Exploring the utility of organo-polyoxometalate hybrids to inhibit SOX transcription factors

PubMed Central

2014-01-01

Background SOX transcription factors constitute an attractive target class for intervention with small molecules as they play a prominent role in the field of regenerative biomedicine and cancer biology. However, rationally engineering specific inhibitors that interfere with transcription factor DNA interfaces continues to be a monumental challenge in the field of transcription factor chemical biology. Polyoxometalates (POMs) are inorganic compounds that were previously shown to target the high-mobility group (HMG) of SOX proteins at nanomolar concentrations. In continuation of this work, we carried out an assessment of the selectivity of a panel of newly synthesized organo-polyoxometalate hybrids in targeting different transcription factor families to enable the usage of polyoxometalates as specific SOX transcription factor drugs. Results The residual DNA-binding activities of 15 different transcription factors were measured after treatment with a panel of diverse polyoxometalates. Polyoxometalates belonging to the Dawson structural class were found to be more potent inhibitors than the Keggin class. Further, organically modified Dawson polyoxometalates were found to be the most potent in inhibiting transcription factor DNA binding activity. The size of the polyoxometalates and its derivitization were found to be the key determinants of their potency. Conclusion Polyoxometalates are highly potent, nanomolar range inhibitors of the DNA binding activity of the Sox-HMG family. However, binding assays involving a limited subset of structurally diverse polyoxometalates revealed a low selectivity profile against different transcription factor families. Further progress in achieving selectivity and deciphering structure-activity relationship of POMs require the identification of POM binding sites on transcription factors using elaborate approaches like X-ray crystallography and multidimensional NMR. In summary, our report reaffirms that transcription factors are

A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

PubMed

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

2015-02-23

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

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%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

Polyoxometalates: from inorganic chemistry to materials science.

PubMed

Casañ-Pastor, Nieves; Gómez-Romero, Pedro

2004-05-01

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

Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies.

PubMed

Robbins, Philip J; Surman, Andrew J; Thiel, Johannes; Long, De-Liang; Cronin, Leroy

2013-03-07

We present the high-resolution (HRES-MS) and ion-mobility (IMS-MS) mass spectrometry studies of icosahedral nanoscale polyoxometalate-based {L(30)}{(Mo)Mo(5)} Keplerate clusters, and demonstrate the use of IMS-MS to resolve and map intact nanoclusters, and its potential for the discovery of new structures, in this case the first gas phase observation of 'proto-clustering' of higher order Keplerate supramolecular aggregates.

Photoelectron Spectroscopy of Free Multiply Charged Keggin Anions α-[PM12O40]3- (M = Mo, W) in the Gas Phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waters, Tom; Huang, Xin; Wang, Xue B.

2006-09-21

Two polyoxometalate Keggin-type anions, a-PM12O403- (M = Mo, W), were transferred to the gas phase by electrospray; their electronic structure and stability were probed by photoelectron spectroscopy. These triply charged anions were found to be highly stable in the gas phase with large adiabatic electron detachment energies of 1.7 and 2.1 eV for M = Mo and W, respectively. The magnitude of the repulsive Coulomb barrier was measured as ~3.4 eV for both anions, providing an experimental estimate for the intramolecular Coulomb repulsion present in these highly charged anions. Density functional theory calculations were carried out and compared with themore » experimental data, providing insight into the electronic structure and valence molecular orbitals of the two Keggin anions. The calculations indicated that the highest occupied molecular orbital and other frontier orbitals for PM12O403- are localized primarily on the u2-oxo bridging ligands of the polyoxometalate framework, consistent with the reactivity on the u2-oxo sites observed in solution. It was shown that the HOMO of PW12O403- is stabilized relative to that of PMo12O403- by ~0.35 eV. The experimental adiabatic electron detachment energies of PM12O403- (i.e., the electron affinities of PM12O402-) are combined with recent calculations on the proton affinity of PM12O403- to yield O-H bond dissociation energies in PM12O39(OH)2- as ~5.1 eV« less

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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buru, Cassandra T.; Li, Peng; Mehdi, B. Layla

2017-05-22

A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

Oxidation catalysis by polyoxometalates fundamental electron-transfer phenomena

Treesearch

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

2002-01-01

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

Porphyrin-Sensitized Evolution of Hydrogen using Dawson and Keplerate Polyoxometalate Photocatalysts.

PubMed

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

2016-11-23

Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP 4+ ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P 2 Mo 18 O 62 6- and P 2 W 18 O 62 6- anions, and one Keplerate {Mo 132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP 4+ sensitization in relation to the direct photoreduction of those compounds; (b) the P 2 Mo 18 O 62 6- anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P 2 W 18 O 62 6- anion; and (c) the high nuclearity Keplerate {Mo 132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Creating Quasi Two-Dimensional Cluster-Assembled Materials through Self-Assembly of a Janus Polyoxometalate-Silsesquioxane Co-Cluster.

PubMed

Wu, Han; Zhang, Yu-Qi; Hu, Min-Biao; Ren, Li-Jun; Lin, Yue; Wang, Wei

2017-05-30

Clusters are an important class of nanoscale molecules or superatoms that exhibit an amazing diversity in structure, chemical composition, shape, and functionality. Assembling two types of clusters is creating emerging cluster-assembled materials (CAMs). In this paper, we report an effective approach to produce quasi two-dimensional (2D) CAMs of two types of spherelike clusters, polyhedral oligomeric silsesquioxanes (POSS), and polyoxometalates (POM). To avoid macrophase separation between the two clusters, they are covalently linked to form a POM-POSS cocluster with Janus characteristics and a dumbbell shape. This Janus characteristics enables the cocluster to self-assemble into diverse nanoaggregates, as conventional amphiphilic molecules and macromolecules do, in selective solvents. In our study, we obtained micelles, vesicles, nanosheets, and nanoribbons by tuning the n-hexane content in mixed solvents of acetone and n-hexane. Ordered packing of clusters in the nanosheets and nanoribbons were directly visualized using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) technique. We infer that the increase of packing order results in the vesicle-to-sheet transition and the change in packing mode causes the sheet-to-ribbon transitions. Our findings have verified the effectivity of creating quasi 2D cluster-assembled materials though the cocluster self-assembly as a new approach to produce novel CAMs.

Synthesis and strong photooxidation power of a supramolecular hybrid comprising a polyoxometalate and Ru(II) polypyridyl complex with zinc(II).

PubMed

Ohashi, Kenji; Takeda, Hiroyuki; Koike, Kazuhide; Ishitani, Osamu

2015-01-01

A novel method for constructing supramolecular hybrids composed of polyoxometalates and photofunctional metal complexes was developed. A Ru(II) complex with phosphonate groups (RuP) strongly interacted with Zn(II) to afford a 2 : 1 trinuclear metal complex ([(RuP)2Zn](3+)). In dimethylsulfoxide, [(RuP)2Zn](3+) strongly interacted with a Keggin-type heteropolyoxometalate (Si-WPOM) to form a 1 : 1 hybrid ([(RuP)2Zn]-POM). Irradiation of [(RuP)2Zn]-POM in the presence of diethanolamine caused rapid accumulation of the one-electron reduced hybrid with a quantum yield of 0.99.

Adsorption of a catalytically accessible polyoxometalate in a mesoporous channel-type metal–organic framework

DOE PAGES

Buru, Cassandra T.; Li, Peng; Mehdi, B. Layla; ...

2017-05-24

A Keggin-type polyoxometalate (H 3PW 12O 40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW 12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Lastly, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW 12@NU-1000 was shown to have a higher catalytic activity than eithermore » of the individual constituents alone.« less

Dioxygen in Polyoxometalate Mediated Reactions.

PubMed

Weinstock, Ira A; Schreiber, Roy E; Neumann, Ronny

2018-03-14

In this review article, we consider the use of molecular oxygen in reactions mediated by polyoxometalates. Polyoxometalates are anionic metal oxide clusters of a variety of structures that are soluble in liquid phases and therefore amenable to homogeneous catalytic transformations. Often, they are active for electron transfer oxidations of a myriad of substrates and upon reduction can be reoxidized by molecular oxygen. For example, the phosphovanadomolybdate, H 5 PV 2 Mo 10 O 40 , can oxidize Pd(0) thereby enabling aerobic reactions catalyzed by Pd and H 5 PV 2 Mo 10 O 40 . In a similar vein, polyoxometalates can stabilize metal nanoparticles, leading to additional transformations. Furthermore, electron transfer oxidation of other substrates such as halides and sulfur-containing compounds is possible. More uniquely, H 5 PV 2 Mo 10 O 40 and its analogues can mediate electron transfer-oxygen transfer reactions where oxygen atoms are transferred from the polyoxometalate to the substrate. This unique property has enabled correspondingly unique transformations involving carbon-carbon, carbon-hydrogen, and carbon-metal bond activation. The pathway for the reoxidation of vanadomolybdates with O 2 appears to be an inner-sphere reaction, but the oxidation of one-electron reduced polyoxotungstates has been shown through intensive research to be an outer-sphere reaction. Beyond electron transfer and electron transfer-oxygen transfer aerobic transformations, there a few examples of apparent dioxygenase activity where both oxygen atoms are donated to a substrate.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chai, Feng; Chen, YiPing, E-mail: ypchen007@sina.com; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

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 atomsmore » 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.« less

A fluorophosphate-based inverse Keggin structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fielden, John; Quasdorf, Kyle; Cronin, Leroy

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.

A fluorophosphate-based inverse Keggin structure.

PubMed

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

2012-09-07

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.

Formation, isomerization, and derivatization of keggin tungstoaluminates.

Treesearch

Jennifer J. Cowan; Alan J. Bailey; Robert A. Heintz; Bao T. Do; Kenneth I. Hardcastle; Craig L. Hill; Ira A. Weinstock

2001-01-01

Trends in the stability of ¥á and ©¬-Keggin heteropolytungstates of the second-row main-group heteroatoms Al(III), Si(IV), and P(V) are elaborated by data that establish the roles of kinetic and thermodynamic control in the formation and isomerization of Keggin tungstoaluminates. Slow, room-temperature co-...

Iontophoretic transport of associates based on porous Keplerate-type cluster polyoxometalate Mo72Fe30 and containing biologically active substances

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Design and synthesis of polyoxometalate-framework materials from cluster precursors

NASA Astrophysics Data System (ADS)

Vilà-Nadal, Laia; Cronin, Leroy

2017-10-01

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

Electrografting of diazonium-functionalized polyoxometalates: synthesis, immobilisation and electron-transfer characterisation from glassy carbon.

PubMed

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

2013-10-04

Polyoxometalates (POMs) are attractive candidates for the rational design of multi-level charge-storage materials because they display reversible multi-step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control of their immobilisation on various substrates can be achieved. Owing to the wide applicability of the diazonium route to surface modification, a functionalized Keggin-type POM [PW11 O39 {Ge(p-C6 H4 -CC-C6 H4 -${{\\rm N}{{+\\hfill \\atop 2\\hfill}}}$)}](3-) bearing a pending diazonium group was prepared and subsequently covalently anchored onto a glassy carbon electrode. Electron transfer with the immobilised POM was thoroughly investigated and compared to that of the free POM in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Aqueous formation and manipulation of the iron-oxo Keggin ion

NASA Astrophysics Data System (ADS)

Sadeghi, Omid; Zakharov, Lev N.; Nyman, May

2015-03-01

There is emerging evidence that growth of synthetic and natural phases occurs by the aggregation of prenucleation clusters, rather than classical atom-by-atom growth. Ferrihydrite, an iron oxyhydroxide mineral, is the common form of Fe3+ in soils and is also in the ferritin protein. We isolated a 10 angstrom discrete iron-oxo cluster (known as the Keggin ion, Fe13) that has the same structural features as ferrihydrite. The stabilization and manipulation of this highly reactive polyanion in water is controlled exclusively by its counterions. Upon dissolution of Fe13 in water with precipitation of its protecting Bi3+-counterions, it rapidly aggregates to ~22 angstrom spherical ferrihydrite nanoparticles. Fe13 may therefore also be a prenucleation cluster for ferrihydrite formation in natural systems, including by microbial and cellular processes.

Temperature-dependent gel-type ionic liquid compounds based on vanadium-substituted polyoxometalates with Keggin structure.

PubMed

Huang, Tianpei; Xie, Zhirong; Wu, Qingyin; Yan, Wenfu

2016-03-07

A series of temperature-dependent gel-type ionic liquid compounds have been synthesized from 1-(3-sulfonic group) propyl-3-methyl imidazolium (abbreviated as MIMPS) and three vanadium-substituted heteropoly acids H5SiW11VO40, H5SiMo11VO40 and H7SiW9V3O40. The designed and synthesized gel-type polyoxometalate ionic liquids (POM-ILs) have demonstrated a tendency to exhibit a layered structure. Moreover, they can undergo a phase transformation from a viscous gel-state to a liquid-state below 100 °C, and ionic conductivity up to 10(-3) S cm(-1) was observed at 120 °C. Cyclic voltammetry was carried out to study their electrochemical properties in organic solutions, and it was found that the oxidizability of the three POM-ILs decreases in the order: [MIMPS]7SiW9V3O40 > [MIMPS]5SiMo11VO40 > [MIMPS]5SiW11VO40. This result indicates that the redox behavior can be tuned by changing the chemical composition of the heteropolyanions.

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.

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.

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.

Exploring the Molecular Growth of Two Gigantic Half‐Closed Polyoxometalate Clusters {Mo180} and {Mo130Ce6}

PubMed Central

Xuan, Weimin; Pow, Robert; Long, De‐Liang

2017-01-01

Abstract Understanding the process of the self‐assembly of gigantic polyoxometalates and their subsequent molecular growth, by the addition of capping moieties onto the oxo‐frameworks, is critical for the development of the designed assembly of complex high‐nuclearity cluster species, yet such processes remain far from being understood. Herein we describe the molecular growth from {Mo150} and {Mo120Ce6} to afford two half‐closed gigantic molybdenum blue clusters {Mo180} (1) and {Mo130Ce6} (2), respectively. Compound 1 features a hat‐shaped structure with the parent wheel‐shaped {Mo150} being capped by a {Mo30} unit on one side. Similarly, 2 exhibits an elliptical lanthanide‐doped wheel {Mo120Ce6} that is sealed by a {Mo10} unit on one side. Moreover, the observation of the parent uncapped {Mo150} and {Mo120Ce6} clusters as minor products during the synthesis of 1 and 2 strongly suggests that the molecular growth process can be initialized from {Mo150} and {Mo120Ce6} in solution, respectively. PMID:28508585

Spectroscopic Study of the Interaction between Horse Heart Myoglobin and Zirconium(IV)-Substituted Polyoxometalates as Artificial Proteases.

PubMed

Ly, Hong Giang T; Parac-Vogt, Tatjana N

2017-09-20

A recent study [Angew. Chem. Int. Ed. 2015, 54, 7391-7394] has shown that horse heart myoglobin (HHM) is selectively hydrolyzed by a range of zirconium(IV)-substituted polyoxometalates (POMs) under mild conditions. In this study, the molecular interactions between the Zr-POM catalysts and HHM are investigated by using a range of complementary techniques, including circular dichroism (CD), UV/Vis spectroscopy, tryptophan fluorescence spectroscopy, and 1 H and 31 P NMR spectroscopy. A tryptophan fluorescence quenching study reveals that, among all examined Zr-POMs, the most reactive POM, 2:2 Zr IV -Keggin, exhibits the strongest interaction with HHM. 31 P NMR spectroscopy studies show that this POM dissociates in solution, resulting in the formation of a monomeric 1:1 Zr IV -Keggin structure, which is likely to be a catalytically active species. In the presence of Zr IV -POMs, HHM does not undergo complete denaturation, as evidenced by CD, UV/Vis, tryptophan fluorescence, and 1 H NMR spectroscopy. CD spectroscopy shows a gradual decrease in the α-helical content of HHM upon addition of Zr IV -POMs. The largest effect is observed in the presence of a large Zr IV -Wells-Dawson structure, whereas small Zr IV -Lindqvist POM has the least influence on the decrease in the α-helical content of HHM. In all cases, the Soret band at λ=409 nm is maintained in the presence of all examined Zr-POMs, which indicates that no conformational changes in the protein occur near the heme group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hill, Craig L.; Gueletii, Iourii V.; Song, Jie

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

Metal Oxide Supported Vanadium Substituted Keggin Type Polyoxometalates as Catalyst For Oxidation of Dibenzothiophene

NASA Astrophysics Data System (ADS)

Lesbani, Aldes; Novri Meilyana, Sarah; Karim, Nofi; Hidayati, Nurlisa; Said, Muhammad; Mohadi, Risfidian; Miksusanti

2018-01-01

Supported polyoxometalatate H4[γ-H2SiV2W10O40]·nH2O with metal oxide i.e. silica, titanium, and tantalum was successfully synthesized via wet impregnation method to form H4[γ-H2SiV2W10O40]·nH2O-Si, H4[γ-H2SiV2W10O40]·nH2O-Ti, and H4[γ-H2SiV2W10O40]·nH2O-Ta. Characterization was performed using FTIR spectroscopy, X-Ray analyses, and morphology analyses using SEM. All compounds were used as the catalyst for desulfurization of dibenzothiophene (DBT). Silica and titanium supported polyoxometalate H4[γ-H2SiV2W10O40]·nH2O better than tantalum due to retaining crystallinity after impregnation process. On the other hand, compound H H4[γ-H2SiV2W10O40]·nH2O-Ta showed high catalytic activity than other supported metal oxides for desulfurization of DBT. Optimization desulfurization process resulted in 99% conversion of DBT under a mild condition at 70 °C, 0.1 g catalyst, and reaction for 3 hours. Regeneration studies showed catalyst H4[γ-H2SiV2W10O40]·nH2O-Ti was remaining catalytic activity for desulfurization of DBT.

Structure-related frustrated magnetism of nanosized polyoxometalates: aesthetics and properties in harmony.

