Science.gov

Sample records for polyoxometalate keggin clusters

  1. Two new polyoxometalate-based hybrids consisting of Keggin-type cluster modified by (Ag{sub 4}) group

    SciTech Connect

    Zhao, Xiaofang; Sun, Xiaowei; Han, Zhangang; Zhao, Chuan; Yu, Haitao; Zhai, Xueliang

    2013-11-15

    Two new supramolecular polyoxometalate compounds [Ag{sub 2}(mbpy){sub 3}][Ag(mbpy){sub 2}][PW{sub 12}O{sub 40}] (1) and [Ag{sub 2}(mbpy){sub 3}]{sub 2}[SiW{sub 12}O{sub 40}] (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. The structural feature of 1–2 is in the cationic moiety of a tetra-core (Ag{sub 4}) cluster through weak Ag…Ag interactions. The silver(I) centers show three-, four- and five-coordinated geometries. In 1 the tetrameric silver atoms in ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} covalently bind to [PW{sub 12}O{sub 40}]{sup 3−} anion via Ag3O bonds, while there is only intermolecular hydrogen bonding between ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} and [SiW{sub 12}O{sub 40}]{sup 4−} in 2. The coordination environments of the tetrameric silver cations have a great influence on the structure richness of the Keggin-based hybrids. The fluorescence properties of compounds 1 and 2 also have been discussed. - Graphical abstract: New polyoxometalate-based hybrids consisting of Keggin-type clusters modified by (Ag{sub 4}) groups had been synthesized and characterized, and their photoluminescence properties were also discussed. Display Omitted - Highlights: • Two Keggin-type polyoxometalates consisting of (Ag{sub 4}) clusters through weak Ag…Ag interactions have been synthesized. • There exist face-to-face and dot-to-face π…π interactions in (Ag-ligand){sub 4} fragment. • The fluorescence properties of (Ag{sub 4}) modified POMs are also discussed.

  2. Bi-antimony capped Keggin polyoxometalate modified with Cu-ligand fragment

    SciTech Connect

    Huang, Jiao; Han, Zhangang; Zhang, Heng; Yu, Haitao; Zhai, Xueliang

    2012-10-15

    Three polyoxometalates consisting of bi-antimony capped Keggin-type clusters: [Cu(mbpy){sub 2}]{sub 2}[PMo{sub 12}O{sub 40}Sb{sub 2}]{center_dot}4H{sub 2}O (1), [Cu(mbpy){sub 2}][PMo{sub 12}O{sub 40}Sb{sub 2}] (2) and {l_brace}Cu(mbpy)[Cu(mbpy){sub 2}]{sub 2}{r_brace}[VMo{sub 8}V{sub 4}O{sub 40}Sb{sub 2}]{center_dot}2H{sub 2}O (3) (mbpy=4,4 Prime -dimethyl-2,2 Prime - dipyridyl in 1 and 2; 5,5 Prime -dimethyl-2,2 Prime -dipyridyl in 3) have been synthesized and characterized by IR, X-ray powder diffraction, TG analysis and electrochemical property. Single-crystal analysis revealed that all of three compounds are built upon bi-antimony capped Keggin-type polyoxoanions and Cu-mbpy cations. In 1-3, two Sb{sup III} centers located at the two opposite of anionic surface adopt fundamentally tetragonal pyramidal coordination geometry. Both compounds 1 and 2 consist of P-centered Keggin structure, while compound 3 presents a V-centered Keggin anion. The Keggin-type anions present different structural features: isolated cluster in 1 and Cu-ligand-supported cluster in 2 and 3. - Graphical abstract: Three hybrid compounds consisting of bi-antimony capped Keggin-type clusters modified with Cu-ligand cations have been synthesized and characterized. Highlights: Black-Right-Pointing-Pointer Three hybrid compounds consisting of bi-antimony capped Keggin-type clusters have been synthesized. Black-Right-Pointing-Pointer Two Sb{sup III} centers located at the two opposite of anionic surface adopt tetragonal pyramidal coordination geometry. Black-Right-Pointing-Pointer The anions present different structural features: isolated and Cu-ligand-supported cluster.

  3. Monolacunary Keggin polyoxometalates connected to ten 4d or 4f metal atoms.

    PubMed

    Pang, Haijun; Gómez-García, Carlos J; Peng, Jun; Ma, Huiyuan; Zhang, Chunjing; Wu, Qingyin

    2013-12-21

    The rational self-assembly of mono-lacunary Keggin clusters with 4d and 4f metal salts via a conventional method has yielded two novel polyoxometalate-based 4d-4f heterometallic compounds containing lacunary Keggin anions connected to ten metal atoms: {[Ag{Ag2(H2O)4}{Ln(H2O)6}2H ⊂ {SiW11Ln(H2O)4O39}2]·nH2O (Ln = Ce and n = 7 for 1, Ln = Pr and n = 3 for 2). Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. A structural feature in 1 and 2 is that each [SiW11O39](8-) cluster (SiW11) is connected to ten metals (five Ag(+) and five Ln(3+) cations), representing the highest number of connected metal atoms to any mono-lacunary Keggin anion to date. This large connectivity leads to a structure with a purely inorganic 3D framework with two kinds of channels along the [100] and [010] directions. The magnetic properties of both compounds show the expected magnetic moments (0.8 and 1.6 amu K mol(-1) per Ce(3+) and Pr(3+) ion, respectively) and confirm the presence of isolated Ce(3+) and Pr(3+) ions.

  4. Monolacunary Keggin polyoxometalates connected to ten 4d or 4f metal atoms.

    PubMed

    Pang, Haijun; Gómez-García, Carlos J; Peng, Jun; Ma, Huiyuan; Zhang, Chunjing; Wu, Qingyin

    2013-12-21

    The rational self-assembly of mono-lacunary Keggin clusters with 4d and 4f metal salts via a conventional method has yielded two novel polyoxometalate-based 4d-4f heterometallic compounds containing lacunary Keggin anions connected to ten metal atoms: {[Ag{Ag2(H2O)4}{Ln(H2O)6}2H ⊂ {SiW11Ln(H2O)4O39}2]·nH2O (Ln = Ce and n = 7 for 1, Ln = Pr and n = 3 for 2). Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. A structural feature in 1 and 2 is that each [SiW11O39](8-) cluster (SiW11) is connected to ten metals (five Ag(+) and five Ln(3+) cations), representing the highest number of connected metal atoms to any mono-lacunary Keggin anion to date. This large connectivity leads to a structure with a purely inorganic 3D framework with two kinds of channels along the [100] and [010] directions. The magnetic properties of both compounds show the expected magnetic moments (0.8 and 1.6 amu K mol(-1) per Ce(3+) and Pr(3+) ion, respectively) and confirm the presence of isolated Ce(3+) and Pr(3+) ions. PMID:24067933

  5. A multifunctional lanthanide metal-organic framework supported by Keggin type polyoxometalates.

    PubMed

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

    2016-06-21

    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. PMID:27242190

  6. Novel intercluster compound between a heptakis{triphenylphosphinegold(I)}dioxonium cation and an α-Keggin polyoxometalate anion.

    PubMed

    Yoshida, Takuya; Nomiya, Kenji; Matsunaga, Satoshi

    2012-09-01

    A novel intercluster compound, [{{Au(PPh(3))}(4)(μ(4)-O)}{{Au(PPh(3))}(3)(μ(3)-O)}][α-PW(12)O(40)]·EtOH (1) constructed between a heptakis{triphenylphosphinegold(i)}dioxonium cation and an α-Keggin polyoxometalate (POM) is synthesized and unequivocally characterized by elemental analysis, TG/DTA, FTIR, X-ray crystallography, solid-state CPMAS (31)P NMR and solution ((1)H, (31)P{(1)H}) NMR. The heptagold(i) cluster was formed during the course of carboxylate elimination of a monomeric phosphinegold(i) carboxylate precursor, i.e., [Au((RS)-pyrrld)(PPh(3))] ((RS)-Hpyrrld = (RS)-2-pyrrolidone-5-carboxylic acid), in the presence of the sodium salt of an α-Keggin POM, Na(3)[α-PW(12)O(40)]·9H(2)O. Compound 1 was formed by ionic interaction between the heptagold(i) cluster cation and the α-Keggin POM anion. The heptagold(i) cluster unit was formed by four inter-cationic aurophilic interactions between the tetragold(i) cluster unit and trigold(i) cluster unit. The tetragold(i) cluster unit and trigold(i) cluster unit contained μ(4)-O and μ(3)-O atoms, respectively.

  7. Two new hybrid compounds assembled from Keggin-type polyoxometalates and transition metal coordination complexes

    SciTech Connect

    Wang Yan; Zou, Bo; Xiao Lina; Jin Ning; Peng Yu; Wu Fengqing; Ding Hong; Wang Tiegang; Gao Zhongmin; Zheng Dafang; Cui Xiaobing; Xu Jiqing

    2011-03-15

    Two new hybrid compounds based on Keggin-type polyoxometalates: {l_brace}[PMo{sub 12}O{sub 40}][Ni(Phen){sub 2}(H{sub 2}O)]{sub 2{r_brace}}.K.2OH{sup -} (1) and [Cd{sub 2}(Phen){sub 4}Cl{sub 2}][HPW{sub 12}O{sub 40}].H{sub 2}O (2) (Phen=1,10-phenanthroline), have been prepared and characterized by IR, UV-vis, XPS, XRD and single crystal X-ray diffraction analyses. Compound 1 exhibits a 1-D chain structure constructed from Pseudo-Keggin polyoxometalate bi-supported transition metal coordination complexes linked by K{sup +} ions. Compound 2 contains Pseudo-Keggin polyoxoanions [HPW{sub 12}O{sub 40}]{sup 2-} and novel metal-chloride-ligand coordination complexes [Cd{sub 2}(Phen){sub 4}Cl{sub 2}]{sup 2+}. -- Graphical abstract: Two new hybrid compounds based on different Keggin-type polyoxometalates have been hydrothermally synthesized and characterized by IR, UV-Vis, XPS, XRD, elemental analysis and single crystal X-ray diffraction analysis. Display Omitted Research highlights: {yields} Two hybrids based on Pseudo-Keggin polyanions and metal coordination complexes. {yields} 1-D structure formed by polyanion bisupported metal coordination units linked by K{sup +}. {yields} A metal-chloride-ligand coordination complex [Cd{sub 2}(Phen){sub 4}Cl{sub 2}]{sup 2+}. {yields} A hybrid based on polyanions and metal-chloride-ligand coordination complexes.

  8. A polyoxometalate-based inorganic-organic hybrid polymer constructed from silver-Schiff base building block and Keggin-type cluster: Synthesis, crystal structure and photocatalytic performance for the degradation of rhodamine B.

    PubMed

    Li, Lei; Cheng, Meng; Bai, Yan; An, Bing; Dang, Dongbin

    2015-11-01

    One polyoxometalate-based inorganic-organic hybrid polymer [Ag3L4(PMo12O40)(CH3OH)]·CH3OH (1), where L is N,N'-bis(furan-2-ylmethylene)hydrazine, has been synthesized at room temperature and structurally characterized by infrared spectroscopy, ultraviolet-visible spectroscopy, elemental analysis, X-ray powder diffraction and X-ray single-crystal crystallography. The structure of 1 exhibits a crystalline one-dimensional polymer constructed by the connections of Keggin-type [PMo12O40](3-) anions and [Ag3L4](3+) units, in which each Ag(I) center adopted a distorted square pyramidal environment. The spectroscopic experiments show that polymer 1 not only is potential semiconductor materials but also displays the obvious photocatalytic performance for the degradation of rhodamine B.

  9. Energetics of Al13 Keggin cluster compounds

    PubMed Central

    Armstrong, Christopher R.; Casey, William H.; Navrotsky, Alexandra

    2011-01-01

    The ϵ-Al13 Keggin aluminum hydroxide clusters are essential models in establishing molecular pathways for geochemical reactions. Enthalpies of formation are reported for two salts of aluminum centered ϵ-Keggin clusters, Al13 selenate, (Na(AlO4)Al12(OH)24(SeO4)4•12H2O) and Al13 sulfate, (NaAlO4Al12(OH)24(SO4)4•12H2O). The measured enthalpies of solution, ΔHsol, at 28 °C in 5 N HCl for the ε-Al13 selenate and sulfate are −924.57 (± 3.83) and −944.30 ( ± 5.66) kJ·mol-1, respectively. The enthalpies of formation from the elements, ΔHf,el, for Al13 selenate and sulfate are −19,656.35 ( ± 67.30) kJ·mol-1, and −20,892.39 ( ± 70.01) kJ·mol-1, respectively. In addition, ΔHf,el for sodium selenate decahydrate was calculated using data from high temperature oxide melt solution calorimetry measurements: −4,006.39 ( ± 11.91) kJ·mol-1. The formation of both ε-Al13 Keggin cluster compounds is exothermic from oxide-based components but energetically unfavorable with respect to a gibbsite-based assemblage. To understand the relative affinity of the ϵ-Keggin clusters for selenate and sulfate, the enthalpy associated with two S-Se exchange reactions was calculated. In the solid state, selenium is favored in the Al13 compound relative to the binary chalcogenate, while in 5 N HCl, sulfur is energetically favored in the cluster compound compared to the aqueous solution. This contribution represents the first thermodynamic study of ε-Al13 cluster compounds and establishes a method for other such molecules, including the substituted versions that have been created for kinetic studies. Underscoring the importance of ε-Al13 clusters in natural and anthropogenic systems, these data provide conclusive thermodynamic evidence that the Al13 Keggin cluster is a crucial intermediate species in the formation pathway from aqueous aluminum monomers to aluminum hydroxide precipitates. PMID:21852572

  10. Chiral heteropoly blues and controllable switching of achiral polyoxometalate clusters.

    PubMed

    Wang, Yizhan; Li, Haolong; Wu, Che; Yang, Yang; Shi, Lei; Wu, Lixin

    2013-04-22

    Managing the blues: Chiral heteropoly blues of achiral polyoxometalate clusters were created through an intermolecular interaction with a chiral organic compound. Controllable chiroptical switching of the cluster complexes was possible through reversible photochromism of the polyoxometalates (see picture).

  11. Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties

    SciTech Connect

    Shi Zhenyu; Peng Jun . E-mail: jpeng@nenu.edu.cn; Gomez-Garcia, Carlos J.

    2006-01-15

    Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen){sub 2}]{sub 2}{l_brace}[Cu(phen)]{sub 2} [SiMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace} (1), {l_brace}[Zn(phen){sub 2}]{sub 2}[GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Zn(phen){sub 2}(H{sub 2}O)]{sub 2} [GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.3H{sub 2}O (2) and {l_brace}[Co(phen){sub 2}]{sub 2}[PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Co(phen){sub 2}(OH)]{sub 2} [PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.2.5H{sub 2}O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo{sub 12}O{sub 4}(VO){sub 2}] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo{sub 12}O{sub 4}(VO){sub 2}]{sup 2-} linked to two [Cu(phen)]{sup +} complexes with two [Cu(phen){sub 2}]{sup +} countercations. Compound 2 contains two bicapped Keggin anions [GeMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-}, one linked to two [Zn(phen){sub 2}(H{sub 2}O)]{sup 2+} cations and the other one linked to two [Zn(phen){sub 2}]{sup 2+} cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-} connected by [Co(phen){sub 2}]{sup 2+} cations. Discrete bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}] linked to two [Co(phen){sub 2}(OH)]{sup +} cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions. -- Graphical

  12. Photocatalytic degradation of dye naphthol blue black in the presence of zirconia-supported Ti-substituted Keggin-type polyoxometalates

    SciTech Connect

    Jiang Chunjie; Guo Yihang; Hu Changwen; Wang Chungang; Li Danfeng

    2004-02-02

    Zirconia-supported Ti-substituted Keggin-type polyoxometalates, Li{sub 5}PW{sub 11}TiO{sub 40}/ZrO{sub 2} (PW{sub 11}Ti/ZrO{sub 2}) and K{sub 7}PW{sub 10}Ti{sub 2}O{sub 40}/ZrO{sub 2} (PW{sub 10}Ti{sub 2}/ZrO{sub 2}), were prepared by incorporating PW{sub 11}Ti and PW{sub 10}Ti{sub 2} cluster into a zirconia matrix via a sol-gel technique. These insoluble and readily separable composites were characterized by DR-UV (DR: diffuse reflectance) and FT-IR spectra, {sup 31}P MAS NMR, ICP-AES, and nitrogen adsorption determination, indicating that the clusters were chemically attached to the zirconia supports, and the primary Keggin structure remained intact. The photocatalytic activity of the supported PW{sub 11}Ti and PW{sub 10}Ti{sub 2} was tested via degradation of an aqueous dye naphthol blue black (NBB). It indicated that the dye NBB can be degraded totally and mineralized into the inorganic products such as CO{sub 2}, NH{sub 4}{sup +}, NO{sub 3}{sup -}, and SO{sub 4}{sup 2-} ions by irradiating the composite slurry in the near-UV area. Dropped of PW{sub 11}Ti or PW{sub 10}Ti{sub 2} cluster from the zirconia matrix into the reaction system was hardly observed during the photocatalytic tests, attributed to the strong chemical interactions between the Keggin units and the zirconia support.

  13. Design, synthesis and excellent third-order NLO properties of two new polyoxometalates constructed from Keggin polyanions bonded by a solvent molecule.

    PubMed

    Miao, Hao; Dong, Yayu; Chen, Ziwang; He, Xingxiang; Hu, Gonghao; Xu, Yan

    2016-08-01

    Two new monosubstituted Keggin structural polyoxometalates [H5PMo11O39Zn(C5H5N)]·(C5H5N)5·H2O (1) and [H5PW11O39Co(C5H5N)]·(C5H5N)2·(C6H8N)2·1.5CH3OH (2) have been successfully synthesized under hydrothermal conditions. Structural analysis indicates that the polyoxoanion of compound 1 is a solvent molecule-bonded zinc-monosubstituted Keggin structural cluster, [PMo11O39Zn(C5H5N)](5-), while the polyoxoanion of compound 2 is a cobalt-monosubstituted phosphotungstate polyanion bonded with one pendant pyridine molecule. Both 1 and 2 show 3D supramolecular interpenetrating structures constructed of inorganic polyanion layers and organic layers. Very interestingly, compounds 1 and 2 exhibit excellent third-order NLO properties, and the TPA cross section σ of 1 and 2 is 2571.3 GM and 2876.3 GM, respectively.

  14. Design, synthesis and excellent third-order NLO properties of two new polyoxometalates constructed from Keggin polyanions bonded by a solvent molecule.

    PubMed

    Miao, Hao; Dong, Yayu; Chen, Ziwang; He, Xingxiang; Hu, Gonghao; Xu, Yan

    2016-08-01

    Two new monosubstituted Keggin structural polyoxometalates [H5PMo11O39Zn(C5H5N)]·(C5H5N)5·H2O (1) and [H5PW11O39Co(C5H5N)]·(C5H5N)2·(C6H8N)2·1.5CH3OH (2) have been successfully synthesized under hydrothermal conditions. Structural analysis indicates that the polyoxoanion of compound 1 is a solvent molecule-bonded zinc-monosubstituted Keggin structural cluster, [PMo11O39Zn(C5H5N)](5-), while the polyoxoanion of compound 2 is a cobalt-monosubstituted phosphotungstate polyanion bonded with one pendant pyridine molecule. Both 1 and 2 show 3D supramolecular interpenetrating structures constructed of inorganic polyanion layers and organic layers. Very interestingly, compounds 1 and 2 exhibit excellent third-order NLO properties, and the TPA cross section σ of 1 and 2 is 2571.3 GM and 2876.3 GM, respectively. PMID:27453327

  15. Ferrihydrite Formation: The Role of Fe13 Keggin Clusters.

    PubMed

    Weatherill, Joshua S; Morris, Katherine; Bots, Pieter; Stawski, Tomasz M; Janssen, Arne; Abrahamsen, Liam; Blackham, Richard; Shaw, Samuel

    2016-09-01

    Ferrihydrite is the most common iron oxyhydroxide found in soil and is a key sequester of contaminants in the environment. Ferrihydrite formation is also a common component of many treatment processes for cleanup of industrial effluents. Here we characterize ferrihydrite formation during the titration of an acidic ferric nitrate solution with NaOH. In situ SAXS measurements supported by ex situ TEM indicate that initially Fe13 Keggin clusters (radius ∼ 0.45 nm) form in solution at pH 0.12-1.5 and are persistent for at least 18 days. The Fe13 clusters begin to aggregate above ∼ pH 1, initially forming highly linear structures. Above pH ∼ 2 densification of the aggregates occurs in conjunction with precipitation of low molecular weight Fe(III) species (e.g., monomers, dimers) to form mass fractal aggregates of ferrihydrite nanoparticles (∼3 nm) in which the Fe13 Keggin motif is preserved. SAXS analysis indicates the ferrihydrite particles have a core-shell structure consisting of a Keggin center surrounded by a Fe-depleted shell, supporting the surface depleted model of ferrihydrite. Overall, we present the first direct evidence for the role of Fe13 clusters in the pathway of ferrihydrite formation during base hydrolysis, showing clear structural continuity from isolated Fe13 Keggins to the ferrihydrite particle structure. The results have direct relevance to the fundamental understanding of ferrihydrite formation in environmental, engineered, and industrial processes. PMID:27480123

  16. Ferrihydrite Formation: The Role of Fe13 Keggin Clusters.

    PubMed

    Weatherill, Joshua S; Morris, Katherine; Bots, Pieter; Stawski, Tomasz M; Janssen, Arne; Abrahamsen, Liam; Blackham, Richard; Shaw, Samuel

    2016-09-01

    Ferrihydrite is the most common iron oxyhydroxide found in soil and is a key sequester of contaminants in the environment. Ferrihydrite formation is also a common component of many treatment processes for cleanup of industrial effluents. Here we characterize ferrihydrite formation during the titration of an acidic ferric nitrate solution with NaOH. In situ SAXS measurements supported by ex situ TEM indicate that initially Fe13 Keggin clusters (radius ∼ 0.45 nm) form in solution at pH 0.12-1.5 and are persistent for at least 18 days. The Fe13 clusters begin to aggregate above ∼ pH 1, initially forming highly linear structures. Above pH ∼ 2 densification of the aggregates occurs in conjunction with precipitation of low molecular weight Fe(III) species (e.g., monomers, dimers) to form mass fractal aggregates of ferrihydrite nanoparticles (∼3 nm) in which the Fe13 Keggin motif is preserved. SAXS analysis indicates the ferrihydrite particles have a core-shell structure consisting of a Keggin center surrounded by a Fe-depleted shell, supporting the surface depleted model of ferrihydrite. Overall, we present the first direct evidence for the role of Fe13 clusters in the pathway of ferrihydrite formation during base hydrolysis, showing clear structural continuity from isolated Fe13 Keggins to the ferrihydrite particle structure. The results have direct relevance to the fundamental understanding of ferrihydrite formation in environmental, engineered, and industrial processes.

  17. Hydrolysis of the RNA model substrate catalyzed by a binuclear Zr(IV)-substituted Keggin polyoxometalate.

    PubMed

    Luong, Thi Kim Nga; Absillis, Gregory; Shestakova, Pavletta; Parac-Vogt, Tatjana N

    2015-09-21

    The reactivity and solution behaviour of the binuclear Zr(IV)-substituted Keggin polyoxometalate (Et2NH2)8[{α-PW11O39Zr(μ-OH)(H2O)}2]·7H2O (ZrK 2 : 2) towards phosphoester bond hydrolysis of the RNA model substrate 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP) was investigated at different reaction conditions (pD, temperature, concentration, and ionic strength). The hydrolysis of the phosphoester bond of HPNP, followed by means of (1)H NMR spectroscopy, proceeded with an observed rate constant, kobs = 11.5(±0.42) × 10(-5) s(-1) at pD 6.4 and 50 °C, representing a 530-fold rate enhancement in comparison with the spontaneous hydrolysis of HPNP. (1)H and (31)P NMR spectra indicate that at these reaction conditions the only products of hydrolysis are p-nitrophenol and the corresponding cyclic phosphate ester. The pD dependence of kobs exhibits a bell-shaped profile, with the fastest rate observed at pD 6.4. The formation constant (Kf = 455 M(-1)) and catalytic rate constant (kc = 42 × 10(-5) s(-1)) for the HPNP-ZrK 2 : 2 complex, activation energy (Ea) of 63.35 ± 1.82 kJ mol(-1), enthalpy of activation (ΔH(‡)) of 60.60 ± 2.09 kJ mol(-1), entropy of activation (ΔS(‡)) of -133.70 ± 6.13 J mol(-1) K(-1), and Gibbs activation energy (ΔG(‡)) of 102.05 ± 0.13 kJ mol(-1) at 37 °C were calculated from kinetic experiments. Binding between ZrK 2 : 2 and the P-O bond of HPNP was evidenced by the change in the (31)P chemical shift and signal line-broadening of the (31)P atom in HPNP upon addition of ZrK 2 : 2. Based on (31)P NMR experiments and isotope effect studies, a mechanism for HPNP hydrolysis in the presence of ZrK 2 : 2 was proposed.

  18. Synthesis, characterization, and reactivity of Ti(IV)-monosubstituted Keggin polyoxometalates.

    PubMed

    Kholdeeva, Oxana A; Trubitsina, Tatiana A; Maksimov, Gennadii M; Golovin, Anatolii V; Maksimovskaya, Raisa I

    2005-03-01

    Ti(IV)-monosubstituted Keggin-type polyoxometalates (Ti-POMs), mu-oxo dimer [Bu4N]8[(PTiW11O39)2O] (1), and three monomers [Bu4N]4[PTi(L)W11O39], where L = OH (2), OMe (3), and OAr (4, ArOH = 2,3,6-trimethylphenol (TMP)), have been prepared starting from mu-hydroxo dimer [Bu4N]7[(PTiW11O39)2OH] (5) or heteropolyacid H5PW11TiO40 or both. The compounds have been characterized by elemental analysis, IR, UV-vis, and multinuclear (31P, 1H, 183W) NMR. The interaction of 1 and 3-5 with H2O in MeCN produces 2. The hydrolysis constants, estimated from 31P and 1H NMR data, are 0.006 and 0.04 for 1 and 3, respectively. Studies by 31P NMR, IR, potentiometric titration, and cyclic voltammetry revealed that 1-3 and 5 afford the same protonated titanium peroxo complex [Bu4N]4[HPTi(O2)W11O39] (I) upon interaction with aqueous H2O2 in MeCN. The rates of formation of I correlate with the rates of hydrolysis of the Ti-POMs and follow the order of 5 > 1 > 3. A two-step mechanism of the reaction of Ti-POMs with H2O2, which involves hydrolysis of the Ti-L bonds to yield 2 followed by fast interaction of 2 with hydrogen peroxide producing I, is suggested. The equilibrium constant for the reaction of 2 with H2O2 to yield I and H2O, estimated using 31P NMR, is 10. The interaction of the Ti-POMs with TMP follows the trends similar to their interaction with H2O) and requires preliminary hydrolysis of the Ti-L bonds. All of the Ti-POMs catalyze the oxidation of TMP with H2O2 in MeCN to give 2,3,5-trimethyl-p-benzoquinone and 2,2',3,3',5,5'-hexamethyl-4,4'-biphenol. The product distribution is similar for all of the Ti-POMs. The catalytic activities of the Ti-POMs correlate with the rates of formation of I and follow the order of 2 > 5 > 1 > 3. The findings lay a basis for a better understanding of the nature of the reactivity of titanium in Ti-catalyzed oxidations. PMID:15733007

  19. Photodegradation of malachite green dye catalyzed by Keggin-type polyoxometalates under visible-light irradiation: Transition metal substituted effects

    NASA Astrophysics Data System (ADS)

    Liu, Chun-Guang; Zheng, Ting; Liu, Shuang; Zhang, Han-Yu

    2016-04-01

    In the present paper, Keggin-type polyoxometalates (POMs) (NH4)3[PW12O40] and its mono-transition-metal-substituted species (NH4)5[{PW11O39}MII(H2O)] (M = Mn, Fe, Co, Ni, Cu, Zn) have been synthesized and used as photocatalyst to activate O2 for the degradation of dye molecule under visible-light irradiation. Because of the strong adsorption on the surface of POM catalyst, malachite green (MG) molecule was employed as a molecular probe to test their photocatalytic activity. The photodegradation study shows that introduction of transition metal ion leads to an increase in the degradation of MG in the following order: Mn < Fe < Co < [PW12O40]3- < Ni < Cu < Zn, which indicates that the photocatalytic activity of these POMs is sensitive to the transition metal substituted effects. Electronic structure analysis based on the density functional theory calculations shows that a moderate decrease of oxidizing ability of POM catalyst may improve the photocatalytic activity in the degradation of dye molecule under visible-light irradiation. Meanwhile, intermediate products about the photocatalytic oxidation of MG molecule were proposed on the basis of gas chromatograph mass spectrometer analysis.

  20. Intercluster compound between a tetrakis{triphenylphosphinegold(I)}oxonium cation and a keggin polyoxometalate (POM): formation during the course of carboxylate elimination of a monomeric triphenylphosphinegold(I) carboxylate in the presence of POMs.

    PubMed

    Nomiya, Kenji; Yoshida, Takuya; Sakai, Yoshitaka; Nanba, Arisa; Tsuruta, Shinichiro

    2010-09-20

    The preparation and structural characterization of a novel intercluster compound, [{Au(PPh(3))}(4)(μ(4)-O)](3)[α-PW(12)O(40)](2)·4EtOH (1), constructed between a tetrakis{triphenylphosphinegold(I)}oxonium cation and a saturated α-Keggin polyoxometalate (POM) are described. The tetragold(I) cluster oxonium cation was formed during the course of carboxylate elimination of a monomeric phosphinegold(I) carboxylate complex, i.e., [Au((R,S)-pyrrld)(PPh(3))] [(R,S)-Hpyrrld = (R,S)-2-pyrrolidone-5-carboxylic acid], in the presence of the free acid form of a Keggin POM, H(3)[α-PW(12)O(40)]·7H(2)O. The liquid-liquid diffusion between the upper water/EtOH phase containing the Keggin POM and the lower CH(2)Cl(2) phase containing the monomeric gold(I) complex gave a pure crystalline sample of 1 in good yield (42.1%, 0.242 g scale). Complex 1 was formed by ionic interaction between the tetragold(I) cluster cation and the Keggin POM anion. As a matter of fact, the POM anion in 1 can be exchanged with the BF(4)(-) anion using an anion-exchange resin (Amberlyst A-27) in BF(4)(-) form. By using other Keggin POMs, such as H(4)[α-SiW(12)O(40)]·10H(2)O and H(3)[α-PMo(12)O(40)]·14H(2)O, the same tetragold(I) cluster cation was also formed, i.e., in the forms of [{Au(PPh(3))}(4)(μ(4)-O)](2)[α-SiW(12)O(40)]·2H(2)O (2) and [{Au(PPh(3))}(4)(μ(4)-O)](3)[α-PMo(12)O(40)](2)·3EtOH (3). Compounds 1-3, as dimethyl sulfoxide-soluble, EtOH- and Et(2)O-insoluble dark-yellowish white solids, were characterized by complete elemental analysis, thermogravimetric and differential thermal analyses, Fourier transform IR, X-ray crystallography, and solid-state (CPMAS (31)P and (29)Si) and solution ((31)P{(1)H} and (1)H) NMR spectroscopy. The molecular structures of 1 and 2 were successfully determined. The tetragold(I) cluster cation was composed of four PPh(3)Au(I) units bridged by a central μ(4)-oxygen atom in the geometry of a trigonal pyramid or distorted tetrahedron.

  1. Effect of the Keggin anions on assembly of Cu{sup I}-bis(tetrazole) thioether complexes containing multinuclear Cu{sup I}-cluster

    SciTech Connect

    Wang Xiuli; Gao Qiang; Tian Aixiang; Hu Hailiang; Liu Guocheng

    2012-03-15

    In order to investigate the effect of polyoxometalate (POM) on the assembly of transition metal-bis(tetrazole) thioether complexes, three new complexes based on different Keggin anions and multinuclear Cu{sup I}-cluster [Cu{sup I}{sub 12}(bmtr){sub 9}(HSiMo{sub 12}O{sub 40}){sub 4}] (1), [Cu{sup I}{sub 3}(bmtr){sub 3}(PM{sub 12}O{sub 40})] (M=W for 2; Mo for 3) (bmtr=1,3-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)propane), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In compound 1, two kinds of nanometer-scale tetranuclear subunits linked by [SiMo{sub 12}O{sub 40}]{sup 4-} polyanions assemble a (3, 4)-connected three-dimensional (3D) self-penetrating framework. Compounds 2 and 3 are isostructural, exhibiting a 1D chain with [PW{sub 12}O{sub 40}]{sup 3-}/[PMo{sub 12}O{sub 40}]{sup 3-} polyanions and trinuclear clusters arranging alternately. The distinct structural differences between these POM-based Cu{sup I}-bmtr complexes of 1 and 2/3 maybe rest on the contrast of Keggin-type polyoxometalate with different central heteroatoms, which have been discussed in detail. In addition, the electrochemical properties of the title complexes have been investigated. - Graphical abstract: Three new complexes based on different Keggin anions and multinuclear Cu{sup I}-cluster have been synthesized under hydrothermal conditions. The Keggin polyanions with different central heteroatoms play a key role. Highlights: Black-Right-Pointing-Pointer The flexible bis(tetrazole)-based thioether ligand with some advantages have been used. Black-Right-Pointing-Pointer The effect of Keggin anions with different central heteroatoms has been discussed in detail. Black-Right-Pointing-Pointer The electrochemical behaviors and electrocatalysis property have been investigated.

  2. Sizing and Discovery of Nanosized Polyoxometalate Clusters by Mass Spectrometry

    PubMed Central

    2016-01-01

    Ion mobility-mass spectrometry (IM-MS) is a powerful technique for structural characterization, e.g., sizing and conformation, particularly when combined with quantitative modeling and comparison to theoretical values. Traveling wave IM-MS (TW-IM-MS) has recently become commercially available to nonspecialist groups and has been exploited in the structural study of large biomolecules, however reliable calibrants for large anions have not been available. Polyoxometalate (POM) species—nanoscale inorganic anions—share many of the facets of large biomolecules, however, the full potential of IM-MS in their study has yet to be realized due to a lack of suitable calibration data or validated theoretical models. Herein we address these limitations by reporting DT-IM (drift tube) data for a set of POM clusters {M12} Keggin 1, {M18} Dawson 2, and two {M7} Anderson derivatives 3 and 4 which demonstrate their use as a TW-IM-MS calibrant set to facilitate characterization of very large (ca. 1–4 nm) anionic species. The data was also used to assess the validity of standard techniques to model the collision cross sections of large inorganic anions using the nanoscale family of compounds based upon the {Se2W29} unit including the trimer, {Se8W86O299} A, tetramer, {Se8W116O408} B, and hexamer {Se12W174O612} C, including their relative sizing in solution. Furthermore, using this data set, we demonstrated how IM-MS can be used to conveniently characterize and identify the synthesis of two new, i.e., previously unreported POM species, {P8W116}, unknown D, and {Te8W116}, unknown E, which are not amenable to analysis by other means with the approximate formulation of [H34W118X8M2O416]44–, where X = P and M = Co for D and X = Te and M = Mn for E. This work establishes a new type of inorganic calibrant for IM-MS allowing sizing, structural analysis, and discovery of molecular nanostructures directly from solution. PMID:26906879

  3. Zeolitic polyoxometalates metal organic frameworks (Z-POMOF) with imidazole ligands and epsilon-Keggin ions as building blocks; computational evaluation of hypothetical polymorphs and a synthesis approach.

    PubMed

    Rodriguez Albelo, L Marleny; Ruiz-Salvador, A Rabdel; Lewis, Dewi W; Gómez, Ariel; Mialane, Pierre; Marrot, Jérome; Dolbecq, Anne; Sampieri, Alvaro; Mellot-Draznieks, Caroline

    2010-08-14

    We investigate here a new family of zeolitic Metal Organic Frameworks (MOFs) based on imidazole (im) as the ligand and epsilon-type Keggin PolyOxoMetalates (POMs) as building units. The POM used in this study is the epsilon-{PMo(12)O(40)} Keggin isomer capped by four Zn(ii) ions (noted epsilon-Zn) in tetrahedral coordination. We describe here our methods to first construct and then evaluate the stability of hypothetical 3-D POMOFs possessing a tetrahedral network, typified by dense silica polymorphs and zeotypes and referred here to as Z-POMOFs. We use the analogy between the connectivity of silicon ion in dense minerals or zeolites and the epsilon-Zn, using imidazolate ligands to mimic the role of oxygen atoms in zeolites. Handling the epsilon-Keggin and imidazole as the constitutive building-blocks, a selection of 40 polymorphs were constructed and their relative stabilities computed. Among these Z-POMOFs, the cristobalite-like and zni-structure were identified as the most stable candidates. In parallel, we have attempted to synthesize Z-POMOF structures with epsilon-Zn POMs, synthesized in situ under hydrothermal conditions, and imidazole ligands. We present our first experimental result, the extended material [NBu(4)][PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)(im)(Him)], named epsilon(im)(2). The structure of the hybrid framework is built by the connection of dimerized epsilon-Zn POMs to imidazole ligands in two directions. The obtaining of the first POMOF based on imidazole ligand is an encouraging step towards the synthesis of a new family of POMOFs.

  4. A new Keggin-like niobium-phosphate cluster that reacts reversibly with hydrogen peroxide.

    PubMed

    Son, Jung-Ho; Casey, William H

    2015-08-18

    Polyoxoniobate clusters that are stable in acidic solutions are rare and particularly useful in industrial processes. Here we report a new pentaphosphate niobate polyoxometalate cluster (TMA)9H3Nb9P5O41·28H2O (Nb9P5) that is stable over a wide pH range and that can be converted reversibly into the peroxo form.

  5. Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

    PubMed

    Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

    2014-06-25

    Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated

  6. Polyoxometalates as a novel class of artificial proteases: selective hydrolysis of lysozyme under physiological pH and temperature promoted by a cerium(IV) Keggin-type polyoxometalate.

    PubMed

    Stroobants, Karen; Moelants, Eva; Ly, Hong Giang T; Proost, Paul; Bartik, Kristin; Parac-Vogt, Tatjana N

    2013-02-18

    Hen-egg-white lysozyme (HEWL) is specifically cleaved at the Trp28-Val29 and Asn44-Arg45 peptide bonds in the presence of a Keggin-type [Ce(α-PW(11)O(39))(2)](10-) polyoxometalate (POM; 1) at pH 7.4 and 37 °C. The reactivity of 1 towards a range of dipeptides was also examined and the calculated reaction rates were comparable to those observed for the hydrolysis of HEWL. Experiments with α-lactalbumin (α-LA), a protein that is structurally highly homologous to HEWL but has a different surface potential, showed no evidence of hydrolysis, which indicates the importance of electrostatic interactions between 1 and the protein surface for the hydrolytic reaction to occur. A combination of spectroscopic techniques was used to reveal the molecular interactions between HEWL and 1 that lead to hydrolysis. NMR spectroscopy titration experiments showed that on protein addition the intensity of the (31)P NMR signal of 1 gradually decreased due to the formation of a large protein/polyoxometalate complex and completely disappeared when the HEWL/1 ratio reached 1:2. Circular dichroism (CD) measurements of HEWL indicate that addition of 1 results in a clear decrease in the signal at λ=208 nm, which is attributed to changes in the α-helical content of the protein. (15)N-(1)H heteronuclear single quantum coherence (HSQC) NMR measurements of HEWL in the presence of 1 reveal that the interaction is mainly observed for residues that are located in close proximity to the first site in the α-helical part of the structure (Trp28-Val29). The less pronounced NMR spectroscopic shifts around the second cleavage site (Asn44-Arg45), which is found in the β-strand region of the protein, might be caused by weaker metal-directed binding, compared with strong POM-directed binding at the first site.

  7. Zr(IV)-monosubstituted Keggin-type dimeric polyoxometalates: synthesis, characterization, catalysis of H2O2-based oxidations, and theoretical study.

    PubMed

    Kholdeeva, Oxana A; Maksimov, Gennadii M; Maksimovskaya, Raisa I; Vanina, Marina P; Trubitsina, Tatiana A; Naumov, Dmitry Yu; Kolesov, Boris A; Antonova, Nadya S; Carbó, Jorge J; Poblet, Josep M

    2006-09-01

    The previously unknown Zr(IV)-monosubstituted Keggin-type polyoxometalates (Zr-POMs), (n-Bu4N)7H[{PW11O39Zr(mu-OH)}2] (1), (n-Bu4N)8[{PW11O39Zr(mu-OH)}2] (2), and (n-Bu4N)9[{PW11O39Zr}2(mu-OH)(mu-O)] (3) differing in their protonation state, have been prepared starting from heteropolyacid H5PW11ZrO40.14H2O. The compounds were characterized by elemental analysis, potentiometric titration, X-ray single-crystal structure, and IR, Raman, and 31P and 183W NMR spectroscopy. The single-crystal X-ray analysis of 2 reveals that two Keggin structural units [PW11O39Zr]3- are linked through two hydroxo bridges Zr-(OH)-Zr with Zr(IV) in 7-fold coordination. The IR spectra of 1 and 2 show a characteristic band at 772 cm(-1), which moves to 767 cm(-1) for 3, reflecting deprotonation of the Zr-(OH)-Zr bond. Potentiometric titration with methanolic Bu4NOH indicates that 1-3 contain 2, 1, and 0 acid protons, respectively. (83W NMR reveals Cs symmetry of 2 and 3 in dry MeCN, while for 1, it discovers nonequivalence of its two subunits and their distortion resulting from localization of the acidic proton on one of the Zr-O-W bridging O atoms. The (31)P NMR spectra of 2 and 3 differ insignificantly in dry MeCN, showing only signals at delta -12.46 and -12.44 ppm, respectively, while the spectrum of 1 displays two resonances at delta -12.3 (narrow) and -13.2 (broad) ppm, indicating slow proton exchange on the (31)P NMR time scale. The theoretical calculations carried out at the density functional theory level on the dimeric species 1-3 propose that protonation at the Zr-O-Zr bridging site is more favorable than protonation at Zr-O-W sites. Calculations also revealed that the doubly bridged hydroxo structure is thermodynamically more stable than the singly bridged oxo structure, in marked contrast with analogous Ti- and Nb-monosubstituted polyoxometalates. The interaction of 1-3 with H(2)O and H(2)O(2) in MeCN has been studied by both (31)P and (183)W NMR. The stability of the [PW(11)O

  8. Two hybrid compounds constructed from Ni-tris(imidazolyl) complexes and Keggin clusters: Syntheses, structures and electrochemical properties

    NASA Astrophysics Data System (ADS)

    Zhang, Zhuanfang; Sun, Xiaojun; Ma, Huiyuan; Pang, Haijun; Li, Shaobin; Zhao, Chunyan

    2016-07-01

    By introducing different polyoxotungstates into the Ni-tib (tib = 1, 3, 5-tris (1-imidazolyl)benzene) system, two new polyoxometalate-based inorganic-organic hybrids with distinct architectures, [Ni(Htib)4][PW12O40]2 (1) and [Nitib]2(H2O)4](GeW12O40)·2H2O (2) have been synthesized under the same hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD) patterns and thermogravimetic (TG) analyses. Structural analyses show that compound 1 is a dimer, in which two neighboring mono-connected [PW12O40]3- (PW12) clusters are linked together by a [Ni(Htib)4] complex cation. In contrast to compound 1, compound 2 presents a 2D grid layer formed by bi-connected [GeW12O40]4- (GeW12) clusters and [Ni2(H2O)4(tib)2] complex cations, and the adjacent layers are further linked together by the hydrogen bondings to form a highly opened 3D framework. The distinct structural features of two hybrids suggest that the charge of the Keggin anions should play a key role in the process of assembly. Additionally, the electrochemical properties of compounds 1 and 2 have been investigated, and the results indicated that 1 and 2 have good electrocatalytic activities towards reduction of nitrite and oxidation of ascorbic acid.

  9. Uranium pyrophosphate / methylenediphosphonate polyoxometalate cage clusters

    SciTech Connect

    Ling, Jie; Qiu, Jie; Sigmon, Ginger E.; Ward, Matt; Szymanowski, Jennifer E.S.; Burns, Peter C

    2010-09-29

    Despite potential applications in advanced nuclear energy systems, nanoscale control of uranium materials is in its infancy. In its hexavalent state, U occurs as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by various ligands to give square, pentagonal, or hexagonal bipyramids. Creation and design of nanostructured uranyl materials requires interruption of the tendency of uranyl bipyramids to share equatorial edges to form infinite sheets that occur in extended structures. Where a bidentate peroxide group bridges uranyl bipyramids, the configuration is inherently bent, fostering formation of cage clusters. Here the bent configurations of four- and five-membered rings of uranyl peroxide hexagonal bipyramids are bridged by pyrophosphate or methylenediphosphonate, creating eight chemically complex cage clusters with specific topologies. Chemical complexity in such clusters provides opportunities for the tuning of cage sizes, pore sizes, and properties such as aqueous solubility. Several of these are topological derivatives of simpler clusters that contain only uranyl bipyramids, whereas others exhibit new topologies.

  10. Two new helical compounds based on Keggin clusters and N-donor multidentate ligand: Syntheses, structures and properties

    SciTech Connect

    Zhou, Shi; Liu, Bo; Li, Xiao-Min; Shi, Tian; Chen, Ya-Guang

    2014-11-15

    Two isostructural polyoxometalate-based inorganic–organic hybrids with 1D helical chain, [CuH{sub 3}L{sub 2}(GeMo{sub 12}O{sub 40})]·2H{sub 2}O (1) and [CuH{sub 3}L{sub 2}(SiMo{sub 12}O{sub 40})]·2H{sub 2}O (2), where L=2,4,5-tri(4-pyridyl)-imidazole have been synthesized under hydrothermal conditions. It is the first time to use the L ligand to synthesis the Keggin-type polyoxometalate-based inorganic–organic hybrids. The two compounds possess the left- and right-handed helical chains and the POMs as pendants attach in the helical chains through Cu–O bonds. The two compounds have been characterized by elemental analyses, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA) and photoluminescent spectroscopy. Moreover, nitrogen adsorption−desorption measurement, electrochemical and photocatalysis properties for degradation of methylene blue (MB) upon a UV irradiation of compound 1 have been examined. - Graphical abstract: Two new compounds, [CuH{sub 3}L{sub 2}(GeMo{sub 12}O{sub 40})]·2H{sub 2}O (1) and [CuH{sub 3}L{sub 2}(SiMo{sub 12}O{sub 40})]·2H{sub 2}O (2) have been synthesized under hydrothermal conditions. The two compounds possess the left- and right-handed helical chains. - Highlights: • The tridentate L ligand is first used to synthesis Keggin-type polyoxometalates. • The two compounds possess the left- and right-handed Cu–L helical chains. • Relationship between surface properties and photocatalytic activity was studied. • Two compounds exhibit photoluminescence of ligand-to-metal charge transfer.

  11. Design of polystyrene latex particles covered with polyoxometalate clusters via multiple covalent bonding

    SciTech Connect

    Chen, Xinyue; Li, Hui; Yin, Panchao; Liu, Tianbo

    2015-02-27

    In this study, polyoxometalates (POMs) covalently functionalized with methyl methacrylate groups were applied as surfactants in the emulsion polymerization reaction of styrene. Due to the copolymerization of the methyl methacrylate groups and the styrene monomers, the polyoxometalate clusters are covalently grafted onto the surface of polystyrene latex nanoparticles. Finally, such latex particles are fully covered with catalytic POM clusters and might serve as quasi-homogeneous catalysts.

  12. Design of polystyrene latex particles covered with polyoxometalate clusters via multiple covalent bonding.

    PubMed

    Chen, Xinyue; Li, Hui; Yin, Panchao; Liu, Tianbo

    2015-04-11

    Polyoxometalates (POMs) covalently functionalized with methyl methacrylate groups were applied as surfactants in the emulsion polymerization reaction of styrene. Due to the copolymerization of the methyl methacrylate groups and the styrene monomers, the polyoxometalate clusters are covalently grafted onto the surface of polystyrene latex nanoparticles. Such latex particles are fully covered with catalytic POM clusters and might serve as quasi-homogeneous catalysts. PMID:25743436

  13. Molecular Insight from DFT Computations and Kinetic Measurements into the Steric Factors Influencing Peptide Bond Hydrolysis Catalyzed by a Dimeric Zr(IV)-Substituted Keggin Type Polyoxometalate.

    PubMed

    Mihaylov, Tzvetan T; Ly, Hong Giang T; Pierloot, Kristine; Parac-Vogt, Tatjana N

    2016-09-19

    Peptide bond hydrolysis of several peptides with a Gly-X sequence (X = Gly, Ala, Val, Leu, Ile, Phe) catalyzed by a dimeric Zr(IV)-substituted Keggin type polyoxometalate (POM), (Et2NH2)8[{α-PW11O39Zr(μ-OH)(H2O)}2]·7H2O (1), was studied by means of kinetic experiments and (1)H NMR spectroscopy. The observed rate of peptide bond hydrolysis was found to decrease with increase of the side chain bulkiness, from 4.44 × 10(-7) s(-1) for Gly-Gly to 0.81 × 10(-7) s(-1) for Gly-Ile. A thorough DFT investigation was performed to elucidate (a) the nature of the hydrolytically active species in solution, (b) the mechanism of peptide bond hydrolysis, and (c) the influence of the aliphatic residues on the rate of hydrolysis. Formation of substrate-catalyst complexes of the dimeric POM 1 was predicted as thermodynamically unlikely. Instead, the substrates prefer to bind to the monomerization product of 1, [α-PW11O39Zr(OH)(H2O)](4-) (2), which is also present in solution. In the hydrolytically active complex two dipeptide ligands are coordinated to the Zr(IV) center of 2. The first ligand is bidentate-bound through its amino nitrogen and amide oxygen atoms, while the second ligand is monodentate-bound through a carboxylic oxygen atom. The mechanism of hydrolysis involves nucleophilic attack by a solvent water molecule on the amide carbon atom of the bidentate-bound ligand. In this process the uncoordinated carboxylic group of the same ligand acts as a general base to abstract a proton from the attacking water molecule. The decrease of the hydrolysis rate with an increase in the side chain bulkiness is mostly due to the increased ligand conformational strain in the rate-limiting transition state, which elevates the reaction activation energy. The conformational strain increases first upon substitution of Hα in Gly-Gly with the aliphatic α substituent and second with the β branching of the α substituent. PMID:27570876

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

    SciTech Connect

    Wang Lamei; Fan Yong; Wang Yan; Xiao Lina; Hu Yangyang; Peng Yu; Wang Tiegang; Gao Zhongmin; Zheng Dafang; Cui Xiaobing; Xu Jiqing

    2012-07-15

    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.

  15. Application of carbon nanotubes modified with a Keggin polyoxometalate as a new sorbent for the hollow-fiber micro-solid-phase extraction of trace naproxen in hair samples with fluorescence spectrophotometry using factorial experimental design.

    PubMed

    Naddaf, Ezzat; Ebrahimi, Mahmoud; Es'haghi, Zarrin; Bamoharram, Fatemeh Farrash

    2015-07-01

    A sensitive technique to determinate naproxen in hair samples was developed using hollow-fiber micro-solid-phase combined with fluorescence spectrophotometry. The incorporation of multi-walled carbon nanotubes modified with a Keggin polyoxometalate into a silica matrix prepared by the sol-gel method was reported. In this research, the Keggin carbon nanotubes /silica composite was used in the pores and lumen of a hollow fiber as the hollow-fiber micro-solid-phase extraction device. The device was used for the microextraction of the analyte from hair and water samples under the optimized conditions. An orthogonal array experimental design with an OA24 (4(6) ) matrix was employed to optimize the conditions. The effect of six factors influencing the extraction efficiency was investigated: pH, salt, volume of donor and desorption phase, extraction and desorption time. The effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance was employed for estimating the main significant factors and their contributions in the extraction. Calibration curve plot displayed linearity over a range of 0.2-10 ng/mL with detection limits of 0.072 and 0.08 ng/mL for hair and aqueous samples, respectively. The relative recoveries in the hair and aqueous matrices ranged from 103-95%. The relative standard deviation for fiber-to-fiber repeatability was 3.9%. PMID:25931376

  16. Application of carbon nanotubes modified with a Keggin polyoxometalate as a new sorbent for the hollow-fiber micro-solid-phase extraction of trace naproxen in hair samples with fluorescence spectrophotometry using factorial experimental design.

    PubMed

    Naddaf, Ezzat; Ebrahimi, Mahmoud; Es'haghi, Zarrin; Bamoharram, Fatemeh Farrash

    2015-07-01

    A sensitive technique to determinate naproxen in hair samples was developed using hollow-fiber micro-solid-phase combined with fluorescence spectrophotometry. The incorporation of multi-walled carbon nanotubes modified with a Keggin polyoxometalate into a silica matrix prepared by the sol-gel method was reported. In this research, the Keggin carbon nanotubes /silica composite was used in the pores and lumen of a hollow fiber as the hollow-fiber micro-solid-phase extraction device. The device was used for the microextraction of the analyte from hair and water samples under the optimized conditions. An orthogonal array experimental design with an OA24 (4(6) ) matrix was employed to optimize the conditions. The effect of six factors influencing the extraction efficiency was investigated: pH, salt, volume of donor and desorption phase, extraction and desorption time. The effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance was employed for estimating the main significant factors and their contributions in the extraction. Calibration curve plot displayed linearity over a range of 0.2-10 ng/mL with detection limits of 0.072 and 0.08 ng/mL for hair and aqueous samples, respectively. The relative recoveries in the hair and aqueous matrices ranged from 103-95%. The relative standard deviation for fiber-to-fiber repeatability was 3.9%.

  17. The effect of counteranions on the molecular structures of phosphanegold(i) cluster cations formed by polyoxometalate (POM)-mediated clusterization.

    PubMed

    Nagashima, Eri; Yoshida, Takuya; Matsunaga, Satoshi; Nomiya, Kenji

    2016-09-14

    The effect of counteranions on the molecular structures of phosphanegold(i) cluster cations formed by polyoxometalate (POM)-mediated clusterization was investigated. A novel intercluster compound, [{(AuLCl)2(μ-OH)}2]3[α-PMo12O40]2·3EtOH (1-PMo12), was obtained as orange-yellow plate crystals in 12.0% yield from a 6 : 1 molar ratio reaction of the monomeric phosphanegold(i) carboxylato complex [Au(RS-pyrrld)(LCl)] (RS-Hpyrrld = RS-2-pyrrolidone-5-carboxylic acid; LCl = tris(4-chlorophenyl)phosphane) in CH2Cl2 with the free acid-form of Keggin polyoxometalate (POM), H3[α-PMo12O40]·14H2O. An EtOH/H2O (5 : 1, v/v) solvent mixture was used. The dimeric cation [{(AuLCl)2(μ-OH)}2](2+) in 1-PMo12 was in a parallel-edge arrangement that was formed by self-assembly through the inter-cationic aurophilic interactions of the μ-OH-bridged dinuclear phosphanegold(i) cation. The POM anion in 1-PMo12 was successfully exchanged with a smaller PF6(-) anion by the use of an anion-exchange resin. POM-free, colorless block crystals of [{(AuLCl)3(μ3-O)}2](PF6)2·4CH2Cl2 (2-PF6) were obtained by vapor diffusion in 14.1% yield. During the synthesis of 2-PF6, a compound with mixed counteranions (one POM and one PF6(-) anion), i.e. [{(AuLCl)4(μ4-O)}]2[α-PMo12O40]PF6 (3-PMo12PF6), was obtained in 66.4% yield. Both products were characterized by elemental analysis, TG/DTA, FT-IR, (31)P{(1)H} NMR, (1)H NMR, and X-ray crystallography. X-ray crystallography revealed that the countercation in 2-PF6 was the dimeric cation of the μ3-O-bridged tris{phosphanegold(i)} species, whereas that in 3-PMo12PF6 consisted of an unusual μ4-O-bridged tetragonal-pyramidal tetrakis{phosphanegold(i)} cation. Therefore, we concluded that the POM anion significantly contributed to the stabilization of these countercations (parallel-edged arrangement in 1-PMo12 and μ4-O-bridged tetragonal-pyramid in 3-PMo12PF6). Moreover, the previously reported yellow crystals of [{(AuLF)2(μ-OH)}2]3[PMo12O40]2·3

  18. Polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds: syntheses and molecular structures of silanol- and/or siloxane bond-containing species grafted on mono- and tri-lacunary Keggin POMs.

    PubMed

    Aoki, Shotaro; Kurashina, Takayuki; Kasahara, Yuhki; Nishijima, Tadashi; Nomiya, Kenji

    2011-02-14

    Using 3-mercaptopropyltrimethoxysilane (HS(CH₂)₃Si(OMe)₃) as a silane-coupling agent (SCA), mono- and tri-lacunary Keggin polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds, (Et₄N)₃[α-PW₁₁O₃₉{(HS(CH₂)₃Si)₂O}] EtN-1 (the 1 : 2 complex of a POM unit and organosilyl groups), (Bu₄N)₃[A-PW₉O₃₄(HS(CH₂)₃SiOH)₃] BuN-2 (the 1 : 3 complex) and (Bu₄N)₃[A-α-PW₉O₃₄(HS(CH₂)₃SiO)₃(Si(CH₂)₃SH)] BuN-3 (the 1 : 4 complex) were synthesized and unequivocally characterized by elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solid-state (²⁹Si and ³¹P) CPMAS NMR, solution (²⁹Si, ³¹P, ¹H and ¹³C) NMR, and X-ray crystallography. [Note: The moieties of their polyoxoanions are abbreviated simply as 1-3, respectively.] The X-ray molecular structures of EtN-1 and BuN-3 were determined. In EtN-1, two organic groups connected through a siloxane bond (-Si-O-Si- bond) were grafted on a mono-lacunary site of a Keggin POM, whereas in BuN-3 four organic groups connected through siloxane bonds were grafted on a tri-lacunary site of a Keggin POM. In BuN-2, three organic groups were grafted in the form of silanol (-SiOH) on a tri-lacunary site, i.e., in BuN-2 there was no siloxane bond. BuN-3 was synthesized as BuN-3a and BuN-3b by two methods, respectively; (1) BuN-3a was obtained by a 1 : 1 molar-ratio reaction of BuN-2 and an SCA in CH₃CN, and (2) BuN-3b was prepared by a direct 1 : 4 molar-ratio reaction of a tri-lacunary Keggin POM and SCA in water-CH₃CN. X-Ray crystallography revealed that BuN-3a is the same as BuN-3b. It is probable that BuN-2 is an intermediate in the formation of BuN-3. Terminal -SH groups in 1-3, as well as -OH groups in 2, can be utilized for immobilization of POMs and, also, as building blocks for the formation of novel hybrid compounds.

  19. Effects of isolobal heteroatoms in divanadium-substituted γ-Keggin-type polyoxometalates on (OV)2(μ-OH)2 diamond and (OV)2(μ-O) core structures and the transformation.

    PubMed

    Uehara, Kazuhiro; Taketsugu, Tatsuya; Yonehara, Kazuhiro; Mizuno, Noritaka

    2013-01-18

    Effects of isolobal heteroatoms in divanadium-substituted γ-Keggin-type polyoxometalates, (TBA)(4)[γ-XV(2)W(10)O(38)(μ-OH)(2)] 1(X) and (TBA)(4)[γ-XV(2)W(10)O(38)(μ-O)] 2(X) (where X = Ge or Si), on (OV)(2)(μ-OH)(2) and (OV)(2)(μ-O) core structures and transformations from 2(X) to 1(X) have been investigated. X-ray crystallography of 1(X) and 2(X) reveals that larger Ge (covalent radius 1.22 Å; covalent radius of Si 1.11 Å) induces (a) expansion of (OV)(2)(μ-OH)(2) and (OV)(2)(μ-O) cores, (b) expansion of lacunary sites, and (c) deep location of divanadium cores inside their lacunary sites. Density functional theory (DFT) calculations for anionic moieties of 1(X) and 2(X) reveal that energy levels of the highest occupied molecular orbital (HOMO)-1 in 1(Ge) and HOMO in 2(Ge) are lower than those in 1(Si) and 2(Si), respectively, because of smaller contribution of p(z) orbitals of oxygen atoms in 1(Ge) and 2(Ge), which would result from shorter V···O(-Ge) distances. Compound 2(Ge) reacts with water vapor to form (TBA)(4)[γ-GeV(2)W(10)O(38)(μ-OH)(2)] 1'(Ge) via a crystal-to-crystal transformation, and the water dissociation proceeds heterolytically. DFT calculations reveal that the reaction proceeds through (1) coordination of water on a coordinatively unsaturated site of vanadium in the lowest unoccupied molecular orbital (LUMO), followed by (2) proton transfer to the bridging oxo moiety. The order is different from that in 2(Si), which would result from the lower energy level of HOMO of 2(Ge) (i.e., lower nucleophilicity toward a proton of water) than that of 2(Si). PMID:23301537

  20. X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates

    DOE PAGESBeta

    Yin, Panchao; Wu, Bin; Mamontov, Eugene; Daemen, Luke L.; Cheng, Yongqiang; Li, Tao; Seifert, Soenke; Hong, Kunlun; Bonnesen, Peter V.; Keum, Jong Kahk; et al

    2016-02-05

    A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types of water molecules,more » the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures. A typical type of core shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small-angle X-ray scattering is used to study the structural features and stability of the core shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.« less

  1. Transformation of layered polyoxometallate cluster salts into mesoporous materials

    SciTech Connect

    Holland, B.T.; Isbester, P.K.; Munson, E.J.; Stein, A. . Dept. of Chemistry)

    1999-02-01

    A new approach to the formation of mesoporous materials has been developed, based on a two-step salt-gel'' synthesis, in which mesoporous aluminophosphates, galloaluminophosphates, and aluminosilicates have been created. The first step involves pre-organizing charged inorganic clusters (MO[sub 4]Al[sub 12](OH)[sub 24](H[sub 2]O)[sub 12][sup 7+], M = Al or Ga) into a layered mesoscopic material with oppositely charged organic surfactant molecules. In the second step, phosphate or silicate linker molecules are added, which diffuse through the cluster/surfactant salt, react with the clusters, and transform the layered precursor into a non-lamellar mesostructured material. Removal of the surfactant from the alumino- and galloaluminophosphates by anion-exchange and from the aluminosilicates by calcination results in mesoporous materials with BET surface areas up to 630, 455, and 431 m[sup 2]/g, respectively. Direct condensation by calcination of polyoxoaluminate cluster salts without additional linkers produces nanometer-sized one-dimensional strings.

  2. Hafnium sulfate prenucleation clusters and the Hf(18) polyoxometalate red herring.

    PubMed

    Ruther, Rose E; Baker, Brenna M; Son, Jung-Ho; Casey, William H; Nyman, May

    2014-04-21

    In prior studies, aqueous Hf sulfate-peroxide solutions were spin-coated, dehydrated, patterned by electron-beam lithography, ion-exchanged (OH(-) for SO4(2-)), and finally converted to HfO2 hard masks via annealing. The atomic-level details of the underlying aqueous chemistries of these processes are complex and yet to be understood. Yet a thorough understanding of this specific chemical system will inspire development of design rules for other aqueous-precursor-to-solid-state metal oxide systems. Often-observed crystallization of the Hf18 polyoxometalate from aqueous Hf sulfate-peroxide precursor solutions has led us to believe that Hf18 may represent an important intermediate step in this process. However, via detailed solution studies described here (small-angle X-ray scattering, electrospray ionization mass spectrometry, and Raman spectroscopy), we ascertained that Hf18 is in fact not a prenucleation cluster of Hf sulfate coatings. Rather, the Hf tetramers, pentamers, and hexamers that are the core building blocks of Hf18 are robustly persistent over variable compositions and aging time of precursor solutions, and therefore they are likely the rudimentary building blocks of the deposited thin-film materials. These Hf clusters are capped and linked by sulfate and peroxide anions in solution, which probably prevents crystallization of Hf18 during the rapid dehydration process of spin-coating. In fact, crystallization of Hf18 from the amorphous gel coating would be detrimental to formation of a high-density conformal coating that we obtain from precursor solutions. Therefore, this study revealed that the well-known Hf18 polyoxometalate is not likely to be an important intermediate in the thin-film process. However, its subunits are, confirming the universal importance of deriving information from the solid state, albeit judiciously and critically, to understand the solution state.

  3. 2D-network of inorganic-organic hybrid material built on Keggin type polyoxometallate and amino acid: [L-C{sub 2}H{sub 6}NO{sub 2}]{sub 3}[(PO{sub 4})Mo{sub 12}O{sub 36}].5H{sub 2}O

    SciTech Connect

    Alizadeh, M.H. Mirzaei, M.; Razavi, H.

    2008-03-04

    A new inorganic-organic hybrid material based on polyoxometallate, [L-C{sub 2}H{sub 6}NO{sub 2}]{sub 3}[(PO{sub 4})Mo{sub 12}O{sub 36}].5H{sub 2}O, has been successfully synthesized and characterized by single-crystal X-ray analysis, elemental analysis, infrared and ultraviolet spectroscopy, proton nuclear magnetic resonance and differential thermal analysis techniques. The title compound crystallizes in the monoclinic space group, P2{sub 1}/c{sub ,} with a = 12.4938 (8) A, b = 19.9326 (12) A, c = 17.9270 (11) A, {beta} = 102.129 (1){sup o}, V = 4364.8 (5) A{sup 3}, Z = 4 and R{sub 1}(wR{sub 2}) = 0.0513, 0.0877. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/{infinity} [(PO{sub 4})Mo{sub 12}O{sub 36}]{sup 3-}) which forming via weak Van der Waals interactions along the z axis. The characteristic band of the Keggin anion [(PO{sub 4})Mo{sub 12}O{sub 36}]{sup 3-} appears at 210 nm in the UV spectrum. Thermal analysis indicates that the Keggin anion skeleton begins to decompose at 520 deg. C.

  4. Gel-assisted crystallization of [Ir4(IMe)7(CO)H10](2+) and [Ir4(IMe)8H9](3+) clusters derived from catalytic glycerol dehydrogenation.

    PubMed

    Sharninghausen, Liam S; Mercado, Brandon Q; Crabtree, Robert H; Balcells, David; Campos, Jesús

    2015-11-14

    The two title clusters were formed during iridium-catalyzed glycerol dehydrogenation and display a remarkably high NHC content. They were crystallized in either agarose or polyethylene oxide gel matrices, while more conventional crystallization techniques proved unsuccessful. Cluster [Ir4(IMe)8H9](3+), with a net charge of +3, was only crystallizable with a polyoxometalate Keggin trianion. The crystal packing of this intercluster compound is discussed. Computational studies position the iridium hydrides and provide insights into the bonding. PMID:26435314

  5. Syntheses, structures and properties of two Keggin polyoxometalates [H5PCo(4,4‧-bipy)Mo11O39][H3PMo12O40]·3.75(4,4‧-bipy)·1.5H2O and [H3PMo12O40]·2(4,4‧-bipy)·1.5H2O

    NASA Astrophysics Data System (ADS)

    Huang, Yuan-Biao; Chen, Jian-Xin; Lan, Ting-Yan; Lu, Xiu-Qing; Wei, Chun-Xia; Li, Zhong-Shui; Zhang, Zhi-Chun

    2006-02-01

    Two novel Keggin polyoxometalates [H 5PCo(4,4'-bipy)Mo 11O 39][H 3PMo 12O 40]·3.75(4,4'-bipy)·1.5H 2O ( 1) and [H 3PMo 12O 40]·2(4,4'-bipy)·1.5H 2O ( 2) (bipy=bipyridine) were prepared by the hydrothermal method for the first time and characterized by elemental analyses, IR spectra and X-ray single crystal diffraction, showing that compound 1 is a novel organic-inorganic hybrid compound which consists of a cobalt-monosubstituted Keggin polyoxoanion [PCo(4,4'-bpy)Mo 11O 39] 5- with one pendant ligand 4,4'-bipy, a well-known Keggin polyoxoanion [PMo 12O 40] 3-, 4,4'-bipy and lattice water molecules. Additionally, the two different heteropolyoxoanions in 1 with alternating alignment, combined with the discrete organic substrates 4,4'-bipy and water molecules by hydrogen bond interactions to afford a pseudo 3D network structure. While compound 2 is an intermolecular compound between polyoxoanion unit [PMo 12O 40] 3- and organic substrate 4,4'-bipy. Furthermore, both the compounds exhibit strong photoluminescence properties in the solid state at room temperature. The catalytic activities of the two compounds were also determined by the oxidation of benzaldehyde to benzoic acid using H 2O 2 as oxidant in a liquid-solid multiphase system. Meanwhile, the catalytic property of the compound 2 was evaluated by the esterification of MeCO 2H (acetic acid) with n-BuOH ( n-butyl alcohol).

  6. Cobalt Clusters with Cubane-Type Topologies Based on Trivacant Polyoxometalate Ligands.

    PubMed

    Duan, Yan; Clemente-Juan, Juan M; Giménez-Saiz, Carlos; Coronado, Eugenio

    2016-01-19

    Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV-vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)](4-) (1) consists of a trilacunary [B-α-PW9O34](9-) unit which accommodates a cubane-like {Co(II)4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2](9-) (2), [Co7(OH)6(H2O)4(PW9O34)2]n(9n-) (3), and [Co7(OH)6(H2O)6(P2W15O56)2](15-) (4), dicubane-like {Co(II)6Co(III)O8} cores are encapsulated between two heptadentate [B-α-PW9O34](9-) (in 2 and 3) or [α-P2W15O56](15-) (in 4) ligands. While 1, 2, and 4 are discrete polyoxometalates, 3 exhibits a polymeric, chain-like structure that results from the condensation of polyoxoanions of type 2. The magnetic properties of these complexes have been fitted according to an anisotropic exchange model in the low-temperature regime and discussed on the basis of ferromagnetic interactions between Co(2+) ions with angles Co-L-Co (L = O, OH) close to orthogonality and weakly antiferromagnetic interactions between Co(2+) ions connected through central diamagnetic Co(3+) ion. Moreover, we will show the interest of the unique spin structures provided by these cubane and dicubane cobalt topologies in molecular spintronics (molecular spins addressed though an electric field) and quantum computing (spin qu-gates). PMID:26731303

  7. Connecting carbon nanotubes to polyoxometalate clusters for engineering high-performance anode materials.

    PubMed

    Chen, Wei; Huang, Lujiang; Hu, Jun; Li, Tengfei; Jia, Feifei; Song, Yu-Fei

    2014-09-28

    Carbon nanotubes (CNTs) possess excellent structural and electronic properties and have been widely investigated as anode materials. Polyoxometalates (POMs) exhibit superior physical properties such as electronic versatility, redox characteristics and unique molecular structures. In this paper, we report the covalent modification of carbon nanotubes (CNTs) with organosilica-containing polyoxometalate (POM) of [Bu4N]4[SiW11O39{O(SiCH2CH2CH2NH2·HCl)2}] (SiW11-NH2) that leads to the formation of the nanocomposite material of CNTs-SiW11, which has been characterized by FT-IR, XRD, HR-TEM, XPS and Raman spectrum, etc. At a current density of 0.5 mA cm(-2), the application of CNTs-SiW11 nanocomposite as anode material in lithium batteries exhibits the first discharge capacity of 1189 mA h g(-1), and the second discharge capacity of 650 mA h g(-1), which remains stable up to 100 cycles. The CNTs-SiW11 nanocomposite exhibits high discharge capacity, good capacity retention and cycling stability.

