graph' in the theory of combinatorial rigidity. The 6|V|-6 counting condition for 3-dimensional body-hinge structures (modulo molecular theorem), and a fast `pebble game' algorithm which tracks this count in the multigraph, have led to the development of the program FIRST, for rapid predictions of the flexibility of proteins. In this study we develop a novel protein hinge prediction algorithm via our extension of the pebble game algorithm (relevant regions detection algorithm). We have tested our hinge prediction algorithm on several proteins chosen from the dataset of manually annotated hinges available on the MOLMOV server. Many of our predictions are in very good agreement with this data set. Our algorithms can also predict `allosteric' interactions in proteins—where binding on one site of a molecule changes the shape or binding at a distance `active site' of the molecule. We also give some promising results which support the sliding piston-like movement of helices with respect to one another as a plausible mechanism by which GCPR receptors propagate conformational changes across membranes.

  8. On the Existence and Utility of Rigid Quasilocal Frames

    CERN Document Server

    Epp, Richard J; McGrath, Paul L


    The notion of a rigid quasilocal frame (RQF) provides a geometrically natural way to define a system in general relativity, and a new way to analyze the problem of motion. An RQF is defined as a two-parameter family of timelike worldlines comprising the boundary (topologically R x S^2) of the history of a finite spatial volume, with the rigidity conditions that the congruence of worldlines be expansion- and shear-free. In other words, the size and shape of the system do not change. In previous work, such systems in Minkowski space were shown to admit precisely the same six degrees of freedom of rigid body motion that we are familiar with in Newtonian space-time, without any constraints, circumventing a century-old theorem due to Herglotz and Noether. This is a consequence of the fact that a two-sphere of any shape always admits precisely six conformal Killing vector fields, which generate an action of the Lorentz group on the sphere. Here we review the previous work in flat spacetime and extend it in three di...

  9. Measuring membrane rigidity and viscosity: New methods, and new insights (United States)

    Parthasarathy, Raghuveer


    Lipid membranes are remarkable materials: flexible, two-dimensional fluids whose physical properties guide cellular function. Bending rigidity and viscosity are two of the key mechanical parameters that characterize membranes. Both, however, are challenging to measure. I describe improvements in experimental techniques to quantify the bending modulus and the two-dimensional viscosity of lipid membranes. First, I show that using selective plane illumination microscopy (SPIM, also known as light sheet fluorescence microscopy) to image the thermal fluctuations of freely suspended giant lipid vesicles enables straightforward measurements of membrane rigidity, and also provides insights into changes in rigidity induced by cargo trafficking proteins. Second, I show that tracking both the rotational and translational diffusion of membrane-anchored tracer particles allows quantification of membrane viscosity, measurement of the effective radii of the tracers, and assessment of theoretical models of membrane hydrodynamics. Surprisingly, we find a wide distribution of effective tracer sizes, due presumably to a wide variety of couplings to the membrane. I also provide an example of protein-mediated changes in lipid viscosity.

  10. The diagnostic role of thoracoscope in undiagnosed pleural effusion: Rigid versus flexible

    Directory of Open Access Journals (Sweden)

    Mostafa Mahmoud Abdel Mageid Shaheen


    Conclusions: Thoracoscopy using either fibreoptic bronchoscope or rigid thoracoscope is safe and well tolerated. Rigid thoracoscope has a higher diagnostic yield, easier handling, better orientation and is less expensive. Nevertheless, fibreoptic bronchoscope is an alternative technique if rigid thoracoscopy is not available.

  11. Synergistic influence of polyoxometalate surface corona towards enhancing the antibacterial performance of tyrosine-capped Ag nanoparticles (United States)

    Daima, Hemant K.; Selvakannan, P. R.; Kandjani, Ahmad E.; Shukla, Ravi; Bhargava, Suresh K.; Bansal, Vipul


    We illustrate a new strategy to improve the antibacterial potential of silver nanoparticles (AgNPs) by their surface modification with the surface corona of biologically active polyoxometalates (POMs). The stable POM surface corona was achieved by utilising zwitterionic tyrosine amino acid as a pH-switchable reducing and capping agent of AgNPs. The general applicability of this approach was demonstrated by developing surface coronas of phosphotungstic acid (PTA) and phosphomolybdic acid (PMA) around AgNPs. Our investigations on Gram negative bacterium Escherichia coli demonstrate that in conjugation with AgNPs, the surface corona of POMs enhances the physical damage to the bacterial cells due to synergistic antibacterial action of AgNPs and POMs, and the ability of tyrosine-reduced AgNPs (AgNPsY) to act as an excellent carrier and stabiliser for the POMs. The further extension of this study towards Gram positive bacterium Staphylococcus albus showed a similar toxicity pattern, whereas these nanomaterials were found to be biocompatible for PC3 epithelial mammalian cells, suggesting the potential of these materials towards specific antimicrobial targeting for topical wound healing applications. The outcomes of this work show that facile tailorability of nanostructured surfaces may play a considerable role in controlling the biological activities of different nanomaterials.We illustrate a new strategy to improve the antibacterial potential of silver nanoparticles (AgNPs) by their surface modification with the surface corona of biologically active polyoxometalates (POMs). The stable POM surface corona was achieved by utilising zwitterionic tyrosine amino acid as a pH-switchable reducing and capping agent of AgNPs. The general applicability of this approach was demonstrated by developing surface coronas of phosphotungstic acid (PTA) and phosphomolybdic acid (PMA) around AgNPs. Our investigations on Gram negative bacterium Escherichia coli demonstrate that in conjugation

  12. Controlled interactions between anhydrous keggin-type heteropolyacids and silica support: Preparation and characterization of well-defined silica-supported polyoxometalate species

    KAUST Repository

    Grinenval, Eva


    Anhydrous Keggin-type phosphorus heteropolyacids were deposited on partially dehydroxylated silica by using the surface organometallic chemistry (SOMC) strategy. The resulting solids were characterized by a combination of physicochemical methods including IR, Raman, 1D and 2D 1H, and 31P MAS NMR, electron microscopy experiments and density functional theory (DFT) calculations. It is shown that the main surface species is [ - Si(OH...H+)]2[H+]1[PM 12O403-] where the polyoxometalate is linked to the support by proton interaction with two silanols. Two other minor species (10% each) are formed by coordination of the polyoxometalate to the surface via the interaction between all three protons with three silanol groups or via three covalent bonds formed by dehydroxylation of the above species. Comparison of the reactivity of these solids and of compounds prepared by a classical way shows that the samples prepared by the SOMC approach contain ca. 7 times more acid sites. © 2010 American Chemical Society.

  13. Polyoxometallate-stabilized Pt-Ru catalysts on multiwalled carbon nanotubes: Influence of preparation conditions on the performance of direct methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Han, D.M. [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Institute of Energy and Environment Materials, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou (China); Guo, Z.P.; Zhao, Z.W.; Zeng, R.; Liu, H.K. [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Meng, Y.Z. [Institute of Energy and Environment Materials, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou (China); Shu, D. [Department of Chemistry, South China Normal University, Guangzhou (China)


    A novel catalyst, polyoxometallate-stabilized platinum-ruthenium alloy nanoparticles supported on multiwalled carbon nanotubes (Pt-Ru-PMo{sub 12}-MWNTs), was synthesized by a microwave-assisted polyol process. The effects of microwave reaction time, microwave reaction power, and pH value of the reaction solution on the electrocatalytic properties of Pt-Ru-PMo{sub 12}-MWNTs catalysts were also investigated. The polyoxometallate (PMo{sub 12}) formed a self-assembled monolayer on the surface of the Pt/Ru nanoparticles and MWNTs, which effectively prevented the agglomeration of Pt, Ru nanoparticles and MWNTs, due to the electrostatic repulsive interactions between the negatively charged PMo{sub 12} monolayers. Energy dispersive spectroscopy examination and electrochemical measurements showed that the loading content of Pt/Ru and their electrochemical activity vary with the synthesis conditions, such as pH, reaction time, and microwave power. It was found that the a Pt-Ru-PMo{sub 12}-MWNTs electrocatalyst with high Pt loading content, small crystallite size, and good electrocatalytic activity could be synthesized using a long reaction time, intermediate microwave power, and a pH value of 7. The electrocatalysts obtained were characterized using X-ray diffraction, and scanning and transmission electron microscopy. Their electrocatalytic properties were also investigated by using the cyclic voltammetry technique. (author)

  14. Polyoxometallate-stabilized Pt-Ru catalysts on multiwalled carbon nanotubes: Influence of preparation conditions on the performance of direct methanol fuel cells (United States)

    Han, D. M.; Guo, Z. P.; Zhao, Z. W.; Zeng, R.; Meng, Y. Z.; Shu, D.; Liu, H. K.

    A novel catalyst, polyoxometallate-stabilized platinum-ruthenium alloy nanoparticles supported on multiwalled carbon nanotubes (Pt-Ru-PMo 12-MWNTs), was synthesized by a microwave-assisted polyol process. The effects of microwave reaction time, microwave reaction power, and pH value of the reaction solution on the electrocatalytic properties of Pt-Ru-PMo 12-MWNTs catalysts were also investigated. The polyoxometallate (PMo 12) formed a self-assembled monolayer on the surface of the Pt/Ru nanoparticles and MWNTs, which effectively prevented the agglomeration of Pt, Ru nanoparticles and MWNTs, due to the electrostatic repulsive interactions between the negatively charged PMo 12 monolayers. Energy dispersive spectroscopy examination and electrochemical measurements showed that the loading content of Pt/Ru and their electrochemical activity vary with the synthesis conditions, such as pH, reaction time, and microwave power. It was found that the a Pt-Ru-PMo 12-MWNTs electrocatalyst with high Pt loading content, small crystallite size, and good electrocatalytic activity could be synthesized using a long reaction time, intermediate microwave power, and a pH value of 7. The electrocatalysts obtained were characterized using X-ray diffraction, and scanning and transmission electron microscopy. Their electrocatalytic properties were also investigated by using the cyclic voltammetry technique.

  15. Cation-mediated optical resolution and anticancer activity of chiral polyoxometalates built from entirely achiral building blocks

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhi-Ming; Duan, Xiaopin; Yao, Shuang; Wang, Zhishu; Lin, Zekai; Li, Yang-Guang; Long, La-Sheng; Wang, En-Bo; Lin, Wenbin


    We report the crystallization of homochiral polyoxometalate (POM) macroanions {CoSb6O4(H2O)3[Co(hmta)SbW8O31]3}15- (1, hmta = hexamethylenetetramine) via the counter cation-mediated chiral symmetry breaking and asymmetric autocatalytic processes. In the presence of low Co2+ concentrations both Δ- and Λ-enantiomers of 1 formed in the reaction, crystallizing into the racemic crystal rac-1. At a high Co2+ concentration, the polyoxoanion enantiomers showed a high level of chiral recognition via H-bonding interactions to crystallize into enantiopure crystals of Δ- or Λ-[Co(H2O)6{CoSb6O4(H2O)3[Co(hmta)SbW8O31]3}]13-. During crystallization, a microscale symmetry-breaking event and a nonlinear asymmetric autocatalysis process make the enantiomers crystallize in different batches, which provides an opportunity to isolate the homochiral bulk materials. The defined structures of the racemic and homochiral crystals thus provide a molecular-level illustration that H-bonding interactions are responsible for such high-level chiral recognition, in a process similar to the supramolecular chirality frequently observed in biology. These POM macroanions showed a high cytotoxicity against various cancer cells, particularly ovarian cancer cells. The antitumor activity of these compounds resulted at least in part from the activation of the apoptotic pathways, as shown by the flow cytometry, Annexin V staining, DNA ladder, and TUNEL assay, likely by blocking the cell cycle and complexing with proteins in cells. The POM macroanions reported herein provide promising and novel antitumor agents for the potential treatment of various cancers.

  16. Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation (United States)

    Boulicault, Jean E.; Alves, Sandra; Cole, Richard B.


    MALDI-MS has been developed for the negative ion mode analysis of polyoxometalates (POMs). Matrix optimization was performed using a variety of matrix compounds. A first group of matrixes offers MALDI mass spectra containing abundant intact singly charged anionic adduct ions, as well as abundant in-source fragmentations at elevated laser powers. A relative ranking of the ability to induce POM fragmentation is found to be: DAN > CHCA > CNA > DIT> HABA > DCTB > IAA. Matrixes of a second group provide poorer quality MALDI mass spectra without observable fragments. Sample preparation, including the testing of salt additives, was performed to optimize signals for a model POM, POMc12, the core structure of which bears four negative charges. The matrix 9-cyanoanthracene (CNA) provided the best signals corresponding to singly charged intact POMc12 anions. Decompositions of these intact anionic species were examined in detail, and it was concluded that hydrogen radical-induced mechanisms were not prevalent, but rather that the observed prompt fragments originate from transferred energy derived from initial electronic excitation of the CNA matrix. Moreover, in obtained MALDI mass spectra, clear evidence of electron transfer to analyte POM species was found: a manifestation of the POMs ability to readily capture electrons. The affinity of polyanionic POMc12 toward a variety of cations was evaluated and the following affinity ranking was established: Fe3+ > Al3+ > Li+ > Ga3+ > Co2+ > Cr3+ > Cu2+ > [Mn2+, Mg2+] > [Na+, K+]. Thus, from the available cationic species, specific adducts are preferentially formed, and evidence is given that these higher affinity POM complexes are formed in the gas phase during the early stages of plume expansion.

  17. Selective hydrolysis of oxidized insulin chain B by a Zr(IV)-substituted Wells-Dawson polyoxometalate. (United States)

    Sap, Annelies; Absillis, Gregory; Parac-Vogt, Tatjana N


    We report for the first time on the selective hydrolysis of a polypeptide system by a metal-substituted polyoxometalate (POM). Oxidized insulin chain B, a 30 amino acid polypeptide, was selectively cleaved by the Zr(IV)-substituted Wells-Dawson POM, K15H[Zr(α2-P2W17O61)2]·25H2O, under physiological pH and temperature conditions in aqueous solution. HPLC-ESI-MS, LC-MS/MS, MALDI-TOF and MALDI-TOF MS/MS data indicate hydrolysis at the Phe1-Val2, Gln4-His5, Leu6-Cys(SO3H)7, and Gly8-Ser9 peptide bonds. The rate of oxidized insulin chain B hydrolysis (0.45 h(-1) at pH 7.0 and 60 °C) was calculated by fitting the integration values of its HPLC-UV signal to a first-order exponential decay function. (1)H NMR measurements show significant line broadening and shifting of the polypeptide resonances upon addition of the Zr(IV)-POM, indicating that interaction between the Zr(IV)-POM and the polypeptide takes place in solution. Circular dichroism (CD) measurements clearly prove that the flexible unfolded nature of the polypeptide was retained in the presence of the Zr(IV)-POM. The thermal stability of the Zr(IV)-POM in the presence of the polypeptide chain during the hydrolytic reaction was confirmed by (31)P NMR spectroscopy. Despite the highly negative charge of the Zr(IV)-POM, the mechanism of interaction appears to be dominated by a strong metal-directed binding between the positively charged Zr(IV) center and negatively charged amino acid side chains.

  18. Cu-containing Keggin-type polyoxometalates-based organic-inorganic hybrids with double electro-catalytic behaviors (United States)

    Zhou, Wanli; Zheng, Yanping; Peng, Jun


    Four new organic-inorganic hybrids consisting of Keggin-type polyoxometalates: [Cu5(bimpy)5(α-BW12O40)]·4H2O (1), [Cu4(bimpy)4(α-SiW12O40)]·2H2O (2), [Cu4(bimpy)4(α-HPMo12O40)2]·2H2O (3), [Cu2(bimpy)4(H2O)2(α-HPW12O40)2]·8H2O (4) (bimpy = 2,5-bis(1H-imidazol-1-yl)pyridine), have been hydrothermally synthesized. Compounds 1-4 are constructed from Cu/bimpy segments modified different types of Keggin POMs. The 1D double chains of compound 1 are featured by {-Cu/bimpy-POM-Cu/bimpy-}n chains and {-Cu-bimpy-Cu-}n metal-organic chains; compound 2 with 1D "ladder-like" structure stemmed from {-Cu-bimpy-Cu-}n wave-like chains and α-SiW12 clusters; In compound 3, [Cu4(bimpy)4]4+ motifs are linked by α-PMo12 clusters to give rise to a (3,4)-connected two-dimensional architecture with the (83)(86) topology, while compound 4 has a (3,4,5)-connected 3D framework with the (42,6)(42,6,83)(42,65,83) topology. Cyclic voltammetries of compounds 1-4 show discrepant double electro-catalytic properties for reduction of nitrite and oxidation of ascorbic acid owing to variant Keggin-type POMs and Cu/bimpy complexes.

  19. Controlling the Charge State and Redox Properties of Supported Polyoxometalates via Soft Landing of Mass Selected Ions

    Energy Technology Data Exchange (ETDEWEB)

    Gunaratne, Kalupathirannehelage Don D.; Johnson, Grant E.; Andersen, Amity; Du, Dan; Zhang, Weiying; Prabhakaran, Venkateshkumar; Lin, Yuehe; Laskin, Julia


    We investigate the controlled deposition of Keggin polyoxometalate (POM) anions, PMo12O403- and PMo12O402-, onto different self-assembled monolayer (SAM) surfaces via soft landing of mass-selected ions. Utilizing in situ infrared reflection absorption spectroscopy (IRRAS), ex situ cyclic voltammetry (CV) and electronic structure calculations, we examine the structure and charge retention of supported multiply-charged POM anions and characterize the redox properties of the modified surfaces. SAMs of alkylthiol (HSAM), perfluorinated alkylthiol (FSAM), and alkylthiol terminated with NH3+ functional groups (NH3+SAM) are chosen as model substrates for soft landing to examine the factors which influence the immobilization and charge retention of multiply charged anionic molecules. The distribution of charge states of POMs on different SAM surfaces are determined by comparing the IRRAS spectra with vibrational spectra calculated using density functional theory (DFT). In contrast to the results obtained previously for multiply charged cations, soft landed anions are found to retain charge on all three SAM surfaces. This charge retention is attributed to the substantial electron binding energy of the POM anions. Investigation of redox properties by CV reveals that, while surfaces prepared by soft landing exhibit similar features to those prepared by adsorption of POM from solution, the soft landed POM2- has a pronounced shift in oxidation potential compared to POM3- for one of the redox couples. These results demonstrate that ion soft landing is uniquely suited for precisely controlled preparation of substrates with specific electronic and chemical properties that cannot be achieved using conventional deposition techniques.

  20. Effect of protonation, composition and isomerism on the redox properties and electron (de)localization of classical polyoxometalates (United States)

    López, Xavier


    This publication reviews some relevant features related with the redox activity of two inorganic compounds: [XM12O40]q- (Keggin structure) and [X2M18O62]q- (Wells-Dawson structure). These are two well-known specimens of the vast Polyoxometalate (POM) family, which has been the subject of extensive experimental and theoretical research owing to their unmatched properties. In particular, their redox activity focus a great deal of attention from scientists due to their prospective related applications. POMs are habitually seen as `electron sponges' since many of them accept several electrons without losing their chemical identity. This makes them excellent models to study mechanisms of electrochemical nature. Their redox properties depend on: (i) the type and number of transition metal atoms in the structure, (ii) the basicity of the first reduced species and, occasionally, of the fully oxidized species; (iii) the size of the molecule, (iv) the overall negative charge of the POM, and (v) the size of the central heteroatom. In the last years, important collaboration between the experimental and theoretical areas has been usual on the development of POM science. In the present chapter three of these synergies are highlighted: the influence of the internal heteroatom upon the redox potentials of Keggin anions; the dependence of the redox waves of Fe-substituted Wells-Dawson compounds with pH; and the role of electron delocalization and pairing in mixed-metal Mo/W Wells-Dawson compounds in their ability to accept electrons. In these three cases, a complete understanding of the problem would not have been possible without the mutual benefit of experimental and computational data.

  1. Supramolecular organization in organic-inorganic heterogeneous hybrid catalysts formed from polyoxometalate and poly(ampholyte) polymer. (United States)

    Raj, Gijo; Swalus, Colas; Guillet, Alain; Devillers, Michel; Nysten, Bernard; Gaigneaux, Eric M


    Hybridization of polyoxometalates (POMs) via the formation of an organic-inorganic association constitutes a new route to develop a heterogeneous POM catalyst with tunable functionality imparted through supramolecular assembly. Herein, we report on strategies to obtain tunable well-defined supramolecular architectures of an organic-inorganic heterogeneous hybrid catalyst formed by the association of a hydrophobically substituted polyampholyte copolymer (poly N, N-diallyl-N-hexylamine-alt-maleic acid) and phosphotungstic acid (H3PW12O40) POMs. The self-assembling property of the initial polyampholyte copolymer matrix is modulated by controlling the pH of the hybridization solution. When deposited on a mica surface, isolated, long and extended polymer chains are formed under basic conditions (pH 7.9), while globular or coiled structures are formed under acidic conditions (pH 2). The supramolecular assembly of the POM-polymer hybrid is found to be directed by the type and quantities of charges present on the polyampholyte copolymer, which themselves depend on the pH conditions. The hypothesis is that the Keggin type [PW12O40](3-) anions, which have a size of ~1 nm, electrostatically bind to the positive charge sites of the polymer backbone. The hybrid material stabilized at pH 5.3 consists of POM-decorated polymer chains. Statistical analysis of distances between pairs of POM entities show narrow density distributions, suggesting that POM entities are attached to the polymer chains with a high level of order. Conversely, under acidic conditions (pH 2), the hybrid shows the formation of a core-shell type of structure. The strategies reported here, to tune the supramolecular assembly of organic-inorganic hybrid materials, are highly valuable for the design and a more rational utilization of POM heterogeneous catalysts in several chemical transformations.