PubMed

Kögerler, Paul; Tsukerblat, Boris; Müller, Achim

2010-01-07

The structural versatility characterizing polyoxometalate chemistry, in combination with the option to deliberately use well-defined building blocks, serves as the foundation for the generation of a large family of magnetic clusters, frequently comprising highly symmetric spin arrays. If the spin centers are coupled by antiferromagnetic exchange, some of these systems exhibit spin frustration, which can result in novel magnetic properties of purely molecular origins. We discuss here the magnetic properties of selected nanosized polyoxometalate clusters featuring spin triangles as their magnetic 'building blocks' or fragments. This includes unique porous Keplerate clusters of the type {(Mo)Mo(5)}(12)M(30) (M = Fe(III), Cr(III), V(IV)) with the spin centers defining a regular icosidodecahedron and the {V(15)As(6)}-type cluster sphere containing a single equilateral spin triangle; these species are widely discussed and studied in the literature for their role in materials science as molecular representations of Kagomé lattices and in relation to quantum computing, respectively. Exhibiting fascinating and unique structural features, these magnetic molecules allow the study of the implications of frustrated spin ordering. Furthermore, this perspective covers the impact of spin frustration on the degeneracy of the ground state and related problems, namely strong magnetic anisotropy and the interplay of antisymmetric exchange and structural Jahn-Teller effects.

The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions

NASA Astrophysics Data System (ADS)

Li, Mu; Zhang, Mingxin; Wang, Weiyu; Cheng, Stephen Z. D.; Yin, Panchao

2018-05-01

Nano-scaled polyoxometalates (POMs) clusters with sizes ranging from 1 to 10 nm attract tremendous attention and have been extensively studied due to POMs' fascinating structural characteristics and prospects for wide-ranging applications. As a unique class of nanoparticles with well-defined structural topologies and monodispersed masses, the structures and properties of POMs in both bulk state and solutions have been explored with several well-developed protocols. Small-angle X-ray scattering (SAXS) technique, as a powerful tool for studying polymers and nanoparticles, has been recently extended to the investigating of solution behaviors of POMs. In this mini-review, the general principle and typical experimental procedures of SAXS are illustrated first. The applications of SAXS in characterizing POMs' morphology, counterion distribution around POMs, and short-range interactions among POMs in solutions are highlighted. [Figure not available: see fulltext.

Polyoxometalate-based Supramolecular Gel

PubMed Central

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

2013-01-01

Self-assemblyings of surfactant-encapsulated Wells-Dawson polyoxometalates (SEPs) nanobuilding blocks in butanone and esters yielded supramolecular gels showing thermo and photo responsive properties. The gels can be further polymerized if unsaturated esters were used and subsequently electrospinned into nanowires and non-woven mats. The as-prepared non-woven mats have a Young's modulus as high as 542.55 MPa. It is believed that this supramolecular gel is a good platform for polyoxometalates processing. PMID:23666013

Effect of protonation, composition and isomerism on the redox properties and electron (de)localization of classical polyoxometalates

NASA Astrophysics Data System (ADS)

López, Xavier

2017-10-01

This publication reviews some relevant features related with the redox activity of two inorganic compounds: [XM12O40]q- (Keggin structure) and [X2M18O62]q- (Wells-Dawson structure). These are two well-known specimens of the vast Polyoxometalate (POM) family, which has been the subject of extensive experimental and theoretical research owing to their unmatched properties. In particular, their redox activity focus a great deal of attention from scientists due to their prospective related applications. POMs are habitually seen as `electron sponges' since many of them accept several electrons without losing their chemical identity. This makes them excellent models to study mechanisms of electrochemical nature. Their redox properties depend on: (i) the type and number of transition metal atoms in the structure, (ii) the basicity of the first reduced species and, occasionally, of the fully oxidized species; (iii) the size of the molecule, (iv) the overall negative charge of the POM, and (v) the size of the central heteroatom. In the last years, important collaboration between the experimental and theoretical areas has been usual on the development of POM science. In the present chapter three of these synergies are highlighted: the influence of the internal heteroatom upon the redox potentials of Keggin anions; the dependence of the redox waves of Fe-substituted Wells-Dawson compounds with pH; and the role of electron delocalization and pairing in mixed-metal Mo/W Wells-Dawson compounds in their ability to accept electrons. In these three cases, a complete understanding of the problem would not have been possible without the mutual benefit of experimental and computational data.

High-field 95 Mo and 183 W static and MAS NMR study of polyoxometalates.

PubMed

Haouas, Mohamed; Trébosc, Julien; Roch-Marchal, Catherine; Cadot, Emmanuel; Taulelle, Francis; Martineau-Corcos, Charlotte

2017-10-01

The potential of high-field NMR to measure solid-state 95 Mo and 183 W NMR in polyoxometalates (POMs) is explored using some archetypical structures like Lindqvist, Keggin and Dawson as model compounds that are well characterized in solution. NMR spectra in static and under magic angle spinning (MAS) were obtained, and their analysis allowed extraction of the NMR parameters, including chemical shift anisotropy and quadrupolar coupling parameters. Despite the inherent difficulties of measurement in solid state of these low-gamma NMR nuclei, due mainly to the low spectral resolution and poor signal-to-noise ratio, the observed global trends compare well with the solution-state NMR data. This would open an avenue for application of solid-state NMR to POMs, especially when liquid-state NMR is not possible, e.g., for poorly soluble or unstable compounds in solution, and for giant molecules with slow tumbling motion. This is the case of Keplerate where we provide here the first NMR characterization of this class of POMs in the solid state. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Rare Earth Polyoxometalates.

PubMed

Boskovic, Colette

2017-09-19

Longstanding and important applications make use of the chemical and physical properties of both rare earth metals and polyoxometalates of early transition metals. The catalytic, optical, and magnetic features of rare earth metal ions are well-known, as are the reversible multielectron redox and photoredox capabilities of polyoxomolybdates and polyoxotungstates. The combination of rare earth ions and polyoxometalates in discrete molecules and coordination polymers is of interest for the unique combination of chemical and physical properties that can arise. This Account surveys our efforts to synthesize and investigate compounds with rare earth ions and polyoxometalates (RE-POMs), sometimes with carboxylate-based organic coligands. Our general synthetic approach is "bottom-up", which affords well-defined nanoscale molecules, typically in crystalline form and amenable to single-crystal X-ray diffraction for structure determination. Our particular focus is on elucidation of the physical properties conferred by the different structural components with a view to ultimately being able to tune these properties chemically. For this purpose, we employ a variety of spectroscopic, magnetochemical, electrochemical, and scattering techniques in concert with theoretical modeling and computation. Studies of RE-POM single-molecule magnets (SMMs) have utilized magnetic susceptibility, inelastic neutron scattering, and ab initio calculations. These investigations have allowed characterization of the crystal field splitting of the rare earth(III) ions that is responsible for the SMM properties of slow magnetic relaxation and magnetization quantum tunneling. Such SMMs are promising for applications in quantum computing and molecular spintronics. Photophysical measurements of a family of hybrid RE-POMs with organic ligands have afforded insights into sensitization of Tb(III) and Eu(III) emission through both organic and polyoxometalate chromophores in the same molecule. Detailed

Sensitive determination of chlorogenic acid in pharmaceutical products based on the decoration of 3D macroporous carbon with Au nanoparticles via polyoxometalates.

PubMed

Zhang, Tongrui; Liu, Mengjun; Zhang, Qianqian; Wang, Yeyu; Kong, Xiangyi; Wang, Lei; Wang, Huan; Zhang, Yufan

2017-07-10

A simple and sensitive electrochemical sensor is constructed for the detection of chlorogenic acid (CGA) based on Au nanoparticles (NPs)/polyoxometalates/3D macroporous carbon (Au-POMs-MPC). Serving as both a reducing and stabilizing agent, the Keggin-type POM, H 3 PW 12 O 40 , is used for the synthesis of stable colloidal Au NPs and then used to link them to MPC at a mild temperature. Because of the unique structural properties and synergetic catalytic effect, Au-POMs-MPC can be developed as an effective sensing platform for the detection of CGA, which showed high activity and excellent analytical performance towards CGA, such as a wide linear range of 2.28 nM-3.24 μM, a high sensitivity of 30 554.71 μA mM -1 , and a low limit of detection of 2.15 nM. Importantly, the successfully fabricated Au-POMs-MPC device accurately measured the amount of CGA in pharmaceutical samples.

Design and fabrication of memory devices based on nanoscale polyoxometalate clusters

NASA Astrophysics Data System (ADS)

Busche, Christoph; Vilà-Nadal, Laia; Yan, Jun; Miras, Haralampos N.; Long, De-Liang; Georgiev, Vihar P.; Asenov, Asen; Pedersen, Rasmus H.; Gadegaard, Nikolaj; Mirza, Muhammad M.; Paul, Douglas J.; Poblet, Josep M.; Cronin, Leroy

2014-11-01

Flash memory devices--that is, non-volatile computer storage media that can be electrically erased and reprogrammed--are vital for portable electronics, but the scaling down of metal-oxide-semiconductor (MOS) flash memory to sizes of below ten nanometres per data cell presents challenges. Molecules have been proposed to replace MOS flash memory, but they suffer from low electrical conductivity, high resistance, low device yield, and finite thermal stability, limiting their integration into current MOS technologies. Although great advances have been made in the pursuit of molecule-based flash memory, there are a number of significant barriers to the realization of devices using conventional MOS technologies. Here we show that core-shell polyoxometalate (POM) molecules can act as candidate storage nodes for MOS flash memory. Realistic, industry-standard device simulations validate our approach at the nanometre scale, where the device performance is determined mainly by the number of molecules in the storage media and not by their position. To exploit the nature of the core-shell POM clusters, we show, at both the molecular and device level, that embedding [(Se(IV)O3)2]4- as an oxidizable dopant in the cluster core allows the oxidation of the molecule to a [Se(V)2O6]2- moiety containing a {Se(V)-Se(V)} bond (where curly brackets indicate a moiety, not a molecule) and reveals a new 5+ oxidation state for selenium. This new oxidation state can be observed at the device level, resulting in a new type of memory, which we call `write-once-erase'. Taken together, these results show that POMs have the potential to be used as a realistic nanoscale flash memory. Also, the configuration of the doped POM core may lead to new types of electrical behaviour. This work suggests a route to the practical integration of configurable molecules in MOS technologies as the lithographic scales approach the molecular limit.

Elimination-Fusion Self-Assembly of a Nanometer-Scale 72-Nucleus Silver Cluster Caging a Pair of [EuW10 O36 ]9- Polyoxometalates.

PubMed

Zhang, Shan-Shan; Su, Hai-Feng; Wang, Zhi; Wang, Xing-Po; Chen, Wen-Xian; Zhao, Quan-Qin; Tung, Chen-Ho; Sun, Di; Zheng, Lan-Sun

2018-02-06

The largest known polyoxometalate (POM)-templated silver-alkynyl cluster, [(EuW 10 O 36 ) 2 @Ag 72 (tBuC≡C) 48 Cl 2 ⋅4 BF 4 ] (SD/Ag20), was isolated under solvothermal conditions and structurally characterized. It was confirmed by single-crystal X-ray diffraction (SCXRD) as a {EuW 10 } 2 -in-{Ag 72 } clusters-in-cluster rod-like compound. The high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) shows that such a double anion-templated cluster is assembled from a crucial single anion-templated Ag 42 intermediate in the solution. The crystallization of Ag 42 species (SD/Ag21), followed by SCXRD, gave an important clue about the assembly route of SD/Ag20 in solution: the Ag 42 cluster eliminates six silver atoms laterally, then fuses together at the vacant face to form the final Ag 72 cluster (elimination-fusion mechanism). The characteristic emission of [EuW 10 O 36 ] 9- is well maintained in SD/Ag20. This work not only provides a new method for the synthesis of larger silver clusters as well as the functional integration of the silver cluster and POMs, but also gives deep insights about the high-nuclear silver cluster assembly mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Octa- and nonanuclear nickel(II) polyoxometalate clusters: synthesis and electrochemical and magnetic characterizations.

PubMed

Pichon, Céline; Mialane, Pierre; Dolbecq, Anne; Marrot, Jérôme; Rivière, Eric; Bassil, Bassem S; Kortz, Ulrich; Keita, Bineta; Nadjo, Louis; Sécheresse, Francis

2008-12-01

Three high-nuclearity NiII-substituted polyoxometalate compounds functionalized by exogenous ligands have been synthesized and characterized. The octanuclear complexes in Na15[Na{(A-R-SiW9O34)Ni4(CH3COO)3(OH)3}2] . 4NaCl . 36H2O (1) and Na15[Na{(A-R-SiW9O34)Ni4(CH3COO)3(OH)2(N3)}2] . 32H2O (2) can be described as two {Ni4} subunits connected via a {Na(CH3COO)6} group, with the acetato ligands also ensuring in each subunit the connection between the paramagnetic centers. In 2, two azido groups replace two of the six mu-hydroxo ligands present in 1. The nonanuclear complex K7Na7[(A-R-SiW9O34)2Ni9(OH)6(H2O)6(CO3)3] . 42H2O (3) exhibits a double cubanestructure with two [(A-R-SiW9O34)Ni4(OH)3]5- subunits linked by three carbonato ligands. A ninth NiII center connected to one subunit via a carbonato ligand and a O=W group completes this asymmetric polyoxometalate.Electronic spectroscopy and electrochemical studies indicate that, while compounds 1-3 decompose in a pure aqueous medium, these complexes are very stable in a pH 6 acetate medium. The cyclic voltammetry pattern of each complex is constituted by a first eight-electron reduction wave followed by a second large-current intensity wave. The characteristics of the first waves of the complexes are clearly distinct from those obtained for their lacunary precursor [A-R-SiW9O34]10-, a feature that is due to the Ni centers in the complexes. Such observations of electroactive, stable, and highly nickel-rich polyoxometalates are not common. Measurements of the magnetic susceptibility revealed the occurrence of concomitant ferromagnetic and antiferromagnetic interactions in 1 and 3.For both of these compounds, the extension of the magnetic exchange has been determined by means of a spin Hamiltonian with three and four J constants, respectively.

Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water.

PubMed

Zhang, Mingfu; Hao, Jingcheng; Neyman, Alevtina; Wang, Yifeng; Weinstock, Ira A

2017-03-06

Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW 11 O 39 ] 7- (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O 2 ) oxidation of CO to CO 2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O 2 + H 2 O = CO 2 + H 2 O 2 . After control experiments verified that the H 2 O 2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H 2 O 2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K + salts): 1, the Wells-Dawson ion [α-P 2 W 18 O 62 ] 6- (2) and the monodefect Keggin anion [α-SiW 11 O 39 ] 8- (3) revealed that binding energies of electrons in the Au 4f 7/2 and 4f 5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O 2 . Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

Delignification of wood and kraft pulp with polyoxometalates

Treesearch

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

1998-01-01

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

Metal Substitution in Keggin-Type Tridecameric Aluminum-Oxo-Hydroxy Clusters.

PubMed

Parker, Wallace O'Neil; Millini, Roberto; Kiricsi, Imre

1997-02-12

The species resulting from a typical preparation for metal-substituted hybrids of the Keggin tridecamer, Al 13 or [AlO 4 Al 12 (OH) 24 (OH 2 ) 12 ] 7+ , were examined by performing 27 Al NMR on the solutions during aging and by studying the precipitated sulfate salts via solid state 27 Al NMR and powder X-ray diffraction (XRD). Aqueous mixtures (0.25 mol L -1 ) of AlCl 3 and another metal ion (M), in a 12:1 mole ratio (Al:M), where M = Fe 3+ , Zn 2+ , Ga 3+ , In 3+ , Sn 2+ , La 3+ , and Bi 3+ , were subjected to forced hydrolysis by addition of NaOH (1.0 mol L -1 ) until OH/(Al + M) = 2.25, and the kinetics of Al 13 formation and disappearance with aging at 80 °C was monitored by 27 Al NMR spectroscopy. Al 13 units polymerize on aging with an apparent rate constant (k) of 4.8(8) × 10 -2 h -1 to form a species referred to as AlP 2 . Only the solutions containing Ga 3+ and Sn 2+ exhibited faster Al 13 conversion rates. GaAl 12 forms quickly at 80 °C (k = 0.54 h -1 ) and is more stable than AlP 2 . Sn 2+ apparently promotes AlP 2 formation (k = 0.38 h -1 ). XRD and solid state NMR reveal that only the Ga hybrid can be prepared by this method. No hybrid formation was evidenced using M = Mg 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , In 3+ , La 3+ , or Ce 3+ at 25 °C or M = Co 2+ or La 3+ under reflux conditions. Isostructural (cubic symmetry) single crystals were obtained for the sulfate salts of Al 13 and GaAl 12 . Single-crystal XRD analysis of these two polyoxocations provides the first rigorous comparison between them and shows they have very similar structures. The main crystallographic data for Al 13 and GaAl 12 are as follows:  Na[AlO 4 Al 12 (OH) 24 (H 2 O) 12 ](SO 4 ) 4 ·10H 2 O, cubic, F4̄3m, a = 17.856(2) Å, Z = 4; Na[GaO 4 Al 12 (OH) 24 (H 2 O) 12 ](SO 4 ) 4 ·10H 2 O, cubic, F4̄3m, a = 17.869(3) Å, Z = 4. Thus, the greater thermal stability of GaAl 12 cannot be rationalized in terms of the overall geometric considerations, as suggested by

Hybrid Materials Based on the Embedding of Organically Modified Transition Metal Oxoclusters or Polyoxometalates into Polymers for Functional Applications: A Review

PubMed Central

Carraro, Mauro; Gross, Silvia

2014-01-01

The covalent incorporation of inorganic building blocks into a polymer matrix to obtain stable and robust materials is a widely used concept in the field of organic-inorganic hybrid materials, and encompasses the use of different inorganic systems including (but not limited to) nanoparticles, mono- and polynuclear metal complexes and clusters, polyhedral oligomeric silsesquioxanes (POSS), polyoxometalates (POM), layered inorganic systems, inorganic fibers, and whiskers. In this paper, we will review the use of two particular kinds of structurally well-defined inorganic building blocks, namely transition metals oxoclusters (TMO) and polyoxometalates (POM), to obtain hybrid materials with enhanced functional (e.g., optical, dielectric, magnetic, catalytic) properties. PMID:28788659

Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide.