  8. Synthesis and characterization of Lanthanide Aluminotungstates and Rhenium Polyoxometalates: Potential Application in Molecular Information Storage Devices

    NASA Astrophysics Data System (ADS)

    Bian, Fang

    2011-12-01

    Polyoxometalates (abbreviated as POMs) are metal-oxide clusters with frameworks built from group 5 or 6 transition metals linked by shared oxide ions. The Keggin structure is one of the most famous structural forms of POMs. Keggin anions have a general formula of [XM12O40 ]n-, where X is a p-block atom and M is a transition metal atom such as W or Mo. Upon removal of one MO4+ unit from the Keggin anion, the monovacant structure [XM11O39] n- is formed. Those POMs that have lost one or more metal center are called lacunary POMs, which are very nice building blocks for the fabrication of coordination polymers. My research focuses on two facets of POM chemistry: 1) Lanthanide chemistry of aluminum tungstate monovacant Keggin and 2) Rhenium chemistry of aluminum tungstate Keggin and Wells-Dawson POM alpha1 -P2W17O61. In lanthanide POM research area, we obtained the following results: 1) The starting material aluminum tungstate monovacant Keggin α-K 9AlW12O39 was synthesized. Its single crystal was firstly identified by multinuclear NMR and X-ray crystallography. Its redox properties on the nano-scale solid state were determined by Conducting Electrostatic Force Mode (EFM) probes. It is well known that for POMs, a number of varies redox states are normally stable and reversible. Thus we estimated that POMs can potentially be used in molecular information storage applications, which we refer to as "redox disk drives". 2) Eight lanthanide aluminum tungstate Keggin complexes were synthesized. In their molecular structures (identified by multinuclear NMR and X-ray crystallography), each α-AlW11O39 is connected by lanthanide (III) cations to form 1D and 2D networks. All AlW11O39 Keggin POMs are regularly aligning on a flat plane. Microscopic data also verified that there is layer-by-layer morphology in this series of compounds. Overall, we postulate that aluminum tungstate Keggin POMs are a very promising materials for making future information storage device because they

  9. Decisive interactions between the heterocyclic moiety and the cluster observed in polyoxometalate-surfactant hybrid crystals.

    PubMed

    Otobe, Saki; Fujioka, Natsumi; Hirano, Takuro; Ishikawa, Eri; Naruke, Haruo; Fujio, Katsuhiko; Ito, Takeru

    2015-04-16

    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.

  10. TETRAALKYLPHOSPHONIUM POLYOXOMETALATES AS NOVEL IONIC LIQUIDS.

    SciTech Connect

    DIETZ,M.L.; RICKERT, P.G.; ANTONIO, M.R.; FIRESTONE, M.A.; WISHART, J.F.; SZREDER, T.

    2007-11-30

    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. Synthesis, structures and properties of new hybrid solids containing ruthenium complexes and polyoxometalates

    SciTech Connect

    Yan Bangbo; Hodsdon, Samantha A.; Li Yanfen; Carmichael, Christopher N.; Cao Yan; Pan Weiping

    2011-12-15

    Two new organic-inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV-vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy){sub 3}]{sub 2}[H{sub 2}W{sub 12}O{sub 40}]{center_dot}8H{sub 2}O (1), the [Ru(bpy){sub 3}]{sup 2+} (bpy=2,2 Prime -bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H{sub 2}W{sub 12}O{sub 40}]{sup 6-} linked through {l_brace}KO{sub 7}{r_brace} and {l_brace}NaO{sub 6}{r_brace} polyhedra, while in K{sub 6}[Ru(pzc){sub 3}]{sub 2}[SiW{sub 12}O{sub 40}] Bullet 12H{sub 2}O (2), the [Ru(pzc){sub 3}]{sup -} (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW{sub 12}O{sub 40}]{sup 4-} clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion Midline-Horizontal-Ellipsis {pi} interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature. - Graphical abstract: Two three-dimensional framework solids are constructed from polyoxoanions and ruthenium-organic complexes through noncovalent interactions. Highlights: Black-Right-Pointing-Triangle Ru complexes form hybrid solids with polyoxometalates. Black-Right-Pointing-Triangle Anion Midline-Horizontal-Ellipsis {pi} interaction between polyoxometalates and metal complexes was observed. Black-Right-Pointing-Triangle Noncovalent interactions play an important role in the assembly of solids. Black-Right-Pointing-Triangle The hybrid solid shows luminescence properties.

  12. Molecule-Based Water-Oxidation Catalysts (WOCs): Cluster-Size-Dependent Dye-Sensitized Polyoxometalates for Visible-Light-Driven O2 Evolution

    NASA Astrophysics Data System (ADS)

    Gao, Junkuo; Cao, Shaowen; Tay, Qiuling; Liu, Yi; Yu, Lingmin; Ye, Kaiqi; Mun, Peter Choon Sze; Li, Yongxin; Rakesh, Ganguly; Loo, Say Chye Joachim; Chen, Zhong; Zhao, Yang; Xue, Can; Zhang, Qichun

    2013-05-01

    From atomic level to understand the cluster-size-dependant behavior of dye-sensitized photocatalysts is very important and helpful to design new photocatalytic materials. Although the relationship between the photocatalytic behaviors and particles' size/shape has been widely investigated by theoretical scientists, the experimental evidences are much less. In this manuscript, we successfully synthesized three new ruthenium dye-sensitized polyoxometalates (POM-n, n relate to different size clusters) with different-sized POM clusters. Under visible-light illumination, all three complexes show the stable O2 evolution with the efficient order POM-3 > POM-2 > POM-1. This cluster-size-dependent catalytic behavior could be explained by the different numbers of M = Ot (terminal oxygen) bonds in each individual cluster because it is well-known that Mo = Ot groups are the catalytically active sites for photooxidation reaction. The proposed mechanism of water oxidation for the dye-sensitized POMs is radical reaction process. This research could open up new perspectives for developing new POM-based WOCs.

  13. Molecule-based water-oxidation catalysts (WOCs): cluster-size-dependent dye-sensitized polyoxometalates for visible-light-driven O2 evolution.

    PubMed

    Gao, Junkuo; Cao, Shaowen; Tay, Qiuling; Liu, Yi; Yu, Lingmin; Ye, Kaiqi; Mun, Peter Choon Sze; Li, Yongxin; Rakesh, Ganguly; Loo, Say Chye Joachim; Chen, Zhong; Zhao, Yang; Xue, Can; Zhang, Qichun

    2013-01-01

    From atomic level to understand the cluster-size-dependant behavior of dye-sensitized photocatalysts is very important and helpful to design new photocatalytic materials. Although the relationship between the photocatalytic behaviors and particles' size/shape has been widely investigated by theoretical scientists, the experimental evidences are much less. In this manuscript, we successfully synthesized three new ruthenium dye-sensitized polyoxometalates (POM-n, n relate to different size clusters) with different-sized POM clusters. Under visible-light illumination, all three complexes show the stable O2 evolution with the efficient order POM-3 > POM-2 > POM-1. This cluster-size-dependent catalytic behavior could be explained by the different numbers of M = Ot (terminal oxygen) bonds in each individual cluster because it is well-known that Mo = Ot groups are the catalytically active sites for photooxidation reaction. The proposed mechanism of water oxidation for the dye-sensitized POMs is radical reaction process. This research could open up new perspectives for developing new POM-based WOCs.

  14. Mixed addenda polyoxometalate "solutions" for stationary energy storage.

    PubMed

    Pratt, Harry D; Anderson, Travis M

    2013-11-28

    A series of redox flow batteries utilizing mixed addenda (vanadium and tungsten), phosphorus-based polyoxometalates (A-α-PV3W9O40(6-), B-α-PV3W9O40(6-), and P2V3W15O62(9-)) were prepared and tested. Cyclic voltammetry and bulk electrolysis experiments on the Keggin compounds (A-α-PV3W9O40(6-) and B-α-PV3W9O40(6-)) established that the vanadium centers of these compounds could be used as the positive electrode (PV(IV)3W(VI)9O40(9-)/PV(V)3W(VI)9O40(6-)), and the tungsten centers could be used as the negative electrode (PV(IV)3W(VI)9O40(9-)/PV(IV)3W(V)3W(VI)6O40(12-)) since these electrochemical processes are separated by about 1 V. The results showed that A-α-PV3W9O40(6-) (where A indicates adjacent, corner-sharing vanadium atoms) had coulombic efficiencies (charge in divided by charge out) above 80%, while the coulombic efficiency of B-α-PV3W9O40(6-) (where B indicates adjacent edge-sharing vanadium atoms) fluctuated between 50% and 70% during cycling. The electrochemical yield, a measurement of the actual charge or discharge observed in comparison with the theoretical charge, was between 40% and 50% for A-α-PV3W9O40(6-), and (31)P NMR showed small amounts of PV2W10O40(5-) and PVW11O40(4-) formed with cycling. The electrochemical yield for B-α-PV3W9O40(6-) decreased from 90% to around 60% due to precipitation of the compound on the electrode, but there were no decomposition products detected in the solution by (31)P NMR, and infrared data on the electrode suggested that the cluster remained intact. Testing of P2V3W15O62(9-) (Wells-Dawson structure) suggested higher charge density clusters were not as suitable as the Keggin structures for a redox flow battery due to the poor stability and inaccessibility of the highly reduced materials.

  15. A polyoxometalate flow battery

    SciTech Connect

    Pratt, Harry D.; Hudak, Nicholas S.; Fang, Xikui; Anderson, Travis M.

    2013-08-01

    A redox flow battery utilizing two, three-electron polyoxometalate redox couples (SiVV3WVI9O407–/SiVIV3WVI9O4010- and SiVIV3WVI9O4010-/SiVIV3WV3WVI6O4013-) was investigated for use in stationary storage in either aqueous or non-aqueous conditions. The aqueous battery had coulombic efficiencies greater than 95% with relatively low capacity fading over 100 cycles. Infrared studies showed there was no decomposition of the compound under these conditions. The non-aqueous analog had a higher operating voltage but at the expense of coulombic efficiency. The spontaneous formation of these clusters by self-assembly facilitates recovery of the battery after being subjected to reversed polarity. Polyoxometalates offer a new approach to stationary storage materials because they are capable of undergoing multi-electron reactions and are stable over a wide range of pH values and temperatures.

  16. Synthesis, crystal structure of α-Keggin heteropolymolybdates with pyridine-2,6-dicarboxylate based frameworks, and associated RhB photocatalytic degradation and 2D-IR COS tests.

    PubMed

    Chen, Xiang-yi; Chen, Yi-ping; Xia, Ze-min; Hu, Heng-bin; Sun, Yan-qiong; Huang, Wei-yuan

    2012-09-01

    Three α-Keggin heteropolymolybdates with the formula [(C(5)H(4)NH)COOH](3)[PMo(12)O(40)] 1, {[Sm(H(2)O)(4)(pdc)](3)}{[Sm(H(2)O)(3)(pdc)]}[SiMo(12)O(40)]·3H(2)O 2 and {[La(H(2)O)(4)(pdc)](4)}[PMo(12)O(40)]F 3 (H(2)pdc = pyridine-2,6-dicarboxylate), have been synthesized under hydrothermal condition and characterized by single crystal X-ray diffraction analyses, elemental analyses, inductively coupled plasma atomic emission spectroscopy (ICP-AES), IR, thermal gravimetric analyses, thermal infrared spectrum analyses and powder X-ray diffraction (PXRD) analyses. Single crystal X-ray diffraction indicates all three compounds comprise ball-shaped Keggin type [XMo(12)O(40)](n-) polyoxometalates (POMs) (n = 3, X = P; n = 4, X = Si, respectively) with different types of carboxylic ligands derived from H(2)pdc, and these cluster anions are isostructural. In order to explore structural characteristics, Rhodamine B photocatalytic (RhB) degradation and two-dimensional infrared correlation spectroscopy (2D-IR COS) tests, are investigated for 1, 2 and 3. In RhB degradation, all compounds show good photocatalytic activity. For 1, the activity mainly comes from POMs. While in 2 and 3, POMs' photocatalytic activity is enhanced by the Ln(iii)-pdc metal-organic frameworks. Structural properties like POM's stability and magnetic sensitivity are discussed by 2D-IR COS under thermal/magnetic perturbations.

  17. Assembly of Cu/Ag-quinoxaline-polyoxotungstate hybrids: Influence of Keggin and Wells-Dawson polyanions on the structure

    NASA Astrophysics Data System (ADS)

    Chi, Ying-Nan; Cui, Feng-Yun; Lin, Zheng-Guo; Xu, Yan; Ma, Xiao-Yu; Shen, Pan-Pan; Huang, Kun-Lin; Hu, Chang-Wen

    2013-03-01

    In order to investigate the influence of Keggin and Wells-Dawson polyoxometalates on the resultant structure, four new organic-inorganic hybrid compounds [Cu4(qx)5(SiW12O40)] (1), [Cu6(qx)6(P2W18O62)(H2O)1.5]·4.5H2O (2), [Ag4(qx)4(SiW12O40)(H2O)]·H2O (3), [Ag6(qx)6(P2W18O62)]·8H2O (4) (qx=quinoxaline) were synthesized and structurally characterized by single-crystal X-ray diffraction. In 1, the 2D layers are linked by the SiW12O404- (SiW12) anions to construct a 3D framework. When the Wells-Dawson type P2W18O626- (P2W18) is used, 2 is prepared, in which the 1D helical chains are connected by P2W18 to form a 3D network. In 3, two kinds of 1D metal-organic chains are connected by SiW12 clusters to construct a 3D framework. In 4, there are also two kinds of 1D chains one kind of 1D chain combines with P2W18 by the AgO weak interaction and the other kind is just metal-organic chain. In addition, the electrochemistry properties of compounds 1-4 have been studied.

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

    PubMed

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

    2007-05-10

    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. New polyoxometalates containing hybrid polymers and their potential for nano-patterning.

    PubMed

    Kalyani, Vishwanath; Satyanarayana, V S V; Singh, Vikram; Pradeep, Chullikkattil P; Ghosh, Subrata; Sharma, Satinder K; Gonsalves, Kenneth E

    2015-01-26

    Two new polyoxometalate (POM)-based hybrid monomers (Bu4 N)5 (H)[P2 V3 W15 O59 {(OCH2 )3 CNHCO(CH3 )CCH2 }] (2) and (S(CH3 )2 C6 H4 OCOC(CH3 )=CH2 )6 [PV  2Mo10 O40 ] (5) were developed by grafting polymerizable organic units covalently or electrostatically onto Wells-Dawson and Keggin-type clusters and were characterized by analytical and spectroscopic techniques including ESI-MS and/or single-crystal X-ray diffraction analyses. Radical initiated polymerization of 2 and 5 with organic monomers (methacryloyloxy)phenyldimethylsulfonium triflate (MAPDST) and/or methylmethacrylate (MMA) yielded a new series of POM/polymer hybrids that were characterized by (1) H, (31) P NMR and IR spectroscopic techniques, gel-permeation chromatography as well as thermal analyses. Preliminary tests were conducted on these POM/polymer hybrids to evaluate their properties as photoresists using electron beam (E-beam)/extreme ultraviolet (EUV) lithographic techniques. It was observed that the POM/polymer hybrid of 2 with MAPDST exhibited improved sensitivity under EUV lithographic conditions in comparison to the MAPDST homopolymer resist possibly due to the efficient photon harvesting by the POM clusters from the EUV source.

  20. New polyoxometalates containing hybrid polymers and their potential for nano-patterning.

    PubMed

    Kalyani, Vishwanath; Satyanarayana, V S V; Singh, Vikram; Pradeep, Chullikkattil P; Ghosh, Subrata; Sharma, Satinder K; Gonsalves, Kenneth E

    2015-01-26

    Two new polyoxometalate (POM)-based hybrid monomers (Bu4 N)5 (H)[P2 V3 W15 O59 {(OCH2 )3 CNHCO(CH3 )CCH2 }] (2) and (S(CH3 )2 C6 H4 OCOC(CH3 )=CH2 )6 [PV  2Mo10 O40 ] (5) were developed by grafting polymerizable organic units covalently or electrostatically onto Wells-Dawson and Keggin-type clusters and were characterized by analytical and spectroscopic techniques including ESI-MS and/or single-crystal X-ray diffraction analyses. Radical initiated polymerization of 2 and 5 with organic monomers (methacryloyloxy)phenyldimethylsulfonium triflate (MAPDST) and/or methylmethacrylate (MMA) yielded a new series of POM/polymer hybrids that were characterized by (1) H, (31) P NMR and IR spectroscopic techniques, gel-permeation chromatography as well as thermal analyses. Preliminary tests were conducted on these POM/polymer hybrids to evaluate their properties as photoresists using electron beam (E-beam)/extreme ultraviolet (EUV) lithographic techniques. It was observed that the POM/polymer hybrid of 2 with MAPDST exhibited improved sensitivity under EUV lithographic conditions in comparison to the MAPDST homopolymer resist possibly due to the efficient photon harvesting by the POM clusters from the EUV source. PMID:25431365

  1. Controlling the dispersion of supported polyoxometalate heterogeneous catalysts: impact of hybridization and the role of hydrophilicity–hydrophobicity balance and supramolecularity

    PubMed Central

    Swalus, Colas; Arendt, Eglantine; Eloy, Pierre; Devillers, Michel

    2014-01-01

    Summary The hybridization of polyoxometalates (POMs) through an organic–inorganic association offers several processing advantages in the design of heterogeneous catalysts. A clear understanding of the organization of these hybrid materials on solid surfaces is necessary to optimise their properties. Herein, we report for the first time the organization of Keggin phosphotungstic [PW12O40]3− and Wells–Dawson (WD) phosphomolybdic [P2Mo18O62]6− anions deposited on mica (hydrophilic), and highly oriented pyrolytic graphite (HOPG) (hydrophobic) surfaces. Next, the supramolecular organization of the organic–inorganic hybrid materials formed from the association of POM anions and dimethyldioctadecylammonium bromide (DODA) is investigated as a function of the hydrophilic or hydrophobic nature of the surfaces. The height of the Keggin-POM anions, measured with tapping mode (TM-AFM) is always in good agreement with the molecular dimension of symmetric Keggin-POM anions (ca. 1 nm). However, the asymmetric WD-POM anions form monolayer assemblies on the surfaces with the orientation of their long molecular axis (ca. 1.6 nm) depending on the hydrophilic or hydrophobic properties of the substrate. Namely, the long axis is parallel on mica, and perpendicular on HOPG. When hybridized with DODA, the organization of the hybrid material is dictated by the interaction of the alkyl side chains of DODA with the substrate surface. On HOPG, the DODA–POM hybrid forms small domains of epitaxially arranged straight nanorod structures with their orientation parallel to each other. Conversely, randomly distributed nanospheres are formed when the hybrid material is deposited on freshly cleaved mica. Finally, a UV–ozone treatment of the hybrid material allows one to obtain highly dispersed isolated POM entities on both hydrophilic and hydrophobic surfaces. The hybridization strategy to prevent the clustering of POMs on various supports would enable to develop highly dispersed POM

  2. Controlling the dispersion of supported polyoxometalate heterogeneous catalysts: impact of hybridization and the role of hydrophilicity-hydrophobicity balance and supramolecularity.

    PubMed

    Raj, Gijo; Swalus, Colas; Arendt, Eglantine; Eloy, Pierre; Devillers, Michel; Gaigneaux, Eric M

    2014-01-01

    The hybridization of polyoxometalates (POMs) through an organic-inorganic association offers several processing advantages in the design of heterogeneous catalysts. A clear understanding of the organization of these hybrid materials on solid surfaces is necessary to optimise their properties. Herein, we report for the first time the organization of Keggin phosphotungstic [PW12O40](3-) and Wells-Dawson (WD) phosphomolybdic [P2Mo18O62](6-) anions deposited on mica (hydrophilic), and highly oriented pyrolytic graphite (HOPG) (hydrophobic) surfaces. Next, the supramolecular organization of the organic-inorganic hybrid materials formed from the association of POM anions and dimethyldioctadecylammonium bromide (DODA) is investigated as a function of the hydrophilic or hydrophobic nature of the surfaces. The height of the Keggin-POM anions, measured with tapping mode (TM-AFM) is always in good agreement with the molecular dimension of symmetric Keggin-POM anions (ca. 1 nm). However, the asymmetric WD-POM anions form monolayer assemblies on the surfaces with the orientation of their long molecular axis (ca. 1.6 nm) depending on the hydrophilic or hydrophobic properties of the substrate. Namely, the long axis is parallel on mica, and perpendicular on HOPG. When hybridized with DODA, the organization of the hybrid material is dictated by the interaction of the alkyl side chains of DODA with the substrate surface. On HOPG, the DODA-POM hybrid forms small domains of epitaxially arranged straight nanorod structures with their orientation parallel to each other. Conversely, randomly distributed nanospheres are formed when the hybrid material is deposited on freshly cleaved mica. Finally, a UV-ozone treatment of the hybrid material allows one to obtain highly dispersed isolated POM entities on both hydrophilic and hydrophobic surfaces. The hybridization strategy to prevent the clustering of POMs on various supports would enable to develop highly dispersed POM-based heterogeneous

  3. Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW9O34](10-) Polyoxometalate.

    PubMed

    Duval, Sylvain; Béghin, Sébastien; Falaise, Clément; Trivelli, Xavier; Rabu, Pierre; Loiseau, Thierry

    2015-09-01

    The reaction of Na10[α-SiW9O34] with tetravalent metallic cations such as 4f ((NH4)2Ce(NO3)6), 5d (HfCl4), or 5f (UCl4 and Th(NO3)4) in a pH 4.7 sodium acetate buffer solution leads to the formation of four sandwich-type polyoxometalates [Ce4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (1), [U4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (2), [Th3(μ(3)-O)(μ(2)-OH)3(SiW9O34)2](13-) (3), and [Hf3(μ(2)-OH)3(SiW9O34)2](11-) (4). All four compounds consist of a polynuclear cluster fragment stabilized by two [α-SiW9O34](10-) polyanions. Compounds 1 and 2 are isostructural with a tetranuclear core (Ce4, U4), while compound 3 presents a trinuclear Th3 core bearing a μ(3)-O-centered bridge. It is an unprecedented configuration in the case of the thorium(IV) cluster. Compound 4 also possesses a trinuclear Hf3 core but with the absence of the μ(3)-O bridge. The molecules have been characterized by single-crystal X-ray diffraction, (183)W and (29)Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis.

  4. Polyoxometalate flow battery

    DOEpatents

    Anderson, Travis M.; Pratt, Harry D.

    2016-03-15

    Flow batteries including an electrolyte of a polyoxometalate material are disclosed herein. In a general embodiment, the flow battery includes an electrochemical cell including an anode portion, a cathode portion and a separator disposed between the anode portion and the cathode portion. Each of the anode portion and the cathode portion comprises a polyoxometalate material. The flow battery further includes an anode electrode disposed in the anode portion and a cathode electrode disposed in the cathode portion.

  5. On the effect of ion pairing of Keggin type polyanions with quaternary ammonium cations on redox potentials in organic solvents.

    PubMed

    Chen, Bo; Neumann, Ronny

    2016-08-10

    The electrochemical properties of Keggin type polyoxometalates Qn[XW12O40] (X = P, Si, B; Q = n-tetraoctylammonium and n-trioctylmethylammonium) in organic solvents were investigated in order to understand the interrelation between the redox potentials, solvents and ion pairing. A logarithmic correlation between the dielectric constant of the solvent (ε ranged from 4.8 to 46.6) and the reduction potential of the [PW12O4](3-)/[PW12O4](4-) couple was found. This reduction potential increased significantly when the surface charge of the polyoxometalate went from 3- to 5-. The investigation of the ion pairing properties by diffusion NMR revealed the presence of intimate ion pairs in less polar solvents (e.g. dichloromethane) and less compact ion pairs in more polar solvents (e.g. DMSO). Using a V atom within the polyoxometalate an NMR experiment showed that a n-trioctylmethyl ammonium cation bonded to the polyoxometalate anion more intimately than a n-tetraoctyl ammonium cation. PMID:27465599

  6. Efficient visible-light photocatalytic activity by band alignment in mesoporous ternary polyoxometalate-Ag2S-CdS semiconductors

    NASA Astrophysics Data System (ADS)

    Kornarakis, I.; Lykakis, I. N.; Vordos, N.; Armatas, G. S.

    2014-07-01

    Porous multicomponent semiconductor materials show improved photocatalytic performance due to the large and accessible pore surface area and high charge separation efficiency. Here we report the synthesis of well-ordered porous polyoxometalate (POM)-Ag2S-CdS hybrid mesostructures featuring a controllable composition and high photocatalytic activity via a two-step hard-templating and topotactic ion-exchange chemical process. Ag2S compounds and polyoxometalate cluster anions with different reduction potentials, such as PW12O403-, SiW12O404- and PMo12O403-, were employed as electron acceptors in these ternary heterojunction photocatalysts. Characterization by small-angle X-ray scattering, X-ray diffraction, transmission electron microscopy and N2 physisorption measurements showed hexagonal arrays of POM-Ag2S-CdS hybrid nanorods with large internal BET surface areas and uniform mesopores. The Keggin structure of the incorporated POM clusters was also verified by elemental X-ray spectroscopy microanalysis, infrared and diffuse-reflectance ultraviolet-visible spectroscopy. These new porous materials were implemented as visible-light-driven photocatalysts, displaying exceptional high activity in aerobic oxidation of various para-substituted benzyl alcohols to the corresponding carbonyl compounds. Our experiments show that the spatial separation of photogenerated electrons and holes at CdS through the potential gradient along the CdS-Ag2S-POM interfaces is responsible for the increased photocatalytic activity.Porous multicomponent semiconductor materials show improved photocatalytic performance due to the large and accessible pore surface area and high charge separation efficiency. Here we report the synthesis of well-ordered porous polyoxometalate (POM)-Ag2S-CdS hybrid mesostructures featuring a controllable composition and high photocatalytic activity via a two-step hard-templating and topotactic ion-exchange chemical process. Ag2S compounds and polyoxometalate cluster

  7. Self-assembly and supramolecular liquid crystals based on organic cation encapsulated polyoxometalate hybrid reverse micelles and pyridine derivatives.

    PubMed

    Yin, Shengyan; Sun, Hang; Yan, Yi; Zhang, Hui; Li, Wen; Wu, Lixin

    2011-09-15

    The controlled self-assembly of multi-components in one system represents the capability integrating intermolecular interactions and functions of components and is believed the key procedure leading to multifunctional materials finally. In pursuing this goal, we used a double-chain cationic surfactant with a benzoic acid group at the end of one tail to encapsulate Keggin-type polyanion clusters via electrostatic interaction, obtaining uniform supramolecular hybrid reverse micelles, which served as hydrogen-bonding donors. Five pyridine derivatives containing conjugated and non-conjugated groups were chosen as hydrogen-bonding acceptors to bind with reverse micelles. Through mixing with these components according to chemical stoichiometry, the hybrid reverse micelle changed to a new self-assembly precursor through intermolecular hydrogen bonding. The as-prepared reverse micelles bearing conjugated pyridine groups exhibit supramolecular liquid crystal properties, which were characterized by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The length and number of the alky chain in the pyridine derivatives, as well as the charges of polyoxometalates were also studied with regard to the liquid crystal structure. The synergistic effect of among three components was analyzed, and the liquid crystal properties could be conveniently adjusted through the modification of the hydrogen-bonding acceptor components.

  8. A fluorophosphate-based inverse Keggin structure

    SciTech Connect

    Fielden, John; Quasdorf, Kyle; Cronin, Leroy; Kogerler, Paul

    2012-07-17

    An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

  9. Reactive N-protonated isocyanate species stabilized by bis(μ-hydroxo)divanadium(IV)-substituted polyoxometalate.

    PubMed

    Uehara, Kazuhiro; Fukaya, Keisuke; Mizuno, Noritaka

    2012-07-27

    O- or N-protonated? The bis(μ-hydroxo)divanadium(IV)-substituted γ-Keggin-type polyoxometalate (see picture, left) (TBA)(4)[γ-SiV(IV)(2)W(10)O(36)(μ-OH)(4)] (TBA = tetra(n-butyl)ammonium) was synthesized and characterized by X-ray crystallography. Its reaction with phenyl isocyanate gave (TBA)(4)[γ-SiV(IV)(2)W(10)O(38)(μ-OH)(2)(PhNHCO)(2)], which contains two N-protonated phenyl isocyanate species and catalyzes the cyclotrimerization of phenyl isocyanate.

  10. Polyoxometalate ionic liquids as self-repairing acid-resistant corrosion protection.

    PubMed

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

    2014-12-01

    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.

  11. Functionalization of cotton fiber by partial etherification and self-assembly of polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework.

    PubMed

    Lange, Laura E; Obendorf, S Kay

    2015-02-25

    A combination of a Keggin-type polyoxometalate (POM), [CuPW11O39](5-), with a Cu3(BTC)2 metal-organic framework (MOF-199/HKUST-1; where BTC is benzene-1,3,5-tricarboxylate), was successfully self-assembled on a cellulose substrate (cotton) with a room-temperature process. Cotton fibers were functionalized by partial etherification. Cu3(BTC)2 metal-organic framework and polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework were self-assembled on the carboxymethylate ion sites initiated with copper nitrate using ethanol and water as solvents. Octahedral crystals were observed on both MOF-cotton and POM-MOF-cotton; both contained copper while the POM-MOF-cotton also contained tungsten. Occupancy of POM in MOF cages was calculated to be about 13%. Moisture content remained at 3 to 4 wt % similar to that of untreated cotton. Reactivity to both hydrogen sulfide and methyl parathion was higher for POM-MOF-cotton due to the Keggin polyoxometalate and the extra-framework cations Cu(2+) ions compensating the charges of the encapsulated Keggins. The POM-MOF material was found to effectively remove 0.089 mg of methyl parathion per mg of MOF from a hexane solution while MOF-cotton removed only 0.054 mg of methyl parathion per mg of MOF.

  12. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates

    SciTech Connect

    Ma Fengji; Liu Shuxia; Liang Dadong; Ren Guojian; Wei Feng; Chen Yaguang; Su Zhongmin

    2011-11-15

    The functionalization of porous metal-organic frameworks (Cu{sub 3}(BTC){sub 2}) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N{sub 2} and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols (C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs. - Graphical Abstract: The adsorption behavior of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates has been systematically evaluated. Highlights: > Functionalization of MOFs was achieved by incorporating Keggin-type POMs. > Introduction of POMs improved the thermal stability and adsorption capacity. > Alkali metal ion-exchange modified the inclusion state and also enhanced the adsorption. > Adsorption enthalpies were estimated to study the impact of POMs and alkali metal cations.

  13. Highly Amino Acid Selective Hydrolysis of Myoglobin at Aspartate Residues as Promoted by Zirconium(IV)-Substituted Polyoxometalates.

    PubMed

    Ly, Hong Giang T; Absillis, Gregory; Janssens, Rik; Proost, Paul; Parac-Vogt, Tatjana N

    2015-06-15

    SDS-PAGE/Edman degradation and HPLC MS/MS showed that zirconium(IV)-substituted Lindqvist-, Keggin-, and Wells-Dawson-type polyoxometalates (POMs) selectively hydrolyze the protein myoglobin at Asp-X peptide bonds under mildly acidic and neutral conditions. This transformation is the first example of highly sequence selective protein hydrolysis by POMs, a novel class of protein-hydrolyzing agents. The selectivity is directed by Asp residues located on the surface of the protein and is further assisted by electrostatic interactions between the negatively charged POMs and positively charged surface patches in the vicinity of the cleavage site.

  14. A highly aluminum-doped β-isomer Keggin-type tungstoaluminate.

    PubMed

    Han, Zhangang; Zhang, Huixia; Yan, Jinshuang; Zhai, Xueliang

    2016-09-28

    A trialuminum-substituted β-isomer Keggin-type tungstoaluminate was synthesized and characterized, in which the pure metal-oxygen cluster [AlW8.5Al0.5{Al(OH2)}3(OH)3O34](6.5-) consists of three kinds of aluminum sites: the central Al(1), the doped Al(5), and the substituted Al(2) and Al(3) centers. PMID:27549221

  15. Hydrothermal synthesis and characterization of the tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate: {l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}{sup 6-}

    SciTech Connect

    Liu Jian; Xu Jianing; Liu Yabing; Lu Yukun; Song Jiangfeng; Zhang Xiao; Cui Xiaobing; Xu Jiqing Wang Tiegang

    2007-12-15

    A novel polyoxometalate [Cu(phen){sub 2}]{sub 3}{l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}.4H{sub 2}O 1 (en=ethylenediamine, phen=1,10-phenanthroline) has been synthesized hydrothermally and characterized by elemental analysis, IR, XPS, TG, EPR and single-crystal X-ray diffraction analysis. The crystal structure analysis shows that compound 1 contains a novel highly reduced tri-capped and mono-supported pseudo-Keggin-type heteropolyanion, {l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}{sup 6-}, three [Cu(phen){sub 2}]{sup 2+} cations and four lattice water molecules. They are further linked to form three-dimensional supramolecular networks through extensive hydrogen bonding and {pi}-{pi} stacking interactions. Interestingly, the water dimer and terminal oxygen of the cluster polyanion constitute a beautiful supramolecular helix chain. The heteropolyanion is the first example of tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate and the pH value is crucial for obtaining compound 1 in synthetic procedure. - Graphical abstract: A novel complex [Cu(phen){sub 2}]{sub 3}{l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}.4H{sub 2}O, the first example of tri-capped and mono-supported highly reduced pseudo-Keggin-type tungstovanadophosphate was synthesized under hydrothermal condition. And the heteropolyanions are linked by water dimer and cation [Cu(phen){sub 2}]{sup 2+} through the hydrogen bond forming a three-dimensional (3D) supramolecular network. Interestingly, the water dimer and terminal oxygen of the polyanion cluster constitute a beautiful supramolecular helix chain.

  16. Charge and pressure-tuned surface patterning of surfactant-encapsulated polyoxometalate complexes at the air-water interface.

    PubMed

    Xu, Miao; Li, Haolong; Zhang, Liying; Wang, Yizhan; Yuan, Yuan; Zhang, Jianming; Wu, Lixin

    2012-10-16

    In this paper, four organic-inorganic hybrid complexes were prepared using a cationic surfactant dimethyldioctadecylammonium (DODA) to replace the counter cations of four Keggin-type polyoxometalate (POM) clusters with gradually increased negative charges, PW(12)O(40)(3-), SiW(12)O(40)(4-), BW(12)O(40)(5-), and CoW(12)O(40)(6-). The formed surfactant-encapsulated POM (SEP) complexes showed typical amphiphilic properties and can be spread onto the air-water interface to form Langmuir monolayers. The interfacial behavior of the SEP monolayer films was systemically studied by multiple in situ and ex situ characterization methods including Brewster angle microscopy (BAM), atomic force microscopy (AFM), reflection-absorption infrared (RAIR), and X-ray photoelectron spectroscopy (XPS). We found that the increasing alkyl chain density of SEPs leads to an enhanced stability and a higher collapse pressure of SEP Langmuir monolayers. Moreover, a second layer evolved as patterns from the initial monolayers of all the SEPs, when the surface pressures approached the collapse values. The rational combination of alkyl chain density and surface pressure can precisely control the size and the morphology of SEP patterns transforming from disk-like to leaf-like structures on a micrometer scale. The pattern formation was demonstrated to be driven by the self-optimized surface energy of SEP monolayers. This finding can direct a new strategy for the fabrication of POM-hybrid films with controllable patterns, which should be instructive for designing POM-based thin film devices. PMID:22991980

  17. Charge and pressure-tuned surface patterning of surfactant-encapsulated polyoxometalate complexes at the air-water interface.

    PubMed

    Xu, Miao; Li, Haolong; Zhang, Liying; Wang, Yizhan; Yuan, Yuan; Zhang, Jianming; Wu, Lixin

    2012-10-16

    In this paper, four organic-inorganic hybrid complexes were prepared using a cationic surfactant dimethyldioctadecylammonium (DODA) to replace the counter cations of four Keggin-type polyoxometalate (POM) clusters with gradually increased negative charges, PW(12)O(40)(3-), SiW(12)O(40)(4-), BW(12)O(40)(5-), and CoW(12)O(40)(6-). The formed surfactant-encapsulated POM (SEP) complexes showed typical amphiphilic properties and can be spread onto the air-water interface to form Langmuir monolayers. The interfacial behavior of the SEP monolayer films was systemically studied by multiple in situ and ex situ characterization methods including Brewster angle microscopy (BAM), atomic force microscopy (AFM), reflection-absorption infrared (RAIR), and X-ray photoelectron spectroscopy (XPS). We found that the increasing alkyl chain density of SEPs leads to an enhanced stability and a higher collapse pressure of SEP Langmuir monolayers. Moreover, a second layer evolved as patterns from the initial monolayers of all the SEPs, when the surface pressures approached the collapse values. The rational combination of alkyl chain density and surface pressure can precisely control the size and the morphology of SEP patterns transforming from disk-like to leaf-like structures on a micrometer scale. The pattern formation was demonstrated to be driven by the self-optimized surface energy of SEP monolayers. This finding can direct a new strategy for the fabrication of POM-hybrid films with controllable patterns, which should be instructive for designing POM-based thin film devices.

  18. Preparation of periodic mesoporous silica-included divacant Keggin units for the catalytic oxidation of styrene to synthesize styrene oxide

    NASA Astrophysics Data System (ADS)

    Yu, Xiaodan; Xu, Leilei; Yang, Xia; Guo, Yingna; Li, Kexin; Hu, Jianglei; Li, Wei; Ma, Fengyan; Guo, Yihang

    2008-05-01

    Periodic mesoporous composite catalysts, [( n-C 4H 9) 4N] 4[γ-SiW 10O 34(H 2O) 2]/SBA-15 (TBA-1*/SBA-15, where TBA-1* = [( n-C 4H 9) 4N] 4[γ-SiW 10O 34(H 2O) 2]), with TBA-1* loadings of 4.3-14.8% were prepared by simultaneous hydrolysis and co-condensation of the tetraethoxysilane (TEOS) in the presence of divacant Keggin-type polyoxometalate and triblock copolymer surfactant (P123) followed by hydrothermal treatment process. Structure integrity of the Keggin unit in as-prepared composites was studied by Fourier transform infrared spectroscopy (FT-IR), Raman scattering spectra, and 29Si magic-angle spinning (MAS) NMR. Periodic mesoporous structure of the composites was evaluated by low-angle X-ray powder diffraction (LXRD) patterns, nitrogen porosimetry, and transmission electron microscope (TEM) measurements. As-prepared TBA-1*/SBA-15 was used as an heterogeneous oxidation catalyst for the styrene epoxidation reaction to synthesize styrene oxide in the presence of dilute H 2O 2 (30%), and influences of solvent, molar ratio of styrene to H 2O 2, TBA-1* loading on the styrene conversion, styrene oxide yield and selectivity were considered.

  19. Synthesis of polyoxometalate-loaded epoxy composites

    DOEpatents

    Anderson, Benjamin J

    2014-10-07

    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.

  20. Classical Keggin Intercalated into Layered Double Hydroxides: Facile Preparation and Catalytic Efficiency in Knoevenagel Condensation Reactions.

    PubMed

    Jia, Yueqing; Fang, Yanjun; Zhang, Yingkui; Miras, Haralampos N; Song, Yu-Fei

    2015-10-12

    The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction.

  1. One-pot, one-step synthesis of 2,5-diformylfuran from carbohydrates over Mo-containing Keggin heteropolyacids.

    PubMed

    Liu, Yu; Zhu, Liangfang; Tang, Jinqiang; Liu, Mingyang; Cheng, Ruodi; Hu, Changwei

    2014-12-01

    In this work, a one-pot strategy for directly converting fructose into 2,5-diformylfuran (DFF) over Mo-containing Keggin heteropolyacids (HPAs) in open air is developed. H3 PMo12 O40 HPA is found to show high activity and selectivity to the formation of DFF owing to its higher Brønsted acidity and moderate redox potential. The partial substitution of the H(+) in H3 PMo12 O40 with Cs(+) leads to the heterogenization of the HPA by forming its cesium salts Csx H3-x PMo12 (x=0.5, 1.5, and 2.5). A satisfactory yield of 69.3% to DFF is obtained over Cs0.5 H2.5 PMo12 polyoxometalate after deliberate optimization of the reaction conditions. The heterogenized polyoxometalate could be recycled and reused without significant loss of catalytic activity for five runs. The produced DFF could be separated from the resulting mixture by an adsorption-desorption method using activated carbon as the adsorbent and furfural as the desorbent. A highest isolated yield of 58.2% is obtained.

  2. Correlating Acid Properties and Catalytic Function: A First-Principles Analysis of Alcohol Dehydration Pathways on Polyoxometalates

    SciTech Connect

    Janik, Michael J.; Macht, Josef; Iglesia, Enrique; Neurock, Matthew

    2009-02-05

    Density functional theory calculations and reactivity data were used to examine the mechanism of alcohol dehydration on Keggin-type polyoxometalate (POM) catalysts and the influence of the POM composition and the degree of substitution of the alcohol on kinetically relevant elimination steps. Dehydration was found to proceed through E1 pathways in which the alcohol CsO bond is cleaved heterolytically via a carbeniumion transition state. Dehydration rates were found to depend on the elimination rate constant and the equilibrium constant for the formation of unreactive alcohol dimers. E2-type elimination transition states, involving concerted CsH and CsO bond cleavage, were not found. The extent of substitution at the R-carbon on the alcohol was found to lead to marked effects on elimination barriers, because substitution increases the proton affinity of the alcohol and the stability of the carbenium-ion transition state. Changes in the central and addenda atoms of the POM cluster and the presence of n-donors, a support, vicinal POM clusters, or charge-compensating cations were found to lead to changes in the deprotonation energy (DPE) of the POM cluster, activation barriers to dehydration, and the stability of the unreactive dimer. These effects are all captured in a general linear relation between activation barriers and deprotonation energy, a rigorous measure of acid strength. The explicit dependence of the E1 activation barrier on the acid deprotonation energy is much weaker than that on reactant proton affinity. This results from the more effective compensation between the acid deprotonation energy and the interaction energy between the cationic hydrocarbon fragment and the anionic POM cluster at the transition state. The direct interactions between the POM protons and the support, other POM clusters, n-donors, base probe molecules, and charge-compensating cations increased the negative charge of the oxide shell of the W12O40 conjugate base, which increased the

  3. An unusual 3D interdigitated architecture assembled from Keggin polyoxometalates and dinuclear copper(II) complexes

    SciTech Connect

    Pang, Haijun; Yang, Ming; Kang, Lu; Ma, Huiyuan; Liu, Bo; Li, Shaobin; Liu, Heng

    2013-02-15

    A novel organic-inorganic hybrid compound, [Cu{sub 2}(bipy){sub 3}({mu}{sub 1}-H{sub 2}O){sub 2}({mu}{sub 2}-H{sub 2}O)({mu}{sub 2}-OH)(H{sub 2}BW{sub 12}O{sub 40})]{center_dot}4 H{sub 2}O (1) (bipy=4,4 Prime -bipy), has been synthesized in hydrothermal condition and characterized by elemental analysis, IR spectrum, TG analysis and single-crystal X-ray diffraction. Compound 1 possesses poly-pendant layered motifs composed of 12-tungstoborates and dinuclear copper(II) complexes, in which the mono-coordinated bipy molecules are orderly appended to both sides of the layer, respectively. Adjacent layers mutually engage in a zipper-like pattern to result in a novel 3D interdigitated architecture. The variable-temperature magnetic susceptibility of 1 showed that there existed weak antiferromagnetic interaction in 1. Toward the reduction of hydrogen peroxide, 1 has good electrocatalytic activity and remarkable stability. - A new compound has been obtained, which represents the first interdigitated architecture assembled by POMs and dinuclear copper(II) complexes. Highlights: Black-Right-Pointing-Pointer The first example of interdigitated architecture assembled by POMs and dinuclear copper(II) complexes is observed. Black-Right-Pointing-Pointer A zipper-like pattern is observed in the structure. Black-Right-Pointing-Pointer The IR, TG, XRPD, magnetism and electrochemical property of the title compound were studied.

  4. Visible-light-driven hydrogen production in a dye sensitized polyoxometalate system without noble metals

    NASA Astrophysics Data System (ADS)

    Liu, Xing; Li, Yuexiang; Peng, Shaoqin; Lai, Hua; Yi, Zhengji

    2016-05-01

    In this work, a noble-metal-free homogeneous system was constructed in one step with Keggin-type polyoxometalate (POM) SiW12O404- as a catalyst, Eosin Y as a photosensitizer, and triethanolamine (TEOA) as a sacrificial electron donor for water splitting to produce hydrogen under visible-light irradiation. A two-electron reduced heteropoly blue SiW12O406- is produced by photosensitization under visible-light irradiation. The effect of various component concentrations and POMs with different central atoms (PW12O403-, GeW12O404-, etc.) on hydrogen production was discussed. This simple system made of earth-abundant elements is expected to contribute toward the development of functional and efficient artificial photosynthetic system.

  5. Ionic liquid polyoxometalates as light emitting materials

    SciTech Connect

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

    2008-01-01

    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.

  6. Systematic Studies on 3 d- and 4 f-Metal Containing Polyoxometalates Suitable for Organic Derivatization.

    PubMed

    Artetxe, Beñat

    2016-06-01

    Premium polyoxometalates! The organic functionalization of 3 d-metalsubstituted polyoxometalates and the synthesis of new metal-oxo clusters with accessible 3 d- and 4 f-metal centers suitable for organic derivatization are discussed in this thesis. A total number of 39 compounds were structurally characterized, and their luminescent and magnetic properties analyzed. The solution behavior was studied by NMR spectroscopy, mass spectrometry, and light-scattering techniques. PMID:27551662

  7. Polymers incorporating covalently attached organoimido polyoxometalates

    DOEpatents

    Maatta, Eric A.; Moore, Aaron R.

    2004-03-16

    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.

  8. Efficient Synthesis of Ir-Polyoxometalate Cluster Using a Continuous Flow Apparatus and STM Investigation of Its Coassembly Behavior on HOPG Surface.

    PubMed

    Zhang, Junyong; Chang, Shaoqing; Suryanto, Bryan H R; Gong, Chunhua; Zeng, Xianghua; Zhao, Chuan; Zeng, Qingdao; Xie, Jingli

    2016-06-01

    Taking advantage of a continuous-flow apparatus, the iridium(III)-containing polytungstate cluster K12Na2H2[Ir2Cl8P2W20O72]·37H2O (1) was obtained in a reasonable yield (13% based on IrCl3·H2O). Compound 1 was characterized by Fourier transform IR, UV-visible, (31)P NMR, electrospray ionization mass spectrometry (ESI-MS), and thermogravimetric analysis measurements. (31)P NMR, ESI-MS, and elemental analysis all indicated 1 was a new polytungstate cluster compared with the reported K14[(IrCl4)KP2W20O72] compound. Intriguingly, the successful isolation of 1 relied on the custom-built flow apparatus, demonstrating the uniqueness of continuous-flow chemistry to achieve crystalline materials. The catalytic properties of 1 were assessed by investigating the activity on catalyzing the electro-oxidation of ruthenium tris-2,2'-bipyridine [Ru(bpy)3](2+/3+). The voltammetric behavior suggested a coupled catalytic behavior between [Ru(bpy)3](3+/2+) and 1. Furthermore, on the highly oriented pyrolytic graphite surface, 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) was used as the two-dimensional host network to coassemble cluster 1; the surface morphology was observed by scanning tunneling microscope technique. "S"-shape of 1 was observed, indicating that the cluster could be accommodated in the cavity formed by two TCDB host molecules, leading to a TCDB/cluster binary structure.

  9. Efficient Synthesis of Ir-Polyoxometalate Cluster Using a Continuous Flow Apparatus and STM Investigation of Its Coassembly Behavior on HOPG Surface.

    PubMed

    Zhang, Junyong; Chang, Shaoqing; Suryanto, Bryan H R; Gong, Chunhua; Zeng, Xianghua; Zhao, Chuan; Zeng, Qingdao; Xie, Jingli

    2016-06-01

    Taking advantage of a continuous-flow apparatus, the iridium(III)-containing polytungstate cluster K12Na2H2[Ir2Cl8P2W20O72]·37H2O (1) was obtained in a reasonable yield (13% based on IrCl3·H2O). Compound 1 was characterized by Fourier transform IR, UV-visible, (31)P NMR, electrospray ionization mass spectrometry (ESI-MS), and thermogravimetric analysis measurements. (31)P NMR, ESI-MS, and elemental analysis all indicated 1 was a new polytungstate cluster compared with the reported K14[(IrCl4)KP2W20O72] compound. Intriguingly, the successful isolation of 1 relied on the custom-built flow apparatus, demonstrating the uniqueness of continuous-flow chemistry to achieve crystalline materials. The catalytic properties of 1 were assessed by investigating the activity on catalyzing the electro-oxidation of ruthenium tris-2,2'-bipyridine [Ru(bpy)3](2+/3+). The voltammetric behavior suggested a coupled catalytic behavior between [Ru(bpy)3](3+/2+) and 1. Furthermore, on the highly oriented pyrolytic graphite surface, 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) was used as the two-dimensional host network to coassemble cluster 1; the surface morphology was observed by scanning tunneling microscope technique. "S"-shape of 1 was observed, indicating that the cluster could be accommodated in the cavity formed by two TCDB host molecules, leading to a TCDB/cluster binary structure. PMID:27163481

  10. Thermotropic liquid crystals of a non-mesogenic group bearing surfactant-encapsulated polyoxometalate complexes.

    PubMed

    Lin, Xiankun; Li, Wen; Zhang, Jing; Sun, Hang; Yan, Yi; Wu, Lixin

    2010-08-17

    A tri(ethylene oxide)octadecyldimethylammonium p-toluenesulfonate (C(18)NEO(3) x Ts) amphiphile was employed to encapsulate Keggin-type polyoxometalates by ion metathesis reactions with phosphotungstic acid, silicotungstic acid, pentapotassium dodecatungstoborate(III), and phosphomolybdic acid, giving the surfactant-encapsulated polyoxometalates (SEPs) in SEP-P, SEP-Si, SEP-B, and SEP-PMo, respectively. Meanwhile, a C(18)NEO(3) x PF(6) amphiphile was prepared by substituting the p-toluenesulfonate of C(18)NEO(3) x Ts with hexafluorophosphate. The chemical composition of all SEPs and amphiphiles was characterized through (1)H NMR, infrared spectroscopy, mass spectroscopy, elemental analysis, and thermogravimetric analysis. The thermal properties of the SEPs and the amphiphiles were investigated by differential scanning calorimetry, polarized optical microscopy, and variable-temperature X-ray diffraction. The types of anions have a remarkable influence on the thermal properties of the prepared compounds or complexes. C(18)NEO(3) x Ts displays a smectic A phase with low transition temperatures, and C(18)NEO(3) x PF(6) is a near-room-temperature ionic liquid. In contrast to the fact that SEP-Si and SEP-PMo decompose upon just reaching or before reaching the isotropic liquid state, both SEP-P and SEP-B reveal smectic B phase structures. The present results indicate that the combination of proper cationic amphiphiles and polyoxometalates can impart typical thermotropic liquid-crystalline behavior to SEPs, although no mesogenic groups are introduced into the complex systems.

  11. Two Keggin-type heteropolytungstates with transition metal as a central atom: Crystal structure and magnetic study with 2D-IR correlation spectroscopy

    SciTech Connect

    Chai, Feng; Chen, YiPing; You, ZhuChai; Xia, ZeMin; Ge, SuZhi; Sun, YanQiong; Huang, BiHua

    2013-06-01

    Two Keggin-type heteropolytungstates, [Co(phen)₃]₃[CoW₁₂O₄₀]·9H₂O 1 (phen=1,10-phenanthroline) and [Fe(phen)₃]₂[FeW₁₂O₄₀]·H₃O·H₂O 2, have been synthesized via the hydrothermal technique and characterized by single crystal X-ray diffraction analyses, IR, XPS, TG analysis, UV–DRS, XRD, thermal-dependent and magnetic-dependent 2D-COS IR (two-dimensional infrared correlation spectroscopy). Crystal structure analysis reveals that the polyanions in compound 1 are linked into 3D supramolecule through hydrogen bonding interactions between lattice water molecules and terminal oxygen atoms of polyanion units, and [Co(phen)₃]²⁺ cations distributed in the polyanion framework with many hydrogen bonding interactions. The XPS spectra indicate that all the Co atoms in 1 are +2 oxidation state, the Fe atoms in 2 existing with +2 and +3 mixed oxidation states. - Graphical abstract: The magnetic-dependent synchronous 2D correlation IR spectra of 1 (a), 2 (b) over 0–50 mT in the range of 600–1000 cm⁻¹, the obvious response indicate two Keggin polyanions skeleton susceptible to applied magnetic field. Highlights: • Two Keggin-type heteropolytungstates with transition metal as a central atom has been obtained. • Compound 1 forms into 3D supramolecular architecture through hydrogen bonding between water molecules and polyanions. • Magnetic-dependent 2D-IR correlation spectroscopy was introduced to discuss the magnetism of polyoxometalate.

  12. Two-dimensional layer architecture assembled by Keggin polyoxotungstate, Cu(II)-EDTA complex and sodium linker: Synthesis, crystal structures, and magnetic properties

    SciTech Connect

    Liu Hong; Xu Lin Gao Guanggang; Li Fengyan; Yang Yanyan; Li Zhikui; Sun Yu

    2007-05-15

    Reaction of Keggin polyoxotungstate with copper(II)-EDTA (EDTA=ethylenediamine tetraacetate) complex under mild conditions led to the formation of hybrid inorganic-organic compounds Na{sub 4}(OH)[(Cu{sub 2}EDTA)PW{sub 12}O{sub 40}].17H{sub 2}O (1) and Na{sub 4}[(Cu{sub 2}EDTA)SiW{sub 12}O{sub 40}].19H{sub 2}O (2). The single-crystal X-ray diffraction analyses reveal their two structural features: (1) one-dimensional chain structure consisting of Keggin polyoxotungstate and copper(II)-EDTA complex; (2) Two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker. The results of magnetic measurements in the temperature range 300-2 K indicated the existence of ferromagnetic exchange interactions between the Cu{sup II} ions for both compounds. In addition, TGA analysis, IR spectra, and electrochemical properties were also investigated to well characterize these two compounds. - Graphical abstract: Two new polyoxometalate-based hybrids, Na{sub 4}(OH)[Cu{sub 2}(EDTA)PW{sub 12}O{sub 40}].17H{sub 2}O (1) and Na{sub 4}[Cu{sub 2}(EDTA)SiW{sub 12}O{sub 40}].19H{sub 2}O (2), have been synthesized and structurally characterized, which consist of one-dimensional chain structure assembled by Keggin polyoxotungstate and copper(II)-EDTA complex. The chains are further connected to form two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker.

  13. Zeolitic polyoxometalate-based metal-organic frameworks (Z-POMOFs): computational evaluation of hypothetical polymorphs and the successful targeted synthesis of the redox-active Z-POMOF1.

    PubMed

    Rodriguez-Albelo, L Marleny; Ruiz-Salvador, A Rabdel; Sampieri, Alvaro; Lewis, Dewi W; Gómez, Ariel; Nohra, Brigitte; Mialane, Pierre; Marrot, Jérôme; Sécheresse, Francis; Mellot-Draznieks, Caroline; Ngo Biboum, Rosa; Keita, Bineta; Nadjo, Louis; Dolbecq, Anne

    2009-11-11

    The targeted design and simulation of a new family of zeolitic metal-organic frameworks (MOFs) based on benzenedicarboxylate (BDC) as the ligand and epsilon-type Keggin polyoxometalates (POMs) as building units, named here Z-POMOFs, have been performed. A key feature is the use of the analogy between the connectivity of silicon in dense minerals and zeolites with that of the epsilon-type Keggin POMs capped with Zn(II) ions. Handling the epsilon-Keggin as a building block, a selection of 21 zeotype structures, together with a series of dense minerals were constructed and their relative stabilities computed. Among these Z-POMOFs, the cristobalite-like structure was predicted to be the most stable structure. This prediction has been experimentally validated by the targeted synthesis of the first experimental Z-POMOF structure, which was strikingly found to possess the cristobalite topology, with three interpenetrated networks. Crystals of [NBu(4)](3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)(BDC)(2)].2H(2)O (Z-POMOF1) have been isolated under hydrothermal conditions from the reduction of ammonium heptamolybdate in the presence of phosphorous acid and Zn(II) ions. Tetrabutylammonium cations play the role of counterions and space-filling agents in this tridimensional interpenetrated framework. Moreover, the electrochemistry of the epsilon-Keggin POM is maintained and can be exploited in the insoluble Z-POMOF1 framework, as demonstrated by the electrocatalytic reduction of bromate.

  14. Keggin polyoxoanion supported organic-inorganic trinuclear lutetium cluster, {Na(H2O)3[Lu(pydc)(H2O)3]3}[SiW12O40]·26.5H2O.

    PubMed

    Li, Suzhi; Zhang, Dongdi; Guo, Yuan Yuan; Ma, Pengtao; Qiu, Xiaoyang; Wang, Jingping; Niu, Jingyang

    2012-09-01

    A novel strawberry-like organic-inorganic hybrid, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O (H(2)pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}(4+) has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.

  15. Self-Assembly of a Giant Tetrahedral 3 d-4 f Single-Molecule Magnet within a Polyoxometalate System.

    PubMed

    Ibrahim, Masooma; Mereacre, Valeriu; Leblanc, Nicolas; Wernsdorfer, Wolfgang; Anson, Christopher E; Powell, Annie K

    2015-12-14

    A giant tetrahedral heterometallic polyoxometalate (POM) [Dy30 Co8 Ge12 W108 O408 (OH)42 (OH2 )30 ](56-) , which shows single-molecule magnet (SMM) behavior, is described. This hybrid contains the largest number of 4f ions of any polyoxometalate (POM) reported to date and is the first to incorporate two different 3d-4f and 4f coordination cluster assemblies within same POM framework.

  16. Self-Assembly of a Giant Tetrahedral 3 d-4 f Single-Molecule Magnet within a Polyoxometalate System.

    PubMed

    Ibrahim, Masooma; Mereacre, Valeriu; Leblanc, Nicolas; Wernsdorfer, Wolfgang; Anson, Christopher E; Powell, Annie K

    2015-12-14

    A giant tetrahedral heterometallic polyoxometalate (POM) [Dy30 Co8 Ge12 W108 O408 (OH)42 (OH2 )30 ](56-) , which shows single-molecule magnet (SMM) behavior, is described. This hybrid contains the largest number of 4f ions of any polyoxometalate (POM) reported to date and is the first to incorporate two different 3d-4f and 4f coordination cluster assemblies within same POM framework. PMID:26390858

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

    SciTech Connect

    Tan, Chunxia; Bu, Weifeng

    2014-11-15

    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.

  18. Synthesis, crystal structure, and properties of a 1-D terbium-substituted monolacunary Keggin-type polyoxotungstate.

    PubMed

    Ma, Pengtao; Si, Yanan; Wan, Rong; Zhang, Shaowei; Wang, Jingping; Niu, Jingyang

    2015-03-01

    A new 1-D linear chainlike terbium-substituted polyoxometalate [Tb(H2O)2(α-PW11O39)](4-) (1) has been synthesized in aqueous solution and characterized by elemental analysis, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRPD), IR spectrum, thermal analysis, electrospray ionization mass spectrometry (ESI-MS), and X-ray single-crystal diffraction. X-ray structural analysis reveals that 1 displays a 1-D linear chain containing [Tb(H2O)2(α-PW11O39)](4-) moieties. The Tb(III) cation incorporated into the monolacunary Keggin-type [α-PW11O39](7-) unit resides in a distorted monocapped triangular prismatic geometry and acts as a linker to join two adjacent [α-PW11O39](7-) units to form a 1-D chain structure. Solid-state photoluminescent property of 1 has been investigated at room temperature and the photoluminescent emission mainly results from the synergistic effect of the Tb(III) cation and the Na7[α-PW11O39] precursor. The ESI-MS spectrum of 1 confirms that the polyanion [Tb(H2O)(HPW11O39)](3-) is stable in aqueous solution.

  19. Polyoxometalate (POM) Macroion Decorated Polymersomes

    NASA Astrophysics Data System (ADS)

    Jing, Benxin; Connor, Erin; Zhu, Y. Elaine

    2014-03-01

    Polymersomes as one of the common self-assembled forms of amphiphilic block copolymers have been widely developed for applications from drug delivery to mirco/nanoreactors. The tunability of their materials properties, such as mechanical strength and permeability often relies on the chemistry of the selected polymer in a liquid medium. We have recently employed the emergent polyoxometalate (POM) nanoclusters as macroions to control their interaction and assembly with different polymersomes. For both neutral and cationic polymersomes decorated with highly charged anionic POM nanoclusters, the dispersion stability and mechanic strength can be significantly enhanced. AFM and TEM characterization further confirms the encapsulation of POM macroions into polymersomes to form inorganic-organic hybrid complexes, which lead to new potential applications in anticancer and antibacterial medicines and catalysts.

  20. New Vistas for Functionalized Polyoxometalates

    SciTech Connect

    Maatta, Eric A.

    2006-04-21

    Polyoxometalates (POMs) - the multimetallic oxoanions [MxOyXz]n? formed by Mo, W, and, to a lesser extent, V, Nb and Ta ? have been described as "a class of inorganic compounds that is unmatched in terms of molecular and electronic structural versatility, reactivity, and relevance". The remarkable breadth of POM chemistry, which extends to areas as diverse as catalysis, medicine, imaging, photo- and electrochromism, and magnetic materials, derives from the confluence of the species' attractive intrinsic characteristics and their extraordinary compositional range. While many of these systems are easy to prepare, it is often difficult to modify POMs in a rational manner. Our goal is to provide for the intrinsic modifcation of POM systems so as to enable their further utility: our approach has provided many examples of fundamentally new types of polyoxometalates in which their ubiquitous oxo [O]2? ligands have been replaced by other isoelectronic entities including organoimido [N-R]2? and diazoalkane [NNCR2]2?ligands. These nitrogenous POM derivatives retain the attractive attributes typical of the class but with altered and tunable characteristics including their redox behavior and electronic absorption patterns. The organoimido and diazoalkane species provide the ability to couple remote and useful functionality via the appended substituents R. We also are now engaged in the preparation and study of nitrido-POM systems: these unprecedented inorganic complexes offer the possibility of effecting various types of nitrido-based transformations (such as nitrogen transfer) which could benefit from the superior oxidative and thermal stability of the POM ligation environment.

  1. Tungsten polyoxometalate molecules as active nodes for dynamic carrier exchange in hybrid molecular/semiconductor capacitors

    SciTech Connect

    Balliou, A.; Douvas, A. M.; Normand, P.; Argitis, P.; Glezos, N.; Tsikritzis, D.; Kennou, S.

    2014-10-14

    In this work we study the utilization of molecular transition metal oxides known as polyoxometalates (POMs), in particular the Keggin structure anions of the formula PW₁₂O₄₀³⁻, as active nodes for potential switching and/or fast writing memory applications. The active molecules are being integrated in hybrid Metal-Insulator/POM molecules-Semiconductor capacitors, which serve as prototypes allowing investigation of critical performance characteristics towards the design of more sophisticated devices. The charging ability as well as the electronic structure of the molecular layer is probed by means of electrical characterization, namely, capacitance-voltage and current-voltage measurements, as well as transient capacitance measurements, C (t), under step voltage polarization. It is argued that the transient current peaks observed are manifestations of dynamic carrier exchange between the gate electrode and specific molecular levels, while the transient C (t) curves under conditions of molecular charging can supply information for the rate of change of the charge that is being trapped and de-trapped within the molecular layer. Structural characterization via surface and cross sectional scanning electron microscopy as well as atomic force microscopy, spectroscopic ellipsometry, UV and Fourier-transform IR spectroscopies, UPS, and XPS contribute to the extraction of accurate electronic structure characteristics and open the path for the design of new devices with on-demand tuning of their interfacial properties via the controlled preparation of the POM layer.

  2. Efficient water oxidation at carbon nanotube-polyoxometalate electrocatalytic interfaces.

    PubMed

    Toma, Francesca M; Sartorel, Andrea; Iurlo, Matteo; Carraro, Mauro; Parisse, Pietro; Maccato, Chiara; Rapino, Stefania; Gonzalez, Benito Rodriguez; Amenitsch, Heinz; Da Ros, Tatiana; Casalis, Loredana; Goldoni, Andrea; Marcaccio, Massimo; Scorrano, Gianfranco; Scoles, Giacinto; Paolucci, Francesco; Prato, Maurizio; Bonchio, Marcella

    2010-10-01

    Water is the renewable, bulk chemical that nature uses to enable carbohydrate production from carbon dioxide. The dream goal of energy research is to transpose this incredibly efficient process and make an artificial device whereby the catalytic splitting of water is finalized to give a continuous production of oxygen and hydrogen. Success in this task would guarantee the generation of hydrogen as a carbon-free fuel to satisfy our energy demands at no environmental cost. Here we show that very efficient and stable nanostructured, oxygen-evolving anodes are obtained by the assembly of an oxygen-evolving polyoxometalate cluster (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes. Our bioinspired electrode addresses the one major challenge of artificial photosynthesis, namely efficient water oxidation, which brings us closer to being able to power the planet with carbon-free fuels.

  3. Computational insight into the initial steps of the Mars-van Krevelen mechanism: electron transfer and surface defects in the reduction of polyoxometalates.

    PubMed

    Efremenko, Irena; Neumann, Ronny

    2012-12-26

    Metal oxides as a rule oxidize and oxygenate substrates via the Mars-van Krevelen mechanism. A well-defined α-Keggin polyoxometalate, H(5)PV(2)Mo(10)O(40), can be viewed as an analogue of discrete structure that reacts via the Mars-van Krevelen mechanism both in solution and in the gas phase. Guided by previous experimental observations, we have studied the key intermediates on the reaction pathways of its reduction by various compounds using high-level DFT calculations. These redox reactions of polyoxometalates require protons, and thus such complexes were explicitly considered. First, the energetics of outer-sphere proton and electron transfer as well as coupled proton and electron transfer were calculated for seven substrates. This was followed by identification of possible key intermediates on the subsequent reaction pathways that feature displacement of the metal atom from the Keggin structure and coordinatively unsaturated sites on the H(5)PV(2)Mo(10)O(40) surface. Such metal defects are favored at vanadium sites. For strong reducing agents the initial outer-sphere electron transfer, alone or possibly coupled with proton transfer, facilitates formation of metal defects. Subsequent coordination allows for formation of reactive ensembles on the catalyst surface, for which the selective oxygen-transfer step becomes feasible. Weak reducing agents do not facilitate defect formation by outer-sphere electron and/or proton transfers, and thus formation of metal defect structures prior to the substrate activation is suggested as an initial step. Calculated geometries and energies of metal defect structures support experimentally observed intermediates and demonstrate the complex nature of the Mars-van Krevelen mechanism.

  4. Polyoxometalates--potent and selective ecto-nucleotidase inhibitors.

    PubMed

    Lee, Sang-Yong; Fiene, Amelie; Li, Wenjin; Hanck, Theodor; Brylev, Konstantin A; Fedorov, Vladimir E; Lecka, Joanna; Haider, Ali; Pietzsch, Hans-Jürgen; Zimmermann, Herbert; Sévigny, Jean; Kortz, Ulrich; Stephan, Holger; Müller, Christa E

    2015-01-15

    Polyoxometalates (POMs) are inorganic cluster metal complexes that possess versatile biological activities, including antibacterial, anticancer, antidiabetic, and antiviral effects. Their mechanisms of action at the molecular level are largely unknown. However, it has been suggested that the inhibition of several enzyme families (e.g., phosphatases, protein kinases or ecto-nucleotidases) by POMs may contribute to their pharmacological properties. Ecto-nucleotidases are cell membrane-bound or secreted glycoproteins involved in the hydrolysis of extracellular nucleotides thereby regulating purinergic (and pyrimidinergic) signaling. They comprise four distinct families: ecto-nucleoside triphosphate diphosphohydrolases (NTPDases), ecto-nucleotide pyrophosphatases/phosphodiesterases (NPPs), alkaline phosphatases (APs) and ecto-5'-nucleotidase (eN). In the present study, we evaluated the inhibitory potency of a series of polyoxometalates as well as chalcogenide hexarhenium cluster complexes at a broad range of ecto-nucleotidases. [Co4(H2O)2(PW9O34)2](10-) (5, PSB-POM142) was discovered to be the most potent inhibitor of human NTPDase1 described so far (Ki: 3.88 nM). Other investigated POMs selectively inhibited human NPP1, [TiW11CoO40](8-) (4, PSB-POM141, Ki: 1.46 nM) and [NaSb9W21O86](18-) (6, PSB-POM143, Ki: 4.98 nM) representing the most potent and selective human NPP1 inhibitors described to date. [NaP5W30O110](14-) (8, PSB-POM144) strongly inhibited NTPDase1-3 and NPP1 and may therefore be used as a pan-inhibitor to block ATP hydrolysis. The polyoxoanionic compounds displayed a non-competitive mechanism of inhibition of NPPs and eN, but appeared to be competitive inhibitors of TNAP. Future in vivo studies with selected inhibitors identified in the current study are warranted. PMID:25449596

  5. Immobilization of Polyoxometalate in the Metal-Organic Framework rht-MOF-1: Towards a Highly Effective Heterogeneous Catalyst and Dye Scavenger.