  2. Method for identification of rigid domains and hinge residues in proteins based on exhaustive enumeration. (United States)

    Sim, Jaehyun; Sim, Jun; Park, Eunsung; Lee, Julian


    Many proteins undergo large-scale motions where relatively rigid domains move against each other. The identification of rigid domains, as well as the hinge residues important for their relative movements, is important for various applications including flexible docking simulations. In this work, we develop a method for protein rigid domain identification based on an exhaustive enumeration of maximal rigid domains, the rigid domains not fully contained within other domains. The computation is performed by mapping the problem to that of finding maximal cliques in a graph. A minimal set of rigid domains are then selected, which cover most of the protein with minimal overlap. In contrast to the results of existing methods that partition a protein into non-overlapping domains using approximate algorithms, the rigid domains obtained from exact enumeration naturally contain overlapping regions, which correspond to the hinges of the inter-domain bending motion. The performance of the algorithm is demonstrated on several proteins. © 2015 Wiley Periodicals, Inc.

  3. [A case of rigid spine syndrome with rimmed vacuole]. (United States)

    Onodera, O; Yamazaki, M; Atsumi, T; Miyatake, T; Izumi, T


    A case of rigid spine syndrome associated with rimmed vacuoles in muscle biopsy is reported. A 36-year-old man was admitted to our hospital because of gait disturbance and limited mortality of the spine. His family was free from any neuromuscular disorders. He was born in normal pregnancy and delivery. His physical development was normal. At age 7, he was unable to run fast. At age 36, he had right hemiparesis and dysarthria. He was diagnosed as cerebral infarction of the left basal ganglia by brain CT. Neurological examination revealed moderate proximal dominant muscular atrophy and weakness. His spine was straight, showing loss of physiological cervical and lumbar lordosis. The neck flexion was limited but the extension was full. And he had contracture of bilateral ankle joint. Laboratory findings were all normal. The electrocardiogram showed negative T wave in V4, V5 and QT interval elongation. The echocardiogram showed diffuse decrease of ventricular wall motion. Respiratory function test revealed decrease of vital capacity. Arterial blood gases on room air showed that the PaO2 and PaCO2 were 70 mmHg and 49 mmHg, respectively. The findings of electromyogram were compatible with myopathic change. Biopsy specimen of the biceps brachii muscle showed marked variation in fiber size, type 1 fiber predominancy and atrophy, and type 2B fiber deficiency. Numerous rimmed vaculoes were found in the same muscle. Four cases of the rigid spine syndrome with rimmed vacuoles have been described. Among them, three patients died in young ages and two suffered from constrictive respiratory failure. In rigid spine syndrome with rimmed vacuole formation, the cardiac and respiratory problems must be taken account intensively.

  4. Accurate free and forced rotational motions of rigid Venus (United States)

    Cottereau, L.; Souchay, J.; Aljbaae, S.


    Context. The precise and accurate modelling of a terrestrial planet like Venus is an exciting and challenging topic, all the more interesting because it can be compared with that of Earth for which such a modelling has already been achieved at the milli-arcsecond level. Aims: We aim to complete a previous study, by determining the polhody at the milli-arcsecond level, i.e. the torque-free motion of the angular momentum axis of a rigid Venus in a body-fixed frame, as well as the nutation of its third axis of figure in space, which is fundamental from an observational point of view. Methods: We use the same theoretical framework as Kinoshita (1977, Celest. Mech., 15, 277) did to determine the precession-nutation motion of a rigid Earth. It is based on a representation of the rotation of a rigid Venus, with the help of Andoyer variables and a set of canonical equations in Hamiltonian formalism. Results: In a first part we computed the polhody, we showed that this motion is highly elliptical, with a very long period of 525 cy compared with 430 d for the Earth. This is due to the very small dynamical flattening of Venus in comparison with our planet. In a second part we precisely computed the Oppolzer terms, which allow us to represent the motion in space of the third Venus figure axis with respect to the Venus angular momentum axis under the influence of the solar gravitational torque. We determined the corresponding tables of the nutation coefficients of the third figure axis both in longitude and in obliquity due to the Sun, which are of the same order of amplitude as for the Earth. We showed that the nutation coefficients for the third figure axis are significantly different from those of the angular momentum axis on the contrary of the Earth. Our analytical results have been validated by a numerical integration, which revealed the indirect planetary effects.

  5. Gaussian Curvature as an Identifier of Shell Rigidity (United States)

    Harutyunyan, Davit


    In the paper we deal with shells with non-zero Gaussian curvature. We derive sharp Korn's first (linear geometric rigidity estimate) and second inequalities on that kind of shell for zero or periodic Dirichlet, Neumann, and Robin type boundary conditions. We prove that if the Gaussian curvature is positive, then the optimal constant in the first Korn inequality scales like h, and if the Gaussian curvature is negative, then the Korn constant scales like h 4/3, where h is the thickness of the shell. These results have a classical flavour in continuum mechanics, in particular shell theory. The Korn first inequalities are the linear version of the famous geometric rigidity estimate by Friesecke et al. for plates in Arch Ration Mech Anal 180(2):183-236, 2006 (where they show that the Korn constant in the nonlinear Korn's first inequality scales like h 2), extended to shells with nonzero curvature. We also recover the uniform Korn-Poincaré inequality proven for "boundary-less" shells by Lewicka and Müller in Annales de l'Institute Henri Poincare (C) Non Linear Anal 28(3):443-469, 2011 in the setting of our problem. The new estimates can also be applied to find the scaling law for the critical buckling load of the shell under in-plane loads as well as to derive energy scaling laws in the pre-buckled regime. The exponents 1 and 4/3 in the present work appear for the first time in any sharp geometric rigidity estimate.

  6. Nonlinear dynamic behavior of microscopic bubbles near a rigid wall (United States)

    Suslov, Sergey A.; Ooi, Andrew; Manasseh, Richard


    The nonlinear dynamic behavior of microscopic bubbles near a rigid wall is investigated. Oscillations are driven by the ultrasonic pressure field that arises in various biomedical applications such as ultrasound imaging or targeted drug delivery. It is known that, when bubbles approach a blood-vessel wall, their linear dynamic response is modified. This modification may be very useful for real-time detection of bubbles that have found targets; in future therapeutic technologies, it may be useful for controlled release of medical agents encapsulating microbubbles. In this paper, the nonlinear response of microbubbles near a wall is studied. The Keller-Miksis-Parlitz equation is adopted, but modified to account for the presence of a rigid wall. This base model describes the time evolution of the bubble surface, which is assumed to remain spherical, and accounts for the effect of acoustic radiation losses owing to liquid compressibility in the momentum conservation. Two situations are considered: the base case of an isolated bubble in an unbounded medium, and a bubble near a rigid wall. In the latter case, the wall influence is modeled by including a symmetrically oscillating image bubble. The bubble dynamics is traced using a numerical solution of the model equation. Subsequently, Floquet theory is used to accurately detect the bifurcation point where bubble oscillations stop following the driving ultrasound frequency and undergo period-changing bifurcations. Of particular interest is the detection of the subcritical period-tripling and -quadrupling transition. The parametric bifurcation maps are obtained as functions of nondimensional parameters representing the bubble radius, the frequency and pressure amplitude of the driving ultrasound field, and the distance from the wall. It is shown that the presence of the wall generally stabilises the bubble dynamics, so that much larger values of the pressure amplitude are needed to generate nonlinear responses. Thus, a

  7. A generic detailed rigid-body lumbar spine model

    DEFF Research Database (Denmark)

    De Zee, Mark; Hansen, Lone; Wong, Christian


    the literature. The work resulted in a detailed lumbar spine model with seven rigid segments with 18 degrees-of-freedom and 154 muscles. The model is able to produce a maximum extension moment of 238 Nm around L5/S1. Moreover, a comparison was made with in vivo intradiscal pressure measurements of the L4-5 disc...... available from the literature. The model is based on inverse dynamics, where the redundancy problem is solved using optimization in order to compute the individual muscle forces and joint reactions. With the presented model it is possible to investigate a range of research questions, because the model...

  8. Dynamic phase separation of fluid membranes with rigid inclusions. (United States)

    Weikl, Thomas R


    Membrane shape fluctuations induce attractive interactions between rigid inclusions. Previous analytical studies showed that the fluctuation-induced pair interactions are rather small compared to thermal energies, but also that multibody interactions cannot be neglected. In this paper, it is shown numerically that shape fluctuations indeed lead to the dynamic separation of the membrane into phases with different inclusion concentrations. The tendency of lateral phase separation strongly increases with the inclusion size. Large inclusions aggregate at very small inclusion concentrations and for relatively small values of the inclusions' elastic modulus.

  9. Centrifuge modelling of rigid piles in soft clay

    DEFF Research Database (Denmark)

    Klinkvort, R.T.; Poder, M.; Truong, P.


    of this study is to employ centrifuge modelling in order to derive experimental p-y curves for rigid piles embedded in over-consolidated soft clay. A kaolin clay sample was prepared and pre-consolidated by applying a constant pressure at the soil surface, while different over-consolidation ratios were achieved...... within the clay sample by carrying out the experiments at different g fields. The findings suggest that the normalised shape of the p-y curves can be predicted within a sufficient accuracy using the current methodology but that the ultimate lat-eral resistance is underestimated at shallow depths...

  10. Spectral rigidity of vehicular streams (random matrix theory approach)

    Energy Technology Data Exchange (ETDEWEB)

    Krbalek, Milan [Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University, Prague (Czech Republic); Seba, Petr [Doppler Institute for Mathematical Physics and Applied Mathematics, Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University, Prague (Czech Republic)


    Using a method originally developed for the random matrix theory, we derive an approximate mathematical formula for the number variance {delta}{sub N}(L) describing the rigidity of particle ensembles with a power-law repulsion. The resulting relation is compared with the relevant statistics of the single-vehicle data measured on the Dutch freeway A9. The detected value of the inverse temperature {beta}, which can be identified as a coefficient of the mental strain of the car drivers, is then discussed in detail with the relation to the traffic density {rho} and flow J.

  11. Control of the rigid body and dynamics with symmetry (United States)

    Lum, Kai-Yew

    This dissertation explores various problems in the control of the rigid body and related dynamical systems with symmetry, utilizing various modeling approaches and control techniques. We first derive a control law that asymptotically stabilizes an unbalanced top to the sleeping motion. We rewrite the classical Euler-Poisson equations by projecting the phase space onto IRsp5. The control law is based on the Hamilton-Jacobi-Bellman theory with zero dynamics and partial stability. Lyapunov techniques are used in the analysis. Next, the control of rotor imbalance with magnetic bearings is considered in the adaptive virtual autobalancing and adaptive autocentering approaches. We derive single-plane and two-plane balancing control algorithms that provide asymptotic estimates of the rotor imbalance, and that guarantee consistent performance under varying spin rate. These algorithms are based on emulation of the mechanical autobalancer. We discuss the theory based on linear analysis, and simulation and experimental results. We go on to investigate symmetry properties associated with mechanical control systems and certain nonlinear control systems. First, we generalize the classical Serret-Andoyer transformation for the free rigid body to left-invariant, hyperregular Hamiltonian systems on Tsp*SO(3), employing the notion of symplectic (Marsden-Weinstein) reduction. We then apply this result to the controlled rigid body, and show that for Hamiltonian controls that preserve the rigid body structure, the generalized Serret-Andoyer transformation yields a two dimensional representation of the closed-loop motion in canonical form. Applications to the stability analysis of relative equilibria and numerical integration are also discussed. Finally, we apply the concept of reduction to certain regulation problems on smooth manifolds. Following the works of Van der Schaft (1981) and Grizzle and Marcus (1985), we show that an output feedback regulation problem possessing certain

  12. Symmetry and Reduction for Coordinated Rigid Body Networks

    CERN Document Server

    Hanszligmann, H; Smith, T R


    Motivated by interest in the collective behavior of autonomous agents, we study networks of rigid bodies and the problem of coordinated orientation and position across the group. Our main result is the reduction of the networked system in the case that individuals are coupled by control inputs that depend only on relative configuration. We use reduction theory based on semi-direct products; this yields flat Poisson spaces which enable efficient formulation of control laws. In the second part of the paper, we apply the reduction results to particular choices of kinetic energy and prove stability of coordinated behaviors.

  13. Rigid supersymmetry from conformal supergravity in five dimensions

    Energy Technology Data Exchange (ETDEWEB)

    Pini, Alessandro [Department of Physics, Universidad de Oviedo, Avda. Calvo Sotelo 18, 33007, Oviedo (Spain); Centre for Research in String Theory, School of Physics, Queen Mary University of London,Mile End Road, London, E1 4NS (United Kingdom); Rodriguez-Gomez, Diego; Schmude, Johannes [Department of Physics, Universidad de Oviedo, Avda. Calvo Sotelo 18, 33007, Oviedo (Spain)


    We study the rigid limit of 5d conformal supergravity with minimal supersymmetry on Riemannian manifolds. The necessary and sufficient condition for the existence of a solution is the existence of a conformal Killing vector. Whenever a certain SU(2) curvature becomes abelian the backgrounds define a transversally holomorphic foliation. Subsequently we turn to the question under which circumstances these backgrounds admit a kinetic Yang-Mills term in the action of a vector multiplet. Here we find that the conformal Killing vector has to be Killing. We supplement the discussion with various appendices.

  14. The market for large rigid haul trucks in surface mining

    Energy Technology Data Exchange (ETDEWEB)

    Gilewicz, P.


    Originally published in 2001 this updated report provides a definition of the market for large rigid haulers in surface mining. The analysis covers changes to the mining market segments buying these machines including the gains made by coal producers, retrenchment in copper mining, the consolidation taking place among gold mining companies, and the expansion of iron ore producers in Australia and Brazil. It includes a detailed accounting of 2001 truck shipments, and an analysis of trends in the Ultra-truck segment. It concludes with a revised forecast for shipments through 2006. 12 charts, 56 tabs., 2 apps.

  15. Reopening modes of a collapsed elasto-rigid channel

    CERN Document Server

    Ducloué, Lucie; Thompson, Alice B; Juel, Anne


    Motivated by the reopening mechanics of strongly collapsed airways, we study the steady propagation of an air finger through a collapsed oil-filled channel with a single compliant wall. In a previous study using fully-compliant elastic tubes, a `pointed' air finger was found to propagate at high speed and low pressure, which may enable rapid reopening of highly collapsed airways with minimal tissue damage (Heap & Juel 2008). In this paper, we identify the selection mechanism of that pointed finger, which remained unexplained, by conducting an experimental study in a rigid rectangular Hele-Shaw channel with an elastic top boundary. The constitutive behaviour of this elasto-rigid channel is broadly similar to that of an elastic tube, but unlike the tube the channel's cross-section adopts self-similar shapes from the undeformed state to the point of first near wall contact. The simplification of the vessel geometry enables the systematic investigation of the reopening dynamics in terms of initial collapse. W...

  16. Synthesis of rigid polyurethane foams from phosphorylated biopolyols. (United States)

    de Haro, Juan Carlos; López-Pedrajas, Daniel; Pérez, Ángel; Rodríguez, Juan Francisco; Carmona, Manuel


    Renewable resources are playing a key role on the synthesis of biodegradable polyols. Moreover, the incorporation of covalently linked additives is increasing in importance in the polyurethane (PU) market. In this work, previously epoxidized grape seed oil and methyl oleate were transformed into phosphorylated biopolyols through an acid-catalyzed ring-opening hydrolysis in the presence of H3PO4. The formation of phosphate polyesters was confirmed by FT-IR and 31P-NMR. However, the synthesis of a high-quality PU rigid foam was not possible using exclusively these polyols attending to their low hydroxyl value. In that way, different rigid PU foams were prepared from the phosphorylated biopolyols and the commercial polyol Alcupol R4520. It was observed that phosphorylated biopolyols can be incorporated up to a 57 wt.% in the PU synthesis without significant structural changes with respect to the commercial foam. Finally, thermogravimetric and EDAX analyses revealed an improvement of thermal stability by the formation of a protective phosphorocarbonaceous char layer.

  17. Collisions of Constrained Rigid Body Systems with Friction

    Directory of Open Access Journals (Sweden)

    Haijun Shen


    Full Text Available A new approach is developed for the general collision problem of two rigid body systems with constraints (e.g., articulated systems, such as massy linkages in which the relative tangential velocity at the point of contact and the associated friction force can change direction during the collision. This is beyond the framework of conventional methods, which can give significant and very obvious errors for this problem, and both extends and consolidates recent work. A new parameterization and theory characterize if, when and how the relative tangential velocity changes direction during contact. Elastic and dissipative phenomena and different values for static and kinetic friction coefficients are included. The method is based on the explicitly physical analysis of events at the point of contact. Using this method, Example 1 resolves (and corrects a paradox (in the literature of the collision of a double pendulum with the ground. The method fundamentally subsumes other recent models and the collision of rigid bodies; it yields the same results as conventional methods when they would apply (Example 2. The new method reformulates and extends recent approaches in a completely physical context.

  18. Rigid motion artifact reduction in CT using frequency domain analysis. (United States)

    Zhang, Yuan; Zhang, Liyi; Sun, Yunshan


    It is often unrealistic to assume that the subject remains stationary during a computed tomography (CT) imaging scan. A patient rigid motion can be decomposed into a translation and a rotation around an origin. How to minimize the motion impact on image quality is important. To eliminate artifacts caused by patient rigid motion during a CT scan, this study investigated a new method based on frequency domain analysis to estimate and compensate motion impact. Motion parameters was first determined by the magnitude correlation of projections in frequency domain. Then, the estimated parameters were applied to compensate for the motion effects in the reconstruction process. Finally, this method was extended to helical CT. In fan-beam CT experiments, the simulation results showed that the proposed method was more accurate and faster on the performance of motion estimation than using Helgason-Ludwig consistency condition method (HLCC). Furthermore, the reconstructed images on both simulated and human head experiments indicated that the proposed method yielded superior results in artifact reduction. The proposed method is a new tool for patient motion compensation, with a potential for practical application. It is not only applicable to motion correction in fan-beam CT imaging, but also to helical CT.

  19. Loading on a Rigid Target from Close Proximity Underwater Explosions

    Directory of Open Access Journals (Sweden)

    Mark Riley


    Full Text Available The study describes recent simulation results for underwater explosions in close-proximity to rigid targets. Simulations are performed using Chinook, an Eulerian computational fluid dynamics (CFD code. Predicted target loadings are compared with measurements taken from a series of experiments conducted under an international collaboration between Canada, The Netherlands, and Sweden. The simulations of the rigid target tests focused on the modelling of gas bubble collapse and water jetting behaviour. Both two-dimensional and three-dimensional simulations were performed. It was found that the two-dimensional analyses produced good bubble periods and reasonable impulse loading compared to experimental data. The time of arrival of the bubble collapse and water jetting were found to be very mesh dependent and refining the mesh did not always produce better results. The two-dimensional approach provides a good initial understanding of the problem for a reasonable computational effort. The three-dimensional simulations were found to produce improved impulse predictions. The numerical gas bubble radii time histories are also compared to empirical time histories.

  20. Polynomials for crystal frameworks and the rigid unit mode spectrum (United States)

    Power, S. C.


    To each discrete translationally periodic bar-joint framework in , we associate a matrix-valued function defined on the d-torus. The rigid unit mode (RUM) spectrum of is defined in terms of the multi-phases of phase-periodic infinitesimal flexes and is shown to correspond to the singular points of the function and also to the set of wavevectors of harmonic excitations which have vanishing energy in the long wavelength limit. To a crystal framework in Maxwell counting equilibrium, which corresponds to being square, the determinant of gives rise to a unique multi-variable polynomial . For ideal zeolites, the algebraic variety of zeros of on the d-torus coincides with the RUM spectrum. The matrix function is related to other aspects of idealized framework rigidity and flexibility, and in particular leads to an explicit formula for the number of supercell-periodic floppy modes. In the case of certain zeolite frameworks in dimensions two and three, direct proofs are given to show the maximal floppy mode property (order N). In particular, this is the case for the cubic symmetry sodalite framework and some other idealized zeolites. PMID:24379422

  1. Dynamics of parallel robots from rigid bodies to flexible elements

    CERN Document Server

    Briot, Sébastien


    This book starts with a short recapitulation on basic concepts, common to any types of robots (serial, tree structure, parallel, etc.), that are also necessary for computation of the dynamic models of parallel robots. Then, as dynamics requires the use of geometry and kinematics, the general equations of geometric and kinematic models of parallel robots are given. After, it is explained that parallel robot dynamic models can be obtained by decomposing the real robot into two virtual systems: a tree-structure robot (equivalent to the robot legs for which all joints would be actuated) plus a free body corresponding to the platform. Thus, the dynamics of rigid tree-structure robots is analyzed and algorithms to obtain their dynamic models in the most compact form are given. The dynamic model of the real rigid parallel robot is obtained by closing the loops through the use of the Lagrange multipliers. The problem of the dynamic model degeneracy near singularities is treated and optimal trajectory planning for cro...