PubMed

Guo, Si-Xuan; Li, Fengwang; Chen, Lu; MacFarlane, Douglas R; Zhang, Jie

2018-04-18

Electrochemical reduction of CO 2 is a promising method to convert CO 2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo 12 O 40 ] 3- (PMo). Metallic Ag is formed upon reduction of Ag + . Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO 2 reduction was evaluated in a CO 2 saturated dimethylformamide medium containing 0.1 M [ n-Bu 4 N]PF 6 and 0.5% (v/v) added H 2 O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO 2 to CO with an onset potential of -1.70 V versus Fc 0/+ , which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90% were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec -1 suggests that rapid formation of *CO 2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO 2 (and presumably CO 2 •- ) and hence promotes the formation of CO 2 •- .

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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.

Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

PubMed

Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

2009-01-01

Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide.

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

PubMed

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

2017-10-12

The answer to the question "Can electron-rich oxygen (O 2- ) withdraw electrons from metal centers?" is seemingly simple, but how the electron population on the M atom behaves when the O-M distance changes is a matter of controversy. A case study has been conducted for Keggin-type polyoxometalate (POM) complexes, and the first-principles electronic structure calculations were carried out not only for real POM species but also for "hypothetical" ones whose heteroatom was replaced with a point charge. From the results of natural population analysis, it was proven that even an electron-rich O 2- , owing to its larger electronegativity as a neutral atom, withdraws electrons when electron redistribution occurs by the change of the bond length. In the case where O 2- coexists with a cation having a large positive charge (e.g., P 5+ (O 2- ) 4 = [PO 4 ] 3- ), the gross electron population (GEP) on the M atom seemingly increases as the O atom comes closer, but this increment in GEP is not due to the role of the O atom but due to a Coulombic effect of the positive charge located on the cation. Furthermore, it was suggested that not GEP but net electron population (NEP) should be responsible for the redox properties.

New Perspectives for Old Clusters: Anderson-Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d-4 f Species.

PubMed

Artetxe, Beñat; Reinoso, Santiago; San Felices, Leire; Lezama, Luis; Gutiérrez-Zorrilla, Juan M; Vicent, Cristian; Haso, Fadi; Liu, Tianbo

2016-03-18

A series of nine [Sb7W36O133Ln3M2(OAc)(H2O)8](17-) heterometallic anions (Ln3M2; Ln=La-Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs-type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9O33} capping unit formed by a planar {MW6O24} fragment to which three {WO2} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ɛ-Keggin cluster. It is shown, for the first time, that classical Anderson-Evans {MW6O24} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk-shaped species is also revealed. The Ln3M2 anions possess chirality owing to a {Sb4O4} cluster being encapsulated in left- or right-handed orientations. Their ability to self-associate in blackberry-type vesicles in solution has been assessed for the Ce3Co2 derivative. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A quantum chemical study of the decomposition of Keggin-structured heteropolyacids.

PubMed

Janik, Michael J; Bardin, Billy B; Davis, Robert J; Neurock, Matthew

2006-03-09

Heterpolyacids (HPAs) demonstrate catalytic activity for oxidative and acid-catalyzed hydrocarbon conversion processes. Deactivation and thermal instability, however, have prevented their widespread use. Herein, ab initio density functional theory is used to study the thermal decomposition of the Keggin molecular HPA structure through the desorption of constitutional water molecules. The overall reaction energy and activation barrier are computed for the overall reaction HnXM12O40-->Hn-2XM12O39+H2O. and subsequently used to predict the effect of HPA composition on thermal stability. For example, the desorption of a constitutional water molecule is found to be increasingly endothermic in the order silicomolybdic acid (H4SiMo12O40)Keggin unit may stabilize the structural defect created by the water desorption, thus suggesting that constitutional water loss is an initial step toward the decomposition into a bulk mixed oxide. The equilibrium concentration of defective Keggin units is determined as a function of temperature and water partial pressure. It is concluded that the loss of constitutional water molecules is a plausible deactivation mechanism of the acid catalyst. The intermediate structures along the decomposition path are proposed as possible active sites for oxidation catalysis. The results presented herein provide molecular level insight into the dynamic nature of the heteropolyacid catalyst structure.

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.…

Preparation and characterization of the nanoporous ultrathin multilayer films based on molybdenum polyoxometalate (Mo 38) n

NASA Astrophysics Data System (ADS)

Wang, L.; Jiang, M.; Wang, E. B.; Duan, L. Y.; Hao, N.; Lan, Y.; Xu, L.; Li, Z.

2003-11-01

Ultrathin multilayer films of the wheel-shaped molybdenum polyoxometalate cluster (Mo 38) n and poly(allylamine hydrochloride)(PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The ((Mo 38) n/PAH) m multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each (Mo 38) n adsorption. The electrochemistry behavior of the film at room temperature was investigated.

Surface induced selective deposition of Dysprosium Polyoxometalate on HOPG surface studied by STM and STS

NASA Astrophysics Data System (ADS)

Costa Milan, David; Pinilla Cienfuegos, Elena; Cardona Serra, Salvador; Coronado Miralles, Eugenio; Untiedt Lecuona, Carlos

2013-03-01

Scanning Tunneling Microscope (STM) and scanning Tunnelling spectroscopy (STS) techniques have been used to study the Preyssler type Polyoxometalate K12[DyP5W30O110] molecules deposited on Highly Oriented Pyrolytic Graphite surface (HOPG). Chainlike arrangements of clusters containing two or three molecules, as well as different cluster sizes are observed. As many structural artifacts are present on the graphite surface, like Moiré patterns, that could look like the molecular deposits, we have studied their STS and size to ensure the presence of the POM molecules on the surface. This article shows the possibility of addressing POMs on a flat surface to obtain their electronic properties through STS.

[New iron-porphyrin/vanadium-substituted polyoxometalate catalyst: synthesis, characterization and catalytic activity].

PubMed

Dong, Xiao-li; Zhang, Zhen-cheng; An, Qing-da; Zhang, Shao-yin; Wang, Shao-jun

2007-12-01

A new kind of iron-porphyrin/vanadium-substituted polyoxometalate coordination compound was synthesized by the ion exchange reaction of FeTTMAPPI and H5PMo10V2o40 in solution. The new catalyst was characterized by IR spectrometry and UV-Vis spectrometry. As an excellent catalyst, its effects on benzene hydroxylation and catalytic capabilities were studied with H2O2 solution as the oxidant. The results indicated that the products contained the conjugated structure of porphyrin and the cage structure of polyoxometalate, the V atom in polyoxometalate is the main centre of catalytic activity, meanwhile the presence of iron-porphyrin could increase its catalytic activity greatly.

A Novel Dimeric Ni-Substituted beta-Keggin Silicotungstate: Structure and Magnetic Properties of K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O.

PubMed

Kortz, Ulrich; Jeannin, Yves P.; Tézé, André; Hervé, Gilbert; Isber, Samih

1999-08-09

The novel dimeric polyoxometalate [{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)](12)(-) (1) has been synthesized and characterized by IR spectroscopy, polarography, elemental analysis, thermogravimetric analysis, and magnetic measurements. An X-ray single-crystal analysis was carried out on K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O, which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.701(4) Å, b = 24.448(11) Å, c = 13.995(5) Å, beta = 99.62(3) degrees, and Z = 4. The anion consists of two [beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)] Keggin moieties linked via two OH bridging groups, leading to a planar Ni(2)(OH)(2) unit. The two half-units are related by an inversion center and each contain one Ni atom in the rotated triad. The formation of the new anion involves insertion, isomerization, and dimerization. Magnetic measurements show that the central Ni(4) unit exhibits ferromagnetic (J' = 4.14 cm(-)(1)) as well as weak antiferromagnetic (J = -0.65 cm(-)(1)) Ni-Ni exchange interactions.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Convenient synthesis of Cu3(BTC)2 encapsulated Keggin heteropolyacid nanomaterial for application in catalysis.

PubMed

Wee, Lik H; Bajpe, Sneha R; Janssens, Nikki; Hermans, Ive; Houthoofd, Kristof; Kirschhock, Christine E A; Martens, Johan A

2010-11-21

Nanomaterial of Cu(3)(BTC)(2) (BTC = benzene tricarboxylic acid) incorporating Keggin heteropolyacid conveniently prepared at room temperature and recovered by freeze drying outperforms ultrastable Y zeolite in acid catalysed esterification reaction.

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces.

PubMed

Aguado-Ureta, Saioa; Rodríguez-Hernández, Juan; Del Campo, Adolfo; Perez-Álvarez, Leyre; Ruiz-Rubio, Leire; Vilas, José Luis; Artetxe, Beñat; Reinoso, Santiago; Gutiérrez-Zorrilla, Juan M

2018-03-02

Herein we describe the preparation of hybrid polymer-inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene- b -poly(acrylic acid)/polystyrene (PS- b -PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [Ln III (α-SiW 11 O 39 )] 5- polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface.

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

PubMed Central

Aguado-Ureta, Saioa; Rodríguez-Hernández, Juan; del Campo, Adolfo; Perez-Álvarez, Leyre

2018-01-01

Herein we describe the preparation of hybrid polymer–inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [LnIII(α-SiW11O39)]5− polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface. PMID:29498656

Atypical titration curves for GaAl12 Keggin-ions explained by a joint experimental and simulation approach

NASA Astrophysics Data System (ADS)

Sulpizi, Marialore; Lützenkirchen, Johannes

2018-06-01

Although they have been widely used as models for oxide surfaces, the deprotonation behaviors of the Keggin-ions (MeAl127+) and typical oxide surfaces are very different. On Keggin-ions, the deprotonation occurs over a very narrow pH range at odds with the broad charging curve of larger oxide surfaces. Depending on the Me concentration, the deprotonation curve levels off sooner (high Me concentration) or later (for low Me concentration). The leveling off shows the onset of aggregation before which the Keggin-ions are present as individual units. We show that the atypical titration data previously observed for some GaAl12 solutions in comparison to the originally reported data can be explained by the presence of Ga2Al11 ions. The pKa value of aquo-groups bound to octahedral Ga was determined from ab initio molecular dynamics simulations relative to the pure GaAl12 ions. Using these results within a surface complexation model, the onset of deprotonation of the crude solution is surprisingly well predicted and the ratio between the different species is estimated to be in the proportion 20 (Ga2Al11) : 20 (Al13) : 60 (GaAl12).

Design of hydrophobic polyoxometalate hybrid assemblies beyond surfactant encapsulation.

PubMed

Song, Yu-Fei; McMillan, Nicola; Long, De-Liang; Thiel, Johannes; Ding, Yulong; Chen, Haisheng; Gadegaard, Nikolaj; Cronin, Leroy

2008-01-01

Grafting of C-6, C-16 and C-18 alkyl chains onto the hydrophilic Mn-Anderson clusters (compounds 2-4) has been achieved. Exchange of the tetrabutyl ammonium (TBA) with dimethyldioctadecyl ammonium (DMDOA) results in the formation of new polyoxometalate (POM) assemblies (compounds 5-6), in which the POM cores are covalently functionalized by hydrophilic alkyl-chains and enclosed by surfactant of DMDOABr. As a result, we have been able to design and synthesize POM-containing hydrophobic materials beyond surfactant encapsulation. In solid state, scanning electron and transmission electron microscopy (SEM and TEM) studies of the TBA salts of compounds 3 and 4 show highly ordered, uniform, reproducible assemblies with unique segmented rodlike morphology. SEM and TEM studies of the DMDOA salts of compounds 5 and 6 show that they form spherical and sea urchin 3D objects in different solvent systems. In solution, the physical properties of compound 5 and 6 (combination of surfactant-encapsulated cluster (SEC) and surface-grafted cluster (SGC)) show a liquid-to-gel phase transition in pure chloroform below 0 degrees C, which are much lower than other reported SECs. By utilizing light scattering measurements, the nanoparticle size for compounds 5 and 6 were measured at 5 degrees C and 30 degrees C, respectively. Other physical properties including differential scanning calorimetry have been reported.

Recent advances in polyoxometalate based delignification

Treesearch

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

1999-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gunaratne, Kalupathirannehelage Don D.; Johnson, Grant E.; Andersen, Amity

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 chargedmore » 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.« less

Tungsten Speciation and Solubility in Munitions-Impacted Soils.

PubMed

Bostick, Benjamín C; Sun, Jing; Landis, Joshua D; Clausen, Jay L

2018-02-06

Considerable questions persist regarding tungsten geochemistry in natural systems, including which forms of tungsten are found in soils and how adsorption regulates dissolved tungsten concentrations. In this study, we examine tungsten speciation and solubility in a series of soils at firing ranges in which tungsten rounds were used. The metallic, mineral, and adsorbed forms of tungsten were characterized using X-ray absorption spectroscopy and X-ray microprobe, and desorption isotherms for tungsten in these soils were used to characterize its solid-solution partitioning behavior. Data revealed the complete and rapid oxidation of tungsten metal to hexavalent tungsten(VI) and the prevalence of adsorbed polymeric tungstates in the soils rather than discrete mineral phases. These polymeric complexes were only weakly retained in the soils, and porewaters in equilibrium with contaminated soils had 850 mg L -1 tungsten, considerably in excess of predicted solubility. We attribute the high solubility and limited adsorption of tungsten to the formation of polyoxometalates such as W 12 SiO 40 4- , an α-Keggin cluster, in soil solutions. Although more research is needed to confirm which of such polyoxometalates are present in soils, their formation may not only increase the solubility of tungsten but also facilitate its transport and influence its toxicity.

Synthesis and Molecular Structure of a Novel Compound Containing a Carbonate-Bridged Hexacalcium Cluster Cation Assembled on a Trimeric Trititanium(IV)-Substituted Wells-Dawson Polyoxometalate.

PubMed

Hoshino, Takahiro; Isobe, Rina; Kaneko, Takuya; Matsuki, Yusuke; Nomiya, Kenji

2017-08-21

A novel compound containing a hexacalcium cluster cation, one carbonate anion, and one calcium cation assembled on a trimeric trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM), [{Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 }(P 2 W 15 Ti 3 O 61 ) 3 Ca(OH 2 ) 3 ] 19- (Ca 7 Ti 9 Trimer), was obtained as the Na 7 Ca 6 salt (NaCa-Ca 7 Ti 9 Trimer) by the reaction of calcium chloride with the monomeric trititanium(IV)-substituted Wells-Dawson POM species "[P 2 W 15 Ti 3 O 59 (OH) 3 ] 9- " (Ti 3 Monomer). Ti 3 Monomer was generated in situ under basic conditions from the separately prepared tetrameric species with bridging Ti(OH 2 ) 3 groups and an encapsulated Cl - ion, [{P 2 W 15 Ti 3 O 59 (OH) 3 } 4 {μ 3 -Ti(H 2 O) 3 } 4 Cl] 21- (Ti 16 Tetramer). The Na 7 Ca 6 salt of Ca 7 Ti 9 Trimer was characterized by complete elemental analysis, thermogravimetric (TG) and differential thermal analyses (DTA), FTIR, single-crystal X-ray structure analysis, and solution 183 W and 31 P NMR spectroscopy. X-ray crystallography revealed that the [Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 ] 9+ cluster cation was composed of six calcium cations linked by one μ 6 -carbonato anion and one μ 3 -OH - anion. The cluster cation was assembled, together with one calcium ion, on a trimeric species composed of three tri-Ti(IV)-substituted Wells-Dawson subunits linked by Ti-O-Ti bonds. Ca 7 Ti 9 Trimer is an unprecedented POM species containing an alkaline-earth-metal cluster cation and is the first example of alkaline-earth-metal ions clustered around a titanium(IV)-substituted POM.

Synthesis and characterization of a new porphyrin-polyoxometalate hybrid material and investigation of its catalytic activity.

PubMed

Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

2012-03-14

In the present work, the preparation of a new organic-inorganic hybrid material in which tetrakis(p-aminophenylporphyrin) is covalently linked to a Lindqvist structure of polyoxometalate, is reported. This new porphyrin-polyoxometalate hybrid material was characterized by (1)H NMR, FT-IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided spectral data of the synthesis of this compound. Cyclic voltammetry showed the influence of the porphyrin on the redox process of the polyoxometalate. The catalytic activity of this hybrid material was investigated in the alkene epoxidation with NaIO(4).

Stable graphene-polyoxometalate nanomaterials for application in hybrid supercapacitors.

PubMed

Suárez-Guevara, Jullieth; Ruiz, Vanesa; Gómez-Romero, Pedro

2014-10-14

We report the synthesis of hybrid supercapacitor electrodes by a novel reduction of GO with simultaneous incorporation of polyoxometalate. These hybrids show a 30% increase in specific capacitance and excellent stability after 10,000 cycles.

New porphyrin-polyoxometalate hybrid materials: synthesis, characterization and investigation of catalytic activity in acetylation reactions.

PubMed

Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

2012-10-14

New hybrid complexes based on covalent interaction between 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatozinc(II) and 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatotin(IV) chloride, and a Lindqvist-type polyoxometalate, Mo(6)O(19)(2-), were prepared. These new porphyrin-polyoxometalate hybrid materials were characterized by (1)H NMR, FT IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided several spectral data for synthesis of these compounds. Cyclic voltammetry showed the influence of the polyoxometalate on the redox process of the porphyrin ring. The catalytic activity of tin(IV)porphyrin-hexamolybdate hybrid material was investigated in the acetylation of alcohols and phenols with acetic anhydride. The reusability of this catalyst was also investigated.