    PubMed

    Sun, Jing-Wen; Yan, Peng-Fei; An, Guang-Hui; Sha, Jing-Quan; Li, Guang-Ming; Yang, Guo-Yu

    2016-01-01

    A series of three remarkable complexes [PMo12O40]@[Cu6O(TZI)3(H2O)9]4·OH·31H2O (H3TZI = 5-tetrazolylisophthalic acid; denoted as HLJU-1, HLJU = Heilongjiang University), [SiMo12O40]@[Cu6O(TZI)3(H2O)9]4·32H2O (denoted as HLJU-2), and [PW12O40]@[Cu6O(TZI)3(H2O)6]4·OH·31H2O (denoted as HLJU-3) have been isolated by using simple one-step solvothermal reaction of copper chloride, 5-tetrazolylisophthalic acid (H3TZI), and various Keggin-type polyoxometalates (POMs), respectively. Crystal analysis of HLJU 1-3 reveals that Keggin-type polyoxoanions have been fitted snuggly in the cages of rht-MOF-1 (MOF: metal-organic framework) with large cell volume in a range of 87968-88800 Å(3) and large pore volume of about 68%. HLJU 1-3 exhibit unique catalytic selectivity and reactivity in the oxidation of alkylbenzene with environmental benign oxidant under mild condition in aqueous phase as well as the uptake capacity towards organic pollutants in aqueous solution. PMID:27157290

  6. Immobilization of Polyoxometalate in the Metal-Organic Framework rht-MOF-1: Towards a Highly Effective Heterogeneous Catalyst and Dye Scavenger

    PubMed Central

    Sun, Jing-Wen; Yan, Peng-Fei; An, Guang-Hui; Sha, Jing-Quan; Li, Guang-Ming; Yang, Guo-Yu

    2016-01-01

    A series of three remarkable complexes [PMo12O40]@[Cu6O(TZI)3(H2O)9]4·OH·31H2O (H3TZI = 5-tetrazolylisophthalic acid; denoted as HLJU-1, HLJU = Heilongjiang University), [SiMo12O40]@[Cu6O(TZI)3(H2O)9]4·32H2O (denoted as HLJU-2), and [PW12O40]@[Cu6O(TZI)3(H2O)6]4·OH·31H2O (denoted as HLJU-3) have been isolated by using simple one-step solvothermal reaction of copper chloride, 5-tetrazolylisophthalic acid (H3TZI), and various Keggin-type polyoxometalates (POMs), respectively. Crystal analysis of HLJU 1−3 reveals that Keggin-type polyoxoanions have been fitted snuggly in the cages of rht-MOF-1 (MOF: metal−organic framework) with large cell volume in a range of 87968−88800 Å3 and large pore volume of about 68%. HLJU 1–3 exhibit unique catalytic selectivity and reactivity in the oxidation of alkylbenzene with environmental benign oxidant under mild condition in aqueous phase as well as the uptake capacity towards organic pollutants in aqueous solution. PMID:27157290

  7. Immobilization of Polyoxometalate in the Metal-Organic Framework rht-MOF-1: Towards a Highly Effective Heterogeneous Catalyst and Dye Scavenger

    NASA Astrophysics Data System (ADS)

    Sun, Jing-Wen; Yan, Peng-Fei; An, Guang-Hui; Sha, Jing-Quan; Li, Guang-Ming; Yang, Guo-Yu

    2016-05-01

    A series of three remarkable complexes [PMo12O40]@[Cu6O(TZI)3(H2O)9]4·OH·31H2O (H3TZI = 5-tetrazolylisophthalic acid; denoted as HLJU-1, HLJU = Heilongjiang University), [SiMo12O40]@[Cu6O(TZI)3(H2O)9]4·32H2O (denoted as HLJU-2), and [PW12O40]@[Cu6O(TZI)3(H2O)6]4·OH·31H2O (denoted as HLJU-3) have been isolated by using simple one-step solvothermal reaction of copper chloride, 5-tetrazolylisophthalic acid (H3TZI), and various Keggin-type polyoxometalates (POMs), respectively. Crystal analysis of HLJU 1‑3 reveals that Keggin-type polyoxoanions have been fitted snuggly in the cages of rht-MOF-1 (MOF: metal‑organic framework) with large cell volume in a range of 87968‑88800 Å3 and large pore volume of about 68%. HLJU 1–3 exhibit unique catalytic selectivity and reactivity in the oxidation of alkylbenzene with environmental benign oxidant under mild condition in aqueous phase as well as the uptake capacity towards organic pollutants in aqueous solution.

  8. Breaking symmetry: spontaneous resolution of a polyoxometalate.

    PubMed

    Hou, Yu; Fang, Xikui; Hill, Craig L

    2007-01-01

    A chiral polyoxometalate [Hf(PW11O39)2]10- (1) has been prepared and structurally characterized. It crystallizes in the chiral space group P2(1)2(1)2, as a conglomerate of two enantiomerically pure crystals in the absence of any chiral source. The absolute configuration of 1 was determined from the Flack parameter by X-ray crystallography. The structure of 1 comprises two lacunary [PW11O39]7- units, each functioning as a tetra-dentate ligand sandwiching an 8-coordinate HfIV centre in a distorted square antiprismatic geometry. Optically active crystals of both enantiomers were spectroscopically distinguishable by means of solid state circular dichroism spectroscopy. This hafnium-substituted polyoxometalate (POM), 1, shows that spontaneous chiral resolution, a rare phenomenon, can be operable in POM systems.

  9. Interaction between Mo132 nanocluster polyoxometalate and solvents

    NASA Astrophysics Data System (ADS)

    Ostroushko, A. A.; Safronov, A. P.; Tonkushina, M. O.; Korotaev, V. Yu.; Barkov, A. Yu.

    2014-12-01

    The interaction between solid Mo132 nanocluster polyoxometalate with the structure of a keplerate and solvents of different natures (e.g., water, alcohols, hexane, and tetrachloromethane) is studied thermochemically. NMR spectroscopy is used to analyze interactions in solid polyoxometalate-organic compound systems in a gaseous medium. Data are collected on sorption interactions between a Mo132 nanocluster and camphor.

  10. Unprecedented χ isomers of single-side triol-functionalized Anderson polyoxometalates and their proton-controlled isomer transformation.

    PubMed

    Zhang, Jiangwei; Liu, Zhenhua; Huang, Yichao; zhang, Jin; Hao, Jian; Wei, Yongge

    2015-06-01

    The μ2-O atom in Anderson polyoxometalates was regioselectively activated by the introduction of protons, which, upon functionalization with triol ligands, could afford a series of unique χ isomers of the organically-derived Anderson cluster {[RCC(CH2O)3]MMo6O18(OH)3}(3-). Herein proton-controlled isomer transformation between the δ and χ isomer was observed by using the fingerprint region in the IR spectra and (13)C NMR spectra.

  11. Reversible proton-switchable fluorescence controlled by conjugation effect in an organically-functionalized polyoxometalate

    PubMed Central

    Lv, Chunlin; Chen, Kun; Hu, Junjie; Zhang, Jin; Khan, Rao Naumaan Nasim; Wei, Yongge

    2016-01-01

    A novel monosubstituted organoimido hexamolybdate containing 6-nitroquinoline moiety has been successfully synthesized. This organically-functionalized polyoxometalate exhibits proton-induced switchable fluorescence property in aqueous acetonitrile solution at room temperature. Experimental and theoretical investigations of this reversible “on” and “off” switching mechanism have been carried out, and it is found that the protonation and deprotonation at the heterocyclic nitrogen atom within quinoline fragment leads to the breaking and reformation of the conjugation through strong d-π interaction between the hexamolybdate anionic cluster and the quinoline moiety, resulting in “on” and “off” luminescence signal. PMID:27321576

  12. Pharmacokinetics of antiviral polyoxometalates in rats.

    PubMed Central

    Ni, L; Boudinot, F D; Boudinot, S G; Henson, G W; Bossard, G E; Martellucci, S A; Ash, P W; Fricker, S P; Darkes, M C; Theobald, B R

    1994-01-01

    Polyoxometalates are soluble mineral compounds formed principally of oxide anions and early transition metal cations. The polyoxometalates K12H2[P2W12O48].24H2O (JM 1591), K10[P2W18Zn4(H2O)2O68].20H2O (JM 1596), and [(CH3)3NH]8[Si2W18Nb6O77] (JM 2820) demonstrate potent antiviral activity against human immunodeficiency virus types 1 and 2, herpes simplex virus, and cytomegalovirus in vitro. The preclinical pharmacokinetics of these three compounds were characterized after single-dose intravenous administration of 50 mg/kg to rats. Plasma, urine, and feces were collected for 168 h, and polyoxometalate concentrations were determined by atomic emission. Serum protein binding was measured by equilibrium dialysis. All three compounds were highly bound to serum proteins in a concentration-dependent manner. Total and unbound concentrations of the three compounds in plasma declined in a triexponential manner with terminal half-lives of 246.0 +/- 127.0, 438.4 +/- 129.4, and 32.2 +/- 5.37 h (mean +/- standard deviation) for JM 1591, JM 1596, and JM 2820, respectively. Systemic clearances based on total concentrations in plasma were low, averaging 0.016 +/- 0.002, 0.015 +/- 0.002, and 0.018 +/- 0.003 liter/h/kg for JM 1591, JM 1596, and JM 2820, respectively. The clearances of unbound compounds from plasma averaged 0.966 +/- 0.136, 0.050 +/- 0.005, and 0.901 +/- 0.165 liter/h/kg for JM 1591, JM 1596, and JM 2820, respectively. For JM 1596, the clearance of unbound compound from the kidneys was lower than the glomerular filtration rate (0.086 liter/h/kg), suggesting this polyoxometalate underwent renal tubular reabsorption. However, JM 1591 and JM 2820 appeared to undergo tubular secretion. The fraction of the dose recovered in urine was 11.5, 46.8, and 10.6% for JM 1591, JM 1596, and JM 2820, respectively. Approximately 5% of the dose of each polyoxometalate was recovered in feces. The steady-state volume of distribution based on total concentrations averaged 1.44 liters

  13. Charge retention of soft-landed phosphotungstate Keggin anions on self-assembled monolayers.

    PubMed

    Gunaratne, K Don D; Prabhakaran, Venkateshkumar; Andersen, Amity; Johnson, Grant E; Laskin, Julia

    2016-04-01

    Soft landing of mass-selected ions onto surfaces often results in partial loss of charge that may affect the structure and reactivity of deposited species. In this study, Keggin phosphotungstate anions in two selected charge states, PW12O40(3-) (WPOM(3-)) and PW12O40(2-) (WPOM(2-)), were soft-landed onto different self-assembled monolayer (SAM) surfaces and examined using in situ infrared reflection absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. Partial retention of the 3- charge was observed when WPOM(3-) was soft-landed onto the fluorinated SAM (FSAM), while the charge state distribution was dominated by the 2- charge after both WPOM(3-) and WPOM(2-) were deposited onto a hydrophilic alkylthiol SAM terminated with cationic NH3(+) functional groups (NH3(+)SAM). We found that during the course of the soft landing of WPOM(3-), the relative abundance of WPOM(3-) on FSAM decreased while that of WPOM(2-) increased. We propose that the higher stability of immobilized WPOM(2-) in comparison with WPOM(3-) makes it the preferred charge state of WPOM on both the FSAM and NH3(+)SAM. We also observe weaker binding of WPOM anions to SAMs in comparison with phosphomolybdate ions (MoPOM) reported previously (J. Phys. Chem. C, 2014, 118, 27611-27622). The weaker binding of WPOM to SAMs is attributed to the lower reactivity of WPOM reported in the literature. This study demonstrates that both the charge retention and the reactivity of deposited anionic POM clusters on surfaces are determined by the type of addenda metal atoms in the cluster. PMID:26966731

  14. Novel Polyoxometalate Containing Membranes for PEM Fuel Cells

    SciTech Connect

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

    2009-03-01

    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.

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

    SciTech Connect

    Yan, Jinshuang; Zhao, Xiaofang; Huang, Jiao; Gong, Kaining; Han, Zhangang Zhai, Xueliang

    2014-03-15

    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.

  16. Bridging the opposite chemistries of tantalum and tungsten polyoxometalates.

    PubMed

    Molina, P I; Sures, D J; Miró, P; Zakharov, L N; Nyman, M

    2015-09-28

    The disparate solubility, redox activity, and pH stability of the group V and group VI polyoxometalates (POMs) confer very different functionality on these species, and tailoring cluster properties by varying the ratio of group V to group VI metals poses both an opportunity and a synthetic challenge. A classic series of studies reported over 40 years ago provided some insight into W/Nb POMs, from which researchers have built on to date. However, the analogous W/Ta series has never been addressed in a systematic manner. Three members of this W/Ta series are presented here, synthesized from simple oxo- and peroxocoltanate precursors. [Ta3W3O19](5-) displays the Lindqvist-type structure, while [TaW9O32](5-) and [Ta2W8O32](6-) are isostructural with decatungstate ([W10O32](4-)). Additionally, the use of peroxoniobate instead of hexaniobate as the starting material drives the formation of the decatungstate-type structure [NbW9O32](5-) instead of the Lindqvist ion that was established to be the foundational cluster geometry in prior work. The electronic structure of the Nb/Ta substituted decatungstates is directly related to the degree of substitution inasmuch as the HOMO-LUMO energy gap (Egap) slightly increases as more Nb/Ta atoms are incorporated into the structure. The poor mixing of the d-orbitals of Nb/Ta and W is responsible for the observed trends in the UV spectra and cyclic voltammetry. Moreover, the stability of the molecular frameworks in the gas phase is also related to the extent of substitution as revealed by electrospray mass-spectrometry (ESI-MS). PMID:26262676

  17. Gas-Phase Fragmentation Pathways of Mixed-Addenda Keggin Anions: PMo12-nWnO403- (n = 0-12)

    SciTech Connect

    Gunaratne, Kalupathirannehelage Don D.; Prabhakaran, Venkateshkumar; Johnson, Grant E.; Laskin, Julia

    2015-06-01

    We report a collision-induced dissociation (CID) investigation of the mixed addenda polyoxometalate (POM) anions, PMo12-nWnO403- (n = 0-12). The anions were generated in solution using a straightforward single-step synthesis approach and introduced into the gas phase by electrospray ionization (ESI). Distinct differences in fragmentation patterns were observed for the range of mixed POMs examined in this study. CID of molybdenum-rich anions, PMo12- nWnO403- (n = 0-2), generates an abundant doubly charged fragment containing seven metal atoms (M) and twenty-two oxygen atoms (M7O222-) and its complementary singly charged PM5O18- ion, while the Lindqvist anion, (M6O192-) and its complementary PM6O21- ion are the dominant fragments of Keggin POMs containing more than two tungsten atoms, PMo12-nWnO403- (n = 3-12). The observed transition in the dissociation pathways with an increase in the number of W atoms may be attributed to the higher stability of tungsten-rich anions towards isomerization. We find that the observed distribution of Mo and W atoms in the major M6O192- and M7O222- fragment ions is different from that predicted by a random distribution indicating substantial segregation of the addenda metal atoms in the POMs. Electron detachment from the triply charged precursor anion resulting in formation of doubly charged anions is observed. This is a dominant dissociation pathway for mixed POMs having a majority (8-11) of W atoms and a minor channel for other precursors indicating a close competition between fragmentation and electron detachment pathways of POM anions.

  18. A nanosized {Ag@Ag12} "molecular windmill" templated by polyoxometalates anions.

    PubMed

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

    2014-11-01

    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.

  19. Hybrid microtubes of polyoxometalate and fluorescence dye with tunable photoluminescence.

    PubMed

    Zhang, Huanqiu; Peng, Jun; Shen, Yan; Yu, Xia; Zhang, Fang; Mei, Jilan; Li, Bin; Zhang, Liming

    2012-05-11

    Fluorescent microtubes based on α-Keggin tungstosilicate and fluorescein (SiW(12)-F) have been obtained by using a simple method, which present tunable photoluminescence from sky blue to green to red by variation of excitation light. The SiW(12) component can inhibit photobleaching of fluorescein.

  20. Supramolecular organization in organic-inorganic heterogeneous hybrid catalysts formed from polyoxometalate and poly(ampholyte) polymer.

    PubMed

    Raj, Gijo; Swalus, Colas; Guillet, Alain; Devillers, Michel; Nysten, Bernard; Gaigneaux, Eric M

    2013-04-01

    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. PMID:23480273

  1. Supramolecular organization in organic-inorganic heterogeneous hybrid catalysts formed from polyoxometalate and poly(ampholyte) polymer.

    PubMed

    Raj, Gijo; Swalus, Colas; Guillet, Alain; Devillers, Michel; Nysten, Bernard; Gaigneaux, Eric M

    2013-04-01

    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. Controlling the Charge State and Redox Properties of Supported Polyoxometalates via Soft Landing of Mass Selected Ions

    SciTech Connect

    Gunaratne, Kalupathirannehelage Don D.; Johnson, Grant E.; Andersen, Amity; Du, Dan; Zhang, Weiying; Prabhakaran, Venkateshkumar; Lin, Yuehe; Laskin, Julia

    2014-12-04

    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.

  3. Nature of Zr-monosubstituted monomeric and dimeric polyoxometalates in water solution at different pH conditions: static density functional theory calculations and dynamic simulations.

    PubMed

    Jiménez-Lozano, Pablo; Carbó, Jorge J; Chaumont, Alain; Poblet, Josep M; Rodríguez-Fortea, Antonio; Wipff, Georges

    2014-01-21

    Static density functional theory (DFT) calculations with a continuous solvent model as well as classical and Car-Parrinello molecular dynamics (MD) simulations with explicit solvent molecules were performed to study the nature of Zr-monosubstituted monomeric and dimeric polyoxometalates (POMs) in water at different pHs. We have analyzed Zr-aqua, -hydroxo, and -aqua-hydroxo species derived from Linqvist- and Keggin-type anions. Both DFT and Car-Parrinello MD methods suggest that the Zr center tends to have coordination number greater than 6 and can bind up to 3 water molecules. Car-Parrinello MD simulations also show that the Zr atom fluctuates within the oxide POM framework, providing a flexible coordination environment. There is a small thermodynamic preference for the Zr-aqua species over the protonated Zr-hydroxo species; however the prevalence of one or the other species might depend on the pH. Classical MD simulations show that H3O(+) interacts mainly with hydroxo ligand, while OH(-) anions prefer the protons of the H2O ligands. In general, an increase of the acidity favors the formation of Zr-aqua species, explaining why dimer dissociation is promoted at low pH. At basic conditions Zr-hydroxo species are generated, providing the reactive groups to form Zr···Zr linkages. PMID:24364825

  4. Differentiation of stem cells into insulin-producing cells under the influence of nanostructural polyoxometalates.

    PubMed

    Bâlici, Ştefana; Şuşman, Sergiu; Rusu, Dan; Nicula, Gheorghe Zsolt; Soriţău, Olga; Rusu, Mariana; Biris, Alexandru S; Matei, Horea

    2016-03-01

    Two polyoxometalates (POMs) with W were synthesized by a two-step, self-assembling method. They were used for stimulation of mesenchymal stem cell differentiation into insulin-producing cells. The nanocompounds (tris(vanadyl)-substituted tungsto-antimonate(III) anions [POM1] and tris-butyltin-21-tungsto-9-antimonate(III) anions [POM2]) were characterized by analytical techniques, including ultraviolet-visible, Fourier transform infrared, nuclear magnetic resonance spectroscopy, and transmission electron microscopy. We found that these polyoxotungstates, with 2-4 nm diameters, did not present toxic effects at the tested concentrations. In vitro, POM1 stimulated differentiation of a greater number of dithizone-positive cells (also organized in clusters) than the second nanocompound (POM2). Based on our in vitro studies, we have concluded that both the POMs tested had significant biological activity acting as active stimuli for differentiation of stem cells into insulin-producing cells. PMID:26397720

  5. Immobilization of polyoxometalates in crystalline solids for highly efficient heterogeneous catalysis.

    PubMed

    Ye, Ji-Jie; Wu, Chuan-De

    2016-06-21

    Polyoxometalates (POMs) are a unique class of molecular metal-oxygen clusters with attractive architecture and tunable properties. Due to their strong acidity, redox chemistry, photoactivity, charge distribution and multielectron transformation, POMs have been used as efficient catalysts in a variety of chemical reactions. To meet the requirement of sustainable chemistry, great effort has been focused on immobilization of the active POMs on different solid supports to realize heterogeneous catalysis. This short review summarizes the recent progress on immobilization of POM moieties in crystalline solids with defined crystal structures, including organic-inorganic hybrid materials, POM-based inorganic crystalline solids and POM-encapsulated metal-organic frameworks (POM@MOFs), and their catalytic properties in oxidation, hydrolysis, cyanosilylation, photocatalysis and electrocatalysis. As illustrated in the text, these crystalline solids exhibit interesting catalytic properties, such as high activity, stability and selectivity, and simple recovery and easy recycling, which are much superior to those of the corresponding constituent species in most cases.

  6. Multifunctional radical-doped polyoxometalate-based host-guest material: photochromism and photocatalytic activity.

    PubMed

    Liao, Jian-Zhen; Zhang, Hai-Long; Wang, Sa-Sa; Yong, Jian-Ping; Wu, Xiao-Yuan; Yu, Rongmin; Lu, Can-Zhong

    2015-05-01

    An effective strategy to synthesize multifunctional materials is the incorporation of functional organic moieties and metal oxide clusters via self-assembly. A rare multifunctional radical-doped zinc-based host-guest crystalline material was synthesized with a fast-responsive reversible ultraviolet visible light photochromism, photocontrolled tunable luminescence, and highly selective photocatalytic oxidation of benzylic alcohols as a result of blending of distinctively different functional components, naphthalenediimide tectons, and polyoxometalates (POMs). It is highly unique to link π-electron-deficient organic tectons and POMs by unusual POMs anion-π interactions, which are not only conducive to keeping the independence of each component but also effectively promoting the charge transfer or exchange among the components to realize the fast-responsive photochromism, photocontrolled tunable luminescence, and photocatalytic activity.

  7. Dye-sensitized polyoxometalate for visible-light-driven photoelectrochemical cells.

    PubMed

    Gao, Junkuo; Miao, Jianwei; Li, Yongxin; Ganguly, Rakesh; Zhao, Yang; Lev, Ovadia; Liu, Bin; Zhang, Qichun

    2015-08-28

    A simple and facile one-step method for the synthesis of an organic dye-functionalized polyoxometalate (POM) hybrid with visible-light photo-response was reported. The POM hybrid was fully characterized via single crystal XRD, powder XRD, FTIR and elemental analysis. The reaction of the organic dye with inorganic salts gave the dye-functionalized POM (MoBB3), in which the POM cluster was formed in situ. The electronic absorption peak of this hybrid was successfully extended beyond 680 nm. Photoelectrochemical measurement indicated that MoBB3 was photoresponsive under visible-light illumination, suggesting that it is an n-type (electron conductive) semiconducting material. This result might offer a method for the design of novel organic dye-functionalized POMs for photoelectric applications.

  8. Dye-sensitized polyoxometalate for visible-light-driven photoelectrochemical cells.

    PubMed

    Gao, Junkuo; Miao, Jianwei; Li, Yongxin; Ganguly, Rakesh; Zhao, Yang; Lev, Ovadia; Liu, Bin; Zhang, Qichun

    2015-08-28

    A simple and facile one-step method for the synthesis of an organic dye-functionalized polyoxometalate (POM) hybrid with visible-light photo-response was reported. The POM hybrid was fully characterized via single crystal XRD, powder XRD, FTIR and elemental analysis. The reaction of the organic dye with inorganic salts gave the dye-functionalized POM (MoBB3), in which the POM cluster was formed in situ. The electronic absorption peak of this hybrid was successfully extended beyond 680 nm. Photoelectrochemical measurement indicated that MoBB3 was photoresponsive under visible-light illumination, suggesting that it is an n-type (electron conductive) semiconducting material. This result might offer a method for the design of novel organic dye-functionalized POMs for photoelectric applications. PMID:26200796

  9. Multifunctional radical-doped polyoxometalate-based host-guest material: photochromism and photocatalytic activity.

    PubMed

    Liao, Jian-Zhen; Zhang, Hai-Long; Wang, Sa-Sa; Yong, Jian-Ping; Wu, Xiao-Yuan; Yu, Rongmin; Lu, Can-Zhong

    2015-05-01

    An effective strategy to synthesize multifunctional materials is the incorporation of functional organic moieties and metal oxide clusters via self-assembly. A rare multifunctional radical-doped zinc-based host-guest crystalline material was synthesized with a fast-responsive reversible ultraviolet visible light photochromism, photocontrolled tunable luminescence, and highly selective photocatalytic oxidation of benzylic alcohols as a result of blending of distinctively different functional components, naphthalenediimide tectons, and polyoxometalates (POMs). It is highly unique to link π-electron-deficient organic tectons and POMs by unusual POMs anion-π interactions, which are not only conducive to keeping the independence of each component but also effectively promoting the charge transfer or exchange among the components to realize the fast-responsive photochromism, photocontrolled tunable luminescence, and photocatalytic activity. PMID:25859742

  10. A dodecanuclear Zn cluster sandwiched by polyoxometalate ligands.

    PubMed

    Zhu, Guibo; Geletii, Yurii V; Zhao, Chongchao; Musaev, Djamaladdin G; Song, Jie; Hill, Craig L

    2012-09-01

    A dodecazinc silicotungstate K(20)Na(2)[Zn(6)(OH)(7)(H(2)O)(Si(2)W(18)O(66))](2)·34H(2)O (1) has been synthesized and characterized by X-ray crystallography, elemental analysis, infrared, UV-vis spectroscopy, cyclic voltammetry, acid-base titration, and DFT calculations. The twelve zinc atoms between the two [Si(2)W(18)O(66)](16-) frameworks make this complex more stable hydrolytically than the heteropolytungstate ligands, [Si(2)W(18)O(66)](16-), themselves. The structurally unique central Zn(12) core is formed by the fusion of two [Zn(6)(OH)(7)(H(2)O)](5+) units through two edge-sharing Zn6 atoms. DFT B3LYP calculations give HOMO-LUMO and (HOMO - 1)-LUMO energy gaps of ∼3.65 and 3.91 eV, respectively, as compared to the band gap in ZnO of 3.35 eV. PMID:22825397

  11. Nucleophilic substitution reaction for post-functionalization of polyoxometalates

    SciTech Connect

    Yin, Panchao; Li, Qiang; Zhang, Jin; Wang, Longsheng; Hao, Jian; Wei, Yongge

    2015-07-06

    In this study, a hexamolybdate-based organic inorganic hybrid molecule containing a chloralkane fragment is synthesized and its Cl atom can be substituted by iodine and nitrate through nucleophilic substitution reactions in high yields, which provide a post-functionalization protocol to bring in various additional functional groups into polyoxometalate-based hybrid materials under mild conditions.

  12. An all-inorganic polyoxometalate-polyoxocation chemical garden.

    PubMed

    Points, Laurie J; Cooper, Geoffrey J T; Dolbecq, Anne; Mialane, Pierre; Cronin, Leroy

    2016-01-31

    Herein, we show it is possible to produce wholly inorganic chemical gardens from a cationic polyoxometalate (POM) seed in an anionic POM solution, demonstrating a wholly POM-based chemical garden system that produces architectures over a wide concentration range. Six concentration dependent growth regimes have been discovered and characterized: clouds, membranes, slugs, tubes, jetting and budding.

  13. A functional mesoporous ionic crystal based on polyoxometalate.

    PubMed

    Kawahara, Ryosuke; Niinomi, Kazuma; Kondo, Junko N; Hibino, Mitsuhiro; Mizuno, Noritaka; Uchida, Sayaka

    2016-02-21

    A mesoporous ionic crystal is synthesized with a polyoxometalate and a macrocation with polar cyano groups. The compound possesses one-dimensional mesopores with an opening of 3.0 × 2.0 nm. The compound shows high proton conductivity and catalytic activity, which are due to the water molecules in the mesopores. PMID:26804446

  14. Open framework complex constructed from polyoxometalate and dinuclear Cu phenanthroline

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Peng, Jun; Liu, Hongsheng; Zhu, Dongxia; Tian, Aixiang; Wang, Lixia

    2008-12-01

    An inorganic-organic hybrid complex, {[Cu 2(phen) 2(OH) 2(H 2O)] 2[α-SiW 12O 40]}·8H 2O 1, (phen = 1,10-phenanthroline), has been synthesized under mild reaction conditions and characterized by single-crystal X-ray diffraction, IR spectrum, thermal analyses (TG-DTA) and fluorescent measurement. The crystallographic analysis reveals that in the compound, the Keggin polyanion [α-SiW 12O 40] 4- acts as the inorganic building block, two [Cu 2(phen) 2(OH) 2(H 2O)] units covalently bond to it via terminal oxygen atoms of the Keggin anion. An open framework is formed through supramolecular interactions with solvent accessible volume of 18% in the unit-cell. Dehydration and re-adsorption of water in 1 were investigated by X-ray powder diffraction (XRPD).The compound shows thermal stability and photoluminescence property in the solid state.

  15. Nanostructured polyoxometalate arrays with unprecedented properties and functions.

    SciTech Connect

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

    2003-11-01

    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

  16. Modifying Randles circuit for analysis of polyoxometalate layer-by-layer films.

    PubMed

    Vyas, Ritesh N; Li, Kuyen; Wang, Bin

    2010-12-01

    Multilayer films with anionic phosphomolybidic acid (PMo(12)) clusters have been fabricated via the electrostatic layer-by-layer (LbL) method. The charged mass transport phenomena of these thin films have been studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) with [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+/2+) as the redox probes. By adding a film resistance and a film capacitance to the conventional Randles equivalent circuit, we can calculate the diffusion coefficient values that help understand the microscopic nature of the thin films. When the negatively charged probe [Fe(CN)(6)](3-/4-) was used, lower diffusion coefficients were obtained for multilayers deposited from higher ionic strength solutions. This relationship was less obvious when the positively charged probe [Ru(NH(3))(6)](3+/2+) was used, in which the electrostatic attraction between PMo(12) clusters and the probe ions complicates the mass-transfer process. It is believed that the addition of salt to dipping solutions increases the tortuosity of the films so the mass transport takes longer paths, inducing lower diffusion coefficients. Higher PMo(12) loading causes lower diffusion coefficients due to the polyoxometalate clusters blocking the paths for charged probe ions. PMID:21077668

  17. Tube-graft-Sheet Nano-Objects Created by A Stepwise Self-Assembly of Polymer-Polyoxometalate Hybrids.

    PubMed

    Tang, Jing; Li, Xue-Ying; Wu, Han; Ren, Li-Jun; Zhang, Yu-Qi; Yao, Hai-Xia; Hu, Min-Biao; Wang, Wei

    2016-01-19

    In this work, we report the preparation of complex nano-objects by means of a stepwise self-assembly of two polymer-polyoxometalate hybrids (PPHs) in solution. The PPHs are designed and synthesized by tethering two linear poly(ε-caprolactone)s (PCL) of different molecular weights (MW) on a complex of a Wells-Dawson-type polyoxometalate (POM) cluster and its countraions. The higher MW PCL-POM self-assembled into nanosheets, while the lower MW PCL-POM assembled into nanotubes just by altering the ratio of water in the DMF-water mixed solvent system. The two nano-objects have a similar membrane structure in which a PCL layer is sandwiched by the two POM-based complex layers. The PCL layer in the nanosheets is semicrystalline, while the PCL layer in the nanotubes is amorphous. We further exploited this MW-dependence to self-assemble the nanotubes on the nanosheet edges to create complex tube-graft-sheet nano-objects. We found that the nanotubes nucleate on the four {110} faces of the PCL crystal and then further grow along the crystallographic b-axis of the PCL crystal. Our findings offer hope for the further development of nano-objects with increasing complexity.

  18. Three new organic-inorganic hybrids based on Keggin ions and aminopyridine: Crystal structure and catalytic property

    NASA Astrophysics Data System (ADS)

    Zhang, Chuanlei; Shen, Xiaoming; Lü, Shuzi; Peng, Zhenshan; Zhu, Wei; Cai, Tiejun

    2012-05-01

    Three new organic-inorganic supramolecular hybrids, namely, (2-C5H7N2)4(PMo12O40)2·(2-C5H6N2)6·(C4H8N4)·H2O (compound 1), (3-C5H7N2)6·(PMo12O40)2·(3-C5H6N2)4·H8O4·(H2O)8 (compound 2), (4-C5H7N2)6(PMo12O40)2·(4-C5H6N2)4·(C4H6N3) (compound 3), have been synthesized by hydrothermal method and characterized by elemental analyses, IR, UV-vis, TGA and single-crystal X-ray diffraction. Compound 1-3 constructed from Keggin polyoxoanions and 2-/3-/4-aminopyridine organic ligands, exhibit an extended three-dimensional supramolecular network via hydrogen bonding and π-π stacking interactions, while compound 2 contains a tetramolecular water clusters. compounds 1 and 3 have a higher catalytic activity for the oxidation of acetone tested in a continuous-flow fixed-bed micro-reactor. When the initial concentration of the acetone is 6.1 g m-3 in air and the flow velocity is 4.5 mL min-1, the acetone is completely eliminated at 160 °C. But compound 2 has lower catalytic activity for the oxidation of acetone.

  19. Keggin (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O: Characterization and crystal structure

    SciTech Connect

    Bonfim, Rodrigo de Paiva Floro; Moura, Luiza Cristina de; Eon, Jean-Guillaume; Mentré, Olivier; Vezin, Hervé; Caldarelli, Stefano

    2014-05-01

    Single crystals of the potassium salt (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O of the vanadium tri-substituted α-Keggin dodecatungstosilicate were prepared and analyzed by vibrational, EPR and {sup 51}V NMR spectroscopy. Varying the synthesis conditions allows crystallization of partially reduced anions. The crystal structure was determined for both oxidized (V{sup 5+}) and partially reduced (V{sup 4+/5+}) potassium salts. Single crystal X-ray diffraction data and solid state {sup 51}V-NMR spectra confirm the occurrence of a single vanadium site in a cubic structure due to rotational disorder of the Keggin ion. Partially reduced compounds crystallize within the same structure as fully oxidized ones. EPR experiments confirm strong interaction of V{sup 4+} with two V{sup 5+} ions, in accordance with insertion of a V{sub 3} subunit into the lacunary Keggin ion as designed in the synthesis method. The 3D-edifice is composed of K{sup +}/H{sub 2}O counter-sublattice with evidence of tunable water occupancy. - Graphical abstract: Relative arrangements of HPA clusters in (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}]·xH{sub 2}O. - Highlights: • We prepared single crystals of the potassium salt (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O. • The synthesis was designed to give the α-1,2,3-[SiV{sub 3}W{sub 9}O{sub 40}] Keggin ion. • Strict pH control was necessary to avoid vanadium partial reduction. • Reduced compounds crystallize within the same structure as fully oxidized ones. • EPR confirms strong interaction of V{sup 4+} with two V{sup 5+} ions in a V{sub 3} subunit.

  20. A novel iron-containing polyoxometalate heterogeneous photocatalyst for efficient 4-chlorophennol degradation by H2O2 at neutral pH

    NASA Astrophysics Data System (ADS)

    Zhai, Qian; Zhang, Lizhong; Zhao, Xiufeng; Chen, Han; Yin, Dongju; Li, Jianhui

    2016-07-01

    An iron-containing polyoxometalate (FeШLysSiW) was synthesized from ferric chloride (FeIII), lysine (Lys) and silicotungstic acid (SiW), and characterized using ICP-AES, TG, FT-IR, UV-vis DRS, XRD and SEM. The chemical formula of FeШLysSiW was determined as [Fe(H2O)5(C6H14N2O2)]HSiW12O40·8H2O, with Keggin-structured SiW12O404- heteropolyanion and lysine moiety. As a heterogeneous catalyst, the as prepared FeШLysSiW showed good performance in the degradation of 4-chlorophenol by H2O2 in both the dark and irradiated systems. Under the conditions of 4-chlorophenol 100 mg/L, FeШLysSiW 1.0 g/L, H2O2 20 mmol/L and pH 6.5, 4-chlorophenol could be completely degraded in ca. 40 min in the dark and ca. 15 min upon irradiation. Prolonging the reaction time to 3 h, the TOC removal reached to ca. 71.3% in the dark and ca. 98.8% under irradiation. The catalytic activity of FeШLysSiW stems from synergetic effect of ferric iron and SiW12O404- in the catalyst, corresponding to Fenton-like catalysis and photocatalysis, respectively. The enhanced degradation of 4-CP under irradiation is due to the simultaneous oxidation of 4-CP through the Fenton-like and photocatalytic processes. The high catalytic activity of FeШLysSiW is also strongly related to the chemisorption of H2O2 on FeШLysSiW surface by hydrogen bonding, which promotes both the Fenton-like and photocatalytic processes.

  1. Recent advances on polyoxometalate-based molecular and composite materials.

    PubMed

    Song, Yu-Fei; Tsunashima, Ryo

    2012-11-21

    Polyoxometalates (POMs) are a subset of metal oxides with unique physical and chemical properties, which can be reliably modified through various techniques and methods to develop sophisticated materials and devices. In parallel with the large number of new crystal structures reported in the literature, the application of these POMs towards multifunctional materials has attracted considerable attention. This critical review summarizes recent progress on POM-based molecular and composite materials, and particularly highlights the emerging areas that are closely related to surface, electronic, energy, environment, life science, etc. (171 references). PMID:22850732

  2. Biofunctionalization of Polyoxometalates with DNA Primers, Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products.

    PubMed

    Debela, Ahmed M; Ortiz, Mayreli; Beni, Valerio; Thorimbert, Serge; Lesage, Denis; Cole, Richard B; O'Sullivan, Ciara K; Hasenknopf, Bernold

    2015-12-01

    The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW11 O39 {Sn(CH2 )2 CO}](8-) and [P2 W17 O61 {Sn(CH2 )2 CO}](6-) have been used to link to a 5'-NH2 terminated 21-mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM-labeled primers was demonstrated through hybridization with a surface-immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.

  3. Polyoxometalate-based eight-connected self-catenated network and fivefold interpenetrating framework

    SciTech Connect

    Zhang Zhiming; Liu Jia; Li Yangguang; Yao Shuang; Wang Enbo; Wang Xinlong

    2010-01-15

    Two entangled compounds [(bpy){sub 6}Cu{sup I}{sub 6}Cl{sub 3}(Mo{sup V}W{sub 5}O{sub 19})] (1) and [(bpy){sub 7}Cu{sup I}{sub 7}Cl{sub 2}(BW{sub 12}O{sub 40})].H{sub 2}O (2) (bpy=4,4'-bipyridine), have been successfully synthesized under hydrothermal conditions and characterized by element analysis, IR spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy, and single crystal X-ray diffraction analyses. Compound 1 represents the first eight-connected self-penetrating network constructed from cuprous chloride clusters [Cu{sub 6}Cl{sub 3}] and Lindquist-type polyoxoanions. Compound 2 exhibits an interesting fivefold interpenetrating network consisting of Keggin polyoxoanions and Cu{sup +}-metal-organic framework. Crystal data of the two compounds are following: 1, triclinic, P1-bar, a=11.502(2) A, b=13.069(3) A, c=13.296(3) A, alpha=90.55(3){sup o}, beta=113.74(3){sup o}, gamma=110.48(3){sup o}, Z=1; 2, triclinic, P1-bar, a=12.341(3) A, b=13.119(3) A, c=15.367(3) A, alpha=99.12(3){sup o}, beta=90.53(3){sup o}, gamma=104.49(3){sup o}, Z=1. - Graphical abstract: Compound 1 is the POM-based unprecedented eight-connected self-penetrating organic-inorganic hybrid network constructed from the cuprous chloride clusters [Cu{sub 6}Cl{sub 3}], Lindquist-type polyoxoanions [Mo{sup V}W{sub 5}O{sub 19}], and the 4,4'-bipyridine ligands.

  4. Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing.

    PubMed

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

    2012-11-21

    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.

  5. Functionalization of Krebs-type polyoxometalates with N,O-chelating ligands: a systematic study.

    PubMed

    Artetxe, Beñat; Reinoso, Santiago; San Felices, Leire; Vitoria, Pablo; Pache, Aroa; Martín-Caballero, Jagoba; Gutiérrez-Zorrilla, Juan M

    2015-01-01

    The first organic derivatives of 3d-metal-disubstituted Krebs-type polyoxometalates have been synthesized under mild bench conditions via straightforward replacement of labile aqua ligands with N,O-chelating planar anions on either preformed or in situ-generated precursors. Nine hybrid clusters containing carboxylate derivatives of five- or six-membered aromatic N-heterocycles as antenna ligands have been obtained as pure crystalline phases and characterized by elemental and thermal analyses, infrared spectroscopy, and single-crystal X-ray diffraction. They all show the general formula [{M(II)L(H2O)}2(WO2)2(B-β-XW9O33)2](n-) and can be classified as follows: 1-SbM, where L = 1H-imidazole-4-carboxylate (imc), X = Sb(III), n = 12, and M(II) = Mn, Co, Ni, Zn; 1-TeM, where L = imc, X = Te(IV), n = 10, and M(II) = Mn, Co; 2-SbNi, where L = 1H-pyrazole-3-carboxylate (pzc), X = Sb(III), n = 12, and M(II) = Ni; and 3-SbM, where L = pyrazine-2-carboxylate (pyzc), X =Sb(III), n = 12, and M(II) = Co, Zn. The 3d-metal-disubstituted tungstotellurate(IV) skeleton of compounds 1-TeM is unprecedented in polyoxometalate chemistry. The stability of these hybrid Krebs-type species in aqueous solution has been confirmed by (1)H NMR spectroscopy performed on the diamagnetic 1-SbZn and 3-SbZn derivatives. Our systematic study of the reactivity of disubtituted Krebs-type polyoxotungstates toward diazole-, pyridine-, and diazinecarboxylates demonstrates that organic derivatization is strongly dependent on the nature of the ligand, as follows: imc displays a "universal ligand" character, as functionalization takes place regardless of the external 3d metal and heteroatom; pzc and pyzc show selectivity toward specific 3d metals; pyridazine-3-carboxylate and pyrimidine-4-carboxylate promote partial decomposition of specific precursors, leading to [M(II)L2(H2O)2] complexes; and picolinate is inert under all conditions tested.

  6. Five inorganic–organic hybrids based on Keggin polyanion [SiMo{sub 12}O{sub 40}]{sup 4−}: From 0D to 2D network

    SciTech Connect

    Yu, Xiao-Yang; Cui, Xiao-Bing; Lu, Jing; Luo, Yu-Hui; Zhang, Hong; Gao, Wei-Ping

    2014-01-15

    Five new inorganic–organic hybrids based on 4,4′-bipyridine and Keggin-type polyoxometalate [SiMo{sub 12}O{sub 40}]{sup 4−}, (SiMo{sub 12}O{sub 40})(H{sub 2}bipy){sub 2}·2H{sub 2}O (1), [Cu(Hbipy){sub 4}(HSiMo{sub 12}O{sub 40})(SiMo{sub 12}O{sub 40})](H{sub 2}bipy){sub 0.5}·7H{sub 2}O (2), [Cu{sub 2}(Hbipy){sub 6}(bipy)(SiMo{sub 12}O{sub 40}){sub 3}](Hbipy){sub 2}·6H{sub 2}O (3), [Cu(bipy){sub 2}(SiMo{sub 12}O{sub 40})](H{sub 2}bipy)·2H{sub 2}O (4) and [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}](SiMo{sub 12}O{sub 40})·13H{sub 2}O (5) (bipy=4,4′-bipyridine), have been hydrothermally synthesized. 1 consists of H{sub 2}bipy{sup 2+} and [SiMo{sub 12}O{sub 40}]{sup 4−} units. In 2, two [SiMo{sub 12}O{sub 40}]{sup 4−} are bridged by [Cu(Hbipy){sub 4}]{sup 6+} to form a [Cu(Hbipy){sub 4}(SiMo{sub 12}O{sub 40}){sub 2}]{sup 2−} dimmer. In 3, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions acting as bidentated bridging ligands and monodentated auxiliary ligands connect [Cu{sub 2}(Hbipy){sub 6}(bipy)]{sup 8+} units into a 1D zigzag chain. In 4, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions bridge neighboring 1D [Cu(bipy){sub 2}]{sup 2+} double chains into a 2D extended layer. In 5, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions acting as templates site alternately upon the grids from both sides of the square grid [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}]{sup 4+} layer. In addition, the electrochemical behaviors of 1, 3 and 4 and the photocatalysis property of 1 have been investigated. - Graphical abstract: Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been successfully generated. [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the structures of the five compounds. Display Omitted - Highlights: • Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been generated. • [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the five structures. • The electrochemical behaviors of 1, 3 and 4 have been

  7. An unusual mono-substituted Keggin anion-chain based 3D framework with 24-membered macrocycles as linker units

    SciTech Connect

    Pang Haijun; Ma Huiyuan; Yu Yan; Yang Ming; Xun Ye; Liu Bo

    2012-02-15

    A new compound, [Cu{sup I}(H{sub 2}O)(Hbpp){sub 2}] Subset-Of {l_brace}[Cu{sup I}(bpp)]{sub 2}[PW{sub 11}Cu{sup II}O{sub 39}]{r_brace} (1) (bpp=1,3-bis(4-pyridyl)propane), has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. In compound 1, the unusual -A-B-A-B- array mono-substituted Keggin anion-chains and 24-membered (Cubpp){sub 2} cation-macrocycles are linked together to form a (2, 4) connected 3D framework with channels of ca. 9.784 Multiplication-Sign 7.771 A{sup 2} along two directions, in which the [Cu(H{sub 2}O)(Hbpp){sub 2}] coordination fragments as guest components are trapped. The photocatalytic experiments of compound 1 were performed, which show a good catalytic activity of compound 1 for photodegradation of RhB. Furthermore, the IR, TGA and electrochemical properties of compound 1 were investigated. - Graphical abstract: An unusual example of mono-substituted Keggin anion-chain based hybrid compound that possesses a 3D structure has been synthesized, which offers a feasible route for synthesis of such compounds. Highlights: Black-Right-Pointing-Pointer The first example of -A-B-A-B- array mono-substituted Keggin chain is observed. Black-Right-Pointing-Pointer An unusual three dimensional structure based mono-substituted Keggin anion-chains. Black-Right-Pointing-Pointer The photocatalysis and electrochemical properties of the title compound were studied.

  8. Heterogeneous Catalysis by Polyoxometalate-Intercalated Layered Double Hydroxides

    NASA Astrophysics Data System (ADS)

    Rives, Vicente; Carriazo, Daniel; Martín, Cristina

    The preparation, characterisation and catalytic performance of layered double hydroxides (LDH) with the hydrotalcite-type structure containing different polyoxometalates (POM) in the interlayer are studied. Special attention is paid to the preparation procedures, as they control the properties of the solids formed and thus their catalytic behaviour. The study is extended to solids prepared upon thermal decomposition of these POM-LDH systems. It is concluded that the LDH does not act as a simple support, but that its specific properties, such as nature of the cations in the brucite-like layers, specific surface area and the method followed for its preparation, have an outstanding effect on the final catalytic properties of the POM-LDH systems.

  9. Polyoxometalate water oxidation catalysts and methods of use thereof

    DOEpatents

    Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

    2014-09-02

    Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

  10. Cationic cure kinetics of a polyoxometalate loaded epoxy nanocomposite

    SciTech Connect

    Anderson, Benjamin J.

    2012-08-06

    The reaction cure kinetics of a novel polyoxometalate (POM) loaded epoxy nanocomposite is described. The POM is dispersed in the epoxy resin up to volume fractions of 0.1. Differential scanning calorimetry measurements show the cure of the epoxy resin to be sensitive to the POM loading. A kinetics study of the cure exotherm confirms that POM acts as a catalyst promoting cationic homopolymerization of the epoxy resin. The cure reaction is shown to propagate through two cure regimes. A fast cure at short time is shown to be propagation by the activated chain end (ACE) mechanism. A slow cure at long time is shown to be propagation by the activated monomer (AM) mechanism. The activation energies for the fast and slow cure regimes agree well with other epoxy based systems that have been confirmed to propagate by the ACE and AM mechanisms.

  11. New polyimide-polyoxometalate nanocomposite materials with nanoporous structure and ultra-low dielectric constant, formed in supercritical carbon dioxide

    NASA Astrophysics Data System (ADS)

    Keshtov, Mukhamed; Said-Galiev, Ernest; Kochurov, Vitaliy; Khokhlov, Alexei

    2012-07-01

    Vinyltrimethoxysilane interaction with K8(SiW11O39) obtained polyoxometalate (Bu4N)4[SiW11O39{(CH2 = CH-Si)2O}](SiW11-CH = CH2). Synthesized two new fluorinated aromatic polyimide in two stages with a dielectric constant (k) in the range 2.70-2.75. On the basis of poly(amic acids) and a mixture of thermal imidization polyoxometalate obtained polyimide/polyoxometalate composite film. It was found that with increasing polyoxometalate in a mixture of 0 to 20 wt% the dielectric constant decreases from 2,75 to 1,70. Nanoporous materials with ultra-low dielectric constant in the range 1.31-1.64 in combination with high thermal (T10% = 536-570°C in N2) and mechanical characteristics using supercritical carbon dioxide have been developed on the basis of the obtained polyimide/polyoxometalate composite films.

  12. Polyoxometalates as efficient catalysts for transformations of cellulose into platform chemicals.

    PubMed

    Deng, Weiping; Zhang, Qinghong; Wang, Ye

    2012-09-01

    Efficient utilisation of renewable biomass resources, particularly lignocellulosic biomass, for the production of chemicals and fuels has attracted much attention in recent years. The catalytic conversion of cellulose, the main component of lignocellulosic biomass, selectively into a platform chemical such as glucose, 5-hydroxymethyl furfural (HMF), sorbitol or gluconic acid under mild conditions is the most desirable route. Acid catalysis plays a crucial role in the conversion of cellulose via the cleavage of its glycosidic bonds. Owing to their unique features such as strong acidity, water-tolerance, low corrosiveness and recoverability, polyoxometalates have shown promising performances in transformations of cellulose into platform chemicals both in homogeneous and heterogeneous systems. This article highlights recent studies on polyoxometalates and polyoxometalate-based bifunctional catalysts or catalytic systems for the selective conversions of cellulose and cellobiose, a model molecule of cellulose, into platform chemicals. PMID:22653050

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

    PubMed

    Sarma, Bidyut Bikash; Neumann, Ronny

    2014-08-01

    Terrestrial plants contain ~70% hemicellulose and cellulose that are a significant renewable bioresource with potential as an alternative to petroleum feedstock for carbon-based fuels. The efficient and selective deconstruction of carbohydrates to their basic components, carbon monoxide and hydrogen, so called synthesis gas, is an important key step towards the realization of this potential, because the formation of liquid hydrocarbon fuels from synthesis gas are known technologies. 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. In this oxidation-reduction reaction, the hydrogen atoms are stored on the polyoxometalate as protons and electrons, and can be electrochemically released from the polyoxometalate as hydrogen. Together, synthesis gas is formed. In a hydrogen economy scenario, this method can also be used to convert carbon monoxide to hydrogen.

  14. Dioxygen and water activation processes on multi-Ru-substituted polyoxometalates: comparison with the "blue-dimer" water oxidation catalyst.

    PubMed

    Kuznetsov, Aleksey E; Geletii, Yurii V; Hill, Craig L; Morokuma, Keiji; Musaev, Djamaladdin G

    2009-05-20

    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

  15. Lanthanoid Template Isolation of the α-1,5 Isomer of Dicobalt(II)-Substituted Keggin Type Phosphotungstates: Syntheses, Characterization, and Magnetic Properties.

    PubMed

    Gupta, Rakesh; Hussain, Firasat; Sadakane, Masahiro; Kato, Chisato; Inoue, Katsuya; Nishihara, Sadafumi

    2016-09-01

    A new series of heterometallic 3d-4f sandwich type phosphotungstates, [Ln{PCo2W10O38(H2O)2}2](11-) (Ln = Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III), denoted 1a-10a, respectively), have been synthesized by a one-pot reaction procedure on reacting the dilacunary K14[P2W19O69(H2O)]·24H2O precursor with Ln(NO3)3·nH2O and Co(NO3)2·6H2O in an aqueous potassium chloride solution. All the compounds were isolated as potassium salts and further characterized with different analytical techniques such as single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, high-resolution electrospray ionization mass spectrometry, elemental analysis by inductively coupled plasma atomic emission spectroscopy, magnetic measurement, and thermogravimetric analysis. Single-crystal X-ray diffraction analysis of the compounds reveals that all these compounds are isostructural and crystallized in the orthorhombic crystal system in space group Iba2. The polyanions contain the α-1,5 isomer of dicobalt-substituted α-Keggin phosphotungstate, which sandwiched lanthanoid cation and formed novel heterometallic dimer species. The temperature-dependent magnetic susceptibilities of 1a, 2a, 4a, and 7a-10a indicate the dominant contribution of the ferromagnetic interaction between Co(II) and Co(II) within the cluster, while the antiferromagnetic interaction between Co(II) and Ln(III) dominates for 3a, 5a, and 6a. The isothermal magnetizations of 1a-10a show a gradual increase in magnetization at low fields and do not reach saturation even at 50 kOe. PMID:27509227

  16. Hybrid Thin Films Based Upon Polyoxometalates-Polymer Assembly

    NASA Astrophysics Data System (ADS)

    Qi, Na; Jing, Benxin; Zhu, Yingxi

    2014-03-01

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

  17. Two proton-conductive hybrids based on 2,2 Prime -biimidazole molecules and Keggin-type heteropolyacids

    SciTech Connect

    Wei, Mei-Lin; Wang, Jun-Hua; Wang, Yu-Xia

    2013-02-15

    Two proton-conductive organic/inorganic complexes were constructed by Keggin-type heteropolyacids and 2,2 Prime -biimidazole molecules. Single-crystal X-ray diffraction analyses revealed that two complexes crystallized in the triclinic space group Pi, exhibited very close unit cell parameters, and presented similar three-dimensional (3D) hydrogen-bonded networks constructed by H{sub 2}biim, [PM{sub 12}O{sub 40}]{sup 3-} (M=W for 1 and Mo for 2) and solvent molecules. The results of thermogravimetric analyses (TG) suggest that two supramolecular complexes have similar thermal stability based on the same 3D packing. Two complexes at 100 Degree-Sign C under 98% relative humidity showed a good proton conductivity of about 10{sup -4} S cm{sup -1}. A possible mechanism of the proton conduction was proposed according to the experimental results. - Graphical Abstract: Two molecular hybrids constructed by Keggin-type heteropolyacids and 2,2 Prime -biimidazole molecules showed good proton conductivities of 10{sup -4} S cm{sup -1} in the temperature range of 85-100 Degree-Sign C under 98% relative humidity. Highlights: Black-Right-Pointing-Pointer H{sub 2}biim shows the ability to form hydrogen bonds via the N-H groups in the context of crystal engineering. Black-Right-Pointing-Pointer Heteropolyacids have suitable characteristics to be used excellent proton conductors. Black-Right-Pointing-Pointer Two new supramolecular complexes based-on Keggin-type heteropolyacids and H{sub 2}biim molecules were constructed. Black-Right-Pointing-Pointer The structure was determined by using single-crystal X-ray diffraction data. Black-Right-Pointing-Pointer Both complexes showed good proton conductivities of 10{sup -4} S cm{sup -1} in the temperature range of 85-100 Degree-Sign C.

  18. Two proton-conductive hybrids based on 2-(3-pyridyl)benzimidazole molecules and Keggin-type heteropolyacids

    SciTech Connect

    Wei, Mei-Lin Wang, Yu-Xia; Wang, Xin-Jun

    2014-01-15

    Two proton-conductive organic/inorganic complexes were constructed by Keggin-type heteropolyacids and 2-(3-pyridyl)benzimidazole molecules. Single-crystal X-ray diffraction analyses revealed that two complexes crystallized in the monoclinic space group P2{sub 1}/c, exhibited different unit cell parameters, and presented different hydrogen-bonded networks constructed by 2-(3-pyridyl)benzimidazole molecules, [PMo{sub 12}O{sub 40}]{sup 3−} anions and solvent molecules. The results of thermogravimetric analyses suggest that two supramolecular complexes have different thermal stability based on the different hydrogen-bonded networks. Two complexes at 100 °C under 35–98% relative humidity showed a good proton conductivity of about 10{sup −3} S cm{sup −1}. The proton conductivities of two complexes under 98% relative humidity both increase on a logarithmic scale with temperature range from 25 to 100 °C. At 100 °C, both complexes showed poor proton conductivities of 10{sup −8}–10{sup −9} S cm{sup −1} under acetonitrile or methanol vapor. - Graphical abstract: Two molecular hybrids constructed by Keggin-type heteropolyacids and 2-(3-pyridyl)benzimidazole molecules showed good proton conductivities of 10{sup −3} S cm{sup −1} at 100 °C under 35–98% relative humidity. Display Omitted - Highlights: • 2-(3-Pyridyl)benzimidazole could form hydrogen bonds via the N–H groups. • Heteropolyacids have suitable characteristics to be used excellent proton conductors. • Two proton-conductive hybrids based on Keggin HPAs and 3-PyBim were constructed. • The structures were determined by using single-crystal X-ray diffraction data. • They showed good proton conductivities of 10{sup −3} S cm{sup −1} at 100 °C under 35–98% RH.

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

    SciTech Connect

    Pope, M.T.

    1997-01-01

    '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.'

  20. Polyoxometalate-supported 3d-4f heterometallic single-molecule magnets.

    PubMed

    Feng, Xiaojia; Zhou, Wenzhe; Li, Yangguang; Ke, Hongshan; Tang, Jinkui; Clérac, Rodolphe; Wang, Yonghui; Su, Zhongmin; Wang, Enbo

    2012-03-01

    The reactions of [CuTbL(Schiff)(H(2)O)(3)Cl(2)]Cl complexes with A- or B-type Anderson polyoxoanions lead to new polyoxometalate-supported 3d-4f heterometallic systems with single-molecule-magnet behavior.

  1. Polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids for flexible, all-solid-state supercapacitors.

    PubMed

    Chen, Yuyun; Han, Min; Tang, Yujia; Bao, Jianchun; Li, Shunli; Lan, Yaqian; Dai, Zhihui

    2015-08-11

    Novel polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids (TNHs) are synthesized via a one-pot redox relay strategy. The TNHs exhibit high areal specific capacitance (2.61 mF cm(-2)), and the fabricated solid device also exhibits good rate capability, excellent flexibility and mechanical stability. PMID:26140676

  2. The supramolecular design of low-dimensional carbon nano-hybrids encoding a polyoxometalate-bis-pyrene tweezer.

    PubMed

    Modugno, Gloria; Syrgiannis, Zois; Bonasera, Aurelio; Carraro, Mauro; Giancane, Gabriele; Valli, Ludovico; Bonchio, Marcella; Prato, Maurizio

    2014-05-18

    A novel bis-pyrene tweezer anchored on a rigid polyoxometalate scaffold fosters a unique interplay of hydrophobic and electrostatic supramolecular interactions, to shape carbon nanostructures (CNSs)-based extended architectures.

  3. Nanostructured H(3+x)PW(12-x)NbxO40 (x = 0-3) Keggin heteropolyacid catalysts.

    PubMed

    Choi, Jung Ho; Park, Dong Ryul; Park, Sunyoung; Song, In Kyu

    2011-09-01

    Nanostructured H(3+x)PW(12-x)NbxO40 (x = 0, 1, 2, 3) Keggin heteropolyacid (HPA) catalysts were investigated by scanning tunneling microscopy (STM) and tunneling spectroscopy to probe their redox property and oxidation catalysis. STM image showed that the HPAs formed two-dimensional well-ordered monolayer arrays on graphite surface. In tunneling spectra of the HPAs deposited on graphite, they exhibited a distinctive current-voltage behavior referred to as negative differential resistance (NDR). NDR peak voltage measured atop HPA molecule was then correlated with reduction potential and absorption edge energy determined by electrochemical method and UV-visible spectroscopy, respectively. It was revealed that NDR peak voltage of the HPAs appeared at less negative voltage with increasing reduction potential and with decreasing absorption edge energy. In order to correlate NDR peak voltage of H(3+x)PW(12-x)NbxO40 Keggin HPAs with oxidation catalysis, oxidative dehydrogenation of isobutyraldehyde to methacrolein was carried out as a model reaction. NDR peak voltage of the HPAs appeared at less negative voltage with increasing yield for methacrolein. PMID:22097499

  4. A ternary nanocomposite electrode of polyoxometalate/carbon nanotubes/gold nanoparticles for electrochemical detection of hydrogen peroxide.

    PubMed

    Guo, Shuyue; Xu, Lin; Xu, Bingbing; Sun, Zhixia; Wang, Lihao

    2015-02-01

    In this work, a nanocomposite film electrode containing polyoxometalate (POM) clusters K6P2W18O62 (P2W18), carbon nanotubes (CNTs) and Au nanoparticles (AuNPs) was fabricated by a smart combination of layer-by-layer (LbL) with the self-assembly technique. The synergistic effect of POM, CNTs and AuNPs on the electrocatalysis of H2O2 was investigated to improve the sensitivity of H2O2 detection. The response of (P2W18/CNTs/P2W18/AuNPs)4 electrodes to H2O2 was remarkably enhanced due to large active sites and good electron conducting ability. The sensor exhibited a quick response (less than 1 second) to H2O2 with a high sensitivity (596.1 μAm M(-1) cm(-2)), and a low detection limit (52 nM). Based on the respective advantages of POMs, CNTs and AuNPs, the nanocomposite multilayer POMs/CNTs/POMs/AuNPs will have special properties and high potential for application.

  5. A ternary nanocomposite electrode of polyoxometalate/carbon nanotubes/gold nanoparticles for electrochemical detection of hydrogen peroxide.

    PubMed

    Guo, Shuyue; Xu, Lin; Xu, Bingbing; Sun, Zhixia; Wang, Lihao

    2015-02-01

    In this work, a nanocomposite film electrode containing polyoxometalate (POM) clusters K6P2W18O62 (P2W18), carbon nanotubes (CNTs) and Au nanoparticles (AuNPs) was fabricated by a smart combination of layer-by-layer (LbL) with the self-assembly technique. The synergistic effect of POM, CNTs and AuNPs on the electrocatalysis of H2O2 was investigated to improve the sensitivity of H2O2 detection. The response of (P2W18/CNTs/P2W18/AuNPs)4 electrodes to H2O2 was remarkably enhanced due to large active sites and good electron conducting ability. The sensor exhibited a quick response (less than 1 second) to H2O2 with a high sensitivity (596.1 μAm M(-1) cm(-2)), and a low detection limit (52 nM). Based on the respective advantages of POMs, CNTs and AuNPs, the nanocomposite multilayer POMs/CNTs/POMs/AuNPs will have special properties and high potential for application. PMID:25431885

  6. Star-like supramolecular polymers fabricated by a Keplerate cluster with cationic terminated polymers and their self-assembly into vesicles.

    PubMed

    Zhang, Qian; He, Lipeng; Wang, Hui; Zhang, Cheng; Liu, Weisheng; Bu, Weifeng

    2012-07-18

    The electrostatic combination of a Keplerate cluster, [Mo(132)O(372)(CH(3)COO)(30)(H(2)O)(72)](42-) with cationic terminated poly(styrene) yields polyoxometalate-based supramolecular star polymers, which can further self-assemble into vesicular aggregates in CHCl(3)-MeOH mixed solvent.

  7. Stabilization of plutonium(III) in the Preyssler polyoxometalate.

    PubMed

    Antonio, Mark R; Chiang, Ming-Hsi

    2008-09-15

    The Na(+) ion encapsulated within the Preyssler heteropolyoxoanion, [NaP5W30O110](14-), was exchanged with Pu(III) under hydrothermal conditions to obtain [Pu(III)P5W30O110](12-) (abbreviated [PuPA](12-)) with hybrid electrochemical properties resulting from the combination of the key redox behaviors of the Pu cation and the P-W-O anion. The electroanalytical chemistry of this two-center, multielectron redox system in a 1 M HCl electrolyte shows that Pu(III) is oxidized to Pu(IV) at the half-wave potential, E(1/2), of +0.960 V versus Ag/AgCl, which is 0.197 V more positive than the corresponding electrode potential for the Pu(III) aqua ion also in 1 M HCl, indicating the stabilization of the trivalent Pu cation by its encapsulation in the Preyssler polyoxometalate (POM). This effect is uncommon in actinide-POM chemistry, wherein electrode potential shifts of the opposite nature (to more negative values), leading to the stabilization of the tetravalent ions by complexation, are renowned. Moreover, in cyclic voltammetry measurements of the Pu(III) aqua ion and [PuPA](12-), the peak currents, i(p), for the one-electron Pu(III)/Pu(IV) processes show different dependencies with the scan rate, nu. The former shows proportionality with nu(1/2), indicating freely diffusing species, whereas the latter shows proportionality with nu, indicating a surface-confined one. The first of the five successive two-electron, W-centered reduction processes in [PuPA](12-) occurs at E(1/2) = -0.117 V versus Ag/AgCl, which is 1.077 V less than the E(1/2) for the Pu(III)/Pu(IV) oxidation, thereby providing an experimental, electrochemical measure of the highest occupied molecular orbital/lowest unoccupied molecular orbital energy gap, which compares well with values previously obtained by density-functional theory, complete active space-self consistent field, and post-Hartree-Fock calculations for a series of M(n+)-exchanged systems, [MPA](n-15) for 1 < or = n < or = 4 (Fernandez, J. A

  8. Synthesis, structure and magnetism of a S-shaped multi-iron substituted arsenotungstate containing a trivacant Keggin [B-{alpha}-As{sup V}W{sub 9}O{sub 34}]{sup 9-} and a hexavacant Keggin [{alpha}-As{sup V}W{sub 6}O{sub 26}]{sup 11-} fragments

    SciTech Connect

    Zhao Junwei; Han Qiuxia; Shi Dongying; Chen Lijuan; Ma Pengtao; Wang Jingping; Niu Jingyang

    2011-10-15

    A S-shaped multi-iron substituted arsenotungstate [enH{sub 2}]{sub 2}[({alpha}-H{sub 2}As{sup V}W{sub 6}O{sub 26})Fe{sub 3}(H{sub 2}O)(B-{alpha}-H{sub 4}As{sup V}W{sub 9}O{sub 34})]{sub 2}[Fe]{sub 2}.8H{sub 2}O (1) (en=ethylenediamine) has been prepared by reaction of K{sub 14}[As{sub 2}{sup III}W{sub 19}O{sub 67}(H{sub 2}O)].nH{sub 2}O with Fe{sub 2}(SO{sub 4}){sub 3}.xH{sub 2}O under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, UV spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The skeleton of 1 consists of two asymmetric sandwich-type subunits [({alpha}-H{sub 2}As{sup V}W{sub 6}O{sub 26})Fe{sub 3}(H{sub 2}O)(B-{alpha}-H{sub 4}As{sup V}W{sub 9}O{sub 34})]{sup 5-} linked by a di-Fe{sup III} cluster. Moreover, magnetic susceptibility measurements demonstrate that 1 indicates the antiferromagnetic coupling interactions within Fe{sup III} centers with the best-fitting set of parameters of J{sub 1}=-7.07 cm{sup -1}, J{sub 2}=-0.45 cm{sup -1} and g=2.05, which are generated by the addition of the expressions of the molar susceptibilities of two tri-Fe{sup III} clusters and one di-Fe{sup III} cluster derived from for spin pairs coupled through the isotropic exchange interactions. - Graphical abstract: S-shaped multi-iron substituted arsenotungstate consisting of two asymmetric sandwich-type subunits has been hydrothermally synthesized and structurally characterized. Its magnetic properties have been investigated. Highlights: > Multi-iron substituted arsenotungstate. > Symmetric sandwich-type subunits. > Antiferromagnetic coupling interactions within Fe{sup III} centers. > Hexavacant Keggin POM fragments.

  9. Spontaneous structuration in coacervate-based protocells by polyoxometalate-mediated membrane assembly.

    PubMed

    Williams, David S; Patil, Avinash J; Mann, Stephen

    2014-05-14

    Molecularly crowded, polyelectrolyte/ribonucleotide-enriched membrane-free coacervate droplets are transformed into membrane-bounded sub-divided vesicles by using a polyoxometalate-mediated surface-templating procedure. The coacervate to vesicle transition results in reconstruction of the coacervate micro-droplets into novel three-tiered micro-compartments comprising a semi-permeable negatively charged polyoxometalate/polyelectrolyte outer membrane, a sub-membrane coacervate shell, and an internal aqueous lumen. We demonstrate that organic dyes, ssDNA, magnetic nanoparticles and enzymes can be concentrated into the interior of the micro-compartments by sequestration into the coacervate micro-droplets prior to vesicle formation. The vesicle-encapsulated proteins are inaccessible to proteases in the external medium, and can be exploited for the spatial localization and coupling of two-enzyme cascade reactions within single or between multiple populations of hybrid vesicles dispersed in aqueous media.