  2. Origami-Inspired Folding of Thick, Rigid Panels (United States)

    Trease, Brian P.; Thomson, Mark W.; Sigel, Deborah A.; Walkemeyer, Phillip E.; Zirbel, Shannon; Howell, Larry; Lang, Robert


    To achieve power of 250 kW or greater, a large compression ratio of stowed-to-deployed area is needed. Origami folding patterns were used to inspire the folding of a solar array to achieve synchronous deployment; however, origami models are generally created for near-zero-thickness material. Panel thickness is one of the main challenges of origami-inspired design. Three origami-inspired folding techniques (flasher, square twist, and map fold) were created with rigid panels and hinges. Hinge components are added to the model to enable folding of thick, rigid materials. Origami models are created assuming zero (or near zero) thickness. When a material with finite thickness is used, the panels are required to bend around an increasingly thick fold as they move away from the center of the model. The two approaches for dealing with material thickness are to use membrane hinges to connect the panels, or to add panel hinges, or hinges of the same thickness, at an appropriate width to enable folding.

  3. Statistics of admixture distribution in flows through rigid foams (United States)

    Denissenko, Petr; Le Fur, Pierre; Vlaskamp, Jozef; Williams, Mark; Fan, Xiaolei; Lapkin, Alexei


    Diffusion and dispersion of admixture in flows through rigid foams need to be accounted for when modelling catalytic reactions on the foam surface. We study diffusion of admixture and scaling exponents of admixture concentration both experimentally and by numerical simulations. A liquid admixture was continuously released from a point source at the upstream boundary of a block of rigid SiC foam. Foam thickness was varied from 20 to 80 average pore sizes. A flow with Re of up to 300 based on the pore size was imposed by a progressive cavity pump. The distribution of the tracer at the exit from the foam was measured using LIF and the concentration moments have been calculated. Numerical simulation of the flow in laminar regime has been performed within OpenFoam for the Re from 1 to 100. Geometry of the sample was acquired by Micro Computed Tomography scanning of the actual foam sample. A steady-state SIMPLE method was used to solve the incompressible steady flow in the volume of 20 × 20 × 40 average pore sizes. Diffusion and dispersion of passive scalar has been studied by following individual streamlines. Results are interpreted in terms of mixing, heat transfer, and selectivity of catalytic reactions at the foam surface. This Research is supported by European Commission under the 7th Framework Program.

  4. Computer-aided rigid choledochoscopy lithotripsy for hepatolithiasis. (United States)

    Fang, Chi-Hua; Li, Gang; Wang, Ping; Fan, Ying-Fang; Zhong, Shi-Zhen


    Hepatolithiasis is challenging for surgeons to treat especially in patients with previous hepatobiliary surgery. The aim of the study was to report our experience of rigid choledochoscopy lithotripsy in targeted treatment of hepatolithiasis under the guidance of a medical image three-dimensional visualization system, which we developed and patented (software copyright no: 2008SR18 798) by comparing it with hepatectomy without a three-dimensional (3D) reconstruction technique. Between December 2007 and March 2013, 64 patients underwent rigid choledochoscopy lithotripsy based on 3D visualization technology conducted by a medical image three-dimensional visualization system for hepatolithiasis (group A). During the same period, 61 patients with hepatolithiasis were selected for hepatectomy (group B). Comparative analysis was made of demographic and perioperative characteristics of the two groups. 3D visualization was instructive for surgeons on how the stones were distributed and what the spatial relationship was between stones and the intrahepatic vascular system. Compared with patients in group B, those in group A had a significantly lower intermediate residual stone rate, a faster operating time, a lower intraoperative blood loss and intraoperative blood transfusion, a shorter postoperative hospital stay, less postoperative complications, and more liver function reserved (P Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Rigidity-induced scale invariance in polymer ejection from capsid (United States)

    Linna, R. P.; Suhonen, P. M.; Piili, J.


    While the dynamics of a fully flexible polymer ejecting a capsid through a nanopore has been extensively studied, the ejection dynamics of semiflexible polymers has not been properly characterized. Here we report results from simulations of ejection dynamics of semiflexible polymers ejecting from spherical capsids. Ejections start from strongly confined polymer conformations of constant initial monomer density. We find that, unlike for fully flexible polymers, for semiflexible polymers the force measured at the pore does not show a direct relation to the instantaneous ejection velocity. The cumulative waiting time t (s ) , that is, the time at which a monomer s exits the capsid the last time, shows a clear change when increasing the polymer rigidity κ . The major part of an ejecting polymer is driven out of the capsid by internal pressure. At the final stage the polymer escapes the capsid by diffusion. For the driven part there is a crossover from essentially exponential growth of t with s of the fully flexible polymers to a scale-invariant form. In addition, a clear dependence of t on polymer length N0 was found. These findings combined give the dependence t (s ) ∝N00.55s1.33 for the strongly rigid polymers. This crossover in dynamics where κ acts as a control parameter is reminiscent of a phase transition. This analogy is further enhanced by our finding a perfect data collapse of t for polymers of different N0 and any constant κ .

  6. Heat Transfer Modeling for Rigid High-Temperature Fibrous Insulation (United States)

    Daryabeigi, Kamran; Cunnington, George R.; Knutson, Jeffrey R.


    Combined radiation and conduction heat transfer through a high-temperature, high-porosity, rigid multiple-fiber fibrous insulation was modeled using a thermal model previously used to model heat transfer in flexible single-fiber fibrous insulation. The rigid insulation studied was alumina enhanced thermal barrier (AETB) at densities between 130 and 260 kilograms per cubic meter. The model consists of using the diffusion approximation for radiation heat transfer, a semi-empirical solid conduction model, and a standard gas conduction model. The relevant parameters needed for the heat transfer model were estimated from steady-state thermal measurements in nitrogen gas at various temperatures and environmental pressures. The heat transfer modeling methodology was evaluated by comparison with standard thermal conductivity measurements, and steady-state thermal measurements in helium and carbon dioxide gases. The heat transfer model is applicable over the temperature range of 300 to 1360 K, pressure range of 0.133 to 101.3 x 10(exp 3) Pa, and over the insulation density range of 130 to 260 kilograms per cubic meter in various gaseous environments.

  7. Modyfication of the Rigid Polyurethane-Polyisocyanurate Foams

    Directory of Open Access Journals (Sweden)

    Bogusław Czupryński


    Full Text Available The effect of polyethylene glycol 1500 on physicomechanical properties of rigid polyurethane-polyisocyanurate (PUR-PIR foams has been studied. It was found that application of polyethylene glycol 1500 for synthesis of foams in amount from 0% to 20% w/w had an effect on reduction of brittleness and softening point, while the greater the increase in compressive strength the higher its content in foam composition was. Wastes from production of these foams were ground and subjected to glycolysis in diethylene glycol with the addition of ethanolamine and zinc stearate. Liquid brown products were obtained. Properties of the resulting products were defined in order to determine their suitability for synthesis of new foams. It was found that glycolysate 6 was the most suitable for reuse and its application in different amounts allowed us to prepare 4 new foams (nos. 25, 26, 27, and 28. Properties of foams prepared in this manner were determined and, on their basis, the suitability of glycolysates for production of rigid PUR-PIR foams was evaluated.

  8. A Soft Gripper with Rigidity Tunable Elastomer Strips as Ligaments. (United States)

    Nasab, Amir Mohammadi; Sabzehzar, Amin; Tatari, Milad; Majidi, Carmel; Shan, Wanliang


    Like their natural counterparts, soft bioinspired robots capable of actively tuning their mechanical rigidity can rapidly transition between a broad range of motor tasks-from lifting heavy loads to dexterous manipulation of delicate objects. Reversible rigidity tuning also enables soft robot actuators to reroute their internal loading and alter their mode of deformation in response to intrinsic activation. In this study, we demonstrate this principle with a three-fingered pneumatic gripper that contains "programmable" ligaments that change stiffness when activated with electrical current. The ligaments are composed of a conductive, thermoplastic elastomer composite that reversibly softens under resistive heating. Depending on which ligaments are activated, the gripper will bend inward to pick up an object, bend laterally to twist it, and bend outward to release it. All of the gripper motions are generated with a single pneumatic source of pressure. An activation-deactivation cycle can be completed within 15 s. The ability to incorporate electrically programmable ligaments in a pneumatic or hydraulic actuator has the potential to enhance versatility and reduce dependency on tubing and valves.

  9. Rigid spherical particles in highly turbulent Taylor-Couette flow (United States)

    Bakhuis, Dennis; Verschoof, Ruben A.; Mathai, Varghese; Huisman, Sander G.; Lohse, Detlef; Sun, Chao


    Many industrial and maritime processes are subject to enormous frictional losses. Reducing these losses even slightly will already lead to large financial and environmental benefits. The understanding of the underlying physical mechanism of frictional drag reduction is still limited, for example, in bubbly drag reduction there is an ongoing debate whether deformability and bubble size are the key parameters. In this experimental study we report high precision torque measurements using rigid non-deformable spherical particles in highly turbulent Taylor-Couette flow with Reynolds numbers up to 2 ×106 . The particles are made of polystyrene with an average density of 1.036 g cm-3 and three different diameters: 8mm, 4mm, and 1.5mm. Particle volume fractions of up to 6% were used. By varying the particle diameter, density ratio of the particles and the working fluid, and volume fraction of the particles, the effect on the torque is compared to the single phase case. These systematic measurements show that adding rigid spherical particles only results in very minor drag reduction. This work is financially supported by Netherlands Organisation for Scientific Research (NWO) by VIDI Grant Number 13477.

  10. Horizontal fall arrest systems: rigid systems vs. flexible line systems. (United States)

    Lough, David


    There are many types of flexible and rigid systems on the market, both permanent and temporary. This article does not mean to encompass all possible systems or hazards and only intends to give an outline of what at a minimum should be examined to make an educated purchasing decision. In many instances, the buyer will use the same type of horizontal system for all situations. This is a good idea in some cases because it will reduce the need for training on a number of different systems, reduce system compatibility issues, and may reduce costs for installation, supply, and maintenance. This may not be the best idea if the hazard areas differ a great deal; as we have illustrated, one system may not function for all areas and tasks. The rigid system is typically the best solution simply based on the fact the worker won't fall as far as when he is connected to a flexible system, because of the elimination of any dynamic sag and horizontal energy absorber deployment. In any case, where you stop the worker from falling farther, you decrease the chance there may be an incident where the worker is injured. From a cost standpoint, flexible fall arrest systems typically are cheapest. In the end, safety professionals must balance the cost and effectiveness of the system to prevent an injury.

  11. Effective Synergistic Effect of Dipeptide-Polyoxometalate-Graphene Oxide Ternary Hybrid Materials on Peroxidase-like Mimics with Enhanced Performance. (United States)

    Ma, Zhuo; Qiu, Yunfeng; Yang, Huihui; Huang, Yanmin; Liu, Jingjing; Lu, Yue; Zhang, Chen; Hu, PingAn


    Dipeptide-polyoxometalates (POMs)-graphene oxide (GO) ternary hybrid is an excellent peroxidase-like mimic, exhibiting enhanced peroxidase-like activity compared to POMs alone. The hybrid was readily prepared through a reprecipitation method involving electrostatic encapsulation of H3PW12O40 (PW12) by cationic diphenylalanine (FF) peptide and coassembly of FF@PW12 spheres with graphene oxide (GO). Using 3,3',5,5'-tetramethylbenzidine (TMB) as the chromogenic substrate, the peroxidase-like activity of FF@PW12 was evaluated in the heterogeneous phase, and it is 13 times higher than that of pristine PW12 in the homogeneous phase. Furthermore, ternary hybrids of FF@PW12@GO containing 5 wt % GO could enhance the activity 1.7 times higher than that of FF@PW12. The noncovalent interactions of hydrogen bonding and ionic interaction between GO and POMs are speculated to result in the synergistic effect for the enhancement of peroxidase-like performance. The strong interactions between rGO and PW12 are evaluated by a four-probe Hall measurement via the van der Pauw method, and rGO is significantly p-doped by the doping effect of PW12 with lower LUMO energy than that of the energy level of rGO and also due to the electron reservoir feature of PW12. Cyclic voltammogram measurements also suggest that GO causes significant influence on the electronic structure of the reduced forms of the redox couples of PW12. The nature of the TMB catalytic reaction may originate from the generation of the hydroxyl radical ((•)OH) from the decomposition of H2O2 by ternary hybrids and the formation of peroxo species of POM. Taking advantage of the UV-vis signals of TMB being correlated to the concentration of H2O2, FF@PW12@GO can be used to detect H2O2 within the limit of detection of 0.11 μM, and the detection range is 1-75 μM. The present method indeed opens up a promising route in constructing heterogeneous peroxidase-like mimics through the use of POMs via the introduction of GO for

  12. Recognition of small polar molecules with an ionic crystal of alpha-Keggin-type polyoxometalate with a macrocation. (United States)

    Uchida, Sayaka; Kawamoto, Ryosuke; Mizuno, Noritaka


    The complexation of Keggin-type polyoxometalates [alpha-XW12O40]n- (X = P, Si, B, Co), macrocation [Cr3O(OOCH)6(H2O)3]+, and alkali-metal ions forms ionic crystals of Na2[Cr3O(OOCH)6(H2O)3][alpha-PW12O40].16H2O (1a), K3[Cr3O(OOCH)6(H2O)3][alpha-SiW12O40].16H2O (2a), Rb4[Cr3O(OOCH)6(H2O)3][alpha-BW12O40].16H2O (3a), and Cs5[Cr3O(OOCH)6(H2O)3][alpha-CoW12O40].7.5H2O (4a). The space volumes of the ionic crystals decrease in the order of 1a > 2a > 3a > 4a. The water of crystallization in 1a-3a is completely desorbed by evacuation at room temperature, while about 50% of the water of crystallization in 4a is desorbed. The respective 1a-4a after evacuation at room temperature are denoted by 1b-4b, which show the close packing of the constituent ions. The calculated cell volumes per formula decreased in the order of 1b > 2b > 3b > 4b, which would be related to the increase in n. Compound 1b sorbs various butanol, valeronitrile, and methyl propionate. Compound 2b sorbs ethanol, acetonitrile, and methyl formate. Compound 3b sorbs water and methanol, and 4b sorbs only water. Thus, the ionic crystals can discriminate < or =C5 polar organic molecules such as alcohols, nitriles, and esters by one methylene chain, and the decrease in n of [alpha-XW12O40]n- enables the sorption of molecules with the longer methylene chain. The nature of the sorption properties of 1b-4b can be explained by the lattice energy needed for the expansion of 1b-4b. The selective sorption properties of 1b-4b are successfully applied to the separation of mixtures of alcohols, nitriles, esters, and water.

  13. A randomized clinical trial of treatment for lumbar segmental rigidity. (United States)

    Mayer, Tom G; Gatchel, Robert J; Keeley, Janice; McGeary, Don; Dersh, Jeffrey; Anagnostis, Christopher


    A randomized single-blind clinical trial of facet injections plus exercise, versus exercise alone, in chronic disabling work-related lumbar spinal disorders (CDWRLSD), accompanied by pilot interrater reliability and facet syndrome prevalence studies. To systematically investigate the use of facet injections as an adjunct to supervised lumbar stretching exercises in regaining lumbar range of motion (ROM) following prolonged deconditioning after work-related lumbar injuries. To assess interrater reliability of visual assessment of segmental rigidity (SR), and to evaluate the prevalence of facet syndrome in cases of lumbar SR. Corticosteroid joint injections have often been used to reduce musculoskeletal inflammation to facilitate joint mobilization in the presence of degenerative arthritis. Lumbar segmental rigidity is a recently described entity usually associated with painful chronic spinal disorders and postoperative spine surgery. Previous work has shown that SR and lumbar ROM improves with a brief intervention consisting of facet injections followed by specific stretching exercises. No systematic study has investigated the potential benefits of a combination of facet injections and exercise over supervised exercises alone to treat lumbar SR. Similarly, no study has assessed the association between SR and the facet syndrome. From a group of consecutive patients (n = 421) with CDWRLSD referred for tertiary rehabilitation between November 1999 and January 2001, 70 were noted to have SR on intake physical examination. The first part of this study assessed interrater reliability for detecting SR, and intrarater reliability for 3-segment true lumbar ROM measurements. Patients randomly assigned to participate in supervised stretching exercises with the addition of fluoroscopically guided bilateral facet injections at the involved levels (Group A, n = 36) also underwent facet syndrome prevalence assessment at the time of injection. They were compared to a randomly

  14. Deep desulphurization of gas oil and model compounds by anatase nanocomposite sandwich type polyoxometalate as a novel, reusable and green nano mercaptan scavenger

    Directory of Open Access Journals (Sweden)

    Shojaei Fallah Abdollah


    Full Text Available Oxidative desulphurization of gas oil and model compounds that exist in gas oil with hydrogen peroxide/acetic acid using nanoparticle (Bu4N7H3[P2W18Cd4(Br2O68]-TiO2 ((Bu4N7H3[P2W18Cd4]-TiO2 as a nano scavenger has been studied. This sandwich-type nanoparticle was shown be able to scavenge hydrogen sulfide and mercaptans with high yield. The addition of acetic acid enhanced the conversion. This system provides an efficient, convenient and practical method for scavenging of sulphur compound. The (Bu4N7H3[P2W18Cd4]-TiO2 nanoparticle was very active catalyst system for the model compound oxidation, while other polyoxometalate systems were much less active.

  15. Functionalized Graphene–Polyoxometalate Nanodots Assembly as “Organic–Inorganic” Hybrid Supercapacitors and Insights into Electrode/Electrolyte Interfacial Processes

    Directory of Open Access Journals (Sweden)

    Sanju Gupta


    Full Text Available The stable high-performance electrochemical electrodes consisting of supercapacitive reduced graphene oxide (rGO nanosheets decorated with pseudocapacitive polyoxometalates (phosphomolybdate acid-H3PMo12O40 (POM and phosphotungstic acid-H3PW12O40 (POW nanodots/nanoclusters are hydrothermally synthesized. The interactions between rGO and POM (and POW components create emergent “organic–inorganic” hybrids with desirable physicochemical properties (specific surface area, mechanical strength, diffusion, facile electron and ion transport enabled by molecularly bridged (covalently and electrostatically tailored interfaces for electrical energy storage. The synergistic hybridization between two electrochemical energy storage mechanisms, electrochemical double-layer from rGO and redox activity (faradaic of nanoscale POM (and POW nanodots, and the superior operating voltage due to high overpotential yielded converge yielding a significantly improved electrochemical performance. They include increase in specific capacitance from 70 F·g−1 for rGO to 350 F·g−1 for hybrid material with aqueous electrolyte (0.4 M sodium sulfate, higher current carrying capacity (>10 A·g−1 and excellent retention (94% resulting higher specific energy and specific power density. We performed scanning electrochemical microscopy to gain insights into physicochemical processes and quantitatively determine associated parameters (diffusion coefficient (D and heterogeneous electron transfer rate (kET at electrode/electrolyte interface besides mapping electrochemical (reactivity and electro-active site distribution. The experimental findings are attributed to: (1 mesoporous network and topologically multiplexed conductive pathways; (2 higher density of graphene edge plane sites; and (3 localized pockets of re-hybridized orbital engineered modulated band structure provided by polyoxometalates anchored chemically on functionalized graphene nanosheets, contribute toward

  16. Structure and properties of a new rigid tripodal oxime ligand (United States)

    Premužić, Dejan; Filarowski, Aleksander; Hołyńska, Małgorzata


    Synthesis and properties of a new rigid tripodal oxime ligand are reported. The ligand is a derivative of phloroglucine with three carboxime arms alternate with hydroxyl groups and three intramolecular Osbnd H⋯N hydrogen bonds. Intermolecular Osbnd H⋯O hydrogen bonds result in formation of a characteristic three-dimensional network. The structure of the compound is further analyzed and confirmed by NMR, IR and MS-techniques. DFT calculations were employed to accomplish the analysis of both the hydrogen bonding and the conformational state of the ligand under study. Additionally, the study addresses the way the conformational state and metal-replacement influence the tautomeric equilibrium OH⋯N ⇆ O-⋯+HN in the studied moieties.

  17. Confining rigid balls by mimicking quadrupole ion trapping (United States)

    Fan, Wenkai; Du, Li; Wang, Sihui; Zhou, Huijun


    The rotating saddle not only is an interesting system that is able to trap a ball near its saddle point, but can also intuitively illustrate the operating principles of quadrupole ion traps in modern physics. Unlike the conventional models based on the mass-point approximation, we study the stability of a ball in a rotating-saddle trap using rigid-body dynamics. The stabilization condition of the system is theoretically derived and subsequently verified by experiments. The results are compared with the previous mass-point model, giving large discrepancy as the curvature of the ball is comparable to that of the saddle. We also point out that the spin angular velocity of the ball is analogous to the cyclotron frequency of ions in an external magnetic field utilized in many prevailing ion-trapping schemes.