27Al MQMAS of the δ-Al 13-Keggin

DOE PAGES

Pilgrim, C. D.; Callahan, J. R.; Colla, C. A.; ...

2017-01-20

Here, one-dimensional 27Al, 23Na Magic-Angle-Spinning (MAS) NMR and 27Al Multiple-Quantum Magic-Angle-Spinning NMR (MQMAS) measurements are reported for the δ-isomer of the Al 13 Keggin structure at high spinning speed and 14.1 T field. Values for the CQ and η parameters are on the same scale as those seen in other isomers of the Al 13 structure. Density functional theory (DFT) calculations are performed for comparison to the experimental fits using the B3PW91/6-31+G* and PBE0/6-31+G* levels of theory, with the Polarizable Continuum Model (PCM).

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

Treesearch

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

2000-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Andersen, Amity

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, PW12O403- (WPOM3-) and PW12O402- (WPOM2-), 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 WPOM3- was soft-landed onto the fluorinated SAM (FSAM), while the charge state distribution was dominated by the 2- charge after both WPOM3- and WPOM2- were deposited ontomore » a hydrophilic alkylthiol SAM terminated with cationic NH3+ functional groups (NH3+SAM). We found that during the course of the soft landing of WPOM3-, the relative abundance of WPOM3- on FSAM decreased while that of WPOM2- increased. We propose that the higher stability of immobilized WPOM2- in comparison with WPOM3- 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.« less

Accurately tuning the charge on giant polyoxometalate type Keplerates through stoichiometric interaction with cationic surfactants.

PubMed

Kistler, Melissa L; Patel, Komal G; Liu, Tianbo

2009-07-07

We report an approach of exploring the interaction between cationic surfactants and a type of structurally well-defined, spherical "Keplerate" polyoxometalate (POM) macroanionic molecular clusters, {Mo72V30}, in aqueous solution. The effectiveness of the interaction can be determined by monitoring the size change of the "blackberry" supramolecular structures formed by the self-assembly of {Mo72V30} macroions, which is determined by the effective charge density on the macroions. Long-chain surfactants (CTAB and CTAT) can interact with {Mo72V30} macroions stoichiometrically and lower their charge density. Consequently, the blackberry size decreases continuously with increasing surfactant concentration in solution. On the other hand, for short-chain surfactants (e.g., OTAB), a larger fraction of surfactants exist as discrete chains in solution and do not strongly interact with the macroions. This approach shows that a controllable amount of suitable surfactants can accurately tune the charge on large molecular clusters.

Nucleophilic substitution reaction for post-functionalization of polyoxometalates

DOE PAGES

Yin, Panchao; Li, Qiang; Zhang, Jin; ...

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.

Electrochemical delignification of wood pulp using polyoxometalate mediators

Treesearch

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

2003-01-01

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

Closed-mill delignification by design using polyoxometalates

Treesearch

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

1999-01-01

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

Polyoxometalates as antitumor agents: Bioactivity of a new polyoxometalate with copper on a human osteosarcoma model.

PubMed

León, I E; Porro, V; Astrada, S; Egusquiza, M G; Cabello, C I; Bollati-Fogolin, M; Etcheverry, S B

2014-10-05

Polyoxometalates (POMs) are early transition metal oxygen anion clusters. They display interesting biological effects mainly related to their antiviral and antitumor properties. On the other hand, copper compounds also show different biological and pharmacological effects in cell culture and in animal models. We report herein for the first time, a detailed study of the mechanisms of action of a copper(II) compound of the group of HPOMs with the formula K7Na3[Cu4(H2O)2(PW9034)2]20H2O (PW9Cu), in a model of human osteosarcoma derived cell line, MG-63. The compound inhibited selectively the viability of the osteosarcoma cells in the range of 25-100μM (p<0.01). Besides, we have clearly shown a more deleterious action of PW9Cu on tumor osteoblasts than in normal cells. Cytotoxicity studies also showed deleterious effects for PW9Cu. The increment of reactive oxygen species (ROS) and the decrease of the GSH/GSSG ratio were involved in the antiproliferative effects of PW9Cu. Moreover, the compound caused cell cycle arrest in G2 phase, triggering apoptosis as determined by flow cytometry. As a whole, these results showed the main mechanisms of the deleterious effects of PW9Cu in the osteosarcoma cell line MG-63, demonstrating that this compound is a promissory agent for cancer treatments. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

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.

Formation, isomerization, and derivatization of Keggin tungstoaluminates.

PubMed

Cowan, J J; Bailey, A J; Heintz, R A; Do, B T; Hardcastle, K I; Hill, C L; Weinstock, I A

2001-12-17

Trends in the stability of alpha- and beta-Keggin heteropolytungstates of the second-row main-group heteroatoms Al(III), Si(IV), and P(V) are elaborated by data that establish the roles of kinetic and thermodynamic control in the formation and isomerization of Keggin tungstoaluminates. Slow, room-temperature co-condensation of Al(III) and W(VI) (2:11 molar ratio) in water gives a pH 7 solution containing beta(1) and beta(2) isomers of [Al(AlOH(2))W(11)O(39)](6)(-) (beta(1)- and beta(2)-1). Partial equilibration of this kinetic product mixture by gentle heating (2 h at 100 degrees C) or, alternatively, co-condensation of Al(III) and W(VI) for 2.5 h at 100 degrees C both give mixtures of beta(2)-, beta(3)-, and alpha-1. Full equilibration, by prolonged heating (25 days at 100 degrees C), gives an isomerically pure solution of alpha-1, thus demonstrating that isomerization occurs in the direction beta(1) --> beta(2) --> beta(3) --> alpha. Furthermore, kinetically controlled conversions of 1 to H(5)[AlW(12)O(40)] (2)-achieved by heating pH 0-0.2 solutions of 1 for 5 days at 100 degrees C-occur with retention of isomeric integrity, such that alpha-1 is converted to alpha-2 (92%; 8% beta), while mixtures of beta(2)- and beta(3)-1 are converted to beta-2 (87%; 13% alpha). These data, when combined with previously reported observations (equilibria between alpha- and beta-2, kinetically controlled hydrolyses of alpha-2 to alpha-[AlW(11)O(39)](9)(-) (alpha-3) and of beta-2 to beta(2)-3, and equilibria between beta(3)- and alpha-3), provide a comprehensive picture regarding the roles of kinetic and thermodynamic control. Finally, a general method for preparation of the isomerically pure derivatives alpha-K(9)(-)(n)()[AlM(n)()(+)W(11)O(39)] (4), M(n)()(+) = Al(III), [V(IV)O](2+), [V(V)O](3+), Mn(II), Mn(III), Mn(IV), Co(II), and Co(III), is provided. The presence of Mn(IV) is confirmed by cyclic voltammetry, pK(a) values of the aquo ligands on 4 are determined by pH titration

{Nb288O768(OH)48(CO3)12}: A Macromolecular Polyoxometalate with Niobium Atoms Close to 300.

PubMed

Wu, Yan-Lan; Li, Xin-Xiong; Qi, Yan-Jie; Yu, Hao; Jin, Lu; Zheng, Shou-Tian

2018-05-29

A protein-sized (ca. 4.2 ᵡ 4.2 ᵡ 3.6 nm3) non-biologically derived molecule {Nb288O768(OH)48(CO3)12} (Nb288) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb288 is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb288 can be described as a giant windmill-like cluster aggregate of six brand-new, nanoscale high-nuclearity PONb units {Nb47O128(OH)6(CO3)2} (Nb47) joined together by six additional Nb ions. Interestingly, the in situ generated 47-nuclearity Nb47 units can be isolated and bridged by copper complexes to form an inorganic-organic hybrid three-dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb47 cluster also provides a new type of topology to very limited family of Nb-O clusters. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao Yuanzhe; College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, Hebei 050016; Xu Yanqing, E-mail: xyq@bit.edu.c

2010-05-15

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

Controllable Synthesis and Catalytic Performance of Nanocrystals of Rare-Earth-Polyoxometalates.

PubMed

Li, Shujun; Zhou, Yanfang; Peng, Qingpo; Wang, Ruoya; Feng, Xiaoge; Liu, Shuxia; Ma, Xiaoming; Ma, Nana; Zhang, Jie; Chang, Yi; Zheng, Zhiping; Chen, Xuenian

2018-06-04

Large-scale isolation of nanocrystals of rare-earth-polyoxometalates (RE-POMs) catalysts is important in fundamental research and applications. Here, we synthesized a family of monomeric RE-POMs by the self-assembly of Ta/W mixed-addendum POM {P 2 W 15 Ta 3 O 62 } and rare-earth (RE) ions. These RE-POMs with molecular formulas of [RE(H 2 O) 7 ] 3 P 2 W 15 Ta 3 O 62 · nH 2 O (RE = Y, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) are all electroneutral molecular clusters, insoluble in water and common organic solvents. The electronic structures, electrochemical properties, and catalytic activities of them have been investigated by experimental and computational methods. In particular, based on a mild and controllable synthetic process, a convenient and controllable approach to prepare nanocrystals and self-organized aggregates of these monomers has been developed. They exhibit remarkable heterogeneous catalytic activity for cyanosilylation. Both the increased Lewis acid strength of RE in the title compounds, as indicated by theoretical calculations, and the decreased particle size contribute to their high catalytic performances.

Probing Polyoxometalate-Protein Interactions Using Molecular Dynamics Simulations.

PubMed

Solé-Daura, Albert; Goovaerts, Vincent; Stroobants, Karen; Absillis, Gregory; Jiménez-Lozano, Pablo; Poblet, Josep M; Hirst, Jonathan D; Parac-Vogt, Tatjana N; Carbó, Jorge J

2016-10-17

The molecular interactions between the Ce IV -substituted Keggin anion [PW 11 O 39 Ce(OH 2 ) 4 ] 3- (CeK) and hen egg-white lysozyme (HEWL) were investigated by molecular dynamics simulations. The analysis of CeK was compared with the Ce IV -substituted Keggin dimer [(PW 11 O 39 ) 2 Ce] 10- (CeK 2 ) and the Zr IV -substituted Lindqvist anion [W 5 O 18 Zr(OH 2 )(OH)] 3- (ZrL) to understand how POM features such as shape, size, charge, or type of incorporated metal ion influence the POM⋅⋅⋅protein interactions. Simulations revealed two regions of the protein in which the CeK anion interacts strongly: cationic sites formed by Arg21 and by Arg45 and Arg68. The POMs chiefly interact with the side chains of the positively charged (arginines, lysines) and the polar uncharged residues (tyrosines, serines, aspargines) via electrostatic attraction and hydrogen bonding with the oxygen atoms of the POM framework. The CeK anion shows higher protein affinity than the CeK 2 and ZrL anions, because it is less hydrophilic and it has the right size and shape for establishing interactions with several residues simultaneously. The larger, more negatively charged CeK 2 anion has a high solvent-accessible surface, which is sub-optimal for the interaction, while the smaller ZrL anion is highly hydrophilic and cannot efficiently interact with several residues simultaneously. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of polymolybdate adsorbates on electrooxidation of ethanol at PtRu nanoparticles: Combined electrochemical, mass spectrometric and X-ray photoelectron spectroscopic studies

NASA Astrophysics Data System (ADS)

Gralec, Barbara; Lewera, Adam; Kulesza, Pawel J.

2016-05-01

The role Keggin-type phosphomolybdate (PMo12O403-) ions (adsorbed on carbon-supported PtRu, PtRu/C) on electrooxidation of ethanol is addressed here. The combined results obtained using Differential Electrochemical Mass Spectrometry, X-ray Photoelectron Spectroscopy and Cyclic Voltammetry are consistent with the view that presence of the Keggin-type polyoxometallate, phosphomolybdate, ions (adsorbates) leads to enlargement of the current densities associated with electrooxidation of ethanol at potentials greater than 700 mV vs. RHE. This increase of the anodic currents is correlated with the higher acetaldehyde yield which is likely to reflect changes in the reaction kinetics (e.g. more dynamic dehydrogenation of ethanol leading to acetaldehyde) or in the reaction mechanism defined by the preferential surface modification resulting not only in faster kinetics but also in higher selectivity with respect to acetaldehyde production. It is apparent from the spectroscopic data that modification of PtRu/C nanoparticles with phosphomolybdate ions leads to suppression of the formation of Ru surface oxides.

Charge Effect on the Formation of Polyoxometalate-Based Supramolecular Polygons Driven by Metal Coordination.

PubMed

Piot, Madeleine; Hupin, Sébastien; Lavanant, Hélène; Afonso, Carlos; Bouteiller, Laurent; Proust, Anna; Izzet, Guillaume

2017-07-17

The metal-driven self-assembly of a Keggin-based hybrid bearing two remote pyridine units was investigated. The resulting supramolecular species were identified by combination of 2D diffusion NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS) as a mixture of molecular triangles and squares. This behavior is different from that of the structural analogue Dawson-based hybrid displaying a higher charge, which only led to the formation of molecular triangles. This study highlights the decisive effect of the charge of the POMs in their self-assembly processes that disfavors the formation of large assemblies. An isothermal titration calorimetry (ITC) experiment confirmed the stronger binding in the case of the Keggin hybrids. A correlation between the diffusion coefficient D and the molecular mass M of the POM-based building block and its coordination oligomers was also observed. We show that the diffusion coefficient of these compounds is mainly determined by their occupied volume rather than by their shape.

Progress in the development and optimization of polyoxometalate delignification systems

Treesearch

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

2002-01-01

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

Progress in the development and optimization of polyoxometalate delignification systems

Treesearch

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

2003-01-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sadeghi, Omid; Falaise, Clément; Molina, Pedro I.

The iron Keggin ion is identified as a structural building block in both magnetite and ferrihydrite, two important iron oxide phases in nature and in technology. Discrete molecular forms of the iron Keggin ion that can be both manipulated in water and chemically converted to the related metal oxides are important for understanding growth mechanisms, in particular non-classical nucleation in which cluster building units are preserved in the aggregation and condensation processes. Here we describe two iron Keggin ion structures, formulated [Bi6FeO4Fe12O12(OH)12(CF3COO)10(H2O)2]3+ and [Bi6FeO4Fe12O12(OH)12(CF3COO)12]1+. Experimental and simulated X-ray scattering studies show indefinite stability of these clusters in water from pHmore » 1-3. The tridecameric iron Keggin-ion core is protected from hydrolysis by a synergistic effect of the capping Bi3+-cations and the trifluoroacetate ligands that respectively bond to the iron and bridge to the bismuth. By introducing electrons to the aqueous solution of clusters, we achieve complete separation of bismuth from the cluster, and the iron Keggin ion rapidly converts to magnetite and/or ferrihydrite, depending on the mechanism of reduction. In this strategy, we take advantage of the easily accessible reduction potential and crystallization energy of bismuth. Reduction was executed in bulk by chemical means, by voltammetry, and by secondary effects of transmission electron microscopy imaging of solutions. Prior, we showed a less stable analogue of the iron Keggin cluster converted to ferrihydrite simply upon dissolution. The prior and currently studied clusters with a range of reactivity provide a chemical system to study molecular cluster metal oxide conversion processes in detail.« less

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

PubMed

Veen, Sandra J; Kegel, Willem K

2009-11-19

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

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).

Microcapsule Structure with a Tunable Textured Surface via the Assembly of Polyoxomolybdate Clusters: A Bioinspired Strategy and Enhanced Activities in Alkene Oxidation.

PubMed

Chilivery, Rakesh; Rana, Rohit Kumar

2017-01-25

A polyamine-mediated bioinspired strategy to assemble Keggin-type phosphomolybdic acid (PMA) clusters is demonstrated for the fabrication of microcapsule (MC) structures with unique surface textures. It involves supramolecular aggregation of polyamines with multivalent anions, which then allows the assembly of negatively charged PMA into MCs in an aqueous medium under ambient conditions. Resembling the role of polyamines in biosilicification of diatoms, the polyamine-anion interaction is shown to be the key for the assembly process. It not only provides structural stability but also facilitates an interesting transition from a smooth to a wrinkled surface alongside a change in the Keggin form to its lacunary form depending on the pH of the medium. Moreover, the presence of isolated PMA units in the hybrid structure enables them to be active in catalyzing the aerobic oxidation of alkenes under solvent-free conditions with better selectivity and reusability. Hence, the assembly approach represents an effective way for heterogenization of PMA-based materials and is expected to find considerable application in the wider hybrid-cluster field.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klonowski, P; Goloboy, JC; Uribe-Romo, FJ

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 anionmore » salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.« less

Polyoxometalate delignification of birch kraft pulp and effect on residual lignin

Treesearch

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

2011-01-01

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

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.

Human versus Robots in the Discovery and Crystallization of Gigantic Polyoxometalates.

PubMed

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

2017-08-28

The discovery of new gigantic molecules formed by self-assembly and crystal growth is challenging as it combines two contingent events; first is the formation of a new molecule, and second its crystallization. Herein, we construct a workflow that can be followed manually or by a robot to probe the envelope of both events and employ it for a new polyoxometalate cluster, Na 6 [Mo 120 Ce 6 O 366 H 12 (H 2 O) 78 ]⋅200 H 2 O (1) which has a trigonal-ring type architecture (yield 4.3 % based on Mo). Its synthesis and crystallization was probed using an active machine-learning algorithm developed by us to explore the crystallization space, the algorithm results were compared with those obtained by human experimenters. The algorithm-based search is able to cover ca. 9 times more crystallization space than a random search and ca. 6 times more than humans and increases the crystallization prediction accuracy to 82.4±0.7 % over 77.1±0.9 % from human experimenters. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Polyoxometalate coordination induced controllable release of quinolone in hybrid film

NASA Astrophysics Data System (ADS)

Yang, Fan; Li, Yang; Lv, Yu-Guang; Zhou, Shu-Jing; Li, Si; Gao, Guang-Gang; Liu, Hong

2018-05-01

Due to some side effects of quinolones in vivo, it is an urgent issue to extend their new applications in vitro. In this paper, structure-determined vanadium-quinolone functionalized polymolybdates of (NH4)2 [(γ-Mo8O26){VO(CF)2}2] (1) and (NH4)2 [(γ-Mo8O26){VO(NF)2}2] (2) (CF = ciprofloxacin; NF = norfloxacin) have been designed and synthesized. Complex 1 or 2 features a γ-type [Mo8O26]4- polyanion functionalized by two monocapped vanadium-quinolone complexes. Different H-bonds and π···π interactions allow 1 or 2 to form a 2D layered structure at solid state. When complex 1 or 2 is transferred into polyvinyl alcohol (PVA) film, its release rate in solution is lower than that of CF- or NF-PVA film and thus forming a novel quinolone delivery system. This is the first time that slow release effect of quinolone is achieved by polyoxometalate coordination effect. The slow release of 1 or 2 in PVA film is mainly ascribed to the coordination of quinolone with polyoxometalate anions.