  10. Predicting (17)O NMR chemical shifts of polyoxometalates using density functional theory.

    PubMed

    Sharma, Rupali; Zhang, Jie; Ohlin, C André

    2016-03-21

    We have investigated the computation of (17)O NMR chemical shifts of a wide range of polyoxometalates using density functional theory. The effects of basis sets and exchange-correlation functionals are explored, and whereas pure DFT functionals generally predict the chemical shifts of terminal oxygen sites quite well, hybrid functionals are required for the prediction of accurate chemical shifts in conjunction with linear regression. By using PBE0/def2-tzvp//PBE0/cc-pvtz(H-Ar), lanl2dz(K-) we have computed the chemical shifts of 37 polyoxometalates, corresponding to 209 (17)O NMR signals. We also show that at this level of theory the protonation-induced pH dependence of the chemical shift of the triprotic hexaniobate Lindqvist anion, [HxNb6O19]((8-x)), can be reproduced, which suggests that hypotheses regarding loci of protonation can be confidently tested. PMID:26925832

  11. New Electrochemical Evaluation of the Antioxidant Capacity of Beverages with Polyoxometalates as Redox Probes.

    PubMed

    Ueda, Tadaharu; Okumura, Takashi; Tanaka, Yukino; Akase, Saki; Shimamura, Tomoko; Ukeda, Hiroyuki

    2016-01-01

    A new method was developed to evaluate antioxidant activity based on the redox properties of polyoxometalates, which are partially reduced by antioxidants to generate a limiting potential. The polyoxometalates [PMo12O40](3-), [PVW11O40](4-) and [SV2W10O40]4- formed in situ were used as electrochemical probes for the new evaluation method, and their formation conditions were optimized to evaluate the antioxidant activities of gallic acid, ellagic acid, catechin, quercetin, morin, trans-ferulic acid, sesamol, α-tocopherol, δ-tocopherol and L-ascorbic acid. The observed difference between initial potential and limiting potential (ΔE) were compared with spectrophotometrically evaluated antioxidant activities. In addition, the antioxidant capacities of five beverages (Japanese green tea, concentrated catechin-containing green tea, grapefruit juice, red wine and Japanese sake) were evaluated. PMID:27506707

  12. Spontaneous structuration in coacervate-based protocells by polyoxometalate-mediated membrane assembly.

    PubMed

    Williams, David S; Patil, Avinash J; Mann, Stephen

    2014-05-14

    Molecularly crowded, polyelectrolyte/ribonucleotide-enriched membrane-free coacervate droplets are transformed into membrane-bounded sub-divided vesicles by using a polyoxometalate-mediated surface-templating procedure. The coacervate to vesicle transition results in reconstruction of the coacervate micro-droplets into novel three-tiered micro-compartments comprising a semi-permeable negatively charged polyoxometalate/polyelectrolyte outer membrane, a sub-membrane coacervate shell, and an internal aqueous lumen. We demonstrate that organic dyes, ssDNA, magnetic nanoparticles and enzymes can be concentrated into the interior of the micro-compartments by sequestration into the coacervate micro-droplets prior to vesicle formation. The vesicle-encapsulated proteins are inaccessible to proteases in the external medium, and can be exploited for the spatial localization and coupling of two-enzyme cascade reactions within single or between multiple populations of hybrid vesicles dispersed in aqueous media. PMID:24515342

  13. Synthesis, molecular structure, and stability of a zirconocene derivative with α-Keggin mono-aluminum-substituted polyoxotungstate.

    PubMed

    Kato, Chika Nozaki; Makino, Yuki; Unno, Wataru; Uno, Hidemitsu

    2013-01-28

    The synthesis and crystal structure of a zirconocene derivative with α-Keggin mono-aluminum-substituted polyoxotungstate, [α-PW(11)Al(OH)O(39)ZrCp(2)](2)(6-) (Cp = C(5)H(5)(-)) (1), which was obtained by the reaction of α-Keggin mono-aluminum-substituted polyoxotungstate with a biscyclopentadienylzirconium(IV) complex, is described herein. Analytically pure, homogeneous, yellow crystals of the tetra-n-butylammonium salt of polyoxoanion 1, [(n-C(4)H(9))(4)N](6)[α-PW(11)Al(OH)O(39)ZrCp(2)](2) (TBA-1), were obtained from the ca. 1 : 1 reaction of [(n-C(4)H(9))(4)N](4)[α-PW(11){Al(OH(2))}O(39)] with Cp(2)Zr(OTf)(2)·THF (OTf = O(3)SCF(3)(-)) in acetonitrile solution under an argon atmosphere, followed by precipitation from water and crystallization from acetonitrile. TBA-1 was characterized based on X-ray structure analysis, elemental analysis, thermogravimetric/differential thermal analysis (TG/DTA), Fourier transform infrared (FTIR), and solution ((31)P, (27)Al, (19)F, (1)H, and (13)C) nuclear magnetic resonance (NMR) spectroscopy. Single-crystal X-ray structure analysis revealed that the two {PW(11)AlO(40)} units are bridged by two "bent sandwich" Cp(2)Zr(2+) fragments with C(2) symmetry. Each zirconium center was bound to a terminal oxygen atom of the aluminum and tungsten sites and an edge-sharing oxygen atom at the Al-O-W linkage. Further, the stability towards water was investigated by NMR ((31)P, (1)H, and (13)C) and FTIR spectroscopy. The η(5)-cyclopentadienylzirconium fragments were not eliminated from the surface of [α-PW(11){Al(OH(2))}O(39)](4-) even after 24 h exposure to 50 equiv. of water.

  14. Donor-acceptor organo-imido polyoxometalates: high transparency, high activity redox-active NLO chromophores.

    PubMed

    Al-Yasari, Ahmed; Van Steerteghem, Nick; El Moll, Hani; Clays, Koen; Fielden, John

    2016-02-21

    We show that polyoxometalates (POMs) are an excellent redox-active acceptor on which to base high performance 2(nd) order non-linear optical (NLO) chromophores. This is demonstrated through three new organoimido-Lindqvist derivatives with HRS β0-values exceeding those of any dipolar organic system with comparable donor, π-system and absorption profile. Thus, organoimido POMs may provide a new generation of high performance, high transparency, and potentially redox-switchable NLO materials. PMID:26815652

  15. A general strategy to fabricate simple polyoxometalate nanostructures: electrochemistry-assisted laser ablation in liquid.

    PubMed

    Liu, Pu; Liang, Ying; Lin, Xianzhong; Wang, Chengxin; Yang, Guowei

    2011-06-28

    Polyoxometalate nanostructures have attracted much attention because of significant technical demands in applications such as catalysts, sensors, and smart windows. Therefore, researchers have recently developed many methods for the synthesis of these nanomaterials. However, these techniques have many visible flaws such as high temperatures or high pressure environments, various templates or additives, demanding and complicated synthesis procedures as well as the presence of impurities in the final products. We therefore propose a general strategy for the fabrication of particular polyoxometalate nanostructures by electrochemically assisted laser ablation in liquid (ECLAL). These polyoxometalates are usually simple as they typically contain two metals and are not soluble in water. This approach is a green, simple, and catalyst-free approach under an ambient environment. Apart from these merits, this novel technique allows researchers to choose and design interesting solid targets and to use an electrochemical approach toward the fabrication of polyoxometalate nanostructures for the purpose of fundamental research and for potential applications. Using the synthesis of Cu(3)Mo(2)O(9) nanorods as an example, we substantiate the validity of the proposed strategy. For the fabrication of Cu(3)Mo(2)O(9) nanostructures, we chose molybdenum as a solid target for laser ablation in liquid copper electrodes for the electrochemical reaction and water as a solvent for the ECLAL synthesis. We successfully fabricated Cu(3)(OH)(2)(MoO(4))(2) nanorods with magnetic properties. Interestingly, we obtained well-defined Cu(3)Mo(2)O(9) nanorods by annealing the Cu(3)(OH)(2)(MoO(4))(2) nanostructures at 500 °C. Additionally, the basic physics and chemistry involved in the ECLAL fabrication of nanostructures are discussed.

  16. Donor-acceptor organo-imido polyoxometalates: high transparency, high activity redox-active NLO chromophores.

    PubMed

    Al-Yasari, Ahmed; Van Steerteghem, Nick; El Moll, Hani; Clays, Koen; Fielden, John

    2016-02-21

    We show that polyoxometalates (POMs) are an excellent redox-active acceptor on which to base high performance 2(nd) order non-linear optical (NLO) chromophores. This is demonstrated through three new organoimido-Lindqvist derivatives with HRS β0-values exceeding those of any dipolar organic system with comparable donor, π-system and absorption profile. Thus, organoimido POMs may provide a new generation of high performance, high transparency, and potentially redox-switchable NLO materials.

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

    SciTech Connect

    Pope, Michael T.

    2000-09-14

    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.

  18. The loading of coordination complex modified polyoxometalate nanobelts on activated carbon fiber: a feasible strategy to obtain visible light active and highly efficient polyoxometalate based photocatalysts.

    PubMed

    Lu, Tingting; Xu, Xinxin; Li, Huili; Li, Zhenyu; Zhang, Xia; Ou, Jinzhao; Mei, Mingliang

    2015-02-01

    To enhance the photocatalytic properties of coordination complex modified polyoxometalates (CC/POMs) in the visible light region, its nanobelts (CC/POMNBs) were loaded on activated carbon fiber (ACF) through a simple colloidal blending process. The resulting coordination complex modified polyoxometalate nanobelts loaded activated carbon fiber composite materials (CC/POMNBs/ACF) exhibited dramatic photocatalytic activity for the degradation of rhodamine B (RhB) under visible light irradiation. Optical and electrochemical methods illustrated the enhanced photocatalytic activity of CC/POMNBs/ACF, which originates from the high separation efficiency of the photogenerated electrons and holes on the interface of the CC/POMNBs and ACF, which results from the synergistic effects between them. In the composite material, the role of ACF could be described as a photosensitizer and a good electron transporter. Furthermore, the influence of the mass ratio between the CC/POMNBs and ACF on the photocatalytic performance of the resulting composite material was discussed, and an ideal value to obtain highly efficient photocatalysts was obtained. The results suggested that the loading of CC/POMNBs on the surface of ACF would be a feasible strategy to enhance their photocatalytic activity.

  19. Keggin type inorganic-organic hybrid material containing Mn(II) monosubstituted phosphotungstate and S-(+)-sec-butyl amine: Synthesis and characterization

    SciTech Connect

    Patel, Ketan; Patel, Anjali

    2012-02-15

    Graphical abstract: A new organic-inorganic hybrid material containing Keggin type manganese substituted phosphotungstate and S-(+)-sec-butyl amine was synthesized and systematically characterized. Highlights: Black-Right-Pointing-Pointer New hybrid material comprising Mn substituted phosphotungstate (PW{sub 11}Mn) and S-(+)-sec-butyl amine (SBA) was synthesized. Black-Right-Pointing-Pointer The spectral studies reveal the attachment of SBA to the PW{sub 11}Mn without any distortion of structure. Black-Right-Pointing-Pointer The synthesized material comprises chirality. Black-Right-Pointing-Pointer The synthesized hybrid material can be used as a heterogeneous catalyst for carrying out asymmetric synthesis. -- Abstract: A new inorganic-organic POM-based hybrid material comprising Keggin type mono manganese substituted phosphotungstate and enantiopure S-(+)-sec-butyl amine was synthesized in an aqueous media by simple ligand substitution method. The synthesized hybrid material was systematically characterized in solid as well as solution by various physicochemical techniques such as elemental analysis, TGA, UV-vis, FT-IR, ESR and multinuclear solution NMR ({sup 31}P, {sup 1}H, {sup 13}C). The presence of chirality in the synthesized material was confirmed by CD spectroscopy and polarimeter. The above study reveals the attachment of S-(+)-sec-butyl amine to Keggin type mono manganese substituted phosphotungstate through N {yields} Mn bond. It also indicates the retainment of Keggin unit and presence of chirality in the synthesized material. An attempt was made to use the synthesized material as a heterogeneous catalyst for carrying out aerobic asymmetric oxidation of styrene using molecular oxygen. The catalyst shows the potential of being used as a stable recyclable catalytic material after simple regeneration without significant loss in conversion.

  20. Keggin (K5, H3O)[SiV3W9O40H]·xH2O: Characterization and crystal structure

    NASA Astrophysics Data System (ADS)

    Bonfim, Rodrigo de Paiva Floro; de Moura, Luiza Cristina; Eon, Jean-Guillaume; Mentré, Olivier; Vezin, Hervé; Caldarelli, Stefano

    2014-05-01

    Single crystals of the potassium salt (K5, H3O)[SiV3W9O40H]·xH2O of the vanadium tri-substituted α-Keggin dodecatungstosilicate were prepared and analyzed by vibrational, EPR and 51V NMR spectroscopy. Varying the synthesis conditions allows crystallization of partially reduced anions. The crystal structure was determined for both oxidized (V5+) and partially reduced (V4+/5+) potassium salts. Single crystal X-ray diffraction data and solid state 51V-NMR spectra confirm the occurrence of a single vanadium site in a cubic structure due to rotational disorder of the Keggin ion. Partially reduced compounds crystallize within the same structure as fully oxidized ones. EPR experiments confirm strong interaction of V4+ with two V5+ ions, in accordance with insertion of a V3 subunit into the lacunary Keggin ion as designed in the synthesis method. The 3D-edifice is composed of K+/H2O counter-sublattice with evidence of tunable water occupancy.

  1. Enhanced Visible Photovoltaic Response of TiO₂ Thin Film with an All-Inorganic Donor-Acceptor Type Polyoxometalate.

    PubMed

    Li, Jian-Sheng; Sang, Xiao-Jing; Chen, Wei-Lin; Zhang, Lan-Cui; Zhu, Zai-Ming; Ma, Teng-Ying; Su, Zhong-Min; Wang, En-Bo

    2015-06-24

    In the field of material chemistry, it is of great significance to develop abundant and sustainable materials for solar energy harvesting and management. Herein, after evaluating the energy band characteristics of 13 kinds of polyoxometalates (POMs), the trisubstituted POM compound K6H4[α-SiW9O37Co3(H2O)3]·17H2O (SiW9Co3) was first studied due to its relatively smaller band gap (2.23 eV) and higher lowest unoccupied molecular orbital (LUMO) level (-0.63 V vs NHE). Additionally, the preliminary computational modeling indicated that SiW9Co3 exhibited the donor-acceptor (D-A) structure, in which the cobalt oxygen clusters and tungsten skeletons act as the electron donor and electron acceptor, respectively. By employing SiW9Co3 to modify the TiO2 film, the visible photovoltaic and photocurrent response were both enhanced, and the light-induced photocurrent at 420 nm was improved by 7.1 times. Moreover, the highly dispersive and small sized SiW9Co3 nanoclusters loading on TiO2 were successfully achieved by fabricating the nanocomposite film of {TiO2/SiW9Co3}3 with the layer-by-layer method, which can result in the photovoltaic performance enhancement of dye-sensitized solar cells (DSSCs), of which the overall power conversion efficiency was improved by 25.6% from 6.79% to 8.53% through the synergistic effect of POMs and Ru-complex.

  2. The atomic level journey from aqueous polyoxometalate to metal oxide

    SciTech Connect

    Hou, Yu; Fast, Dylan B.; Ruther, Rose E.; Amador, Jenn M.; Fullmer, Lauren B.; Decker, Shawn R.; Zakharov, Lev N.; Dolgos, Michelle R. Nyman, May

    2015-01-15

    Aqueous precursors tailored for the deposition of thin film materials are desirable for sustainable, simple, low energy production of advanced materials. Yet the simple practice of using aqueous precursors is complicated by the multitude of interactions that occur between ions and water during dehydration. Here we use lithium polyoxoniobate salts to investigate the fundamental interactions in the transition from precursor cluster to oxide film. Small-angle X-ray scattering of solutions, total X-ray scattering of intermediate gels, and morphological and structural characterization of the lithium niobate thin films reveal the atomic level transitions between these states. The studies show that (1) lithium–[H{sub 2}Nb{sub 6}O{sub 19}]{sup 6−} has drastically different solution behaviour than lithium–[Nb{sub 6}O{sub 19}]{sup 8−}, linked to the precursor salt structure (2) in both compositions, the intermediate gel preserves the polyoxoniobate clusters and show similar local order and (3) the morphology and phases of deposited films reflect the ions behaviour throughout the journey from cluster solution to metal oxide. - Graphical abstract: Aqueous lithium polyoxoniobate salts were used to prepare lithium niobate (LiNbO{sub 3}) thin films. Fundamental studies were performed to investigate the interactions in the transition from precursor cluster to the oxide film. It was found that acid–base and ion-association chemistries of the aqueous and gel systems significantly affect the key processes in this atom-level journey. - Highlights: • Lithium polyoxoniobate clusters were synthesized with control over Li:Nb ratio as precursors for LiNbO{sub 3} films. • X-ray scattering studies in solution and the solid-state revealed differences controlled by Li:Nb ratio. • Film deposition studies revealed phase, composition and morphology is controlled by Li:Nb ratio. • Cluster to film transformation was revealed using total X-ray scattering and TGA.

  3. A co-crystal of polyoxometalates exhibiting single-molecule magnet behavior: the structural origin of a large magnetic anisotropy

    SciTech Connect

    Fang, Xikui; McCallum, Kendall; Pratt III, Harry D.; Anderson, Travis M.; Dennis, Kevin; Luban, Marshall

    2012-03-29

    A polyoxometalate-based {MnIII3MnIV} single-molecule magnet exhibits a large axial anisotropy (D = −0.86 cm−1) resulting from a near-parallel alignment of Jahn–Teller axes. Its rigorous three-fold symmetry (i.e. rhombicity E → 0) and increased intercluster separation via co-crystallization effectively hamper quantum tunnelling of the magnetization. Graphical abstract: A co-crystal of polyoxometalates exhibiting single-molecule magnet behavior: the structural origin of a large magnetic anisotropy

  4. Low-Dimensional Polyoxometalate Molecules/Tantalum Oxide Hybrids for Non-Volatile Capacitive Memories.

    PubMed

    Balliou, Angelika; Papadimitropoulos, Giorgos; Skoulatakis, George; Kennou, Stella; Davazoglou, Dimitrios; Gardelis, Spiros; Glezos, Nikos

    2016-03-23

    Transition-metal-oxide hybrids composed of high surface-to-volume ratio Ta2O5 matrices and a molecular analogue of transition metal oxides, tungsten polyoxometalates ([PW12O40](3-)), are introduced herein as a charge storage medium in molecular nonvolatile capacitive memory cells. The polyoxometalate molecules are electrostatically self-assembled on a low-dimensional Ta2O5 matrix, functionalized with an aminosilane molecule with primary amines as the anchoring moiety. The charge trapping sites are located onto the metal framework of the electron-accepting molecular entities as well as on the molecule/oxide interfaces which can immobilize negatively charged mobile oxygen vacancies. The memory characteristics of this novel nanocomposite were tested using no blocking oxide for extraction of structure-specific characteristics. The film was formed on top of the 3.1 nm-thick SiO2/n-Si(001) substrates and has been found to serve as both SiO2/Si interface states' reducer (i.e., quality enhancer) and electron storage medium. The device with the polyoxometalates sandwiched between two Ta2O5 films results in enhanced internal scattering of carriers. Thanks to this, it exhibits a significantly larger memory window than the one containing the plain hybrid and comparable retention time, resulting in a memory window of 4.0 V for the write state and a retention time around 10(4) s without blocking medium. Differential distance of molecular trapping centers from the cell's gate and electronic coupling to the space charge region of the underlying Si substrate were identified as critical parameters for enhanced electron trapping for the first time in such devices. Implementing a numerical electrostatic model incorporating structural and electronic characteristics of the molecular nodes derived from scanning probe and spectroscopic characterization, we are able to interpret the hybrid's electrical response and gain some insight into the electrostatics of the trapping medium. PMID

  5. N-alkylation of organo-imido substituted polyoxometalates: an efficient and stoichiometric approach for the easy post-modification of polyoxometalates.

    PubMed

    Khan, Rao Naumaan Nasim; Lv, Chunlin; Zhang, Jin; Hao, Jian; Wei, Yongge

    2015-03-14

    An efficient protocol for post-functionalization of organo-imido polyoxometalates is developed via creating a remote tertiary “N” atom over the surface of organo-imido hexamolybdates and subsequently post-functionalizing it with the help of allyl or alkyl halides to afford stoichiometric, “in situ” crystalline products at moderate temperatures. The parent organo-imido product 2 and post-functionalized crystalline products 3 and 4 are compared for their solid state structures. The post-functionalization protocol introduced here allows the inclusion of the desired functional groups as remote reactive organic groups over a POM's highly negative surface. The in situ crystallization of post-functionalized products further guarantees an 100% purity of final products, along with 95% yield. PMID:25651928

  6. Selective hydrogenation of phenylacetylene on Ni and Ni-Pd catalysts modified with heteropoly compounds of the Keggin type

    NASA Astrophysics Data System (ADS)

    Navalikhina, M. D.; Kavalerskaya, N. E.; Lokteva, E. S.; Peristyi, A. A.; Golubina, E. V.; Lunin, V. V.

    2012-12-01

    It is established that unmodified Ni catalysts and Ni catalysts modified with Mo- and W-heteropoly compounds (HPC) of the Keggin type (6 wt %) along with catalyst containing 6% K4SiW12O40/Al2O3 appear to be active in the reaction of phenylacetylene (PA) hydrogenation. At low temperatures (100-150°C), the selectivity of the process strongly depends on the nature of the modifier or second active metal (Pd). It is demonstrated that in the presence of 6% Ni-0.015% Pd/Al2O3 modified by HPC K4SiMo6W6O40, the conversion of PA at 100°C was 87% at a styrene: ethylbenzene ratio of 1: 1. The acidity of HPC is found to influence the side reactions of alkylation and condensation. Transmission electron microscopy demonstrates that Ni in modified HPC 6% Ni/Al2O3 is present in the form of the particles below 2 nm in size, and these particles of Ni become larger when affected by the reaction medium during PA hydrogenation.

  7. Smart high-κ nanodielectrics using solid supported polyoxometalate-rich nanostructures.

    PubMed

    Musumeci, Chiara; Rosnes, Mali H; Giannazzo, Filippo; Symes, Mark D; Cronin, Leroy; Pignataro, Bruno

    2011-12-27

    Utilizing Langmuir-Blodgett deposition and scanning probe microscopy, we have investigated the extent to which cations alter the self-assembly processes of hybrid polyoxometalates (POMs) on surfaces. The well-defined 2D hexagonal nanostructures obtained were extensively characterized and their properties were studied, and this has revealed fascinating dielectric behavior and reversible capacitive properties. The nanostructures are extremely stable under ambient conditions, and yet exhibit fascinating self-patterning upon heating. These findings present POMs as effective smart nanodielectrics and open up a new field for future POM applications.

  8. On the electronic structure of giant polyoxometalates: Mo132vs. W72Mo60.

    PubMed

    Bo, Carles; Miró, Pere

    2012-09-01

    The molecular and electronic structure of the spherical Keplerates [{(Mo(VI))Mo(VI)(5)O(21)}(12)(Mo(V)(2)O(4))(30)](12-) (Mo(132)) and [{(W(VI))W(VI)(5)O(21)}(12)(Mo(V)(2)O(4))(30)](12-) (W(72)Mo(60)) has been determined, for the first time, using first-principles density functional theory (DFT) based methods including solvent effects. Computed geometric parameters are in very good agreement with X-ray data, whereas the electronic structure reveals the archetypal nature of polyoxometalates. PMID:22717598

  9. Recent advances in porous polyoxometalate-based metal-organic framework materials.

    PubMed

    Du, Dong-Ying; Qin, Jun-Sheng; Li, Shun-Li; Su, Zhong-Min; Lan, Ya-Qian

    2014-07-01

    Polyoxometalate (POM)-based metal-organic framework (MOF) materials contain POM units and generally generate MOF materials with open networks. POM-based MOF materials, which utilize the advantages of both POMs and MOFs, have received increasing attention, and much effort has been devoted to their preparation and relevant applications over the past few decades. They have good prospects in catalysis owing to the electronic and physical properties of POMs that are tunable by varying constituent elements. In this review, we present recent developments in porous POM-based MOF materials, including their classification, synthesis strategies, and applications, especially in the field of catalysis. PMID:24676127

  10. The atomic level journey from aqueous polyoxometalate to metal oxide

    NASA Astrophysics Data System (ADS)

    Hou, Yu; Fast, Dylan B.; Ruther, Rose E.; Amador, Jenn M.; Fullmer, Lauren B.; Decker, Shawn R.; Zakharov, Lev N.; Dolgos, Michelle R.; Nyman, May

    2015-01-01

    Aqueous precursors tailored for the deposition of thin film materials are desirable for sustainable, simple, low energy production of advanced materials. Yet the simple practice of using aqueous precursors is complicated by the multitude of interactions that occur between ions and water during dehydration. Here we use lithium polyoxoniobate salts to investigate the fundamental interactions in the transition from precursor cluster to oxide film. Small-angle X-ray scattering of solutions, total X-ray scattering of intermediate gels, and morphological and structural characterization of the lithium niobate thin films reveal the atomic level transitions between these states. The studies show that (1) lithium-[H2Nb6O19]6- has drastically different solution behaviour than lithium-[Nb6O19]8-, linked to the precursor salt structure (2) in both compositions, the intermediate gel preserves the polyoxoniobate clusters and show similar local order and (3) the morphology and phases of deposited films reflect the ions behaviour throughout the journey from cluster solution to metal oxide.

  11. Manganese-Substituted Polyoxometalate as an Effective Shuttle Redox Mediator in Z-Scheme Water Splitting under Visible Light.

    PubMed

    Tsuji, Kohei; Tomita, Osamu; Higashi, Masanobu; Abe, Ryu

    2016-08-23

    In the present study, a polyoxometalate is for the first time applied as a shuttle redox in two-step (Z-Scheme) photocatalytic water splitting. Photocatalytic H2 evolution using a Mn-substituted polyoxometalate [SiW11 O39 Mn(II) (H2 O)](6-) as an electron donor proceeded over a Ru-loaded SrTiO3 :Rh photocatalyst under visible light with relatively high selectivity, accompanied by the stoichiometric production of its oxidized form [SiW11 O39 Mn(III) (H2 O)](5-) . Photocatalytic O2 evolution using the oxidized [SiW11 O39 Mn(III) (H2 O)](5-) as an electron acceptor proceeded over PtOx -loaded WO3 photocatalyst under visible light with relatively high quantum efficiency and selectivity, whereas the loading of effective PtOx cocatalyst was necessary to facilitate the reduction of polyoxometalate. Finally, a two-step water splitting into H2 and O2 was demonstrated under visible light using the couple of Mn-substituted polyoxometalate as shuttle redox between Ru/SrTiO3 :Rh and PtOx /WO3 photocatalysts, under mildly acidic conditions with pH≈4.5.

  12. Efficient visible light-driven water oxidation catalyzed by an all-inorganic copper-containing polyoxometalate.

    PubMed

    Yu, Li; Du, Xiaoqiang; Ding, Yong; Chen, Hongli; Zhou, Panpan

    2015-12-21

    [Cu5(OH)4(H2O)2(A-α-SiW9O33)2](10-) (1) was tested as the first copper-containing polyoxometalate catalyst for O2 production via visible light-driven water oxidation. Multiple experiments confirm that 1 is an active and dominant catalyst during water oxidation. PMID:26468511

  13. A series of new supramolecular structures constructed from triethylenediamine and different polyoxometalates

    SciTech Connect

    Wang, Yan; Pan, Cheng-Ling; Xiao, Li-Na; Wu, Feng-Qing; Ding, Hong; Liu, Ya-Bing; Gao, Zhong-Min; Zheng, Da-Fang; Wang, Tie-Gang; Yang, Guang-Di; Cui, Xiao-Bing; Xu, Ji-Qing

    2010-12-15

    Three new supramolecular compounds based on triethylenediamine and different polyoxometalates [W{sup VI}{sub 3}V{sup V}{sub 3}O{sub 19}H]{l_brace}[Cu(HDABCO)]{sub 2}(H{sub 2}O){r_brace} (1), [P{sub 2}Mo{sup VI}{sub 18}O{sub 62}][HDABCO]{sub 2}[H{sub 2}DABCO]{sub 2}.12 H{sub 2}O (2) and [Mo{sup VI}{sub 7.5}W{sup VI}{sub 0.5}O{sub 27}][Cu(HDABCO)]{sub 2}.2 H{sub 3}O.2 H{sub 2}O (3) (DABCO=triethylenediamine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 exhibits a face-centered cubic packing motif, compound 2 displays a supramolecular structure constructed form the 'chains' arranged hexagonally, compound 3 contains [Mo{sub 7.5}W{sub 0.5}O{sub 27}]{sub {infinity}} chain decorated by [Cu(HDABCO)]{sup 2+} cations, which was then packed into a layer structure. These results show that the same organonitrogen combining with the different POMs will yield different supramolecular networks. -- Graphical abstract: Three new supramolecular compounds based on triethylenediamine and different polyoxometalates have been hydrothermally synthesized and characterized by IR, XPS, TG, elemental analysis and X-ray diffraction analysis.

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

    PubMed

    Lunkenbein, Thomas; Kamperman, Marleen; Li, Zihui; Bojer, Carina; Drechsler, Markus; Förster, Stephan; Wiesner, Ulrich; Müller, Axel H E; Breu, Josef

    2012-08-01

    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 selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices. PMID:22757978

  15. Controllable fabrication of platinum nanospheres with a polyoxometalate-assisted process

    SciTech Connect

    Sun Guoying; Li Qiuyu; Xu Rui; Gu Jianmin; Ju Mingliang; Wang Enbo

    2010-11-15

    Pt nanospheres with an average diameter of 60{+-}10 nm have been successfully synthesized at room temperature through a facile polyoxometalate(POM)-assisted process. Characterization by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) clearly showed that these Pt nanospheres consisted of 2-7 nm Pt nanodots. During the formation of such unique nanostructures, POMs were found to serve as both catalyst and stabilizer. The size of the as-synthesized Pt nanospheres could be controlled solely by adjusting the molar ratio of POMs to H{sub 2}PtCl{sub 6}. A possible formation mechanism based on POMs-mediated electron transfer from ascorbic acid (AA) to PtCl{sub 6}{sup 2-} and AA-assisted aggregation was tentatively proposed to rationalize the formation of such nanostructures. Importantly, these specific Pt nanospheres exhibited good electrocatalytic activity towards the oxidation of methanol, making them promising for applications in direct methanol fuel cells. - Graphical abstract: Large-scale Pt nanospheres were synthesized through a polyoxometalate-assisted process, and exhibited good electrocatalytic activity towards the oxidation of methanol, making them promising for applications in fuel cells. Display Omitted

  16. Control of the grafting of hybrid polyoxometalates on metal and carbon surfaces: toward submonolayers.

    PubMed

    Gam Derouich, Sarra; Rinfray, Corentin; Izzet, Guillaume; Pinson, Jean; Gallet, Jean-Jacques; Kanoufi, Frédéric; Proust, Anna; Combellas, Catherine

    2014-03-01

    A Keggin-type POM is attached to gold or glassy carbon surfaces by electro(chemical) or peptidic coupling. In addition to demonstrating the robust attachment of the POMs (by electrochemistry, XPS, and IRRAS), the surface concentration, layer thickness, and rate constant for electron transfer from the surface to the POMs have been measured. The use of such complementary techniques is mandatory to characterize the modified electrodes properly. Whatever the grafting method, experimental conditions are found to allow monolayer or submonolayer coverage. Besides covalently grafted species, additional electrostatically bonded POMs are present in the film. Cathodic polarization allows removing them to get a grafted film that is stable with time and potential, which is a requirement in the design of molecular memories.

  17. Synthesis and structural characterization of polyoxometalates incorporating with anilinium cations and facile preparation of hybrid film

    NASA Astrophysics Data System (ADS)

    Fukaya, Keisuke; Srifa, Atthapon; Isikawa, Eri; Naruke, Haruo

    2010-08-01

    The self-assembly reaction of tungstate and copper(II) in the presence of aniline (ANI) and phosphoric acid led to the formation of an anilinium (ANIH +) salt of mono-substituted Keggin-type polyoxotungstophosphate (ANIH) 5[PCu(H 2O)W 11O 39](ANI)·8H 2O ( 1), while the reaction of heptamolybdate in the coexistence of copper(II), phosphoric acid and ANI yielded an ANIH + salt of Strandberg-type pentamolybdodiphosphate, (ANIH) 2[(PO 4) 2Mo 5O 15{Cu(ANI) 2(H 2O)} 2](ANI)·2H 2O ( 2). These compounds were characterized by elemental analysis, infrared spectroscopy and X-ray single-crystal analysis. The compound 1, crystallizing in trigonal, P3¯,a = 13.883(4), c = 10.187(3) Å, Z = 1, consists of copper mono-substituted Keggin-typed [PCu(H 2O)W 11O 39] 5- anion surrounded by six ANI molecules, of which five are protonated (ANIH +). The compound 2, crystallizing in triclinic, P1¯,a = 13.98(2), b = 14.73(1), c = 16.24(1) Å, α = 111.27(3), β = 97.42(3), γ = 99.54(4)°, Z = 2, consists of Strandberg-type pentamolybdodiphospate [(PO 4) 2Mo 5O 15] 6- anions interconnected by two Cu(ANI) 2(H 2O) linkers to form a 1D-chain structure. A potentiostatic electrolysis of 1 in aqueous solution gave rise to electropolymerization of the ANIH + cations (and ANI) and deposition with the [PCu(H 2O)W 11O 39] 5- anion on an ITO electrode, forming a nano-structured polyaniline/[PCu(H 2O)W 11O 39] 5- hybrid thin film.

  18. Synthesis, structure and luminescent property of a new hybrid solid based on Keggin anions and silver-organonitrogen fragments

    SciTech Connect

    Lue Jian; Xiao Fuxian; Shi Linxi; Cao Rong

    2008-02-15

    A new hybrid solid, {l_brace}Ag(phen){sub 2}{r_brace}{sub 2}{l_brace}[Ag(phen)]{sub 2}[PMo{sub 12}O{sub 40}]{r_brace} (phen=1,10-phenanthroline) 1, constructed from one-electron-reduced mono-supported {alpha}-Keggin polyanions and silver-phenanthroline fragments via either covalent bonds or supramolecular interactions, is described. In the structure of 1, mono-supported {l_brace}Ag(phen)[PMo{sub 12}O{sub 40}]{r_brace}{sup 3-} polyanions are connected by {l_brace}Ag(phen){r_brace}{sup +} linking fragments to form a hybrid chain structure with engrafted phen ligands. {l_brace}Ag(phen){sub 2}{r_brace}{sup +} counter-cations occur in pairs trapping in strong inter-chain {pi}-{pi} stacking to form a three-dimensional supramolecular framework. Luminescent investigation of the compound indicates that 1 displays fascinating orange luminescent property at ambient temperature. - Graphical abstract: A novel hybrid solid, {l_brace}Ag(phen){sub 2}{r_brace}{sub 2}{l_brace}[Ag(phen)]{sub 2}[PMo{sub 12}O{sub 40}]{r_brace} (phen=1,10-phenanthroline) 1, is reported. In the structure of 1, {l_brace}Ag(phen)[PMo{sub 12}O{sub 40}]{r_brace}{sup 3-} polyanions are connected by {l_brace}Ag(phen){r_brace}{sup +} fragments to form a hybrid chain structure. {l_brace}Ag(phen){sub 2}{r_brace}{sup +} counter-cations are involved in inter-chain {pi}-{pi} stacking to form a three-dimensional supramolecular framework. Luminescent investigation of 1 indicates that 1 displays fascinating orange luminescent property at ambient temperature.

  19. di Synthesis and Characterization of the Platinum-Substituted Keggin Anion alpha-H2SiPtW11O404-

    SciTech Connect

    Klonowski, P; Goloboy, JC; Uribe-Romo, FJ; Sun, FR; Zhu, LY; Gandara, F; Wills, C; Errington, RJ; Yaghi, OM; Klemperer, WG

    2014-12-15

    Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)(6) to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O404- (1) and SiW12O404- (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The a-H2SiPtW11O404- was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, Pt-195 NMR spectroscopy, (183)W NMR spectroscopy, and W-183-W-183 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anion salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.

  20. Polyoxometalate-grafted graphene nanohybrid for electrochemical detection of hydrogen peroxide and glucose.

    PubMed

    Yang, MinHo; Kim, Dong Seok; Lee, Tae Jae; Lee, Seok Jae; Lee, Kyoung G; Choi, Bong Gill

    2016-04-15

    The electrochemical performances of electrochemical biosensors largely depend on electrode characteristics, such as size, composition, surface area, and electron and ion conductivities. Herein, highly efficient electrocatalytic polyoxometalate (POM) was directly deposited on polymeric ionic liquid (PIL)-functionalized reduced graphene oxide (rGO) in a simple manner. The nano-sized POM with PIL functional groups was uniformly distributed on the surface of rGO sheets. The unique nanostructure of the resultant POM-g-rGO nanohybrids enabled well-defined multiple redox reaction of POMs and rapid electron transfer. In particular, as-prepared nanohybrids demonstrated high electrocatalytic activity for the electrochemical detection of H2O2 and glucose molecules in flow-injection biosensor device with high sensitivity, rapid response time, and low detection limit. PMID:26828273

  1. Light- and Solvent-Controlled Self-Assembly Behavior of Spiropyran-Polyoxometalate-Alkyl Hybrid Molecules.

    PubMed

    Chu, Yang; Saad, Ali; Yin, Panchao; Wu, Jiayingzi; Oms, Olivier; Dolbecq, Anne; Mialane, Pierre; Liu, Tianbo

    2016-08-01

    A molecular photochromic spiropyran-polyoxometalate-alkyl organic-inorganic hybrid has been synthesized and fully characterized. The reversible switching of the hydrophobic spiropyran fragment to the hydrophilic merocyanine one can be easily achieved under light irradiation at different wavelengths. This switch changes the amphiphilic feature of the hybrid, leading to a light-controlled self-assembly behavior in solution. It has been shown that the hybrid can reversibly self-assemble into vesicles in polar solvents and irreversibly into reverse vesicles in non-polar solvents. The sizes of the vesicles and the reverse vesicles are both tunable by the polarity of the solvent, with the hydrophobic interactions being the main driving force. PMID:27404486

  2. Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

    2016-09-01

    Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

  3. Use of Lanthanide-Containing Polyoxometalates to Sensitise the Emission of Fluorescent Labelled Serum Albumin.

    PubMed

    Holmes-Smith, A Sheila; Crisp, Jacob; Hussain, Firasat; Patzke, Greta R; Hungerford, Graham

    2016-02-01

    Monitoring the interaction of biomolecules is important, and the use of energy transfer is a principal technique in elucidating nanoscale interactions. Lanthanide compounds are promising luminescent probes for biological samples as their emission is longer-lived than any native autofluorescence. Polyoxometalates (POMs) are interesting structural motifs to incorporate lanthanides, offering low toxicity and a size pertinent for biological applications. Here, we employ iso-structured POMs containing either terbium or europium and assess their interaction with serum albumin by sensitisation of a fluorescent tag on the protein via LRET (luminescence resonance energy transfer) by exciting the lanthanide. Time-resolved measurements showed energy transfer with an efficiency of over 90% for the POM-protein systems. The Tb-POM results were relatively straightforward, while those with the iso-structured Eu-POM were complicated by the effect of protein shielding from the aqueous environment.

  4. Development of α-polyoxometalate-polypyrrole-Au nanoparticles modified sensor applied for detection of folic acid.

    PubMed

    Babakhanian, Arash; Kaki, Samineh; Ahmadi, Mahtab; Ehzari, Hosna; Pashabadi, Afshin

    2014-10-15

    In this work, electrochemically synthesized gold nanoparticles (AuNPs) and α-polyoxometalate (α-POM) (K7PMO2W9O39 · H2O) were simultaneously doped into electropolymerized polypyrrole (PPy) film using the cyclic voltammetry (CV) technique. Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and CVs were used to characterize the composite films. The PPy-α-POM-AuNPs modified gold (Au) electrode was used to determine folic acid (FA) using square-wave voltammetry (SWV). The modified electrode exhibited excellent electrocatalytic ability to the reduction of FA at 0.3 V (vs. SCE) with the electron transfer rate constant (ks) of 1.15 × 10(-19)s(-1). The common coexisting substances showed no interferences on the response of modified electrode to FA. The modified electrode indicated reproducible behavior and a high level stability during the experiments, making it particularly suitable for the analytical purposes.

  5. Designing artificial photosynthetic devices using hybrid organic-inorganic modules based on polyoxometalates.

    PubMed

    Symes, Mark D; Cogdell, Richard J; Cronin, Leroy

    2013-08-13

    Artificial photosynthesis aims at capturing solar energy and using it to produce storable fuels. However, while there is reason to be optimistic that such approaches can deliver higher energy conversion efficiencies than natural photosynthetic systems, many serious challenges remain to be addressed. Perhaps chief among these is the issue of device stability. Almost all approaches to artificial photosynthesis employ easily oxidized organic molecules as light harvesters or in catalytic centres, frequently in solution with highly oxidizing species. The 'elephant in the room' in this regard is that oxidation of these organic moieties is likely to occur at least as rapidly as oxidation of water, meaning that current device performance is severely curtailed. Herein, we discuss one possible solution to this problem: using self-assembling organic-polyoxometalate hybrid structures to produce compartments inside which the individual component reactions of photosynthesis can occur without such a high incidence of deleterious side reactions.

  6. Degradable Organically-Derivatized Polyoxometalate with Enhanced Activity against Glioblastoma Cell Line

    NASA Astrophysics Data System (ADS)

    She, Shan; Bian, Shengtai; Huo, Ruichao; Chen, Kun; Huang, Zehuan; Zhang, Jiangwei; Hao, Jian; Wei, Yongge

    2016-09-01

    High efficacy and low toxicity are critical for cancer treatment. Polyoxometalates (POMs) have been reported as potential candidates for cancer therapy. On accounts of the slow clearance of POMs, leading to long-term toxicity, the clinical application of POMs in cancer treatment is restricted. To address this problem, a degradable organoimido derivative of hexamolybdate is developed by modifying it with a cleavable organic group, leading to its degradation. Of note, this derivative exhibits favourable pharmacodynamics towards human malignant glioma cell (U251), the ability to penetrate across blood brain barrier and low toxicity towards rat pheochromocytoma cell (PC12). This line of research develops an effective POM-based agent for glioblastoma inhibition and will pave a new way to construct degradable anticancer agents for clinical cancer therapy.

  7. Perfluorinated quaternary ammonium salts of polyoxometalate anions: Fluorous biphasic oxidation catalysis with and without fluorous solvents

    SciTech Connect

    Maayan, Galia; Fish, Richard H.; Neumann, Ronny

    2003-05-28

    Perfluorinated quaternary ammonium cations, [CF{sub 3}(CF{sub 2}){sub 7}(CH{sub 2}){sub 3}]{sub 3}CH{sub 3}N{sup +} (RFN{sup +}), were synthesized and used as counter cations for the [WZnM{sub 2}(H{sub 2}O){sub 2}(ZnW{sub 9}O{sub 34}){sub 2}]{sup 12-} (M = Mn(II), Zn(II)), polyoxometalate. The (RFN{sup +}){sub 12}[WZnM{sub 2}(H{sub 2}O){sub 2}(ZnW9O{sub 34}){sub 2}] compounds were fluorous biphasic catalysts for alcohol and alkenol oxidation, and alkene epoxidation with aqueous hydrogen peroxide. Reaction protocols with or without a fluorous solvent were tested. The catalytic activity and selectivity was affected both by the hydrophobicity of the solvent and the substrate.

  8. Degradable Organically-Derivatized Polyoxometalate with Enhanced Activity against Glioblastoma Cell Line

    PubMed Central

    She, Shan; Bian, Shengtai; Huo, Ruichao; Chen, Kun; Huang, Zehuan; Zhang, Jiangwei; Hao, Jian; Wei, Yongge

    2016-01-01

    High efficacy and low toxicity are critical for cancer treatment. Polyoxometalates (POMs) have been reported as potential candidates for cancer therapy. On accounts of the slow clearance of POMs, leading to long-term toxicity, the clinical application of POMs in cancer treatment is restricted. To address this problem, a degradable organoimido derivative of hexamolybdate is developed by modifying it with a cleavable organic group, leading to its degradation. Of note, this derivative exhibits favourable pharmacodynamics towards human malignant glioma cell (U251), the ability to penetrate across blood brain barrier and low toxicity towards rat pheochromocytoma cell (PC12). This line of research develops an effective POM-based agent for glioblastoma inhibition and will pave a new way to construct degradable anticancer agents for clinical cancer therapy. PMID:27658479

  9. Mechanism of polyoxometalate-mediated inactivation of DNA polymerases: an analysis with HIV-1 reverse transcriptase indicates specificity for the DNA-binding cleft.

    PubMed Central

    Sarafianos, S G; Kortz, U; Pope, M T; Modak, M J

    1996-01-01

    The anti-DNA polymerase activity of a structural family of polyoxometalates has been determined. Two representative compounds of this family, possessing a saddle-like structure [(O3POPO3)4W12O36]16- (polyoxometalate I) and [(O3PCH2PO3)4W12O36]16- (polyoxometalate II) were found to inhibit all the DNA polymerases tested, with IC50 values ranging from 2 to 10 microM. A comparative study with HIV-1 reverse transcriptase (RT) and Klenow polymerase as representative DNA polymerases indicated that protection from inactivation was achieved by inclusion of DNA but not by deoxynucleotide triphosphates (dNTPs). Kinetic analysis revealed that the mode of HIV-1 RT inhibition is competitive with respect to DNA, and non-competitive with respect to dNTP binding. Cross-linking experiments confirmed that the inhibitors interfere with the DNA-binding function of HIV-1 reverse transcriptase. Interestingly, a number of drug-resistant mutants of HIV-1 RT exhibit a sensitivity to polyoxometalate comparable to the wild-type HIV-1 RT, suggesting that these polyoxometalates interact at a novel site. Because different polymerases contain DNA-binding clefts of various dimensions, it should be possible to modify polyoxometalates or to add a link to an enzyme-specific drug so that more effective inhibitors could be developed. Using a computer model of HIV-1 RT we performed docking studies in a binary complex (enzyme-polyoxometalate I) to propose tentatively a possible interacting site in HIV-1 RT consistent with the available biochemical results as well as with the geometric and charge constraints of the two molecules. PMID:8912703

  10. DFT characterization on the mechanism of water splitting catalyzed by single-Ru-substituted polyoxometalates.

    PubMed

    Lang, Zhong-Ling; Yang, Guo-Chun; Ma, Na-Na; Wen, Shi-Zheng; Yan, Li-Kai; Guan, Wei; Su, Zhong-Min

    2013-08-01

    Water oxidation is a key half reaction in the energy conversion scheme. The reaction mechanism for the oxidation of H2O to O2 catalyzed by single-Ru-substituted polyoxometalates, [Ru(III)(H2O)XW11O39](n-) (X = Si(IV), Ge(IV)), was investigated by means of density functional calculations. The electronic structure of the pre-activation intermediates indicates that the aqua ligand is prone to accommodate the proton coupled electron transfer (PCET) process to achieve the active group [Ru(V)=Oa], and the high valent oxo-ruthenium(V) species are responsible for the O-O forming event. Three possible proton acceptors were designed for the rate-determining step (Ob, Oa, and H2O), the calculated results support that the bridge Ob atom of the polytungstate ligand will act as the most favorable proton acceptor in the O-O bond formation, with an energy barrier of 28.43 kcal mol(-1). A detailed information of the peroxidic intermediates in the oxidation process was also characterized, both the peroxo-species [Ru(IV)(OO)SiW11O39](6-) and [Ru(V)(OO)SiW11O39](5-) show the six-coordinate isomer with an open terminal geometry is more favorable than the close seven-coordinate ones. In addition, the replacement of the heteroatom in XO4(n-) can effectively tune the catalytic activity of polyoxometalates, in the order of Ge(IV) > Si(IV).

  11. Anti-influenza Activity of a Novel Polyoxometalate Derivative (POM-4960)

    PubMed Central

    Hosseini, Seyed Masoud; Amini, Elham; Tavassoti Kheiri, Masoumeh; Mehrbod, Parvaneh; Shahidi, Mahsa; Zabihi, Ebrahim

    2012-01-01

    There are many effective chemotherapeutic agents used in influenza disease which some of them inhibit virus replication by interfering with FluV (influenza virus) viral binding or its penetration into cell membrane. A series of polyoxometalates compounds such as POM-523 and PM-504 have been synthesized and have showed inhibitory effects on viruses. In this study we examined anti influenza activity of a novel polyoxometalate derivative (POM-4960) synthesized in the Faculty of Chemistry of Damghan University of Basic Sciences. To evaluate the anti-influenza activity of POM, following the treatment of FluV with POM at different temperatures and incubation periods, viral titer reduction was assessed by haemaglutination assay (HA). The 3-(4,5- dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was used to determine TCID50 (tissue culture infective dose) of virus, CC50 (median cytotoxic concentration) of POM, protection percentage and antiviral activity of POM in cell culture. RT-PCR and direct Immunofluorescent assays were performed to evaluate the effect of POM on viral infection and viral RNA load, respectively. POM reduced HA titer near to zero in all cell culture specimens and showed high protection against viral infection of the cells. Reduction in viral infection was confirmed by RT-PCR and Immunofluorescent staining methods. Moreover, this POM derivative has a dual (cumulative) effect on attachment and penetration inhibition compared to other POM’s with just one inhibitory effect. POM-4960 could be considered as a powerful anti-influenza agent with low toxicity and high antiviral potency. PMID:24551755

  12. Enhancement of fuel cell performance with less-water dependent composite membranes having polyoxometalate anchored nanofibrous interlayer

    NASA Astrophysics Data System (ADS)

    Abouzari-lotf, Ebrahim; Jacob, Mohan V.; Ghassemi, Hossein; Ahmad, Arshad; Nasef, Mohamed Mahmoud; Zakeri, Masoumeh; Mehdipour-Ataei, Shahram

    2016-09-01

    Polyoxometalate immobilized nanofiber was used to fabricate low gas permeable layer for composite membranes designed for proton exchange membrane fuel cell (PEMFC) operating at low relative humidity (RH). The composite membranes revealed enhanced proton conductivity in dry conditions compared with state-of-the-art pristine membrane (Nafion 112, N112). This was coupled with a low fuel crossover inheriting the composite membranes about 100 mV higher OCV than N112 when tested in PEMFC at 60 °C and 40% RH. A maximum power density of up to 930 mW cm-2 was also achieved which is substantially higher than the N112 under similar conditions (577 mW cm-2). Such remarkable performance enhancement along with undetectable leaching of immobilized polyoxometalate, high dimensional stability and low water uptake of the composite membranes suggest a strong potential for PEMFC under low RH operation.

  13. A series of Keggin-based compounds constructed by conjugate ring-rich pyrazine and quinoxaline derivatives.

    PubMed

    Tian, Aixiang; Tian, Yan; Ning, Yali; Hou, Xue; Ni, Huaiping; Ji, Xuebin; Liu, Guocheng; Ying, Jun

    2016-09-21

    Through the use of conjugate ring-rich pyrazine and quinoxaline derivatives, five new Keggin polymolybdate based compounds, [Ag(I)3L(1)2(H2O)2(PMo12O40)] (1), [Ag(I)4L(1)5(SiMo12O40)] (2), [Ag(I)6L(2)6(PMo12O40)2] (3), [Ag(I)2L(2)2(C16H36N)2](SiMo12O40)] (4), [Cu(I)3L(2)3(PMo12O40)] (5) (L(1) = 2,3-diphenylpyrazine, L(2) = 2,3-diphenylquinoxaline, C16H36N = tetrabutylammonium), were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. In compound 1, three Ag(I) ions are fused by two L(1) molecules to form a [Ag3L(1)2](3+) subunit, and these subunits link the PMo12 anions to construct two kinds of 1D chains (I and II). Chains I and II connect to each other by sharing the same PMo12 anions and a 2D grid-like layer is built. The asymmetric unit of compound 2 is linked to form a dimer by sharing Ag ions, and a 1D double strand is formed. The SiMo12 anions connect adjacent 1D double strands through Ag3-O23 bonds and a 2D network is built. In compound 3, there exists a 1D ladder-like double chain with PMo12 anions as linking bars. A 2D layer is formed by linkage Ag2-O24 between adjacent chains. In compound 4, the PMo12 anions act as inorganic linkages to connect adjacent zigzag chains through Ag1-O3 bonds to construct a 2D grid-like layer. In compound 5 two Cu(I)-L(2) lines are fused by PMo12 anions to build a 1D ladder-like chain. Additionally, the electrochemical and photocatalytic properties of the title compounds have been studied.

  14. Addition of N-heterocyclic carbenes to a ruthenium(VI) nitrido polyoxometalate: a new route to cyclic guanidines.

    PubMed

    Besson, Claire; Mirebeau, Jean-Hugues; Renaudineau, Séverine; Roland, Sylvain; Blanchard, Sébastien; Vezin, Hervé; Courillon, Christine; Proust, Anna

    2011-03-21

    The scope of N-atom transfer from the electrophilic ruthenium(VI) nitrido containing polyoxometalate [PW(11)O(39)Ru(VI)N](4-) has been extended to the N-heterocyclic carbene {CH(2)(Mes)N}(2)C and the coupling product {CH(2)(Mes)N}(2)CNH(2)(+) characterized by (1)H NMR and high-resolution mass spectrometry. Because guanidines display many fields of applications ranging from biology to supramolecular chemistry, this could afford an original route to the synthesis of cyclic guanidines. This also enlarges the potential of nitrido complexes in the synthesis of heterocycles, mainly illustrated in the literature through the formation of aziridines through N-atom transfer to alkenes. In the course of the reaction, the ruthenium(III)-containing polyoxometallic intermediate [PW(11)O(39)Ru(III){NC{N(Mes)CH(2)}(2)}](5-) has been thoroughly characterized by continuous-wave and pulsed electron paramagnetic resonance, which nicely confirms the presence of the organic moiety on the polyoxometallic framework, Ru K-edge X-ray absorption near-edge structure, and electrochemistry.

  15. Photo-catalytic H 2 evolution over a series of Keggin-structure heteropoly blue sensitized Pt/TiO 2 under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Fu, Ning; Lu, Gongxuan

    2009-02-01

    We report the visible light-induced hydrogen generation over a series of Keggin-structure heteropoly blue (HPB) anions (PW 12O 403-, phosphotungstic blue (PTB), GeW 12O 404- (GTB), SiW 12O 404- (STB), BW 12O 405- (BTB)) sensitized Pt/TiO 2 photo-catalysts. The sensitization of TiO 2 by HPB was certified using photo-electrochemical measurements and UV-vis absorption spectra. PTB showed the most pronounced sensitization effect for TiO 2 in those HPB anions and Pt/TiO 2-PTB showed the highest hydrogen generation activity. The sensitization of TiO 2 was significantly dependent on the reduction potential of HPA, which was determined by the kind of central atom in HPA.

  16. Solid state and aqueous behavior of uranyl peroxide cage clusters

    NASA Astrophysics Data System (ADS)

    Pellegrini, Kristi Lynn

    Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl

  17. Photoassisted and photocatalytic degradation of sulfur mustard using TiO2 nanoparticles and polyoxometalates.

    PubMed

    Naseri, Mohammad Taghi; Sarabadani, Mansour; Ashrafi, Davood; Saeidian, Hamdollah; Babri, Mehran

    2013-02-01

    The decomposition of highly toxic chemical warfare agent, sulfur mustard (bis(2-chloroethyl) sulfide or HD), has been studied by homogeneous photolysis and heterogeneous photocatalytic degradation on titania nanoparticles. Direct photolysis degradation of HD with irradiation system was investigated. The photocatalytic degradation of HD was investigated in the presence of TiO(2) nanoparticles and polyoxometalates embedded in titania nanoparticles in liquid phase at room temperature (33 ± 2 °C). Degradation products during the treatment were identified by gas chromatography-mass spectrometry. Whereas apparent first-order kinetics of ultraviolet (UV) photolysis were slow (0.0091 min(-1)), the highest degradation rate is obtained in the presence of TiO(2) nanoparticles as nanophotocatalyst. Simultaneous photolysis and photocatalysis under the full UV radiation leads to HD complete destruction in 3 h. No degradation products observed in the presence of nanophotocatalyst without irradiation in 3 h. It was found that up to 90 % of agent was decomposed under of UV irradiation without TiO(2), in 6 h. The decontamination mechanisms are often quite complex and multiple mechanisms can be operable such as hydrolysis, oxidation, and elimination. By simultaneously carrying out photolysis and photocatalysis in hexane, we have succeeded in achieving faster HD decontamination after 90 min with low catalyst loading. TiO(2) nanoparticles proved to be a superior photocatalyst under UV irradiation for HD decontamination. PMID:22707206

  18. Polyoxometalate incorporated porous polymer monoliths, a versatile separation media for nano liquid chromatography.

    PubMed

    Zhang, Zheng; Xu, Jing; Hussain, Dilshad; Feng, Yu-Qi

    2016-07-01

    Here in, we present a strategy to incorporate NBu4SiW11O39(SiCHCH2)2, an organic-modified polyoxometalates (POM) monomer, into the monolithic poly(butyl methacrylate-co-ethylene glycol dimethacrylate) capillary columns. SEM analysis and permeability test indicated that the addition of POM lead to larger skeleton size and better permeability. BET and pore size distribution test confirmed the uniform porosity of the resulting POM incorporated monoliths. Hydrophobic, strong cation-exchange and H-bond interactions of the prepared monolith were evaluated by testing a series of chromatographic probes. The performance of monolith was further elaborated by separating 5 nucleobases, and 6 neurotransmitters. Chromatographic separation results showed that POM incorporated monolith exhibited much better resolution for the analytes as compared to the monolith without POM. This type of monolithic material has been reported for the first time and the work provided a promising way for preparation and application of various POM-incorporated monolithic materials in separation science. PMID:27236481

  19. Use of polyoxometalate catalysts in ionic liquids to enhance the dissolution and delignification of woody biomass.

    PubMed

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

    2011-01-17

    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. PMID:21226213

  20. Nanocomposite film of TiO{sub 2} nanotube and polyoxometalate towards photocatalytic degradation of nitrobenzene

    SciTech Connect

    Sun, Zhixia; Zhao, Mingliang; Li, Fengyan Wang, Tianqi; Xu, Lin

    2014-12-15

    Highlights: • The film of POMs and TiO{sub 2} nanotubes was prepared by electrodeposition. • The photocatalytic activity of the composite film for nitrobenzene was investigated. • The composite film showed higher photocatalytic activity than pure TiO{sub 2} nanotubes. • The introduction of POMs into TiO{sub 2} could retard electron–hole recombination. - Abstract: The composite film based on polyoxometalates (POMs)-modified TiO{sub 2} nanotubes was prepared by electrodeposition method for the photocatalytic degradation of nitrobenzene. The composite film was characterized by field-emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy, which indicated that the POMs were well introduced into the TiO{sub 2} nanotubes. Furthermore, the photocatalytic properties of the TiO{sub 2} nanotubes and POMs-modified TiO{sub 2} nanotubes were evaluated by the decomposition of nitrobenzene. POMs-modified TiO{sub 2} nanotubes showed much higher photocatalytic activity than pure TiO{sub 2} nanotubes. These results provide a promising route to effectively photocatalytic degradation of nitrobenzene by POMs-modified TiO{sub 2} nanotubes.

  1. A general and highly regioselective synthesis approach to multi-functionalized organoimido derivatives of Polyoxometalates

    PubMed Central

    Huang, Yichao; Zhang, Jiangwei; Hao, Jian; Wei, Yongge

    2016-01-01

    Organoimidoylization of Polyoxometalates (POMs) can dramatically modify the electronic structures of POMs and gives rise to novel “value-adding” properties of the POMs for promising material applications including photo-electronic transformation and catalysis. To date, the preparation of multi-functionalized organoimido derivatives of POMs is generally conducted under strict condition and is time-consuming with limited yields. Herein, a series of regioselective polyorganoimido derivatives of POMs, ocatant- [Mo6O13(NAr)3(μ2-NAr)3]2− (Ar = phenyl (1), p-methoxyphenyl (2) and p-ethylphenyl (3)), were synthesized with high selectivity and in good yields via a general and highly regioselective synthesis method, called as the one-octant synthesis protocol. The reaction was monitored by ESI-MS and the as-prepared products were studied by ESI-MS, IR, UV-Vis, EA, 1HNMR, single crystal XRD analysis and DFT calculations. The one-octant synthesis protocol here may serve as an idea method to design novel nanoscale POM-based organic-inorganic multi-functional hybrids. PMID:27108955

  2. Self-Assembly of Polyoxometalate and Polyelectrolyte Macroions into Mechanically Strong Supramolecular Hydrogels

    NASA Astrophysics Data System (ADS)

    Jing, Benxin; Zhu, Y. Elaine

    Polyoxometalate (POM) macroions are the nanoclusters of transition metal oxide with size 1-10 nm and well-defined structure at the atom level. Because of their stoichiometric surface groups and high solubility in polar solvents to form thermodynamically stable solution, POMs are studied as excellent model macroions at nanoscale. In this work, we explore the electrostatic controlled self-assembly of anionic POMs and cationic or zwitterionic polyelectrolytes (PEs) in aqueous solution. Specifically we examine the complex formation of zwitterionic poly (3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide) (PSBMA) and cationic poly(diallyldimethylammonium chloride) (PDADMAC) with tungstate based POMs of varied valence. The phase diagram of POM/polyelectrolyte complexes is determined with varied POM/PE charge ratios. It is interesting to observe the coacervation of POMs with PSBMA. With cationic PDADMAC, hybrid POM-PDADMAC hydrogels can be formed. Nevertheless, POM-PDADMAC complexes exhibit much enhanced mechanical properties in comparison to polymer hydrogel. The viscoelastic properties of hybrid macroion complexes strongly depend on PDADMAC concentration, POM-to-PDADMAC molar ratio, the size and valence of POMs. At the intermediate range of POM-to-PDADMAC concentration ratio, shear thickening and strain hardening are observed with soft supramolecular hydrogels, which is resulted from the non-Gaussian stretching of polymer chains.

  3. Sensitive analysis of simazine based on platinum nanoparticles on polyoxometalate/multi-walled carbon nanotubes.

    PubMed

    Ertan, Bengü; Eren, Tanju; Ermiş, İsmail; Saral, Hasan; Atar, Necip; Yola, Mehmet Lütfi

    2016-05-15

    In this report, a novel molecular imprinted voltammetric sensor based on glassy carbon electrode (GCE) modified with platinum nanoparticles (PtNPs) involved in a polyoxometalate (H3PW12O40, POM) functionalized multi-walled carbon nanotubes (MWCNs) sheets was prepared for the determination of simazine (SIM). The developed surfaces were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) method. SIM imprinted GCE was prepared via electropolymerization process of 100mM pyrrole as monomer in the presence of 0.1M acetate buffer (pH 4.0) containing 25mM SIM. The linearity range and the detection limit of the developed method were calculated as 1.0×10(-10)-5.0×10(-9)M and 2.0×10(-11)M, respectively. In addition, the voltammetric sensor was applied to wastewater samples. The stability and reproducibility of the voltammetric sensor were also reported.

  4. A general and highly regioselective synthesis approach to multi-functionalized organoimido derivatives of Polyoxometalates

    NASA Astrophysics Data System (ADS)

    Huang, Yichao; Zhang, Jiangwei; Hao, Jian; Wei, Yongge

    2016-04-01

    Organoimidoylization of Polyoxometalates (POMs) can dramatically modify the electronic structures of POMs and gives rise to novel “value-adding” properties of the POMs for promising material applications including photo-electronic transformation and catalysis. To date, the preparation of multi-functionalized organoimido derivatives of POMs is generally conducted under strict condition and is time-consuming with limited yields. Herein, a series of regioselective polyorganoimido derivatives of POMs, ocatant- [Mo6O13(NAr)3(μ2-NAr)3]2- (Ar = phenyl (1), p-methoxyphenyl (2) and p-ethylphenyl (3)), were synthesized with high selectivity and in good yields via a general and highly regioselective synthesis method, called as the one-octant synthesis protocol. The reaction was monitored by ESI-MS and the as-prepared products were studied by ESI-MS, IR, UV-Vis, EA, 1HNMR, single crystal XRD analysis and DFT calculations. The one-octant synthesis protocol here may serve as an idea method to design novel nanoscale POM-based organic-inorganic multi-functional hybrids.

  5. Efficiency of Polyoxometalate-Based Mesoporous Hybrids as Covalently Anchored Catalysts.

    PubMed

    Bentaleb, Faiza; Makrygenni, Ourania; Brouri, Dalil; Coelho Diogo, Cristina; Mehdi, Ahmad; Proust, Anna; Launay, Franck; Villanneau, Richard

    2015-08-01

    Polyoxometalate (POM) hybrids have been covalently immobilized through the formation of amide bonds on several types of mesoporous silica. This work allows the comparison of three POM-based mesoporous systems, obtained with three different silica supports in which either the organic functions of the support (amine vs carboxylic acid) and/or the structure of the support itself (SBA-15 vs mesocellular foams (MCF)) were varied. The resulting POM-based mesoporous systems have been studied in particular by high resolution transmission electronic microscopy (HR-TEM) in order to characterize the nanostructuration of the POMs inside the pores/cells of the different materials. We thus have shown that the best distribution and loading in POMs have been reached with SBA-15 functionalized with aminopropyl groups. In this case, the formation of amide bonds in the materials has led to the nonaggregation of the POMs inside the channels of the SBA-15. The catalytic activity of the anchored systems has been evaluated through the epoxidation of cyclooctene and cyclohexene with H2O2 in acetonitrile. The reactivity of the different grafted POMs hybrids has been compared to that in solution (homogeneous conditions). Parallels can be drawn between the distribution of the POMs and the activity of the supported systems. Furthermore, recycling tests together with catalyst filtration experiments during the reaction allowed us to preclude the hypothesis of a significant leaching of the supported catalyst. PMID:26161980

  6. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution.

    PubMed

    Rustad, James R; Casey, William H

    2012-03-01

    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. PMID:22231599

  7. Polyoxometalate incorporated porous polymer monoliths, a versatile separation media for nano liquid chromatography.

    PubMed

    Zhang, Zheng; Xu, Jing; Hussain, Dilshad; Feng, Yu-Qi

    2016-07-01

    Here in, we present a strategy to incorporate NBu4SiW11O39(SiCHCH2)2, an organic-modified polyoxometalates (POM) monomer, into the monolithic poly(butyl methacrylate-co-ethylene glycol dimethacrylate) capillary columns. SEM analysis and permeability test indicated that the addition of POM lead to larger skeleton size and better permeability. BET and pore size distribution test confirmed the uniform porosity of the resulting POM incorporated monoliths. Hydrophobic, strong cation-exchange and H-bond interactions of the prepared monolith were evaluated by testing a series of chromatographic probes. The performance of monolith was further elaborated by separating 5 nucleobases, and 6 neurotransmitters. Chromatographic separation results showed that POM incorporated monolith exhibited much better resolution for the analytes as compared to the monolith without POM. This type of monolithic material has been reported for the first time and the work provided a promising way for preparation and application of various POM-incorporated monolithic materials in separation science.

  8. Polyoxometalates as peroxidase mimetics and their applications in H2O2 and glucose detection.

    PubMed

    Wang, Jingjing; Han, Dongxue; Wang, Xiaohong; Qi, Bin; Zhao, Meisheng

    2012-01-01

    Polyoxometalates (H(3)PW(12)O(40), H(4)SiW(12)O(40) and H(3)PMo(12)O(40)) have been proven to possess intrinsic peroxidase-like activity for the first time, which can catalyze oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) by H(2)O(2) to form a blue color in aqueous solution. Among them, H(3)PW(12)O(40) (PW(12)) exhibits higher catalytic activity to TMB than natural enzyme HRP and other two POMs. In addition, H(3)PW(12)O(40)/graphene exhibited higher activity than H(3)PW(12)O(40) in this catalytic oxidation reaction due to the effect of graphene in promoting the electron transfer between the substrate and catalyst. POMs/H(2)O(2)/TMB system provides a simple, accurate approach to colorimetric detection for H(2)O(2) or glucose. The colorimetric method based on POMs showed good response toward H(2)O(2) and glucose detection with a linear range from 1.34×10(-7) to 6.7×10(-5) mol/L and 1×10(-7) to 1×10(-4) mol/L, respectively. The results showed that it is a simple, cheap, more convenient, highly selective, sensitive, and easy handling colorimetric assay. PMID:22560441

  9. Multi-stimuli Responsive Supramolecular Structures Based on Azobenzene Surfactant-Encapsulated Polyoxometalate.

    PubMed

    Guo, Yongxian; Gong, Yanjun; Gao, Yan'an; Xiao, Jianhong; Wang, Tao; Yu, Li

    2016-09-13

    Multi-stimuli responsive materials have attracted intense attention as extensive application prospect in many fields, yet achievement of multi-stimuli responsiveness remains a challenge. Herein, we report a tri-stimuli responsive supramolecular structure fabricated by a cationic surfactant, 4-ethyl-4'-(trimethylaminohexyloxy) azobenzene bromide (ETAB), and anionic Eu-containing polyoxometalates (Eu-POM), based on an ionic self-assembly (ISA) strategy. Following different responsive mechanisms, the resultant ETAB/Eu-POM supramolecular materials are responsive to UV light, pH, and Cu(2+), respectively. The response to UV irradiation is based on the configuration change of azobenzene molecules. The response to H(+) can be attributed to the formation of a hydrogen bond W-O···H···O-H among Eu-POM, H(+), and H2O, which blocks the energy transfer pathway from O → W, while the coordination interaction between Cu(2+) and Oc (bridged oxygen of two octahedra sharing an edge in the Eu-POM molecule) causes the response to Cu(2+). The multi-stimuli responsive characteristics for the ETAB/Eu-POM supramolecular structures maybe provide a potential application in ultraviolet detection, optical storage devices, and chemical substance sensors, etc. PMID:27548373

  10. A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

    PubMed

    Wei, Jie; Feng, Yingying; Zhou, Panpan; Liu, Yan; Xu, Jingyin; Xiang, Rui; Ding, Yong; Zhao, Chongchao; Fan, Linyuan; Hu, Changwen

    2015-08-24

    To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts.

  11. Langmuir and Langmuir-Blodgett films of hybrid amphiphiles with a polyoxometalate headgroup.

    PubMed

    Wang, Xiao-Le; Wang, Yong-Liang; Miao, Wen-Ke; Hu, Min-Biao; Tang, Jing; Yu, Wei; Hou, Zhan-Yao; Zheng, Ping; Wang, Wei

    2013-06-01

    A hybrid was at first synthesized by a postfunctionalization of an aminomethane trisalkoxo-functionalized Anderson-type polyoxometalate (POM) encapsulated by three tetrabutylammonium ions using a 3,5-bis(tetradecyloxy)benzoic acid by amidation. Then the three TBA(+) counter cations were programmatically replaced by protons (H(+)) following a molecule-to-amphiphile conversion. In this way one hybrid and three POM-containing hybrid amphiphiles (PCHAs) were acquired by adjusting the number (n) of TBA(+) ions and number (3 - n) of H(+) ions (n = 3, 2, 1, and 0). These compounds can be spread onto a water surface to form a Langmuir monolayer film at the air-water interface. Surface pressure-molecular area measurements exhibit the TBA(+) (H(+)) number playing an important role in the forming ability and stability of Langmuir monolayer films. Also, the Langmuir-Blodgett (LB) technique has been used to transfer the monolayer film onto solid supports to fabricate solid multilayer films. It was found that the PCHA with three H(+) ions had the best Langmuir film-forming ability and thus formed stable LB films with a two-dimensional ordered structure. Our findings are instructive in fabricating and using solid films of the amphiphiles with POM headgroups.