  18. Dynamics of Rigid Bodies and Flexible Beam Structures

    DEFF Research Database (Denmark)

    Nielsen, Martin Bjerre

    of rigid bodies and flexible beam structures with emphasis on the rotational motion. The first part deals with motion in a rotating frame of reference. A novel approach where the equations of motion are formulated in a hybrid state-space in terms of local displacements and global velocities is presented...... quaternion parameters or nine convected base vector components. In both cases, the equations of motion are obtained via Hamilton’s equations by including the kinematic constraints associated with the redundant rotation description by means of Lagrange multipliers. A special feature of the formulation...... of the global components of the position vectors and associated convected base vectors for the element nodes. The kinematics is expressed in a homogeneous quadratic form and the constitutive stiffness is derived from complementary energy of a set of equilibrium modes, each representing a state of constant...

  19. Percutaneous antegrade ureteric stent removal using a rigid alligator forceps.

    LENUS (Irish Health Repository)

    Given, M F


    To evaluate the safety and efficacy of percutaneous antegrade ureteric stent removal using a rigid alligator forceps. Twenty patients were included in our study. Indications for ureteric stent insertion included stone disease (n = 7), malignancy (n = 8) and transplant anastomotic strictures (n = 5). Stent retrieval was carried out for proximal stent placement\\/migration in seven patients and encrustation in the remaining 13. Twenty-two stents were successfully retrieved in 20 patients. There was one technical failure (5%). There were no major complications. We had four minor complications, which included nephrostomy site pain (n = 2), periprocedural sepsis (n = 1) and a small urinoma (n = 1). All patients settled with conservative management. Percutaneous radiologically guided antegrade ureteric stent removal with an alligator forceps is safe and effective, particularly when initial surgical removal has failed.

  20. Controlling elastic waves with small phononic crystals containing rigid inclusions

    KAUST Repository

    Peng, Pai


    We show that a two-dimensional elastic phononic crystal comprising rigid cylinders in a solid matrix possesses a large complete band gap below a cut-off frequency. A mechanical model reveals that the band gap is induced by negative effective mass density, which is affirmed by an effective medium theory based on field averaging. We demonstrate, by two examples, that such elastic phononic crystals can be utilized to design small devices to control low-frequency elastic waves. One example is a waveguide made of a two-layer anisotropic elastic phononic crystal, which can guide and bend elastic waves with wavelengths much larger than the size of the waveguide. The other example is the enhanced elastic transmission of a single-layer elastic phononic crystal loaded with solid inclusions. The effective mass density and reciprocal of the modulus of the single-layer elastic phononic crystal are simultaneously near zero. © CopyrightEPLA, 2014.

  1. Testing the disturbed zone around a rigid inclusion in salt

    Energy Technology Data Exchange (ETDEWEB)

    Knowles, M.K.; Borns, D.; Fredrich, J.; Holcomb, D.; Price, R.; Zeuch, D. [Sandia National Labs., Albuquerque, NM (United States); Dale, T.; Van Pelt, R.S. [INTERA, Inc., Austin, TX (United States)


    Deformational processes within a zone of rock surrounding excavations in salt result in alteration of the geophysical and hydrologic properties as compared to the undisturbed condition. The disturbed rock zone offers little resistance to fluid flow. It is hypothesized that rigid inclusions such as concrete seals will arrest and subsequently reverse the disturbance process and induce healing in the disturbed This experiment gathered in situ data that substantiates this hypothesis. A series of tests was conducted in a volume of rock surrounding concrete seals that were placed in a 1-m borehole approximately eight years ago. Fluid flow measurements, measurements of geophysical parameters of the surrounding rock and petrographic analyses on core samples were performed to characterize the rock. This paper presents the testing methodology and summarizes the data gathered from the field test program.

  2. Non-rigid registration by geometry-constrained diffusion

    DEFF Research Database (Denmark)

    Andresen, Per Rønsholt; Nielsen, Mads


    Assume that only partial knowledge about a non-rigid registration is given so that certain point, curves, or surfaces in one 3D image map to certain points, curves, or surfaces in another 3D image. We are facing the aperture problem because along the curves and surfaces, point correspondences...... are not given. We will advocate the viewpoint that the aperture and the 3D interpolation problem may be solved simultaneously by finding the simplest displacement field. This is obtained by a geometry-constrained diffusion which yields the simplest displacement field in a precise sense. The point registration...... obtained may be used for growth modelling, shape statistics, or kinematic interpolation. The algorithm applies to geometrical objects of any dimensionality. We may thus keep any number of fiducial points, curves, and/or surfaces fixed while finding the simplest registration. Examples of inferred point...

  3. Random Matrix Theory of Rigidity in Soft Matter (United States)

    Yamanaka, Masanori


    We study the rigidity or softness of soft matter using the characteristic scale of coupling formation developed in random matrix theory. The eigensystems of the timescale-dependent cross-correlation matrix, which are obtained from the time series data of the atomic coordinates of a protein produced by the all-atom molecular dynamics of the solvent, are analyzed. As an example, we present a result for a protein lysozyme, PDBID:1AKI. We find that there are at least three different time scales involved in the coupling formation of correlated sectors of atoms and at least two different time scales for the size of the correlated sectors. These five time scales coexist simultaneously. We compare the results with those of the normal mode analysis and find a crossover of the distribution of the dominant vibrational components.

  4. Asynchronous oscillations of rigid rods drive viscous fluid to swirl (United States)

    Hayashi, Rintaro; Takagi, Daisuke


    We present a minimal system for generating flow at low Reynolds number by oscillating a pair of rigid rods in silicone oil. Experiments show that oscillating them in phase produces no net flow, but a phase difference alone can generate rich flow fields. Tracer particles follow complex trajectory patterns consisting of small orbital movements every cycle and then drifting or swirling in larger regions after many cycles. Observations are consistent with simulations performed using the method of regularized Stokeslets, which reveal complex three-dimensional flow structures emerging from simple oscillatory actuation. Our findings reveal the basic underlying flow structure around oscillatory protrusions such as hairs and legs as commonly featured on living and nonliving bodies.

  5. Inertial and viscoelastic forces on rigid colloids in microfluidic channels. (United States)

    Howard, Michael P; Panagiotopoulos, Athanassios Z; Nikoubashman, Arash


    We perform hybrid molecular dynamics simulations to study the flow behavior of rigid colloids dispersed in a dilute polymer solution. The underlying Newtonian solvent and the ensuing hydrodynamic interactions are incorporated through multiparticle collision dynamics, while the constituent polymers are modeled as bead-spring chains, maintaining a description consistent with the colloidal nature of our system. We study the cross-stream migration of the solute particles in slit-like channels for various polymer lengths and colloid sizes and find a distinct focusing onto the channel center under specific solvent and flow conditions. To better understand this phenomenon, we systematically measure the effective forces exerted on the colloids. We find that the migration originates from a competition between viscoelastic forces from the polymer solution and hydrodynamically induced inertial forces. Our simulations reveal a significantly stronger fluctuation of the lateral colloid position than expected from thermal motion alone, which originates from the complex interplay between the colloid and polymer chains.

  6. Slip Morphology of Elastic Strips on Frictional Rigid Substrates. (United States)

    Sano, Tomohiko G; Yamaguchi, Tetsuo; Wada, Hirofumi


    The morphology of an elastic strip subject to vertical compressive stress on a frictional rigid substrate is investigated by a combination of theory and experiment. We find a rich variety of morphologies, which-when the bending elasticity dominates over the effect of gravity-are classified into three distinct types of states: pinned, partially slipped, and completely slipped, depending on the magnitude of the vertical strain and the coefficient of static friction. We develop a theory of elastica under mixed clamped-hinged boundary conditions combined with the Coulomb-Amontons friction law and find excellent quantitative agreement with simulations and controlled physical experiments. We also discuss the effect of gravity in order to bridge the difference in the qualitative behaviors of stiff strips and flexible strings or ropes. Our study thus complements recent work on elastic rope coiling and takes a significant step towards establishing a unified understanding of how a thin elastic object interacts vertically with a solid surface.

  7. Complexity management theory: motivation for ideological rigidity and social conflict. (United States)

    Peterson, Jordan B; Flanders, Joseph L


    We are doomed to formulate conceptual structures that are much simpler than the complex phenomena they are attempting to account for. These simple conceptual structures shield us, pragmatically, from real-world complexity, but also fail, frequently, as some aspect of what we did not take into consideration makes itself manifest. The failure of our concepts dysregulates our emotions and generates anxiety, necessarily, as the unconstrained world is challenging and dangerous. Such dysregulation can turn us into rigid, totalitarian dogmatists, as we strive to maintain the structure of our no longer valid beliefs. Alternatively, we can face the underlying complexity of experience, voluntarily, gather new information, and recast and reconfigure the structures that underly our habitable worlds.

  8. Plasma surface modification of rigid contact lenses decreases bacterial adhesion. (United States)

    Wang, Yingming; Qian, Xuefeng; Zhang, Xiaofeng; Xia, Wei; Zhong, Lei; Sun, Zhengtai; Xia, Jing


    Contact lens safety is an important topic in clinical studies. Corneal infections usually occur because of the use of bacteria-carrying contact lenses. The current study investigated the impact of plasma surface modification on bacterial adherence to rigid contact lenses made of fluorosilicone acrylate materials. Boston XO and XO2 contact lenses were modified using plasma technology (XO-P and XO2-P groups). Untreated lenses were used as controls. Plasma-treated and control lenses were incubated in solutions containing Staphylococcus aureus or Pseudomonas aeruginosa. MTT colorimetry, colony-forming unit counting method, and scanning electron microscopy were used to measure bacterial adhesion. MTT colorimetry measurements showed that the optical density (OD) values of XO-P and XO2-P were significantly lower than those of XO and XO2, respectively, after incubation with S. aureus (P plasma technology in contact lens surface modification.

  9. Osseous adaptation to continuous loading of rigid endosseous implants (United States)

    Roberts, W. E.; Smith, R. K.; Mozsary, P. G.; Zilberman, Y.; Smith, R. S.


    The effect of loading on etched Ti implants in the femurs of young (3 mo) and adult (6 mo) rabbits is investigated experimentally. The results are presented in photographs, fluorescence and polarization micrographs, radiographs, and drawings and discussed. Implantation is followed by formation of coarse woven bone within 3 d and mature lamellar bone by 6 wks, with nonspecific subperiosteal bony hypertrophy in the young rabbits only. Spring loading at 100 g produces spontaneous spiral-type fractures when applied immediately, but the implants remain rigid when loads are applied after 6-12 wks of healing. The mechanisms of bone formation involved are examined, and the potential of endosseous implants as anchors in orthodontics or dentofacial-orthopedics is confirmed.

  10. Impedances of rigid cylindrical foundations embedded in transversely isotropic soils (United States)

    Barros, P. L. A.


    A complete formulation and implementation for assessment of the response to dynamic loads of cylindrical rigid structures embedded in transversely isotropic elastic half-spaces is presented. The analysis is performed in the frequency domain and the steady-state structure response is obtained. The method is based on a non-singular version of the indirect boundary element method which uses influence functions, instead of Green's functions, as fundamental solutions. These influence functions are the response of an elastic half-space to distributed, internally applied loads. The proposed method imposes full bonding contact between the foundation and the surrounding soil. Numerical results for displacement (vertical and horizontal) and rotation (twisting and rocking) impedances, showing the influence of the soil anisotropy, are presented. Results for the soil-structure interface tractions and for the displacement field throughout the half-space are also shown.

  11. A rigid motion correction method for helical computed tomography (CT) (United States)

    Kim, J.-H.; Nuyts, J.; Kyme, A.; Kuncic, Z.; Fulton, R.


    We propose a method to compensate for six degree-of-freedom rigid motion in helical CT of the head. The method is demonstrated in simulations and in helical scans performed on a 16-slice CT scanner. Scans of a Hoffman brain phantom were acquired while an optical motion tracking system recorded the motion of the bed and the phantom. Motion correction was performed by restoring projection consistency using data from the motion tracking system, and reconstructing with an iterative fully 3D algorithm. Motion correction accuracy was evaluated by comparing reconstructed images with a stationary reference scan. We also investigated the effects on accuracy of tracker sampling rate, measurement jitter, interpolation of tracker measurements, and the synchronization of motion data and CT projections. After optimization of these aspects, motion corrected images corresponded remarkably closely to images of the stationary phantom with correlation and similarity coefficients both above 0.9. We performed a simulation study using volunteer head motion and found similarly that our method is capable of compensating effectively for realistic human head movements. To the best of our knowledge, this is the first practical demonstration of generalized rigid motion correction in helical CT. Its clinical value, which we have yet to explore, may be significant. For example it could reduce the necessity for repeat scans and resource-intensive anesthetic and sedation procedures in patient groups prone to motion, such as young children. It is not only applicable to dedicated CT imaging, but also to hybrid PET/CT and SPECT/CT, where it could also ensure an accurate CT image for lesion localization and attenuation correction of the functional image data.

  12. Rigidity and Fluidity in Living and Nonliving Matter (United States)

    Lopez, Jorge H.

    Many of the standard equilibrium statistical mechanics techniques do not readily apply to non-equilibrium phase transitions such as the fluid-to-disordered solid transition found in repulsive particulate systems. Examples of repulsive particulate systems are sand grains and colloids. The first part of this thesis contributes to methods beyond equilibrium statistical mechanics to ultimately understand the nature of the fluid-to-disordered solid transition, or jamming, from a microscopic basis. In Chapter 2 we revisit the concept of minimal rigidity as applied to frictionless, repulsive soft sphere packings in two dimensions with the introduction of the jamming graph. Minimal rigidity is a purely combinatorial property encoded via Laman's theorem in two dimensions. It constrains the global, average coordination number of the graph, for instance. Minimal rigidity, however, does not address the geometry of local mechanical stability. The jamming graph contains both properties of global mechanical stability at the onset of jamming and local mechanical stability. We demonstrate how jamming graphs can be constructed using local rules via the Henneberg construction such that these graphs are of the constraint percolation type, where percolation is the study of connected structures in disordered networks. We then probe how jamming graphs destabilize, or become fluid-like, by deleting an edge/contact in the graph and computing the resulting rigid cluster distribution. We also uncover a new potentially diverging lengthscale associated with the random deletion of contacts. In Chapter 3 we study several constraint percolation models, such as k-core percolation and counter-balance percolation, on hyperbolic lattices to better understand the role of loops in such models. The constraints in these percolation models incorporate aspects of local mechanical rigidity found in jammed systems. The expectation is that since these models are indeed easier to analyze than the more

  13. Rigid-Plastic Post-Buckling Analysis of Columns and Quadratic Plates

    DEFF Research Database (Denmark)

    Jönsson, Jeppe


    the compressive load as a function of the transverse displacement. An estimate of the magnitude of the transverse displacement prior to the forming of the collapse mechanism is introduced into the compressive load function, determined by the virtual work equation, thereby revealing a qualified estimate...... yield lines accommodate differential rotations of rigid parts and the area “collapse” yield lines accommodate local area changes of the rigid parts thereby preserving compatibility of the rigid parts of a plate. The approach will be illustrated for rigid plastic column analysis and for a quadratic plate...

  14. Synthesis and characterization of a series of novel perovskite-type LaMnO.sub.3./sub./Keggin-type polyoxometalate hybrid nanomaterials for fast and selective removal of cationic dyes from aqueous solutions

    Czech Academy of Sciences Publication Activity Database

    Farhadi, S.; Mahmoudi, F.; Amini, M.M.; Dušek, Michal; Jarošová, Markéta


    Roč. 46, č. 10 (2017), s. 3252-3264 ISSN 1477-9226 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : organic dyes * polyoxometalate hybrid nanomaterials * perovskite * aqueous solutions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.029, year: 2016

  15. A new nanohybrid material constructed from Keggin-type polyoxometalate and Cd(II) semicarbazone Schiff base complex with excellent adsorption properties for the removal of cationic dye pollutants

    Czech Academy of Sciences Publication Activity Database

    Farhadi, S.; Amini, M.M.; Dušek, Michal; Kučeráková, Monika; Mahmoudi, F.


    Roč. 1130, Oct (2017), s. 592-602 ISSN 0022-2860 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : nanohybrid material * polyoxometalate * single crystal * adsorption activity * cationic dye pollutants Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.753, year: 2016

  16. Continuum-based 4D Plate Reconstructions: Linking Non-rigid Lithospheric Kinematics to Rigid Plate Motion (United States)

    Kneller, E. A.; Johnson, C. A.; Queffelec, T. A.; Nachtegaele, L.


    Non-rigid deformation in regions of continental extension and compression can lead to large lateral strain and changes in the shape and surface area of continental plates. This large lateral strain in turn leads to vertical strain in the lithosphere, which is a fundamental control on mechanical and thermal subsidence. Traditional plate reconstruction approaches only describe 2D changes in the shape of tectonic plates and do not include lateral strain gradients and vertical strain. Incorporating lateral and vertical strain into kinematic plate tectonic models is necessary for quantifying the past configuration of tectonic plates, modeling paleogeography and for linking subsidence and heat flow to lateral plate motion. Furthermore, traditional approaches are limited to describing processes at the surface of the Earth and cannot be used to investigate 3D slab kinematics. We build on previous work and overcome the limitations of traditional methods by developing an inverse non-rigid continuum-based plate reconstruction approach that links lateral plate tectonic motion to large-scale 4D deformation of continental plates and subducting slabs. We also describe how this approach can be implemented in open source 3D animation software that can be used to create extendable and easily maintained interactive tools. These tools allow the modeler to rapidly reconstruct deformation and map data and constrain plate models with 3D information. The methods presented in this work can improve paleogeographic reconstructions, help visualize complicated 4D deformation processes in a reconstructed framework, and constrain subsidence and lithospheric stretching, all of which are important for understanding thermal history and estimating heat flow in sedimentary basins.

  17. Implant stability measurements of two immediate loading protocols for the edentulous mandible: rigid and semi-rigid splinting of the implants. (United States)

    Lee, Hyung Joo; Aparecida de Mattias Sartori, Ivete; Alcântara, Paola Rebelatto; Vieira, Rogéria Acedo; Suzuki, Dalton; Gasparini Kiatake Fontão, Flávia; Tiossi, Rodrigo


    Primary and secondary stabilities of immediately loaded mandibular implants restored with fixed prostheses (FP) using rigid or semi-rigid splinting systems were clinically and radiographically evaluated. Fifteen edentulous patients were rehabilitated using hybrid FP; each had 5 implants placed between the mental foramens. Two groups were randomly divided: group 1-FP with the conventional rigid bar splinting the implants and group 2-semi-rigid cantilever extension system with titanium bars placed in the 2 distal abutment cylinders. Primary stability was evaluated using resonance frequency analysis after installation of the implant abutments. The measurements were made at 3 times: T0, at baseline; T1, 4 months after implant placement; and T2, 8 months after implant placement. Presence of mobility and inflammation in the implant surrounding regions were checked. Stability data were submitted to statistical analysis for comparison between groups (P < 0.05). Implant survival rate for the implants was of 100% in both groups. No significant differences in the mean implant stability quotient values were found for both groups from baseline and after the 8-month follow-up. The immediate loading of the implants was satisfactory, and both splinting conditions (rigid and semi-rigid) can be successfully used for the restoration of edentulous mandibles.