Oxidizing of ferulic acid with the use of polyoxometalates as catalysts

NASA Astrophysics Data System (ADS)

Povarnitsyna, T. V.; Popova, N. R.; Bogolitsyn, K. G.; Beloglazova, A. L.; Pryakhin, A. N.; Lunin, V. V.

2010-12-01

The kinetics of catalytic oxidation for ferulic acid with polyoxometalates used as catalysts was studied. The effect of pH and concentrations of the principal reacting components on the process kinetics was studied. A kinetic scheme of oxidation is proposed, and the values of a number of kinetic parameters of the process are determined.

Studies of lignin transformation in polyoxometalate (POM) bleaching of kraft pulp

Treesearch

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

2005-01-01

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

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.

Photoisomerisation and light-induced morphological switching of a polyoxometalate-azobenzene hybrid.

PubMed

Markiewicz, Grzegorz; Pakulski, Dawid; Galanti, Agostino; Patroniak, Violetta; Ciesielski, Artur; Stefankiewicz, Artur R; Samorì, Paolo

2017-06-29

The functionalization of a spherical Keplerate-type polyoxometalate {Mo 72 V 30 } with a cationic azobenzene surfactant has been achieved through ionic self-assembly. The photoisomerisation reaction of this complex, which emerges in a light-triggered aggregation-disaggregation process, has been followed by 1 H NMR spectroscopy, dynamic light scattering, absorption spectroscopy and scanning electron microscopy analyses.

The two-step assemblies of basic-amino-Acid-rich Peptide with a highly charged polyoxometalate.

PubMed

Zhang, Teng; Li, Hong-Wei; Wu, Yuqing; Wang, Yizhan; Wu, Lixin

2015-06-15

Two-step assembly of a peptide from HPV16 L1 with a highly charged europium-substituted polyoxometalate (POM) cluster, accompanying a great luminescence enhancement of the inorganic polyanions, is reported. The mechanism is discussed in detail by analyzing the thermodynamic parameters from isothermal titration calorimetry (ITC), time-resolved fluorescent and NMR spectra. By comparing the actions of the peptide analogues, a binding process and model are proposed accordingly. The driving forces in each binding step are clarified, and the initial POM aggregation, basic-sequence and hydrophobic C termini of peptide are revealed to contribute essentially to the two-step assembly. The present study demonstrates both a meaningful preparation for bioinorganic materials and a strategy using POMs to modulate the assembly of peptides and even proteins, which could be extended to other proteins and/or viruses by using peptides and POMs with similar properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Polyoxometalate-based Catalysts for Toxic Compound Decontamination and Solar Energy Conversion

NASA Astrophysics Data System (ADS)

Guo, Weiwei

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

Targeted delivery of polyoxometalate nanocomposites.

PubMed

Geisberger, Georg; Paulus, Susann; Gyenge, Emina Besic; Maake, Caroline; Patzke, Greta R

2011-10-04

Polyoxometalate/carboxymethyl chitosan nanocomposites with an average diameter of 130 nm are synthesized and labeled with fluorescein isothiocyanate (FITC) for a combined drug-carrier and cellular-monitoring approach. [Eu(β(2) -SiW(11) O(39) )(2) ](13-) /CMC nanospheres as a representative example do not display cytotoxicity for POM concentrations up to 2 mg mL(-1) . Cellular uptake of fluoresecently labelled {EuSiW(11) O(39) }/FITC-CMC nanoparticles is monitored with confocal laser scanning microscopy. Nanoparticle uptake occurs after incubation times of around 1 h and no cyctotoxic effects are observed upon prolonged treatment. The preferential location of the POM/CMC nanocomposites in the perinuclear region is furthermore verified with transmission electron microscopy investigations on unlabeled nanoparticles. Therefore, this approach is a promising dual strategy for the safe cellular transfer and monitoring of bioactive POMs. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular growth from a Mo176 to a Mo248 cluster

NASA Astrophysics Data System (ADS)

Müller, A.; Shah, Syed Q. N.; Bögge, H.; Schmidtmann, M.

1999-01-01

In polyoxometalate chemistry a large variety of compounds, clusters and solid-state structures can be formed by the linking together of well-defined metal-oxygen building blocks, . These species exhibit unusual topological and electronic properties, andfind applications ranging from medicine to industrial processes. The recently reported ring-shaped mixed-valence polyoxomolybdates of the type {Mo154} (refs 5, 6) and {Mo176} (refs 7, 8) represent a new class of giant clusters with nanometre-sized cavities and interesting properties for host-guest chemistry. Here we describe the formation of related clusters of the type {Mo248} formed by addition of further units to the inner surface of the {Mo176 } `wheel'. The additional units arrange themselves into two {Mo36} `hub-caps' on the initial wheel-clusters that are not stable in isolation. These findings reveal a new pathway to the development of complex coordination clusters.

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

Coherent manipulation of spin qubits based on polyoxometalates: the case of the single ion magnet [GdW30P5O110]14-.

PubMed

Baldoví, José J; Cardona-Serra, Salvador; Clemente-Juan, Juan M; Coronado, Eugenio; Gaita-Ariño, Alejandro; Prima-García, Helena

2013-10-11

Polyoxometalate single ion magnet [GdW30P5O110](14-) (1) has been studied by generalized Rabi oscillation experiments. It was possible to increase the number of coherent rotations tenfold through matching the Rabi frequency with the frequency of the proton. Achieving high coherence with polyoxometalate chemistry, we show its excellent potential not only for the storage of quantum information but even for the realization of quantum algorithms.

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).

Silver nanocrystal-decorated polyoxometalate single-walled nanotubes as nanoreactors for desulfurization catalysis at room temperature.

PubMed

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

2017-09-14

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

Water decontamination by polyoxometalate-functionalized 3D-printed hierarchical porous devices.

PubMed

Ji, Yuanchun; Ma, Yuan; Ma, Yanjiao; Asenbauer, Jakob; Passerini, Stefano; Streb, Carsten

2018-03-25

The design of organic-inorganic hybrid composites has revolutionized application-driven materials design. Here, we show how hierarchically structured, 3D-printed ABS polymers can be surface-functionalized with lacunary polyoxometalate anions ([α-PW 9 O 34 ] 9- ) featuring heavy-metal binding sites. The resulting composite is highly porous and can be used for the removal of transition-metal pollutants from water. Thus, a facile blueprint for decentralized production of water filtration devices is reported.

Kinetic analysis of polyoxometalate (POM) oxidation of non-phenolic lignin model compound

Treesearch

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

2003-01-01

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

Keeping the ball rolling: fullerene-like molecular clusters.

PubMed

Kong, Xiang-Jian; Long, La-Sheng; Zheng, Zhiping; Huang, Rong-Bin; Zheng, Lan-Sun

2010-02-16

The discovery of fullerenes in 1985 opened a new chapter in the chemistry of highly symmetric molecules. Fullerene-like metal clusters, characterized by (multi)shell-like structures, are one rapidly developing class of molecules that share this shape. In addition to creating aesthetically pleasing molecular structures, the ordered arrangement of metal atoms within such frameworks provides the opportunity to develop materials with properties not readily achieved in corresponding mononuclear or lower-nuclearity complexes. In this Account, we survey the great variety of fullerene-like metal-containing clusters with an emphasis on their synthetic and structural chemistry, a first step in the discussion of this fascinating field of cluster chemistry. We group the compounds of interest into three categories based on the atomic composition of the cluster core: those with formal metal-metal bonding, those characterized by ligand participation, and those supported by polyoxometalate building blocks. The number of clusters in the first group, containing metal-metal bonds, is relatively small. However, because of the unique and complex bonding scenarios observed for some of these species, these metalloid clusters present a number of research questions with significant ramifications. Because these cores contain molecular clusters of precious metals at the nanoscale, they offer an opportunity to study chemical properties at size ranges from the molecular to nanoscale and to gain insights into the electronic structures and properties of nanomaterials of similar chemical compositions. Clusters of the second type, whose core structures are facilitated by ligand participation, could aid in the development of functional materials. Of particular interest are the magnetic clusters containing both transition and lanthanide elements. A series of such heterometallic clusters that we prepared demonstrates diverse magnetic properties including antiferromagnetism, ferrimagnetism, and

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ou, Jinzhao; Mei, Mingliang; Xu, Xinxin, E-mail: xuxx@mail.neu.edu.cn

2016-06-15

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

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.

Oxidative Polyoxometalates Modified Graphitic Carbon Nitride for Visible-Light CO2 Reduction.

PubMed

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

2017-04-05

Developing a photocatalysis system for converting CO 2 to valuable fuels or chemicals is a promising strategy to address global warming and fossil fuel consumption. Exploring photocatalysts with high-performance and low-cost has been two ultimate goals toward photoreduction of CO 2 . Herein, noble-metal-free polyoxometalates (Co4) with oxidative ability was first introduced into g-C 3 N 4 resulted in inexpensive hybrid materials (Co4@g-C 3 N 4 ) with staggered band alignment. The staggered composited materials show a higher activity of CO 2 reduction than bare g-C 3 N 4 . An optimized Co4@g-C 3 N 4 hybrid sample exhibited a high yield (107 μmol g -1 h -1 ) under visible-light irradiation (λ ≥ 420 nm), meanwhile maintaining high selectivity for CO production (94%). After 10 h of irradiation, the production of CO reached 896 μmol g -1 . Mechanistic studies revealed the introduction of Co4 not only facilitate the charge transfer of g-C 3 N 4 but greatly increased the surface catalytic oxidative ability. This work creatively combined g-C 3 N 4 with oxidative polyoxometalates which provide novel insights into the design of low-cost photocatalytic materials for CO 2 reduction.

Structure and magnetism of [n-BuNH3]12[Cu4(GeW9O34)2].14H2O sandwiching a rhomblike Cu4(8+) tetragon through alpha-Keggin linkage.

PubMed

Yamase, Toshihiro; Abe, Hiroko; Ishikawa, Eri; Nojiri, Hiroyuki; Ohshima, Yuhgo

2009-01-05

A sandwich-type polyoxometalate, [Cu(4)(GeW(9)O(34))(2)](12-) (1a), in which two B-alpha-[GeW(9)O(34)](12-) ligands sandwich a rhomblike Cu(4)(8+) tetragon through alpha-Kappaeggin linkage, is first isolated as a [n-BuNH(3)](+) salt, [n-BuNH(3)](12)[Cu(4)(GeW(9)O(34))(2)].14H(2)O (1). A Cu(4)O(14) cluster for the rhomblike Cu(4)(8+) tetragon in 1a with C(2h) local symmetry consists of two Jahn-Teller (JT) distorted CuO(6) octahedra (at internal sites) with a short diagonal Cu(int)...Cu(int) distance of 3.10-3.11 A and two CuO(5) square pyramids (at external site) with a long diagonal Cu(ext)...Cu(ext) distance of 5.34-5.35 A, the feature of which is different from [Cu(4)(H(2)O)(2)(GeW(9)O(34))(2)](12-) (2a), comprising the four JT-distorted CuO(6) octahedral Cu(4)(8+) tetragons through beta-Keggin linkage: the axial Cu(ext)-O bond distance (2.27-2.29 A) for 1a is shorter than the corresponding JT-axial distance (2.36 A) for 2a. Measurements of magnetic susceptibility, magnetization, and electron spin resonance spectroscopy for 1 are carried out for better understanding of the molecular magnetism of the Cu(4)(8+) tetragon in comparison with 2a. The analysis of the magnetic behavior, based on the isotropic Heisenberg spin Hamiltonian comprising three exchange parameters (J, J', and J''), gives J = -24.1 cm(-1) for the Cu(ext)..Cu(int) sides, J' = -99.1 cm(-1) for the Cu(int)...Cu(int) diagonal, and J'' = +0.04 cm(-1) for the Cu(ext)...Cu(ext) diagonal of the Cu(4)(8+) rhombus. The S = 1 ground state of 1 displays g(||) = 2.42, g( perpendicular)= 2.07, D = -1.44 x 10(-2) cm(-1), and |A(Cu||)| = 46.5 x 10(-4) cm(-1). An observation of the asymmetric magnetization between a positive and a negative pulsed field (up to 10(3) T/s) at 0.5 K on the hysteresis loop indicates the quantum tunneling at zero field. The magnetic exchange interactions of four unpaired d(x(2)-y(2))-electron spins are discussed in terms of the point-dipole approximation, and the primary contribution

Heterogeneous Catalysis of Polyoxometalate Based Organic–Inorganic Hybrids

PubMed Central

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

2015-01-01

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

Noncovalent fabrication and tunable fusion of block copolymer-giant polyoxometalate hybrid micelles.

PubMed

Zhang, Liying; Li, Haolong; Wu, Lixin

2014-09-21

The block copolymers (BCs), as structure-directing agents, co-assembling with nanoscale inorganic additives is an important route to fabricate nanostructured hybrid materials. In this work, we present a facile approach to fabricate hybrid micelles composed of BCs and polyoxometalates (POMs), in which the POM clusters are premodified with the groups that can specifically interact with a certain BC block. A representative POM (NH4)42[Mo(132)O(372)(CH(3)COO)(30)(H2O)72] (Mo(132)) is chosen as the example and encapsulated with cationic molecules containing carboxyphenyl groups through electrostatic interactions, and then the resulting hybrid complex can further co-assemble with poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) through hydrogen bonding with the pyridine groups, which leads to the formation of hybrid micelles and the localization of Mo(132) in the micelle cores. The micelles exhibit a high stability despite time and dilution. Furthermore, the fusion of the micelles can be readily adjusted by varying the length of PS blocks, which is promising to be used in constructing polymer-POM hybrid materials with discrete or continuous hybrid domains. This work is based on the electrostatic premodification of POMs and thus its concept is generally suitable for the whole anionic POM system, which may create a large class of BC-POM nanocomposites with tunable structures.

Catalytic self-propulsion of supramolecular capsules powered by polyoxometalate cargos.

PubMed

del Mercato, Loretta L; Carraro, Mauro; Zizzari, Alessandra; Bianco, Monica; Miglietta, Ruggero; Arima, Valentina; Viola, Ilenia; Nobile, Concetta; Sorarù, Antonio; Vilona, Debora; Gigli, Giuseppe; Bonchio, Marcella; Rinaldi, Rosaria

2014-08-25

Multicompartment, spherical microcontainers were engineered through a layer-by-layer polyelectrolyte deposition around a fluorescent core while integrating a ruthenium polyoxometalate (Ru4POM), as molecular motor, vis-à-vis its oxygenic, propeller effect, fuelled upon H2O2 decomposition. The resulting chemomechanical system, with average speeds of up to 25 μm s(-1), is amenable for integration into a microfluidic set-up for mixing and displacement of liquids, whereby the propulsion force and the resulting velocity regime can be modulated upon H2O2-controlled addition. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyoxometalate-modified TiO2 nanotube arrays photoanode materials for enhanced dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Structural changes of residual lignin of softwood and hardwood kraft pulp upon oxidative treatment with polyoxometalates

Treesearch

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

2005-01-01

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

A General Approach to Access Morphologies of Polyoxometalates in Solution by Using SAXS: An Ab Initio Modeling Protocol.

PubMed

Li, Mu; Wang, Weiyu; Yin, Panchao

2018-05-02

Herein, we reported a general protocol for an ab initio modeling approach to deduce structure information of polyoxometalates (POMs) in solutions from scattering data collected by the small-angle X-ray scattering (SAXS) technique. To validate the protocol, the morphologies of a serious of known POMs in either aqueous or organic solvents were analyzed. The obtained particle morphologies were compared and confirmed with previous reported crystal structures. To extend the feasibility of the protocol to an unknown system of aqueous solutions of Na 2 MoO 4 with the pH ranging from -1 to 8.35, the formation of {Mo 36 } clusters was probed, identified, and confirmed by SAXS. The approach was further optimized with a multi-processing capability to achieve fast analysis of experimental data, thereby, facilitating in situ studies of formations of POMs in solutions. The advantage of this approach is to generate intuitive 3D models of POMs in solutions without confining information such as symmetries and possible sizes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Treesearch

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

2007-01-01

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

The Role of Bi3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid.

PubMed

Sadeghi, Omid; Amiri, Mehran; Reinheimer, Eric W; Nyman, May

2018-05-22

Metal oxo clusters and metal oxides assemble and precipitate from water in processes that depend on pH, temperature, and concentration. Other parameters that influence the structure, composition, and nuclearity of "molecular" and bulk metal oxides are poorly understood, and have thus not been exploited. Herein, we show that Bi 3+ drives the formation of aqueous Fe 3+ clusters, usurping the role of pH. We isolated and structurally characterized a Bi/Fe cluster, Fe 3 BiO 2 (CCl 3 COO) 8 (THF)(H 2 O) 2 , and demonstrated its conversion into an iron Keggin ion capped by six Bi 3+ irons (Bi 6 Fe 13 ). The reaction pathway was documented by X-ray scattering and mass spectrometry. Opposing the expected trend, increased cluster nuclearity required a pH decrease instead of a pH increase. We attribute this anomalous behavior of Bi/Fe(aq) solutions to Bi 3+ , which drives hydrolysis and condensation. Likewise, Bi 3+ stabilizes metal oxo clusters and metal oxides in strongly acidic conditions, which is important in applications such as water oxidation for energy storage. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatically self-assembled polyoxometalates on molecular-dye-functionalized diamond.