  12. Facile decoration of Au nanoparticles on CdS nanorods by polyoxometalate with enhanced photocatalytic activities toward hydrogen evolution.

    PubMed

    Xing, Xiaolin; Liu, Rongji; Wang, Zhanli; Ren, Baozeng; Jiang, Zhenxi; Zhao, Hui; Cao, Hongbin; Zhang, Guangjin; Zhang, Tao

    2013-07-01

    The tri-component hybrid CdS nanorods (NRs)/Au nanoparticles (NPs)@polyoxometalate (POM) was successfully prepared by a facile, efficient and green method. The structural properties and component analysis were studied by Transmission electron microscopy (TEM), X-ray Diffraction (XRD) and UV-Vis spectra. The POMs sever as not only reductant and bridge molecules, but also as co-catalyst to play an important role in the photocatalytic process. The as-prepared nanohybrid shows obviously enhanced photocatalytic activity toward photocatalytic evolution of hydrogen. PMID:23901482

  13. Visible-light-responsive multielectron redox catalysis of lacunary polyoxometalates induced by substrate coordination to their lacuna.

    PubMed

    Suzuki, Kosuke; Jeong, Jinu; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-01-01

    We describe herein the efficient visible-light-responsive polyoxometalate-based multielectron photoredox catalysis induced by in situ coordination of alcohols to the lacuna of TBA4 H4 [γ-SiW10 O36 ] (I, TBA=tetra-n-butylammonium). The coordination of alcohols to the lacuna of I generated a new highest occupied molecular orbital as the electron donor level and enabled the visible-light-responsive multielectron transfer from alcohols to I, which could be utilized for aerobic alcohol oxidation and one-pot synthesis of N-arylimines starting from nitroarenes and primary alcohols.

  14. A polyoxometalate-based single-molecule magnet with a mixed-valent {Mn(IV)2Mn(III)6Mn(II)4} core.

    PubMed

    Zhang, Zhi-Ming; Yao, Shuang; Li, Yang-Guang; Wu, Hai-Hong; Wang, Yong-Hui; Rouzières, Mathieu; Clérac, Rodolphe; Su, Zhong-Min; Wang, En-Bo

    2013-03-28

    A polyoxometalate (POM)-based {Mn(IV)2Mn(III)6Mn(II)4} complex with single-molecule magnet (SMM) behaviour was prepared, exhibiting the largest known Mn nuclearity and the most Mn valence states in the POM-based SMM family.

  15. Polyoxometalates-based heterometallic organic-inorganic hybrid materials for rapid adsorption and selective separation of methylene blue from aqueous solutions.

    PubMed

    Yi, Fei-Yan; Zhu, Wei; Dang, Song; Li, Jian-Ping; Wu, Dai; Li, Yun-hui; Sun, Zhong-Ming

    2015-02-25

    A series of LnCu-polyoxometalates (POMs) were used for dye-wastewater treatment with rapid (within 1 min) and large-scale adsorption (up to 391.3 mg g(-1)) as well as excellent selective separation of cationic dyes. Furthermore, the adsorbed dyes can be easily desorbed, and the POMs still work very efficiently even after three cycles.

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

    NASA Astrophysics Data System (ADS)

    Ou, Jinzhao; Mei, Mingliang; Xu, Xinxin

    2016-06-01

    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

  17. Mo polyoxometalate nanoclusters capable of inhibiting the aggregation of Aβ-peptide associated with Alzheimer's disease

    NASA Astrophysics Data System (ADS)

    Chen, Qingchang; Yang, Licong; Zheng, Chuping; Zheng, Wenjing; Zhang, Jingnan; Zhou, Yunshan; Liu, Jie

    2014-05-01

    A neuropathological hallmark of Alzheimer's disease (AD) is aggregation of a forty-residue peptide known as amyloid beta forty (Aβ40). While past work has indicated that blocking Aβ40 aggregation could be an effective strategy for the treatment of AD, developing therapies with this goal has been met with limited success. Polyoxometalates (POMs) have been previously investigated for their anti-viral and anti-tumoral properties and we report here that three representative POM nanoclusters have been synthesized for use against Aβ40 aggregation. Through the use of thioflavin T fluorescence, turbidity, circular dichroism spectroscopy, and transmission electron microscopy (TEM), we found that all three POM complexes can significantly inhibit both natural Aβ40 self-aggregation and metal-ion induced Aβ40 aggregation. We also evaluated the protective effect of POM complexes on Aβ40-induced neurotoxicity in cultured PC12 cells and found that treatment with POM complexes can elevate cell viability, decrease levels of intracellular reactive oxygen species, and stabilize mitochondrial membrane potential. These findings indicate that all three representative POM complexes are capable of inhibiting Aβ40 aggregation and subsequent neurotoxicity. While a complete mechanistic understanding remains to be elucidated, the synthesized POM complexes may work through a synergistic interaction with metal ions and Aβ40. These data indicate that POM complexes have high therapeutic potential for use against one of the primary neuropathological features of AD.A neuropathological hallmark of Alzheimer's disease (AD) is aggregation of a forty-residue peptide known as amyloid beta forty (Aβ40). While past work has indicated that blocking Aβ40 aggregation could be an effective strategy for the treatment of AD, developing therapies with this goal has been met with limited success. Polyoxometalates (POMs) have been previously investigated for their anti-viral and anti-tumoral properties

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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. Mixed-Metal, Structural, and Substitution Effects of Polyoxometalates on Electrochemical Behavior in a Redox Flow Battery

    SciTech Connect

    Pratt, Harry D; Pratt, William R; Fang, Xikui; Hudak, Nicholas S; Anderson, Travis M

    2014-08-01

    A pair of redox flow batteries containing polyoxometalates was tested as part of an ongoing program in stationary energy storage. The iron-containing dimer, (SiFe3W9(OH)3O34)2(OH)311-, cycled between (SiFe3W9(OH)3O34)2(OH)311-/(SiFe3W9(OH)3O34)2(OH)314-and (SiFe3W9(OH)3O34)2(OH)317-/(SiFe3W9(OH)3O34)2(OH)314- for the positive and negative electrode, respectively. This compound demonstrated a coulombic efficiency of 83% after 20 cycles with an electrochemical yield (measured discharge capacity as a percentage of theoretical capacity) of 55%. Cyclic voltammetry on the Lindqvist ion, cis-V2W4O194-, showed quasi-reversible vanadium electrochemistry, but tungsten reduction was mostly irreversible. In a flow cell configuration, cis-V2W4O194-had a coulombic efficiency of 45% (for a two-electron process) and an electrochemical yield of 16% after 20 cycles. The poor performance of cis-V2W4O194-was attributed primarily to its higher charge density. Collectively, the results showed that both polyoxometalate size and charge density are both important parameters to consider in battery material performance.

  20. Precursor salt assisted syntheses of high-index faceted concave hexagon and nanorod-like polyoxometalates.

    PubMed

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

    2015-01-14

    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. PMID:25500856

  1. Symbolic clustering

    SciTech Connect

    Reinke, R.E.

    1991-01-01

    Clustering is the problem of finding a good organization for data. Because there are many kinds of clustering problems, and because there are many possible clusterings for any data set, clustering programs use knowledge and assumptions about individual problems to make clustering tractable. Cluster-analysis techniques allow knowledge to be expressed in the choice of a pairwise distance measure and in the choice of clustering algorithm. Conceptual clustering adds knowledge and preferences about cluster descriptions. In this study the author describes symbolic clustering, which adds representation choice to the set of ways a data analyst can use problem-specific knowledge. He develops an informal model for symbolic clustering, and uses it to suggest where and how knowledge can be expressed in clustering. A language for creating symbolic clusters, based on the model, was developed and tested on three real clustering problems. The study concludes with a discussion of the implications of the model and the results for clustering in general.

  2. A molecular hybrid polyoxometalate-organometallic moieties and its relevance to supercapacitors in physiological electrolytes

    NASA Astrophysics Data System (ADS)

    Chinnathambi, Selvaraj; Ammam, Malika

    2015-06-01

    Supercapacitors operating in physiological electrolytes are of great relevance for both their environmentally friendly aspect as well as the possibility to be employed for powering implantable microelectronic devices using directly biological fluids as electrolytes. Polyoxometalate (POMs) have been proven to be useful for supercapacitors in acidic media. However, in neutral pH, POMs are usually not stable. One relevant alternative is to stabilize POMs by pairing them with organic moieties to form hybrids. In this study, we combined K6P2Mo18O62·12H2O (P2Mo18) with Ru(bpy)3Cl2.6H2O (Ru(bpy)). The synthesis was carried out with and without the mild reducing agent KI. The hybrids were characterized by CHN analysis, TEM, FT-IR, XRD, TGA and cyclic voltammetry. CHN elemental analysis revealed that one mole [P2Mo18O62]6- is paired with 3 mol [Ru(bpy)3]2+ to form [Ru(bpy)3]3PMo18O62·nH2O. With KI present, [P2Mo18O62]6- is linked to 3.33 mol to yield [Ru(bpy)3]3.33PMo18O62·mH2O. Excess of Ru(bpy) in [Ru(bpy)3]3.33PMo18O62·mH2O was further confirmed by TEM, FT-IR, XRD, TGA and cyclic voltammetry. In turn, hybrid composition is found to strongly influence the supercapacitor behavior. The hybrid rich in Ru(bpy) is found to perform better for supercapacitors in physiological electrolytes. 125 F g-1 and 68 F g-1 are the capacitance values obtained with [Ru(bpy)3]3.33PMo18O62·mH2O and [Ru(bpy)3]3PMo18O62·nH2O, respectively. In terms of specific energy densities, 3.5 Wh kg-1 and 2 Wh kg-1 were obtained for both hybrid simultaneously. The difference in supercapacitor performance between both hybrids is also noticed in impedance spectroscopy which showed that [Ru(bpy)3]3.33PMo18O62·mH2O has lower electron transfer resistance if compared to [Ru(bpy)3]3PMo18O62·nH2O. Finally, if compared of parent K6P2Mo18O62·12H2O, the stability of both hybrids is found to be highly improved.

  3. Kinetic studies of phosphoester hydrolysis promoted by a dimeric tetrazirconium(iv) Wells-Dawson polyoxometalate.

    PubMed

    Luong, Thi Kim Nga; Shestakova, Pavletta; Parac-Vogt, Tatjana N

    2016-07-26

    The catalytic hydrolysis of a phosphoester bond in the DNA-model substrate 4-nitrophenyl phosphate (NPP) promoted by Zr(iv)-substituted Wells-Dawson Na14[Zr4(P2W16O59)2(μ3-O)2(OH)2(H2O)4]·57H2O polyoxometalate (ZrWD 4 : 2) was followed by means of (1)H and (31)P NMR spectroscopy. The hydrolytic reaction proceeded with a rate constant of 8.44 (±0.36) × 10(-5) s(-1) at pD 6.4 and 50 °C, representing a 300-fold rate enhancement in comparison with the spontaneous hydrolysis of NPP (kobs = 2.81 (±0.25) × 10(-7) s(-1)) under the same reaction conditions. The ZrWD 4 : 2 was also active towards hydrolysis of bis(4-nitrophenyl) phosphate (BNPP) and the RNA model substrate 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP). The pD dependence of kobs shows that the rate constants for NPP hydrolysis decrease significantly when the pD values of the reaction mixtures increase. The formation constant (Kf = 190 M(-1)) and catalytic rate constant (kc = 6.40 × 10(-4) s(-1)) for the NPP-ZrWD 4 : 2 complex, activation energy (Ea) of 110.15 ± 7.06 kJ mol(-1), enthalpy of activation (ΔH(‡)) of 109.03 ± 6.86 kJ mol(-1), entropy of activation (ΔS(‡)) of 15.20 ± 2.49 J mol(-1) K(-1), and Gibbs activation energy (ΔG(‡)) of 104.32 ± 6.09 kJ mol(-1) at 37 °C were calculated from kinetic studies. The recyclability of ZrWD 4 : 2 was examined by adding an extra amount (5.0 mM) of NPP twice to a fully hydrolyzed mixture of 5.0 mM NPP and 1.0 mM ZrWD 4 : 2. The interaction between ZrWD 4 : 2 and the P-O bond of NPP was evidenced by a change in the (31)P chemical shift of the (31)P atom in NPP upon addition of ZrWD 4 : 2. Based on (31)P NMR experiments and the kinetic studies, a mechanism for NPP hydrolysis promoted by ZrWD 4 : 2 has been proposed. PMID:27406623

  4. Sensitization of lanthanoid luminescence by organic and inorganic ligands in lanthanoid-organic-polyoxometalates.

    PubMed

    Ritchie, Chris; Baslon, Valérie; Moore, Evan G; Reber, Christian; Boskovic, Colette

    2012-01-16

    The reaction of terbium and europium salts with the lacunary polyxometalate (POM) [As(2)W(19)O(67)(H(2)O)](14-) and 2-picolinic acid (picH) affords the ternary lanthanoid-organic-polyoxometalate (Ln-org-POM) complexes [Tb(2)(pic)(H(2)O)(2)(B-β-AsW(8)O(30))(2)(WO(2)(pic))(3)](10-) (1), [Tb(8)(pic)(6)(H(2)O)(22)(B-β-AsW(8)O(30))(4)(WO(2)(pic))(6)](12-) (2), and [Eu(8)(pic)(6)(H(2)O)(22)(B-β-AsW(8)O(30))(4)(WO(2)(pic))(6)](12-) (3). A detailed synthetic investigation has established the conditions required to isolate pure bulk samples of the three complexes as the mixed salts H(0.5)K(8.5)Na[1]·30H(2)O, K(4)Li(4)H(4)[2]·58H(2)O, and Eu(1.66)K(7)[3]·54H(2)O, each of which has been characterized by single crystal X-ray diffraction. Complexes 2 and 3 are isostructural and can be considered to be composed of two molecules of 1 linked through an inversion center with four additional picolinate-chelated lanthanoid centers. When irradiated with a laboratory UV lamp at room temperature, compounds K(4)Li(4)H(4)[2]·58H(2)O and Eu(1.66)K(7)[3]·54H(2)O visibly luminesce green and red, respectively, while compound H(0.5)K(8.5)Na[1]·30H(2)O is not luminescent. A variable temperature photophysical investigation of the three compounds has revealed that both the organic picolinate ligands and the inorganic POM ligands sensitize the lanthanoid(III) luminescence, following excitation with UV light. However, considerably different temperature dependencies are observed for Tb(III) versus Eu(III) through the two distinct sensitization pathways. PMID:22220495

  5. Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties

    SciTech Connect

    Tang Qun; Liu Shuxia; Liang Dadong; Ma Fengji; Ren Guojian; Wei Feng; Yang Yuan; Li Congcong

    2012-06-15

    A series of lanthanide-organic complexes based on polyoxometalates (POMs) [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}][W{sub 6}O{sub 19}] (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 [W{sub 6}O{sub 19}]{sup 2-} and dimeric [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}]{sup 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 [Ln{sub 2}(DNBA){sub 4}]{sup 2+} remains unchanged in solution. The conservation of red luminescence is attributed to the maintenance of the aggregated state structures of dimeric cations. - Graphical abstract: 3D POMs-based lanthanide-organic complexes performed the solvent effect on the luminescence property. The origin of such solvent effect can be understood and explained on the basis of the existence of coordinated active sites by the studies of ESI-MS. Highlights: Black-Right-Pointing-Pointer The solvent effect on the luminescence property of POMs-based lanthanide-organic complexes. Black-Right-Pointing-Pointer ESI-MS analyses illuminate the correlation between the structure and luminescence property. Black-Right-Pointing-Pointer The dimeric cations have eight active sites of solvent coordination. Black-Right-Pointing-Pointer The aggregated state structure of dimer cation remains unchanged in solution. Black-Right-Pointing-Pointer Luminescence associating with ESI-MS is a new method for investigating the interaction of complex and solvent.

  6. Preparation of α1- and α2-isomers of mono-Ru-substituted Dawson-type phosphotungstates with an aqua ligand and comparison of their redox potentials, catalytic activities, and thermal stabilities with Keggin-type derivatives.

    PubMed

    Nishiki, Kensuke; Umehara, Naoya; Kadota, Yusuke; López, Xavier; Poblet, Josep M; Mezui, Charyle Ayingone; Teillout, Anne-Lucie; Mbomekalle, Israël M; de Oliveira, Pedro; Miyamoto, Mayumi; Sano, Tsuneji; Sadakane, Masahiro

    2016-03-01

    Both the α1- and the α2-isomers of mono-ruthenium (Ru)-substituted Dawson-type phosphotungstates with terminal aqua ligands, [α1-P2W17O61Ru(III)(H2O)](7-) (α1-RuH2O) and [α2-P2W17O61Ru(III)(H2O)](7-) (α2-RuH2O), were prepared in pure form by cleavage of the Ru-S bond of the corresponding DMSO derivatives, [α1-P2W17O61Ru(DMSO)](8-) (α1-RuDMSO) and [α2-P2W17O61Ru(DMSO)](8-) (α2-RuDMSO), respectively. Redox studies indicated that α1-RuH2O and α2-RuH2O show proton-coupled electron transfer (PCET), and the Ru(III)(H2O) species was reversibly reduced to Ru(II)(H2O) species and oxidized to Ru(IV)([double bond, length as m-dash]O) species and further to Ru(V)([double bond, length as m-dash]O) species in aqueous solution depending on the pH. Their redox potentials and thermal stabilities were compared with those of the corresponding α-Keggin-type derivatives ([α-XW11O39Ru(H2O)](n-); X = Si(4+) (n = 5), Ge(4+) (n = 5), or P(5+) (n = 4)). The basic electronic and redox features of Ru(L)-substituted Keggin- and Dawson-type heteropolytungstates (with L = H2O or O(2-)) were analyzed by means of density functional calculations. Similar to the corresponding α-Keggin-type derivatives, both α1-RuH2O and α2-RuH2O show catalytic activity for water oxidation. PMID:26672976

  7. Structural diversity of polyoxomolybdate clusters along the three-fold axis of the molybdenum storage protein.

    PubMed

    Poppe, Juliane; Warkentin, Eberhard; Demmer, Ulrike; Kowalewski, Björn; Dierks, Thomas; Schneider, Klaus; Ermler, Ulrich

    2014-09-01

    The molybdenum storage protein (MoSto) can store more than 100 Mo or W atoms as discrete polyoxometalate (POM) clusters. Here, we describe the three POM cluster sites along the threefold axis of the protein complex based on four X-ray structures with slightly different polyoxomolybdate compositions between 1.35 and 2 Å resolution. In contrast to the Moα-out binding site occupied by an Mo3 cluster, the Moα-in and Moβ binding sites contain rather weak and non-uniform electron density for the Mo atoms (but clearly identifiable by anomalous data), suggesting the presence of POM cluster ensembles and/or degradation products of larger aggregates. The "Moα-in cluster ensemble" was interpreted as an antiprism-like Mo6 species superimposed with an Mo7 pyramide and the "Moβ cluster ensemble" as an Mo13 cluster (present mostly in a degraded form) composed of a pyramidal Mo7 and a Mo3 building block linked by three spatially separated MoOx units. Inside the ball-shaped Mo13 cluster sits an occluded central atom, perhaps a metal ion. POM cluster formation at the Moα-in and Moβ sites appears to be driven by filtering out and binding/protecting self-assembled transient species complementary to the protein template.

  8. A dual-responsive superparamagnetic Fe 3O 4/Silica/PAH/PSS material used for controlled release of chemotherapeutic agent, keggin polyoxotungstate, PM-19

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

    A bicontrollable drug release system was developed by layer-by-layer assembly of poly(allylamine hydrochloride) (PAH)/sodium poly(styrene sulfonate) (PSS) multilayers onto a Fe 3O 4/SiO 2 composite core. The saturated magnetization of this system reaches up to 38.6 emu/g at RT, making targeting easily controlled by an external magnetic field. Meanwhile, the packing of the polyelectrolyte multilayers is sensitive to pH values, generating a pH-switch on-off mode for the release of loaded drugs. In this specific case, the release of a chemotherapeutic polyoxometalate K 7Ti 2W 10PO 40·6H 2O (PM-19) was tested. Transmission electron microscopy (TEM) was used to examine the nanostructure of the composite drug release system. UV-vis absorption was used to monitor the drug release. Fourier transform infrared (FTIR), Powder X-ray diffraction, and Elemental analyses were used to study the composition of tested systems. The structure and composition of the composite system was also studied using magnetism measurement and nitrogen adsorption-desorption.

  9. CLUSTER CHEMISTRY

    SciTech Connect

    Muetterties, Earl L.

    1980-05-01

    Metal cluster chemistry is one of the most rapidly developing areas of inorganic and organometallic chemistry. Prior to 1960 only a few metal clusters were well characterized. However, shortly after the early development of boron cluster chemistry, the field of metal cluster chemistry began to grow at a very rapid rate and a structural and a qualitative theoretical understanding of clusters came quickly. Analyzed here is the chemistry and the general significance of clusters with particular emphasis on the cluster research within my group. The importance of coordinately unsaturated, very reactive metal clusters is the major subject of discussion.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    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. Solar-induced direct biomass-to-electricity hybrid fuel cell using polyoxometalates as photocatalyst and charge carrier.

    PubMed

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

    2014-01-01

    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.

  12. The use of polyoxometalates in protein crystallography – An attempt to widen a well-known bottleneck

    PubMed Central

    Bijelic, Aleksandar; Rompel, Annette

    2015-01-01

    Polyoxometalates (POMs) are discrete polynuclear metal-oxo anions with a fascinating variety of structures and unique chemical and physical properties. Their application in various fields is well covered in the literature, however little information about their usage in protein crystallization is available. This review summarizes the impact of the vast class of POMs on the formation of protein crystals, a well-known (frustrating) bottleneck in macromolecular crystallography, with the associated structure elucidation and a particular emphasis focused on POM's potential as a powerful crystallization additive for future research. The Protein Data Bank (PDB) was scanned for protein structures with incorporated POMs which were assigned a PDB ligand ID resulting in 30 PDB entries. These structures have been analyzed with regard to (i) the structure of POM itself in the immediate protein environment, (ii) the kind of interaction and position of the POM within the protein structure and (iii) the beneficial effects of POM on protein crystallography apparent so far. PMID:26339074

  13. Polyoxometalate-based homochiral metal-organic frameworks for tandem asymmetric transformation of cyclic carbonates from olefins

    PubMed Central

    Han, Qiuxia; Qi, Bo; Ren, Weimin; He, Cheng; Niu, Jingyang; Duan, Chunying

    2015-01-01

    Currently, great interest is focused on developing auto-tandem catalytic reactions; a substrate is catalytically transferred through mechanistically distinct reactions without altering any reaction conditions. Here by incorporating a pyrrolidine moiety as a chiral organocatalyst and a polyoxometalate as an oxidation catalyst, a powerful approach is devised to achieve a tandem catalyst for the efficient conversion of CO2 into value-added enantiomerically pure cyclic carbonates. The multi-catalytic sites are orderly distributed and spatially matched in the framework. The captured CO2 molecules are synergistically fixed and activated by well-positioned pyrrolidine and amine groups, providing further compatibility with the terminal W=O activated epoxidation intermediate and driving the tandem catalytic process in a single workup stage and an asymmetric fashion. The structural simplicity of the building blocks and the use of inexpensive and readily available chemical reagents render this approach highly promising for the development of practical homochiral materials for CO2 conversion. PMID:26678963

  14. Revisiting the Polyoxometalate-Based Late-Transition-Metal-Oxo Complexes: The “Oxo Wall” Stands

    SciTech Connect

    O; Halloran, Kevin P.; Zhao, Chongchao; Ando, Nicole S.; Schultz, Arthur J.; Koetzle, Thomas F.; Piccoli, Paula M. B.; Hedman, Britt; Hodgson, Keith O.; Bobyr, Elena; Kirk, Martin L.; Knottenbelt, Sushilla; Depperman, Ezra C.; Stein, Benjamin: Anderson, Travis M.; Cao, Rui; Geletii, Yurii V.; Hardcastle, Kenneth I.; Musaev, Djamaladdin G.; Neiwert, Wade A.; Fang, Xikui; Morokuma, Keiji; Wu, Shaoxiong; Koegerler, Paul, Hill, Craig L.

    2012-06-13

    Terminal oxo complexes of the late transition metals Pt, Pd, and Au have been reported by us in Science and Journal of the American Chemical Society. Despite thoroughness in characterizing these complexes (multiple independent structural methods and up to 17 analytical methods in one case), we have continued to study these structures. Initial work on these systems was motivated by structural data from X-ray crystallography and neutron diffraction and 17O and 31P NMR signatures which all indicated differences from all previously published compounds. With significant new data, we now revisit these studies. New X-ray crystal structures of previously reported complexes K14[P2W19O69(OH2)] and “K10Na3[PdIV(O)(OH)WO(OH2)(PW9O34)2]” and a closer examination of these structures are provided. Also presented are the 17O NMR spectrum of an 17O-enriched sample of [PW11O39]7– and a careful combined 31P NMR-titration study of the previously reported “K7H2[Au(O)(OH2)P2W20O70(OH2)2].” These and considerable other data collectively indicate that previously assigned terminal Pt-oxo and Au-oxo complexes are in fact cocrystals of the all-tungsten structural analogues with noble metal cations, while the Pd-oxo complex is a disordered Pd(II)-substituted polyoxometalate. The neutron diffraction data have been re-analyzed, and new refinements are fully consistent with the all-tungsten formulations of the Pt-oxo and Au-oxo polyoxometalate species.

  15. Green and facile synthesis of an Au nanoparticles@polyoxometalate/ordered mesoporous carbon tri-component nanocomposite and its electrochemical applications.

    PubMed

    Zhang, Yufan; Bo, Xiangjie; Nsabimana, Anaclet; Munyentwali, Alexis; Han, Ce; Li, Mian; Guo, Liping

    2015-04-15

    The one-pot synthesis of a well-defined Au nanoparticles@polyoxometalates/ordered mesoporous carbon (Au@POMs/OMC) tri-component nanocomposite is reported, which is facile, green and rapid. The polyoxometalates were used as both reductant and bridging molecules. The formation of these composite materials was verified by a comprehensive characterization using X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectra, scanning electron microscopy, and transmission electron microscopy. The novel nanohybrids of Au@POMs/OMC can provide new features of electrocatalytic activities, because of the synergetic effects of Au nanoparticles and OMC materials. Most importantly, the amperometric measurements show that the Au@POMs/OMC nanohybrids have a high catalytic activity with a good sensitivity, long-term stability, wide linear range, low detection limit, and fast response towards acetaminophenol, H2O2, and NADH detection for application as an enzyme-free biosensor. PMID:25460901

  16. SO3H-functionalized organic-inorganic ionic liquids based on polyoxometalates characterization and their application in Csbnd C coupling reaction

    NASA Astrophysics Data System (ADS)

    Rafiee, Ezzat; Mirnezami, Fakhrosadat; Kahrizi, Masoud

    2016-09-01

    Different ionic liquids (ILs) with SO3H as functional group were achieved by combining SO3H-functionalized organic cations and polyoxometalates (POM). The obtained salts were characterized and their catalytic activities investigated in Csbnd C coupling between benzhydrol and aromatic compounds at neat conditions, including the effect of organic cations, influence of POMs, optimization of reaction conditions, and reusability of the catalyst. Furthermore, Recovery, reusability and activity of ILs as heterogeneous catalysts were studied at least four times.

  17. Co-assembly and luminescence tuning of hybrids with task-specified ionic liquid encapsulating and linking lanthanide-polyoxometalates and complexes.

    PubMed

    Yan, Bing; Cuan, Jing

    2014-10-01

    A class of novel multifunctional hybrids assembled by lanthanide polyoxometalates, ionic liquid and lanthanide complexes were prepared through the reactions of ion exchange and coordination in mild conditions. These hybrids possess two luminescence centers, one is lanthanide polyoxometalates ([EuW10O36](9-) or [TbW10O36](9-)), the other is lanthanide complexes of 1,10-phenanthroline (phen) (or 2,2'-bipyridine (bpy)) and ionic liquid (1-methyl-3-propionic imidazole unit). Fourier transform infrared (FTIR) spectra, X-ray diffraction (XRD) analysis, thermo-gravimetric analysis (TGA), UV/vis diffuse reflectance spectra and photoluminescent properties are utilized to characterize these hybrid materials. The results reveal that all hybrids possess amorphous microstructures and are composed of inorganic polyoxometalates and lanthanide nitrate through chemical bonds. Most hybrids exhibit outstanding luminescent properties such as high quantum efficiency and long lifetimes. Moreover, the luminescent color of them can be tuned and even the white luminescence can be integrated. PMID:25082218

  18. Localization and orientation of heavy-atom cluster compounds in protein crystals using molecular replacement

    PubMed Central

    Dahms, Sven O.; Kuester, Miriam; Streb, Carsten; Roth, Christian; Sträter, Norbert; Than, Manuel E.

    2013-01-01

    Heavy-atom clusters (HA clusters) containing a large number of specifically arranged electron-dense scatterers are especially useful for experimental phase determination of large complex structures, weakly diffracting crystals or structures with large unit cells. Often, the determination of the exact orientation of the HA cluster and hence of the individual heavy-atom positions proves to be the critical step in successful phasing and subsequent structure solution. Here, it is demonstrated that molecular replacement (MR) with either anomalous or isomorphous differences is a useful strategy for the correct placement of HA cluster compounds. The polyoxometallate cluster hexasodium α-metatungstate (HMT) was applied in phasing the structure of death receptor 6. Even though the HA cluster is bound in alternate partially occupied orientations and is located at a special position, its correct localization and orientation could be determined at resolutions as low as 4.9 Å. The broad applicability of this approach was demonstrated for five different derivative crystals that included the compounds tantalum tetradeca­bromide and trisodium phosphotungstate in addition to HMT. The correct placement of the HA cluster depends on the length of the intramolecular vectors chosen for MR, such that both a larger cluster size and the optimal choice of the wavelength used for anomalous data collection strongly affect the outcome. PMID:23385464

  19. Cluster headache

    MedlinePlus

    Histamine headache; Headache - histamine; Migrainous neuralgia; Headache - cluster; Horton's headache; Vascular headache - cluster ... be related to the body's sudden release of histamine (chemical in the body released during an allergic ...

  20. Meaningful Clusters

    SciTech Connect

    Sanfilippo, Antonio P.; Calapristi, Augustin J.; Crow, Vernon L.; Hetzler, Elizabeth G.; Turner, Alan E.

    2004-05-26

    We present an approach to the disambiguation of cluster labels that capitalizes on the notion of semantic similarity to assign WordNet senses to cluster labels. The approach provides interesting insights on how document clustering can provide the basis for developing a novel approach to word sense disambiguation.

  1. Abell Clusters

    NASA Astrophysics Data System (ADS)

    Katgert, P.; Murdin, P.

    2000-11-01

    Abell clusters are the most conspicuous groupings of galaxies identified by George Abell on the plates of the first photographic survey made with the SCHMIDT TELESCOPE at Mount Palomar in the 1950s. Sometimes, the term Abell clusters is used as a synonym of nearby, optically selected galaxy clusters....

  2. Polyoxometalates from heteropoly "brown" precursors. A new structural class of mixed valence heteropolytungstates, [(XO4)W3IVW17VIO 62Hx]n-

    USGS Publications Warehouse

    Dickman, M.H.; Ozeki, T.; Evans, H.T.; Rong, C.; Jameson, G.B.; Pope, M.T.

    2000-01-01

    Reduction of the ??-Keggin anion [Xn+O4W12O36][8-n]- (X = H22+, B3+, Si4+) by six electrons results in the known tungsten "brown" species [Xn+O4(H2O)3WIV3WVI9O33][8-n]- in which three W atoms have been reduced from WVI to WIV, forming a metal-metal bonded triad. The WIV atoms have terminal water coordinated in place of terminal oxo groups. Additional tungstate can condense onto these water molecules in aqueous solution between pH = 4 and 6.5 to form the species reported here, [(XO4)WIV3WVI17O 62Hx]y-. The boron derivative (X = B3+) is more stable than the metatungstate (X = H22+), both of which have been characterized by elemental analysis, 183W NMR and X-ray crystal structure analysis. Eight additional tungstate groups condense in the form of a partial Keggin structure containing two triads and one dyad which is rotated 60?? relative to a hypothetical ??-isomer. ?? The Royal Society of Chemistry 2000.

  3. A Pyridazine-Bridged Sandwiched Cluster Incorporating Planar Hexanuclear Cobalt Ring and Bivacant Phosphotungstate.

    PubMed

    Guo, Ling-Yu; Zeng, Su-Yuan; Jagličić, Zvonko; Hu, Qi-Dong; Wang, Shi-Xuan; Wang, Zhi; Sun, Di

    2016-09-01

    A planar hexanuclear cobalt ring was clamped by two bivacant α1-[PW10O37](9-) with the assistance of the pyridazine bridges to form a novel sandwiched Co(II)-polyoxometalate cluster compound, [Na(H2O)6][Co3(OH) (pydz)4(H2O)7][Co6(PW10O37)2(pydz)4(H2O)6]·43H2O (1; pydz = pyridazine).This cluster was identified by X-ray single-crystal diffraction, elemental analysis, Fourier transform IR and UV-visible spectroscopies, and cyclic voltammetry (CV). Structural analysis reveals that 1 comprises a hexahydrated sodium, a trinuclear [Co3(OH) (pydz)4(H2O)7](5+) cationic cluster, and an anionic [Co6(PW10O37)2(pydz)4(H2O)6](6-) sandwiched cluster, thus giving an intrinsical intercluster compound. The isolation of such cluster was dependent on the in situ transformation of trivacant [α-P2W15O56](12-) to α1-[PW10O37](9-) under the hydrothermal condition. The CV shows reversible multielectron waves from the redox of W(VI) in 1. Cluster 1 exhibits remarkable electrocatalytic activity toward the reduction of nitrite. Magnetism studies indicated a weak anti-ferromagnetic exchange interaction between Co(II) ions within 1. PMID:27548500

  4. A molecular placeholder strategy to access a family of transition-metal-functionalized vanadium oxide clusters.

    PubMed

    Kastner, Katharina; Margraf, Johannes T; Clark, Timothy; Streb, Carsten

    2014-09-15

    Systematic access to metal-functionalized polyoxometalates has thus far been limited to lacunary tungsten oxide and molybdenum oxide clusters. The first controlled, stepwise bottom-up assembly route to metal-functionalized molecular vanadium oxides is now presented. A di-vacant vanadate cluster with two metal binding sites, (DMA)2[V12O32Cl](3-) (DMA = dimethylammonium) is formed spontaneously in solution and characterized by single-crystal X-ray diffraction, ESI mass spectrometry, (51)V NMR spectroscopy, and elemental analyses. In the cluster, the metal binding sites are selectively blocked by hydrogen-bonded DMA placeholder cations. Reaction of the cluster with transition metals TM (Fe(3+), Co(2+), Cu(2+), Zn(2+)) gives access to mono-functionalized vanadate clusters (DMA)[{TM(L)}V12O32Cl](n-) (L = ligand). Metal binding is accomplished by significant distortions of the vanadium oxide framework reminiscent of a pincer movement. Cluster stability under technologically relevant conditions in the solid-state and solution is demonstrated.

  5. Single-Molecule Magnet Behavior of Individual Polyoxometalate Molecules Incorporated within Biopolymer or Metal-Organic Framework Matrices.

    PubMed

    Salomon, William; Lan, Yanhua; Rivière, Eric; Yang, Shu; Roch-Marchal, Catherine; Dolbecq, Anne; Simonnet-Jégat, Corine; Steunou, Nathalie; Leclerc-Laronze, Nathalie; Ruhlmann, Laurent; Mallah, Talal; Wernsdorfer, Wolfgang; Mialane, Pierre

    2016-05-01

    The chemically and structurally highly stable polyoxometalate (POM) single-molecule magnet (SMM) [(FeW9 O34 )2 Fe4 (H2 O)2 ](10-) (Fe6 W18 ) has been incorporated by direct or post-synthetic approaches into a biopolymer gelatin (Gel) matrix and two crystalline metal-organic frameworks (MOFs), including one diamagnetic (UiO-67) and one magnetic (MIL-101(Cr)). Integrity of the POM in the Fe6 W18 @Gel, Fe6 W18 @UiO-67 and Fe6 W18 @MIL-101(Cr) composites was confirmed by a set of complementary techniques. Magnetic studies indicate that the POMs are magnetically well isolated. Remarkably, in Fe6 W18 @Gel, the SMM properties of the embedded molecules are close to those of the crystals, with clear quantum tunneling steps in the hysteresis loops. For the Fe6 W18 @UiO-67 composite, the molecules retain their SMM properties, the energy barrier being slightly reduced in comparison to the crystalline material and the molecules exhibiting a tunneling rate of magnetization significantly faster than for Fe6 W18 @Gel. When Fe6 W18 is introduced into MIL-101(Cr), the width of the hysteresis loops is drastically reduced and the quantum tunneling steps are smeared out because of the magnetic interactions between the antiferromagnetic matrix and the SMM guest molecules. PMID:27080557

  6. Protein-resistant cross-linked poly(vinyl alcohol) micropatterns via photolithography using removable polyoxometalate photocatalyst.

    PubMed

    Pavli, Pagona; Petrou, Panagiota S; Douvas, Antonios M; Dimotikali, Dimitra; Kakabakos, Sotirios E; Argitis, Panagiotis

    2014-10-22

    In the last years, there has been an increasing interest in controlling the protein adsorption properties of surfaces because this control is crucial for the design of biomaterials. On the other hand, controlled immobilization of proteins is also important for their application as solid surfaces in immunodiagnostics and biosensors. Herein we report a new protein patterning method where regions of the substrate are covered by a hydrophilic film that minimizes protein adsorption. Particularly, poly(vinyl alcohol) (PVA) cross-linked structures created by an especially developed photolithographic process are proved to prevent protein physisorption and they are used as a guide for selective protein adsorption on the uncovered areas of a protein adsorbing substrate such as polystyrene. The PVA cross-linking is induced by photo-oxidation using, as a catalyst, polyoxometalate (H3PW12O40 or α-(NH4)6P2W18O62), which is removed using a methyl alcohol/water mixed solvent as the developer. We demonstrate that the polystyrene and the cross-linked PVA exhibit dramatically different performances in terms of protein physisorption. In particular, the polystyrene areas presented up to 130 times higher protein binding capacity than the PVA ones, whereas the patterning resolution could easily reach dimensions of a few micrometers. The proposed approach can be applied on any substrate where PVA films can be coated for controlling protein adsorption onto surface areas custom defined by the user.

  7. Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air–Water Interface

    DOE PAGESBeta

    Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

    2016-07-23

    The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. In this paper, we report on the equilibrium properties of two common SEPs adsorbed to the air–water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated localmore » chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo132-based SEPs are more polar than Mo72V30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air–water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo132 and Mo72V30 SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is discussed.« less

  8. Efficient Conversion of Lignin to Electricity Using a Novel Direct Biomass Fuel Cell Mediated by Polyoxometalates at Low Temperatures.

    PubMed

    Zhao, Xuebing; Zhu, J Y

    2016-01-01

    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.

  9. One-pot transformation of cellobiose to formic acid and levulinic acid over ionic-liquid-based polyoxometalate hybrids.

    PubMed

    Li, Kaixin; Bai, Linlu; Amaniampong, Prince Nana; Jia, Xinli; Lee, Jong-Min; Yang, Yanhui

    2014-09-01

    Currently, levulinic acid (LA) and formic acid (FA) are considered as important carbohydrates for the production of value-added chemicals. Their direct production from biomass will open up a new opportunity for the transformation of biomass resource to valuable chemicals. In this study, one-pot transformation of cellobiose into LA and FA was demonstrated, using a series of multiple-functional ionic liquid-based polyoxometalate (IL-POM) hybrids as catalytic materials. These IL-POMs not only markedly promoted the production of valuable chemicals including LA, FA and monosaccharides with high selectivities, but also provided great convenience of the recovery and the reuse of the catalytic materials in an environmentally friendly manner. Cellobiose conversion of 100%, LA selectivity of 46.3%, and FA selectivity of 26.1% were obtained at 423 K and 3 MPa for 3 h in presence of oxygen. A detailed catalytic mechanism for the one-pot transformation of cellobiose was also presented. PMID:25110998

  10. The photophysics of europium and terbium polyoxometalates and their interaction with serum albumin: a time-resolved luminescence study.

    PubMed

    Hungerford, Graham; Hussain, Firasat; Patzke, Greta R; Green, Mark

    2010-07-14

    Polyoxometalates (POMs) are emerging as useful materials for a variety of applications. Many show potential for use in the biological and medical fields. Those incorporating lanthanides, with their narrow emission bands, large Stokes' shift and tuneable emission are of particular interest for the labelling and imaging of biological molecules. Their longer emission timescale (micros to ms) also allows autofluorescence from the biological samples to be removed by time gating the emission decay. This means that the characterisation of their photophysical properties is required to enable their application. In this work we present a time-resolved emission study of two types of POM structure, a simple europium containing decatungstate and a more complex high nuclear polyoxotungstate, containing either europium or terbium. A concentration study, made monitoring the lanthanide emission helped elucidate POM-POM interactions. The use of global analysis hints at the presence of defined POM aggregates. Interaction with serum albumin was ascertained, both by monitoring the lanthanide emission of the POM and the tryptophan emission from the serum albumin. This showed that the more complex structure had a significantly higher affinity for the protein than the simple structure.

  11. Binary Superlattices from {Mo132} Polyoxometalates and Maghemite Nanocrystals: Long-Range Ordering and Fine-Tuning of Dipole Interactions.

    PubMed

    Breitwieser, Romain; Auvray, Thomas; Volatron, Florence; Salzemann, Caroline; Ngo, Anh-Tu; Albouy, Pierre-Antoine; Proust, Anna; Petit, Christophe

    2016-01-13

    In the present article, the successful coassembly of spherical 6.2 nm maghemite (γ-Fe2O3) nanocrystals and giant polyoxometalates (POMs) such as 2.9 nm {Mo132} is demonstrated. To do so, colloidal solutions of oleic acid-capped γ-Fe2O3 and long-chain alkylammonium-encapsulated {Mo132 } dispersed in chloroform are mixed together and supported self-organized binary superlattices are obtained upon the solvent evaporation on immersed substrates. Both electronic microscopy and small angles X-ray scattering data reveal an AB-type structure and an enhanced structuration of the magnetic nanocrystals (MNCs) assembly with POMs in octahedral interstices. Therefore, {Mo132} acts as an efficient binder constituent for improving the nanocrystals ordering in 3D films. Interestingly, in the case of didodecyldimethylammonium (C12)-encapsulated POMs, the long-range ordered binary assemblies are obtained while preserving the nanocrystals magnetic properties due to weak POMs-MNCs interactions. On the other hand, POMs of larger effective diameter can be employed as spacer blocks for MNCs as shown by using {Mo132} capped with dioctadecyldimethylammonium (C18) displaying longer chains. In that case, it is shown that POMs can also be used for fine-tuning the dipolar interactions in γ-Fe2O3 nanocrystal assemblies. PMID:26578032

  12. Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air-Water Interface.

    PubMed

    Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

    2016-08-16

    The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. Here, we report on the equilibrium properties of two common SEPs adsorbed to the air-water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated local chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo132-based SEPs are more polar than Mo72V30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air-water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo132 and Mo72V30 SEPs, respectively, indicating a strong propensity for the fluid surface. The influence of intermolecular interactions on the surface adsorption energies is discussed. PMID:27452922

  13. Efficient Conversion of Lignin to Electricity Using a Novel Direct Biomass Fuel Cell Mediated by Polyoxometalates at Low Temperatures.

    PubMed

    Zhao, Xuebing; Zhu, J Y

    2016-01-01

    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. PMID:26692572

  14. Construction of adsorptive nanorods from polyoxometalates and ionic liquid and their adsorption properties for silver ion from AMD.

    PubMed

    Zhang, Huixin; Zhang, Jie; Cui, Manli; Jin, Xiu-Hong; Han, Xu; Wang, Youchen

    2016-01-01

    A new structure of hybrid nanorods adsorbent ([n-BBIM]9PW9O34) was synthesized by a simple molecular assembly of polyoxometalates with ionic liquids (ILs). The nanocomposite was characterized by Fourier transform infrared (FT-IR), ultraviolet-visible (UV-Vis), scanning electron microscope, energy dispersive X-ray and X-ray diffractometer. Adsorption of silver from acid mine drainage (AMD) was studied using batch experiments. The impact of several parameters, like ion concentration, pH, adsorbent dosage, and temperature was elucidated and optimization was carried out by single-factor experiment and response surface methodology. Analysis of variance of the quadratic model suggested that experimental data were excellently fitted to the quadratic model. Optimum conditions for removal of Ag(+) from AMD were determined to be an initial concentration 143 mg/L, adsorbent dosage 2.69 g/L, temperature 35 °C to achieve the maximum adsorption of Ag(+) 99.03%, which was very close to the predicted value (100%). The adsorption was confirmed as oxidation-reduction mechanism following a complexation process, and has been verified according to results from FT-IR and UV-vis spectra. The selective experiment suggested that the nanorods adsorbent could adsorb silver ions in AMD well. Based on the adsorption/desorption study result, the adsorbent can be efficiently recovered. PMID:27533874

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

    NASA Astrophysics Data System (ADS)

    Tsuboi, Masaki; Hibino, Mitsuhiro; Mizuno, Noritaka; Uchida, Sayaka

    2016-02-01

    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, Cs2.7H0.3[PW12O40]·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 (1.2×10-5 S cm-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 13C-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+) 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.

  16. The First Demonstration of the Gyroid in a Polyoxometalate-Based Open Framework with High Proton Conductivity.

    PubMed

    Gao, Qiang; Wang, Xiu-Li; Xu, Jian; Bu, Xian-He

    2016-06-27

    The fabrication of extended open frameworks with crystalline ordering on the atomic level by following peculiar mathematical geometry (e.g. Möbius band, Klein bottle, periodic minimal surfaces, etc.) is challenging, but extremely beneficial for discovering non-trivial structure-dependent properties. In light of this, we herein report the first polyoxometalate-based open framework (POM-OF) that definitely lies on the gyroid (G)-minimal surface, which was constructed by a rare pair of chiral POM enantiomers and zinc ions. Due to the presence of the proton carriers (i.e., water, Na(+) , [(Bu)4 N](+) , etc.) in the resultant gyroidal channels, with pore dimensions on the order of the quasi-mesoporous scale, this compound shows a high proton conductivity of 1.04×10(-2)  S cm(-1) at a relative humidity of 75 % (80 °C), and also exhibits enormous potential in the application of electrochemical catalysis. PMID:26994563

  17. Data Clustering

    NASA Astrophysics Data System (ADS)

    Wagstaff, Kiri L.

    2012-03-01

    On obtaining a new data set, the researcher is immediately faced with the challenge of obtaining a high-level understanding from the observations. What does a typical item look like? What are the dominant trends? How many distinct groups are included in the data set, and how is each one characterized? Which observable values are common, and which rarely occur? Which items stand out as anomalies or outliers from the rest of the data? This challenge is exacerbated by the steady growth in data set size [11] as new instruments push into new frontiers of parameter space, via improvements in temporal, spatial, and spectral resolution, or by the desire to "fuse" observations from different modalities and instruments into a larger-picture understanding of the same underlying phenomenon. Data clustering algorithms provide a variety of solutions for this task. They can generate summaries, locate outliers, compress data, identify dense or sparse regions of feature space, and build data models. It is useful to note up front that "clusters" in this context refer to groups of items within some descriptive feature space, not (necessarily) to "galaxy clusters" which are dense regions in physical space. The goal of this chapter is to survey a variety of data clustering methods, with an eye toward their applicability to astronomical data analysis. In addition to improving the individual researcher’s understanding of a given data set, clustering has led directly to scientific advances, such as the discovery of new subclasses of stars [14] and gamma-ray bursts (GRBs) [38]. All clustering algorithms seek to identify groups within a data set that reflect some observed, quantifiable structure. Clustering is traditionally an unsupervised approach to data analysis, in the sense that it operates without any direct guidance about which items should be assigned to which clusters. There has been a recent trend in the clustering literature toward supporting semisupervised or constrained

  18. A Novel Application of Ti-Substituted Polyoxometalates: Anti-Inflammatory Activity in OVA-Induced Asthma Murine Model

    PubMed Central

    Gao, Xiuzhu; Tian, Yuan; Liu, Yaqing; Jin, Zheng; Yan, Dongmei; Zhu, Xun

    2016-01-01

    Objective. Asthma is a chronic inflammatory disorder. Despite extensive researches into the treatment and management of it, current treatments and management strategies are still limited. The search for a novel approach to its treatments is urgently needed. Researches on the potential medical use of polyoxometalates (POMs) have already shown it has antiviral and antitumor bioactivities. But the effects of POM in immune systems are still largely unknown. Methods. In order to investigate the role of POM in the asthmatic disease, we used OVA-induced asthma murine model and observed the pathological changes between mice that received three different Ti-substituted POMs (0.3 μg per mouse per dose) when challenged with OVA. We also measured the type 2 cytokine expressions to reveal the potential mechanism. Results and Conclusions. Our results showed that two Ti-substituted POMs, K5H2[FeW11TiO40]·17H2O and K5H[H2ZnW11TiO40]·35H2O, could reduce OVA-induced lung inflammation, serum IgE level (around 2000 ng/mL to less than 1000 ng/mL), leukocytes infiltration in the lung, and cytokines levels (including IL-4, IL-5, IL-13, and TNF-α) but Ti-centered POM K4[TiW12O40]·10H2O did not. Thus, Ti-substituted POMs may have pharmaceutical values especially in treatments for asthmatic diseases. PMID:27436993

  19. Selective adsorption of cationic dyes from aqueous solution by polyoxometalate-based metal-organic framework composite

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoxia; Gong, Wenpeng; Luo, Jing; Zou, Chentao; Yang, Yun; Yang, Shuijin

    2016-01-01

    A novel environmental friendly adsorbent H6P2W18O62/MOF-5 was synthesized by a simple one-step reaction under solvothermal conditions and characterized by XRD, FTIR, thermogravimetric analyses (TGA) and N2 adsorption-desorption isotherms. The removal rate of H6P2W18O62/MOF-5 was quite greater (85%) than that of MOF-5 (almost zero), showing that the adsorption performance of porous MOF-5 can be improved through the modification of H6P2W18O62. Further study revealed that H6P2W18O62/MOF-5 exhibited a fast adsorption rate and selective adsorption ability towards the cationic dyes in aqueous solution. The removal rate was up to 97% for cationic dyes methylene blue (MB) and 68% for rhodamine B(Rhb) within 10 min. However, anionicdye methyl orange(MO) can only reach to 10%. The influences including initial concentration, contact time, initial solution pH and temperature of MB adsorption onto H6P2W18O62/MOF-5 were investigated in detail. The kinetic study indicated that the adsorption of MB onto H6P2W18O62/MOF-5 followed the pseudo second-order model well. The isotherm obtained from experimental data fitted the Langmuir model, yielding maximum adsorption capacity of 51.81 mg/g. The thermodynamic parameters analysis illustrated that the MB adsorption onto H6P2W18O62 immobilized MOF-5 was spontaneous and endothermic process. Besides, these results implied that designing a novel material polyoxometalate-based metal-organic frameworks is great potential for removing cationic organic pollutants and even extended to improve other specific application.

  20. Effect of electron (de)localization and pairing in the electrochemistry of polyoxometalates: study of Wells-Dawson molybdotungstophosphate derivatives.

    PubMed

    Parent, Loïc; Aparicio, Pablo A; de Oliveira, Pedro; Teillout, Anne-Lucie; Poblet, Josep M; López, Xavier; Mbomekallé, Israël M

    2014-06-16

    Polyoxometalates (POMs) are inorganic entities featuring extensive and sometimes unusual redox properties. In this work, several experimental techniques as well as density functional theory (DFT) calculations have been applied to identify and assess the relevance of factors influencing the redox potentials of POMs. First, the position of the Mo substituent atom in the Wells-Dawson structure, α1- or α2-P2W17Mo, determines the potential of the first 1e(-) reduction wave. For P2W(18-x)Mox systems containing more than one Mo atom, reduction takes place at successively more positive potentials. We attribute this fact to the higher electron delocalization when some Mo oxidizing atoms are connected. After having analyzed the experimental and theoretical data for the monosubstituted α1- and α2-P2W17Mo anions, some relevant facts arise that may help to rationalize the redox behavior of POMs in general. Three aspects concern the stability of systems: (i) the favorable electron delocalization, (ii) the unfavorable e(-)-e(-) electrostatic repulsion, and (iii) the favorable electron pairing. They explain trends such as the second reduction wave occurring at more positive potentials in α1- than in α2-P2W17Mo, and also the third electron reduction taking place at a less negative potential in the case of α2, reversing the observed behavior for the first and the second waves. In P2W17V derivatives, the nature of the first "d" electron is more localized because of the stronger oxidant character of V(V). Thus, the reduction potentials as well as the computed reduction energies (REs) for the second reduction of either isomer are closer to each other than in Mo-substituted POMs. This may be explained by the lack of electron delocalization in monoreduced P2W17V(IV) systems. PMID:24892769

  1. A Novel Application of Ti-Substituted Polyoxometalates: Anti-Inflammatory Activity in OVA-Induced Asthma Murine Model.

    PubMed

    Li, Dong; Gao, Xiuzhu; Gu, Jingmin; Tian, Yuan; Liu, Yaqing; Jin, Zheng; Yan, Dongmei; Chen, Ya-Guang; Zhu, Xun

    2016-01-01

    Objective. Asthma is a chronic inflammatory disorder. Despite extensive researches into the treatment and management of it, current treatments and management strategies are still limited. The search for a novel approach to its treatments is urgently needed. Researches on the potential medical use of polyoxometalates (POMs) have already shown it has antiviral and antitumor bioactivities. But the effects of POM in immune systems are still largely unknown. Methods. In order to investigate the role of POM in the asthmatic disease, we used OVA-induced asthma murine model and observed the pathological changes between mice that received three different Ti-substituted POMs (0.3 μg per mouse per dose) when challenged with OVA. We also measured the type 2 cytokine expressions to reveal the potential mechanism. Results and Conclusions. Our results showed that two Ti-substituted POMs, K5H2[FeW11TiO40]·17H2O and K5H[H2ZnW11TiO40]·35H2O, could reduce OVA-induced lung inflammation, serum IgE level (around 2000 ng/mL to less than 1000 ng/mL), leukocytes infiltration in the lung, and cytokines levels (including IL-4, IL-5, IL-13, and TNF-α) but Ti-centered POM K4[TiW12O40]·10H2O did not. Thus, Ti-substituted POMs may have pharmaceutical values especially in treatments for asthmatic diseases. PMID:27436993

  2. Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation

    NASA Astrophysics Data System (ADS)

    Boulicault, Jean E.; Alves, Sandra; Cole, Richard B.

    2016-08-01

    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.

  3. Single-Molecule Magnet Properties of Transition-Metal Ions Encapsulated in Lacunary Polyoxometalates: A Theoretical Study.

    PubMed

    Aravena, Daniel; Venegas-Yazigi, Diego; Ruiz, Eliseo

    2016-07-01

    Single-molecule magnet (SMM) properties of transition-metal complexes coordinated to lacunary polyoxometalates (POM) are studied by means of state of the art ab initio methodology. Three [M(γ-SiW10O36)2] (M = Mn(III), Fe(III), Co(II)) complexes synthesized by Sato et al. (Chem. Commun. 2015, 51, 4081-4084) are analyzed in detail. SMM properties for the Co(II) and Mn(III) systems can be rationalized due to the presence of low-energy excitations in the case of Co(II), which are much higher in energy in the case of Mn(III). The magnetic behavior of both cases is consistent with simple d-orbital splitting considerations. The case of the Fe(III) complex is special, as it presents a sizable demagnetization barrier for a high-spin d(5) configuration, which should be magnetically isotropic. We conclude that a plausible explanation for this behavior is related to the presence of low-lying quartet and doublet states from the iron(III) center. This scenario is supported by ab initio ligand field analysis based on complete active space self-consistent field results, which picture a d-orbital splitting that resembles more a square-planar geometry than an octahedral one, stabilizing lower multiplicity states. This coordination environment is sustained by the rigidity of the POM ligand, which imposes a longer axial bond distance to the inner oxygen atom in comparison to the more external, equatorial donor atoms.

  4. Single-Molecule Magnet Properties of Transition-Metal Ions Encapsulated in Lacunary Polyoxometalates: A Theoretical Study.

    PubMed

    Aravena, Daniel; Venegas-Yazigi, Diego; Ruiz, Eliseo

    2016-07-01

    Single-molecule magnet (SMM) properties of transition-metal complexes coordinated to lacunary polyoxometalates (POM) are studied by means of state of the art ab initio methodology. Three [M(γ-SiW10O36)2] (M = Mn(III), Fe(III), Co(II)) complexes synthesized by Sato et al. (Chem. Commun. 2015, 51, 4081-4084) are analyzed in detail. SMM properties for the Co(II) and Mn(III) systems can be rationalized due to the presence of low-energy excitations in the case of Co(II), which are much higher in energy in the case of Mn(III). The magnetic behavior of both cases is consistent with simple d-orbital splitting considerations. The case of the Fe(III) complex is special, as it presents a sizable demagnetization barrier for a high-spin d(5) configuration, which should be magnetically isotropic. We conclude that a plausible explanation for this behavior is related to the presence of low-lying quartet and doublet states from the iron(III) center. This scenario is supported by ab initio ligand field analysis based on complete active space self-consistent field results, which picture a d-orbital splitting that resembles more a square-planar geometry than an octahedral one, stabilizing lower multiplicity states. This coordination environment is sustained by the rigidity of the POM ligand, which imposes a longer axial bond distance to the inner oxygen atom in comparison to the more external, equatorial donor atoms. PMID:27299178

  5. Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation.

    PubMed

    Boulicault, Jean E; Alves, Sandra; Cole, Richard B

    2016-08-01

    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: Fe(3+) > Al(3+) > Li(+) > Ga(3+) > Co(2+) > Cr(3+) > Cu(2+) > [Mn(2+), Mg(2+)] > [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. Graphical Abstract ᅟ. PMID:27142457

  6. Quintuplet Cluster

    NASA Technical Reports Server (NTRS)

    1999-01-01

    Penetrating 25,000 light-years of obscuring dust and myriad stars, NASA's Hubble Space Telescope has provided the clearest view yet of one of the largest young clusters of stars inside our Milky Way galaxy, located less than 100 light-years from the very center of the Galaxy. Having the equivalent mass greater than 10,000 stars like our sun, the monster cluster is ten times larger than typical young star clusters scattered throughout our Milky Way. It is destined to be ripped apart in just a few million years by gravitational tidal forces in the galaxy's core. But in its brief lifetime it shines more brightly than any other star cluster in the Galaxy. Quintuplet Cluster is 4 million years old. It has stars on the verge of blowing up as supernovae. It is the home of the brightest star seen in the galaxy, called the Pistol star. This image was taken in infrared light by Hubble's NICMOS camera in September 1997. The false colors correspond to infrared wavelengths. The galactic center stars are white, the red stars are enshrouded in dust or behind dust, and the blue stars are foreground stars between us and the Milky Way's center. The cluster is hidden from direct view behind black dust clouds in the constellation Sagittarius. If the cluster could be seen from earth it would appear to the naked eye as a 3rd magnitude star, 1/6th of a full moon's diameter apart.

  7. Galaxy Clusters

    NASA Astrophysics Data System (ADS)

    Miller, Christopher J. Miller

    2012-03-01

    There are many examples of clustering in astronomy. Stars in our own galaxy are often seen as being gravitationally bound into tight globular or open clusters. The Solar System's Trojan asteroids cluster at the gravitational Langrangian in front of Jupiter’s orbit. On the largest of scales, we find gravitationally bound clusters of galaxies, the Virgo cluster (in the constellation of Virgo at a distance of ˜50 million light years) being a prime nearby example. The Virgo cluster subtends an angle of nearly 8◦ on the sky and is known to contain over a thousand member galaxies. Galaxy clusters play an important role in our understanding of theUniverse. Clusters exist at peaks in the three-dimensional large-scale matter density field. Their sky (2D) locations are easy to detect in astronomical imaging data and their mean galaxy redshifts (redshift is related to the third spatial dimension: distance) are often better (spectroscopically) and cheaper (photometrically) when compared with the entire galaxy population in large sky surveys. Photometric redshift (z) [Photometric techniques use the broad band filter magnitudes of a galaxy to estimate the redshift. Spectroscopic techniques use the galaxy spectra and emission/absorption line features to measure the redshift] determinations of galaxies within clusters are accurate to better than delta_z = 0.05 [7] and when studied as a cluster population, the central galaxies form a line in color-magnitude space (called the the E/S0 ridgeline and visible in Figure 16.3) that contains galaxies with similar stellar populations [15]. The shape of this E/S0 ridgeline enables astronomers to measure the cluster redshift to within delta_z = 0.01 [23]. The most accurate cluster redshift determinations come from spectroscopy of the member galaxies, where only a fraction of the members need to be spectroscopically observed [25,42] to get an accurate redshift to the whole system. If light traces mass in the Universe, then the locations

  8. Structural and electronic properties of hetero-transition-metal Keggin anions: a DFT Study of alpha/beta-[XW12O40]n- (X = CrVI, VV, TiIV, FeIII, CoIII, NiIII, CoII, and ZnII) relative stability.

    PubMed

    Zhang, Fu-Qiang; Zhang, Xian-Ming; Wu, Hai-Shun; Jiao, Haijun

    2007-01-11

    Density functional theory calculations have been carried out to investigate the electronic structures and the alpha/beta relative stability of Keggin-typed [XW(12)O(40)]n- anions with transition metal as heteroatom X (X = Cr(VI), V(V), Ti(IV), Fe(III), Co(III), Ni(III), Co(II) and Zn(II)). Nice agreement in geometries between computation and experiment has been obtained, and the higher stability of the alpha isomer over the beta one has been confirmed. Structural parameter analysis reveals that the {M(3)O(13)} triads in both alpha and beta isomers contract considerably with the increase of the negative anionic charge, while the overall size of both isomers shrinks only slightly. Fragment molecular orbital analysis shows that except alpha/beta-[TiW(12)O(40)]4-, the electronic structures of Keggin anions can be described by the insertion of the e and/or t2 orbital of XO4n- into the frontier orbitals of W(12)O(36) cage, and this leads to the specific redox property, which is different from that of the Keggin anions with main-group elements as heteroatoms. Energy decomposition analysis shows that the enhanced intrinsic stability of the alpha isomer in Td arrangement of W(12)O(36) shell and the larger deformation of the alpha over the beta isomer are two dominating factors and contribute oppositely to the alpha/beta relative stability. PMID:17201398

  9. Occupational Clusters.

    ERIC Educational Resources Information Center

    Pottawattamie County School System, Council Bluffs, IA.

    The 15 occupational clusters (transportation, fine arts and humanities, communications and media, personal service occupations, construction, hospitality and recreation, health occupations, marine science occupations, consumer and homemaking-related occupations, agribusiness and natural resources, environment, public service, business and office…

  10. Cluster generator

    DOEpatents

    Donchev, Todor I.; Petrov, Ivan G.

    2011-05-31

    Described herein is an apparatus and a method for producing atom clusters based on a gas discharge within a hollow cathode. The hollow cathode includes one or more walls. The one or more walls define a sputtering chamber within the hollow cathode and include a material to be sputtered. A hollow anode is positioned at an end of the sputtering chamber, and atom clusters are formed when a gas discharge is generated between the hollow anode and the hollow cathode.

  11. Peptide bond hydrolysis catalyzed by the Wells-Dawson Zr(α2-P2W17O61)2 polyoxometalate.

    PubMed

    Absillis, Gregory; Parac-Vogt, Tatjana N

    2012-09-17

    In this paper we report the first example of peptide hydrolysis catalyzed by a polyoxometalate complex. A series of metal-substituted Wells-Dawson polyoxometalates were synthesized, and their hydrolytic activity toward the peptide bond in glycylglycine (GG) was examined. Among these, the Zr(IV)- and Hf(IV)-substituted ones were the most reactive. Detailed kinetic studies were performed with the Zr(IV)-substituted Wells-Dawson type polyoxometalate K(15)H[Zr(α(2)-P(2)W(17)O(61))(2)]·25H(2)O which was shown to act as a catalyst for the hydrolysis of the peptide bond in GG. The speciation of K(15)H[Zr(α(2)-P(2)W(17)O(61))(2)]·25H(2)O which is highly dependent on the pD, concentration, and temperature of the solution, was fully determined with the help of (31)P NMR spectroscopy and its influence on the GG hydrolysis rate was examined. The highest reaction rate (k(obs) = 9.2 (±0.2) × 10(-5) min(-1)) was observed at pD 5.0 and 60 °C. A 10-fold excess of GG was hydrolyzed in the presence of K(15)H[Zr(α(2)-P(2)W(17)O(61))(2)]·25H(2)O proving the principles of catalysis. (13)C NMR data suggested the coordination of GG to the Zr(IV) center in K(15)H[Zr(α(2)-P(2)W(17)O(61))(2)]·25H(2)O via its N-terminal amine group and amide carbonyl oxygen. These findings were confirmed by the inactivity of K(15)H[Zr(α(2)-P(2)W(17)O(61))(2)]·25H(2)O toward the N-blocked analogue acetamidoglycylglycinate and the inhibitory effect of oxalic, malic, and citric acid. Triglycine, tetraglycine, and pentaglycine were also fully hydrolyzed in the presence of K(15)H[Zr(α(2)-P(2)W(17)O(61))(2)]·25H(2)O yielding glycine as the final product of hydrolysis. K(15)H[Zr(α(2)-P(2)W(17)O(61))(2)]·25H(2)O also exhibited hydrolytic activity toward a series of other dipeptides.

  12. Reactivity of Dimeric Tetrazirconium(IV) Wells-Dawson Polyoxometalate toward Dipeptide Hydrolysis Studied by a Combined Experimental and Density Functional Theory Approach.

    PubMed

    Ly, Hong Giang T; Mihaylov, Tzvetan; Absillis, Gregory; Pierloot, Kristine; Parac-Vogt, Tatjana N

    2015-12-01

    Detailed kinetic studies on the hydrolysis of glycylglycine (Gly-Gly) in the presence of the dimeric tetrazirconium(IV)-substituted Wells-Dawson-type polyoxometalate Na14[Zr4(P2W16O59)2(μ3-O)2(OH)2(H2O)4] · 57H2O (1) were performed by a combination of (1)H, (13)C, and (31)P NMR spectroscopies. The catalyst was shown to be stable under a broad range of reaction conditions. The effect of pD on the hydrolysis of Gly-Gly showed a bell-shaped profile with the fastest hydrolysis observed at pD 7.4. The observed rate constant for the hydrolysis of Gly-Gly at pD 7.4 and 60 °C was 4.67 × 10(-7) s(-1), representing a significant acceleration as compared to the uncatalyzed reaction. (13)C NMR data were indicative for coordination of Gly-Gly to 1 via its amide oxygen and amine nitrogen atoms, resulting in a hydrolytically active complex. Importantly, the effective hydrolysis of a series of Gly-X dipeptides with different X side chain amino acids in the presence of 1 was achieved, and the observed rate constant was shown to be dependent on the volume, chemical nature, and charge of the X amino acid side chain. To give a mechanistic explanation of the observed catalytic hydrolysis of Gly-Gly, a detailed quantum-chemical study was performed. The theoretical results confirmed the nature of the experimentally suggested binding mode in the hydrolytically active complex formed between Gly-Gly and 1. To elucidate the role of 1 in the hydrolytic process, both the uncatalyzed and the polyoxometalate-catalyzed reactions were examined. In the rate-determining step of the uncatalyzed Gly-Gly hydrolysis, a carboxylic oxygen atom abstracts a proton from a solvent water molecule and the nascent OH nucleophile attacks the peptide carbon atom. Analogous general-base activity of the free carboxylic group was found to take place also in the case of polyoxometalate-catalyzed hydrolysis as the main catalytic effect originates from the -C═O···Zr(IV) binding.

  13. Effective Synergistic Effect of Dipeptide-Polyoxometalate-Graphene Oxide Ternary Hybrid Materials on Peroxidase-like Mimics with Enhanced Performance.

    PubMed

    Ma, Zhuo; Qiu, Yunfeng; Yang, Huihui; Huang, Yanmin; Liu, Jingjing; Lu, Yue; Zhang, Chen; Hu, PingAn

    2015-10-01

    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

  14. Theoretical exploration of photoisomerization-switchable second-order nonlinear optical responses of two-dimendional λ- and w-shaped polyoxometalate derivatives of dithienylperfluorocyclopentene.

    PubMed

    Ma, Teng-Ying; Ma, Na-Na; Yan, Li-Kai; Zhang, Ting; Su, Zhong-Min

    2013-10-17

    The switchable second-order nonlinear optical (NLO) properties on two-dimensional (2D) molecules based on Lindqvist-type [Mo6O19](2-) and dithienylperfluorocyclopentene (DTE) have been investigated at density functional theory (DFT) level. The CAM-B3LYP and M06-2X functionals were employed to study the switching behavior on NLO properties by photoisomerization reaction. The βtot value of system 2c (closed-ring form) is 15920.5 au, which is 150.1 times larger than that of the corresponding open-ring form (system 2o). The time-dependent DFT calculations predict that the charge transfer from DTE to polyoxometalate, and DTE intramolecular charge transfer in closed-ring systems effectively improve the static first hyperpolarizability. Furthermore, the Λ-shaped systems possess a larger u value than those of W-shaped systems owing to different orientation for substituent groups.

  15. Synthesis and photoelectric properties of new Dawson-type polyoxometalate-based dimeric and oligomeric Pt(II)-acetylide inorganic-organic hybrids.

    PubMed

    Liu, Li; Hu, Lei; Liu, Qian; Du, Zu-Liang; Li, Fa-Bao; Li, Guang-Hua; Zhu, Xun-Jin; Wong, Wai-Yeung; Wang, Lei; Li, Hua

    2015-01-01

    A new synthesis route for preparing Dawson-type polyoxometalate (POM) based inorganic-organic hybrid materials is presented. Two new heteropolytungstate-based dimeric and oligomeric Pt(II) acetylide inorganic-organic hybrid compounds (2PtOD and PPtOD) were prepared by Hagihara's dehydrohalogenating coupling of a terminal diacetylene POM hybrid containing diphosphoryl functionality and an appropriate platinum(II) halide precursor. This method provides a rigid covalent linkage between the POM and the organometallic Pt(II) acetylide moiety. The redox potential of the polyanion can be tuned by grafting the organic and organometallic groups on it. The photoelectric properties of hybrid LB films derived from these inorganic-organic composites were studied.