  18. Dioxygen and water activation processes on multi-Ru-substituted polyoxometalates: comparison with the "blue-dimer" water oxidation catalyst. (United States)

    Kuznetsov, Aleksey E; Geletii, Yurii V; Hill, Craig L; Morokuma, Keiji; Musaev, Djamaladdin G


    Dioxygen and water activation on multi-Ru-substituted polyoxometalates were studied using the B3LYP density functional method. It was shown that the reaction of the Ru(2)-substituted gamma-Keggin polyoxotungstate {gamma-[(H(2)O)Ru(III)-(mu-OH)(2)-Ru(III)(H(2)O)][SiW(10)O(36)]}(4-), I(H(2)O), with O(2) is a 4-electron highly exothermic [DeltaE(gas) = 62.5 (DeltaE(gas) + DeltaG(solv(water)) = 24.6) kcal/mol] process and leads to formation of (H(2)O){gamma-[(O)Ru-(mu-OH)(2)-Ru(O)](H(2)O)[SiW(10)O(36)]}(4-), IV(H(2)O). Both the stepwise (or dissociative) and the concerted (or associative) pathways of this reaction occurring with and without water dissociation, respectively, were examined, and the latter has been found to be kinetically more favorable. It was shown that the first 1e-oxidation is achieved by the H(2)O-to-O(2) substitution, which might occur with a maximum of 23.1 (10.5) kcal/mol barrier and leads to the formation of {gamma-[(OO)Ru-(mu-OH)(2)-Ru(H(2)O)](H(2)O)[SiW(10)O(36)]}(4-), II(H(2)O). The second 1e-oxidation is initiated by the proton transfer from the coordinated water molecule to the superoxide (OO(-)) ligand in II(H(2)O) and is completed upon formation of hydroperoxo-hydroxo intermediate {gamma-[(OOH)Ru-(mu-OH)(2)-Ru(OH)](H(2)O)[SiW(10)O(36)]}(4-), III-1(H(2)O). The final 2e-oxidation occurs upon the proton transfer from the terminal OH-ligand to the Ru-coordinated OOH fragment and is completed at the formation of (H(2)O)...{gamma-[(O)Ru-(mu-OH)(2)-Ru(O)](H(2)O)[SiW(10)O(36)]}(4-), IV(H(2)O), with two Ru=O bonds. Each step in the associative pathway is exothermic and occurs with small energy barriers. During the process, the oxidation state of Ru centers increases from +3 to +4. The resulting IV(H(2)O) with a {Ru(O)-(mu-OH)(2)-Ru(O)} core should be formulated to have the Ru(IV)=O(*) units, rather than the Ru(V)=O groups. The reverse reaction, water oxidation by IV(H(2)O), is found to be highly endothermic and cannot occur; this finding is

  19. Large scale Brownian dynamics of confined suspensions of rigid particles. (United States)

    Sprinkle, Brennan; Balboa Usabiaga, Florencio; Patankar, Neelesh A; Donev, Aleksandar


    We introduce methods for large-scale Brownian Dynamics (BD) simulation of many rigid particles of arbitrary shape suspended in a fluctuating fluid. Our method adds Brownian motion to the rigid multiblob method [F. Balboa Usabiaga et al., Commun. Appl. Math. Comput. Sci. 11(2), 217-296 (2016)] at a cost comparable to the cost of deterministic simulations. We demonstrate that we can efficiently generate deterministic and random displacements for many particles using preconditioned Krylov iterative methods, if kernel methods to efficiently compute the action of the Rotne-Prager-Yamakawa (RPY) mobility matrix and its "square" root are available for the given boundary conditions. These kernel operations can be computed with near linear scaling for periodic domains using the positively split Ewald method. Here we study particles partially confined by gravity above a no-slip bottom wall using a graphical processing unit implementation of the mobility matrix-vector product, combined with a preconditioned Lanczos iteration for generating Brownian displacements. We address a major challenge in large-scale BD simulations, capturing the stochastic drift term that arises because of the configuration-dependent mobility. Unlike the widely used Fixman midpoint scheme, our methods utilize random finite differences and do not require the solution of resistance problems or the computation of the action of the inverse square root of the RPY mobility matrix. We construct two temporal schemes which are viable for large-scale simulations, an Euler-Maruyama traction scheme and a trapezoidal slip scheme, which minimize the number of mobility problems to be solved per time step while capturing the required stochastic drift terms. We validate and compare these schemes numerically by modeling suspensions of boomerang-shaped particles sedimented near a bottom wall. Using the trapezoidal scheme, we investigate the steady-state active motion in dense suspensions of confined microrollers, whose

  20. Large scale Brownian dynamics of confined suspensions of rigid particles (United States)

    Sprinkle, Brennan; Balboa Usabiaga, Florencio; Patankar, Neelesh A.; Donev, Aleksandar


    We introduce methods for large-scale Brownian Dynamics (BD) simulation of many rigid particles of arbitrary shape suspended in a fluctuating fluid. Our method adds Brownian motion to the rigid multiblob method [F. Balboa Usabiaga et al., Commun. Appl. Math. Comput. Sci. 11(2), 217-296 (2016)] at a cost comparable to the cost of deterministic simulations. We demonstrate that we can efficiently generate deterministic and random displacements for many particles using preconditioned Krylov iterative methods, if kernel methods to efficiently compute the action of the Rotne-Prager-Yamakawa (RPY) mobility matrix and its "square" root are available for the given boundary conditions. These kernel operations can be computed with near linear scaling for periodic domains using the positively split Ewald method. Here we study particles partially confined by gravity above a no-slip bottom wall using a graphical processing unit implementation of the mobility matrix-vector product, combined with a preconditioned Lanczos iteration for generating Brownian displacements. We address a major challenge in large-scale BD simulations, capturing the stochastic drift term that arises because of the configuration-dependent mobility. Unlike the widely used Fixman midpoint scheme, our methods utilize random finite differences and do not require the solution of resistance problems or the computation of the action of the inverse square root of the RPY mobility matrix. We construct two temporal schemes which are viable for large-scale simulations, an Euler-Maruyama traction scheme and a trapezoidal slip scheme, which minimize the number of mobility problems to be solved per time step while capturing the required stochastic drift terms. We validate and compare these schemes numerically by modeling suspensions of boomerang-shaped particles sedimented near a bottom wall. Using the trapezoidal scheme, we investigate the steady-state active motion in dense suspensions of confined microrollers, whose

  1. Space geodetic constraints on plate rigidity and global plate motions (United States)

    Sella, Giovanni Federico

    The Global Positioning System (GPS) has emerged over the last 10 years as the premier space geodetic technique for geologic observation with the benefits of both accuracy and economy. GPS data from more than 260 stations were processed utilizing GIPSY-OASIS software, and all available RINEX files for these stations beginning on January 1, 1993. The uniform processing strategy, combined with a rigorous independent error estimate of site velocities and the broad geographical distribution of these sites resulted in a global high-precision surface velocity data set. This data set has been used to: (1) compare the effects of different GPS antenna and monument types on data noise; (2) examine in detail the rigidity of the North America plate; (3) constrain the rate of deformation in the northern Gulf of Mexico; (4) define a model for Recent (Holocene) time global plate motions. The weighted root mean square scatter about the best fit line through the daily position estimates are used to assess the effects of different antenna and monument types on North America. The data set is sensitive to glacial isostatic adjustment as indicated by the decrease in chinu 2 from 1.3 to 1.0 by excluding those sites on rigid North America within a radius of 1,800 km of Hudson Bay. The resulting 64 site solution for the angular velocity of North America give a mean rate residual of 1 mm/yr. GULFNET, a regional GPS network created in 1997 in the northern Gulf Coast to measure strain across this active "passive margin" is described. Preliminary results suggest that deformation is occurring as predicted by the regional paradigm for deformation, i.e. Gulfward motion along normal faults. A new model for Recent global plate velocities (REVEL) describes the relative velocities of 14 plates. For several plate pairs, statistically significant differences are observed between the geodetically and geologically determined velocities reflecting changes in plate velocity through time. Some of the rate

  2. [Aphakia correction with rigid contact lenses in congenital cataract]. (United States)

    Loudot, C; Jourdan, F; Benso, C; Denis, D


    To describe follow-up and evaluate functional results of rigid gas-permeable contact lens wear for the correction of aphakia in infants after surgery for congenital cataract. This retrospective study was performed on 23 eyes of 17 children (12 boys and five girls), between three days and 36 months of age (median 3.5 months), undergoing cataract extraction without primary intraocular lens implantation and fitted only with Menicon(®) Z material contact lenses. Initial fitting visits included history and family education. Subsequent examinations were performed at eight days, 15 days, 1 month, 6 months and 1 year. The four main parameters studied were fit characteristics, ease of manipulation, ocular integrity and lens integrity. Concurrently, functional results (visual acuity, oculomotor balance) and various prognostic factors (associated pathology, age at time of surgery, cataract density, unilaterality versus bilaterality, postoperative complications) were evaluated. Rigorous systematic amblyopia rehabilitation was performed. At the one-month exam, 60% of parents demonstrated proficiency with manipulating the lens. On one-year follow-up, three cases of failure were attributable to difficulties with lens manipulation. At one year, one infectious complication was detected. The lens material demonstrated good resistance to breakage (9% at one month) and only a mild tendency toward deposits (few or no deposits in 95% of cases at 1 month). With regard to visual outcome, among the children old enough to cooperate, visual acuity was better than 3/10 for nine out of 12 eyes, of which five eyes were 10/10. With regard to alignment, we noted 12 cases (70.6%) of strabismus postoperatively (ten esotropia, two exotropia). The factors predictive of good visual acuity correlated with those described in the literature: partial cataract, bilateral cataract, and absence of postoperative oculomotor disturbance. The characteristics of rigid gas-permeable contact lenses provide safety

  3. Port-Based Modeling and Simulation of Mechanical Systems With Rigid and Flexible Links

    NARCIS (Netherlands)

    Macchelli, A.; Melchiorri, C.; Stramigioli, Stefano


    In this paper, a systematic procedure for the defi- nition of the dynamical model in port-Hamiltonian form of me- chanical systems is presented as the result of the power-conserving interconnection of a set of basic components (rigid bodies, flexible links, and kinematic pairs). Since rigid bodies

  4. Risk of perforation using rigid oesophagoscopy in the distal part of oesophagus

    DEFF Research Database (Denmark)

    Wennervaldt, Kasper; Melchiors, Jacob


    Endoscopic examination and treatment of disorders in the oesophagus have been a part of the otolaryngological specialty since the introduction of the rigid endoscope. Today, both flexible and rigid oesophagoscopy (RO) is used to that end. The aim of this study was to evaluate the safety of the RO....

  5. 30 CFR 7.28 - Test for flame resistance of rigid ventilation tubing. (United States)


    ... material that falls on the floor of the test gallery during the igniting period. However, the suspended... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Test for flame resistance of rigid ventilation... and Ventilation Tubing § 7.28 Test for flame resistance of rigid ventilation tubing. (a) Test...

  6. Mental set and creative thought in social conflict : Threat rigidity versus motivated focus

    NARCIS (Netherlands)

    De Dreu, Carsten K. W.; Nijstad, Bernard A.

    According to the traditional threat-rigidity reasoning, people in social conflict will be less flexible, less creative, more narrow-minded, and more rigid in their thinking when they adopt a conflict rather than a cooperation mental set. The authors propose and test an alternative, motivated focus

  7. Rigid covariance as a natural extension of Painlev\\'e--Gullstrand space-times: gravitational waves

    CERN Document Server

    Jaén, Xavier


    The group of rigid motions is considered to guide the search for a natural system of space-time coordinates in General Relativity. This search leads us to a natural extension of the space-times that support Painlev\\'{e}--Gullstrand synchronization. As an interesting example, here we describe a system of rigid coordinates for the cross mode of gravitational linear plane waves.

  8. 21 CFR 886.5918 - Rigid gas permeable contact lens care products. (United States)


    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Rigid gas permeable contact lens care products. 886.5918 Section 886.5918 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Therapeutic Devices § 886.5918 Rigid gas permeable contact lens care products. (a)...

  9. The general motion of three mutually-interacting, axisymmetric spherical rigid bodies (United States)

    El-Shaboury, S. M.; Dessoky, A. E. A.


    In this paper, the translational-rotational motions of an axisymmetric rigid body and two spherical rigid bodies under the influence of their mutual gravitational attraction are considered. The equations of motion in the canonical elements of Delaunay-Andoyer are obtained. The elements of motion in the zero and first approximations can be determined.

  10. Effect of various factors on the rigidity of furniture cases | Tankut ...

    African Journals Online (AJOL)

    In general, the stiffer the end connection, the less the deflection of the case was observed. The results also indicated that rigidity of case furniture comes mainly from the gluing of the joining surfaces. Therefore, knowing the rigidity of the case furniture made of wood composites is fundamental to the design of safe, cost ...

  11. Understanding Behavioural Rigidity in Autism Spectrum Conditions: The Role of Intentional Control (United States)

    Poljac, Edita; Hoofs, Vincent; Princen, Myrthe M.; Poljac, Ervin


    Although behavioural rigidity belongs to the core symptoms of autism spectrum conditions, little is known about its underlying cognitive mechanisms. The current study investigated the role of intentional control mechanisms in behavioural rigidity in autism. Autistic individuals and their matched controls were instructed to repeatedly choose…

  12. A new cantilever beam-rigid-body MEMS gyroscope: mathematical model and linear dynamics

    CERN Document Server

    Lajimi, Seyed Amir Mousavi; Abdel-Rahman, Eihab


    A new microbeam-rigid-body gyroscope is introduced and its static and dynamic behaviours are studied. The main structure includes a microbeam and an eccentric end-rigid-body influencing the dynamic and static characteristics of the sensor. The sensitivity of the device and the effect of system parameters on the microsystem's response are investigated.

  13. 21 CFR 177.1010 - Acrylic and modified acrylic plastics, semirigid and rigid. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylic and modified acrylic plastics, semirigid... Acrylic and modified acrylic plastics, semirigid and rigid. Semirigid and rigid acrylic and modified acrylic plastics may be safely used as articles intended for use in contact with food, in accordance with...

  14. 21 CFR 178.3790 - Polymer modifiers in semirigid and rigid vinyl chloride plastics. (United States)


    ... chloride plastics. 178.3790 Section 178.3790 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF... modifiers in semirigid and rigid vinyl chloride plastics. The polymers identified in paragraph (a) of this... semirigid and rigid vinyl chloride plastic food-contact articles prepared from vinyl chloride homopolymers...

  15. The shape of a drop between two rigid fibers (United States)

    Protiere, Suzie; Duprat, Camille; Stone, Howard A.


    Wetting of fibrous media is observed in many engineered systems, e.g. filters, textiles, paper etc. and may also be found in Nature (e.g. hair or feathers). To understand the basic response of such material when interacting with a liquid we study the model system of a finite volume of liquid on two parallel rigid fibers. A liquid wetting the fibers can adopt two distinct equilibrium shapes: a compact hemispherical drop shape or a long liquid column of constant cross-section. These two morphologies depend on the inter-fiber distance, the liquid volume, the fiber radius and the liquid-fiber contact angle. We study the transitions between a drop shape and a column by incrementally varying the inter-fiber distance and find that the transition depends on the global geometry of the system as well as on the volume of liquid. More surprisingly we find that these two morphological states may coexist for certain parameter values. These switches in morphologies may be used to manipulate or transport liquid at a small scale.

  16. Bevel toric multicurve rigid gas-permeable lens for keratoconus. (United States)

    Yanai, Ryoji; Ueda, Kiichi; Sonoda, Koh-Hei


    To evaluate the efficacy and safety of Twinbel bevel toric, a newly designed rigid gas-permeable (RGP) lens with a toric bevel curvature, for keratoconus. A retrospective analysis of nine eyes of patients with keratoconus who had been wearing RGP contact lenses and were switched to Twinbel bevel toric at Yamaguchi University Hospital. Visual acuity and contrast sensitivity were measured under photopic conditions. Complaint symptoms were recorded as primary outcome measures at follow-up visits. Efficacy and safety were evaluated at 12 weeks after the switch to Twinbel bevel toric or later. Five eyes (55.6 %) showed an improvement in visual acuity with Twinbel bevel toric compared with the previous lens, whereas four eyes (44.4 %) maintained the same visual acuity as before. The mean best corrected visual acuity ± SD with Twinbel bevel toric was 0.01 ± 0.40 logMAR, significantly better (P = 0.044, paired Student's t test) than that (0.23 ± 0.51 logMAR) with the previous lens. Contrast sensitivity and subjective complaint scores did not differ significantly between Twinbel bevel toric and the previous lens. No serious complications of Twinbel bevel toric wear were observed. Fitting of Twinbel bevel toric improved visual acuity in eyes affected by keratoconus, thus providing a viable alternative for management of such eyes.

  17. Non-rigid registration of cervical spine MRI volumes. (United States)

    Aktar, Mst Nargis; Alam, Md Jahangir; Pickering, Mark; Webb, Alexandra; Perriman, Diana


    Whiplash is the colloquial term for neck injuries caused by sudden extension of the cervical spine. Patients with chronic whiplash associated disorder (WAD) can experience neck pain for many years after the original injury. Researchers have found some evidence to suggest that chronic whiplash is related to the amount of intra-muscular fat in the cervical spine muscles. Hence, an important step towards developing a treatment for chronic WAD is a technique to accurately and efficiently measure the amount of intra-muscular fat in the muscles of the cervical spine. Our proposed technique for making this measurement is to automatically segment the cervical spine muscles using a fused volume created from multi-modal MRI volumes of the cervical spine. Multiple modes are required to enhance the boundaries between the different muscles to assist the following automatic segmentation process. However, before these multiple modes can be fused it is first necessary to accurately register these volumes. Hence, in this paper, we have proposed a new non-rigid multi-modal registration algorithm using the sum of conditional variance (SCV) with partial volume interpolation (PVI) similarity measure and Gauss-Newton (GN) optimization for the accurate registration of multi-modal cervical spine MRI volumes. The performance of the proposed approach is compared with the existing SCV based registration algorithm and the sum of the conditional squared deviation from the mode (SCSDM) method. The experimental results demonstrate that the proposed approach provides superior performance than the best existing approaches.

  18. Rigid sphere room impulse response simulation: algorithm and applications. (United States)

    Jarrett, D P; Habets, E A P; Thomas, M R P; Naylor, P A


    Simulated room impulse responses have been proven to be both useful and indispensable for comprehensive testing of acoustic signal processing algorithms while controlling parameters such as the reverberation time, room dimensions, and source-array distance. In this work, a method is proposed for simulating the room impulse responses between a sound source and the microphones positioned on a spherical array. The method takes into account specular reflections of the source by employing the well-known image method, and scattering from the rigid sphere by employing spherical harmonic decomposition. Pseudocode for the proposed method is provided, taking into account various optimizations to reduce the computational complexity. The magnitude and phase errors that result from the finite order spherical harmonic decomposition are analyzed and general guidelines for the order selection are provided. Three examples are presented: an analysis of a diffuse reverberant sound field, a study of binaural cues in the presence of reverberation, and an illustration of the algorithm's use as a mouth simulator.

  19. Non-rigid registration for qualitiy control of printed materials (United States)

    Badshah, Amir; O'Leary, Paul; Harker, Matthew; Sallinger, Christian


    This paper presents a new approach to non-rigid elastic registration. The method is applied to hyper spectral imaging data for the automatic quality control of decorative foils which are subject to deformation during lamination. A new image decimation procedure based on Savitzky-Golay smoothing is presented and applied in a multiresolution pyramid. Modified Fourier basis functions implemented by projection onto the orthogonal complement of a truncated Gram polynomial basis are presented. The modified functions are used to compute spectra whereby the Gibbs error associated with local gradients in the image are reduced. The paper also presents the first direct linear solution to weighted tensor product polynomial approximation. This method is used to regularize the patch coordinates, the solution is equivalent to a Galerkin type solution to a partial differential equations. The new solution is applied to published standard data set and to data acquired in a production environment. The speed of the new solution justifies explicit reference: the present solution implemented in MATLAB requires approximatly 1.3s to register an image of size 800 ×× 500 pixels. This is approximately a factor 10 to 100 faster than previously published results for the same data set.

  20. A Condition Number for Non-Rigid Shape Matching

    KAUST Repository

    Ovsjanikov, Maks


    © 2011 The Author(s). Despite the large amount of work devoted in recent years to the problem of non-rigid shape matching, practical methods that can successfully be used for arbitrary pairs of shapes remain elusive. In this paper, we study the hardness of the problem of shape matching, and introduce the notion of the shape condition number, which captures the intuition that some shapes are inherently more difficult to match against than others. In particular, we make a connection between the symmetry of a given shape and the stability of any method used to match it while optimizing a given distortion measure. We analyze two commonly used classes of methods in deformable shape matching, and show that the stability of both types of techniques can be captured by the appropriate notion of a condition number. We also provide a practical way to estimate the shape condition number and show how it can be used to guide the selection of landmark correspondences between shapes. Thus we shed some light on the reasons why general shape matching remains difficult and provide a way to detect and mitigate such difficulties in practice.

  1. Rigid fibrescope Bonfils: use in simulated difficult airway by novices

    Directory of Open Access Journals (Sweden)

    Piepho Tim


    Full Text Available Abstract Background The Bonfils intubation fibrescope is a promising alternative device for securing the airway. We examined the success rate of intubation and the ease of use in standardized simulated difficult airway scenarios by physicians. We compared the Bonfils to a classical laryngoscope with Macintosh blade. Methods 30 physicians untrained in the use of rigid fibrescopes but experienced in airway management performed endotracheal intubation in an airway manikin (SimMan, Laerdal, Kent, UK with three different airway conditions. We evaluated the success rate using the Bonfils (Karl Storz, Tuttlingen, Germany or the Macintosh laryngoscope, the time needed for securing the airway, and subjective rating of both techniques. Results In normal airway all intubations were successful using laryngoscope (100% vs. 82% using the Bonfils (p Conclusion The Bonfils can be successfully used by physicians unfamiliar with this technique in an airway manikin. The airway could be secured with at least the same success rate as using a Macintosh laryngoscope in difficult airway scenarios. Use of the Bonfils did not delay intubation in the presence of a difficult airway. These results indicate that intensive special training is advised to use the Bonfils effectively in airway management.

  2. Impact of a Liquid Cone on a Plain Rigid Wall

    Directory of Open Access Journals (Sweden)

    A.A. Aganin


    Full Text Available A numerical study of high-speed (with the velocity of 250 m/s impact of a liquid cone (cone-like jet on a plain rigid wall has been performed. The range of the angles of inclination of the cone surface to the wall corresponds to that of their variation in the process of impact on the wall of a cylindrical jet with the semi-spherical end. The direct numerical simulation has been used on the basis of the gas dynamics equations by the CIP-CUP method on the dynamically adaptive Soroban-grids without explicit tracking of the interphase boundary. It has been found that three regimes of impact are set in the examined range of the angles. At the small angles the impact with shock wave attached to the wall without liquid spreading is realized. An abrupt transition to the regime with the shock wave detached from the wall together with the radial jet of the liquid spreading on the wall takes place with increasing the angle. A smooth transition to the shockless regime with the radial liquid jet is realized with further increasing the angle.