PubMed

Zhong, Yu Lin; Ng, Wibowo; Yang, Jia-Xiang; Loh, Kian Ping

2009-12-30

We have successfully immobilized phosphotungstic acid (PTA), a polyoxometalate, on the surface of boron-doped diamond (BDD) surface through electrostatic self-assembly of PTA on pyridinium dye-functionalized-BDD. The inorganic/organic bilayer structure on BDD is found to exhibit fast surface-confined reversible electron transfer. The molecular dye-grafted BDD can undergo controllable electrical stripping and regeneration of PTA which can be useful for electronics or sensing applications. Furthermore, we have demonstrated the use of PTA as a molecular switch in which the direction of photocurrent from diamond to methyl viologen is reversed by the surface bound PTA. Robust photocurrent converter based on such molecular system-diamond platform can operate in corrosive medium which is not tolerated by indium tin oxide electrodes.

Resonance tunneling electron-vibrational spectroscopy of polyoxometalates.

PubMed

Dalidchik, F I; Kovalevskii, S A; Balashov, E M

2017-05-21

The tunneling spectra of the ordered monolayer films of decamolybdodicobaltate (DMDC) compounds deposited from aqueous solutions on HOPG were measured by scanning tunnel microscopy in air. The DMDC spectra, as well as the tunneling spectra of other polyoxometalates (POMs), exhibit well-defined negative differential resistances (NDRs). The mechanism of formation of these spectral features was established from the collection of revealed NDR dependences on the external varying parameters and found to be common to all systems exhibiting Wannier-Stark localization. A model of biresonance tunneling was developed to provide an explanation for the totality of experimental data, both the literature and original, on the tunneling POM probing. A variant of the tunneling electron-vibrational POM spectroscopy was proposed allowing the determination of the three basic energy parameters-energy gaps between the occupied and unoccupied states, frequencies of the vibrational transitions accompanying biresonance electron-tunneling processes, and electron-vibrational interaction constants on the monomolecular level.

Resonance tunneling electron-vibrational spectroscopy of polyoxometalates

PubMed Central

Dalidchik, F. I.; Kovalevskii, S. A.

2017-01-01

The tunneling spectra of the ordered monolayer films of decamolybdodicobaltate (DMDC) compounds deposited from aqueous solutions on HOPG were measured by scanning tunnel microscopy in air. The DMDC spectra, as well as the tunneling spectra of other polyoxometalates (POMs), exhibit well-defined negative differential resistances (NDRs). The mechanism of formation of these spectral features was established from the collection of revealed NDR dependences on the external varying parameters and found to be common to all systems exhibiting Wannier–Stark localization. A model of biresonance tunneling was developed to provide an explanation for the totality of experimental data, both the literature and original, on the tunneling POM probing. A variant of the tunneling electron-vibrational POM spectroscopy was proposed allowing the determination of the three basic energy parameters—energy gaps between the occupied and unoccupied states, frequencies of the vibrational transitions accompanying biresonance electron-tunneling processes, and electron-vibrational interaction constants on the monomolecular level. PMID:28527451

Crystallization of a Keplerate-type polyoxometalate into a superposed kagome-lattice with huge channels.

PubMed

Saito, Masaki; Ozeki, Tomoji

2012-09-07

Crystal structures of two Sr(2+) salts of the Keplerate-type polyoxometalate, [Mo(VI)(72)Mo(V)(60)O(372)(CH(3)COO)(30)(H(2)O)(72)](42-), have been determined by single crystal X-ray diffraction. One compound exhibits a superposed kagome-lattice with huge channels whose diameters measure approximately 3.0 nm, while the arrangement of the Keplerate anions in the other compound approximates to a distorted cubic close packing.

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.

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

2016-11-07

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Two New Preyssler-Type Polyoxometalate-Based Coordination Polymers and Their Application in Horseradish Peroxidase Immobilization.

PubMed

Du, Jing; Cao, Mei-Da; Feng, Shu-Li; Su, Fang; Sang, Xiao-Jing; Zhang, Lan-Cui; You, Wan-Sheng; Yang, Mei; Zhu, Zai-Ming

2017-10-17

Enzyme immobilization is of increasing importance for biocatalysis, for which good supports are critical. Herein, two new Preyssler-type polyoxometalate (POM)-based coordination polymers, namely, {[Cu(H 2 biim) 2 ][{Cu(H 2 biim) 2 (μ-H 2 O)} 2 Cu(H 2 biim)(H 2 O) 2 ]H[({Cu(H 2 biim)(H 2 O) 2 } 0.5 ) 2 ((μ-C 3 HN 2 Cl 2 ){Cu(H 2 biim)} 2 ){Z(H 2 O)P 5 W 30 O 110 }]⋅x H 2 O} n (1: Z=Na, x=9; 2: Z=Ag, x=10; H 2 biim=2,2'-biimidazole) were designed and synthesized. Compounds 1 and 2 exhibit the same skeletons, which contain multiple Cu II complex fragments and penta-supported {ZP 5 W 30 } (Z=Na, Ag) clusters. They were first employed to immobilize horseradish peroxidase (HRP). Results show that compounds 1 and 2 are good supports for HRP immobilization, and exhibit higher enzyme loading, lower loading times, and excellent reusability. The immobilized HRP (HRP/1 or HRP/2) was further applied to detect H 2 O 2 , and good sensitivity, wide linear range, low detection limit, and fast response were achieved. This work shows that POM-based hybrid materials are a new kind of promising support for enzyme immobilization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic ion channels via self-assembly: a route for embedding porous polyoxometalate nanocapsules in lipid bilayer membranes.

PubMed

Carr, Rogan; Weinstock, Ira A; Sivaprasadarao, Asipu; Müller, Achim; Aksimentiev, Aleksei

2008-11-01

Porous polyoxometalate nanocapsules of Keplerate type are known to exhibit the functionality of biological ion channels; however, their use as an artificial ion channel is tempered by the high negative charge of the capsules, which renders their spontaneous incorporation into a lipid bilayer membrane unlikely. In this Letter we report coarse-grained molecular dynamics simulations that demonstrate a route for embedding negatively charged nanocapsules into lipid bilayer membranes via self-assembly. A homogeneous mixture of water, cationic detergent, and phospholipid was observed to spontaneously self-assemble around the nanocapsule into a layered, liposome-like structure, where the nanocapsule was enveloped by a layer of cationic detergent followed by a layer of phospholipid. Fusion of such a layered liposome with a lipid bilayer membrane was observed to embed the nanocapsule into the lipid bilayer. The resulting assembly was found to remain stable even after the surface of the capsule was exposed to electrolyte. In the latter conformation, water was observed to flow into and out of the capsule as Na(+) cations entered, suggesting that a polyoxometalate nanocapsule can form a functional synthetic ion channel in a lipid bilayer membrane.

Synthetic Ion Channels via Self-Assembly: a Route for Embedding Porous Polyoxometalate Nanocapsules in Lipid Bilayer Membranes

PubMed Central

Carr, Rogan; Weinstock, Ira A.; Sivaprasadarao, Asipu; Müller, Achim; Aksimentiev, Aleksei

2010-01-01

Porous polyoxometalate nanocapsules of Keplerate type are known to exhibit the functionality of biological ion channels, however, their use as artificial ion channel is tempered by the high negative charge of the capsules, which renders their spontaneous incorporation into a lipid bilayer membrane unlikely. In this letter we report coarse-grained molecular dynamics simulations that demonstrate a route for embedding negatively charged nanocapsules into lipid bilayer membranes via self-assembly. A homogeneous mixture of water, cationic detergent, and phospholipid was observed to spontaneously self-assemble around the nanocapsule into a layered, liposome-like structure, where the nanocapsule was enveloped by a layer of cationic detergent followed by a layer of phospholipid. Fusion of such a layered liposome with a lipid bilayer membrane was observed to embed the nanocapsule into the lipid bilayer. The resulting assembly was found to remain stable even after the surface of the capsule was exposed to electrolyte. In the latter conformation, water was observed to flow into and out of the capsule as Na+ cations entered, suggesting that a polyoxometalate nanocapsule can form a functional synthetic ion channel in a lipid bilayer membrane. PMID:18844424

[The UV-Vis spectra and substituent effect of organoimido derivatives of polyoxometalates].

PubMed

Li, Qiang; Wei, Yong-ge; Wang, Yuan; Guo, Hong-you

2005-06-01

In the presence of a carbodiimine, i.e. DCC, a series of organoimido derivatives of polyoxometalates have been synthesized via the reaction of [alpha-Mo8O26]4- with aromatic amines and its hydrochloride salt. Elemental analysis, IR, 1H-NMR and UV-Vis spectra were used to characterize those hybrids, in particular their UV-Vis spectra have been studied. The results show that typical metal-ligand charge transfer (MLCT) transitions occur in the organic-inorganic hybrid molecules. There is a good linear relationship between the shift of UV-Vis absorptions (delta lamda max) and conjugation effect of the p-substituted group (sigmaR).

Polyoxometalate oxidation of non-phenolic lignin subunits in water : effect of substrate structure on reaction kinetics

Treesearch

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

2004-01-01

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

Cationic cure kinetics of a polyoxometalate loaded epoxy nanocomposite

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 atmore » 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.« less

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.

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

Mechanistic Details and Reactivity Descriptors in Oxidation and Acid Catalysis of Methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deshlahra, Prashant; Carr, Robert T.; Chai, Song-Hai

2015-02-06

Acid and redox reaction rates of CH₃OH-O₂ mixtures on polyoxometalate (POM) clusters, together with isotopic, spectroscopic, and theoretical assessments of catalyst properties and reaction pathways, were used to define rigorous descriptors of reactivity and to probe the compositional effects for oxidative dehydrogenation (ODH) and dehydration reactions. ³¹P-MAS NMR, transmission electron microscopy and titrations of protons with di-tert-butylpyridine during catalysis showed that POM clusters retained their Keggin structure upon dispersion on SiO₂ and after use in CH₃OH reactions. The effects of CH₃OH and O₂ pressures and of D-substitution on ODH rates show that C-H activation in molecularly adsorbed CH₃OH is themore » sole kinetically relevant step and leads to reduced centers as intermediates present at low coverages; their concentrations, measured from UV-vis spectra obtained during catalysis, are consistent with the effects of CH₃OH/O₂ ratios predicted from the elementary steps proposed. First-order ODH rate constants depend strongly on the addenda atoms (Mo vs W) but weakly on the central atom (P vs Si) in POM clusters, because C-H activation steps inject electrons into the lowest unoccupied molecular orbitals (LUMO) of the clusters, which are the d-orbitals at Mo⁶⁺ and W⁶⁺ centers. H-atom addition energies (HAE) at O-atoms in POM clusters represent the relevant theoretical probe of the LUMO energies and of ODH reactivity. The calculated energies of ODH transition states at each O-atom depend linearly on their HAE values with slopes near unity, as predicted for late transition states in which electron transfer and C-H cleavage are essentially complete. HAE values averaged over all accessible O-atoms in POM clusters provide the appropriate reactivity descriptor for oxides whose known structures allow accurate HAE calculations. CH₃OH dehydration proceeds via parallel pathways mediated by late carbenium-ion transition states

Nature's polyoxometalate chemistry: X-ray structure of the Mo storage protein loaded with discrete polynuclear Mo-O clusters.

PubMed

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

2012-06-13

Some N(2)-fixing bacteria prolong the functionality of nitrogenase in molybdenum starvation by a special Mo storage protein (MoSto) that can store more than 100 Mo atoms. The presented 1.6 Å X-ray structure of MoSto from Azotobacter vinelandii reveals various discrete polyoxomolybdate clusters, three covalently and three noncovalently bound Mo(8), three Mo(5-7), and one Mo(3) clusters, and several low occupied, so far undefinable clusters, which are embedded in specific pockets inside a locked cage-shaped (αβ)(3) protein complex. The structurally identical Mo(8) clusters (three layers of two, four, and two MoO(n) octahedra) are distinguishable from the [Mo(8)O(26)](4-) cluster formed in acidic solutions by two displaced MoO(n) octahedra implicating three kinetically labile terminal ligands. Stabilization in the covalent Mo(8) cluster is achieved by Mo bonding to Hisα156-N(ε2) and Gluα129-O(ε1). The absence of covalent protein interactions in the noncovalent Mo(8) cluster is compensated by a more extended hydrogen-bond network involving three pronounced histidines. One displaced MoO(n) octahedron might serve as nucleation site for an inhomogeneous Mo(5-7) cluster largely surrounded by bulk solvent. In the Mo(3) cluster located on the 3-fold axis, the three accurately positioned His140-N(ε2) atoms of the α subunits coordinate to the Mo atoms. The formed polyoxomolybdate clusters of MoSto, not detectable in bulk solvent, are the result of an interplay between self- and protein-driven assembly processes that unite inorganic supramolecular and protein chemistry in a host-guest system. Template, nucleation/protection, and catalyst functions of the polypeptide as well as perspectives for designing new clusters are discussed.

Extremely efficient crystallization of HKUST-1 and Keggin-loaded related phases through the epoxide route.

PubMed

Oestreicher, Víctor; Jobbágy, Matías

2017-03-25

Highly crystalline HKUST-1 and COK-16-like phases were obtained based on a mild in situ alkalinization one-pot epoxide driven method. A slurry composed of finely ground trimesic acid, H 3 BTC, dispersed in a CuCl 2 aqueous solution quantitatively developed well crystallized HKUST-1 after the addition of propylene oxide. The use of solid H 3 BTC ensures a low concentration of free linker, favoring crystalline growth over the precipitation of amorphous or metastable impurities. An extreme space-time yield of 2.1 × 10 5 kg m -3 day -1 was reached, with no linker excess and minimum use of solvent. The method was equally efficient in the achievement of pure NENU/COK-16 phases, containing [PW 12 O 40 ] 3- , [PMo 12 O 40 ] 3- and [SiMo 12 O 40 ] 4- polyoxometalates.

Syntheses, structures and properties of two new organic-inorganic hybrid materials based on ε-Zn Keggin units {ε-PMo(V)8Mo(VI)4O(40-x)(OH)(x)Zn4}.

PubMed

Miao, Hao; Hu, Gonghao; Guo, Jiuyu; Wan, Hongxiang; Mei, Hua; Zhang, Yu; Xu, Yan

2015-01-14

Two novel organic-inorganic hybrids, Na[PMo(V)8Mo(VI)4O38(OH)2Zn4][pyim]2·1.5H2O [ε(pyim)2] (pyim = 2-(2-pyridyl)-imidazole) and [PMo(V)8Mo(VI)4O37(OH)3Zn4]2[pyim]6·4H2O [ε2(pyim)6], based on ε-Zn Keggin units {ε-PMo(V)8Mo(VI)4O(40-x)(OH)(x)Zn4}, have been successfully synthesized under hydrothermal conditions by controlling the pH values. Structural analysis indicates that the framework of ε(pyim)2 is a 1D chain constructed by monomeric ε-Zn units modified by pyim ligands, while ε2(pyim)6 is an isolated structural compound with dimeric ε-Zn units modified by pyim ligands. This is the first isolated structure of the ε-Keggin POMs system. The luminescent and electrochemical properties of ε(pyim)2 and ε2(pyim)6 were investigated. ε2(pyim)6 also shows high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester (MAP).

Polyoxometalate active charge-transfer material for mediated redox flow battery

DOEpatents

Anderson, Travis Mark; Hudak, Nicholas; Staiger, Chad; Pratt, Harry

2017-01-17

Redox flow batteries including a half-cell electrode chamber coupled to a current collecting electrode are disclosed herein. In a general embodiment, a separator is coupled to the half-cell electrode chamber. The half-cell electrode chamber comprises a first redox-active mediator and a second redox-active mediator. The first redox-active mediator and the second redox-active mediator are circulated through the half-cell electrode chamber into an external container. The container includes an active charge-transfer material. The active charge-transfer material has a redox potential between a redox potential of the first redox-active mediator and a redox potential of the second redox-active mediator. The active charge-transfer material is a polyoxometalate or derivative thereof. The redox flow battery may be particularly useful in energy storage solutions for renewable energy sources and for providing sustained power to an electrical grid.

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.

Pd0@Polyoxometalate Nanostructures as Green Electrocatalysts: Illustrative Example of Hydrogen Production

PubMed Central

Biboum, Rosa N.; Keita, Bineta; Franger, Sylvain; Njiki, Charles P. Nanseu; Zhang, Guangjin; Zhang, Jie; Liu, Tianbo; Mbomekalle, Israel-Martyr; Nadjo, Louis

2010-01-01

Green-chemistry type procedures were used to synthesize Pd0 nanostructures encapsulated by a vanadium-substituted Wells-Dawson-type polyoxometalate (Pd0@POM). The cyclic voltammogram run with the Pd0@POM-modified glassy carbon electrode shows well-defined waves, associated with Pd0 nanostructures and the VV/VIV redox couple. The Pd0@POM-modified electrode displayed remarkably reproducible cyclic voltammetry patterns. The hydrogen evolution reaction (HER) was selected as an illustrative example to test the electrocatalytic behavior of the electrode. The kinetic parameters of the HER show the high efficiency of the Pd0@POM-modified electrode. This is the first example of electrochemical characterization of a modified electrode based on a vanado-tungstic POM and Pd0 nanostructures.

Structural link between giant molybdenum oxide based ions and derived Keggin structure: modular assemblies based on the [BW11O39]9- ion and pentagonal {M'M5} units (M' = W; M = Mo,W).