  16. Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Species to Dense Monodisperse Nanoparticles.

    PubMed

    Izzet, Guillaume; Abécassis, Benjamin; Brouri, Dalil; Piot, Madeleine; Matt, Benjamin; Serapian, Stefano Artin; Bo, Carles; Proust, Anna

    2016-04-20

    The metal-driven self-assembly processes of a covalent polyoxometalate (POM)-based hybrid bearing remote terpyridine binding sites have been investigated. In a strongly dissociating solvent, a discrete metallomacrocycle, described as a molecular triangle, is formed and characterized by 2D diffusion NMR spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and molecular modeling. In a less dissociating solvent, the primary supramolecular structure, combining negatively charged POMs and cationic metal linkers, further self-assemble through intermolecular electrostatic interactions in a reversible process. The resulting hierarchical assemblies are dense monodisperse nanoparticles composed of ca. 50 POMs that were characterized by SAXS and transmission electron microscopy (TEM). This multiscale organized system directed by metal coordination and electrostatic interactions constitutes a promising step for the future design of POM self-assemblies with controllable structure-directing factors. PMID:27019075

  17. Scanning tunneling microscopy study of nano-structured polyatom-substituted H4PW11M1O40 Keggin and H7P2W17M1O62 (M = Nb, Ta) Wells-Dawson heteropolyacid catalysts.

    PubMed

    Choi, Jung Ho; Park, Dong Ryul; Park, Sunyoung; Song, In Kyu

    2012-07-01

    Polyatom-substituted H4PW11M1O40 Keggin and H7P2W17M1O62 (M = Nb, Ta) Wells-Dawson heteropolyacid (HPA) catalysts were investigated by scanning tunneling microscopy (STM) and tunneling spectroscopy to elucidate their redox property and oxidation catalysis. STM images clearly showed that HPAs formed nano-structured monolayer arrays on graphite surface. In tunneling spectroscopy, HPAs exhibited a distinctive current-voltage behavior called negative differential resistance (NDR). NDR peak voltage of the HPAs was then correlated with reduction potential determined by electrochemical method in solution. NDR peak voltage of the HPAs appeared at less negative voltage with increasing reduction potential. Vapor-phase oxidative dehydrogenation of isobutyraldehyde to methacrolein was also carried out as a model reaction to probe oxidation catalysis of the HPAs. NDR peak voltage of the HPAs appeared at less negative voltage with increasing yield for methacrolein. NDR peak voltage could be utilized as a correlating parameter for the reduction potential and as a probe of oxidation catalysis in the oxidative dehydrogenation of isobutyraldehyde. PMID:22966671

  18. Scanning tunneling microscopy investigation of nano-structured α-K5PW11(M x OH2)O39(M = Mn(II), Co(II), Ni(II), and Zn(II)) Keggin heteropolyacid catalyst monolayers.

    PubMed

    Choi, Jung Ho; Kang, Tae Hun; Bang, Yongju; Yoo, Jaekyeong; Jun, Jin Oh; Song, In Kyu

    2014-11-01

    Nano-structured α-K5PW11(M x OH2)O39 (M = Mn(II), Co(II), Ni(II), and Zn(II)) Keggin heteropolyacids (HPAs) were investigated by scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) measurements in order to elucidate their redox property and oxidation catalysis. HPA molecules formed two-dimensional self-assembled monolayer arrays on highly oriented pyrolytic graphite (HOPG) surface. Furthermore, HPAs exhibited a distinctive current-voltage behavior referred to as negative differential resistance (NDR) phenomenon. The measured NDR peak voltage of HPAs was correlated with the reduction potential and the absorption edge energy determined by electrochemical method and UV-visible spectroscopy, respectively. NDR peak voltage of HPAs appeared at less negative voltage with increasing reduction potential and with decreasing UV-visible absorption edge energy. The correlations strongly suggested that NDR phenomenon was closely related to the redox property of HPAs. Vapor-phase oxidation of benzyl alcohol to benzaldehyde was carried out as a model reaction to track the oxidation catalysis of HPAs. NDR peak voltage appeared at less negative voltage with increasing yield for benzaldehyde. PMID:25958620

  19. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    PubMed

    McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

    2012-08-20

    The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

  20. Cluster headache

    PubMed Central

    2010-01-01

    Introduction The revised International Headache Society (IHS) criteria for cluster headache are: attacks of severe or very severe, strictly unilateral pain, which is orbital, supraorbital, or temporal pain, lasting 15 to 180 minutes and occurring from once every other day to eight times daily. Methods and outcomes We conducted a systematic review and aimed to answer the following clinical questions: What are the effects of interventions to abort cluster headache? What are the effects of interventions to prevent cluster headache? We searched: Medline, Embase, The Cochrane Library, and other important databases up to June 2009 (Clinical Evidence reviews are updated periodically; please check our website for the most up-to-date version of this review). We included harms alerts from relevant organisations, such as the US Food and Drug Administration (FDA) and the UK Medicines and Healthcare products Regulatory Agency (MHRA). Results We found 23 systematic reviews, RCTs, or observational studies that met our inclusion criteria. We performed a GRADE evaluation of the quality of evidence for interventions. Conclusions In this systematic review, we present information relating to the effectiveness and safety of the following interventions: baclofen (oral); botulinum toxin (intramuscular); capsaicin (intranasal); chlorpromazine; civamide (intranasal); clonidine (transdermal); corticosteroids; ergotamine and dihydroergotamine (oral or intranasal); gabapentin (oral); greater occipital nerve injections (betamethasone plus xylocaine); high-dose and high-flow-rate oxygen; hyperbaric oxygen; leuprolide; lidocaine (intranasal); lithium (oral); melatonin; methysergide (oral); octreotide (subcutaneous); pizotifen (oral); sodium valproate (oral); sumatriptan (oral, subcutaneous, and intranasal); topiramate (oral); tricyclic antidepressants (TCAs); verapamil; and zolmitriptan (oral and intranasal). PMID:21718584

  1. Visible light absorption of TiO{sub 2} materials impregnated with tungstophosphoric acid ethanol–aqueous solution at different pH values. Evidence about the formation of a surface complex between Keggin anion and TiO{sub 2} surfaces

    SciTech Connect

    Rengifo-Herrera, Julián A. Blanco, Mirta N.; Pizzio, Luis R.

    2014-01-01

    Graphical abstract: - Highlights: • TPA impregnation on TiO{sub 2} particles was done at different initial pH values. • Powders characterization evidenced the possible existence of TPA–TiO{sub 2} complexes. • Keggin anion complexed on TiO{sub 2} would be responsible of visible light absorption. - Abstract: TiO{sub 2} particles prepared by the sol–gel method were impregnated at different pH values (1.0, 2.0, 5.0 and 10.0) with a water–ethanol solution (50% V/V) of tungstophosphoric acid (TPA) (0.012 M). Similar preparation was carried out to synthesize TiO{sub 2} impregnated with [WO{sub 4}]{sup 2−} (TiW). These materials were characterized by different techniques such as UV–vis diffuse reflectance spectroscopy (UV–vis DRS), magic angle spinning nuclear magnetic resonance of {sup 31}P ({sup 31}P MAS NMR), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Fourier transform Raman spectroscopy (FT-Raman). Results revealed that TPA–TiO{sub 2} materials exhibit visible light absorption only when impregnation was done at pH 1.0 (TiTPA1) and 2.0 (TiTPA2). TiW powder did not show visible light absorption. XRD patterns show the presence of peaks at 2θ = 25.4° (1 0 1), 37.9° (0 0 4), 47.8° (2 0 0) and 54.3° associated to the anatase phase. Solid NMR, FT-IR and FT-Raman characterization showed that TiTPA1 and TiTPA2 samples contain Keggin ([PW{sub 12}O{sub 40}]{sup 3−}) and lacunary anions ([PW{sub 11}O{sub 39}]{sup 7−}) respectively. On the other hand, FT-Raman results revealed a blue shifting and broadening of the band at 141 cm{sup −1} corresponding to anatase TiO{sub 2} and moreover, a broadening of bands at 900–1100 cm{sup −1} attributed to Keggin structures of TPA. Both spectral changes could be related to the formation of a surface complex between the Keggin anion of TPA and TiO{sub 2} surfaces. This interaction should be responsible for visible light absorption.

  2. Spectroscopic and electrochemical study of the interconversion and decomplexation of cobalt(II) sandwich polyoxometalates based on a Dawson-type anion.

    PubMed

    Ruhlmann, Laurent; Schaming, Delphine; Ahmed, Iftikhar; Courville, Aimeric; Canny, Jacqueline; Thouvenot, René

    2012-08-01

    The reaction of the trivacant Dawson polyoxometalate α-[P(2)W(15)O(56)](12-) and the divalent cations Co(2+) is known to form a symmetrically derived sandwich complex of formula ββ-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-) [symbolized as ββ-Co(4)(P(2)W(15))(2)] at low pH (ca. pH 3). We have shown previously that, by a slight modification of the reaction conditions, trinuclear αβ-[(NaOH(2))Co(3)(H(2)O)(P(2)W(15)O(56))(2)](17-) and dinuclear [(NaOH(2))(2)Co(2)(P(2)W(15)O(56))(2)](18-) complexes [symbolized as αβ-NaCo(3)(P(2)W(15))(2) and Na(2)Co(2)(P(2)W(15))(2), respectively] can be synthesized as aqueous-soluble sodium salts. αβ-NaCo(3)(P(2)W(15))(2) is a "lacunary" sandwich complex that can add a Co(2+) cation to form nearly quantitatively an unsymmetrical Dawson tetracobalt sandwich polyoxometalate, αβ-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-) [symbolized as αβ-Co(4)(P(2)W(15))(2)]. Thus, for Co(4)(P(2)W(15))(2), the junctions between the trivacant {P(2)W(15)} subunits and the central tetrameric unit can be either both β type or β and α types. The interconversion between αβ-Co(4)(P(2)W(15))(2) and ββ-Co(4)(P(2)W(15))(2) and the decomplexation process at low pH, leading to the formation of αβ-NaCo(3)(P(2)W(15))(2) and/or Na(2)Co(2)(P(2)W(15))(2), have been followed in aqueous solution at various pH values by electrochemistry, UV-visible absorption spectroscopy, and (31)P NMR spectroscopy.

  3. TiO2 film decorated with highly dispersed polyoxometalate nanoparticles synthesized by micelle directed method for the efficiency enhancement of dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    He, Lifei; Chen, Li; Zhao, Yue; Chen, Weilin; Shan, Chunhui; Su, Zhongmin; Wang, Enbo

    2016-10-01

    In this work, two kinds of polyoxometalate (POM) nanoparticles with controlled shapes and structures were synthesized by micelle directed method and then composited with TiO2 via calcination to remove the surfactants owing to the excellent electronic storage and transmission ability of POM, finally obtaining two kinds of TiO2 composites with highly dispersed and small-sized POM nanoparticles (∼1 nm). The TiO2 composites were then induced into the photoanodes of dye-sensitized (N719) solar cells (DSSCs). The separation of electron-holes becomes more favorable due to the nanostructure and high dispersion of POM which provide more active sites than pure POM tending to agglomeration. The TiO2 composite photoanodes finally yielded the power conversion efficiency (PCE) of 8.4% and 8.2%, respectively, which were 42% and 39% higher than the pristine TiO2 based anodes. In addition, the mechanisms of POM in DSSC are proposed.

  4. Polyoxometalate-enhanced oxidation of organic compounds by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen.

    PubMed

    Lee, Changha; Keenan, Christina R; Sedlak, David L

    2008-07-01

    In the presence of oxygen, organic compounds can be oxidized by zerovalent iron or dissolved Fe(II). However, this process is not a very effective means of degrading contaminants because the yields of oxidants are usually low (i.e., typically less than 5% of the iron added is converted into oxidants capable of transforming organic compounds). The addition of polyoxometalate (POM) greatly increases the yield of oxidants in both systems. The mechanism of POM enhancement depends on the solution pH. Under acidic conditions, POM mediates the electron transfer from nanoparticulate zerovalent iron (nZVI) or Fe(II) to oxygen, increasing the production of hydrogen peroxide, which is subsequently converted to hydroxyl radical through the Fenton reaction. At neutral pH values, iron forms a complex with POM, preventing iron precipitation on the nZVI surface and in bulk solution. At pH 7, the yield of oxidant approaches the theoretical maximum in the nZVI/O2 and the Fe(II)/O2 systems when POM is present, suggesting that coordination of iron by POM alters the mechanism of the Fenton reaction by converting the active oxidant from ferryl ion to hydroxyl radical. Comparable enhancements in oxidant yields are also observed when nZVI or Fe(II) is exposed to oxygen in the presence of silica-immobilized POM. PMID:18678027

  5. Mechanistic Investigation into Olefin Epoxidation with H2O2 Catalyzed by Aqua‐Coordinated Sandwich‐Type Polyoxometalates: Role of the Noble Metal and Active Oxygen Position

    PubMed Central

    Ci, Chenggang; Liu, Hongsheng

    2016-01-01

    Abstract Aqua‐coordinated sandwich‐type polyoxometalates (POMs), {[WZnTM2(H2O)2](ZnW9O34)2}n− (TM=RhIII, PdII, and PtII), catalyze olefin epoxidation with hydrogen peroxide and have been well established, and they present an advance toward the utilization of olefins. To elucidate the epoxidation mechanism, we systematically performed density functional calculations. The reaction proceeds through a two‐step mechanism: activation of H2O2 and oxygen transfer. The aqua‐coordinated complexes show two distinct H2O2 activation pathways: “two‐step” and “concerted”. The concerted processes are more facile and proceed with similar and rate‐determining energy barriers at the Rh‐, Pd‐, and Pt‐containing transition states, which agrees well with the experimental results. Next, the resulting TM−OH−(μ‐OOH) intermediate transfers an O atom to olefin to form an epoxide. The higher reactivity of the Rh‐containing POM is attributed to more interactions between the Rh and hydroperoxo unit. We also calculated all active oxygen positions to locate the most favorable pathway. The higher reactivity of the two‐metal‐bonded oxygen position is predominantly ascribed to its lower stereoscopic hindrance. Furthermore, the presence of one and two explicit water solvent molecules significantly reduces the energy barriers, making these sandwich POMs very efficient for the olefin epoxidation with H2O2. PMID:27777840

  6. Surface immobilization of a tetra-ruthenium substituted polyoxometalate water oxidation catalyst through the employment of conducting polypyrrole and the layer-by-layer (LBL) technique.

    PubMed

    Anwar, Nargis; Sartorel, Andrea; Yaqub, Mustansara; Wearen, Kevin; Laffir, Fathima; Armstrong, Gordon; Dickinson, Calum; Bonchio, Marcella; McCormac, Timothy

    2014-06-11

    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. PMID:24758586

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

    PubMed

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

    2016-06-27

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

  8. New organic-inorganic hybrid assemblies based on copper(I) ion, bichelate-bridging ligand and Lindqvist-type polyoxometalate

    NASA Astrophysics Data System (ADS)

    Zhang, Mao-Mao; Hao, Xiu-Li; Xu, Li-Jie; Wang, Yong-Hui; Wang, Xin; Li, Yang-Guang

    2014-07-01

    Three new organic-inorganic hybrid compounds, namely [CuILp]2[W6O19]·H2O (1), [CuILp]3[W6O19]Cl (2) and [CuILp]2[W6O19]·2H2O (3) (Lp=α,α‧-bis-[3-(2-pyridyl)pyrazol-1-yl]-1,4-dimethylbenzene) based on copper(I) ion, a neutral N-donor bichelate-bridging ligand (Lp) and a Lindqvist-type polyoxometalate (POM) [W6O19]2-, have been hydrothermally prepared under different synthetic conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction analyses. Compounds 1 and 2 contain two different but topologically similar meso-helical chainlike coordination moieties. Compound 3 contains both left- and right-handed chiral “mobius strip” units. These cationic meso-helical chains and “mobius strip” units in compounds 1-3 are further combined with Lindqvist-type polyoxoanions to form 3-D supramolecular assemblies through extensive electrostatic forces and/or π-π interactions. The photo-luminescent properties of 1-3 have also been investigated, which are mainly attributed to the Lp ligand-centered emission.

  9. Esterification Reaction Utilizing Sense of Smell and Eyesight for Conversion and Catalyst Recovery Monitoring

    ERIC Educational Resources Information Center

    Janssens, Nikki; Wee, Lik H.; Martens, Johan A.

    2014-01-01

    The esterification reaction of salicylic acid with ethanol is performed in presence of dissolved 12-tungstophosphoric Brønsted-Lowry acid catalyst, a Keggin-type polyoxometalate (POM). The monitoring of the reaction with smell and the recovery of the catalyst with sight is presented. Formation of the sweet-scented ester is apparent from the smell.…

  10. Self-assembly of Alkali-uranyl-peroxide Clusters

    SciTech Connect

    Nyman, May; Rodriquez, Mark A.; Campana, Charles F.

    2010-08-11

    The hexavalent uranium specie, uranyl triperoxide, UO2(O2)34-, has been shown recently to behave like high oxidation-state d0 transition-metals, self-assembling into polyoxometalate-like clusters that contain up to 60 uranyl cations bridged by peroxide ligands. There has been much less focus on synthesis and structural characterization of salts of the monomeric UO2(O2)34- building block of these clusters. However, these could serve as water-soluble uranyl precursors for both clusters and materials, and also be used as simple models to study aqueous behavior by experiment and modeling. The countercation is of utmost importance to the assembly of these clusters, and Li+ has proven useful for the crystallization of many of the known cluster geometries to date. We present in this paper synthesis and structural characterization of two monomeric lithium uranyl-peroxide salts, Li4[UO2(O2)3]·10H2O (1) and [UO2(O2)3]12[(UO2(OH)4)Li16(H2O)28]3·Li6[H2O]26 (2). They were obtained from aqueous-alcohol solutions rather than the analogous aqueous solutions from which lithium uranyl-peroxide clusters are crystallized. Rapid introduction of the alcohol gives the structure of (1) whereas slow diffusion of alcohol results in crystallization of (2). (2) is an unusual structure featuring uranyl-centered alkali clusters that are linked into ring and spherical arrangements via [UO2(O2)3] anions. Furthermore, partial substitution of Rb or Cs into the synthesis results in formation of (2) with substitution of these larger alkalis into the uranyl-centered clusters. We surmise that the slow crystallization allows for direct bonding of alkali metals to the

  11. Manipulation of Self-Assembled Nanostructure Dimensions in Molecular Janus Particles.

    PubMed

    Liu, Hao; Luo, Jiancheng; Shan, Wenpeng; Guo, Dong; Wang, Jing; Hsu, Chih-Hao; Huang, Mingjun; Zhang, Wei; Lotz, Bernard; Zhang, Wen-Bin; Liu, Tianbo; Yue, Kan; Cheng, Stephen Z D

    2016-07-26

    The ability to manipulate self-assembly of molecular building blocks is the key to achieving precise "bottom-up" fabrications of desired nanostructures. Herein, we report a rational design, facile synthesis, and self-assembly of a series of molecular Janus particles (MJPs) constructed by chemically linking α-Keggin-type polyoxometalate (POM) nanoclusters with functionalized polyhedral oligomeric silsesquioxane (POSS) cages. Diverse nanostructures were obtained by tuning secondary interactions among the building blocks and solvents via three factors: solvent polarity, surface functionality of POSS derivatives, and molecular topology. Self-assembled morphologies of KPOM-BPOSS (B denotes isobutyl groups) were found dependent on solvent polarity. In acetonitrile/water mixtures with a high dielectric constant, colloidal nanoparticles with nanophase-separated internal lamellar structures quickly formed, which gradually turned into one-dimensional nanobelt crystals upon aging, while stacked crystalline lamellae were dominantly observed in less polar methanol/chloroform solutions. When the crystallizable BPOSS was replaced with noncrystallizable cyclohexyl-functionalized CPOSS, the resulting KPOM-CPOSS also formed colloidal spheres; however, it failed to further evolve into crystalline nanobelt structures. In less polar solvents, KPOM-CPOSS crystallized into isolated two-dimensional nanosheets, which were composed of two inner crystalline layers of Keggin POM covered by two monolayers of amorphous CPOSS. In contrast, self-assembly of KPOM-2BPOSS was dominated by crystallization of the BPOSS cages, which was hardly sensitive to solvent polarity. The BPOSS cages formed the crystalline inner bilayer, sandwiched by two outer layers of Keggin POM clusters. These results illustrate a rational strategy to purposely fabricate self-assembled nanostructures with diverse dimensionality from MJPs with controlled molecular composition and topology. PMID:27337531

  12. Manipulation of Self-Assembled Nanostructure Dimensions in Molecular Janus Particles.

    PubMed

    Liu, Hao; Luo, Jiancheng; Shan, Wenpeng; Guo, Dong; Wang, Jing; Hsu, Chih-Hao; Huang, Mingjun; Zhang, Wei; Lotz, Bernard; Zhang, Wen-Bin; Liu, Tianbo; Yue, Kan; Cheng, Stephen Z D

    2016-07-26

    The ability to manipulate self-assembly of molecular building blocks is the key to achieving precise "bottom-up" fabrications of desired nanostructures. Herein, we report a rational design, facile synthesis, and self-assembly of a series of molecular Janus particles (MJPs) constructed by chemically linking α-Keggin-type polyoxometalate (POM) nanoclusters with functionalized polyhedral oligomeric silsesquioxane (POSS) cages. Diverse nanostructures were obtained by tuning secondary interactions among the building blocks and solvents via three factors: solvent polarity, surface functionality of POSS derivatives, and molecular topology. Self-assembled morphologies of KPOM-BPOSS (B denotes isobutyl groups) were found dependent on solvent polarity. In acetonitrile/water mixtures with a high dielectric constant, colloidal nanoparticles with nanophase-separated internal lamellar structures quickly formed, which gradually turned into one-dimensional nanobelt crystals upon aging, while stacked crystalline lamellae were dominantly observed in less polar methanol/chloroform solutions. When the crystallizable BPOSS was replaced with noncrystallizable cyclohexyl-functionalized CPOSS, the resulting KPOM-CPOSS also formed colloidal spheres; however, it failed to further evolve into crystalline nanobelt structures. In less polar solvents, KPOM-CPOSS crystallized into isolated two-dimensional nanosheets, which were composed of two inner crystalline layers of Keggin POM covered by two monolayers of amorphous CPOSS. In contrast, self-assembly of KPOM-2BPOSS was dominated by crystallization of the BPOSS cages, which was hardly sensitive to solvent polarity. The BPOSS cages formed the crystalline inner bilayer, sandwiched by two outer layers of Keggin POM clusters. These results illustrate a rational strategy to purposely fabricate self-assembled nanostructures with diverse dimensionality from MJPs with controlled molecular composition and topology.

  13. PREFACE: Nuclear Cluster Conference; Cluster'07

    NASA Astrophysics Data System (ADS)

    Freer, Martin

    2008-05-01

    The Cluster Conference is a long-running conference series dating back to the 1960's, the first being initiated by Wildermuth in Bochum, Germany, in 1969. The most recent meeting was held in Nara, Japan, in 2003, and in 2007 the 9th Cluster Conference was held in Stratford-upon-Avon, UK. As the name suggests the town of Stratford lies upon the River Avon, and shortly before the conference, due to unprecedented rainfall in the area (approximately 10 cm within half a day), lay in the River Avon! Stratford is the birthplace of the `Bard of Avon' William Shakespeare, and this formed an intriguing conference backdrop. The meeting was attended by some 90 delegates and the programme contained 65 70 oral presentations, and was opened by a historical perspective presented by Professor Brink (Oxford) and closed by Professor Horiuchi (RCNP) with an overview of the conference and future perspectives. In between, the conference covered aspects of clustering in exotic nuclei (both neutron and proton-rich), molecular structures in which valence neutrons are exchanged between cluster cores, condensates in nuclei, neutron-clusters, superheavy nuclei, clusters in nuclear astrophysical processes and exotic cluster decays such as 2p and ternary cluster decay. The field of nuclear clustering has become strongly influenced by the physics of radioactive beam facilities (reflected in the programme), and by the excitement that clustering may have an important impact on the structure of nuclei at the neutron drip-line. It was clear that since Nara the field had progressed substantially and that new themes had emerged and others had crystallized. Two particular topics resonated strongly condensates and nuclear molecules. These topics are thus likely to be central in the next cluster conference which will be held in 2011 in the Hungarian city of Debrechen. Martin Freer Participants and Cluster'07

  14. Enhanced photocatalytic activity of nanocomposites of TiO2 doped with Zr, Y or Ce polyoxometalates for degradation of methyl orange dye.

    PubMed

    Khoshnavazi, Roushan; Fereydouni, Shler; Bahrami, Leila

    2016-01-01

    The synergistic effect of polyoxometalate (POM) and metal-doped TiO2 (metal = Zr, Y and Ce) was examined, to fabricate nanocomposites with enhanced photocatalytic activities toward the degradation of methyl orange (MO), as a model textile dye. A series of new nanocomposites, containing different loading amounts of H9Na3[WZn3(H2O)2(ZnW9O34)2].24H2O (HZnW) (10-30%) on each of the metal-doped TiO2 nanoparticles, were synthesized using impregnation method. The morphology and crystal phase of the as-prepared nanocomposites were investigated by various characterization techniques: Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray analysis and diffuse reflectance spectroscopy, indicating that the HZnW and metal-doped TiO2 had been successfully incorporated into the nanocomposite structure. The effects of parameters such as loading amount of HZnW, catalyst dose, pH and initial concentration of dye solution were investigated on the degradation kinetics and it was interestingly found that the prepared nanocomposites could efficiently degrade the MO dye in 5-7 min under UV light irradiation. The best results were obtained for the HZnW-Zr-TiO2 among the different nanocomposites. Also, control studies showed the superior photocatalytic properties of composites compared to that of the individual components. The facile preparation and their improved photocatalytic activities suggest that these materials can have a promising future for water and wastewater purifications.

  15. Enhanced photocatalytic activity of nanocomposites of TiO2 doped with Zr, Y or Ce polyoxometalates for degradation of methyl orange dye.

    PubMed

    Khoshnavazi, Roushan; Fereydouni, Shler; Bahrami, Leila

    2016-01-01

    The synergistic effect of polyoxometalate (POM) and metal-doped TiO2 (metal = Zr, Y and Ce) was examined, to fabricate nanocomposites with enhanced photocatalytic activities toward the degradation of methyl orange (MO), as a model textile dye. A series of new nanocomposites, containing different loading amounts of H9Na3[WZn3(H2O)2(ZnW9O34)2].24H2O (HZnW) (10-30%) on each of the metal-doped TiO2 nanoparticles, were synthesized using impregnation method. The morphology and crystal phase of the as-prepared nanocomposites were investigated by various characterization techniques: Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray analysis and diffuse reflectance spectroscopy, indicating that the HZnW and metal-doped TiO2 had been successfully incorporated into the nanocomposite structure. The effects of parameters such as loading amount of HZnW, catalyst dose, pH and initial concentration of dye solution were investigated on the degradation kinetics and it was interestingly found that the prepared nanocomposites could efficiently degrade the MO dye in 5-7 min under UV light irradiation. The best results were obtained for the HZnW-Zr-TiO2 among the different nanocomposites. Also, control studies showed the superior photocatalytic properties of composites compared to that of the individual components. The facile preparation and their improved photocatalytic activities suggest that these materials can have a promising future for water and wastewater purifications. PMID:27054748

  16. Systematic Investigation of High-Sensitivity Luminescent Sensing for Polyoxometalates and Iron(III) by MOFs Assembled with a New Resorcin[4]arene-Functionalized Tetracarboxylate.

    PubMed

    Zhang, Shuai-Tong; Yang, Jin; Wu, Hua; Liu, Ying-Ying; Ma, Jian-Fang

    2015-10-26

    A new family of resorcin[4]arene-based metal-organic frameworks (MOFs), namely, [Eu(HL)(DMF)(H2 O)2 ]⋅3 H2 O (1), [Tb(HL)(DMF)(H2 O)2 ] 3 H2 O (2), [Cd4 (L)2 (DMF)4 (H2 O)2 ] 3 H2 O (3) and [Zn3 (HL)2 (H2 O)2 ] 2 DMF⋅7 H2 O (4), have been constructed from a new resorcin[4]arene-functionalized tetracarboxylic acid (H4 L=2,8,14,20-tetra-ethyl-6,12,18,24-tetra-methoxy-4,10,16,22-tetra-carboxy-methoxy-calix[4]arene). Isostructural 1 and 2 exhibit charming 1D motifs built with the cup-like HL(3-) anions and rare earth cations. Compounds 3 and 4 show a unique sandwich-based 2D layer and a fascinating 3D framework, respectively. Remarkably, compounds 1 and 2 display intensive red and green emissions triggered by the efficient antenna effect of organic ligands under UV light. More importantly, systematic luminescence studies demonstrate that Ln-MOFs 1 and 2, as efficient multifunctional fluorescent materials, show highly selective and sensitive sensing of Fe(3+) , polyoxometalates (POMs), and acetone, which represents a rare example of a sensor for quantitatively detecting three different types of analytes. This is also an exceedingly rare example of Fe(3+) and POMs detection in aqueous solutions employing resorcin[4]arene-based luminescent Ln-MOFs. Furthermore, the possible mechanism of the sensing properties is deduced.

  17. Construction of a general library for the rational design of nanomagnets and spin qubits based on mononuclear f-block complexes. The polyoxometalate case.

    PubMed

    Baldoví, José J; Clemente-Juan, Juan M; Coronado, Eugenio; Duan, Yan; Gaita-Ariño, Alejandro; Giménez-Saiz, Carlos

    2014-09-15

    This paper belongs to a series of contributions aiming at establishing a general library that helps in the description of the crystal field (CF) effect of any ligand on the splitting of the J ground states of mononuclear f-element complexes. Here, the effective parameters associated with the oxo ligands (effective charges and metal-ligand distances) are extracted from the study of the magnetic properties of the first two families of single-ion magnets based on lanthanoid polyoxometalates (POMs), formulated as [Ln(W5O18)2](9-) and [Ln(β2-SiW11O39)2](13-) (Ln = Tb, Dy, Ho, Er, Tm, Yb). This effective CF approach provides a good description of the lowest-lying magnetic levels and the associated wave functions of the studied systems, which is fully consistent with the observed magnetic behavior. In order to demonstrate the predictive character of this model, we have extended our model in a first step to calculate the properties of the POM complexes of the early 4f-block metals. In doing so, [Nd(W5O18)2](9-) has been identified as a suitable candidate to exhibit SMM behavior. Magnetic experiments have confirmed such a prediction, demonstrating the usefulness of this strategy for the directed synthesis of new nanomagnets. Thus, with an effective barrier of 51.4 cm(-1) under an applied dc field of 1000 Oe, this is the second example of a Nd(3+)-based single-ion magnet. PMID:25156530

  18. Ionic Liquid-Derived Imidazolium Cation Linkers for the Layer-by-Layer Assembly of Polyoxometalate-MWCNT Composite Electrodes with High Power Capability.

    PubMed

    Genovese, Matthew; Lian, Keryn

    2016-07-27

    Imidazolium cations derived from ionic liquids were demonstrated as effective linker molecules for the layer-by-layer (LbL) deposition of polyoxometalates (POMs) to increase the charge storage of multi-walled carbon nanotube (MWCNT) electrodes. MWCNTs modified with GeMo12O40(4-) (GeMo12) via an imidazolium cation linker demonstrated highly reversible redox reactions and a capacitance of 84 F cm(-3), close to 4 times larger than bare CNT. Compared to CNT-GeMo12 composites fabricated with a conventional polyelectrolyte linker poly(diallyldimethylammonium chloride), (PDDA), the imidazolium cations resulted in lower POM loading, but higher conductivity and in turn superior performance at fast charge-discharge conditions. A polymerized imidazolium linker (PIL) was also synthesized based on the ethyl-vinyl-imidazolium monomer. CNT-GeMo12 composites fabricated with this PIL achieved high POM loading comparable to PDDA, while still maintaining the good conductivity and high rate capabilities shown by the monomer imidazolium units. The high conductivity imparted by the PIL is especially valuable for the fabrication of multilayer POM composites. Dual-layer GeMo12 O40(4-)-SiMo12O40(4-) (GeMo12-SiMo12) electrodes built with this PIL demonstrated a combined contribution of the individual POMs resulting in a capacitance of 191 F cm(-3), over nine times larger than bare MWCNT. The PIL dual layer composites also maintained 72% of this capacitance at a fast rate of 2 V s(-1), compared to just over 50% retention for similar electrodes fabricated with PDDA. PMID:27384442

  19. Survey on granularity clustering.

    PubMed

    Ding, Shifei; Du, Mingjing; Zhu, Hong

    2015-12-01

    With the rapid development of uncertain artificial intelligent and the arrival of big data era, conventional clustering analysis and granular computing fail to satisfy the requirements of intelligent information processing in this new case. There is the essential relationship between granular computing and clustering analysis, so some researchers try to combine granular computing with clustering analysis. In the idea of granularity, the researchers expand the researches in clustering analysis and look for the best clustering results with the help of the basic theories and methods of granular computing. Granularity clustering method which is proposed and studied has attracted more and more attention. This paper firstly summarizes the background of granularity clustering and the intrinsic connection between granular computing and clustering analysis, and then mainly reviews the research status and various methods of granularity clustering. Finally, we analyze existing problem and propose further research.

  20. Cluster automorphism groups of cluster algebras with coefficients

    NASA Astrophysics Data System (ADS)

    Chang, Wen; Zhu, Bin

    2016-10-01

    We study the cluster automorphism group of a skew-symmetric cluster algebra with geometric coefficients. For this, we introduce the notion of gluing free cluster algebra, and show that under a weak condition the cluster automorphism group of a gluing free cluster algebra is a subgroup of the cluster automorphism group of its principal part cluster algebra (i.e. the corresponding cluster algebra without coefficients). We show that several classes of cluster algebras with coefficients are gluing free, for example, cluster algebras with principal coefficients, cluster algebras with universal geometric coefficients, and cluster algebras from surfaces (except a 4-gon) with coefficients from boundaries. Moreover, except four kinds of surfaces, the cluster automorphism group of a cluster algebra from a surface with coefficients from boundaries is isomorphic to the cluster automorphism group of its principal part cluster algebra; for a cluster algebra with principal coefficients, its cluster automorphism group is isomorphic to the automorphism group of its initial quiver.

  1. Matlab Cluster Ensemble Toolbox

    SciTech Connect

    Sapio, Vincent De; Kegelmeyer, Philip

    2009-04-27

    This is a Matlab toolbox for investigating the application of cluster ensembles to data classification, with the objective of improving the accuracy and/or speed of clustering. The toolbox divides the cluster ensemble problem into four areas, providing functionality for each. These include, (1) synthetic data generation, (2) clustering to generate individual data partitions and similarity matrices, (3) consensus function generation and final clustering to generate ensemble data partitioning, and (4) implementation of accuracy metrics. With regard to data generation, Gaussian data of arbitrary dimension can be generated. The kcenters algorithm can then be used to generate individual data partitions by either, (a) subsampling the data and clustering each subsample, or by (b) randomly initializing the algorithm and generating a clustering for each initialization. In either case an overall similarity matrix can be computed using a consensus function operating on the individual similarity matrices. A final clustering can be performed and performance metrics are provided for evaluation purposes.

  2. Star cluster dynamics.

    PubMed

    Vesperini, Enrico

    2010-02-28

    Dynamical evolution plays a key role in shaping the current properties of star clusters and star cluster systems. A detailed understanding of the effects of evolutionary processes is essential to be able to disentangle the properties that result from dynamical evolution from those imprinted at the time of cluster formation. In this review, I focus my attention on globular clusters, and review the main physical ingredients driving their early and long-term evolution, describe the possible evolutionary routes and show how cluster structure and stellar content are affected by dynamical evolution.

  3. A new clustering strategy

    NASA Astrophysics Data System (ADS)

    Feng, Jian-xin; Tang, Jia-fu; Wang, Guang-xing

    2007-04-01

    On the basis of the analysis of clustering algorithm that had been proposed for MANET, a novel clustering strategy was proposed in this paper. With the trust defined by statistical hypothesis in probability theory and the cluster head selected by node trust and node mobility, this strategy can realize the function of the malicious nodes detection which was neglected by other clustering algorithms and overcome the deficiency of being incapable of implementing the relative mobility metric of corresponding nodes in the MOBIC algorithm caused by the fact that the receiving power of two consecutive HELLO packet cannot be measured. It's an effective solution to cluster MANET securely.

  4. Unconventional methods for clustering

    NASA Astrophysics Data System (ADS)

    Kotyrba, Martin

    2016-06-01

    Cluster analysis or clustering is a task of grouping a set of objects in such a way that objects in the same group (called a cluster) are more similar (in some sense or another) to each other than to those in other groups (clusters). It is the main task of exploratory data mining and a common technique for statistical data analysis used in many fields, including machine learning, pattern recognition, image analysis, information retrieval, and bioinformatics. The topic of this paper is one of the modern methods of clustering namely SOM (Self Organising Map). The paper describes the theory needed to understand the principle of clustering and descriptions of algorithm used with clustering in our experiments.

  5. Synthesis, structure elucidation and redox properties of 99Tc complexes of lacunary Wells Dawson polyoxometalates: insights into molecular 99Tc - metal oxide interactions

    SciTech Connect

    McGregor, Donna; Burton-Pye, Benjamin P.; Howell, Robertha C.; Mbomekalle, Israel M.; Lukens Jr, Wayne W.; Bian, Fang; Mausolf, Edward; Poineau, Frederic; Czerwinski, Kenneth R; Francesconi, Lynn C.

    2011-01-10

    The isotope 99Tc (beta max: 250 keV, half-life: 2 x 105 year) is an abundant product of uranium-235 fission in nuclear reactors and is present throughout the radioactive waste stored in underground tanks at Hanford and Savannah River. Understanding and controlling the extensive redox chemistry of 99Tc is important to identify tunable strategies to separate 99Tc from spent fuel and from waste tanks and once separated, to identify and develop an appropriately stable waste-form for 99Tc. Polyoxometalates (POMs), nanometer sized models for metal oxide solid-state materials, are used in this study to provide a molecular level understanding of the speciation and redox chemistry of incorporated 99Tc. In this study, 99Tc complexes of the (alpha 2-P2W17O61)10- and (alpha 1-P2W17O61)10- isomers were prepared. Ethylene glycol was used as a"transfer ligand" to minimize the formation of TcO2 cdot xH2O. The solution structures, formulations, and purity of TcVO(alpha 1/alpha 2-P2W17O61)7- were determined by multinuclear NMR. X-ray Absorption Spectroscopy of the complexes are in agreement with the formulation and structures determined from 31P and 183W NMR. Preliminary electrochemistry results are consistent with the EXAFS results, showing a facile reduction of the TcVO(alpha 1-P2W17O61)7- species compared to the TcVO(alpha 2-P2W17O61)7- analog. The alpha1- defect is unique in that a basic oxygen atom is positioned toward the alpha1- site and the TcVO center appears to form a dative metal-metal bond with a framework W site. These attributes may lead to the assistance of protonation events that facilitate reduction. Electrochemistry comparison shows that the ReV analogs are about 200 mV more difficult to reduce in accordance with periodic trends.

  6. A series of Anderson-type polyoxometalate-based metal-organic complexes: their pH-dependent electrochemical behaviour, and as electrocatalysts and photocatalysts.

    PubMed

    Wang, Xiuli; Sun, Junjun; Lin, Hongyan; Chang, Zhihan; Wang, Xiang; Liu, Guocheng

    2016-08-01

    Seven polyoxometalate-based (POM) metal-organic complexes (MOCs) with different pyridyl-amide ligands were hydrothermally synthesized and structurally characterized. In 1, the [CrMo6(OH)5O19](4-) (CrMo6) polyoxoanions bridge the Cu(II) ions to generate a 1D Cu-CrMo6 inorganic double chain, which is further consolidated by the μ2-bridging 2-pdya ligands. Complex 2 exhibits a 2D layer based on [γ-Mo8O26]n(4n-) chains. In complex 3, the β-Mo8O26 anions link the metal-organic units [Cu(4-Hdpyp)2](4+) to construct a 1D fishbone-like chain. Complex 4 shows a 3D (6,6)-connected framework constructed by the 2D inorganic network [Cu4(μ3-OH)2(H2O)4(γ-Mo8O27)] and 3-dpyh bridging ligands. In 2-4, all the [CoMo6(OH)6O18](3-) (CoMo6) anions were in situ transformed to Mo8O26(4-) or Mo8O27(6-) anions. Complexes 5 and 7 are isostructural, each [TeMo6O24](6-) (TeMo6) polyoxoanion coordinates to two Cu(II) ions to generate a discrete copper complex [Cu2(4-Hdpye)2(TeMo6O24)(H2O)6] and [Cu2(4-Hdpyb)2(TeMo6O24)(H2O)6], respectively. In complex 6, the TeMo6 polyoxoanions bridge the Cu(II) ions to generate a 2D [Cu3(TeMo6)]n inorganic layer, which is further linked by the μ2-bridging 3-dpyb ligands to form a 3D metal-organic framework. The effects of POM types and their various coordination modes, as well as the pyridyl-amide ligands on the structures of the title complexes have been discussed. Their electrochemical behavior reveals characteristic multi-electron redox processes related to Mo(VI) centers. The electrocatalytic reduction performance toward hydrogen peroxide and bromate was fully measured and discussed; both complexes exhibit excellent electrocatalytic activity towards the reduction of bromate and hydrogen peroxide. In addition, the redox potentials of complexes 5-7 are highly pH sensitive and may be used as a kind of potential pH sensor. The photocatalytic activities of the title complexes are also investigated in detail. PMID:27434753

  7. Synthesis, structure elucidation, and redox properties of 99Tc complexes of lacunary Wells-Dawson polyoxometalates: insights into molecular 99Tc-metal oxide interactions.

    PubMed

    McGregor, Donna; Burton-Pye, Benjamin P; Howell, Robertha C; Mbomekalle, Israel M; Lukens, Wayne W; Bian, Fang; Mausolf, Edward; Poineau, Frederic; Czerwinski, Kenneth R; Francesconi, Lynn C

    2011-03-01

    The isotope (99)Tc (β(max), 293.7; half-life, 2.1 × 10(5) years) is an abundant product of uranium-235 fission in nuclear reactors and is present throughout the radioactive waste stored in underground tanks at the Hanford and Savannah River sites. Understanding and controlling the extensive redox chemistry of (99)Tc is important in identifying tunable strategies to separate (99)Tc from spent fuel and from waste tanks and, once separated, to identify and develop an appropriately stable waste form for (99)Tc. Polyoxometalates (POMs), nanometer-sized models for metal oxide solid-state materials, are used in this study to provide a molecular level understanding of the speciation and redox chemistry of incorporated (99)Tc. In this study, (99)Tc complexes of the (α(2)-P(2)W(17)O(61))(10-) and (α(1)-P(2)W(17)O(61))(10-) isomers were prepared. Ethylene glycol was used as a "transfer ligand" to minimize the formation of TcO(2)·xH(2)O. The solution structures, formulations, and purity of Tc(V)O(α(1)/α(2)-P(2)W(17)O(61))(7-) were determined by multinuclear NMR. X-ray absorption spectroscopy of the complexes is in agreement with the formulation and structures determined from (31)P and (183)W NMR. Preliminary electrochemistry results are consistent with the EXAFS results, showing a facile reduction of the Tc(V)O(α(1)-P(2)W(17)O(61))(7-) species compared to the Tc(V)O(α(2)-P(2)W(17)O(61))(7-) analog. The α(1) defect is unique in that a basic oxygen atom is positioned toward the α(1) site, and the Tc(V)O center appears to form a dative metal-metal bond with a framework W site. These attributes may lead to the assistance of protonation events that facilitate reduction. Electrochemistry comparison shows that the Re(V) analogs are about 200 mV more difficult to reduce in accordance with periodic trends.

  8. New organic–inorganic hybrid assemblies based on copper(I) ion, bichelate-bridging ligand and Lindqvist-type polyoxometalate

    SciTech Connect

    Zhang, Mao-Mao; Hao, Xiu-Li; Xu, Li-Jie; Wang, Yong-Hui Wang, Xin; Li, Yang-Guang

    2014-07-01

    Three new organic–inorganic hybrid compounds, namely [Cu{sup I}L{sub p}]{sub 2}[W{sub 6}O{sub 19}]·H{sub 2}O (1), [Cu{sup I}L{sub p}]{sub 3}[W{sub 6}O{sub 19}]Cl (2) and [Cu{sup I}L{sub p}]{sub 2}[W{sub 6}O{sub 19}]·2H{sub 2}O (3) (L{sub p}=α,α′-bis-[3-(2-pyridyl)pyrazol-1-yl]-1,4-dimethylbenzene) based on copper(I) ion, a neutral N-donor bichelate-bridging ligand (L{sub p}) and a Lindqvist-type polyoxometalate (POM) [W{sub 6}O{sub 19}]{sup 2−}, have been hydrothermally prepared under different synthetic conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction analyses. Compounds 1 and 2 contain two different but topologically similar meso-helical chainlike coordination moieties. Compound 3 contains both left- and right-handed chiral “mobius strip” units. These cationic meso-helical chains and “mobius strip” units in compounds 1–3 are further combined with Lindqvist-type polyoxoanions to form 3-D supramolecular assemblies through extensive electrostatic forces and/or π–π interactions. The photo-luminescent properties of 1–3 have also been investigated, which are mainly attributed to the L{sub p} ligand-centered emission. - Graphical abstract: Three new hybrid compounds based on same Cu(I) ion, bichelate-bridging ligand and [W{sub 6}O{sub 19}]{sup 2−} building blocks were synthesized. Various structural features of three compounds were tuned by different synthetic conditions. - Highlights: • New compounds based on Cu(I), bichelate-bridging ligand and POM were prepared. • Compounds 1 and 2 contain two different but topologically similar meso-helical chains. • Compound 3 contains both left- and right-handed chiral “mobius strip” units. • Compounds 1–3 exhibit the ligand-centered luminescent property.

  9. Information-based clustering

    PubMed Central

    Slonim, Noam; Atwal, Gurinder Singh; Tkačik, Gašper; Bialek, William

    2005-01-01

    In an age of increasingly large data sets, investigators in many different disciplines have turned to clustering as a tool for data analysis and exploration. Existing clustering methods, however, typically depend on several nontrivial assumptions about the structure of data. Here, we reformulate the clustering problem from an information theoretic perspective that avoids many of these assumptions. In particular, our formulation obviates the need for defining a cluster “prototype,” does not require an a priori similarity metric, is invariant to changes in the representation of the data, and naturally captures nonlinear relations. We apply this approach to different domains and find that it consistently produces clusters that are more coherent than those extracted by existing algorithms. Finally, our approach provides a way of clustering based on collective notions of similarity rather than the traditional pairwise measures. PMID:16352721

  10. Convex Discriminative Multitask Clustering.

    PubMed

    Zhang, Xiao-Lei

    2015-01-01

    Multitask clustering tries to improve the clustering performance of multiple tasks simultaneously by taking their relationship into account. Most existing multitask clustering algorithms fall into the type of generative clustering, and none are formulated as convex optimization problems. In this paper, we propose two convex Discriminative Multitask Clustering (DMTC) objectives to address the problems. The first one aims to learn a shared feature representation, which can be seen as a technical combination of the convex multitask feature learning and the convex Multiclass Maximum Margin Clustering (M3C). The second one aims to learn the task relationship, which can be seen as a combination of the convex multitask relationship learning and M3C. The objectives of the two algorithms are solved in a uniform procedure by the efficient cutting-plane algorithm and further unified in the Bayesian framework. Experimental results on a toy problem and two benchmark data sets demonstrate the effectiveness of the proposed algorithms. PMID:26353206

  11. Clusters of galaxies

    NASA Astrophysics Data System (ADS)

    Vikhlinin, A. A.; Kravtsov, A. V.; Markevich, M. L.; Sunyaev, R. A.; Churazov, E. M.

    2014-04-01

    Galaxy clusters are formed via nonlinear growth of primordial density fluctuations and are the most massive gravitationally bound objects in the present Universe. Their number density at different epochs and their properties depend strongly on the properties of dark matter and dark energy, making clusters a powerful tool for observational cosmology. Observations of the hot gas filling the gravitational potential well of a cluster allows studying gasdynamic and plasma effects and the effect of supermassive black holes on the heating and cooling of gas on cluster scales. The work of Yakov Borisovich Zeldovich has had a profound impact on virtually all cosmological and astrophysical studies of galaxy clusters, introducing concepts such as the Harrison-Zeldovich spectrum, the Zeldovich approximation, baryon acoustic peaks, and the Sunyaev-Zeldovich effect. Here, we review the most basic properties of clusters and their role in modern astrophysics and cosmology.

  12. Determination of Sn(II) and Sn(IV) after mixed micelle-mediated cloud point extraction using alpha-polyoxometalate as a complexing agent by flame atomic absorption spectrometry.

    PubMed

    Gholivand, M B; Babakhanian, A; Rafiee, E

    2008-07-30

    The cloud point extraction behavior of Sn(II) and Sn(IV) using alpha-polyoxometalate and mixed surfactants solution was investigated. The mixture of a nonionic surfactant (Triton X-100) and a cationic surfactant (CTAB) was utilized as a suitable micellar medium for preconcentration and extraction of tin complexes. Sn(II) in the presence of Sn(IV) was extracted with alpha-polyoxometalate, 0.3% (w/v) Triton X-100 and 3.5x10(-5) mol L(-1) CTAB at pH 1.2. Whereas the pH value of 3.7 were used for the individual determination of Sn(II) and Sn(IV) and also for total tin determination at the same conditions. Enrichment factors of 100 were obtained for the preconcentration of both metal ions. Under the optimal conditions, linearity was obeyed in the ranges of 55-670 microg L(-1) of Sn(II) and 46-750 microg L(-1) of Sn(IV) ion concentration. The detection limit of the method was also found to be 12.6 microg L(-1) for Sn(IV) and 8.4 microg L(-1) for Sn(II). The relative standard deviation of seven replicate determination of 100 microg L(-1) both metal ions were obtained about 2.4%. The diverse ion effect of some anions and cations on the extraction efficiency of target ions were tested. Finally, the optimized conditions developed were successfully utilized for the determination of each metal ion in various alloy, juice fruit, tape and waste water samples with satisfactory results. PMID:18585313

  13. Mini-clusters

    NASA Technical Reports Server (NTRS)

    Chinellato, J. A.; Dobrigkeit, C.; Bellandifilho, J.; Lattes, C. M. G.; Menon, M. J.; Navia, C. E.; Pamilaju, A.; Sawayanagi, K.; Shibuya, E. H.; Turtelli, A., Jr.

    1985-01-01

    Experimental results of mini-clusters observed in Chacaltaya emulsion chamber no.19 are summarized. The study was made on 54 single core shower upper and 91 shower clusters of E(gamma) 10 TeV from 30 families which are visible energy greater than 80 TeV and penetrate through both upper and lower detectors of the two-story chamber. The association of hadrons in mini-cluster is made clear from their penetrative nature and microscopic observation of shower continuation in lower chamber. Small P sub t (gamma) of hadrons in mini-clusters remained in puzzle.

  14. Reactions of intermetallic clusters

    NASA Astrophysics Data System (ADS)

    Farley, R. W.; Castleman, A. W., Jr.

    1990-02-01

    Reaction of bismuth-alkali clusters with closed-shell HX acids provides insight into the structures, formation, and stabilities of these intermetallic species. HC1 and HI are observed to quantitatively strip BixNay and BixKy, respectively, of their alkali component, leaving bare bismuth clusters as the only bismuth-containing species detected. Product bismuth clusters exhibit the same distribution observed when pure bismuth is evaporated in the source. Though evaporated simultaneously from the same crucible, this suggests alkali atoms condense onto existing bismuth clusters and have negligible effect on their formation and consequent distribution. The indistinguishibility of reacted and pure bismuth cluster distributions further argues against the simple replacement of alkali atoms with hydrogen in these reactions. This is considered further evidence that the alkali atoms are external to the stable bismuth Zintl anionic structures. Reactivities of BixNay clusters with HC1 are estimated to lie between 3×10-13 for Bi4Na, to greater than 4×10-11 for clusters possessing large numbers of alkali atoms. Bare bismuth clusters are observed in separate experiments to react significantly more slowly with rates of 1-9×10-14 and exhibit little variation of reactivity with size. The bismuth clusters may thus be considered a relatively inert substrate upon which the alkali overlayer reacts.

  15. Management of cluster headache.

    PubMed

    Tfelt-Hansen, Peer C; Jensen, Rigmor H

    2012-07-01

    The prevalence of cluster headache is 0.1% and cluster headache is often not diagnosed or misdiagnosed as migraine or sinusitis. In cluster headache there is often a considerable diagnostic delay - an average of 7 years in a population-based survey. Cluster headache is characterized by very severe or severe orbital or periorbital pain with a duration of 15-180 minutes. The cluster headache attacks are accompanied by characteristic associated unilateral symptoms such as tearing, nasal congestion and/or rhinorrhoea, eyelid oedema, miosis and/or ptosis. In addition, there is a sense of restlessness and agitation. Patients may have up to eight attacks per day. Episodic cluster headache (ECH) occurs in clusters of weeks to months duration, whereas chronic cluster headache (CCH) attacks occur for more than 1 year without remissions. Management of cluster headache is divided into acute attack treatment and prophylactic treatment. In ECH and CCH the attacks can be treated with oxygen (12 L/min) or subcutaneous sumatriptan 6 mg. For both oxygen and sumatriptan there are two randomized, placebo-controlled trials demonstrating efficacy. In both ECH and CCH, verapamil is the prophylactic drug of choice. Verapamil 360 mg/day was found to be superior to placebo in one clinical trial. In clinical practice, daily doses of 480-720 mg are mostly used. Thus, the dose of verapamil used in cluster headache treatment may be double the dose used in cardiology, and with the higher doses the PR interval should be checked with an ECG. At the start of a cluster, transitional preventive treatment such as corticosteroids or greater occipital nerve blockade can be given. In CCH and in long-standing clusters of ECH, lithium, methysergide, topiramate, valproic acid and ergotamine tartrate can be used as add-on prophylactic treatment. In drug-resistant CCH, neuromodulation with either occipital nerve stimulation or deep brain stimulation of the hypothalamus is an alternative treatment strategy

  16. The youngest globular clusters

    NASA Astrophysics Data System (ADS)

    Beck, Sara

    2015-11-01

    It is likely that all stars are born in clusters, but most clusters are not bound and disperse. None of the many protoclusters in our Galaxy are likely to develop into long-lived bound clusters. The super star clusters (SSCs) seen in starburst galaxies are more massive and compact and have better chances of survival. The birth and early development of SSCs takes place deep in molecular clouds, and during this crucial stage the embedded clusters are invisible to optical or UV observations but are studied via the radio-infrared supernebulae (RISN) they excite. We review observations of embedded clusters and identify RISN within 10 Mpc whose exciting clusters have ≈ 106 M⊙ or more in volumes of a few pc3 and which are likely to not only survive as bound clusters, but to evolve into objects as massive and compact as Galactic globulars. These clusters are distinguished by very high star formation efficiency η, at least a factor of 10 higher than the few percent seen in the Galaxy, probably due to the violent disturbances their host galaxies have undergone. We review recent observations of the kinematics of the ionized gas in RISN showing outflows through low-density channels in the ambient molecular cloud; this may protect the cloud from feedback by the embedded H II region.

  17. Clustering versus non-clustering phase synchronizations

    SciTech Connect

    Liu, Shuai; Zhan, Meng

    2014-03-15

    Clustering phase synchronization (CPS) is a common scenario to the global phase synchronization of coupled dynamical systems. In this work, a novel scenario, the non-clustering phase synchronization (NPS), is reported. It is found that coupled systems do not transit to the global synchronization until a certain sufficiently large coupling is attained, and there is no clustering prior to the global synchronization. To reveal the relationship between CPS and NPS, we further analyze the noise effect on coupled phase oscillators and find that the coupled oscillator system can change from CPS to NPS with the increase of noise intensity or system disorder. These findings are expected to shed light on the mechanism of various intriguing self-organized behaviors in coupled systems.

  18. A nonparametric clustering technique which estimates the number of clusters

    NASA Technical Reports Server (NTRS)

    Ramey, D. B.

    1983-01-01

    In applications of cluster analysis, one usually needs to determine the number of clusters, K, and the assignment of observations to each cluster. A clustering technique based on recursive application of a multivariate test of bimodality which automatically estimates both K and the cluster assignments is presented.

  19. Mixed-Initiative Clustering

    ERIC Educational Resources Information Center

    Huang, Yifen

    2010-01-01

    Mixed-initiative clustering is a task where a user and a machine work collaboratively to analyze a large set of documents. We hypothesize that a user and a machine can both learn better clustering models through enriched communication and interactive learning from each other. The first contribution or this thesis is providing a framework of…

  20. Cluster Interest Inventory.

    ERIC Educational Resources Information Center

    Herzog, Douglas

    The Cluster Interest Inventory is designed to familiarize students with representative occupations in 13 career clusters: (1) agribusiness and natural resources, (2) business marketing, and office occupations, (3) communications and media, (4) consumer and homemaker, (5) fine arts and humanities, (6) health, (7) manufacturing and processing, (8)…

  1. Matlab Cluster Ensemble Toolbox

    2009-04-27

    This is a Matlab toolbox for investigating the application of cluster ensembles to data classification, with the objective of improving the accuracy and/or speed of clustering. The toolbox divides the cluster ensemble problem into four areas, providing functionality for each. These include, (1) synthetic data generation, (2) clustering to generate individual data partitions and similarity matrices, (3) consensus function generation and final clustering to generate ensemble data partitioning, and (4) implementation of accuracy metrics. Withmore » regard to data generation, Gaussian data of arbitrary dimension can be generated. The kcenters algorithm can then be used to generate individual data partitions by either, (a) subsampling the data and clustering each subsample, or by (b) randomly initializing the algorithm and generating a clustering for each initialization. In either case an overall similarity matrix can be computed using a consensus function operating on the individual similarity matrices. A final clustering can be performed and performance metrics are provided for evaluation purposes.« less

  2. [Cluster headache differential diagnosis].

    PubMed

    Guégan-Massardier, Evelyne; Laubier, Cécile

    2015-11-01

    Cluster headache is characterized by disabling stereotyped headache. Early diagnosis allows appropriate treatment, unfortunately diagnostic errors are frequent. The main differential diagnoses are other primary or essential headaches. Migraine, more frequent and whose diagnosis is carried by excess, trigeminal neuralgia or other trigemino-autonomic cephalgia. Vascular or tumoral underlying condition can mimic cluster headache, neck and brain imaging is recommended, ideally MRI.

  3. Blue emitting undecaplatinum clusters

    NASA Astrophysics Data System (ADS)

    Chakraborty, Indranath; Bhuin, Radha Gobinda; Bhat, Shridevi; Pradeep, T.

    2014-07-01

    A blue luminescent 11-atom platinum cluster showing step-like optical features and the absence of plasmon absorption was synthesized. The cluster was purified using high performance liquid chromatography (HPLC). Electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) suggest a composition, Pt11(BBS)8, which was confirmed by a range of other experimental tools. The cluster is highly stable and compatible with many organic solvents.A blue luminescent 11-atom platinum cluster showing step-like optical features and the absence of plasmon absorption was synthesized. The cluster was purified using high performance liquid chromatography (HPLC). Electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) suggest a composition, Pt11(BBS)8, which was confirmed by a range of other experimental tools. The cluster is highly stable and compatible with many organic solvents. Electronic supplementary information (ESI) available: Details of experimental procedures, instrumentation, chromatogram of the crude cluster; SEM/EDAX, DLS, PXRD, TEM, FT-IR, and XPS of the isolated Pt11 cluster; UV/Vis, MALDI MS and SEM/EDAX of isolated 2 and 3; and 195Pt NMR of the K2PtCl6 standard. See DOI: 10.1039/c4nr02778g

  4. Muster: Massively Scalable Clustering

    2010-05-20

    Muster is a framework for scalable cluster analysis. It includes implementations of classic K-Medoids partitioning algorithms, as well as infrastructure for making these algorithms run scalably on very large systems. In particular, Muster contains algorithms such as CAPEK (described in reference 1) that are capable of clustering highly distributed data sets in-place on a hundred thousand or more processes.

  5. Illinois' Career Cluster Model

    ERIC Educational Resources Information Center

    Jankowski, Natasha A.; Kirby, Catherine L.; Bragg, Debra D.; Taylor, Jason L.; Oertle, Kathleen M.

    2009-01-01

    This booklet provides information to multiple stakeholders on the implementation of career clusters in Illinois. The booklet is an extension of the previous edition titled "An Introduction to Illinois CTE Programs of Study" (2008), and provides a resource for partners to understand Illinois' Career Cluster Model as its own adaptation of the…

  6. Brightest Cluster Galaxy Identification

    NASA Astrophysics Data System (ADS)

    Leisman, Luke; Haarsma, D. B.; Sebald, D. A.; ACCEPT Team

    2011-01-01

    Brightest cluster galaxies (BCGs) play an important role in several fields of astronomical research. The literature includes many different methods and criteria for identifying the BCG in the cluster, such as choosing the brightest galaxy, the galaxy nearest the X-ray peak, or the galaxy with the most extended profile. Here we examine a sample of 75 clusters from the Archive of Chandra Cluster Entropy Profile Tables (ACCEPT) and the Sloan Digital Sky Survey (SDSS), measuring masked magnitudes and profiles for BCG candidates in each cluster. We first identified galaxies by hand; in 15% of clusters at least one team member selected a different galaxy than the others.We also applied 6 other identification methods to the ACCEPT sample; in 30% of clusters at least one of these methods selected a different galaxy than the other methods. We then developed an algorithm that weighs brightness, profile, and proximity to the X-ray peak and centroid. This algorithm incorporates the advantages of by-hand identification (weighing multiple properties) and automated selection (repeatable and consistent). The BCG population chosen by the algorithm is more uniform in its properties than populations selected by other methods, particularly in the relation between absolute magnitude (a proxy for galaxy mass) and average gas temperature (a proxy for cluster mass). This work supported by a Barry M. Goldwater Scholarship and a Sid Jansma Summer Research Fellowship.

  7. Marketing Occupations. Cluster Guide.

    ERIC Educational Resources Information Center

    Oregon State Dept. of Education, Salem.

    This cluster guide, which is designed to show teachers what specific knowledge and skills qualify high school students for entry-level employment (or postsecondary training) in marketing occupations, is organized into three sections: (1) cluster organization and implementation, (2) instructional emphasis areas, and (3) assessment. The first…

  8. Probability and Cancer Clusters

    ERIC Educational Resources Information Center

    Hamilton-Keene, Rachael; Lenard, Christoper T.; Mills, Terry M.

    2009-01-01

    Recently there have been several news items about possible cancer clusters in the Australian media. The term "cancer cluster" is used when an unusually large number of people in one geographic area, often a workplace, are diagnosed with cancer in a short space of time. In this paper the authors explore this important health issue using probability…

  9. Extended utility of molten-salt chemistry: unprecedented synthesis of a water-soluble salt-inclusion solid comprised of high-nuclearity vanadium oxide clusters.

    PubMed

    Queen, Wendy L; West, J Palmer; Hudson, Joan; Hwu, Shiou-Jyh

    2011-11-01

    Polyoxometallates (POMs) are desirable in materials applications ranging from uses as catalysts in selective oxidation reactions to molecular-like building blocks for the preparation of new extended solids. With the use of an unprecedented approach involving high temperature, molten salt methods, a fascinating series of salt-inclusion solids (SISs) that contain high nuclearity POMs has been isolated for the first time. Cs(11)Na(3)(V(15)O(36))Cl(6) (1) was synthesized using the eutectic NaCl/CsCl flux (mp 493 °C) which serves as a reactive solvent in crystal growth and allows for the SIS formation. Its framework can be viewed as an "ionic" lattice composed of alternately packed counterions of Cl-centered [V(15)O(36)Cl](9-) clusters (V15; S = 11/2) and multinuclear [Cs(9)Na(3)Cl(5)](7+) cations. In light of the structural analysis, 1 was proven to be soluble in water giving rise to a dark green solution that is similar in color to single crystals of the title compound. Infrared spectroscopy of the solid formed from fast evaporation of the solution supports the presence of dissolved V15 clusters. Also noteworthy is the magnetization of 1 at 2 K, which reveals an s-shaped plot resembling that of superparamagnetic materials.

  10. Cosmology with galaxy clusters

    NASA Astrophysics Data System (ADS)

    Sartoris, Barbara

    2015-08-01

    Clusters of galaxies are powerful probes to constrain parameters that describe the cosmological models and to distinguish among different models. Since, the evolution of the cluster mass function and large-scale clustering contain the informations about the linear growth rate of perturbations and the expansion history of the Universe, clusters have played an important role in establishing the current cosmological paradigm. It is crucial to know how to determine the cluster mass from observational quantities when using clusters as cosmological tools. For this, numerical simulations are helpful to define and study robust cluster mass proxies that have minimal and well understood scatter across the mass and redshift ranges of interest. Additionally, the bias in cluster mass determination can be constrained via observations of the strong and weak lensing effect, X-ray emission, the Sunyaev- Zel’dovic effect, and the dynamics of galaxies.A major advantage of X-ray surveys is that the observable-mass relation is tight. Moreover, clusters can be easily identified in X-ray as continuous, extended sources. As of today, interesting cosmological constraints have been obtained from relatively small cluster samples (~102), X-ray selected by the ROSAT satellite over a wide redshift range (0clusters, the ROSAT All-Sky Survey.The next generation of X-ray telescopes will enhance the statistics of detected clusters and enlarge their redshift coverage. In particular, eROSITA will produce a catalog of >105 clusters with photometric redshifts from multi-band optical surveys (e.g. PanSTARRS, DES, and LSST). This will vastly improve upon current cosmological constraints, especially by the synergy with other cluster surveys that

  11. Cool Cluster Correctly Correlated

    SciTech Connect

    Varganov, Sergey Aleksandrovich

    2005-01-01

    Atomic clusters are unique objects, which occupy an intermediate position between atoms and condensed matter systems. For a long time it was thought that physical and chemical properties of atomic dusters monotonically change with increasing size of the cluster from a single atom to a condensed matter system. However, recently it has become clear that many properties of atomic clusters can change drastically with the size of the clusters. Because physical and chemical properties of clusters can be adjusted simply by changing the cluster's size, different applications of atomic clusters were proposed. One example is the catalytic activity of clusters of specific sizes in different chemical reactions. Another example is a potential application of atomic clusters in microelectronics, where their band gaps can be adjusted by simply changing cluster sizes. In recent years significant advances in experimental techniques allow one to synthesize and study atomic clusters of specified sizes. However, the interpretation of the results is often difficult. The theoretical methods are frequently used to help in interpretation of complex experimental data. Most of the theoretical approaches have been based on empirical or semiempirical methods. These methods allow one to study large and small dusters using the same approximations. However, since empirical and semiempirical methods rely on simple models with many parameters, it is often difficult to estimate the quantitative and even qualitative accuracy of the results. On the other hand, because of significant advances in quantum chemical methods and computer capabilities, it is now possible to do high quality ab-initio calculations not only on systems of few atoms but on clusters of practical interest as well. In addition to accurate results for specific clusters, such methods can be used for benchmarking of different empirical and semiempirical approaches. The atomic clusters studied in this work contain from a few atoms to

  12. Document clustering methods, document cluster label disambiguation methods, document clustering apparatuses, and articles of manufacture

    DOEpatents

    Sanfilippo, Antonio; Calapristi, Augustin J.; Crow, Vernon L.; Hetzler, Elizabeth G.; Turner, Alan E.

    2009-12-22

    Document clustering methods, document cluster label disambiguation methods, document clustering apparatuses, and articles of manufacture are described. In one aspect, a document clustering method includes providing a document set comprising a plurality of documents, providing a cluster comprising a subset of the documents of the document set, using a plurality of terms of the documents, providing a cluster label indicative of subject matter content of the documents of the cluster, wherein the cluster label comprises a plurality of word senses, and selecting one of the word senses of the cluster label.

  13. Studies in clustering theory

    NASA Astrophysics Data System (ADS)

    Stell, George

    In recent years the properties of percolation models have been studied intensively. The purpose of our project was to develop a general theory of percolation and clustering between particles of arbitrary size and shape, with arbitrary correlations between them. The goal of such a theory includes the treatment of continuum percolation as well as a novel treatment of lattice percolation. We made substantial progress toward this goal. The quantities basic to a description of clustering, the mean cluster size, mean number of clusters, etc., were developed. Concise formulas were given for the terms in such series, and proved, at least for sufficiently low densities, that the series are absolutely convergent. These series can now be used to construct Pade approximants that will allow one to probe the percolation transition. A scaled-particle theory of percolation was developed which gives analytic approximants for the mean number of clusters in a large class of two and three dimensional percolation models. Although this quantity is essential in many applications, e.g., explaining colligative properties, and interpreting low-angle light-scattering data, no systematic studies of it have been done before this work. Recently carried out detailed computer simulations show that the mean number of clusters is given to high accuracy by several of there approximations. Extensions of this work will allow calculation of the complete cluster size distribution.

  14. Extending Beowulf Clusters

    USGS Publications Warehouse

    Steinwand, Daniel R.; Maddox, Brian; Beckmann, Tim; Hamer, George

    2003-01-01

    Beowulf clusters can provide a cost-effective way to compute numerical models and process large amounts of remote sensing image data. Usually a Beowulf cluster is designed to accomplish a specific set of processing goals, and processing is very efficient when the problem remains inside the constraints of the original design. There are cases, however, when one might wish to compute a problem that is beyond the capacity of the local Beowulf system. In these cases, spreading the problem to multiple clusters or to other machines on the network may provide a cost-effective solution.