  3. Optical characterization and polarization calibration for rigid endoscopes (United States)

    Garcia, Missael; Gruev, Viktor


    Polarization measurements give orthogonal information to spectral images making them a great tool in the characterization of environmental parameters in nature. Thus, polarization imagery has proven to be remarkably useful in a vast range of biomedical applications. One such application is the early diagnosis of flat cancerous lesions in murine colorectal tumor models, where polarization data complements NIR fluorescence analysis. Advances in nanotechnology have led to compact and precise bio-inspired imaging sensors capable of accurately co-registering multidimensional spectral and polarization information. As more applications emerge for these imagers, the optics used in these instruments get very complex and can potentially compromise the original polarization state of the incident light. Here we present a complete optical and polarization characterization of three rigid endoscopes of size 1.9mm x 10cm (Karl Storz, Germany), 5mm x 30cm, and 10mm x 33cm (Olympus, Germany), used in colonoscopy for the prevention of colitis-associated cancer. Characterization results show that the telescope optics act as retarders and effectively depolarize the linear component. These incorrect readings can cause false-positives or false-negatives leading to an improper diagnosis. In this paper, we offer a polarization calibration scheme for these endoscopes based on Mueller calculus. By modeling the optical properties from training data as real-valued Mueller matrices, we are able to successfully reconstruct the initial polarization state acquired by the imaging system.

  4. Glass fiber and silica reinforced rigid polyurethane foams

    Directory of Open Access Journals (Sweden)

    M. W. Kim


    Full Text Available Ternary composites of rigid polyurethane foam (RPUF/glass fiber/silica as well as RPUF/glass fiber have been fabricated from glass fiber, silica, polymeric 4,4′-di-phenylmethane diisocyanate (PMDI and polyol using HFC 365mfc as blowing agent. Foam formation kinetics, morphology, thermal conductivity, glass transition temperature, decomposition temperatures as well as the mechanical strengths of the foam have been studied. With the addition an increasing amount of glass fiber cream time, rise time, gel time, tack free time, density, compression strength, thermal conductivity (k monotonically increased while the glass transition temperature showed a maximum at 2%. At constant glass fiber content (2%, addition of silica further increased the process times, density and compression strength while the Tg and thermal decomposition temperature showed a maximum at 3% silica. The k value of RFUF/glass fiber composite decreased with the addition of silica up to 3%, where it was even lower than the virgin RPUF. However, beyond the content k value increased. Overall, the variation of k value with silica content showed identical tendency with cells size and closed cells content.

  5. Collapsed fat navigators for brain 3D rigid body motion. (United States)

    Engström, Mathias; Mårtensson, Magnus; Avventi, Enrico; Norbeck, Ola; Skare, Stefan


    To acquire high-resolution 3D multi-slab echo planar imaging data without motion artifacts, using collapsed fat navigators. A fat navigator module (collapsed FatNav) was added to a diffusion-weighted 3D multi-slab echo planar imaging (DW 3D-MS EPI) sequence, comprising three orthogonal echo planar imaging readouts to track rigid body head motion in the image domain and performing prospective motion correction. The stability, resolution and accuracy of the navigator were investigated on phantoms and healthy volunteers. The experiments on phantoms and volunteers show that the navigator, depicting projections of the subcutaneous fat in of the head, is capable of correcting for head motion with insignificant bias compared to motion estimates derived from the water-signaling DWI images. Despite that this projection technique implies a non-sparse image appearance, collapsed FatNav data could be highly accelerated with parallel imaging, allowing three orthogonal 2D EPI readouts in about 6ms. By utilizing signal from the leading fat saturation RF pulse of the diffusion sequence, only the readout portion of the navigator needs to be added, resulting in a scan time penalty of only about 5%. Motion can be detected and corrected for with a 5-10Hz update frequency when combined with a sequence like the DW 3D-MS EPI. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Canonical formalism for modelling and control of rigid body dynamics. (United States)

    Gurfil, P


    This paper develops a new paradigm for stabilization of rigid-body dynamics. The state-space model is formulated using canonical elements, known as the Serret-Andoyer (SA) variables, thus far scarcely used for engineering applications. The main feature of the SA formalism is the reduction of the dynamics via the underlying symmetry stemming from conservation of angular momentum and rotational kinetic energy. The controllability of the system model is examined using the notion of accessibility, and is shown to be accessible from all points. Based on the accessibility proof, two nonlinear asymptotic feedback stabilizers are developed: a damping feedback is designed based on the Jurdjevic-Quinn method, and a Hamiltonian controller is derived by using the Hamiltonian as a natural Lyapunov function for the closed-loop dynamics. It is shown that the Hamiltonian control is both passive and inverse optimal with respect to a meaningful performance index. The performance of the new controllers is examined and compared using simulations of realistic scenarios from the satellite attitude dynamics field.

  7. Unifying Rigid and Soft Bodies Representation: The Sulfur Physics Engine

    Directory of Open Access Journals (Sweden)

    Dario Maggiorini


    Full Text Available Video games are (also real-time interactive graphic simulations: hence, providing a convincing physics simulation for each specific game environment is of paramount importance in the process of achieving a satisfying player experience. While the existing game engines appropriately address many aspects of physics simulation, some others are still in need of improvements. In particular, several specific physics properties of bodies not usually involved in the main game mechanics (e.g., properties useful to represent systems composed by soft bodies, are often poorly rendered by general-purpose engines. This issue may limit game designers when imagining innovative and compelling video games and game mechanics. For this reason, we dug into the problem of appropriately representing soft bodies. Subsequently, we have extended the approach developed for soft bodies to rigid ones, proposing and developing a unified approach in a game engine: Sulfur. To test the engine, we have also designed and developed “Escape from Quaoar,” a prototypal video game whose main game mechanic exploits an elastic rope, and a level editor for the game.

  8. Obstacles to developing sustainable cities: the real estate rigidity trap

    Directory of Open Access Journals (Sweden)

    V. Kelly Turner


    Full Text Available Sprawl patterns of urbanization have large environmental consequences, and sustainable alternatives to conventional urban patterns of development have been promoted by a subset of planners, design professionals, and municipalities. These alternatives have not been widely adopted among real estate developers, actors with large influence over urban form and function. Existing explanations for this failure enumerate market and regulatory barriers but do not sufficiently describe the institutional structures that allow conventional approaches to prevail. A failure of real estate developers to adopt alternative forms of development can best be described in terms of a rigidity trap. Specifically, norms of practice within the real estate development industry combine with market and regulatory factors to favor existing practices and limit innovation. Moreover, these institutional factors also buffer the real estate development industry from feedback mechanisms and external signals that might otherwise trigger adaptation. Addressing the environmental consequences of urbanization not only requires novel approaches to urban design, but will also necessitate addressing systemic pathologies in the design implementation process.

  9. Microscopic theory of topologically entangled fluids of rigid macromolecules (United States)

    Sussman, Daniel M.; Schweizer, Kenneth S.


    We present a first-principles theory for the slow dynamics of a fluid of entangling rigid crosses of zero excluded volume based on a generalization of the dynamic mean-field approach of Szamel for infinitely thin nonrotating rods. The latter theory exactly includes topological constraints at the two-body collision level and self-consistently renormalizes an effective diffusion tensor to account for many-body effects. Remarkably, it predicts scaling laws consistent with the phenomenological reptation-tube predictions of Doi and Edwards for the long-time diffusion and the localization length in the heavily entangled limit. We generalize this approach to a different macromolecular architecture, infinitely thin three-dimensional crosses, and also extend the range of densities over which a dynamic localization length can be calculated for rods. Ideal gases of nonrotating crosses have recently received attention in computer simulations and are relevant as a simple model of both a strong-glass former and entangling star-branched polymers. Comparisons of our theory with these simulations reveal reasonable agreement for the magnitude and reduced density dependence of the localization length and also the self-diffusion constant if the consequences of local density fluctuations are taken into account.

  10. Active elastic dimers: Cells moving on rigid tracks (United States)

    Lopez, J. H.; Das, Moumita; Schwarz, J. M.


    Experiments suggest that the migration of some cells in the three-dimensional extracellular matrix bears strong resemblance to one-dimensional cell migration. Motivated by this observation, we construct and study a minimal one-dimensional model cell made of two beads and an active spring moving along a rigid track. The active spring models the stress fibers with their myosin-driven contractility and α-actinin-driven extendability, while the friction coefficients of the two beads describe the catch and slip-bond behaviors of the integrins in focal adhesions. In the absence of active noise, net motion arises from an interplay between active contractility (and passive extendability) of the stress fibers and an asymmetry between the front and back of the cell due to catch-bond behavior of integrins at the front of the cell and slip-bond behavior of integrins at the back. We obtain reasonable cell speeds with independently estimated parameters. We also study the effects of hysteresis in the active spring, due to catch-bond behavior and the dynamics of cross linking, and the addition of active noise on the motion of the cell. Our model highlights the role of α-actinin in three-dimensional cell motility and does not require Arp2/3 actin filament nucleation for net motion.

  11. Finite Element Investigation of the Deterioration of Doweled Rigid Pavements

    CERN Document Server

    Ghauch, Ziad G


    The purpose of this study is to describe the failure of concrete around dowel bars in jointed rigid pavements, and the resulting effect on the pavement performance. In fact, under repetitive vehicle loading, concrete in contact with the dowel bar deteriorates, particularly at the joint face. The degradation of concrete around the dowel negatively affects the latter's performance in terms of transferring wheel loads through vertical shear action. In this context, a nonlinear 3D Finite Element analysis was performed using the commercial FE code Abaqus (v-6.11). The FE model was validated with classical analytical solutions of shear and moment along the dowel. A concrete damaged plasticity model was used for the PCC slab to model the degradation of concrete matrix around the dowels under incremental loading. Results obtained show, among other things, that the degradation of concrete matrix around the dowel was found to initiate at the face of the joint and propagate towards the interior of the dowel. Also, resul...

  12. Thermally-Induced Structural Disturbances of Rigid Panel Solar Arrays (United States)

    Johnston, John D.; Thornton, Earl A.


    The performance of a significant number of spacecraft has been impacted negatively by attitude disturbances resulting from thermally-induced motions of flexible structures. Recent examples of spacecraft affected by these disturbances include the Hubble Space Telescope (HST) and the Upper Atmosphere Research Satellite (UARS). Thermally-induced structural disturbances occur as the result of rapid changes in thermal loading typically initiated as a satellite exits or enters the Earth's shadow. Temperature differences in flexible appendages give rise to structural deformations, which in turn result in disturbance torques reacting back on the spacecraft. Structures which have proven susceptible to these disturbances include deployable booms and solar arrays. This paper investigates disturbances resulting from thermally-induced deformations of rigid panel solar arrays. An analytical model for the thermal-structural response of the solar array and the corresponding disturbance torque are presented. The effect of these disturbances on the attitude dynamics of a simple spacecraft is then investigated using a coupled system of governing equations which includes the effects of thermally-induced deformations. Numerical results demonstrate the effect of varying solar array geometry on the dynamic response of the system.

  13. Semi-Implicit Reversible Algorithms for Rigid Body Rotational Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Nukala, Phani K [ORNL; Shelton Jr, William Allison [ORNL


    This paper presents two semi-implicit algorithms based on splitting methodology for rigid body rotational dynamics. The first algorithm is a variation of partitioned Runge-Kutta (PRK) methodology that can be formulated as a splitting method. The second algorithm is akin to a multiple time stepping scheme and is based on modified Crouch-Grossman (MCG) methodology, which can also be expressed as a splitting algorithm. These algorithms are second-order accurate and time-reversible; however, they are not Poisson integrators, i.e., non-symplectic. These algorithms conserve some of the first integrals of motion, but some others are not conserved; however, the fluctuations in these invariants are bounded over exponentially long time intervals. These algorithms exhibit excellent long-term behavior because of their reversibility property and their (approximate) Poisson structure preserving property. The numerical results indicate that the proposed algorithms exhibit superior performance compared to some of the currently well known algorithms such as the Simo-Wong algorithm, Newmark algorithm, discrete Moser-Veselov algorithm, Lewis-Simo algorithm, and the LIEMID[EA] algorithm.

  14. Use of Terrestrial Laser Scanner for Rigid Airport Pavement Management. (United States)

    Barbarella, Maurizio; D'Amico, Fabrizio; De Blasiis, Maria Rosaria; Di Benedetto, Alessandro; Fiani, Margherita


    The evaluation of the structural efficiency of airport infrastructures is a complex task. Faulting is one of the most important indicators of rigid pavement performance. The aim of our study is to provide a new method for faulting detection and computation on jointed concrete pavements. Nowadays, the assessment of faulting is performed with the use of laborious and time-consuming measurements that strongly hinder aircraft traffic. We proposed a field procedure for Terrestrial Laser Scanner data acquisition and a computation flow chart in order to identify and quantify the fault size at each joint of apron slabs. The total point cloud has been used to compute the least square plane fitting those points. The best-fit plane for each slab has been computed too. The attitude of each slab plane with respect to both the adjacent ones and the apron reference plane has been determined by the normal vectors to the surfaces. Faulting has been evaluated as the difference in elevation between the slab planes along chosen sections. For a more accurate evaluation of the faulting value, we have then considered a few strips of data covering rectangular areas of different sizes across the joints. The accuracy of the estimated quantities has been computed too.

  15. Use of Terrestrial Laser Scanner for Rigid Airport Pavement Management

    Directory of Open Access Journals (Sweden)

    Maurizio Barbarella


    Full Text Available The evaluation of the structural efficiency of airport infrastructures is a complex task. Faulting is one of the most important indicators of rigid pavement performance. The aim of our study is to provide a new method for faulting detection and computation on jointed concrete pavements. Nowadays, the assessment of faulting is performed with the use of laborious and time-consuming measurements that strongly hinder aircraft traffic. We proposed a field procedure for Terrestrial Laser Scanner data acquisition and a computation flow chart in order to identify and quantify the fault size at each joint of apron slabs. The total point cloud has been used to compute the least square plane fitting those points. The best-fit plane for each slab has been computed too. The attitude of each slab plane with respect to both the adjacent ones and the apron reference plane has been determined by the normal vectors to the surfaces. Faulting has been evaluated as the difference in elevation between the slab planes along chosen sections. For a more accurate evaluation of the faulting value, we have then considered a few strips of data covering rectangular areas of different sizes across the joints. The accuracy of the estimated quantities has been computed too.

  16. Non-Invasive Ocular Rigidity Measurement: A Differential Tonometry Approach

    Directory of Open Access Journals (Sweden)

    Efstathios T. Detorakis


    Full Text Available Purpose: Taking into account the fact that Goldmann applanation tonometry (GAT geometrically deforms the corneal apex and displaces volume from the anterior segment whereas Dynamic Contour Tonometry (DCT does not, we aimed at developing an algorithm for the calculation of ocular rigidity (OR based on the differences in pressure and volume between deformed and non-deformed status according to the general Friedenwald principle of differential tonometry. Methods: To avoid deviations of GAT IOP from true IOP in eyes with corneas different from the “calibration cornea” we applied the previously described Orssengo-Pye algorithm to calculate an error coefficient “C/B”. To test the feasibility of the proposed model, we calculated the OR coefficient (r in 17 cataract surgery candidates (9 males and 8 females. Results: The calculated r according to our model (mean ± SD, range was 0.0174 ± 0.010 (0.0123–0.022 mmHg/μL. A negative statistically significant correlation between axial length and r was detected whereas correlations between r and other biometric parameters examined were statistically not significant. Conclusions: The proposed method may prove a valid non-invasive tool for the measurement method of OR, which could help in introducing OR in the decision-making of the routine clinical practice.

  17. Determination of Weight Suspension Rigidity in the Transport-Erector Aggregates

    Directory of Open Access Journals (Sweden)

    V. A. Zverev


    Full Text Available The aim is to determine weight suspension rigidity in aggregates designed to perform technological transport-erector operations at the miscellaneous launch complexes.We consider the weight suspension comprising the following distinctive structural components: the executive weight-lowering mechanism, polyspast mechanism, rope, traverse, and rods. A created structural dynamic model of suspension allowed us to define weight suspension rigidity. Within the framework of design analysis of a dynamic model we determined the rigidity of its structural units, i.e. traverse, rope, and polyspast.Known analytical relationships were used to calculate the rope rigidity. To determine rigidity of polyspast and traverse have been created special models based on the finite element method. For each model deformation in the specific points under the test load have been defined. Data obtained were used to determine trigidity of traverses and polyspast, and also rigidity of suspension in total. The rigidity models of polispast mechanism and traverse have been developed and calculated using the software complex "Zenit-95".As the research results, the paper presents a dynamic model of the weight suspension of the transport-erector aggregate, the finite element models of the polispast mechanism and traverse, an algorithm for determining the weight suspension rigidity and relevant analytical relationships.Independent calculation of weight suspension rigidity enables us to simplify further dynamic calculation of the aggregate-weight system because it allows attaining a simpler model of the aggregate-weight system that uses the weight suspension model as an element of equivalent rigidity. Despite this simplification the model allows us to determine correctly weight movement parameters and overloads in the aggregate-weight system in the process of technical operations.

  18. Wetting properties and performance test of modified rigid collector in wet electrostatic precipitators. (United States)

    Xu, Chunyan; Chang, Jingcai; Meng, Zhen; Wang, Xiang; Zhang, Jing; Cui, Lin; Ma, Chunyuan


    The fine particles are considered a significant pollution problem. The wet electrostatic precipitators (ESPs) have advantages of efficient collection of the fine particles with lower pressure drop and eliminating reentrainment. The wetting properties of the collector surfaces have significantly important effect on wet ESPs' stable and secure operation. The modified rigid collector (MRC) was modified by coating specific vinyl ester resin composites and loose glass fiber cloth over the conventional carbon steel in a certain way. The rigid collector surfaces before and after modification had been characterized by scanning electron microscopy (SEM) and interface tensiometer. The effect of operating temperatures on the wetting properties of the rigid collector surfaces before and after modification was investigated. The temperature range was 40~90 °C, and the wetting properties contained liquid holdup, surface flow rate, film rate, average film thickness, and critical saturation time. The modified rigid collector surface exhibited excellent wetting properties at the operating temperatures. The fine particles collection performance compared among the MRC, the conventional rigid collector (CRC), and the flexible collector (FC) in the wet ESPs was investigated. The effects of the applied voltage, the water film, corona power, and the specific collecting area on the fine particles collection were evaluated. The modified rigid collector provided high fine particles collection effect with lower energy and water consumption. To improve the submicron particles collection efficiency and decrease energy and water consumption, the formation of uniform water film over the collector surfaces has been widely studied. The modified rigid collector was modified by coating specific vinyl ester resin composites and loose glass fiber cloth (ERGF) over the conventional carbon steel (CCS) in a certain way. The modified rigid collector surface exhibited excellent wetting properties. The wet

  19. Flexible Versus Rigid Methods Of Intravenous Thrombolysis In Iran

    Directory of Open Access Journals (Sweden)

    Kavian Ghandehari


    exclusion critera as illustrated above. This method will increase the probability of symptomatic intracerebral hemorrhage and death and may increase  numbers of legal condemnations for treating physician. Rigid method is prohibition of violations from standard protocols of thrombolysis which decreases both numbers of managed patients and thrombolysis contraindications. Physicians who prefer the first therapeutic strategy refer to data of published articles and guidelines of American and European stroke societies. There are two points of view; first, the Iranian neurologists do not have thrombolysis experience as well as western neurologusts. For instance very limited number of Iranian neurologists have enough experience for detection of ASPECT score. Second, due to some social factors number of legal condemnations  due to medical malpractice has been hugely increased in recent two decades in Iran. Based on these points second strategy is more wise for Iranian neurologists. The speaker has made a standard protocol of thrombolysis based on international gudelines and his experience. This standard protocol which is designed according to the rigid method is available by search in Google engine and is provided in Persian language.

  20. Rigid polyurethane/oil palm fibre biocomposite foam (United States)

    Alis, Adilah; Majid, Rohah A.; Nasir, Izzah Athirah Ahmad; Mustaffa, Nor Syatika; Hassan, Wan Hasamuddin Wan


    Rigid polyurethane (PU) biocomposite foam had been successfully prepared by reacting palm oil-derived polyol (PO-p) with polymeric 4, 4-diphenylmethane diisocynate (p-MDI). Two types of alkali-treated oil palm fibres namely, empty fruit bunch (EFB) and palm pressed fibre (PPF) were used as fillers to be incorporated into PU foam at 2.5 wt%, 5 wt% and 7.5 wt% fibre loadings. The effects of these fibres on surface morphology, compressive strength and thermal transition behaviours of biocomposite foams were investigated. Fourier transform infra-red (FTIR) analysis confirmed the formation of urethane linkages (-NHCOO) in all samples at 1530-1540 cm-1. Differential scanning calorimetry (DSC) analysis showed the average melting peak temperature (Tm) of biocomposite foams (132°C) were lower Tm than that of pure PU foam (161.67°C) and the increase amount of fibres did not give significant effect on the Tm of both biocomposite systems. Meanwhile, the microscopic images of PU-PPF foams exhibited smaller and uniform cell size morphologies compared with the PU-EFB foams that had coarse and irregular cell sizes, especially at 7.5wt% EFB. These findings were manifested with the gradually increase of compressive strength of PU-PPF at all PPF ratios while for PU-EFB system, the compressive strength increased up to 5 wt% before reduced at 7.5 wt% loading. It was thought due to the residual oil in PPF fibre had plasticized the PU matrix to a little extent, thus helping the dispersion of PPF fibre across the matrix.