PubMed

Leclerc-Laronze, Nathalie; Marrot, Jérôme; Thouvenot, René; Cadot, Emmanuel

2009-01-01

Linked to the Pentagon: The addition of molybdate to [HBW(11)O(39)](8-) ions leads to the formation of mixed pentagonal units {W(Mo(5))} and {W(WMo(4))} trapped as linkers in the resulting modular assemblies, thus establishing the first link between the conventional Keggin ion derivatives and the giant molybdenum oxide and keplerate ions.

Polyoxometalate-Based Organic-Inorganic Hybrids as Antitumor Drugs.

PubMed

Fu, Lei; Gao, Hanqin; Yan, Mei; Li, Shouzhu; Li, Xinyu; Dai, Zhifei; Liu, Shaoqin

2015-06-24

Polyoxometalates (POMs) have shown encouraging antitumor activity. However, their cytotoxicity in normal cells and unspecific interactions with biomolecules are two major obstacles that impede the practical applications of POMs in clinical cancer treatment. Derivatization of POMs with more biocompatible organic ligands is expected to cause a synergetic effect and achieve improved bioactivity and biospecificity. Herein, the synthesis of an amphiphilic organic-inorganic hybrid is reported by grafting a long-chain organoalkoxysilane lipid onto a POM. The amphiphilic POM hybrid could spontaneously assemble into the vesicles and exhibits enhanced antitumor activity for human colorectal cancer cell lines (HT29) compared to that of parent POMs. This detailed study reveals that the amphiphilic nature of POM hybrids enables the as-formed vesicles to easily bind to the cell membranes and then be uptaken by the cells, thus leading to a substantial increase in antitumor activity. Such prominent antitumor action is mostly accomplished via cell apoptosis, which ultimately results in cell death. Our finding demonstrates that novel POM hybrids-based drugs with increased bioactivity could be obtained by decorating POMs with selective organic ligands. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Active PdNi/RGO/Polyoxometalate Nanocomposite Electrocatalyst for Alcohol Oxidation.

PubMed

Hu, Jing; Wu, Xiaofeng; Zhang, Qingfan; Gao, Mingyan; Qiu, Haifang; Huang, Keke; Feng, Shouhua; Wang, Tingting; Yang, Ying; Liu, Zhelin; Zhao, Bo

2018-02-27

A PdNi/RGO/polyoxometalate nanocomposite has been successfully synthesized by a simple wet-chemical method. Characterizations such as transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction analysis, and X-ray photoelectron spectroscopy are employed to verify the morphology, structure, and elemental composition of the as-prepared nanocomposite. Inspired by the fast-developing fuel cells, the electrochemical catalytic performance of the nanocomposite toward methanol and ethanol oxidation in alkaline media is further tested. Notably, the nanocomposite exhibits excellent catalytic activity and long-term stability toward alcohol electrooxidation compared with the PdNi/RGO and commercial Pd/C catalyst. Furthermore, the electrochemical results reveal that the prepared nanocomposite is attractive as a promising electrocatalyst for direct alcohol fuel cells, in which the phosphotungstic acid plays a crucial role in enhancing the electrocatalytic activities of the catalyst.

An Electrostatically Self-Assembled Thin Film Made of Zn-Substituted Tungstoborate and Rhodamine B with Photoelectrochemical Properties.

PubMed

Mao, Xu; Zhang, Jia-Ning; Gao, Li-Hua; Su, Yu; Chen, Peng-Xia; Wang, Ke-Zhi

2016-04-01

An electrostatically self-assembled multilayer thin film consisting of alternating layers of Keggin polyoxometalate of Zn-substituted tungstoborate (BW11Zn) and Rhodamine B (RhB) has successfully been prepared on a quartz and indium-tin oxide (ITO) glass substrate. The ultraviolet-visible (UV-vis) absorption spectra demonstrated that the electrostatically self-assembled film of (BW11Zn/RhB)n was uniformly deposited layer by layer, and the RhB molecules in the film formed the J-aggregation. The photoelectrochemical investigations showed that the films generated stable cathodic photocurrents that originated from RhB, and the maximal cathodic photocurrent density generated by an eight-layer film was 4.9 µA/cm2 while the film was irradiated with 100 mW/cm2 polychromatic light of 730 nm > λ > 325 nm at an applied potential of 0 V versus a saturated calomel electrode.

Complexation of polyoxometalates with cyclodextrins.

PubMed

Wu, Yilei; Shi, Rufei; Wu, Yi-Lin; Holcroft, James M; Liu, Zhichang; Frasconi, Marco; Wasielewski, Michael R; Li, Hui; Stoddart, J Fraser

2015-04-01

Although complexation of hydrophilic guests inside the cavities of hydrophobic hosts is considered to be unlikely, we demonstrate herein the complexation between γ- and β-cyclodextrins (γ- and β-CDs) with an archetypal polyoxometalate (POM)--namely, the [PMo12O40](3-) trianion--which has led to the formation of two organic-inorganic hybrid 2:1 complexes, namely [La(H2O)9]{[PMo12O40]⊂[γ-CD]2} (CD-POM-1) and [La(H2O)9] {[PMo12O40]⊂[β-CD]2} (CD-POM-2), in the solid state. The extent to which these complexes assemble in solution has been investigated by (i) (1)H, (13)C, and (31)P NMR spectroscopies and (ii) small- and wide-angle X-ray scattering, as well as (iii) mass spectrometry. Single-crystal X-ray diffraction reveals that both complexes have a sandwich-like structure, wherein one [PMo12O40](3-) trianion is encapsulated by the primary faces of two CD tori through intermolecular [C-H···O═Mo] interactions. X-ray crystal superstructures of CD-POM-1 and CD-POM-2 show also that both of these 2:1 complexes are lined up longitudinally in a one-dimensional columnar fashion by means of [O-H···O] interactions. A beneficial nanoconfinement-induced stabilizing effect is supported by the observation of slow color changes for these supermolecules in aqueous solution phase. Electrochemical studies show that the redox properties of [PMo12O40](3-) trianions encapsulated by CDs in the complexes are largely preserved in solution. The supramolecular complementarity between the CDs and the [PMo12O40](3-) trianion provides yet another opportunity for the functionalization of POMs under mild conditions by using host-guest chemistry.

On the possibility of controlling the hydrophilic/hydrophobic characteristics of toroid Mo138 nanocluster polyoxometalates

NASA Astrophysics Data System (ADS)

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

2017-03-01

The possibility of changing the hydrophilic (polar) surfaces of toroid nanocluster polyoxomolibdates to hydrophobic (nonpolar) surfaces via the modification of Mo138 nanoclusters by surfactant molecules (dodecylpyridinium chloride) as a result of the interaction between these compounds in solutions is demonstrated. Benzene and methanol are used as molecular probes (indicators of the condition of nanocluster surfaces). Comparative characteristics of the equilibrium sorption of benzene and methanol vapors on the initial and modified surfaces of the solid polyoxometalate, and data on the sorption of organic molecules on the surfaces of Rhodamine B-modified nanoclusters of the toroid (Mo138) and keplerate (Mo132) types are obtained.

Early Transition Metal Oxides as Catalysts: Crossing Scales from Clusters to Single Crystals to Functioning Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai-Sheng Wang

2009-07-07

The overall goal of this program is to investigate the electronic structure and chemical bonding of early transition metal oxide clusters and use them as well-defined molecular models to obtain insight into properties and mechanisms of oxide catalysts, as well as to provide accurate spectroscopic and molecular information to verify theoretical methods used to predict materials properties. A laser vaporization cluster source is used to produce metal oxide clusters with different sizes, structures, and compositions. Well-defined inorganic polyoxometalate clusters in solution are transported in the gas phase using electrospray. Two state-of-the-art photoelectron spectroscopy apparatuses are used to interrogate the oxidemore » clusters and polyoxometalate anions in the gas phase to obtain spectroscopic and electronic structure information. The experimental effort is assisted by theoretical calculations to understanding the structures, chemical bonding, and catalytical properties of the transition metal oxide clusters. The research approach combines novel and flexible experimental techniques and advanced theoretical/computational methodologies and seeks molecular-level information to aiding the design of new catalysts, as well as mechanistic understanding. We have focused on the investigation of tungsten oxide clusters containing three W atoms: W{sub 3}O{sub x}{sup -} (x = 7-11). A number of interesting findings have been made. We observed that the oxygen-poor W{sub 3}O8 cluster contains a localized W{sup 4+} center, which can be used as a molecular model for O-deficient defect sites. A chemisorption energy was obtained through density functional calculations for W{sub 3}O8 + O{sub 2} {yields} W{sub 3}O{sub 10} as -78 kcal/mol. We further found that the neutral stoichiometric W{sub 2}O{sub 6} and W{sub 3}O{sub 9} clusters do not react with O{sub 2} and they only form physi-sorbed complexes, W{sub 2}O{sub 6}(O{sub 2}) and W{sub 3}O{sub 9}(O{sub 2}). However, the

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Xiao-Yang, E-mail: yangyangyu0103@sohu.com; Jilin Institute of Chemical Technology, Jilin City, Jilin 132022; Cui, Xiao-Bing

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{submore » 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

The Cooperativity of Fe3O4 and Metal-Organic Framework as Multifunctional Nanocomposites for Laser Desorption Ionization Process.

PubMed

Fu, Chung-Wei; Lirio, Stephen; Shih, Yung-Han; Liu, Wan-Ling; Lin, Chia-Her; Huang, Hsi-Ya

2018-05-10

We report a novel and facile strategy for developing a water stable magnetic metal organic framework nanocomposite (Fe3O4@MOF), in which a Keggin polyoxometalate, phosphotungstic acid (HPW), was encapsulated within the MOF framework via one-pot synthesis method. The combination of HPW-embedded MOF and Fe3O4 endowed the composite with high surface area, strong UV absorption, good hydrophilicity, and enhanced water stability. With these unique properties, the Fe3O4@MOF embedded HPW were served as adsorbent as well as matrix for (surface-assisted laser desorption ionization mass spectrometry) SALDI-MS analysis of polar and non-polar compounds. The synergistic effect of Fe3O4 and MOF showed an interference-free background at low mass region than the pristine MOF or Fe3O4 counterpart. This simple approach can be used as new platform in developing magnetic MOF composites without the time consuming and labor-intensive preparation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsuboi, Masaki; Hibino, Mitsuhiro; Mizuno, Noritaka

2016-02-15

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

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.

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

2015-12-07

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.

Preparation of magnetic photocatalyst nanohybrid decorated by polyoxometalate for the degradation of a pharmaceutical pollutant under solar light.

PubMed

Bastami, Tahereh Rohani; Ahmadpour, Ali

2016-05-01

Magnetic polyoxometalate nanohybrid was prepared by the surface modification of γ-Fe2O3/SrCO3 nanoparticles with PW 12 O 40 (3 -) polyoxometalate (POM) anions. The results of Fourier transform infrared (FTIR) and energy-dispersive X-ray (EDX) confirm the presence of POM on the surface of γ-Fe2O3/SrCO3 nanoparticles. TEM results revealed the ellipsoid-like structure of nanohybrid which was 23 nm in length and 6 nm in width. The activity of the photocatalyst was investigated by the photocatalytic degradation of ibuprofen (IBP) in an aqueous solution under solar light. It was found that in comparison with the γ-Fe2O3/SrCO3, the degradation of IBP after 2-h exposure to the solar light irradiation was significantly higher for POM-γ-Fe2O3/SrCO3 nanohybrids. The degradation of IBP was enhanced by the addition of H2O2 to the air saturated solution, while the addition of NaHCO3 and isopropanol restricted the degradation process. In the presence of H2O2, the Fenton photocatalyst degradation under solar light irradiation led to relatively complete degradation of IBP. Furthermore, the photocatalytic activity and magnetization properties of this magnetic photocatalyst nanohybrid provide a promising solution for the degradation of water pollutants and photocatalyst recovery. Graphical Abstract Schematic illustration for preparation of POM-γ-Fe2O3/SrCO3 nanohybrid and photocatalytic reaction of IBP on POM-γ-Fe2O3/SrCO3 nanohybrid.

Comment on: "Synthesis of dodecamolybdoantimonate(v) salts containing the Keggin structure" by Raj P. Singh, Radheshyam P. Khatri, Jean Dubois, Sushma S. Gaur and Mitsuo Abe, J. Chem. Soc., Dalton Trans., 1990, 947-951.

PubMed

Hartl, Hans; Lunk, Hans-Joachim

2018-04-18

The existence of a dodecamolybdoantimonate(v) anion with the Keggin structure would be a highlight of the heteropolyoxometalate chemistry as a whole. However, we could not confirm the existence of ammonium, potassium, rubidium and cesium dodecamolybdoantimonate as claimed by the authors. As a matter of fact, the authors misinterpreted their presented experimental data. Instead of the dodecamolybdoantimonates, the well-known hexagonal molybdenum oxide was prepared. The given misinformation has to be corrected, even 28 years after its publication.

Role of Anions Associated with the Formation and Properties of Silver Clusters.

PubMed

Wang, Quan-Ming; Lin, Yu-Mei; Liu, Kuan-Guan

2015-06-16

Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties

Selective conversion of {Mo132} Keplerate ion into 4-electron reduced crown-capped Keggin derivative [Te5Mo15O57](8-). A key intermediate to single-phase M1 multielement MoVTeO light-alkanes oxidation catalyst.

PubMed

Canioni, Romain; Marchal-Roch, Catherine; Leclerc-Laronze, Nathalie; Haouas, Mohamed; Taulèlle, Francis; Marrot, Jérôme; Paul, Sebastien; Lamonier, Carole; Paul, Jean-François; Loridant, Stéphane; Millet, Jean-Marc M; Cadot, Emmanuel

2011-06-14

{Mo(132)} Keplerate anion reacts with tellurites to give a soluble precursor to produce in hydrothermal conditions single-phase M1 MoVTeO light-alkanes oxidation catalyst. Characterization of this Te-containing intermediate by single-crystal X-ray diffraction, (125)Te NMR, UV-visible and redox titration reveals a molybdotellurite anion as a crown-capped Keggin derivative. This journal is © The Royal Society of Chemistry 2011

Synthesis and characterization of a novel inorganic-organic hybrid material based on polyoxometalates and dicyclohexylcarbodiimide

NASA Astrophysics Data System (ADS)

Huang, Bo; Hu, Xiaokang; Hu, Xunliang; Wang, Nan; Yang, Kang; Xiao, Zicheng; Wu, Pingfan

2017-12-01

Towards design and synthesis of bulky molecules and molecular machines, we reported a new inorganic-organic hybrid material based on polyoxometalates and 1, 3-dicyclohexylcarbodiimide (DCC): (Bu4N)2[V6O13{(OCH2)3CCH2OOCCH2CH2CON(C6H11)CONHC6H11}2]. The hybrid was characterized by FT-IR, 1H NMR, UV-Vis, ESI-MS, and the structure of the compound was determined through single-crystal X-ray diffraction. There was an interesting supramolecular assembly in the hybrid material through intermolecular hydrogen bonding, and each cyclohexyl in the polymer looks like one of blades in the propeller. Furthermore, the thermal stability of the hybrid was tested by TGA analyses, and the electrochemical property has also been studied by cyclic voltammogram.

Structural Investigation of Dinuclear Clusters Incorporated in Polyoxotungstates

NASA Astrophysics Data System (ADS)

Nagy, C.; Rusu, D.; Somesan, C.; Filip, S.; Rusu, M.; David, L.

2011-10-01

The new K10[M2Bi2W20O70]ṡH2O (M = Mn(II), Co(II), Ni(II), Cu(II)) sandwich-type complex have been investigated by spectroscopic (FT-IR, UV-VIS, ESR) methods. The main goal was to obtain information about the metal ions coordination to the trilacunary regions of Keggin polioxoanion ligands, the local symmetry around the metal ions and the presence of possible metal-metal couplings.

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

NASA Astrophysics Data System (ADS)

Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

2014-01-01

Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway.

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

PubMed Central

Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

2014-01-01

Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway. PMID:24413448

Synthesis and PPy loading for enhanced visible-light photocatalytic activity of new POMOFs containing silver chains

NASA Astrophysics Data System (ADS)

Sha, Jing-Quan; Yang, Xi-Ya; Sheng, Ning; Liu, Guo-Dong; Li, Ji-Sen; Yang, Jian-Bo

2018-07-01

A new polyoxometalate based hybrid compound containing Ag-Ag chain, [Ag29(trz)18][SiWV7WVI5O40] (Ag29SiW12), was synthesized by the simple one-step hydrothermal reaction of silver nitrate, 1, 2, 3- triazole (trz), and [SiW12O40]4- polyanion. Single crystal X-ray diffraction analysis shows that the [SiW12O40]4- polyanions as coordinating guests were successfully encapsulated into the metal-organic framework host matrix. The Keggin [SiW12O40]n- polyanions as templates and trz molecules as the small and delicate ligands play the decisive factors to the formation of silver chain. In addition, to improve the photocatalytic activity of the new compound Ag29SiW12, its polypyrrole (PPy) composite (PPy@Ag29SiW12) has been prepared and exhibits excellent photocatalytic activity (93.1% for MB and 48.8% for RhB) and selectivity adsorption (16.2 mg/g for MB and 1.60 mg/g for RhB) for organic dyes under the visible light radiation.

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.

Controlling transformations in the assembly of polyoxometalate clusters: {Mo11V7}, {Mo17V8} and {Mo72V30}.

PubMed

Miras, Haralampos N; Ochoa, M Nieves Corella; Long, De-Liang; Cronin, Leroy

2010-11-21

The reaction of molybdate with vanadium(V) in the presence of sulfite anions is explored showing how, via cation control, stepwise assembly through the {Mo(11)V(7)} cluster yields a {M(25)} cluster-based compound, [Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(μ(9)-SO(3))(Mo(VI)(6)V(V)O(22))](10-) (1a), which was first discovered using cryospray mass spectrometry, whereas switching the cation away from ammonium allows the direct formation of the spherical 'Keplerate' {Mo(72)V(30)} cluster.