  15. Partially supervised speaker clustering.

    PubMed

    Tang, Hao; Chu, Stephen Mingyu; Hasegawa-Johnson, Mark; Huang, Thomas S

    2012-05-01

    Content-based multimedia indexing, retrieval, and processing as well as multimedia databases demand the structuring of the media content (image, audio, video, text, etc.), one significant goal being to associate the identity of the content to the individual segments of the signals. In this paper, we specifically address the problem of speaker clustering, the task of assigning every speech utterance in an audio stream to its speaker. We offer a complete treatment to the idea of partially supervised speaker clustering, which refers to the use of our prior knowledge of speakers in general to assist the unsupervised speaker clustering process. By means of an independent training data set, we encode the prior knowledge at the various stages of the speaker clustering pipeline via 1) learning a speaker-discriminative acoustic feature transformation, 2) learning a universal speaker prior model, and 3) learning a discriminative speaker subspace, or equivalently, a speaker-discriminative distance metric. We study the directional scattering property of the Gaussian mixture model (GMM) mean supervector representation of utterances in the high-dimensional space, and advocate exploiting this property by using the cosine distance metric instead of the euclidean distance metric for speaker clustering in the GMM mean supervector space. We propose to perform discriminant analysis based on the cosine distance metric, which leads to a novel distance metric learning algorithm—linear spherical discriminant analysis (LSDA). We show that the proposed LSDA formulation can be systematically solved within the elegant graph embedding general dimensionality reduction framework. Our speaker clustering experiments on the GALE database clearly indicate that 1) our speaker clustering methods based on the GMM mean supervector representation and vector-based distance metrics outperform traditional speaker clustering methods based on the “bag of acoustic features” representation and statistical

  16. H-cluster stars

    NASA Astrophysics Data System (ADS)

    Lai, X. Y.; Gao, C. Y.; Xu, R. X.

    2013-06-01

    The study of dense matter at ultrahigh density has a very long history, which is meaningful for us to understand not only cosmic events in extreme circumstances but also fundamental laws of physics. It is well known that the state of cold matter at supranuclear density depends on the non-perturbative nature of quantum chromodynamics (QCD) and is essential for modelling pulsars. A so-called H-cluster matter is proposed in this paper as the nature of dense matter in reality. In compact stars at only a few nuclear densities but low temperature, quarks could be interacting strongly with each other there. That might render quarks grouped in clusters, although the hypothetical quark clusters in cold dense matter have not been confirmed due to the lack of both theoretical and experimental evidence. Motivated by recent lattice QCD simulations of the H-dibaryons (with structure uuddss), we therefore consider here a possible kind of quark clusters, H-clusters, that could emerge inside compact stars during their initial cooling as the dominant components inside (the degree of freedom could then be H-clusters there). Taking into account the in-medium stiffening effect, we find that at baryon densities of compact stars H-cluster matter could be more stable than nuclear matter. We also find that for the H-cluster matter with lattice structure, the equation of state could be so stiff that it would seem to be `superluminal' in the most dense region. However, the real sound speed for H-cluster matter is in fact difficult to calculate, so at this stage we do not put constraints on our model from the usual requirement of causality. We study the stars composed of H-clusters, i.e. H-cluster stars, and derive the dependence of their maximum mass on the in-medium stiffening effect, showing that the maximum mass could be well above 2 M⊙ as observed and that the resultant mass-radius relation fits the measurement of the rapid burster under reasonable parameters. Besides a general

  17. Combining cluster number counts and galaxy clustering

    NASA Astrophysics Data System (ADS)

    Lacasa, Fabien; Rosenfeld, Rogerio

    2016-08-01

    The abundance of clusters and the clustering of galaxies are two of the important cosmological probes for current and future large scale surveys of galaxies, such as the Dark Energy Survey. In order to combine them one has to account for the fact that they are not independent quantities, since they probe the same density field. It is important to develop a good understanding of their correlation in order to extract parameter constraints. We present a detailed modelling of the joint covariance matrix between cluster number counts and the galaxy angular power spectrum. We employ the framework of the halo model complemented by a Halo Occupation Distribution model (HOD). We demonstrate the importance of accounting for non-Gaussianity to produce accurate covariance predictions. Indeed, we show that the non-Gaussian covariance becomes dominant at small scales, low redshifts or high cluster masses. We discuss in particular the case of the super-sample covariance (SSC), including the effects of galaxy shot-noise, halo second order bias and non-local bias. We demonstrate that the SSC obeys mathematical inequalities and positivity. Using the joint covariance matrix and a Fisher matrix methodology, we examine the prospects of combining these two probes to constrain cosmological and HOD parameters. We find that the combination indeed results in noticeably better constraints, with improvements of order 20% on cosmological parameters compared to the best single probe, and even greater improvement on HOD parameters, with reduction of error bars by a factor 1.4-4.8. This happens in particular because the cross-covariance introduces a synergy between the probes on small scales. We conclude that accounting for non-Gaussian effects is required for the joint analysis of these observables in galaxy surveys.

  18. Statistical properties of convex clustering

    PubMed Central

    Tan, Kean Ming; Witten, Daniela

    2016-01-01

    In this manuscript, we study the statistical properties of convex clustering. We establish that convex clustering is closely related to single linkage hierarchical clustering and k-means clustering. In addition, we derive the range of the tuning parameter for convex clustering that yields a non-trivial solution. We also provide an unbiased estimator of the degrees of freedom, and provide a finite sample bound for the prediction error for convex clustering. We compare convex clustering to some traditional clustering methods in simulation studies.

  19. [Treatment of cluster headache].

    PubMed

    Fabre, N

    2005-07-01

    Remarkable therapeutic improvements have come forward recently for trigemino-autonomic cephalalgias. Attack treatment in cluster headache is based on sumatriptan and oxygen. Non-vasoconstrictive treatments are opening a new post-triptan era but are not yet applicable. Prophylactic treatment of cluster headache is based on verapamil and lithium. The efficacy of anti-epileptic drugs in cluster headache remains to be demonstrated. Surgical treatment aimed at the parasympathetic pathways and at the trigeminal nerve demonstrates a high rate of recurrence and adverse events and questions about the relevance of a "peripheral" target in cluster headache. The efficacy of continuous hypothalamic stimulation in patients with intractable headache constitutes a breakthrough, but must be demonstrated at a larger scale and the benefice/risk ratio must be carefully evaluated. Indomethacin still remains the gold standard in paroxysmal hemicrania treatment. Until recently SUNCT was considered an intractable condition. However there are some reports of complete relief with lamotrigine, topiramate and gabapentin.

  20. Mantis BT Cluster Support

    SciTech Connect

    Riot, V.

    2009-06-05

    The software is a modidication to the Mantis BT V1.5 open source application provided by the mantis BT group to support cluster web servers. It also provides various cosmetic modifications used a LLNL.

  1. Spotlight on Cluster

    NASA Astrophysics Data System (ADS)

    1994-09-01

    For the first and only time during the development and construction of Cluster, all four satellites will be together in the space testing facilities of IABG in Munich. On this unique occasion, ESA invites you, and in particular the visual media, to a joint ESA/Industry briefing on the Cluster project at 10h30 on Tuesday, 11 October at IABG, Einsteinstrasse 20, OTTOBRUNN (Germany). After the meeting, ESA and Industry representatives as well as mission specialists will be available for interviews. A detailed agenda is enclosed. If you intend to participate please return the attached registration form by fax (33.1) 42.73.76.90 to ESA Public Relations Division. CLUSTER BRIEFING Tuesday 11 October 1994 - IABG (Munich) Agenda 09h30 Welcome and first photo opportunity 10h30-10h35 Welcome by IABG Director 10h35-10h40 Introduction by Kurt-Johann Gluitz, Dornier, Vice-President Satellite Systems 10h40-10h55 The ESA science programme by Roger Bonnet, Director of the ESA Science programme 10h55-11h10 The mission overview by Rudi Schmidt, ESA, Cluster Project Scientist 11h10-11h20 The Cluster project by John Credland, ESA Cluster Project Manager 11h20-11h30 Cluster and the European Industry by Gunther Lehn, Dornier Cluster Project Manager 11h30-12h00 Question and answer session 12h00-14h00 Interviews and buffet lunch 13h00-14h00 Second photo opportunity 14h00 End

  2. Wild Duck Cluster

    NASA Technical Reports Server (NTRS)

    2005-01-01

    On April 7, 2005, the Deep Impact spacecraft's Impactor Target Sensor camera recorded this image of M11, the Wild Duck cluster, a galactic open cluster located 6 thousand light years away. The camera is located on the impactor spacecraft, which will image comet Tempel 1 beginning 22 hours before impact until about 2 seconds before impact. Impact with comet Tempel 1 is planned for July 4, 2005.

  3. Cluster functional renormalization group

    NASA Astrophysics Data System (ADS)

    Reuther, Johannes; Thomale, Ronny

    2014-01-01

    Functional renormalization group (FRG) has become a diverse and powerful tool to derive effective low-energy scattering vertices of interacting many-body systems. Starting from a free expansion point of the action, the flow of the RG parameter Λ allows us to trace the evolution of the effective one- and two-particle vertices towards low energies by taking into account the vertex corrections between all parquet channels in an unbiased fashion. In this work, we generalize the expansion point at which the diagrammatic resummation procedure is initiated from a free UV limit to a cluster product state. We formulate a cluster FRG scheme where the noninteracting building blocks (i.e., decoupled spin clusters) are treated exactly, and the intercluster couplings are addressed via RG. As a benchmark study, we apply our cluster FRG scheme to the spin-1/2 bilayer Heisenberg model (BHM) on a square lattice where the neighboring sites in the two layers form the individual two-site clusters. Comparing with existing numerical evidence for the BHM, we obtain reasonable findings for the spin susceptibility, the spin-triplet excitation energy, and quasiparticle weight even in coupling regimes close to antiferromagnetic order. The concept of cluster FRG promises applications to a large class of interacting electron systems.

  4. Anti-tumor and immunomodulatory activity of iron hepta-tungsten phosphate oxygen clusters complex.

    PubMed

    Zhang, Bisong; Qiu, Jianping; Wu, Changsheng; Li, Yunxia; Liu, Zhenxiang

    2015-12-01

    Polyoxometalates (POMs) have attracted a considerable attention due to their unique structural characteristics, physicochemical properties and biological activities. In this study, iron hepta-tungsten phosphate oxygen clusters complex Na12H[Fe(HPW7O28)2]·44H2O (IHTPO) was synthesized and evaluated for in vitro cytotoxic activities on human hepatoma HepG2, leukemia K562, lung carcinoma A549, and large cell lung cancer NCI-H460 cells, therapeutic efficacies on mice transplantable tumor, and immunomodulatory potentials on the immune response in tumor-bearing mice. IHTPO exhibited lower in vitro cytotoxic activities against four human tumor cell lines, with the IC50 values being higher than 62.5μM (ca. 300μg/ml). IHTPO, however, significantly inhibited the growth of S180 sarcoma transplanted in mice. It was further showed that IHTPO could not only significantly promote splenocytes proliferation, NK cell and CTL activity from splenocytes, but remarkably enhance serum antigen-specific IgG, IgG2a and IgG2b antibody levels in S180-bearing mice. IHTPO also significantly promoted Th1 cytokines IFN-γ and IL-2 production, and up-regulated the mRNA expression levels of IFN-γ, IL-2 and Th1 transcription factors T-bet and STAT-4 in splenocytes from the S180-bearing mice. These results suggested that IHTPO significantly inhibited the growth of mice transplantable tumor, and that its in vivo antitumor activity might be achieved by improving Th1 protective cell-mediated immunity. IHTPO could act as antitumor agent with immunomodulatory activity.

  5. Behavioral Clustering of School Children.

    ERIC Educational Resources Information Center

    Huberty, Carl J.; And Others

    This article illustrates how a cluster analysis can be conducted, validated, and interpreted. Data normed for a behavioral assessment instrument with 14 scales on a nationally representative sample of U.S. school children were utilized. The discussion explores the similarity index, cluster method, cluster typology, cluster validity, cluster…

  6. ROTATING GLOBULAR CLUSTERS

    SciTech Connect

    Bianchini, P.; Varri, A. L.; Bertin, G.; Zocchi, A.

    2013-07-20

    Internal rotation is thought to play a major role in the dynamics of some globular clusters. However, in only a few cases has internal rotation been studied by the quantitative application of realistic and physically justified global models. Here, we present a dynamical analysis of the photometry and three-dimensional kinematics of {omega} Cen, 47 Tuc, and M15, by means of a recently introduced family of self-consistent axisymmetric rotating models. The three clusters, characterized by different relaxation conditions, show evidence of differential rotation and deviations from sphericity. The combination of line-of-sight velocities and proper motions allows us to determine their internal dynamics, predict their morphology, and estimate their dynamical distance. The well-relaxed cluster 47 Tuc is interpreted very well by our model; internal rotation is found to explain the observed morphology. For M15, we provide a global model in good agreement with the data, including the central behavior of the rotation profile and the shape of the ellipticity profile. For the partially relaxed cluster {omega} Cen, the selected model reproduces the complex three-dimensional kinematics; in particular, the observed anisotropy profile, characterized by a transition from isotropy to weakly radial anisotropy and then to tangential anisotropy in the outer parts. The discrepancy found for the steep central gradient in the observed line-of-sight velocity dispersion profile and for the ellipticity profile is ascribed to the condition of only partial relaxation of this cluster and the interplay between rotation and radial anisotropy.

  7. Clustering in bubbly liquids

    NASA Astrophysics Data System (ADS)

    Figueroa, Bernardo; Zenit, Roberto

    2004-11-01

    We are conducting experiments to determine the amount of clustering that occurs when small gas bubbles ascend in clean water. In particular, we are interested in flows for which the liquid motion around the bubbles can be described, with a certain degree of accuracy, using potential flow theory. This model is applicable for the case of bubbly liquids in which the Reynolds number is large and the Weber number is small. To clearly observe the formation of bubble clusters we propose the use of a Hele-Shaw-type channel. In this thin channel the bubbles cannot overlap in the depth direction, therefore the identification of bubble clusters cannot be misinterpreted. Direct video image analysis is performed to calculate the velocity and size of the bubbles, as well as the formation of clusters. Although the walls do affect the motion of the bubbles, the clustering phenomena does occur and has the same qualitative behavior as in fully three-dimensional flows. A series of preliminary measurements are presented. A brief discussion of our plans to perform PIV measurements to obtain the liquid velocity fields is also presented.

  8. Supervised clustering of genes

    PubMed Central

    Dettling, Marcel; Bühlmann, Peter

    2002-01-01

    Background We focus on microarray data where experiments monitor gene expression in different tissues and where each experiment is equipped with an additional response variable such as a cancer type. Although the number of measured genes is in the thousands, it is assumed that only a few marker components of gene subsets determine the type of a tissue. Here we present a new method for finding such groups of genes by directly incorporating the response variables into the grouping process, yielding a supervised clustering algorithm for genes. Results An empirical study on eight publicly available microarray datasets shows that our algorithm identifies gene clusters with excellent predictive potential, often superior to classification with state-of-the-art methods based on single genes. Permutation tests and bootstrapping provide evidence that the output is reasonably stable and more than a noise artifact. Conclusions In contrast to other methods such as hierarchical clustering, our algorithm identifies several gene clusters whose expression levels clearly distinguish the different tissue types. The identification of such gene clusters is potentially useful for medical diagnostics and may at the same time reveal insights into functional genomics. PMID:12537558

  9. Multiferroic rhodium clusters.

    PubMed

    Ma, Lei; Moro, Ramiro; Bowlan, John; de Heer, Walt A; Kirilyuk, Andrei

    2014-10-10

    Simultaneous magnetic and electric deflection measurements of rhodium clusters (Rh(N), 6 ≤ N ≤ 40) reveal ferromagnetism and ferroelectricity at low temperatures, while neither property exists in the bulk metal. Temperature-independent magnetic moments (up to 1 μ(B) per atom) are observed, and superparamagnetic blocking temperatures up to 20 K. Ferroelectric dipole moments on the order of 1D with transition temperatures up to 30 K are observed. Ferromagnetism and ferroelectricity coexist in rhodium clusters in the measured size range, with size-dependent variations in the transition temperatures that tend to be anticorrelated in the range n = 6-25. Both effects diminish with size and essentially vanish at N = 40. The ferroelectric properties suggest a Jahn-Teller ground state. These experiments represent the first example of multiferroic behavior in pure metal clusters. PMID:25375737

  10. Design of polyoxometallate-titania composite film (H3PW12O40/TiO2) for the degradation of an aqueous dye Rhodamine B under the simulated sunlight irradiation.

    PubMed

    Lu, Nan; Zhao, Yahui; Liu, Hongbo; Guo, Yihang; Yuan, Xing; Xu, Hui; Peng, Huifang; Qin, Hongwei

    2012-01-15

    A series of polyoxometallate/titania (H(3)PW(12)O(40)/TiO(2)) composite films with different H(3)PW(12)O(40) loadings (6.3%, 7.7%, 14.7% and 16.7%) were prepared by a modified sol-gel-hydrothermal route followed by a spin-coating method. The smooth films are constructed by the well-distributed H(3)PW(12)O(40)/TiO(2) sphere with particle size in the range from 80 to 100 nm, and the bandgap of the composite films is somewhat narrower compared with as-prepared pure TiO(2) film. As a novel photocatalytic material, the photocatalytic performances of the H(3)PW(12)O(40)/TiO(2) composite films were evaluated by the degradation and mineralization of an aqueous dye Rhodamine B (RB) under solar simulating Xe lamp irradiation (320 nm<λ<780 nm), and the enhanced photocatalytic activity in comparison to pure TiO(2) film as well as the H(3)PW(12)O(40)/TiO(2) and Degussa P25 TiO(2) powder was obtained. Additionally, the composite films can be reused at least for three times without losing their catalytic activity.

  11. Synthesis and characterization of novel Wells-Dawson-type mono vanadium(V)-substituted tungsto-polyoxometalate isomers: 1- and 4-[S2VW17O62](5-).

    PubMed

    Ueda, Tadaharu; Ohnishi, Miho; Shiro, Motoo; Nambu, Jun-ichi; Yonemura, Toshiaki; Boas, John F; Bond, Alan M

    2014-05-19

    Two vanadium(V)-substituted tungsto-polyoxometalate isomers, 1- and 4-[S2VW17O62](5-), were prepared as their tetra-alkyl ammonium salts from a W(VI)-H2SO4-V(V) reaction mixture in aqueous CH3CN solution. X-ray crystallographic structural analysis revealed that both isomers have a Wells-Dawson-type structure with a higher occupancy of vanadium at polar sites and belt sites for 1- and 4-[S2VW17O62](5-), respectively. The isomers were also characterized by elemental analysis, infrared, Raman, UV-vis, and (51)V NMR spectroscopies as well as voltammetry, and the data obtained were compared with that derived from [S2W18O62](4-). Significantly, the reversible potentials for the vanadium(V/IV) couple for both 1- and 4-[S2VW17O62](5-) in CH3CN (0.1 M n-Bu4NPF6) are considerably more positive than the tungstate reduction process exhibited by the [S2W18O62](4-) framework, implying that the presence of vanadium should be useful in catalytic reactions. The one-electron-reduced [S2V(IV)W17O62](6-) forms of both isomers were prepared in solution by controlled potential bulk electrolysis and characterized by voltammetry and EPR spectroscopy.

  12. Health Occupations Cluster.

    ERIC Educational Resources Information Center

    Walraven, Catherine; And Others

    These instructional materials consist of a series of curriculum worksheets that cover tasks to be mastered by students in health occupations cluster programs. Covered in the curriculum worksheets are diagnostic procedures; observing/recording/reporting/planning; safety; nutrition/elimination; hygiene/personal care/comfort;…

  13. Nuclear Cluster Physics

    SciTech Connect

    Kamimura, Masayasu

    2011-05-06

    Predictive power of theory needs good models and accurate calculation methods to solve the Schroedinger equations of the systems concerned. We present some examples of successful predictions based on the nuclear cluster models of light nuclei and hypernuclei and on the calculation methods that have been developed by Kyushu group.

  14. Clustering in Bubble Suspensions

    NASA Astrophysics Data System (ADS)

    Zenit, Roberto

    2000-11-01

    A monidisperse bubble suspension is studied experimentally for the limit in which the Weber number is small and the Reynolds number is large. For this regime the suspension can be modeled using potential flow theory to describe the dynamics of the interstitial fluid. Complete theoretical descriptions have been composed (Spelt and Sangani, 1998) to model the behavior of these suspensions. Bubble clustering is a natural instability that arises from the potential flow considerations, in which bubbles tend to align in horizontal rafts as they move upwards. The appearance of bubble clusters was recently corroborated experimentally by Zenit et al. (2000), who found that although clusters did appear, their strength was not as strong as the predictions. Experiments involving gravity driven shear flows are used to explain the nature of the clustering observed in these type of flows. Balances of the bubble phase pressure (in terms of a calculated diffusion coefficient) and the Maxwell pressure (from the potential flow description) are presented to predict the stability of the bubble suspension. The predictions are compared with experimental results.

  15. Infrared Coronet Cluster

    NASA Technical Reports Server (NTRS)

    2007-01-01

    While perhaps not quite as well known as its star formation cousin of Orion, the Corona Australis region (containing, at its heart, the Coronet cluster) is one of the nearest and most active regions of ongoing star formation. The Spitzer image shows young stars plus diffuse emission from dust.

  16. Health Occupations Cluster Guide.

    ERIC Educational Resources Information Center

    Oregon State Dept. of Education, Salem.

    Intended to assist the vocational teacher in designing and implementing a cluster program in health occupations, this guide suggests ideas for teaching the specific knowledge and skills that qualify students for entry-level employment in the health occupations field. The knowledge and skills are applicable to 12 occupations: dental assistant;…

  17. FUEL ROD CLUSTERS

    DOEpatents

    Schultz, A.B.

    1959-08-01

    A cluster of nuclear fuel rods and a tubular casing therefor through which a coolant flows in heat-exchange contact with the fuel rods is described. The fuel rcds are held in the casing by virtue of the compressive force exerted between longitudinal ribs of the fuel rcds and internal ribs of the casing or the internal surfaces thereof.

  18. Buckets, Clusters and Dienst

    NASA Technical Reports Server (NTRS)

    Nelson, Michael L.; Maly, Kurt; Shen, Stewart N. T.

    1997-01-01

    In this paper we describe NCSTRL+, a unified, canonical digital library for scientific and technical information (STI). NCSTRL+ is based on the Networked Computer Science Technical Report Library (NCSTRL), a World Wide Web (WWW) accessible digital library (DL) that provides access to over 80 university departments and laboratories. NCSTRL+ implements two new technologies: cluster functionality and publishing "buckets." We have extended the Dienst protocol, the protocol underlying NCSTRL, to provide the ability to "cluster" independent collections into a logically centralized digital library based upon subject category classification, type of organization, and genres of material. The concept of "buckets" provides a mechanism for publishing and managing logically linked entities with multiple data formats. The NCSTRL+ prototype DL contains the holdings of NCSTRL and the NASA Technical Report Server (NTRS). The prototype demonstrates the feasibility of publishing into a multi-cluster DL, searching across clusters, and storing and presenting buckets of information. We show that the overhead for these additional capabilities is minimal to both the author and the user when compared to the equivalent process within NCSTRL.

  19. Detecting alternative graph clusterings.

    PubMed

    Mandala, Supreet; Kumara, Soundar; Yao, Tao

    2012-07-01

    The problem of graph clustering or community detection has enjoyed a lot of attention in complex networks literature. A quality function, modularity, quantifies the strength of clustering and on maximization yields sensible partitions. However, in most real world networks, there are an exponentially large number of near-optimal partitions with some being very different from each other. Therefore, picking an optimal clustering among the alternatives does not provide complete information about network topology. To tackle this problem, we propose a graph perturbation scheme which can be used to identify an ensemble of near-optimal and diverse clusterings. We establish analytical properties of modularity function under the perturbation which ensures diversity. Our approach is algorithm independent and therefore can leverage any of the existing modularity maximizing algorithms. We numerically show that our methodology can systematically identify very different partitions on several existing data sets. The knowledge of diverse partitions sheds more light into the topological organization and helps gain a more complete understanding of the underlying complex network.

  20. Construction Cluster Skills Standards.

    ERIC Educational Resources Information Center

    DePaul Univ., Chicago, IL. Built Environment Partnership.

    Twelve construction cluster skill standards and associated benchmarks were developed as part of a federally funded school-to-work initiative that included the following parties: the Chicago Public Schools; City Colleges of Chicago; and business, labor, and community organizations. The standards, which include core academic, generic workplace…

  1. PVM Support for Clusters

    NASA Technical Reports Server (NTRS)

    Springer, P.

    2000-01-01

    The latest version of PVM (3.4.3) now contains support for a PC cluster running Linux, also known as a Beowulf system. A PVM user of a computer outside the Beowulf system can add the Beowulf as a single machine.

  2. Curriculum Guide Construction Cluster.

    ERIC Educational Resources Information Center

    Kline, Ken

    As part of a model construction cluster curriculum development project, this guide was developed and implemented in the Beaverton (Oregon) School District. The curriculum guide contains 16 units covering the following topics: introduction to construction jobs; safety and first aid; blueprint readings; basic mathematics; site work; framing; roofing…

  3. PDMS embedded Ag clusters: Coalescence and cluster-matrix interaction

    NASA Astrophysics Data System (ADS)

    Roese, S.; Engemann, D.; Hoffmann, S.; Latussek, K.; Sternemann, C.; Hövel, H.

    2016-05-01

    Polydimethylsiloxane (PDMS) has proven to be a suitable embedding medium for silver clusters to prevent aggregation. In order to investigate the influence of the PDMS on the electronic and local atomic structure of the clusters the measurement of x-ray absorption near edge structure (XANES) spectra for different coverages of silver clusters in PDMS and calculations of corresponding XANES spectra have been performed. The coalescence process and the cluster-PDMS interaction were investigated with XANES.

  4. Femtosecond dynamics of cluster expansion

    NASA Astrophysics Data System (ADS)

    Gao, Xiaohui; Wang, Xiaoming; Shim, Bonggu; Arefiev, Alexey; Tushentsov, Mikhail; Breizman, Boris; Downer, Mike

    2010-03-01

    Noble gas clusters irradiated by intense ultrafast laser expand quickly and become typical plasma in picosecond time scale. During the expansion, the clustered plasma demonstrates unique optical properties such as strong absorption and positive contribution to the refractive index. Here we studied cluster expansion dynamics by fs-time-resolved refractive index and absorption measurements in cluster gas jets after ionization and heating by an intense pump pulse. The refractive index measured by frequency domain interferometry (FDI) shows the transient positive peak of refractive index due to clustered plasma. By separating it from the negative contribution of the monomer plasma, we are able to determine the cluster fraction. The absorption measured by a delayed probe shows the contribution from clusters of various sizes. The plasma resonances in the cluster explain the enhancement of the absorption in our isothermal expanding cluster model. The cluster size distribution can be determined. A complete understanding of the femtosecond dynamics of cluster expansion is essential in the accurate interpretation and control of laser-cluster experiments such as phase-matched harmonic generation in cluster medium.

  5. The Rotation of Galaxy Clusters

    NASA Astrophysics Data System (ADS)

    Tovmassian, H. M.

    2015-09-01

    The method for detection of the galaxy cluster rotation based on the study of distribution of member galaxies with velocities lower and higher than the cluster mean velocity over the cluster image is proposed. The search for rotation is made for flat clusters with a/b > 1.8 and BMI type clusters which are expected to be rotating. For comparison there were studied also round clusters and clusters of NBMI type, the second by brightness galaxy, which does not differ significantly from the cluster cD galaxy. Seventeen out of studied 65 clusters are found to be rotating. It was found that the detection rate is sufficiently high for flat clusters, over 60%, and clusters of BMI type with dominant cD galaxy, ≈ 35% . The obtained results show that clusters were formed from the huge primordial gas clouds and preserved the rotation of the primordial clouds, unless they did not experience mergings with other clusters and groups of galaxies, as a result of which the rotation was prevented.

  6. Choosing the Number of Clusters in K-Means Clustering

    ERIC Educational Resources Information Center

    Steinley, Douglas; Brusco, Michael J.

    2011-01-01

    Steinley (2007) provided a lower bound for the sum-of-squares error criterion function used in K-means clustering. In this article, on the basis of the lower bound, the authors propose a method to distinguish between 1 cluster (i.e., a single distribution) versus more than 1 cluster. Additionally, conditional on indicating there are multiple…

  7. Nuclear Cluster Aspects in Astrophysics

    SciTech Connect

    Kubono, Shigeru

    2010-03-01

    The role of nuclear clustering is discussed for nucleosynthesis in stellar evolution with Cluster Nucleosynthesis Diagram (CND) proposed before. Special emphasis is placed on alpha-induced stellar reactions together with molecular states for O and C burning.

  8. Animation of the Phoenix Cluster

    NASA Video Gallery

    This animation shows how large numbers of stars form in the Phoenix Cluster. It begins by showing several galaxies in the cluster and hot gas (in red). This hot gas contains more normal matter than...

  9. Observations of Distant Clusters

    NASA Technical Reports Server (NTRS)

    Donahue, Megan

    2004-01-01

    The is the proceedings and papers supported by the LTSA grant: Homer, D. J.\\& Donahue, M. 2003, in "The Emergence of Cosmic Structure": 13'h Astrophysics Conference Proceedings, Vol. 666,3 1 1-3 14, (AIP). Baumgartner, W. H., Loewenstein, M., Horner, D. J., Mushotzky, R. F. 2003, HEAD- AAS, 35.3503. Homer, D. J. , Donahue, M., Voit G. M. 2003, HEAD-AAS, 35.1309. Nowak, M. A., Smith, B., Donahue, M., Stocke, J. 2003, HEAD-AAS, 35.1316. Scott, D., Borys, C., Chapman, S. C., Donahue, M., Fahlman, G. G., Halpem, M. Newbury, P. 2002, AAS, 128.01. Jones, L. R. et al. 2002, A new era in cosmology, ASP Conference Proceedings, Vol. 283, p. 223 Donahue, M., Daly, R. A., Homer, D. J. 2003, ApJ, 584, 643, Constraints on the Cluster Environments and Hotspot magnetic field strengths for radio sources 3280 and 3254. Donahue, M., et al. 2003, ApJ, 598, 190. The mass, baryonic fraction, and x-ray temperature of the luminous, high-redshift cluster of galaxies MS045 1.6-0305 Perlman, E. S. et al. 2002, ApJS, 140, 256. Smith, B. J., Nowak, M., Donahue, M., Stocke, J. 2003, AJ, 126, 1763. Chandra Observations of the Interacting NGC44 10 Group of Galaxies. Postman, M., Lauer, T. R., Oegerle, W., Donahue, M. 2002, ApJ, 579, 93. The KPNO/deep-range cluster survey I. The catalog and space density of intermediate-redshift clusters. Molnar, S. M., Hughes, J. P., Donahue, M., Joy, M. 2002, ApJ, 573, L91, Chandra Observations of Unresolved X-Ray Sources around Two Clusters of Galaxies. Donahue, M., Mack, J., 2002 NewAR, 46, 155, HST NIcmos and WFPC2 observations of molecular hydrogen and dust around cooling flows. Koekemoer, A. M. et al. 2002 NewAR, 46, 149, Interactions between the A2597 central radio source and dense gas host galaxy. Donahue, M. et al. 2002 ApJ, 569,689, Distant cluster hunting II.

  10. Massive star clusters in galaxies.

    PubMed

    Harris, William E

    2010-02-28

    The ensemble of all star clusters in a galaxy constitutes its star cluster system. In this review, the focus of the discussion is on the ability of star clusters, particularly the systems of old massive globular clusters (GCs), to mark the early evolutionary history of galaxies. I review current themes and key findings in GC research, and highlight some of the outstanding questions that are emerging from recent work.

  11. The Assembly of Galaxy Clusters

    SciTech Connect

    Berrier, Joel C.; Stewart, Kyle R.; Bullock, James S.; Purcell, Chris W.; Barton, Elizabeth J.; Wechsler, Risa H.

    2008-05-16

    We study the formation of fifty-three galaxy cluster-size dark matter halos (M = 10{sup 14.0-14.76} M{sub {circle_dot}}) formed within a pair of cosmological {Lambda}CDM N-body simulations, and track the accretion histories of cluster subhalos with masses large enough to host {approx} 0.1L{sub *} galaxies. By associating subhalos with cluster galaxies, we find the majority of galaxies in clusters experience no 'pre-processing' in the group environment prior to their accretion into the cluster. On average, {approx} 70% of cluster galaxies fall into the cluster potential directly from the field, with no luminous companions in their host halos at the time of accretion; and less than {approx} 12% are accreted as members of groups with five or more galaxies. Moreover, we find that cluster galaxies are significantly less likely to have experienced a merger in the recent past ({approx}< 6 Gyr) than a field halo of the same mass. These results suggest that local, cluster processes like ram-pressure stripping, galaxy harassment, or strangulation play the dominant role in explaining the difference between cluster and field populations at a fixed stellar mass; and that pre-evolution or past merging in the group environment is of secondary importance for setting cluster galaxy properties for most clusters. The accretion times for z = 0 cluster members are quite extended, with {approx} 20% incorporated into the cluster halo more than 7 Gyr ago and {approx} 20% within the last 2 Gyr. By comparing the observed morphological fractions in cluster and field populations, we estimate an approximate time-scale for late-type to early-type transformation within the cluster environment to be {approx} 6 Gyr.

  12. [Cluster analysis in biomedical researches].

    PubMed

    Akopov, A S; Moskovtsev, A A; Dolenko, S A; Savina, G D

    2013-01-01

    Cluster analysis is one of the most popular methods for the analysis of multi-parameter data. The cluster analysis reveals the internal structure of the data, group the separate observations on the degree of their similarity. The review provides a definition of the basic concepts of cluster analysis, and discusses the most popular clustering algorithms: k-means, hierarchical algorithms, Kohonen networks algorithms. Examples are the use of these algorithms in biomedical research. PMID:24640781

  13. The Orion nebula star cluster

    NASA Technical Reports Server (NTRS)

    Panek, R. J.

    1982-01-01

    Photography through filters which suppress nebular light reveal a clustering of faint red stars centered on the Trapezium, this evidences a distinct cluster within the larger OB1 association. Stars within about 20 ft of trapezium comprise the Orion Nebula star cluster are considered. Topics discussed re: (1) extinction by dust grains; (2) photometric peculiarities; (3) spectroscopic peculiarities; (4) young variables; (5) the distribution and motion of gas within the cluster.

  14. Derivatized gold clusters and antibody-gold cluster conjugates

    DOEpatents

    Hainfeld, J.F.; Furuya, F.R.

    1994-11-01

    Antibody- or antibody fragment-gold cluster conjugates are shown wherein the conjugate size can be as small as 5.0 nm. Methods and reagents are disclosed in which antibodies, Fab' or F(ab')[sub 2] fragments are covalently bound to a stable cluster of gold atoms. The gold clusters may contain 6, 8, 9, 11, 13, 55 or 67 gold atoms in their inner core. The clusters may also contain radioactive gold. The antibody-cluster conjugates are useful in electron microscopy applications as well as in clinical applications that include imaging, diagnosis and therapy. 7 figs.

  15. Derivatized gold clusters and antibody-gold cluster conjugates

    DOEpatents

    Hainfeld, James F.; Furuya, Frederic R.

    1994-11-01

    Antibody- or antibody fragment-gold cluster conjugates are shown wherein the conjugate size can be as small as 5.0 nm. Methods and reagents are disclosed in which antibodies, Fab' or F(ab').sub.2 fragments thereof are covalently bound to a stable cluster of gold atoms. The gold clusters may contain 6, 8, 9, 11, 13, 55 or 67 gold atoms in their inner core. The clusters may also contain radioactive gold. The antibody-cluster conjugates are useful in electron microscopy applications as well as in clinical applications that include imaging, diagnosis and therapy.

  16. Adaptive Clustering of Hypermedia Documents.

    ERIC Educational Resources Information Center

    Johnson, Andrew; Fotouhi, Farshad

    1996-01-01

    Discussion of hypermedia systems focuses on a comparison of two types of adaptive algorithm (genetic algorithm and neural network) in clustering hypermedia documents. These clusters allow the user to index into the nodes to find needed information more quickly, since clustering is "personalized" based on the user's paths rather than representing…

  17. Connecting Remote Clusters with ATM

    SciTech Connect

    Hu, T.C.; Wyckoff, P.S.

    1998-10-01

    Sandia's entry into utilizing clusters of networked workstations is called Computational Plant or CPlant for short. The design of CPlant uses Ethernet to boot the individual nodes, Myrinet to communicate within a node cluster, and ATM to connect between remote clusters. This SAND document covers the work done to enable the use of ATM on the CPlant nodes in the Fall of 1997.

  18. Toward Parallel Document Clustering

    SciTech Connect

    Mogill, Jace A.; Haglin, David J.

    2011-09-01

    A key challenge to automated clustering of documents in large text corpora is the high cost of comparing documents in a multimillion dimensional document space. The Anchors Hierarchy is a fast data structure and algorithm for localizing data based on a triangle inequality obeying distance metric, the algorithm strives to minimize the number of distance calculations needed to cluster the documents into “anchors” around reference documents called “pivots”. We extend the original algorithm to increase the amount of available parallelism and consider two implementations: a complex data structure which affords efficient searching, and a simple data structure which requires repeated sorting. The sorting implementation is integrated with a text corpora “Bag of Words” program and initial performance results of end-to-end a document processing workflow are reported.

  19. Binaries in globular clusters

    NASA Technical Reports Server (NTRS)

    Hut, Piet; Mcmillan, Steve; Goodman, Jeremy; Mateo, Mario; Phinney, E. S.; Pryor, Carlton; Richer, Harvey B.; Verbunt, Frank; Weinberg, Martin

    1992-01-01

    Recent observations have shown that globular clusters contain a substantial number of binaries most of which are believed to be primordial. We discuss different successful optical search techniques, based on radial-velocity variables, photometric variables, and the positions of stars in the color-magnitude diagram. In addition, we review searches in other wavelengths, which have turned up low-mass X-ray binaries and more recently a variety of radio pulsars. On the theoretical side, we give an overview of the different physical mechanisms through which individual binaries evolve. We discuss the various simulation techniques which recently have been employed to study the effects of a primordial binary population, and the fascinating interplay between stellar evolution and stellar dynamics which drives globular-cluster evolution.

  20. Clusterization in Ternary Fission

    NASA Astrophysics Data System (ADS)

    Kamanin, D. V.; Pyatkov, Y. V.

    This lecture notes are devoted to the new kind of ternary decay of low excited heavy nuclei called by us "collinear cluster tri-partition" (CCT) due to the features of the effect observed, namely, decay partners fly away almost collinearly and at least one of them has magic nucleon composition. At the early stage of our work the process of "true ternary fission" (fission of the nucleus into three fragments of comparable masses) was considered to be undiscovered for low excited heavy nuclei. Another possible prototype—three body cluster radioactivity—was also unknown. The most close to the CCT phenomenon, at least cinematically, stands so called "polar emission", but only very light ions (up to isotopes of Be) were observed so far.

  1. Gravitational clustering: an overview

    NASA Astrophysics Data System (ADS)

    Labini, Francesco Sylos

    2008-01-01

    We discuss the differences and analogies of gravitational clustering in finite and infinite systems. The process of collective, or violent, relaxation leading to the formation of quasi-stationary states is one of the distinguished features in the dynamics of self-gravitating systems. This occurs, in different conditions, both in a finite than in an infinite system, the latter embedded in a static or in an expanding background. We then discuss, by considering some simple and paradigmatic examples, the problems related to the definition of a mean-field approach to gravitational clustering, focusing on role of discrete fluctuations. The effect of these fluctuations is a basic issue to be clarified to establish the range of scales and times in which a collision-less approximation may describe the evolution of a self-gravitating system and for the theoretical modeling of the non-linear phase.

  2. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  3. Tailoring and Scaling Energetic Aluminum Clusters into Cluster Assembled Materials

    NASA Astrophysics Data System (ADS)

    Smith, Jordan Cesar

    As matter decreases in size the importance of a single atom increases exponentially. The properties of clusters, molecules with less than 100 atoms, will change drastically with the addition or removal of a single atom. Clusters have been shown to have properties that mimic other elements and properties that are completely unique. Cluster assemblies could enable the tailoring of precise properties in materials, providing cheap replacements for expensive elements, or novel materials for new applications. Aluminum clusters show great potential use in many applications including energy and catalysis. This work is focused on gaining a better understanding of how geometry and electronic structure affect aluminum cluster reactivity and how useful clusters might be successfully assembled into materials. The effects of doping aluminum cluster ions with boron atoms are reported and show that the addition of a single boron atom usually stabilizes the cluster while adding more boron atoms results in a breaking of symmetry and destabilization. A new analytical technique, matrix isolation cavity ring-down spectroscopy (MICRDS) was developed to help bridge the gap between gas phase cluster studies and condensed phase cluster materials. Molecules are trapped in an inert matrix and studied using cavity ring-down spectroscopy. MICRDS has the potential to also combine clusters into small stable units that would maintain their advantageous gas phase properties.

  4. Properties of the Brightest Cluster Galaxy and Its Host Cluster

    NASA Astrophysics Data System (ADS)

    Katayama, Haruyoshi; Hayashida, Kiyoshi; Takahara, Fumio; Fujita, Yutaka

    2003-03-01

    We investigate the relation between the properties of brightest cluster galaxies (BCGs) and those of their host clusters. To quantify the properties of cluster hot gas, we employ the parameter Z of the fundamental plane of X-ray clusters. It is found that the offset of the BCG from the peak of cluster X-ray emission is larger for smaller Z clusters. The parameter Z (not the redshift z), which depends mainly on virial density ρvir, is considered to represent the formation epoch of a cluster. We thus consider that the offset of the BCG is correlated with the dynamical equilibrium state of its host cluster. On the contrary, no significant correlation is found between the absolute optical magnitude of the BCG and the parameter Z. If the extreme brightness of the BCG is acquired mainly in the course of cluster evolution by environmental effect, BCGs are expected to be brighter in large Z clusters. Our result is not consistent with this simplified view. On the contrary, it is possible that the extreme brightness of the BCG is likely to be determined in the early history of cluster collapse.

  5. Basic cluster compression algorithm

    NASA Technical Reports Server (NTRS)

    Hilbert, E. E.; Lee, J.

    1980-01-01

    Feature extraction and data compression of LANDSAT data is accomplished by BCCA program which reduces costs associated with transmitting, storing, distributing, and interpreting multispectral image data. Algorithm uses spatially local clustering to extract features from image data to describe spectral characteristics of data set. Approach requires only simple repetitive computations, and parallel processing can be used for very high data rates. Program is written in FORTRAN IV for batch execution and has been implemented on SEL 32/55.

  6. Cosmology, Clusters and Calorimeters

    NASA Technical Reports Server (NTRS)

    Figueroa-Feliciano, Enectali

    2005-01-01

    I will review the current state of Cosmology with Clusters and discuss the application of microcalorimeter arrays to this field. With the launch of Astro-E2 this summer and a slew of new missions being developed, microcalorimeters are the next big thing in x-ray astronomy. I will cover the basics and not-so-basic concepts of microcalorimeter designs and look at the future to see where this technology will go.

  7. Astrophysics of galaxy clusters

    NASA Astrophysics Data System (ADS)

    Ettori, Stefano

    2016-07-01

    As the nodes of the cosmic web, clusters of galaxies trace the large-scale distribution of matter in the Universe. They are thus privileged sites in which to investigate the complex physics of structure formation. However, the complete story of how these structures grow, and how they dissipate the gravitational and non-thermal components of their energy budget over cosmic time, is still beyond our grasp. Most of the baryons gravitationally bound to the cluster's halo is in the form of a diffuse, hot, metal-enriched plasma that radiates primarily in the X-ray band. X-ray observations of the evolving cluster population provide a unique opportunity to address such fundamental open questions as: How do hot diffuse baryons accrete and dynamically evolve in dark matter potentials? How and when was the energy that we observe in the ICM generated and distributed? Where and when are heavy elements produced and how are they circulated? We will present the ongoing activities to define the strategy on how an X-ray observatory with large collecting area and an unprecedented combination of high spectral and angular resolution, such as Athena, can address these questions.

  8. Cluster headache after orbital exenteration.

    PubMed

    Evers, S; Sörös, P; Brilla, R; Gerding, H; Husstedt, I W

    1997-10-01

    A 37-year-old man developed an ipsilateral headache which fulfilled the criteria for cluster headache after orbital extenteration because of a traumatic lesion of the bulb. The headache could be treated successfully by drugs usually applied in the therapy of cluster headache. Six similar cases of cluster headache after orbital exenteration could be identified in the literature suggesting that the eye itself is not necessarily part of the pathogenesis of cluster headache. We hypothesize that orbital exenteration can cause cluster headache by lesions of sympathetic structures. Possibly, these mechanisms are similar to those of sympathetic reflex dystrophy (Sudeck-Leriche syndrome) causing pain of the limbs. PMID:9350391

  9. Cluster AAR Campaign Summary Plots

    NASA Astrophysics Data System (ADS)

    Fazakerley, A. N.; Walsh, A. P.; Garza, K. J.; Christopher, I.; Sadeghi, S.; Lindqvist, P.; Mihaljcic, B.; Forsyth, C.; Pickett, J. S.; Marklund, G. T.; Lucek, E. A.; Dandouras, I. S.

    2010-12-01

    Since late 2008 the Cluster spacecraft have been making the first four-point measurements of the Auroral Acceleration Region, opening up an exciting new opportunity for the auroral science, Cluster and wider magnetospheric physics communities. In order to stimulate auroral research with Cluster and aid in event selection, we have produced a set of summary plots for those Cluster perigee passes best suited for addressing open questions in auroral physics. The plots incorporate data from WBD, FGM, EFW, PEACE and CIS and are available from the Cluster PEACE website.

  10. Stormy weather in galaxy clusters

    PubMed

    Burns

    1998-04-17

    Recent x-ray, optical, and radio observations coupled with particle and gas dynamics numerical simulations reveal an unexpectedly complex environment within clusters of galaxies, driven by ongoing accretion of matter from large-scale supercluster filaments. Mergers between clusters and continuous infall of dark matter and baryons from the cluster periphery produce long-lived "stormy weather" within the gaseous cluster atmosphere-shocks, turbulence, and winds of more than 1000 kilometers per second. This weather may be responsible for shaping a rich variety of extended radio sources, which in turn act as "barometers" and "anemometers" of cluster weather.

  11. Cluster energetics: Models and data

    NASA Astrophysics Data System (ADS)

    Ford, Ian; Vehkamäki, Hanna; Knott, Michael

    2000-08-01

    A wealth of information about the energies of clusters of several tens of molecules has been obtained recently through the analysis of nucleation rate data using the nucleation theorems. We describe here studies of n-pentanol and dibutylphthalate clusters, and using multicomponent nucleation theorems, we present data for binary clusters of water and ethanol, and n- and i-octane. We then attempt a synthesis of alkane cluster information obtained to date, and find that the cluster excess energies show a rough proportionality to the molecular size raised to the 2/3 power.

  12. Stormy weather in galaxy clusters

    PubMed

    Burns

    1998-04-17

    Recent x-ray, optical, and radio observations coupled with particle and gas dynamics numerical simulations reveal an unexpectedly complex environment within clusters of galaxies, driven by ongoing accretion of matter from large-scale supercluster filaments. Mergers between clusters and continuous infall of dark matter and baryons from the cluster periphery produce long-lived "stormy weather" within the gaseous cluster atmosphere-shocks, turbulence, and winds of more than 1000 kilometers per second. This weather may be responsible for shaping a rich variety of extended radio sources, which in turn act as "barometers" and "anemometers" of cluster weather. PMID:9545210

  13. Stellar Snowflake Cluster

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site] Figure 1 Stellar Snowflake Cluster Combined Image [figure removed for brevity, see original site] Figure 2 Infrared Array CameraFigure 3 Multiband Imaging Photometer

    Newborn stars, hidden behind thick dust, are revealed in this image of a section of the Christmas Tree cluster from NASA's Spitzer Space Telescope, created in joint effort between Spitzer's infrared array camera and multiband imaging photometer instruments.

    The newly revealed infant stars appear as pink and red specks toward the center of the combined image (fig. 1). The stars appear to have formed in regularly spaced intervals along linear structures in a configuration that resembles the spokes of a wheel or the pattern of a snowflake. Hence, astronomers have nicknamed this the 'Snowflake' cluster.

    Star-forming clouds like this one are dynamic and evolving structures. Since the stars trace the straight line pattern of spokes of a wheel, scientists believe that these are newborn stars, or 'protostars.' At a mere 100,000 years old, these infant structures have yet to 'crawl' away from their location of birth. Over time, the natural drifting motions of each star will break this order, and the snowflake design will be no more.

    While most of the visible-light stars that give the Christmas Tree cluster its name and triangular shape do not shine brightly in Spitzer's infrared eyes, all of the stars forming from this dusty cloud are considered part of the cluster.

    Like a dusty cosmic finger pointing up to the newborn clusters, Spitzer also illuminates the optically dark and dense Cone nebula, the tip of which can be seen towards the bottom left corner of each image.

    This combined image shows the presence of organic molecules mixed with dust as wisps of green, which have been illuminated by nearby star formation. The larger yellowish dots neighboring the baby red stars in the Snowflake Cluster are massive stellar infants forming

  14. Color segmentation using MDL clustering

    NASA Astrophysics Data System (ADS)

    Wallace, Richard S.; Suenaga, Yasuhito

    1991-02-01

    This paper describes a procedure for segmentation of color face images. A cluster analysis algorithm uses a subsample of the input image color pixels to detect clusters in color space. The clustering program consists of two parts. The first part searches for a hierarchical clustering using the NIHC algorithm. The second part searches the resultant cluster tree for a level clustering having minimum description length (MDL). One of the primary advantages of the MDL paradigm is that it enables writing robust vision algorithms that do not depend on user-specified threshold parameters or other " magic numbers. " This technical note describes an application of minimal length encoding in the analysis of digitized human face images at the NTT Human Interface Laboratories. We use MDL clustering to segment color images of human faces. For color segmentation we search for clusters in color space. Using only a subsample of points from the original face image our clustering program detects color clusters corresponding to the hair skin and background regions in the image. Then a maximum likelyhood classifier assigns the remaining pixels to each class. The clustering program tends to group small facial features such as the nostrils mouth and eyes together but they can be separated from the larger classes through connected components analysis.

  15. Scale free processes in stellar cluster formation

    NASA Astrophysics Data System (ADS)

    Bastian, Nate

    2015-08-01

    I will review what is known about stellar cluster formation, focussing on scale free processes, such as how lower mass open clusters related to their giant cousins, the young massive clusters, and potentially globular cluster as well.

  16. Convex Clustering: An Attractive Alternative to Hierarchical Clustering

    PubMed Central

    Chen, Gary K.; Chi, Eric C.; Ranola, John Michael O.; Lange, Kenneth

    2015-01-01

    The primary goal in cluster analysis is to discover natural groupings of objects. The field of cluster analysis is crowded with diverse methods that make special assumptions about data and address different scientific aims. Despite its shortcomings in accuracy, hierarchical clustering is the dominant clustering method in bioinformatics. Biologists find the trees constructed by hierarchical clustering visually appealing and in tune with their evolutionary perspective. Hierarchical clustering operates on multiple scales simultaneously. This is essential, for instance, in transcriptome data, where one may be interested in making qualitative inferences about how lower-order relationships like gene modules lead to higher-order relationships like pathways or biological processes. The recently developed method of convex clustering preserves the visual appeal of hierarchical clustering while ameliorating its propensity to make false inferences in the presence of outliers and noise. The solution paths generated by convex clustering reveal relationships between clusters that are hidden by static methods such as k-means clustering. The current paper derives and tests a novel proximal distance algorithm for minimizing the objective function of convex clustering. The algorithm separates parameters, accommodates missing data, and supports prior information on relationships. Our program CONVEXCLUSTER incorporating the algorithm is implemented on ATI and nVidia graphics processing units (GPUs) for maximal speed. Several biological examples illustrate the strengths of convex clustering and the ability of the proximal distance algorithm to handle high-dimensional problems. CONVEXCLUSTER can be freely downloaded from the UCLA Human Genetics web site at http://www.genetics.ucla.edu/software/ PMID:25965340

  17. Measuring Cluster Relaxedness

    SciTech Connect

    Moreland, Blythe; /Michigan U. /SLAC

    2012-08-24

    When is a dark matter halo 'relaxed'? In our efforts to understand the structure of the universe, dark matter simulations have provided essential grounds for theoretical predictions. These simulations provide a wealth of ways of parameterizing and measuring the features of astronomical objects. It is these measurements on which we base comparisons of our world and our attempts to re-create it. One of the essential questions dark matter simulations help address is how dark matter halos evolve. How does one characterize different states of that evolution? The focus of this project is identifying cluster relaxedness and how it relates to the internal structure of the halo. A dark matter simulation consists of an N-body simulation which takes an initial set of positions and velocities of the dark matter particles and evolves them under the influence of gravity [6]. Though scientists have so far not been able to detect dark matter particles, the information from these simulations is still valuable especially given the relationship between dark matter halos and galaxy clusters. Galaxies sit within dark matter halos and recent evidence points to filaments of dark matter forming the framework on which galaxy clusters grow [7]. A dark matter halo is a collapsed group of gravitationally bound dark matter particles. Subsets of bound particles form subhalos or substructures. The dark matter simulation is carried out over time - with decreasing redshift (z) or increasing scale factor (a = 1/1+z ). (Thus, z = 0 or a = 1.0 is present-day.) The merger history of a halo can be represented pictorally by a merger tree. A major merger event occurs when a structure joins the main halo with the mass ratio between it and the main halo being above a certain threshold. These events mark important points in the halo's evolution. And it is at these events that one hopes, and perhaps is more likely, to relate measures of relaxedness to this mass accretion. Cluster relaxedness is not a well

  18. Dicobalt-μ-oxo polyoxometalate compound, [(α(2)-P2W17O61Co)2O](14-): a potent species for water oxidation, C-H bond activation, and oxygen transfer.

    PubMed

    Barats-Damatov, Delina; Shimon, Linda J W; Weiner, Lev; Schreiber, Roy E; Jiménez-Lozano, Pablo; Poblet, Josep M; de Graaf, Coen; Neumann, Ronny

    2014-02-01

    High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-μ-oxo polyoxometalate compound [(α2-P2W17O61Co)2O](14-), [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [α2-P2W17O61Co(II)(H2O)](8-), [POMCo(II)H2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ∼1.77 Å. In aqueous solution [(POMCo)2O] was identified by (31)P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo)2O]2O] is an active compound for the oxidation of H2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms.

  19. Are Earthquake Magnitudes Clustered?

    SciTech Connect

    Davidsen, Joern; Green, Adam

    2011-03-11

    The question of earthquake predictability is a long-standing and important challenge. Recent results [Phys. Rev. Lett. 98, 098501 (2007); ibid.100, 038501 (2008)] have suggested that earthquake magnitudes are clustered, thus indicating that they are not independent in contrast to what is typically assumed. Here, we present evidence that the observed magnitude correlations are to a large extent, if not entirely, an artifact due to the incompleteness of earthquake catalogs and the well-known modified Omori law. The latter leads to variations in the frequency-magnitude distribution if the distribution is constrained to those earthquakes that are close in space and time to the directly following event.

  20. The galactic globular cluster system

    NASA Technical Reports Server (NTRS)

    Djorgovski, S.; Meylan, G.

    1994-01-01

    We explore correlations between various properties of Galactic globular clusters, using a database on 143 objects. Our goal is identify correlations and trends which can be used to test and constrain theoretical models of cluster formation and evolution. We use a set of 13 cluster parameters, 9 of which are independently measured. Several arguments suggest that the number of clusters still missing in the obscured regions of the Galaxy is of the order of 10, and thus the selection effects are probably not severe for our sample. Known clusters follow a power-law density distribution with a slope approximately -3.5 to -4, and an apparent core with a core radius approximately 1 kpc. Clusters show a large dynamical range in many of their properties, more so for the core parameters (which are presumably more affected by dynamical evolution) than for the half-light parameters. There are no good correlations with luminosity, although more luminous clusters tend to be more concentrated. When data are binned in luminosity, several trends emerge: more luminous clusters tend to have smaller and denser cores. We interpret this as a differential survival effect, with more massive clusters surviving longer and reaching more evolved dynamical states. Cluster core parameters and concentrations also correlate with the position in the Galaxy, with clusters closer to the Galactic center or plane being more concentrated and having smaller and denser cores. These trends are more pronounced for the fainter (less massive) clusters. This is in agreement with a picture where tidal shocks form disk or bulge passages accelerate dynamical evolution of clusters. Cluster metallicities do not correlate with any other parameter, including luminosity and velocity dispersion; the only detectable trend is with the position in the Galaxy, probably reflecting Zinn's disk-halo dichotomy. This suggests that globular clusters were not self-enriched systems. Velocity dispersions show excellent correlations

  1. Query Results Clustering by Extending SPARQL with CLUSTER BY

    NASA Astrophysics Data System (ADS)

    Ławrynowicz, Agnieszka

    The task of dynamic clustering of the search results proved to be useful in the Web context, where the user often does not know the granularity of the search results in advance. The goal of this paper is to provide a declarative way for invoking dynamic clustering of the results of queries submitted over Semantic Web data. To achieve this goal the paper proposes an approach that extends SPARQL by clustering abilities. The approach introduces a new statement, CLUSTER BY, into the SPARQL grammar and proposes semantics for such extension.

  2. Properties of The Brightest Cluster Galaxy and Its Host Cluster

    NASA Astrophysics Data System (ADS)

    Katayama, H.; Hayashida, K.; Takahara, F.

    2001-09-01

    We investigate the relation between the brightest cluster galaxy (BCG) and its host cluster. A BCG is a bright and massive elliptical galaxy in a cluster of galaxies. The luminosity of a BCG is 10 times larger than that of normal field galaxy and the mass of a BCG is about 1013Msolar which corresponds to that of galaxy group. In order to explain the origin of BCGs, the following three models are proposed: (1) star formation from cooling flow. In this model, intracluster gas gradually condenses at the center of the cluster and forms the BCG. (2) ``Galactic cannibalism'' or the accretion of smaller galaxies. In this model, dynamical friction accounts for the formation of the BCG. These two models predict the BCG evolves with the evolution of cluster. (3) Galaxy merging in the early history of the formation of the cluster. In this model, the property of BCGs is determined no later than cluster collapse. In any model, the formation of BCGs is related to the collapse and formation of its host cluster. The relation between the BCG and its host cluster was studied by Edge (1991). Edge (1991) found that the optical luminosity of the BCG is positively correlated with the X-ray luminosity and temperature of its host cluster. Edge (1991) concludes that these correlations indicate that the BCG responds to the overall cluster properties. In order to investigate the other relation between the BCG and its host cluster, we analyzed ROSAT archival data and compared the displacement between the X-ray peak and the BCG with the Z parameter of the fundamental relation found by Fujita and Takahara (1999). It is found that the displacement is larger with decreasing Z. Furthermore, the large Z clusters tend to have a regular X-ray profile, which implies a relaxed system. The fundamental parameter Z depends mainly on the virial density ρvir, and is considered to be related to the formation epoch of the cluster, i.e., large Z clusters are old clusters and small Z clusters are young

  3. Cluster synchronization in oscillatory networks

    NASA Astrophysics Data System (ADS)

    Belykh, Vladimir N.; Osipov, Grigory V.; Petrov, Valentin S.; Suykens, Johan A. K.; Vandewalle, Joos

    2008-09-01

    Synchronous behavior in networks of coupled oscillators is a commonly observed phenomenon attracting a growing interest in physics, biology, communication, and other fields of science and technology. Besides global synchronization, one can also observe splitting of the full network into several clusters of mutually synchronized oscillators. In this paper, we study the conditions for such cluster partitioning into ensembles for the case of identical chaotic systems. We focus mainly on the existence and the stability of unique unconditional clusters whose rise does not depend on the origin of the other clusters. Also, conditional clusters in arrays of globally nonsymmetrically coupled identical chaotic oscillators are investigated. The design problem of organizing clusters into a given configuration is discussed.

  4. Rough Clustering for Cancer Datasets

    NASA Astrophysics Data System (ADS)

    Herawan, Tutut

    Cancer is becoming a leading cause of death among people in the whole world. It is confirmed that the early detection and accurate diagnosis of this disease can ensure a long survival of the patients. Expert systems and machine learning techniques are gaining popularity in this field because of the effective classification and high diagnostic capability. This paper presents the application of rough set theory for clustering two cancer datasets. These datasets are taken from UCI ML repository. The method is based on MDA technique proposed by [11]. To select a clustering attribute, the maximal degree of the rough attributes dependencies in categorical-valued information systems is used. Further, we use a divide-and-conquer method to partition/cluster the objects. The results show that MDA technique can be used to cluster to the data. Further, we present clusters visualization using two dimensional plot. The plot results provide user friendly navigation to understand the cluster obtained.

  5. Decaying neutrinos in galaxy clusters

    NASA Technical Reports Server (NTRS)

    Melott, Adrian L.; Splinter, Randall J.; Persic, Massimo; Salucci, Paolo

    1994-01-01

    Davidsen et al. (1991) have argued that the failure to detect UV photons from the dark matter (DM) in cluster A665 excludes the decaying neutrino hypothesis. Sciama et al. (1993) argued that because of high central concentration the DM in that cluster must be baryonic. We study the DM profile in clusters of galaxies simulated using the Harrison-Zel'dovich spectrum of density fluctuations, and an amplitude previously derived from numerical simulations (Melott 1984b; Anninos et al. 1991) and in agreement with microwave background fluctuations (Smoot et al. 1992). We find that with this amplitude normalization cluster neutrino DM densities are comparable to observed cluster DM values. We conclude that given this normalization, the cluster DM should be at least largely composed of neutrinos. The constraint of Davidsen et al. can be somewhat weakened by the presence of baryonic DM; but it cannot be eliminated given our assumptions.

  6. Mass Determinations of Star Clusters

    NASA Astrophysics Data System (ADS)

    Meylan, Georges

    Mass determinations are difficult to obtain and still frequently characterised by deceptively large uncertainties. We review below the various mass estimators used for star clusters of all ages and luminosities. We highlight a few recent results related to (i) very massive old star clusters, (ii) the differences and similarities between star clusters and cores of dwarf elliptical galaxies, and (iii) the possible strong biases on mass determination induced by tidal effects.

  7. The SMART CLUSTER METHOD - adaptive earthquake cluster analysis and declustering

    NASA Astrophysics Data System (ADS)

    Schaefer, Andreas; Daniell, James; Wenzel, Friedemann

    2016-04-01

    Earthquake declustering is an essential part of almost any statistical analysis of spatial and temporal properties of seismic activity with usual applications comprising of probabilistic seismic hazard assessments (PSHAs) and earthquake prediction methods. The nature of earthquake clusters and subsequent declustering of earthquake catalogues plays a crucial role in determining the magnitude-dependent earthquake return period and its respective spatial variation. Various methods have been developed to address this issue from other researchers. These have differing ranges of complexity ranging from rather simple statistical window methods to complex epidemic models. This study introduces the smart cluster method (SCM), a new methodology to identify earthquake clusters, which uses an adaptive point process for spatio-temporal identification. Hereby, an adaptive search algorithm for data point clusters is adopted. It uses the earthquake density in the spatio-temporal neighbourhood of each event to adjust the search properties. The identified clusters are subsequently analysed to determine directional anisotropy, focussing on a strong correlation along the rupture plane and adjusts its search space with respect to directional properties. In the case of rapid subsequent ruptures like the 1992 Landers sequence or the 2010/2011 Darfield-Christchurch events, an adaptive classification procedure is applied to disassemble subsequent ruptures which may have been grouped into an individual cluster using near-field searches, support vector machines and temporal splitting. The steering parameters of the search behaviour are linked to local earthquake properties like magnitude of completeness, earthquake density and Gutenberg-Richter parameters. The method is capable of identifying and classifying earthquake clusters in space and time. It is tested and validated using earthquake data from California and New Zealand. As a result of the cluster identification process, each event in

  8. Brightest Cluster Galaxies and Core Gas Density in REXCESS Clusters

    NASA Astrophysics Data System (ADS)

    Haarsma, Deborah B.; Leisman, Luke; Donahue, Megan; Bruch, Seth; Böhringer, Hans; Croston, Judith H.; Pratt, Gabriel W.; Voit, G. Mark; Arnaud, Monique; Pierini, Daniele

    2010-04-01

    We investigate the relationship between brightest cluster galaxies (BCGs) and their host clusters using a sample of nearby galaxy clusters from the Representative XMM-Newton Cluster Structure Survey. The sample was imaged with the Southern Observatory for Astrophysical Research in R band to investigate the mass of the old stellar population. Using a metric radius of 12 h -1 kpc, we found that the BCG luminosity depends weakly on overall cluster mass as L BCG vprop M 0.18±0.07 cl, consistent with previous work. We found that 90% of the BCGs are located within 0.035 r 500 of the peak of the X-ray emission, including all of the cool core (CC) clusters. We also found an unexpected correlation between the BCG metric luminosity and the core gas density for non-cool-core (non-CC) clusters, following a power law of ne vprop L 2.7±0.4 BCG (where ne is measured at 0.008 r 500). The correlation is not easily explained by star formation (which is weak in non-CC clusters) or overall cluster mass (which is not correlated with core gas density). The trend persists even when the BCG is not located near the peak of the X-ray emission, so proximity is not necessary. We suggest that, for non-CC clusters, this correlation implies that the same process that sets the central entropy of the cluster gas also determines the central stellar density of the BCG, and that this underlying physical process is likely to be mergers.

  9. Synthesis of α-Dawson-type silicotungstate [α-Si2W18O62]8- and protonation and deprotonation inside the aperture through intramolecular hydrogen bonds.

    PubMed

    Minato, Takuo; Suzuki, Kosuke; Kamata, Keigo; Mizuno, Noritaka

    2014-05-12

    The design of structurally well-defined anionic molecular metal-oxygen clusters, polyoxometalates (POMs), leads to inorganic receptors with unique and tunable properties. Herein, an α-Dawson-type silicotungstate, TBA8[α-Si2W18O62]⋅3 H2O (II) that possesses a -8 charge was successfully synthesized by dimerization of a trivacant lacunary α-Keggin-type silicotungstate TBA4H6[α-SiW9O34]⋅2 H2O (I) in an organic solvent. POM II could be reversibly protonated (in the presence of acid) and deprotonated (in the presence of base) inside the aperture by means of intramolecular hydrogen bonds with retention of the POM structure. In contrast, the aperture of phosphorus-centered POM TBA6[α-P2W18O62]⋅H2O (III) was not protonated inside the aperture. The density functional theory (DFT) calculations revealed that the basicities and charges of internal μ3-oxygen atoms were increased by changing the central heteroatoms from P(5+) to Si(4+), thereby supporting the protonation of II. Additionally, II showed much higher catalytic performance for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde than I and III.

  10. Independent variables in foam clusters

    NASA Astrophysics Data System (ADS)

    Fortes, M. A.; Teixeira, P. I. C.

    2001-11-01

    We find, by counting the degrees of freedom of two-dimensional bubble clusters (finite or periodic) of given topology and bubble areas, that the Plateau laws determine a unique configuration of a finite free cluster, but allow an infinite number of configurations of a periodic cluster. Each of these configurations is associated with a particular strain (stress) state of the cluster; there is in general one unstrained configuration, which corresponds to the minimum of the (surface) energy. Configurations of given topology that satisfy Plateau's laws may only exist in certain ranges of bubble area ratios and/or strains.

  11. Digging Deep in Pandora's Cluster

    NASA Astrophysics Data System (ADS)

    Blakeslee, John P.; Alamo-Martinez, Karla; Toloba, Elisa; Barro, Guillermo; Peng, Eric W.

    2015-01-01

    Abell 2744, the first and nearest (z=0.31) of the Hubble Frontier Fields, is extraordinarily rich in the number and variety of galaxies it contains. Nicknamed "Pandora's Cluster," it exhibits multiple peaks in the dark matter, X-ray, and galaxy density distributions, suggesting an ongoing collision of several massive clusters. The exceptional depth of the Hubble Frontier Field imaging now makes it possible to throw open Pandora's cluster and peer deep inside. To do this, we first model and remove the stellar light of the cluster galaxies; underneath we find not only distant background galaxies, but (like the Hope that lay at the bottom of Pandora's box) a large population of globular star clusters and compact cluster members within Abell 2744 itself. Our earlier work on the massive lensing cluster Abell 1689 (Alamo-Martinez et al. 2013) revealed the largest known population of globular clusters, with a spatial profile intermediate between the galaxy light and the dark matter. Abell 2744 is similarly massive, but far less regular in its density distribution; we examine what implications this has for the copious globular clusters coursing through its multiple cores.

  12. Active matter clusters at interfaces.

    NASA Astrophysics Data System (ADS)

    Copenhagen, Katherine; Gopinathan, Ajay

    2016-03-01

    Collective and directed motility or swarming is an emergent phenomenon displayed by many self-organized assemblies of active biological matter such as clusters of embryonic cells during tissue development, cancerous cells during tumor formation and metastasis, colonies of bacteria in a biofilm, or even flocks of birds and schools of fish at the macro-scale. Such clusters typically encounter very heterogeneous environments. What happens when a cluster encounters an interface between two different environments has implications for its function and fate. Here we study this problem by using a mathematical model of a cluster that treats it as a single cohesive unit that moves in two dimensions by exerting a force/torque per unit area whose magnitude depends on the nature of the local environment. We find that low speed (overdamped) clusters encountering an interface with a moderate difference in properties can lead to refraction or even total internal reflection of the cluster. For large speeds (underdamped), where inertia dominates, the clusters show more complex behaviors crossing the interface multiple times and deviating from the predictable refraction and reflection for the low velocity clusters. We then present an extreme limit of the model in the absence of rotational damping where clusters can become stuck spiraling along the interface or move in large circular trajectories after leaving the interface. Our results show a wide range of behaviors that occur when collectively moving active biological matter moves across interfaces and these insights can be used to control motion by patterning environments.

  13. Teaching In a Cluster College

    ERIC Educational Resources Information Center

    Lawler, Nancy

    1977-01-01

    Report on the advantages and disadvantages of the interdisciplinary cluster system at Oakton Community College (Illinois) after five years. Reviews effects on students, faculty, administrators, and curriculum. (RT)

  14. Adaptive cluster detection

    NASA Astrophysics Data System (ADS)

    Friedenberg, David

    2010-10-01

    the rate of falsely detected active regions. Additionally we examine the more general field of clustering and develop a framework for clustering algorithms based around diffusion maps. Diffusion maps can be used to project high-dimensional data into a lower dimensional space while preserving much of the structure in the data. We demonstrate how diffusion maps can be used to solve clustering problems and examine the influence of tuning parameters on the results. We introduce two novel methods, the self-tuning diffusion map which replaces the global scaling parameter in the typical diffusion map framework with a local scaling parameter and an algorithm for automatically selecting tuning parameters based on a cross-validation style score called prediction strength. The methods are tested on several example datasets.