  1. Diagnostic value of rigid body rotation in noncompaction cardiomyopathy. (United States)

    van Dalen, Bas M; Caliskan, Kadir; Soliman, Osama I I; Kauer, Floris; van der Zwaan, Heleen B; Vletter, Wim B; van Vark, Laura C; Ten Cate, Folkert J; Geleijnse, Marcel L


    The diagnosis of noncompaction cardiomyopathy (NCCM) remains subject to controversy. Because NCCM is probably caused by an intrauterine arrest of the myocardial fiber compaction during embryogenesis, it may be anticipated that the myocardial fiber helices, normally causing left ventricular (LV) twist, will also not develop properly. The resultant LV rigid body rotation (RBR) may strengthen the diagnosis of NCCM. The purpose of the current study was to explore the diagnostic value of RBR in a large group of patients with prominent trabeculations. The study comprised 15 patients with dilated cardiomyopathy, 52 healthy subjects, and 52 patients with prominent trabeculations, of whom a clinical expert in NCCM defined 34 as having NCCM. LV rotation patterns were determined by speckle-tracking echocardiography and defined as follows: pattern 1A, completely normal rotation (initial counterclockwise basal and clockwise apical rotation, followed by end-systolic clockwise basal and counterclockwise apical rotation); pattern 1B, partly normal rotation (normal end-systolic rotation but absence of initial rotation in the other direction); and pattern 2, RBR (rotation at the basal and apical level predominantly in the same direction). The majority of normal subjects had LV rotation pattern 1A (98%), whereas the 18 subjects with hypertrabeculation not fulfilling diagnostic criteria for NCCM predominantly had pattern 1B (71%), and the 34 patients with NCCM predominantly had pattern 2 (88%). None of the patients with dilated cardiomyopathy showed RBR. Sensitivity and specificity of RBR for differentiating NCCM from "hypertrabeculation" were 88% and 78%, respectively. RBR is an objective, quantitative, and reproducible functional criterion with good predictive value for the diagnosis of NCCM as determined by expert opinion. Copyright © 2011 American Society of Echocardiography. Published by Mosby, Inc. All rights reserved.

  2. Apical clearance rigid contact lenses induce corneal steepening. (United States)

    Swarbrick, Helen A; Hiew, Ross; Kee, Ai Vy; Peterson, Sophia; Tahhan, Nina


    Anecdotal reports suggest that steeply fitted rigid contact lenses can induce corneal steepening and myopic shifts in refraction. This study investigated changes in corneal topography, corneal thickness, and refraction after short-term wear of apical clearance lenses. : Ten young adults participated in the study in which apical clearance lenses (Conoid, Hydron Pty. Ltd., Frenchs Forest, NSW, Australia), fitted approximately 0.3 mm steeper than the flattest keratometric reading, were worn for 4 h. A polymethyl methacrylate (PMMA) lens was worn in one eye, and a Boston XO lens (Bausch & Lomb, Rochester, NY) was worn in the other. Lenses were nonfenestrated in the first trial, and a single midperipheral fenestration was incorporated for a second trial. Corneal topography was monitored using the EyeSys topographic analysis system (EyeSys Vision, Inc., Houston, TX); central corneal thickness was quantified using ultrasonic pachometry; and refraction and anterior ocular response were also monitored. Significant central corneal edema (8.2 +/- 2.2%) was demonstrated in the PMMA lens-wearing eye only. Fenestration did not reduce the edema response. We found significant corneal steepening over a 5- to 6-mm central zone, which was more pronounced in the PMMA lens-wearing eye and was modified by lens fenestration. The curvature changes altered central corneal shape from prolate (Q = -0.06 +/- 0.10) to oblate (Q = -0.26 +/- 0.31). A slight myopic shift in refraction (-0.38 +/- 0.60 D) was found with the PMMA lenses only. : Apical clearance lenses induce corneal steepening after short-term wear. Although corneal molding is implicated as the primary factor driving the shape change, corneal edema and postlens tear film pressures can modify this response.

  3. Success of Rigid Gas Permeable Contact Lens Fitting. (United States)

    Ortiz-Toquero, Sara; Martin, Mario; Rodriguez, Guadalupe; de Juan, Victoria; Martin, Raul


    To assess the percentage of successful rigid gas permeable (GP) contact lenses (CLs) fit for both refractive and therapeutic reasons. New CLs (soft or GP) fittings were retrospectively analyzed and divided into refractive and therapeutic prescriptions. A standardized fitting protocol that included complete CLs information after a first eye examination, a diagnostic fitting visit, a dispensing visit, and a prescribing visit was used in all fittings. A GP fitting was defined as successful if full-time wear and optimal ocular surface physiology were both achieved at the review assessment 2 to 3 weeks after lens dispensing. Of 232 new CLs fittings analyzed, 166 were refractive fittings (71.6%) and 66 were therapeutic (28.4%). Of the refractive fittings, 88 subjects (53%) were initially fitted with GP CLs and 61 (69.3%) of these met the criteria for successful GP fitting. Within this group, a different percentage of successful fits were found for neophyte (72%), previous soft lens wearers (62%), and previous GP wearers (92.3%). Of the therapeutic fittings, 61 subjects (92.4%) were initially fitted with GP CLs and 59 (96.7%) of these met the criteria for successful GP fitting. Following a standardized CLs fitting protocol, a relatively high percentage of successful GP fits was achieved for refractive (7/10 subjects) and therapeutic (9/10 subjects) prescriptions. These results will improve the information available to patients and aid in their CL choices by providing them with a realistic attitude. It will also help eye care practitioners in their clinical activities by providing evidence-based information.

  4. Survey of Non-Rigid Registration Tools in Medicine. (United States)

    Keszei, András P; Berkels, Benjamin; Deserno, Thomas M


    We catalogue available software solutions for non-rigid image registration to support scientists in selecting suitable tools for specific medical registration purposes. Registration tools were identified using non-systematic search in Pubmed, Web of Science, IEEE Xplore® Digital Library, Google Scholar, and through references in identified sources (n = 22). Exclusions are due to unavailability or inappropriateness. The remaining (n = 18) tools were classified by (i) access and technology, (ii) interfaces and application, (iii) living community, (iv) supported file formats, and (v) types of registration methodologies emphasizing the similarity measures implemented. Out of the 18 tools, (i) 12 are open source, 8 are released under a permissive free license, which imposes the least restrictions on the use and further development of the tool, 8 provide graphical processing unit (GPU) support; (ii) 7 are built on software platforms, 5 were developed for brain image registration; (iii) 6 are under active development but only 3 have had their last update in 2015 or 2016; (iv) 16 support the Analyze format, while 7 file formats can be read with only one of the tools; and (v) 6 provide multiple registration methods and 6 provide landmark-based registration methods. Based on open source, licensing, GPU support, active community, several file formats, algorithms, and similarity measures, the tools Elastics and Plastimatch are chosen for the platform ITK and without platform requirements, respectively. Researchers in medical image analysis already have a large choice of registration tools freely available. However, the most recently published algorithms may not be included in the tools, yet.

  5. Single homopolypeptide chains collapse into mechanically rigid conformations (United States)

    Dougan, Lorna; Li, Jingyuan; Badilla, Carmen L.; Berne, B. J.; Fernandez, Julio M.


    Huntington's disease is linked to the insertion of glutamine (Q) in the protein huntingtin, resulting in polyglutamine (polyQ) expansions that self-associate to form aggregates. While polyQ aggregation has been the subject of intense study, a correspondingly thorough understanding of individual polyQ chains is lacking. Here we demonstrate a single molecule force-clamp technique that directly probes the mechanical properties of single polyQ chains. We have made polyQ constructs of varying lengths that span the length range of normal and diseased polyQ expansions. Each polyQ construct is flanked by the I27 titin module, providing a clear mechanical fingerprint of the molecule being pulled. Remarkably, under the application of force, no extension is observed for any of the polyQ constructs. This is in direct contrast with the random coil protein PEVK of titin, which readily extends under force. Our measurements suggest that polyQ chains form mechanically stable collapsed structures. We test this hypothesis by disrupting polyQ chains with insertions of proline residues and find that their mechanical extensibility is sensitive to the position of the proline interruption. These experiments demonstrate that polyQ chains collapse to form a heterogeneous ensemble of conformations that are mechanically resilient. We further use a heat-annealing molecular dynamics protocol to extensively search the conformation space and find that polyQ can exist in highly mechanically stable compact globular conformations. The mechanical rigidity of these collapsed structures may exceed the functional ability of eukaryotic proteasomes, resulting in the accumulation of undigested polyQ sequences in vivo. PMID:19549822

  6. Rigid Polyurethane Foam Thermal Insulation Protected with Mineral Intumescent Mat

    Directory of Open Access Journals (Sweden)

    Kirpluks Mikelis


    Full Text Available One of the biggest disadvantages of rigid polyurethane (PU foams is its low thermal resistance, high flammability and high smoke production. Greatest advantage of this thermal insulation material is its low thermal conductivity (λ, which at 18-28 mW/(m•K is superior to other materials. To lower the flammability of PU foams, different flame retardants (FR are used. Usually, industrially viable are halogenated liquid FRs but recent trends in EU regulations show that they are not desirable any more. Main concern is toxicity of smoke and health hazard form volatiles in PU foam materials. Development of intumescent passive fire protection for foam materials would answer problems with flammability without using halogenated FRs. It is possible to add expandable graphite (EG into PU foam structure but this increases the thermal conductivity greatly. Thus, the main advantage of PU foam is lost. To decrease the flammability of PU foams, three different contents 3%; 9% and 15% of EG were added to PU foam formulation. Sample with 15% of EG increased λ of PU foam from 24.0 to 30.0 mW/(m•K. This paper describes the study where PU foam developed from renewable resources is protected with thermally expandable intumescent mat from Technical Fibre Products Ltd. (TFP as an alternative to EG added into PU material. TFP produces range of mineral fibre mats with EG that produce passive fire barrier. Two type mats were used to develop sandwich-type PU foams. Also, synergy effect of non-halogenated FR, dimethyl propyl phosphate and EG was studied. Flammability of developed materials was assessed using Cone Calorimeter equipment. Density, thermal conductivity, compression strength and modulus of elasticity were tested for developed PU foams. PU foam morphology was assessed from scanning electron microscopy images.

  7. Patient preferences and comparative ocular responses to rigid and soft contact lenses. (United States)

    Fonn, D; Gauthier, C A; Pritchard, N


    Patient preferences and ocular responses were compared between rigid and soft contact lenses by randomly fitting 32 neophyte subjects with a rigid lens in 1 eye and a soft lens in the contralateral eye. Twenty-seven of 32 subjects completed the 3-month study and 16 subjects were willing to continue for an additional 3-month extension. Subjects preferred the comfort and handling of the soft lens but preferred the vision provided by the rigid lens and initially its ease of maintenance. There was also a marked preference for the soft lens when all aspects of lens wear were compared. Objectively, the rigid lenses were responsible for more ocular changes than the soft lenses. Palpebral aperture sizes of the rigid gas permeable (RGP) wearing eyes decreased significantly (0.5 mm; p lens wearing eyes. The incidence of corneal staining was significantly greater in the rigid lens wearing eye (50% RGP vs. 22% soft) but limbal injection was greater in the soft lens wearing eye (18% soft vs. 6% RGP). Refractive sphere, cylinder, and corneal astigmatism decreased in the rigid lens wearing eye after 3 months. This daily wear clinical trial has shown a marked subjective preference for wearing soft lenses with fewer short-term ocular effects.

  8. Polyoxometalates: Toward new materials

    Indian Academy of Sciences (India)

    As8V14} cluster containing compound ... tungstovanadate–heteropolyanion clusters get linked via capped V = O groups into one-dimensional chains. All these systems have ..... components in water were taken in two branches to mix slowly and ...

  9. NoRMCorre: An online algorithm for piecewise rigid motion correction of calcium imaging data. (United States)

    Pnevmatikakis, Eftychios A; Giovannucci, Andrea


    Motion correction is a challenging pre-processing problem that arises early in the analysis pipeline of calcium imaging data sequences. The motion artifacts in two-photon microscopy recordings can be non-rigid, arising from the finite time of raster scanning and non-uniform deformations of the brain medium. We introduce an algorithm for fast Non-Rigid Motion Correction (NoRMCorre) based on template matching. NoRMCorre operates by splitting the field of view (FOV) into overlapping spatial patches along all directions. The patches are registered at a sub-pixel resolution for rigid translation against a regularly updated template. The estimated alignments are subsequently up-sampled to create a smooth motion field for each frame that can efficiently approximate non-rigid artifacts in a piecewise-rigid manner. Existing approaches either do not scale well in terms of computational performance or are targeted to non-rigid artifacts arising just from the finite speed of raster scanning, and thus cannot correct for non-rigid motion observable in datasets from a large FOV. NoRMCorre can be run in an online mode resulting in comparable to or even faster than real time motion registration of streaming data. We evaluate its performance with simple yet intuitive metrics and compare against other non-rigid registration methods on simulated data and in vivo two-photon calcium imaging datasets. Open source Matlab and Python code is also made available. The proposed method and accompanying code can be useful for solving large scale image registration problems in calcium imaging, especially in the presence of non-rigid deformations. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

  10. Comparison of elastic versus rigid suture material for peripheral sutures in tendon repair. (United States)

    Nozaki, Kenji; Mori, Ryuji; Ryoke, Koji; Uchio, Yuji


    For secure tendon repair, while core suture materials have been previously investigated, the optimum material for peripheral sutures remains unclear. Transected bovine gastrocnemius tendons were repaired by 2-strand side-locking loop technique using no.2 braided polyblend polyethylene thread for the core suture. Then, 8-strand peripheral cross-stitches were added using either 2-0 rigid sutures (braided polyblend polyethylene) or USP 2-0-sized elastic sutures (nylon). The holding area of each peripheral suture was set at either 3 × 1 mm (shallow holding) or 6 × 2 mm (deep holding). Therefore, 4 groups were compared (the shallow-rigid, deep-rigid, shallow-elastic, and deep-elastic groups). The gap formation, ultimate tensile strength, and suture migration state were measured after 500 cyclic loadings (from 10 to 200 N). The shallow-rigid group had inferior outcomes compared to the other groups. Although the deep-rigid group had the smallest gap and highest ultimate strength, all peripheral sutures had failure prior to core suture rupture. The two elastic groups showed no significant differences, irrespective of the size of the holding area. Suture migration did not occur in the two elastic groups until the ultimate strength was reached and the core suture ruptured. Depending on the suturing method, rigid suture material may not be appropriate for peripheral sutures, when accompanying rigid core suture material. If peripheral sutures can be made with accurate deep holding, rigid suture material will provide favorable outcome. However, in other cases, elastic suture material is considered best for supporting a rigid core suture, as elasticity is another important factor for peripheral sutures. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. RPTPalpha is required for rigidity-dependent inhibition of extension and differentiation of hippocampal neurons

    DEFF Research Database (Denmark)

    Kostic, Ana; Sap, Jan; Sheetz, Michael P


    Receptor-like protein tyrosine phosphatase alpha (RPTPalpha)-knockout mice have severe hippocampal abnormalities similar to knockouts of the Src family kinase Fyn. These enzymes are linked to the matrix-rigidity response in fibroblasts, but their function in neurons is unknown. The matrix...... response in hippocampal neuron growth cones, like in fibroblasts. In control neurons, rigid FN surfaces inhibit neurite extension and neuron differentiation relative to soft surfaces. In RPTPalpha(-/-) neurons, no inhibition of extension and differentiation is found on both rigid and soft surfaces...

  12. Multivalent, high-relaxivity MRI contrast agents using rigid cysteine-reactive gadolinium complexes. (United States)

    Garimella, Praveena D; Datta, Ankona; Romanini, Dante W; Raymond, Kenneth N; Francis, Matthew B


    MRI contrast agents providing very high relaxivity values can be obtained through the attachment of multiple gadolinium(III) complexes to the interior surfaces of genome-free viral capsids. In previous studies, the contrast enhancement was predicted to depend on the rigidity of the linker attaching the MRI agents to the protein surface. To test this hypothesis, a new set of Gd-hydroxypyridonate based MRI agents was prepared and attached to genetically introduced cysteine residues through flexible and rigid linkers. Greater contrast enhancements were seen for MRI agents that were attached via rigid linkers, validating the design concept and outlining a path for future improvements of nanoscale MRI contrast agents.

  13. Comparative clinical performance of rigid versus soft hyper Dk contact lenses used for continuous wear. (United States)

    Maldonado-Codina, Carole; Morgan, Philip B; Efron, Nathan; Efron, Suzanne


    The purpose of this study is to investigate the comparative clinical performance of two hyper Dk contact lenses: a silicone hydrogel lens (Focus Night & Day, Ciba Vision) and a rigid lens (Z-alpha, Menicon Co. Ltd.) when worn for up to 30 days of continuous wear (CW). The rigid lens was worn on an unplanned replacement basis, whereas the soft lens was replaced monthly. One hundred subjects were recruited. Fifty neophyte subjects were randomly assigned into one of the lens types (25 subjects per lens type). Twenty-five existing daily wear (DW) rigid lens users wore the rigid study lens and 25 existing DW soft lens users wore the soft study lens. Visual acuity, lens fit, keratometry, refraction, lens surface assessment, physiological response, and subjective response were investigated at baseline and after 1 week of DW and 24 hours, 1 week, and 1, 3, 6, 9, and 12 months of CW. Analysis compared lens type (rigid vs. soft) and subject group (experienced vs. neophyte). Sixty-eight subjects completed the study. Visual acuity was similar for the two lens types and subject groups. Lens fit was judged to be adequate in all subjects. Corneal curvature of subjects in the rigid groups became flatter by 0.13 mm compared with 0.04 mm for subjects in the soft lens groups (F = 14.7, p = 0.0003); the refractive findings mirrored these corneal changes. The increasing rate of deposition on rigid lenses was consistent with the fact that these lenses were not replaced during the study. Conjunctival hyperemia and staining were similar for the two lens types but greater among experienced wearers at baseline (F = 13.8, p = 0.0005; F = 5.3, p = 0.02, respectively). Corneal staining was higher for the rigid lens wearers (F = 5.6, p = 0.02) but this was mainly the result of the initial higher scores in the rigid lens experienced group. The change in papillary conjunctivitis was greater for subjects in the soft lens groups than rigid lens groups (F = 4.6, p = 0.04). Comfort was initially

  14. Free surface flow of a suspension of rigid particles in a non-Newtonian fluid

    DEFF Research Database (Denmark)

    Svec, Oldrich; Skocek, Jan; Stang, Henrik


    A numerical framework capable of predicting the free surface flow of a suspension of rigid particles in a non-Newtonian fluid is described. The framework is a combination of the lattice Boltzmann method for fluid flow, the mass tracking algorithm for free surface representation, the immersed...... boundary method for two-way coupled interactions between fluid and rigid particles and an algorithm for the dynamics and mutual interactions of rigid particles. The framework is able to simulate the flow of suspensions at the level of the largest suspended particles and, at the same time, the model is very...