  15. Analyzing geographic clustered response

    SciTech Connect

    Merrill, D.W.; Selvin, S.; Mohr, M.S.

    1991-08-01

    In the study of geographic disease clusters, an alternative to traditional methods based on rates is to analyze case locations on a transformed map in which population density is everywhere equal. Although the analyst's task is thereby simplified, the specification of the density equalizing map projection (DEMP) itself is not simple and continues to be the subject of considerable research. Here a new DEMP algorithm is described, which avoids some of the difficulties of earlier approaches. The new algorithm (a) avoids illegal overlapping of transformed polygons; (b) finds the unique solution that minimizes map distortion; (c) provides constant magnification over each map polygon; (d) defines a continuous transformation over the entire map domain; (e) defines an inverse transformation; (f) can accept optional constraints such as fixed boundaries; and (g) can use commercially supported minimization software. Work is continuing to improve computing efficiency and improve the algorithm. 21 refs., 15 figs., 2 tabs.

  16. Clustered engine study

    NASA Technical Reports Server (NTRS)

    Shepard, Kyle; Sager, Paul; Kusunoki, Sid; Porter, John; Campion, AL; Mouritzan, Gunnar; Glunt, George; Vegter, George; Koontz, Rob

    1993-01-01

    Several topics are presented in viewgraph form which together encompass the preliminary assessment of nuclear thermal rocket engine clustering. The study objectives, schedule, flow, and groundrules are covered. This is followed by the NASA groundrules mission and our interpretation of the associated operational scenario. The NASA reference vehicle is illustrated, then the four propulsion system options are examined. Each propulsion system's preliminary design, fluid systems, operating characteristics, thrust structure, dimensions, and mass properties are detailed as well as the associated key propulsion system/vehicle interfaces. A brief series of systems analysis is also covered including: thrust vector control requirements, engine out possibilities, propulsion system failure modes, surviving system requirements, and technology requirements. An assessment of vehicle/propulsion system impacts due to the lessons learned are presented.

  17. Ionized cluster beam deposition

    NASA Astrophysics Data System (ADS)

    Kirkpatrick, A. R.

    1983-11-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  18. Ionized cluster beam deposition

    NASA Technical Reports Server (NTRS)

    Kirkpatrick, A. R.

    1983-01-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  19. Cross-Clustering: A Partial Clustering Algorithm with Automatic Estimation of the Number of Clusters

    PubMed Central

    Tellaroli, Paola; Bazzi, Marco; Donato, Michele; Brazzale, Alessandra R.; Drăghici, Sorin

    2016-01-01

    Four of the most common limitations of the many available clustering methods are: i) the lack of a proper strategy to deal with outliers; ii) the need for a good a priori estimate of the number of clusters to obtain reasonable results; iii) the lack of a method able to detect when partitioning of a specific data set is not appropriate; and iv) the dependence of the result on the initialization. Here we propose Cross-clustering (CC), a partial clustering algorithm that overcomes these four limitations by combining the principles of two well established hierarchical clustering algorithms: Ward’s minimum variance and Complete-linkage. We validated CC by comparing it with a number of existing clustering methods, including Ward’s and Complete-linkage. We show on both simulated and real datasets, that CC performs better than the other methods in terms of: the identification of the correct number of clusters, the identification of outliers, and the determination of real cluster memberships. We used CC to cluster samples in order to identify disease subtypes, and on gene profiles, in order to determine groups of genes with the same behavior. Results obtained on a non-biological dataset show that the method is general enough to be successfully used in such diverse applications. The algorithm has been implemented in the statistical language R and is freely available from the CRAN contributed packages repository. PMID:27015427

  20. Steroid hormones in cluster headaches.

    PubMed

    Stillman, Mark

    2006-04-01

    For decades, glucocorticoid therapy has been a well-recognized abortive treatment for cluster headaches. However, the role of steroid hormones, including both glucocorticoids and sex steroids, in the pathophysiology and therapy of cluster headaches has been a topic of much debate and speculation. Current research now points to the importance of cortisol and testosterone in the pathogenesis of cluster headaches, and they appear to be linked mechanistically to another hormone, melatonin. Melatonin, unlike cortisol or testosterone, is not a product of the hypothalamic pituitary axis but of the retinohypothalamic pineal axis, and is the major biomarker of circadian rhythms. The regulation of steroids and melatonin in the pathogenesis of cluster headaches in turn depends on the sympathetic nervous system. Accumulated evidence suggests sympathetic dysfunction--embodied in the Horner sign so commonly seen in the cluster headache--as a necessary ingredient in the inception of the cluster headache. Sympathetic dysfunction now is thought to be associated with the hypercortisolism, hypotestosteronism, and lower-than-normal melatonin levels in the active cluster patient. Future research may hold the key to a fuller explanation of the complex interaction of hormonal systems in the cluster headache.

  1. Hot subdwarfs in globular clusters

    SciTech Connect

    Drukier, G.A.; Fahlman, G.G.; Richter, H.B. )

    1989-07-01

    Spectra of faint blue stars in the globular clusters M71 and M4 are presented. The spectra suggest that they are hot subdwarfs. Arguments in favor of membership in their respective clusters and comments regarding their evolutionary status are given. 18 refs.

  2. Antibody-gold cluster conjugates

    DOEpatents

    Hainfeld, J.F.

    1988-06-28

    Antibody- or antibody fragment-gold cluster conjugates are shown wherein the conjugate size can be about 5.0 nm. Methods and reagents are disclosed in which antibodies or Fab' fragments thereof are covalently bound to a stable cluster of gold atoms. 2 figs.

  3. Two generalizations of Kohonen clustering

    NASA Technical Reports Server (NTRS)

    Bezdek, James C.; Pal, Nikhil R.; Tsao, Eric C. K.

    1993-01-01

    The relationship between the sequential hard c-means (SHCM), learning vector quantization (LVQ), and fuzzy c-means (FCM) clustering algorithms is discussed. LVQ and SHCM suffer from several major problems. For example, they depend heavily on initialization. If the initial values of the cluster centers are outside the convex hull of the input data, such algorithms, even if they terminate, may not produce meaningful results in terms of prototypes for cluster representation. This is due in part to the fact that they update only the winning prototype for every input vector. The impact and interaction of these two families with Kohonen's self-organizing feature mapping (SOFM), which is not a clustering method, but which often leads ideas to clustering algorithms is discussed. Then two generalizations of LVQ that are explicitly designed as clustering algorithms are presented; these algorithms are referred to as generalized LVQ = GLVQ; and fuzzy LVQ = FLVQ. Learning rules are derived to optimize an objective function whose goal is to produce 'good clusters'. GLVQ/FLVQ (may) update every node in the clustering net for each input vector. Neither GLVQ nor FLVQ depends upon a choice for the update neighborhood or learning rate distribution - these are taken care of automatically. Segmentation of a gray tone image is used as a typical application of these algorithms to illustrate the performance of GLVQ/FLVQ.

  4. Active matter clusters at interfaces

    NASA Astrophysics Data System (ADS)

    Copenhagen, Katherine; Gopinathan, Ajay

    Collective and directed motility or swarming is an emergent phenomenon displayed by many self-organized assemblies of active biological matter such as clusters of embryonic cells during tissue development and flocks of birds. Such clusters typically encounter very heterogeneous environments. What happens when a cluster encounters an interface between two different environments has implications for its function and fate. Here we study this problem by using a mathematical model of a cluster that treats it as a single cohesive unit whose movement depends on the nature of the local environment. We find that low speed clusters which exert forces but no active torques, encountering an interface with a moderate difference in properties can lead to refraction or even total internal reflection of the cluster. For large speeds and clusters with active torques, they show more complex behaviors crossing the interface multiple times, becoming trapped at the interface and deviating from the predictable refraction and reflection of the low velocity clusters. Our results show a wide range of behaviors that occur when collectively moving active biological matter moves across interfaces and these insights can be used to control motion by patterning environments.

  5. Protonated water clusters in TPC's

    NASA Astrophysics Data System (ADS)

    Kaya, Yunus; Kalkan, Yalçın; Veenhof, Rob

    2016-07-01

    Water vapour is added to the ALICE TPC gas to enhance its stability. These polar molecules create large protonated water clusters around a H+ core. In this context, the reactions H3O+(H2 O) n - 1 +H2 O →H3O+(H2O)n (n=1-9) were studied in the gas phase. Structures for these clusters are suggested and the most stable structures for each cluster size are shown. The thermodynamic parameters Δ Hn-1,n0, Δ Gn-1,n0, Δ Sn-1,n0 and equilibrium constants K n - 1 , n for the reaction were calculated to determine the size of the water clusters. The results are close to experimental data found in the literature. Protonated water clusters at stp have a size of 6-9 which corresponds to a mass of 127.1 - 181.2 g / mole.

  6. SACS: Spitzer Archival Cluster Survey

    NASA Astrophysics Data System (ADS)

    Stern, Daniel

    Emerging from the cosmic web, galaxy clusters are the most massive gravitationally bound structures in the universe. Thought to have begun their assembly at z > 2, clusters provide insights into the growth of large-scale structure as well as the physics that drives galaxy evolution. Understanding how and when the most massive galaxies assemble their stellar mass, stop forming stars, and acquire their observed morphologies in these environments remain outstanding questions. The redshift range 1.3 < z < 2 is a key epoch in this respect: elliptical galaxies start to become the dominant population in cluster cores, and star formation in spiral galaxies is being quenched. Until recently, however, this redshift range was essentially unreachable with available instrumentation, with clusters at these redshifts exceedingly challenging to identify from either ground-based optical/nearinfrared imaging or from X-ray surveys. Mid-infrared (MIR) imaging with the IRAC camera on board of the Spitzer Space Telescope has changed the landscape. High-redshift clusters are easily identified in the MIR due to a combination of the unique colors of distant galaxies and a negative k-correction in the 3-5 μm range which makes such galaxies bright. Even 90-sec observations with Spitzer/IRAC, a depth which essentially all extragalactic observations in the archive achieve, is sufficient to robustly detect overdensities of L* galaxies out to z~2. Here we request funding to embark on a ambitious scientific program, the “SACS: Spitzer Archival Cluster Survey”, a comprehensive search for the most distant galaxy clusters in all Spitzer/IRAC extragalactic pointings available in the archive. With the SACS we aim to discover ~2000 of 1.3 < z < 2.5 clusters, thus provide the ultimate catalog for high-redshift MIR selected clusters: a lasting legacy for Spitzer. The study we propose will increase by more than a factor of 10 the number of high-redshift clusters discovered by all previous surveys

  7. Decaying neutrinos in galaxy clusters

    NASA Technical Reports Server (NTRS)

    Melott, Adrian L.; Splinter, Randall J.; Persic, Massimo; Salucci, Paolo

    1993-01-01

    The DM profile in clusters of galaxies was studied and simulated using the Harrison-Zel'dovich spectrum of density fluctuations, and an amplitude previously derived from numerical simulations and in agreement with microwave background fluctuations. Neutrino DM densities, with this amplitude normalization cluster, are comparable to observed cluster DM values. It was concluded that given this normalization, the cluster DM should be al least largely composed of neutrinos. The constraint of Davidson et al., who argued that the failure to detect uv photons from the dark matter (DM) in cluster A665 excludes the decaying neutrino hypothesis, could be somewhat weakened by the presence of baryonic DM; but it cannot be eliminated given our assumptions.

  8. Single System Image Cluster Management

    2004-02-13

    Cluster computing has quickly proven itself to be a capable workhorse for a wide variety of production computing tasks; however, setting up and maintaining a cluster still requires significantly more effort than administrating just a single machine. As computing hardware descreases in price and cluster sizes grow, it is becoming increasingly important to manage clusters cleverly so that a system administration effort can "scale" as well. To ease the task of mananging many machines, administratorsmore » often deploy an environment that is homogeneous across all nodes of a cluster, and maintain a snapshot of the filesystem as a 'master image'. However due to operational, behavioral, and physical constraints, many nodes often require numerous deviations from the master image in order to operate as desired.« less

  9. Magnetic anisotropy in single clusters

    NASA Astrophysics Data System (ADS)

    Jamet, Matthieu; Wernsdorfer, Wolfgang; Thirion, Christophe; Dupuis, Véronique; Mélinon, Patrice; Pérez, Alain; Mailly, Dominique

    2004-01-01

    The magnetic measurements on single cobalt and iron nanoclusters containing almost 1000 atoms are presented. Particles are directly buried within the superconducting film of a micro-SQUID (superconducting quantum interference device) which leads to the required sensitivity. The angular dependence of the switching field in three dimensions turns out to be in good agreement with a uniform rotation of cluster magnetization. The Stoner and Wohlfarth model yields therefore an estimation of magnetic anisotropy in a single cluster. In particular, uniaxial, biaxial, and cubic contributions can be separated. Results are interpreted on the basis of a simple atomic model in which clusters are assimilated to “giant spins.” We present an extension of the Néel model to clusters in order to estimate surface anisotropy. In the case of cobalt, this last contribution dominates and numerical simulations allow us to get the morphology of the investigated clusters.

  10. Information Clustering Based on Fuzzy Multisets.

    ERIC Educational Resources Information Center

    Miyamoto, Sadaaki

    2003-01-01

    Proposes a fuzzy multiset model for information clustering with application to information retrieval on the World Wide Web. Highlights include search engines; term clustering; document clustering; algorithms for calculating cluster centers; theoretical properties concerning clustering algorithms; and examples to show how the algorithms work.…

  11. A Linear Algebra Measure of Cluster Quality.

    ERIC Educational Resources Information Center

    Mather, Laura A.

    2000-01-01

    Discussion of models for information retrieval focuses on an application of linear algebra to text clustering, namely, a metric for measuring cluster quality based on the theory that cluster quality is proportional to the number of terms that are disjoint across the clusters. Explains term-document matrices and clustering algorithms. (Author/LRW)

  12. A new class of functionalized polyoxometalates: Synthetic, structural, spectroscopic, and electrochemical studies of organoimido derivatives of [Mo{sub 6}O{sub 19}]{sup 2{minus}}

    SciTech Connect

    Strong, J.B.; Yap, G.P.A.; Ostrander, R.; Liable-Sands, L.M.; Rheingold, A.L.; Thouvenot, R.; Gouzerh, P.; Maatta, E.A.

    2000-02-02

    A convenient method for the systematic introduction of a variety of organoimido ligands at terminal oxo sites in the hexamolybdate cluster [Bu{sub 4}N]{sub 2}[Mo{sub 6}O{sub 19}] is described, consisting of reaction with the appropriate organic isocyanate RNCO (R = n-butyl, cyclohexyl, 2,6-diisopropylphenyl) in pyridine solution. Singly functionalized imido-hexamolybdates [Mo{sub 6O{sub 18}}(NR)]{sup 2{minus}} incorporating each of the above substituents are described. In the case of the 2,6-(diisopropyl)phenylimido ligand (NAr), multiple functionalization has also been achieved: hexamolybdate derivatives [Mo{sub 6}O{sub (19{minus}x)}(NAr){sub x}]{sup 2{minus}} incorporating two, three, four, and five NAr ligands at terminal sites have been prepared. The complexes have been characterized by cyclic voltammetry, multinuclear ({sup 1}H, {sup 14}N, {sup 17}O, and {sup 95}Mo) NMR and electronic spectroscopy, and single-crystal X-ray diffraction studies.

  13. Luminescent iron clusters in solution

    NASA Astrophysics Data System (ADS)

    Goswami, Nirmal; Baksi, Ananya; Giri, Anupam; Xavier, Paulrajpillai Lourdu; Basu, Gautam; Pradeep, Thalappil; Pal, Samir Kumar

    2014-01-01

    Metal clusters, composed of a few atoms at the core, exhibit unique properties and have potential applications. Although atomically precise clusters of noble metals have been synthesized, analogous systems of reactive metals, such as iron, have not been realized in solution due to high reactivity. Here we report the synthesis and characterization of novel iron clusters in the hemoglobin matrix that are highly luminescent (quantum yield 10% at 565 nm). The super-paramagnetic iron clusters, after successful ligand exchange from protein and phase transfer from water to chloroform using tri-octylphosphineoxide (TOPO), were detected as [Fe10(TOPO)3(H2O)3]+, [Fe13(TOPO)2(H2O)]+ and [Fe8(TOPO)(H2O)2]+ by mass spectrometry. This study lays the groundwork for exploiting unique properties of soluble iron clusters.Metal clusters, composed of a few atoms at the core, exhibit unique properties and have potential applications. Although atomically precise clusters of noble metals have been synthesized, analogous systems of reactive metals, such as iron, have not been realized in solution due to high reactivity. Here we report the synthesis and characterization of novel iron clusters in the hemoglobin matrix that are highly luminescent (quantum yield 10% at 565 nm). The super-paramagnetic iron clusters, after successful ligand exchange from protein and phase transfer from water to chloroform using tri-octylphosphineoxide (TOPO), were detected as [Fe10(TOPO)3(H2O)3]+, [Fe13(TOPO)2(H2O)]+ and [Fe8(TOPO)(H2O)2]+ by mass spectrometry. This study lays the groundwork for exploiting unique properties of soluble iron clusters. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05784d

  14. Evolution of brightest cluster galaxies in X-ray clusters

    NASA Astrophysics Data System (ADS)

    Brough, S.; Collins, C. A.; Burke, D. J.; Mann, R. G.; Lynam, P. D.

    2002-01-01

    A recent paper presents the analysis of the K-band Hubble diagram of 76 brightest cluster galaxies (BCGs) in X-ray clusters and shows that the properties of BCGs depend on the X-ray luminosity (LX) of their host clusters. Unfortunately, the low numbers of nearby clusters in this sample makes it difficult to constrain evolutionary trends. In this letter we extend the Hubble diagram of Burke, Collins & Mann to a total of 155 clusters using new data on 79 BCGs at z<=0.1 from the 2MASS extended source catalogue. We show that the major division between BCGs in high- and low-LX clusters disappears at z<=0.1, with BCGs having similar absolute magnitudes independent of the X-ray luminosity of their host clusters. At larger redshifts, the K-band light of BCGs in high-LX systems is consistent with little or no merging back to z~0.8, whereas BCGs in the low-LX systems have a different evolutionary history, with many increasing their mass by a factor >=4 since z~=1. This provides direct evidence of hierarchical merging in a galaxy population.

  15. Plug cluster module demonstration

    NASA Technical Reports Server (NTRS)

    Rousar, D. C.

    1978-01-01

    The low pressure, film cooled rocket engine design concept developed during two previous ALRC programs was re-evaluated for application as a module for a plug cluster engine capable of performing space shuttle OTV missions. The nominal engine mixture ratio was 5.5 and the engine life requirements were 1200 thermal cycles and 10 hours total operating life. The program consisted of pretest analysis; engine tests, performed using residual components; and posttest analysis. The pretest analysis indicated that operation of the operation of the film cooled engine at O/F = 5.5 was feasible. During the engine tests, steady state wall temperature and performance measurement were obtained over a range of film cooling flow rates, and the durability of the engine was demonstrated by firing the test engine 1220 times at a nominal performance ranging from 430 - 432 seconds. The performance of the test engine was limited by film coolant sleeve damage which had occurred during previous testing. The post-test analyses indicated that the nominal performance level can be increased to 436 seconds.

  16. Dust cluster explosion

    SciTech Connect

    Saxena, Vikrant; Avinash, K.; Sen, A.

    2012-09-15

    A model for the dust cluster explosion where micron/sub-micron sized particles are accelerated at the expense of plasma thermal energy, in the afterglow phase of a complex plasma discharge is proposed. The model is tested by molecular dynamics simulations of dust particles in a confining potential. The nature of the explosion (caused by switching off the discharge) and the concomitant dust acceleration is found to depend critically on the pressure of the background neutral gas. At low gas pressure, the explosion is due to unshielded Coulomb repulsion between dust particles and yields maximum acceleration, while in the high pressure regime it is due to shielded Yukawa repulsion and yields much feebler acceleration. These results are in agreement with experimental findings. Our simulations also confirm a recently proposed electrostatic (ES) isothermal scaling relation, P{sub E}{proportional_to}V{sub d}{sup -2} (where P{sub E} is the ES pressure of the dust particles and V{sub d} is the confining volume).

  17. Novae in globular clusters

    SciTech Connect

    Kato, Mariko; Hachisu, Izumi; Henze, Martin

    2013-12-10

    We present the first light-curve analysis of Population II novae that appeared in M31 globular clusters. Our light-curve models, based on the optically thick wind theory, reproduce well both the X-ray turn-on and turnoff times with the white dwarf (WD) mass of about 1.2 M {sub ☉} for M31N 2007-06b in Bol 111 and about 1.37 M {sub ☉} for M31N 2010-10f in Bol 126. The transient supersoft X-ray source CXO J004345 in Bol 194 is highly likely a nova remnant of 1.2-1.3 M {sub ☉} WD. These WD masses are quite consistent with the temperatures deduced from X-ray spectra. We also present the dependence of nova light curves on the metallicity in the range from [Fe/H] = 0.4 to –2.7. Whereas strong optically thick winds are accelerated in Galactic disk novae owing to a large Fe opacity peak, only weak winds occur in Population II novae with low Fe abundance. Thus, nova light curves are systematically slow in low Fe environment. For an extremely low Fe abundance normal nova outbursts may not occur unless the WD is very massive. We encourage V or y filter observation rather than R as well as high cadence X-ray monitorings to open quantitative studies of extragalactic novae.

  18. Clusterization and quadrupole deformation in nuclei

    SciTech Connect

    Cseh, J.; Algora, A.; Antonenko, N. V.; Jolos, R. V.; Scheid, W.; Darai, J.; Hess, P. O.

    2006-04-26

    We study the interrelation of the clusterization and quadrupole deformation of atomic nuclei, by applying cluster models. Both the energetic stability and the exclusion principle is investigated. Special attention is paid to the relative orientations of deformed clusters.

  19. Cluster-assembled metallic glasses

    NASA Astrophysics Data System (ADS)

    Kartouzian, Aras

    2013-07-01

    A bottom-up approach to nanofabricate metallic glasses from metal clusters as building blocks is presented. Considering metallic glasses as a subclass of cluster-assembled materials, the relation between the two lively fields of metal clusters and metallic glasses is pointed out. Deposition of selected clusters or collections of them, generated by state-of-the-art cluster beam sources, could lead to the production of a well-defined amorphous material. In contrast to rapidly quenched glasses where only the composition of the glass can be controlled, in cluster-assembled glasses, one can precisely control the structural building blocks. Comparing properties of glasses with similar compositions but differing in building blocks and therefore different in structure will facilitate the study of structure-property correlation in metallic glasses. This bottom-up method provides a novel alternative path to the synthesis of glassy alloys and will contribute to improving fundamental understanding in the field of metallic glasses. It may even permit the production of glassy materials for alloys that cannot be quenched rapidly enough to circumvent crystallization. Additionally, gaining deeper insight into the parameters governing the structure-property relation in metallic glasses can have a great impact on understanding and design of other cluster-assembled materials.

  20. Cluster-assembled metallic glasses.

    PubMed

    Kartouzian, Aras

    2013-07-30

    A bottom-up approach to nanofabricate metallic glasses from metal clusters as building blocks is presented. Considering metallic glasses as a subclass of cluster-assembled materials, the relation between the two lively fields of metal clusters and metallic glasses is pointed out. Deposition of selected clusters or collections of them, generated by state-of-the-art cluster beam sources, could lead to the production of a well-defined amorphous material. In contrast to rapidly quenched glasses where only the composition of the glass can be controlled, in cluster-assembled glasses, one can precisely control the structural building blocks. Comparing properties of glasses with similar compositions but differing in building blocks and therefore different in structure will facilitate the study of structure-property correlation in metallic glasses. This bottom-up method provides a novel alternative path to the synthesis of glassy alloys and will contribute to improving fundamental understanding in the field of metallic glasses. It may even permit the production of glassy materials for alloys that cannot be quenched rapidly enough to circumvent crystallization. Additionally, gaining deeper insight into the parameters governing the structure-property relation in metallic glasses can have a great impact on understanding and design of other cluster-assembled materials.

  1. Galactic Globular Cluster Relative Ages

    NASA Astrophysics Data System (ADS)

    De Angeli, Francesca; Piotto, Giampaolo; Cassisi, Santi; Busso, Giorgia; Recio-Blanco, Alejandra; Salaris, Maurizio; Aparicio, Antonio; Rosenberg, Alfred

    2005-07-01

    We present accurate relative ages for a sample of 55 Galactic globular clusters. The ages have been obtained by measuring the difference between the horizontal branch and the turnoff in two internally photometrically homogeneous databases. The mutual consistency of the two data sets has been assessed by comparing the ages of 16 globular clusters in common between the two databases. We have also investigated the consistency of our relative age determination within the recent stellar model framework. All clusters with [Fe/H]<-1.7 are found to be old and coeval, with the possible exception of two objects, which are marginally younger. The age dispersion for the metal-poor clusters is 0.6 Gyr (rms), consistent with a null age dispersion. Intermediate-metallicity clusters (-1.7<[Fe/H]<-0.8) are on average 1.5 Gyr younger than the metal-poor ones, with an age dispersion of 1.0 Gyr (rms) and a total age range of ~3 Gyr. About 15% of the intermediate-metallicity clusters are coeval with the oldest clusters. All the clusters with [Fe/H]>-0.8 are ~1 Gyr younger than the most metal-poor ones, with a relatively small age dispersion, although the metal-rich sample is still too small to allow firmer conclusions. There is no correlation of the cluster age with the galactocentric distance. We briefly discuss the implication of these observational results for the formation history of the Galaxy. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 5-26555, and on observations made at the European Southern Observatory, La Silla, Chile, and with the Isaac Newton Group Telescopes.

  2. THE EXTENDED VIRGO CLUSTER CATALOG

    SciTech Connect

    Kim, Suk; Rey, Soo-Chang; Lee, Youngdae; Chung, Jiwon; Pak, Mina; Yi, Wonhyeong; Lee, Woong; Jerjen, Helmut; Lisker, Thorsten; Sung, Eon-Chang

    2015-01-01

    We present a new catalog of galaxies in the wider region of the Virgo cluster, based on the Sloan Digital Sky Survey (SDSS) Data Release 7. The Extended Virgo Cluster Catalog (EVCC) covers an area of 725 deg{sup 2} or 60.1 Mpc{sup 2}. It is 5.2 times larger than the footprint of the classical Virgo Cluster Catalog (VCC) and reaches out to 3.5 times the virial radius of the Virgo cluster. We selected 1324 spectroscopically targeted galaxies with radial velocities less than 3000 km s{sup –1}. In addition, 265 galaxies that have been overlooked in the SDSS spectroscopic survey but have available redshifts in the NASA Extragalactic Database are also included. Our selection process secured a total of 1589 galaxies, 676 of which are not included in the VCC. The certain and possible cluster members are defined by means of redshift comparison with a cluster infall model. We employed two independent and complementary galaxy classification schemes: the traditional morphological classification based on the visual inspection of optical images and a characterization of galaxies from their spectroscopic features. SDSS u, g, r, i, and z passband photometry of all EVCC galaxies was performed using Source Extractor. We compare the EVCC galaxies with the VCC in terms of morphology, spatial distribution, and luminosity function. The EVCC defines a comprehensive galaxy sample covering a wider range in galaxy density that is significantly different from the inner region of the Virgo cluster. It will be the foundation for forthcoming galaxy evolution studies in the extended Virgo cluster region, complementing ongoing and planned Virgo cluster surveys at various wavelengths.

  3. Systolic architecture for heirarchical clustering

    SciTech Connect

    Ku, L.C.

    1984-01-01

    Several hierarchical clustering methods (including single-linkage complete-linkage, centroid, and absolute overlap methods) are reviewed. The absolute overlap clustering method is selected for the design of systolic architecture mainly due to its simplicity. Two versions of systolic architectures for the absolute overlap hierarchical clustering algorithm are proposed: one-dimensional version that leads to the development of a two dimensional version which fully takes advantage of the underlying data structure of the problems. The two dimensional systolic architecture can achieve a time complexity of O(m + n) in comparison with the conventional computer implementation of a time complexity of O(m/sup 2*/n).

  4. Exploring Web Search Results Clustering

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoxia; Bramer, Max

    As the number of documents on the web has proliferated, the low precision of conventional web search engines and the flat ranked search results presentation make it difficult for users to locate specific information of interest. Grouping web search results into a hierarchy of topics provides an alternative to the flat ranked list and facilitates searching and browsing. In this paper, we present a brief survey of previous work on web search results clustering and existing commercial search engines using this technique, discuss two key issues of web search results clustering: cluster summarisation and evaluation and propose some directions for future research.

  5. Neurostimulation for chronic cluster headache

    PubMed Central

    Kaube, Holger

    2012-01-01

    Neurostimulation techniques for the treatment of primary headache syndromes, particularly of chronic cluster headache, have received much interest in recent years. Occipital nerve stimulation (ONS) has yielded favourable clinical results and, despite the limited numbers of published cases, is becoming a routine treatment for refractory chronic cluster headache in specialized centres. Meanwhile, other promising techniques such as spinal cord stimulation (SCS) or sphenopalate ganglion stimulation have emerged. In this article the current state of clinical research for neurostimulation techniques for chronic cluster headache is reviewed. PMID:22590481

  6. Cluster Model of the Nucleus

    NASA Astrophysics Data System (ADS)

    Horiuchi, Hisashi; Ikeda, Kiyomi

    The following sections are included: * INTRODUCTION * CLUSTER STRUCTURE OF NUCLEI * Typical Clustering States * Molecule-like Structure of Nuclei and the Threshold-energy Rule * Microscopic Cluster Model * Characteristic Points of the Structure Study by the Microscopic Cluster Model * Several Subjects Related to the Study of the Cluster Structure * Connection with the Neighbouring Fields in Nuclear Physics * MANY-CENTER MODEL AND ROTATIONAL STATES * Brink Model * Relation of the Brink Model Wave Function with the Shell Model Wave Function * Molecular Orbital Method * Projection of Parity and Angular Momentum * DESCRIPTION OF THE INTER-CLUSTER RELATIVE MOTION BY THE GENERATOR COORDINATE METHOD * Griffin-Hill-Wheeler Equation * GCM Kernel of Two-spinless-cluster System * DESCRIPTION OF THE INTER-CLUSTER RELATIVE MOTION BY THE RESONATING GROUP METHOD * Formulation * Equivalence of RGM and GCM * Calculation of RGM Kernels by using GCM Kernels * Calculation of Direct Potential * IMPOSITION OF THE SCATTERING BOUNDARY CONDITION * Brief Survey of the Calculational Methods of the Scattering Matrix in RGM and GCM * Wave Functions in the Outside Region and Matrix Elements in the Interaction Region * R-matrix Type Method * Variational Method * CLUSTER MODEL SPACE - RGM NORM KERNEL AND PAULI-FORBIDDEN STATES * Orthonormal Basis Wave Functions of the System and the Eigenvalue Problem of the Norm Kernel * Explicit Solution of the Eigenvalue Problem of the RGM Norm Kernel * Relation between Cluster Model States with Shell Model States * Almost Forbidden States * ORTHOGONALITY CONDITION MODEL * Inner Oscillation of the Inter-cluster Relative Wave Function * Formulation of the OCM * FEW EXAMPLES OF THE MICROSCOPIC CLUSTER MODEL STUDY * α+16O Model for 20Ne * α+12C Model for 16O * 3α Model for 12C * ACKNOWLEDGEMENTS * APPENDIX I SEPARATION OF THE CENTER-OF-MASS COORDINATE IN THE CASE OF THE HARMONIC OSCILLATOR SHELL MODEL * APPENDIX II ANTISYMMETRIZER, LAPLACE EXPANSION OF

  7. AMOEBA clustering revisited. [cluster analysis, classification, and image display program

    NASA Technical Reports Server (NTRS)

    Bryant, Jack

    1990-01-01

    A description of the clustering, classification, and image display program AMOEBA is presented. Using a difficult high resolution aircraft-acquired MSS image, the steps the program takes in forming clusters are traced. A number of new features are described here for the first time. Usage of the program is discussed. The theoretical foundation (the underlying mathematical model) is briefly presented. The program can handle images of any size and dimensionality.

  8. Brightest cluster galaxies in the extended GMRT radio halo cluster sample. Radio properties and cluster dynamics

    NASA Astrophysics Data System (ADS)

    Kale, R.; Venturi, T.; Cassano, R.; Giacintucci, S.; Bardelli, S.; Dallacasa, D.; Zucca, E.

    2015-09-01

    Aims: First-ranked galaxies in clusters, usually referred to as brightest cluster galaxies (BCGs), show exceptional properties over the whole electromagnetic spectrum. They are the most massive elliptical galaxies and show the highest probability to be radio loud. Moreover, their special location at the centres of galaxy clusters raises the question of the role of the environment in shaping their radio properties. In the attempt to separate the effect of the galaxy mass and of the environment on their statistical radio properties, we investigate the possible dependence of the occurrence of radio loudness and of the fractional radio luminosity function on the dynamical state of the hosting cluster. Methods: We studied the radio properties of the BCGs in the Extended GMRT Radio Halo Survey (EGRHS), which consists of 65 clusters in the redshift range 0.2-0.4, with X-ray luminosity LX ≥ 5 × 1044 erg s-1, and quantitative information on their dynamical state from high-quality Chandra imaging. We obtained a statistical sample of 59 BCGs, which we divided into two classes, depending on whether the dynamical state of the host cluster was merging (M) or relaxed (R). Results: Of the 59 BCGs, 28 are radio loud and 31 are radio quiet. The radio-loud sources are favourably located in relaxed clusters (71%), while the reverse is true for the radio-quiet BCGs, which are mostly located in merging systems (81%). The fractional radio luminosity function for the BCGs in merging and relaxed clusters is different, and it is considerably higher for BCGs in relaxed clusters, where the total fraction of radio loudness reaches almost 90%, to be compared to the ~30% in merging clusters. For relaxed clusters, we found a positive correlation between the radio power of the BCGs and the strength of the cool core, consistent with previous studies on local samples. Conclusions: Our study suggests that the radio loudness of the BCGs strongly depends on the cluster dynamics; their fraction is

  9. A Clustering Graph Generator

    SciTech Connect

    Winlaw, Manda; De Sterck, Hans; Sanders, Geoffrey

    2015-10-26

    In very simple terms a network can be de ned as a collection of points joined together by lines. Thus, networks can be used to represent connections between entities in a wide variety of elds including engi- neering, science, medicine, and sociology. Many large real-world networks share a surprising number of properties, leading to a strong interest in model development research and techniques for building synthetic networks have been developed, that capture these similarities and replicate real-world graphs. Modeling these real-world networks serves two purposes. First, building models that mimic the patterns and prop- erties of real networks helps to understand the implications of these patterns and helps determine which patterns are important. If we develop a generative process to synthesize real networks we can also examine which growth processes are plausible and which are not. Secondly, high-quality, large-scale network data is often not available, because of economic, legal, technological, or other obstacles [7]. Thus, there are many instances where the systems of interest cannot be represented by a single exemplar network. As one example, consider the eld of cybersecurity, where systems require testing across diverse threat scenarios and validation across diverse network structures. In these cases, where there is no single exemplar network, the systems must instead be modeled as a collection of networks in which the variation among them may be just as important as their common features. By developing processes to build synthetic models, so-called graph generators, we can build synthetic networks that capture both the essential features of a system and realistic variability. Then we can use such synthetic graphs to perform tasks such as simulations, analysis, and decision making. We can also use synthetic graphs to performance test graph analysis algorithms, including clustering algorithms and anomaly detection algorithms.

  10. Cluster Randomized Controlled Trial

    PubMed Central

    Young, John; Chapman, Katie; Nixon, Jane; Patel, Anita; Holloway, Ivana; Mellish, Kirste; Anwar, Shamaila; Breen, Rachel; Knapp, Martin; Murray, Jenni; Farrin, Amanda

    2015-01-01

    Background and Purpose— We developed a new postdischarge system of care comprising a structured assessment covering longer-term problems experienced by patients with stroke and their carers, linked to evidence-based treatment algorithms and reference guides (the longer-term stroke care system of care) to address the poor longer-term recovery experienced by many patients with stroke. Methods— A pragmatic, multicentre, cluster randomized controlled trial of this system of care. Eligible patients referred to community-based Stroke Care Coordinators were randomized to receive the new system of care or usual practice. The primary outcome was improved patient psychological well-being (General Health Questionnaire-12) at 6 months; secondary outcomes included functional outcomes for patients, carer outcomes, and cost-effectiveness. Follow-up was through self-completed postal questionnaires at 6 and 12 months. Results— Thirty-two stroke services were randomized (29 participated); 800 patients (399 control; 401 intervention) and 208 carers (100 control; 108 intervention) were recruited. In intention to treat analysis, the adjusted difference in patient General Health Questionnaire-12 mean scores at 6 months was −0.6 points (95% confidence interval, −1.8 to 0.7; P=0.394) indicating no evidence of statistically significant difference between the groups. Costs of Stroke Care Coordinator inputs, total health and social care costs, and quality-adjusted life year gains at 6 months, 12 months, and over the year were similar between the groups. Conclusions— This robust trial demonstrated no benefit in clinical or cost-effectiveness outcomes associated with the new system of care compared with usual Stroke Care Coordinator practice. Clinical Trial Registration— URL: http://www.controlled-trials.com. Unique identifier: ISRCTN 67932305. PMID:26152298

  11. Distant Massive Clusters and Cosmology

    NASA Technical Reports Server (NTRS)

    Donahue, Megan

    1999-01-01

    We present a status report of our X-ray study and analysis of a complete sample of distant (z=0.5-0.8), X-ray luminous clusters of galaxies. We have obtained ASCA and ROSAT observations of the five brightest Extended Medium Sensitivity (EMSS) clusters with z > 0.5. We have constructed an observed temperature function for these clusters, and measured iron abundances for all of these clusters. We have developed an analytic expression for the behavior of the mass-temperature relation in a low-density universe. We use this mass-temperature relation together with a Press-Schechter-based model to derive the expected temperature function for different values of Omega-M. We combine this analysis with the observed temperature functions at redshifts from 0 - 0.8 to derive maximum likelihood estimates for the value of Omega-M. We report preliminary results of this analysis.

  12. Architecture of Eph receptor clusters

    SciTech Connect

    Himanen, Juha P.; Yermekbayeva, Laila; Janes, Peter W.; Walker, John R.; Xu, Kai; Atapattu, Lakmali; Rajashankar, Kanagalaghatta R.; Mensinga, Anneloes; Lackmann, Martin; Nikolov, Dimitar B.; Dhe-Paganon, Sirano

    2010-10-04

    Eph receptor tyrosine kinases and their ephrin ligands regulate cell navigation during normal and oncogenic development. Signaling of Ephs is initiated in a multistep process leading to the assembly of higher-order signaling clusters that set off bidirectional signaling in interacting cells. However, the structural and mechanistic details of this assembly remained undefined. Here we present high-resolution structures of the complete EphA2 ectodomain and complexes with ephrin-A1 and A5 as the base unit of an Eph cluster. The structures reveal an elongated architecture with novel Eph/Eph interactions, both within and outside of the Eph ligand-binding domain, that suggest the molecular mechanism underlying Eph/ephrin clustering. Structure-function analysis, by using site-directed mutagenesis and cell-based signaling assays, confirms the importance of the identified oligomerization interfaces for Eph clustering.

  13. Clustering of financial time series

    NASA Astrophysics Data System (ADS)

    D'Urso, Pierpaolo; Cappelli, Carmela; Di Lallo, Dario; Massari, Riccardo

    2013-05-01

    This paper addresses the topic of classifying financial time series in a fuzzy framework proposing two fuzzy clustering models both based on GARCH models. In general clustering of financial time series, due to their peculiar features, needs the definition of suitable distance measures. At this aim, the first fuzzy clustering model exploits the autoregressive representation of GARCH models and employs, in the framework of a partitioning around medoids algorithm, the classical autoregressive metric. The second fuzzy clustering model, also based on partitioning around medoids algorithm, uses the Caiado distance, a Mahalanobis-like distance, based on estimated GARCH parameters and covariances that takes into account the information about the volatility structure of time series. In order to illustrate the merits of the proposed fuzzy approaches an application to the problem of classifying 29 time series of Euro exchange rates against international currencies is presented and discussed, also comparing the fuzzy models with their crisp version.

  14. Cluster randomization and political philosophy.

    PubMed

    Chwang, Eric

    2012-11-01

    In this paper, I will argue that, while the ethical issues raised by cluster randomization can be challenging, they are not new. My thesis divides neatly into two parts. In the first, easier part I argue that many of the ethical challenges posed by cluster randomized human subjects research are clearly present in other types of human subjects research, and so are not novel. In the second, more difficult part I discuss the thorniest ethical challenge for cluster randomized research--cases where consent is genuinely impractical to obtain. I argue that once again these cases require no new analytic insight; instead, we should look to political philosophy for guidance. In other words, the most serious ethical problem that arises in cluster randomized research also arises in political philosophy.

  15. Infrared spectroscopy of ionic clusters

    SciTech Connect

    Price, J.M. . Dept. of Chemistry Lawrence Berkeley Lab., CA )

    1990-11-01

    This thesis describes new experiments wherein the infrared vibrational predissociation spectra of a number of mass-selected ionic cluster systems have been obtained and analyzed in the 2600 to 4000 cm{sup {minus}1} region. The species studied include: the hydrated hydronium ions, H{sub 3}O{sup +} (H{sub 2}O){sub 3 {minus}10}, ammoniated ammonium ions, NH{sub 4}{sup +}(NH{sub 3}){sub 1 {minus}10} and cluster ions involving both water and ammonia around an ammonium ion core, (mixed clusters) NH{sub 4}{sup +}(NH{sub 3}){sub n}(H{sub 2}O){sub m} (n+m=4). In each case, the spectra reveal well resolved structures that can be assigned to transitions arising from the vibrational motions of both the ion core of the clusters and the surrounding neutral solvent molecules. 154 refs., 19 figs., 8 tabs.

  16. Re-shaping colloidal clusters

    NASA Astrophysics Data System (ADS)

    Kraft, Daniela

    2015-03-01

    Controlling the geometry and yield of anisotropic colloidal particles remains a challenge for hierarchical self-assembly. I will discuss a synthetic strategy for fabricating colloidal clusters by creating order in randomly aggregated polymer spheres using surface tension and geometrical constraints. The technique can be extended to a variety of charge-stabilized polymer spheres and offers control over the cluster size distribution. VENI grant from The Netherlands Organization for Scientific Research (NWO).

  17. Binary Stars in Globular Clusters

    NASA Astrophysics Data System (ADS)

    Mateo, M.; Murdin, P.

    2000-11-01

    Globular clusters have long been known to be among the richest stellar groupings within our Galaxy, but for many years they were believed to be largely devoid of the most minimal stellar group: binary stars (see BINARY STARS: OVERVIEW). For many years, the only evidence that any binaries existed in these clusters came from the presence of BLUE STRAGGLERS—stars that appear to be significantly you...

  18. Diverse Ligand-Functionalized Mixed-Valent Hexamanganese Sandwiched Silicotungstates with Single-Molecule Magnet Behavior.

    PubMed

    Xue, Han; Zhao, Jun-Wei; Pan, Rui; Yang, Bai-Feng; Yang, Guo-Yu; Liu, Hong-Sheng

    2016-08-22

    Under hydrothermal conditions, replacement of the water molecules in the [Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](8+) cluster of mixed-valent Mn6 sandwiched silicotungstate [(B-α-SiW9 O34 )2 Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](12-) (1 a) with organic N ligands led to the isolation of five organic-inorganic hybrid, Mn6 -substituted polyoxometalates (POMs) 2-6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse-reflectance spectroscopy, and powder and single-crystal X-ray diffraction. Compounds 2-6 represent the first series of mixed-valent {Mn(III) 4 Mn(II) 2 O4 (H2 O)4-n (L)n } sandwiched POMs covalently functionalized by organic ligands. The preparation of 1-6 not only indicates that the double-cubane {Mn(III) 4 Mn(II) 2 O4 (H2 O)4-n (L)n } clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](8+) cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed-valent POMs substituted with transition-metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single-molecule magnet behavior. PMID:27373550

  19. Diverse Ligand-Functionalized Mixed-Valent Hexamanganese Sandwiched Silicotungstates with Single-Molecule Magnet Behavior.

    PubMed

    Xue, Han; Zhao, Jun-Wei; Pan, Rui; Yang, Bai-Feng; Yang, Guo-Yu; Liu, Hong-Sheng

    2016-08-22

    Under hydrothermal conditions, replacement of the water molecules in the [Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](8+) cluster of mixed-valent Mn6 sandwiched silicotungstate [(B-α-SiW9 O34 )2 Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](12-) (1 a) with organic N ligands led to the isolation of five organic-inorganic hybrid, Mn6 -substituted polyoxometalates (POMs) 2-6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse-reflectance spectroscopy, and powder and single-crystal X-ray diffraction. Compounds 2-6 represent the first series of mixed-valent {Mn(III) 4 Mn(II) 2 O4 (H2 O)4-n (L)n } sandwiched POMs covalently functionalized by organic ligands. The preparation of 1-6 not only indicates that the double-cubane {Mn(III) 4 Mn(II) 2 O4 (H2 O)4-n (L)n } clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](8+) cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed-valent POMs substituted with transition-metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single-molecule magnet behavior.

  20. Collective thermoregulation in bee clusters.

    PubMed

    Ocko, Samuel A; Mahadevan, L

    2014-02-01

    Swarming is an essential part of honeybee behaviour, wherein thousands of bees cling onto each other to form a dense cluster that may be exposed to the environment for several days. This cluster has the ability to maintain its core temperature actively without a central controller. We suggest that the swarm cluster is akin to an active porous structure whose functional requirement is to adjust to outside conditions by varying its porosity to control its core temperature. Using a continuum model that takes the form of a set of advection-diffusion equations for heat transfer in a mobile porous medium, we show that the equalization of an effective 'behavioural pressure', which propagates information about the ambient temperature through variations in density, leads to effective thermoregulation. Our model extends and generalizes previous models by focusing the question of mechanism on the form and role of the behavioural pressure, and allows us to explain the vertical asymmetry of the cluster (as a consequence of buoyancy-driven flows), the ability of the cluster to overpack at low ambient temperatures without breaking up at high ambient temperatures, and the relative insensitivity to large variations in the ambient temperature. Our theory also makes testable hypotheses for the response of the cluster to external temperature inhomogeneities and suggests strategies for biomimetic thermoregulation. PMID:24335563

  1. Understanding Galaxy Cluster MKW10

    NASA Astrophysics Data System (ADS)

    Sanders, Tim; Henry, Swain; Coble, Kimberly A.; Rosenberg, Jessica L.; Koopmann, Rebecca A.

    2015-01-01

    As part of the Undergraduate ALFALFA Team (UAT), we are studying the galaxy cluster MKW 10 (RA = 175.454, Dec = 10.306, z ~ 0.02), a poor cluster with a compact core in which tidal interactions have occurred. This cluster has been observed in HI and Hα. We used SDSS and NED to search for optical counterparts. By comparing data at multiple wavelengths, we hope to understand the structure, environment, and star formation history of this cluster. Following the techniques of others involved in the groups project and using the program TOPCAT to manipulate the data, we explored both the spatial and velocity distributions to determine cluster membership. We have determined that this cluster consists of 11 galaxies, mostly spiral in shape. Chicago State University is new the UAT and we began our work after taking part in the winter workshop at Arecibo.This work was supported by: Undergraduate ALFALFA Team NSF Grant AST-1211005 and the Illinois Space Grant Consortium.

  2. Multi-focus cluster labeling.

    PubMed

    Eikvil, Line; Jenssen, Tor-Kristian; Holden, Marit

    2015-06-01

    Document collections resulting from searches in the biomedical literature, for instance, in PubMed, are often so large that some organization of the returned information is necessary. Clustering is an efficient tool for organizing search results. To help the user to decide how to continue the search for relevant documents, the content of each cluster can be characterized by a set of representative keywords or cluster labels. As different users may have different interests, it can be desirable with solutions that make it possible to produce labels from a selection of different topical categories. We therefore introduce the concept of multi-focus cluster labeling to give users the possibility to get an overview of the contents through labels from multiple viewpoints. The concept for multi-focus cluster labeling has been established and has been demonstrated on three different document collections. We illustrate that multi-focus visualizations can give an overview of clusters along axes that general labels are not able to convey. The approach is generic and should be applicable to any biomedical (or other) domain with any selection of foci where appropriate focus vocabularies can be established. A user evaluation also indicates that such a multi-focus concept is useful.

  3. The formation of star clusters

    NASA Astrophysics Data System (ADS)

    Whitmore, Bradley C.

    The ability of HST to resolve objects ten times smaller than possible from the ground has re-juvenated the study of young star clusters. A recurrent morphological theme found in nearby resolved systems is the observation of young (typically 1-10 Myr), massive (103 - 104 Msolar), compact (ρ≍105 Msolar pc-3) clusters which have evacuated the gas and dust from a spherical region around themselves. New stars are being triggered into formation along the edges of the envelopes, with pillars (similar to the Eagle Nebula) of molecular gas streaming away from the regions of star formation. The prototype for these objects is 30 Doradus. Another major theme has been the discovery of large numbers of young (typically 1-500 Myr), massive (103 - 108 Msolar), compact star clusters in merging, starbursting, and even some barred and spiral galaxies. The brightest of these clusters have all the attributes expected of protoglobular clusters, hence allowing us to study the formation of globular clusters in the local universe rather than trying to ascertain how they formed ≍14 Gyr ago. The prototype is the Antennae Galaxy.

  4. AMIC@: All MIcroarray Clusterings @ once.

    PubMed

    Geraci, Filippo; Pellegrini, Marco; Renda, M Elena

    2008-07-01

    The AMIC@ Web Server offers a light-weight multi-method clustering engine for microarray gene-expression data. AMIC@ is a highly interactive tool that stresses user-friendliness and robustness by adopting AJAX technology, thus allowing an effective interleaved execution of different clustering algorithms and inspection of results. Among the salient features AMIC@ offers, there are: (i) automatic file format detection, (ii) suggestions on the number of clusters using a variant of the stability-based method of Tibshirani et al. (iii) intuitive visual inspection of the data via heatmaps and (iv) measurements of the clustering quality using cluster homogeneity. Large data sets can be processed efficiently by selecting algorithms (such as FPF-SB and k-Boost), specifically designed for this purpose. In case of very large data sets, the user can opt for a batch-mode use of the system by means of the Clustering wizard that runs all algorithms at once and delivers the results via email. AMIC@ is freely available and open to all users with no login requirement at the following URL http://bioalgo.iit.cnr.it/amica.

  5. Collective thermoregulation in bee clusters.

    PubMed

    Ocko, Samuel A; Mahadevan, L

    2014-02-01

    Swarming is an essential part of honeybee behaviour, wherein thousands of bees cling onto each other to form a dense cluster that may be exposed to the environment for several days. This cluster has the ability to maintain its core temperature actively without a central controller. We suggest that the swarm cluster is akin to an active porous structure whose functional requirement is to adjust to outside conditions by varying its porosity to control its core temperature. Using a continuum model that takes the form of a set of advection-diffusion equations for heat transfer in a mobile porous medium, we show that the equalization of an effective 'behavioural pressure', which propagates information about the ambient temperature through variations in density, leads to effective thermoregulation. Our model extends and generalizes previous models by focusing the question of mechanism on the form and role of the behavioural pressure, and allows us to explain the vertical asymmetry of the cluster (as a consequence of buoyancy-driven flows), the ability of the cluster to overpack at low ambient temperatures without breaking up at high ambient temperatures, and the relative insensitivity to large variations in the ambient temperature. Our theory also makes testable hypotheses for the response of the cluster to external temperature inhomogeneities and suggests strategies for biomimetic thermoregulation.

  6. Electrodynamic properties of fractal clusters

    NASA Astrophysics Data System (ADS)

    Maksimenko, V. V.; Zagaynov, V. A.; Agranovski, I. E.

    2014-07-01

    An influence of interference on a character of light interaction both with individual fractal cluster (FC) consisting of nanoparticles and with agglomerates of such clusters is investigated. Using methods of the multiple scattering theory, effective dielectric permeability of a micron-size FC composed of non-absorbing nanoparticles is calculated. The cluster could be characterized by a set of effective dielectric permeabilities. Their number coincides with the number of particles, where space arrangement in the cluster is correlated. If the fractal dimension is less than some critical value and frequency corresponds to the frequency of the visible spectrum, then the absolute value of effective dielectric permeability becomes very large. This results in strong renormalization (decrease) of the incident radiation wavelength inside the cluster. The renormalized photons are cycled or trapped inside the system of multi-scaled cavities inside the cluster. A lifetime of a photon localized inside an agglomerate of FCs is a macroscopic value allowing to observe the stimulated emission of the localized light. The latter opens up a possibility for creation of lasers without inverse population of energy levels. Moreover, this allows to reconsider problems of optical cloaking of macroscopic objects. One more feature of fractal structures is a possibility of unimpeded propagation of light when any resistance associated with scattering disappears.

  7. Cancer clusters: findings vs feelings.

    PubMed

    Robinson, David

    2002-11-01

    The issue of cancer clusters, which has been in the spotlight recently, is plagued by a wide disparity between public perceptions and scientific findings. Movies like Erin Brockovich have led the public to think that industrial pollution in the environment is causing local "cancer clusters" where cancer cases are more prevalent due to cancer-causing chemicals. There are many scientifically documented instances in which chemical exposure has caused cancer in humans, but the evidence for purely environmental exposures causing cancer is sparse. The clusters that scientists have been able to attribute successfully to a particular cause have been occupational (such as workers in a factory developing a particular type of cancer from daily exposure to a specific chemical), linked to a particular medicine, or linked to behaviors such as smoking or sunbathing. There is some indication that chemicals dissolved in drinking water may elevate the risk of gastrointestinal and bladder/urinary tract cancers and that living next to a smelter or other "point source" of air pollution may elevate risk of lung cancer. The many efforts that have been made to demonstrate links between other types of cancer and environmental contamination have not conclusively identified such links. Several challenges bedevil any cancer cluster investigation and can result in ambiguous or misleading conclusions. This report discusses the potential cancer clusters in Toms River, New Jersey and Long Island, New York, because they contain many elements typical of cancer cluster investigations and have received considerable media attention. PMID:12817212

  8. Collective thermoregulation in bee clusters

    PubMed Central

    Ocko, Samuel A.; Mahadevan, L.

    2014-01-01

    Swarming is an essential part of honeybee behaviour, wherein thousands of bees cling onto each other to form a dense cluster that may be exposed to the environment for several days. This cluster has the ability to maintain its core temperature actively without a central controller. We suggest that the swarm cluster is akin to an active porous structure whose functional requirement is to adjust to outside conditions by varying its porosity to control its core temperature. Using a continuum model that takes the form of a set of advection–diffusion equations for heat transfer in a mobile porous medium, we show that the equalization of an effective ‘behavioural pressure’, which propagates information about the ambient temperature through variations in density, leads to effective thermoregulation. Our model extends and generalizes previous models by focusing the question of mechanism on the form and role of the behavioural pressure, and allows us to explain the vertical asymmetry of the cluster (as a consequence of buoyancy-driven flows), the ability of the cluster to overpack at low ambient temperatures without breaking up at high ambient temperatures, and the relative insensitivity to large variations in the ambient temperature. Our theory also makes testable hypotheses for the response of the cluster to external temperature inhomogeneities and suggests strategies for biomimetic thermoregulation. PMID:24335563

  9. Autophagy selectivity through receptor clustering

    NASA Astrophysics Data System (ADS)

    Rutenberg, Andrew; Brown, Aidan

    Substrate selectivity in autophagy requires an all-or-none cellular response. We focus on peroxisomes, for which autophagy receptor proteins NBR1 and p62 are well characterized. Using computational models, we explore the hypothesis that physical clustering of autophagy receptor proteins on the peroxisome surface provides an appropriate all-or-none response. We find that larger peroxisomes nucleate NBR1 clusters first, and lose them due to competitive coarsening last, resulting in significant size-selectivity. We then consider a secondary hypothesis that p62 inhibits NBR1 cluster formation. We find that p62 inhibition enhances size-selectivity enough that, even if there is no change of the pexophagy rate, the volume of remaining peroxisomes can significantly decrease. We find that enhanced ubiquitin levels suppress size-selectivity, and that this effect is more pronounced for individual peroxisomes. Sufficient ubiquitin allows receptor clusters to form on even the smallest peroxisomes. We conclude that NBR1 cluster formation provides a viable physical mechanism for all-or-none substrate selectivity in pexophagy. We predict that cluster formation is associated with significant size-selectivity. Now at Simon Fraser University.

  10. Identification of Urban Leprosy Clusters

    PubMed Central

    Paschoal, José Antonio Armani; Paschoal, Vania Del'Arco; Nardi, Susilene Maria Tonelli; Rosa, Patrícia Sammarco; Ismael, Manuela Gallo y Sanches; Sichieri, Eduvaldo Paulo

    2013-01-01

    Overpopulation of urban areas results from constant migrations that cause disordered urban growth, constituting clusters defined as sets of people or activities concentrated in relatively small physical spaces that often involve precarious conditions. Aim. Using residential grouping, the aim was to identify possible clusters of individuals in São José do Rio Preto, Sao Paulo, Brazil, who have or have had leprosy. Methods. A population-based, descriptive, ecological study using the MapInfo and CrimeStat techniques, geoprocessing, and space-time analysis evaluated the location of 425 people treated for leprosy between 1998 and 2010. Clusters were defined as concentrations of at least 8 people with leprosy; a distance of up to 300 meters between residences was adopted. Additionally, the year of starting treatment and the clinical forms of the disease were analyzed. Results. Ninety-eight (23.1%) of 425 geocoded cases were located within one of ten clusters identified in this study, and 129 cases (30.3%) were in the region of a second-order cluster, an area considered of high risk for the disease. Conclusion. This study identified ten clusters of leprosy cases in the city and identified an area of high risk for the appearance of new cases of the disease. PMID:24288467

  11. Identification of urban leprosy clusters.

    PubMed

    Paschoal, José Antonio Armani; Paschoal, Vania Del'Arco; Nardi, Susilene Maria Tonelli; Rosa, Patrícia Sammarco; Ismael, Manuela Gallo y Sanches; Sichieri, Eduvaldo Paulo

    2013-01-01

    Overpopulation of urban areas results from constant migrations that cause disordered urban growth, constituting clusters defined as sets of people or activities concentrated in relatively small physical spaces that often involve precarious conditions. Aim. Using residential grouping, the aim was to identify possible clusters of individuals in São José do Rio Preto, Sao Paulo, Brazil, who have or have had leprosy. Methods. A population-based, descriptive, ecological study using the MapInfo and CrimeStat techniques, geoprocessing, and space-time analysis evaluated the location of 425 people treated for leprosy between 1998 and 2010. Clusters were defined as concentrations of at least 8 people with leprosy; a distance of up to 300 meters between residences was adopted. Additionally, the year of starting treatment and the clinical forms of the disease were analyzed. Results. Ninety-eight (23.1%) of 425 geocoded cases were located within one of ten clusters identified in this study, and 129 cases (30.3%) were in the region of a second-order cluster, an area considered of high risk for the disease. Conclusion. This study identified ten clusters of leprosy cases in the city and identified an area of high risk for the appearance of new cases of the disease.

  12. Spectroscopy of the Perseus Cluster

    NASA Technical Reports Server (NTRS)

    Jones, Christine; Mushotzky, Richard F. (Technical Monitor)

    2004-01-01

    We present preliminary results of a XMM-Newton 50 ks observation of the Perseus Cluster that provides an unprecedented view of the central 0.5 Mpc region. The projected gas temperature declines smoothly by a factor of 2 from a maximum value of approx. 7 keV in the outer regions to just above 3 keV at the cluster center. Over this same range, the heavy-element abundance rises slowly from 0.4 to 0.5 solar as the radius decreases from 14 ft. to 5 ft., and then it rises to a peak of almost 0.7 solar at 1&farcm;25 before declining to 0.4 at the center. Th global east-west asymmetry of the gas temperature and surface brightness distributions, approximately aligned with the chain of bright galaxies, suggests an ongoing merger, although the modest degree of the observed asymmetry certainly excludes a major merger interpretation. The chain of galaxies probably traces the filament along which accretion started some time ago and is continuing at the present time. A cold and dense (low-entropy) cluster core like Perseus is probably well "protected" against the penetration of the gas of infalling groups and poor clusters, whereas in non-cooling core clusters such as Coma and A1367, infalling subclusters can penetrate deeply into the core region. In Perseus, gas associated with infalling groups may be stripped completely at the outskirts of the main cluster and only compression waves (shocks) may reach the central regions. We argue, and show supporting simulations, that the passage of such a wave(s) can qualitatively explain the overall horseshoe shaped appearance of the gas temperature map (the hot horseshoe surrounds the colder, low-entropy core) as well as other features of the Perseus Cluster core. These simulations also show that as compression waves traverse the cluster core, they can induce oscillatory motion of the cluster gas that can generate multiple sharp "edges" on opposite sides of the central galaxy. Gas motions induced by mergers may be a natural way to explain

  13. Nonlocalized clustering: a new concept in nuclear cluster structure physics.

    PubMed

    Zhou, Bo; Funaki, Y; Horiuchi, H; Ren, Zhongzhou; Röpke, G; Schuck, P; Tohsaki, A; Xu, Chang; Yamada, T

    2013-06-28

    We investigate the α+^{16}O cluster structure in the inversion-doublet band (Kπ=0(1)±}) states of 20Ne with an angular-momentum-projected version of the Tohsaki-Horiuchi-Schuck-Röpke (THSR) wave function, which was successful "in its original form" for the description of, e.g., the famous Hoyle state. In contrast with the traditional view on clusters as localized objects, especially in inversion doublets, we find that these single THSR wave functions, which are based on the concept of nonlocalized clustering, can well describe the Kπ=0(1)- band and the Kπ=0(1)+ band. For instance, they have 99.98% and 99.87% squared overlaps for 1- and 3- states (99.29%, 98.79%, and 97.75% for 0+, 2+, and 4+ states), respectively, with the corresponding exact solution of the α+16O resonating group method. These astounding results shed a completely new light on the physics of low energy nuclear cluster states in nuclei: The clusters are nonlocalized and move around in the whole nuclear volume, only avoiding mutual overlap due to the Pauli blocking effect.

  14. Cluster Wideband Data Products in the Cluster Active Archive

    NASA Astrophysics Data System (ADS)

    Pickett, J. S.; Seeberger, J. M.; Christopher, I. W.; Santolík, O.; Sigsbee, K. M.

    Cluster Wideband Data (WBD) plasma wave receivers are mounted on all four of the Cluster spacecraft providing approximately 4-7% orbit coverage since mission operations began in February 2001. Data obtained by the WBD instruments are downlinked in real time to various Deep Space Network (DSN) and Panska Ves (PV) ground stations. The strengths of the WBD instruments lie in their high time and frequency resolution data, which allow analysis of the wave fine structure in order to more accurately investigate the linear and nonlinear nature of the waves, and in their use in carrying out Very Long Baseline Interferometry (VLBI) investigations to locate and characterize remote wave sources and their characteristics. The WBD team has already archived at the Cluster Active Archive (CAA) the documentation, software and data plots required for carrying on an independent scientific investigation. A document on interpretation issues has also been archived to help ensure that signals which are not naturally in the plasma are not misinterpreted. The WBD team also plans to archive digital, calibrated data files for the entire mission in cdf format at NASA's CDAWeb and submit these files for conversion to the Cluster standard cef format and archiving at the CAA. In order to ensure that the calibration of the WBD data has been done properly, WBD has taken part in Cluster cross calibration activities with the other wave instruments with regard to wave amplitudes in the time and frequency domains and with the PEACE instruments with regard to low density measurements.

  15. Growth of atmospheric clusters involving cluster-cluster collisions: comparison of different growth rate methods

    NASA Astrophysics Data System (ADS)

    Kontkanen, Jenni; Olenius, Tinja; Lehtipalo, Katrianne; Vehkamäki, Hanna; Kulmala, Markku; Lehtinen, Kari E. J.

    2016-05-01

    We simulated the time evolution of atmospheric cluster concentrations in a one-component system where not only do clusters grow by condensation of monomers, but cluster-cluster collisions also significantly contribute to the growth of the clusters. Our aim was to investigate the consistency of the growth rates of sub-3 nm clusters determined with different methods and the validity of the common approach to use them to estimate particle formation rates. We compared the growth rate corresponding to particle fluxes (FGR), the growth rate derived from the appearance times of clusters (AGR), and the growth rate calculated based on irreversible vapor condensation (CGR). We found that the relation between the different growth rates depends strongly on the external conditions and the properties of the model substance. The difference between the different growth rates was typically highest at the smallest, sub-2 nm sizes. FGR was generally lower than AGR and CGR; at the smallest sizes the difference was often very large, while at sizes larger than 2 nm the growth rates were closer to each other. AGR and CGR were in most cases close to each other at all sizes. The difference between the growth rates was generally lower in conditions where cluster concentrations were high, and evaporation and other losses were thus less significant. Furthermore, our results show that the conventional method used to determine particle formation rates from growth rates may give estimates far from the true values. Thus, care must be taken not only in how the growth rate is determined but also in how it is applied.

  16. Career Clusters. Trends and Issues Alert.

    ERIC Educational Resources Information Center

    Wonacott, Michael E.

    Many states and local districts use career clusters as a means of broadening the focus of secondary education, particularly career and technical education, as preparation for both further education and work. One continuing trend in career clusters is sheer variety. Cluster frameworks vary in the number, nomenclature, and organization of clusters.…

  17. Bayesian Decision Theoretical Framework for Clustering

    ERIC Educational Resources Information Center

    Chen, Mo

    2011-01-01

    In this thesis, we establish a novel probabilistic framework for the data clustering problem from the perspective of Bayesian decision theory. The Bayesian decision theory view justifies the important questions: what is a cluster and what a clustering algorithm should optimize. We prove that the spectral clustering (to be specific, the…

  18. Cluster galaxy evolution with the Las Campanas Distant Cluster Survey

    NASA Astrophysics Data System (ADS)

    Nelson, Amy Elizabeth

    Understanding the formation and evolution of galaxies is a principal goal of modern cosmology. In this thesis, we place constraints on galaxy evolution models using the largest sample of high redshift clusters to date. Our sample consists of 63 clusters at 0.3 ≲ z ≲ 0.9 drawn from the Las Campanas Distant Cluster Survey (LCDCS). This survey differs from traditional optical surveys in that we detect clusters as regions of excess surface brightness relative to the background sky rather than selecting overdensities of resolved galaxies. Therefore, not only does this sample result in a significant increase in the number of known clusters at these redshifts, but because our cluster identification criteria is independent of those utilized in previous surveys, this catalog provides an independent, well-defined sample with which to compare the results of more traditional surveys. In this work, we take a two-pronged approach to studying galaxy evolution. First, we examine the luminosity and color evolution of the bright cluster galaxies as a class. Specifically, we measure the evolution of: (1) M*I , the characteristic luminosity of cluster galaxies, (2) the location of the red envelope in V--I and I--K', and (3) the fraction of blue galaxies (i.e. the Butcher-Oemler effect; Butcher & Oemler 1984). Our data suggest that luminous early type galaxies (or the progenitors of current day early type galaxies) form the bulk of their stellar populations at high redshifts ( ≲ 5) and that many of these galaxies, if not all, experience a short term episode of star formation at lower redshifts (1.5 < z < 2). Second, we narrow the focus and study a single type of cluster galaxy, the brightest cluster galaxy (BCG). We constrain the amount of luminosity and color evolution of BCGs, particularly in the context of recent claims in the literature of significant mass accretion since z ˜ 1 (Aragon-Salamanca 1998; Burke, Collins, & Mann 2000). Consistent with previous results (Burke

  19. A Nonparametric Bayesian Model for Nested Clustering.

    PubMed

    Lee, Juhee; Müller, Peter; Zhu, Yitan; Ji, Yuan

    2016-01-01

    We propose a nonparametric Bayesian model for clustering where clusters of experimental units are determined by a shared pattern of clustering another set of experimental units. The proposed model is motivated by the analysis of protein activation data, where we cluster proteins such that all proteins in one cluster give rise to the same clustering of patients. That is, we define clusters of proteins by the way that patients group with respect to the corresponding protein activations. This is in contrast to (almost) all currently available models that use shared parameters in the sampling model to define clusters. This includes in particular model based clustering, Dirichlet process mixtures, product partition models, and more. We show results for two typical biostatistical inference problems that give rise to clustering. PMID:26519174

  20. Quantum Monte Carlo methods and lithium cluster properties. [Atomic clusters

    SciTech Connect

    Owen, R.K.

    1990-12-01

    Properties of small lithium clusters with sizes ranging from n = 1 to 5 atoms were investigated using quantum Monte Carlo (QMC) methods. Cluster geometries were found from complete active space self consistent field (CASSCF) calculations. A detailed development of the QMC method leading to the variational QMC (V-QMC) and diffusion QMC (D-QMC) methods is shown. The many-body aspect of electron correlation is introduced into the QMC importance sampling electron-electron correlation functions by using density dependent parameters, and are shown to increase the amount of correlation energy obtained in V-QMC calculations. A detailed analysis of D-QMC time-step bias is made and is found to be at least linear with respect to the time-step. The D-QMC calculations determined the lithium cluster ionization potentials to be 0.1982(14) (0.1981), 0.1895(9) (0.1874(4)), 0.1530(34) (0.1599(73)), 0.1664(37) (0.1724(110)), 0.1613(43) (0.1675(110)) Hartrees for lithium clusters n = 1 through 5, respectively; in good agreement with experimental results shown in the brackets. Also, the binding energies per atom was computed to be 0.0177(8) (0.0203(12)), 0.0188(10) (0.0220(21)), 0.0247(8) (0.0310(12)), 0.0253(8) (0.0351(8)) Hartrees for lithium clusters n = 2 through 5, respectively. The lithium cluster one-electron density is shown to have charge concentrations corresponding to nonnuclear attractors. The overall shape of the electronic charge density also bears a remarkable similarity with the anisotropic harmonic oscillator model shape for the given number of valence electrons.