  15. A sequence-dependent rigid-base model of DNA. (United States)

    Gonzalez, O; Petkevičiūtė, D; Maddocks, J H


    A novel hierarchy of coarse-grain, sequence-dependent, rigid-base models of B-form DNA in solution is introduced. The hierarchy depends on both the assumed range of energetic couplings, and the extent of sequence dependence of the model parameters. A significant feature of the models is that they exhibit the phenomenon of frustration: each base cannot simultaneously minimize the energy of all of its interactions. As a consequence, an arbitrary DNA oligomer has an intrinsic or pre-existing stress, with the level of this frustration dependent on the particular sequence of the oligomer. Attention is focussed on the particular model in the hierarchy that has nearest-neighbor interactions and dimer sequence dependence of the model parameters. For a Gaussian version of this model, a complete coarse-grain parameter set is estimated. The parameterized model allows, for an oligomer of arbitrary length and sequence, a simple and explicit construction of an approximation to the configuration-space equilibrium probability density function for the oligomer in solution. The training set leading to the coarse-grain parameter set is itself extracted from a recent and extensive database of a large number of independent, atomic-resolution molecular dynamics (MD) simulations of short DNA oligomers immersed in explicit solvent. The Kullback-Leibler divergence between probability density functions is used to make several quantitative assessments of our nearest-neighbor, dimer-dependent model, which is compared against others in the hierarchy to assess various assumptions pertaining both to the locality of the energetic couplings and to the level of sequence dependence of its parameters. It is also compared directly against all-atom MD simulation to assess its predictive capabilities. The results show that the nearest-neighbor, dimer-dependent model can successfully resolve sequence effects both within and between oligomers. For example, due to the presence of frustration, the model can

  16. Predictors of Difficult Intubation with the Bonfils Rigid Fiberscope. (United States)

    Nowakowski, Michal; Williams, Stephan; Gallant, Jason; Ruel, Monique; Robitaille, Arnaud


    Endotracheal intubation is commonly performed via direct laryngoscopy (DL). However, in certain patients, DL may be difficult or impossible. The Bonfils Rigid Fiberscope® (BRF) is an alternative intubation device, the design of which raises the question of whether factors that predict difficult DL also predict difficult BRF. We undertook this study to determine which demographic, morphologic, and morphometric factors predict difficult intubation with the BRF. Four hundred adult patients scheduled for elective surgery were recruited. Patients were excluded if awake intubation, rapid sequence induction, or induction without neuromuscular blocking agents was planned. Data were recorded, including age, sex, weight, height, American Society of Anesthesiologist classification, history of snoring and sleep apnea, Mallampati class, upper lip bite test score, interincisor, thyromental and sternothyroid distances, manubriomental distances in flexion and extension, neck circumference, maximal neck flexion and extension, neck skinfold thickness at the cricoid cartilage, and Cormack and Lehane grade obtained via DL after paralysis was confirmed. Quality of glottic visualization (good or poor), as well as the number of intubation attempts and time to successful intubation with the BRF, was noted. Univariate analyses were performed to evaluate the association between patient characteristics and time required for intubation. Variables that exhibited a significant correlation were included in a multivariate analysis using a standard least squares model. A P 1 attempt; 4 patients could not be intubated by using the BRF alone. These 4 patients were intubated by using a combination of DL and BRF (2 patients), DL and a Frova bougie (1 patient), and DL and an endotracheal tube shaped with a semirigid stylet (1 patient). Mean time for successful intubation was 26 ± 13 seconds. Multivariate analysis showed that decreased mouth opening (P = 0.008), increased body mass index (P = 0

  17. PiSQRD: a web server for decomposing proteins into quasi-rigid dynamical domains. (United States)

    Aleksiev, T; Potestio, R; Pontiggia, F; Cozzini, S; Micheletti, C


    The PiSQRD web resource can be used to subdivide protein structures in quasi-rigid dynamical domains. The latter are groups of amino acids behaving as approximately rigid units in the course of protein equilibrium fluctuations. The PiSQRD server takes as input a biomolecular structure and the desired fraction of protein internal fluctuations that must be accounted for by the relative rigid-body motion of the dynamical domains. Next, the lowest energy modes of fluctuation of the protein (optionally provided by the user) are calculated and used to identify the rigid subunits. The resulting optimal subdivision is returned through a web page containing both interactive graphics and detailed data output. The PiSQRD web server, which requires Java, is available free of charge for academic users at

  18. Fiber Optic Systems for Light Curing Rigidization of Inflatable Structures Project (United States)

    National Aeronautics and Space Administration — Light (UV and visible) curing composite matrix resins are being explored as an attractive means for rigidizing inflatable spacecraft for large space-deployed...

  19. Water retention of rigid soils from a two-factor model for clay

    CERN Document Server

    Chertkov, V Y


    Water retention is one of the key soil characteristics. Available models of soil water retention relate to the curve-fitting type. The objective of this work is to suggest a physical model of water retention (drying branch) for soils with a rigid matrix. "Physical" means the prediction based on the a priori measured or estimated soil parameters with a clear physical meaning. We rely on the two-factor model of clay that takes into account the factors of capillarity and shrinkage. The key points of the model to be proposed are some weak pseudo shrinkage that the rigid soils demonstrate according to their experimental water retention curves, and some specific properties of the rigid grain matrix. The three input parameters for prediction of soil water retention with the rigid grain matrix include inter-grain porosity, as well as maximum and minimum grain sizes. The comparison between measured and predicted sand water retention curves for four different sands is promising.

  20. A Sensitivity Analysis of the Rigid Pavement Life-Cycle Cost Analysis Program (United States)


    Original Report Date: September 1999. This report describes the sensitivity analysis performed on the Rigid Pavement Life-Cycle Cost Analysis program, a computer program developed by the Center for Transportation Research for the Texas Department of ...


    Directory of Open Access Journals (Sweden)

    Jan-Cristian GRIGORE


    Full Text Available In this paper an algorithm based on [1] [2] are numerical simulations, achieving generalized coordinates of motion, positions, speeds of a rigid rotating kinematic coupling with big clearance in joint, case without friction

  2. An Algorithmic Approach to Wireless Sensor Networks Localization Using Rigid Graphs

    Directory of Open Access Journals (Sweden)

    Shamantha Rai B


    Full Text Available In this work estimating the position coordinates of Wireless Sensor Network nodes using the concept of rigid graphs is carried out in detail. The range based localization approaches use the distance information measured by the RSSI, which is prone to noise, due to effects of path loss, shadowing, and so forth. In this work, both the distance and the bearing information are used for localization using the trilateration technique. Rigid graph theory is employed to analyze the localizability, that is, whether the nodes of the WSN are uniquely localized. The WSN graph is divided into rigid patches by varying appropriately the communication power range of the WSN nodes and then localizing the patches by trilateration. The main advantage of localizing the network using rigid graph approach is that it overcomes the effect of noisy perturbed distance. Our approach gives a better performance compared to robust quads in terms of percentage of localizable nodes and computational complexity.

  3. A filmed hanging without decerebrate and decorticate rigidity: a case report and pathophysiological considerations. (United States)

    Sauvageau, Anny; Kelly, Sean; Ambrosi, Corinne


    The study of filmed hangings in the recent has reveal a striking similarity in the agonal sequences, with a sequence of rapid loss of consciousness, convulsions, and then a complex pattern of decerebrate rigidity and decorticate rigidity. We report a case of filmed hanging not presenting with decerebrate and decorticate rigidity. A 52-year-old man stepped off a stool, hanging himself in a complete suspension in an upright position. The movement of the body stepping off the stool created a rotary movement around the ceiling's ring and the body of the hanging man immediately started to revolve around the ring. Apart for the rolling around the ceiling's ring, the body stayed motionless for the duration of the movie, without any evidence of decerebrate or decorticate rigidity. A review of the pathophysiology of these reflex posturing gives some insight as to the possible elucidation for their absence in this specific case.

  4. Comparison of the effect of semi-rigid ankle bracing on performance ...

    African Journals Online (AJOL)

    Comparison of the effect of semi-rigid ankle bracing on performance among injured v. non-injured adolescent female hockey players. TJ Ellapen, N Acampora, S Dawson, J Arling, C van Niekerk, HJ van Heerden ...

  5. Level set motion assisted non-rigid 3D image registration (United States)

    Yang, Deshan; Deasy, Joseph O.; Low, Daniel A.; El Naqa, Issam


    Medical imaging applications of rigid and non-rigid elastic deformable image registration are undergoing wide scale development. Our approach determines image deformation maps through a hierarchical process, from global to local scales. Vemuri (2000) reported a registration method, based on levelset evolution theory, to morph an image along the motion gradient until it deforms to the reference image. We have applied this level set motion method as basis to iteratively compute the incremental motion fields and then we approximated the field using a higher-level affine and non-rigid motion model. In such a way, we combine sequentially the global affine motion, local affine motion and local non-rigid motion. Our method is fully automated, computationally efficient, and is able to detect large deformations if used together with multi-grid approaches, potentially yielding greater registration accuracy.

  6. Anaesthesia and peri-interventional morbidity of rigid bronchoscopy: A retrospective analysis

    Directory of Open Access Journals (Sweden)

    Jerry Tan


    Conclusion: The choice of anaesthetic technique possibly affects the complication of patients undergoing rigid bronchoscopy. Volatile anaesthetics appeared to be driven by presumably shorter procedure, but was associated with higher systemic complication.

  7. Building America Top Innovations 2013 Profile – Exterior Rigid Insulation Best Practices

    Energy Technology Data Exchange (ETDEWEB)



    In this Top Innovation profile, field and lab studies by BSC, PHI, and NorthernSTAR characterize the thermal, air, and vapor resistance properties of rigid foam insulation and describe best practices for their use on walls, roofs, and foundations.

  8. Semi-rigid brace and taping decrease variability of the ankle joint position sense

    Directory of Open Access Journals (Sweden)

    Márcia Barbanera


    Full Text Available The present study investigated the effect of taping and the semi-rigid ankle brace on ankle joint position sense. Sixteen healthy women (20.8 ± 2.3 years old actively placed the ankle in a target position. The experimental conditions were: 1 wearing no orthosis device, 2 using semi-rigid brace, and 3 wearing ankle taping. Absolute error (AE and variable error (VE were calculated to obtain the joint position sense. We found an interaction effect between condition and target angle at 15o of plantar flexion for the variable VE, which showed smaller errors during the use of taping and semi-rigid brace. In conclusion, the use of ankle joint orthoses, whether taping or semi-rigid brace, decrease the variability of the position sense at 15o of plantar flexion, potentially decreasing ankle sprains occurrence.

  9. Heat Transfer Measurement and Modeling in Rigid High-Temperature Reusable Surface Insulation Tiles (United States)

    Daryabeigi, Kamran; Knutson, Jeffrey R.; Cunnington, George R.


    Heat transfer in rigid reusable surface insulations was investigated. Steady-state thermal conductivity measurements in a vacuum were used to determine the combined contribution of radiation and solid conduction components of heat transfer. Thermal conductivity measurements at higher pressures were then used to estimate the effective insulation characteristic length for gas conduction modeling. The thermal conductivity of the insulation can then be estimated at any temperature and pressure in any gaseous media. The methodology was validated by comparing estimated thermal conductivities with published data on a rigid high-temperature silica reusable surface insulation tile. The methodology was also applied to the alumina enhanced thermal barrier tiles. Thermal contact resistance for thermal conductivity measurements on rigid tiles was also investigated. A technique was developed to effectively eliminate thermal contact resistance on the rigid tile s cold-side surface for the thermal conductivity measurements.

  10. Convergent Synthesis of Rigid Macrocycles Containing One and Two Tetrathiafulvalene Units

    DEFF Research Database (Denmark)

    Simonsen, Klaus B.; Thorup, Niels; Becher, Jan


    The synthesis of rigid tetrathiafulvalenophanes containing one or two tetrathiafulvalene units is presented, together with a stepwise convergent synthesis of macrocyclic bis-tetrathiafulvalenes via several open dimeric tetrathiafulvalenes. These systems were investigated by cyclic voltammetry...

  11. Positive semidefinite matrix completion, universal rigidity and the Strong Arnold Property

    NARCIS (Netherlands)

    M. Laurent (Monique); A. Varvitsiotis (Antonios)


    htmlabstractThis paper addresses the following three topics: positive semidefinite (psd) matrix completions, universal rigidity of frameworks, and the Strong Arnold Property (SAP). We show some strong connections among these topics, using semidefinite programming as unifying theme. Our main

  12. Positive semidefinite matrix completion, universal rigidity and the Strong Arnold Property

    NARCIS (Netherlands)

    M. Laurent (Monique); A. Varvitsiotis (Antonios)


    htmlabstractThis paper addresses the following three topics: positive semidefinite (psd) matrix completions, universal rigidity of frameworks, and the Strong Arnold Property (SAP). We show some strong connections among these topics, using semidefinite programming as unifying theme. Our main

  13. Market structure, price rigidity, and performance in the Indonesian food and beverages industry

    NARCIS (Netherlands)

    Setiawan, M.


    Keywords: industrial concentration, price rigidity, technical efficiency, price-cost margin, Structure-Conduct-Performance (SCP), new empirical industrial organization (NEIO), Indonesian food and beverages industry, Data Envelopment Analysis (DEA), system of equations The

  14. Molecularly Rigid Microporous Polyamine Captures and Stabilizes Conducting Platinum Nanoparticle Networks. (United States)

    He, Daping; He, Dong Sheng; Yang, Jinlong; Low, Ze-Xian; Malpass-Evans, Richard; Carta, Mariolino; McKeown, Neil B; Marken, Frank


    A molecularly rigid polyamine based on a polymer of intrinsic microporosity (PIM-EA-TB) is shown to capture and stabilize platinum nanoparticles during colloid synthesis in the rigid framework. Stabilization here refers to avoiding aggregation without loss of surface reactivity. In the resulting rigid framework with embedded platinum nanoparticles, the volume ratio of platinum to PIM-EA-TB in starting materials is varied systematically from approximately 1.0 to 0.1 with the resulting platinum nanoparticle diameter varying from approximately 4.2 to 3.1 nm, respectively. Elemental analysis suggests that only a fraction of the polymer is "captured" to give nanocomposites rich in platinum. A transition occurs from electrically conducting and electrochemically active (with shorter average interparticle distance) to nonconducting and only partially electrochemically active (with longer average interparticle distance) polymer-platinum composites. The conducting nanoparticle network in the porous rigid macromolecular framework could be beneficial in electrocatalysis and in sensing applications.

  15. Old metal oxide clusters in new applications: spontaneous reduction of Keggin and Dawson polyoxometalate layers by a metallic electrode for improving efficiency in organic optoelectronics. (United States)

    Vasilopoulou, Maria; Douvas, Antonios M; Palilis, Leonidas C; Kennou, Stella; Argitis, Panagiotis


    The present study is aimed at investigating the solid state reduction of a representative series of Keggin and Dawson polyoxometalate (POM) films in contact with a metallic (aluminum) electrode and at introducing them as highly efficient cathode interlayers in organic optoelectronics. We show that, upon reduction, up to four electrons are transferred from the metallic electrode to the POM clusters of the Keggin series dependent on addenda substitution, whereas a six electron reduction was observed in the case of the Dawson type clusters. The high degree of their reduction by Al was found to be of vital importance in obtaining effective electron transport through the cathode interface. A large improvement in the operational characteristics of organic light emitting devices and organic photovoltaics based on a wide range of different organic semiconducting materials and incorporating reduced POM/Al cathode interfaces was achieved as a result of the large decrease of the electron injection/extraction barrier, the enhanced electron transport and the reduced recombination losses in our reduced POM modified devices.

  16. In situ growth of gold nanoparticles on SiO{sub 2}/lanthanide–polyoxometalates composite spheres: An efficient catalytic and luminescent system

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail:; Lu, Xuelian; Fan, Shaohua; Zhao, Weiqian; Li, Wuke


    Graphical abstract: TEM picture of SiO{sub 2−a}/EuW{sub 10}/Au. - Highlights: • A method for in situ Au nanoparticles growth on luminescent spheres was developed. • The bifunctional composites show high catalytic activity and good luminescence. • HAuCl{sub 4} solution could be reduced by luminescent composites. • The sizes of Au particles on spheres could be tuned by using different SiO{sub 2}. - Abstract: In this paper, bifunctional composite particles were synthesized by in situ grafting Au nanoparticles on the surface of SiO{sub 2}/polyethyleneimine/Eu-polyoxometalates (SiO{sub 2}/PEI/Eu-POM) spheres. It was found that the PEI layer on SiO{sub 2}/PEI/Eu-POM spheres could act as a reductant for in situ reduction of metal ions to Au nanoparticles. The sizes of Au particles grafted on spheres could be tuned by adjusting the sizes of SiO{sub 2} spheres. The composite particles showed excellent red luminescence under UV light, which could be observed by naked eyes. In addition, they exhibited good catalytic activity in the oxidation of styrene and reduction of 4-nitrophenol. The smaller composite particles show the better overall performance in the catalytic reaction because of their lager active surface. The present strategy gives a promising way to prepare bifunctional composites for broad applications in catalysis and labeling.

  17. Various Oxygen-Centered Phosphanegold(I Cluster Cations Formed by Polyoxometalate (POM-Mediated Clusterization: Effects of POMs and Phosphanes

    Directory of Open Access Journals (Sweden)

    Takuya Yoshida


    Full Text Available Novel phosphanegold(I cluster cations combined with polyoxometalate (POM anions, i.e., intercluster compounds, [(Au{P(m-FPh3}4(μ4-O]2[{(Au{P(m-FPh3}2 (μ-OH}2][α-PMo12O40]2·EtOH (1, [(Au{P(m-FPh3}4(μ4-O]2[α-SiMo12O40]·4H2O (2, [(Au{P(m-MePh3}4(μ4-O]2[α-SiM12O40] (M = W (3, Mo (4 and [{(Au {P(p-MePh3}4(μ4-O}{(Au{P(p-MePh3}3(μ3-O}][α-PW12O40] (5 were synthesized by POM-mediated clusterization, and unequivocally characterized by elemental analysis, TG/DTA, FT-IR, X-ray crystallography, solid-state CPMAS 31P NMR and solution (1H, 31P{1H} NMR. Formation of the these gold(I cluster cations was strongly dependent upon the charge density and acidity of the POMs, and the substituents and substituted positions on the aryl group of triarylphosphane ligands. These gold(I cluster cations contained various bridged-oxygen atoms such as μ4-O, μ3-O and μ-OH groups.

  18. Surface immobilization of a tetra-ruthenium substituted polyoxometalate water oxidation catalyst through the employment of conducting polypyrrole and the layer-by-layer (LBL) technique. (United States)

    Anwar, Nargis; Sartorel, Andrea; Yaqub, Mustansara; Wearen, Kevin; Laffir, Fathima; Armstrong, Gordon; Dickinson, Calum; Bonchio, Marcella; McCormac, Timothy


    A tetra Ru-substituted polyoxometalate Na10[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2] (Ru4POM) has been successfully immobilised onto glassy carbon electrodes and indium tin oxide (ITO) coated glass slides through the employment of a conducting polypyrrole matrix and the layer-by-layer (LBL) technique. The resulting Ru4POM doped polypyrrole films showed stable redox behavior associated with the Ru centres within the Ru4POM, whereas, the POM's tungsten-oxo redox centres were not accessible. The films showed pH dependent redox behavior within the pH range 2-5 whilst exhibiting excellent stability towards redox cycling. The layer-by-layer assembly was constructed onto poly(diallyldimethylammonium chloride) (PDDA) modified carbon electrodes by alternate depositions of Ru4POM and a Ru(II) metallodendrimer. The resulting Ru4POM assemblies showed stable redox behavior for the redox processes associated with Ru4POM in the pH range 2-5. The charge transfer resistance of the LBL films was calculated through AC-Impedance. Surface characterization of both the polymer and LBL Ru4POM films was carried out using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Initial investigations into the ability of the Ru4POM LBL films to electrocatalytically oxidise water at pH 7 have also been conducted.

  19. Photoluminescent Honeycomb Structures from Polyoxometalates and an Imidazolium-Based Ionic Liquid Bearing a π-Conjugated Moiety and a Branched Aliphatic Chain. (United States)

    Zhang, Geping; Zhu, Hongxia; Chen, Mengjun; Li, Hongguang; Yuan, Ye; Ma, Tiantai; Hao, Jingcheng


    Honeycomb-structured films represent an intriguing class of two-dimensional porous materials. Specifically, polyoxometalate (POM) macroanions can be introduced into these films by complexing with oppositely charged, double-tailed surfactants. Here highly-ordered honeycomb structures are reported that can be constructed by the complexes between POMs and a room temperature ionic liquid (IL1) having an imidazolium moiety in the middle and a naphthyl unit and a branched aliphatic chain at the ends. The complexes can be produced through phase transfer between an aqueous solution of POMs (typically {Mo72 Fe30 }) and a CS2 (or chloroform) solution of IL1. Based on the intrinsic properties of {Mo72 Fe30 } and the functional groups of the IL1, the honeycomb structures show multiple functions with bright photoluminescence and rich electrochemical properties. This work shows that by simply engineering the organic ligands involved in the POM-based inorganic-organic complexes, supramolecular structures with improved properties and wide applications can be obtained. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Four-shell polyoxometalates featuring high-nuclearity Ln{sub 26} clusters. Structural transformations of nanoclusters into frameworks triggered by transition-metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhong; Li, Xin-Xiong; Yang, Tao; Cai, Zhen-Wen; Zheng, Shou-Tian [State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fujian (China)


    A series of polyoxometalates (POMs) that incorporate the highest-nuclearity Ln clusters that have been observed in such structures to date (Ln{sub 26}, Ln=La and Ce) are described, which exhibit giant multishell configurations (Ln is contained in W{sub 6} is contained in Ln{sub 26} is contained in W{sub 100}). Their structures are remarkably different from known giant POMs that feature multiple Ln ions. In particular, the incorporated Ln-O clusters with a nuclearity of 26 are significantly larger than known high-nuclearity (≤10) Ln-O clusters in POM chemistry. Furthermore, they also contain the largest number of La and Ce centers for any POM reported to date and represent a new kind of rare giant POMs with more than 100 W atoms. Interestingly, the La{sub 26}-containing POM can undergo a single-crystal to single-crystal structural transformation in the presence of various transition-metal ions, such as Cu{sup 2+}, Co{sup 2+}, and Ni{sup 2+}, from an inorganic molecular nanocluster into an inorganic-organic hybrid extended framework that is built from POM building blocks with even higher-nuclearity La{sub 28} clusters bridged by transition-metal complexes. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)