Redox-Activated Near-Infrared-Responsive Polyoxometalates Used for Photothermal Treatment of Alzheimer's Disease.

PubMed

Ma, Mengmeng; Gao, Nan; Sun, Yuhuan; Du, Xiubo; Ren, Jinsong; Qu, Xiaogang

2018-06-19

Adjustable structure, excellent physiochemical properties, and good biocompatibility render polyoxometalates (POMs) as a suitable drug agent for the treatment of Alzheimer's disease (AD). However, previous works using POMs against AD just focus on the inhibition of amyloid-β (Aβ) monomer aggregation. In consideration that both Aβ fibrils and reactive oxygen species (ROS) are closely associated with clinical development of AD symptoms, it would be more effective if POMs can disaggregate Aβ fibrils and eliminate ROS as well. Herein, a redox-activated near-infrared (NIR) responsive POMs-based nanoplaform (rPOMs@MSNs@copolymer) is developed with high photothermal effect and antioxidant activity. The rPOMs@MSNs@copolymer can generate local hyperthermia to disaggregate Aβ fibrils under NIR laser irradiation because of POMs (rPOMs) with strong NIR absorption. Furthermore, Aβ-induced ROS can be scavenged by the antioxidant activity of rPOMs. To the authors' knowledge, there is no report of using rPOMs for NIR photothermal treatment of AD. This work may promote the development of multifunctional inorganic agents for biomedical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

2016-06-06

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.

Self-Assembled Carbon-Polyoxometalate Composites for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Genovese, Matthew

The development of high performance yet cost effective energy storage devices is critical for enabling the growth of important emerging sectors from the internet of things to grid integration of renewable energy. Material costs are by far the largest contributor to the overall cost of energy storage devices and thus research into cost effective energy storage materials will play an important role in developing technology to meet real world storage demands. In this thesis, low cost high performance composite electrode materials for supercapacitors (SCs) have been developed through the surface modification of electrochemically double layer capacitive (EDLC) carbon substrates with pseudocapacitive Polyoxometalates (POMs). Significant fundamental contributions have been made to the understanding of all components of the composite electrode including the POM active layer, cation linker, and carbon substrate. The interaction of different POM chemistries in solution has been studied to elucidate the novel ways in which these molecules combine and the mechanism underlying this combination. A more thorough understanding regarding the cation linker's role in electrode fabrication has been developed through examining the linker properties which most strongly affect electrode performance. The development of porosity in biomass derived carbon materials has also been examined leading to important insights regarding the effect of substrate porosity on POM modification and electrochemical properties. These fundamental contributions enabled the design and performance optimization of POM-carbon composite SC electrodes. Understanding how POMs combine in solution, allowed for the development of mixed POM molecular coatings with tunable electrochemical properties. These molecular coatings were used to modify low cost biomass derived carbon substrates that had been structurally optimized to accommodate POM molecules. The resulting electrode composites utilizing low cost materials

Archimedean Synthesis and Magic Numbers: "Sizing" Giant Molybdenum-Oxide-Based Molecular Spheres of the Keplerate Type.

PubMed

Müller; Sarkar; Shah; Bögge; Schmidtmann; Kögerler; Hauptfleisch; Trautwein; Schünemann

1999-11-02

Pythagorean harmony can be found in the spherical polyoxometalate clusters described here (see illustration for an example of a structure), since there are interesting relationships between the so-called magic numbers (12, 32, 42, 72, 132) relevant for spherical viruses and the number of the building blocks in the cluster. The size of these Keplerate clusters can be tailored by varying the type of connections between the pentagons by means of different spacers.

A new 3D POMOF based on CuI/CuII-bis(triazole) complexes and BW12 Keggin polyoxoanions: Synthesis, characterization and electrochemical properties

NASA Astrophysics Data System (ADS)

Zhang, Yanjun; Fu, Xin; Zhang, Chunjing; Pang, Hainjun; Ma, Huiyuan; Zhao, Xi; Wang, Cheng

2018-02-01

A novel organic-inorganic hybrid compound, {[CuI(btpe)2][CuII2(H2O)2(btpe)2][BW12O40]}·2H2O, (btpe = 1,5-bis(1,2,4-triazol-1-yl)pentane) (1) has been synthesized by hydrothermal reaction, and characterized by elemental analyses, IR spectroscopy, TG and single X-ray diffraction. Compound 1 is composed of α-Keggin type [BW12O40]5- (BW12) polyoxoanions and copper-btpe complexes. The copper-btpe complexes are stagger-packed to form an open framework containing the two kinds of channels with parallelogram-like apertures, in which the BW12 guests are encapsulated into the bigger channels. The electrochemical studies show that 1 has a good electrocatalytic activity towards reduction of hydrogen peroxide (H2O2), thanking to its special porous POMOF structure. The molecular design of 1 not only generates a new POMOF, but also opens a new avenue to the electrocatalytic materials.

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.

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.

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Fine-Tuning the Antimicrobial Profile of Biocompatible Gold Nanoparticles by Sequential Surface Functionalization Using Polyoxometalates and Lysine

PubMed Central

Daima, Hemant K.; Selvakannan, P. R.; Shukla, Ravi; Bhargava, Suresh K.; Bansal, Vipul

2013-01-01

Antimicrobial action of nanomaterials is typically assigned to the nanomaterial composition, size and/or shape, whereas influence of complex corona stabilizing the nanoparticle surface is often neglected. We demonstrate sequential surface functionalization of tyrosine-reduced gold nanoparticles (AuNPsTyr) with polyoxometalates (POMs) and lysine to explore controlled chemical functionality-driven antimicrobial activity. Our investigations reveal that highly biocompatible gold nanoparticles can be tuned to be a strong antibacterial agent by fine-tuning their surface properties in a controllable manner. The observation from the antimicrobial studies on a gram negative bacterium Escherichia coli were further validated by investigating the anticancer properties of these step-wise surface-controlled materials against A549 human lung carcinoma cells, which showed a similar toxicity pattern. These studies highlight that the nanomaterial toxicity and biological applicability are strongly governed by their surface corona. PMID:24147146

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

PubMed

Daima, Hemant K; Selvakannan, P R; Shukla, Ravi; Bhargava, Suresh K; Bansal, Vipul

2013-01-01

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

A novel SWCNT-polyoxometalate nanohybrid material as an electrode for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Chen, Han-Yi; Al-Oweini, Rami; Friedl, Jochen; Lee, Ching Yi; Li, Linlin; Kortz, Ulrich; Stimming, Ulrich; Srinivasan, Madhavi

2015-04-01

A novel nanohybrid material that combines single-walled carbon nanotubes (SWCNTs) with a polyoxometalate (TBA)5[PVV2MoVI10O40] (TBA-PV2Mo10, TBA: [(CH3(CH2)3)4N]+, tetra-n-butyl ammonium) is investigated for the first time as an electrode material for supercapacitors (SCs) in this study. The SWCNT-TBA-PV2Mo10 material has been prepared by a simple solution method which electrostatically attaches anionic [PV2Mo10O40]5- anions with organic TBA cations on the SWCNTs. The electrochemical performance of SWCNT-TBA-PV2Mo10 electrodes is studied in an acidic aqueous electrolyte (1 M H2SO4) by galvanostatic charge/discharge and cyclic voltammetry. In this SWCNT-TBA-PV2Mo10 nanohybrid material, TBA-PV2Mo10 provides redox activity while benefiting from the high electrical conductivity and high double-layer capacitance of the SWCNTs that improve both energy and power density. An assembled SWCNT-TBA-PV2Mo10 symmetric SC exhibits a 39% higher specific capacitance as compared to a symmetric SC employing only SWCNTs as electrode materials. Furthermore, the SWCNT-TBA-PV2Mo10 SC exhibits excellent cycling stability, retaining 95% of its specific capacitance after 6500 cycles.

A novel SWCNT-polyoxometalate nanohybrid material as an electrode for electrochemical supercapacitors.

PubMed

Chen, Han-Yi; Al-Oweini, Rami; Friedl, Jochen; Lee, Ching Yi; Li, Linlin; Kortz, Ulrich; Stimming, Ulrich; Srinivasan, Madhavi

2015-05-07

A novel nanohybrid material that combines single-walled carbon nanotubes (SWCNTs) with a polyoxometalate (TBA)5[PVMoO40] (TBA-PV2Mo10, TBA: [(CH3(CH2)3)4N](+), tetra-n-butyl ammonium) is investigated for the first time as an electrode material for supercapacitors (SCs) in this study. The SWCNT-TBA-PV2Mo10 material has been prepared by a simple solution method which electrostatically attaches anionic [PV2Mo10O40](5-) anions with organic TBA cations on the SWCNTs. The electrochemical performance of SWCNT-TBA-PV2Mo10 electrodes is studied in an acidic aqueous electrolyte (1 M H2SO4) by galvanostatic charge/discharge and cyclic voltammetry. In this SWCNT-TBA-PV2Mo10 nanohybrid material, TBA-PV2Mo10 provides redox activity while benefiting from the high electrical conductivity and high double-layer capacitance of the SWCNTs that improve both energy and power density. An assembled SWCNT-TBA-PV2Mo10 symmetric SC exhibits a 39% higher specific capacitance as compared to a symmetric SC employing only SWCNTs as electrode materials. Furthermore, the SWCNT-TBA-PV2Mo10 SC exhibits excellent cycling stability, retaining 95% of its specific capacitance after 6500 cycles.

Organic-inorganic hybrid polyionic liquid based polyoxometalate as nano porous material for selective oxidation of sulfides

NASA Astrophysics Data System (ADS)

Rafiee, Ezzat; Shahebrahimi, Shabnam

2017-07-01

Organic-inorganic hybrid nano porous materials based on poly(ionic liquid)-polyoxometalate (PIL-POM) were reported. These hybrid materials were synthesized by the reaction of 4-vinyl pyridine with 1,3-propanesultone, followed by the polymerization and also sulfonate-functionalized cross-linked poly(4-vinylpyridine) and combining these polymers with H5PMo10V2O40 (PMo10V2). Activity of prepared PIL-PMo10V2 hybrids were investigated as catalysts for oxidation of sulfides with H2O2 as oxidant. For understanding catalytic activities of the PIL-PMo10V2 hybrids in oxidation of sulfides, effect of catalyst composition, substrate, and reaction conditions were studied. The results show that the PIL-PMo10V2 hybrids are active as selective heterogeneous catalysts for oxidation of sulfides and can be recovered and reused. The catalyst was characterized by FT-IR, TGA-DSC, XRD, SEM/EDX, BET, CV and zeta potential measurement. Also, average molecular weight of prepared catalysts were measured.

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

Iterative absolute electroanalytical approach to characterization of bulk redox conducting systems.

PubMed

Lewera, Adam; Miecznikowski, Krzysztof; Chojak, Malgorzata; Makowski, Oktawian; Golimowski, Jerzy; Kulesza, Pawel J

2004-05-15

A novel electroanalytical approach is proposed here, and it is demonstrated with the direct and simultaneous determination of two unknowns: the concentration of redox sites and the apparent diffusion coefficient for charge propagation in a single crystal of dodecatungstophosphoric acid. This Keggin-type polyoxometalate serves as a model bulk redox conducting inorganic material for solid-state voltammetry. The system has been investigated using an ultramicrodisk working electrode in the absence of external liquid supporting electrolyte. The analytical method requires numerical solution of the combination of two equations in which the first one describes current (or charge) in a well-defined (either spherical or linear) diffusional regime and the second general equation describes chronoamperometric (or normal pulse voltammetric current) under mixed (linear-spherical) conditions. The iterative approach is based on successive approximations through calculation and minimizing the least-squares error function. The method is fairly universal, and in principle, it can be extended to the investigation of other bulk systems including sol-gel processed materials, redox melts, and solutions on condition that they are electroactive and well behaved, they contain redox centers at sufficiently high level, and a number of electrons for the redox reaction considered is known.

Deep desulfurization by amphiphilic lanthanide-containing polyoxometalates in ionic-liquid emulsion systems under mild conditions.

PubMed

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

2013-01-07

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

Heterogeneous oxidative desulfurization of diesel fuel catalyzed by mesoporous polyoxometallate-based polymeric hybrid.

PubMed

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

2017-07-05

In this work, the simple preparation of novel polymer supported polyoxometallates (POMs) catalysts has been reported. Soluble task-specific cross-linked poly (ionic liquid) (PIL) was prepared with N,​N-​dimethyl-​dodecyl-​(4-​vinylbenzyl) ammonium chloride and divinylbenzene as co-monomers. The as-prepared cationic PILs were assembled with different commercial POMs to form the interlinked mesoporous catalysts, and the formation mechanism was provided. The catalytic oxidation activities of the catalysts were closely related to the formation pathway of their corresponding peroxide active species. The catalyst with H 2 W 12 O 42 10- as counterion, which exhibited the best activity in the oxidation of benzothiophene (BT) and dibenzothiophene (DBT) to sulfones in model oil with hydrogen peroxide (H 2 O 2 , 30wt%) as oxidant, was characterized by different techniques and systematically studied for its sulfur removal performance. As for the oxidative desulfurization of a real diesel, it was observed that almost all of the original sulfur compounds could be completely converted, and the catalyst could be reused for at least eight cycles without noticeable changes in both catalytic activity and chemical structure. In the end, a catalytic mechanism was put forward with the assistant of Raman analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Crystal Facets Make a Profound Difference in Polyoxometalate-Containing Metal-Organic Frameworks as Catalysts for Biodiesel Production.

PubMed

Liu, Yiwei; Liu, Shumei; He, Danfeng; Li, Ning; Ji, Yujuan; Zheng, Zhiping; Luo, Fang; Liu, Shuxia; Shi, Zhan; Hu, Changwen

2015-10-07

An inherent challenge in using metal-organic frameworks (MOFs) for catalysis is how to access the catalytic sites generally confined inside the porous structure, in particular for substrates larger than the pores. We present here a promising solution to bypass this roadblock by modulating the facets of a crystalline MOF NENU-3a to enhance the facet exposure of the catalytic sites and the adsorption of substrates. Specifically, by transforming it with encapsulated catalysis-responsible polyoxometalate from octahedron characterized entirely by {111} facets to cube with only {100} facets, much enhanced catalytic activities were observed, especially for sterically demanding substrates that are otherwise hard to diffuse into the pores. Crystallographic analysis and adsorption/desorption experiments collectively established the critical effects of morphological control on the enhanced catalysis. The cubic crystals were then applied for biodiesel production, reaching more than 90% conversion of fatty acids (C12-C22) in comparison to <22% using octahedral crystals.

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

PubMed

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

Fabrication and electrocatalytic properties of chitosan and keplerate-type polyoxometalate {Mo72Fe30} hybrid films.

PubMed

Fan, Dawei; Hao, Jingcheng

2009-05-28

Hybrid films composed of chitosan and Keplerate-type polyoxometalate, {Mo72Fe30} (Mo72VIFe30IIIO252L102.ca.180H2O, L=H2O/CH3COO-/Mo2O8/9n-), were fabricated on quartz, silicon, and ITO substrates by layer-by-layer (LbL) method. The LbL films were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and cyclic voltammetry (CV). UV-vis spectra show that the absorbance values at characteristic wavelengths of the multilayer films increase almost linearly with the number of chitosan/{Mo72Fe30} bilayers. XPS spectra confirm the incorporation of chitosan and {Mo72Fe30} into the films. The electrocatalytic reduction of ClO3-, BrO3-, and IO3- by chitosan/{Mo72Fe30} hybrid films in an acidic aqueous solution shows an electrocatalytic reduction activity of IO3->BrO3->ClO3-. In particular, the modified electrodes exhibited high electrocatalytic activity for reduction of IO3-.

Analysis of charge transport in gels containing polyoxometallates using methods of different sensitivity to migration.

PubMed

Caban, Karolina; Lewera, Adam; Zukowska, Grazyna Z; Kulesza, Pawel J; Stojek, Zbigniew; Jeffrey, Kenneth R

2006-08-04

Two methods have been used for examination of transport of charge in gels soaked with DMF and containing dissolved polyoxometallates. The first method is based on the analysis of both Cottrellian and steady-state currents and therefore is capable of giving the concentration of the electroactive redox centres and their transport (diffusion-type) coefficient. The second method provides the real diffusion coefficients, i.e. transport coefficients free of migrational influence, for both the substrate and the product of the electrode reaction. Several gels based on poly(methyl methacrylate), with charged (addition of 1-acrylamido-2-methyl-2-propanesulphonic acid to the polymerization mixture) and uncharged chains, have been used in the investigation. The ratio obtained for the diffusion coefficient (second method) and transport coefficient (first method) was smaller for the gels containing charged polymer chains than for the gels with uncharged chains. In part these changes could be explained by the contribution of migration to the transport of polyoxomatallates in the gels. However, the impact of the changes in the polymer-channel capacity at the electrode surface while the electrode process proceeds was also considered. These structural changes should affect differently the methods based on different time domains.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Zhixia; Zhao, Mingliang; Li, Fengyan, E-mail: lify525@nenu.edu.cn

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 weremore » 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.« less

Selective monovalent cation association and exchange around Keplerate polyoxometalate macroanions in dilute aqueous solutions.

PubMed

Pigga, Joseph M; Teprovich, Joseph A; Flowers, Robert A; Antonio, Mark R; Liu, Tianbo

2010-06-15

The interaction between water-soluble Keplerate polyoxometalate {Mo(72)Fe(30)} macroions and small countercations is explored by laser light scattering, anomalous small-angle X-ray scattering (ASAXS), and isothermal titration calorimetry (ITC) techniques. The macroions are found to be able to select the type of associated counterions based upon the counterions' valence state and hydrated size, when multiple types of additional cations are present in solution (even among different monovalent cations). The preference goes to the cations with higher valences or smaller hydrated sizes if the valences are identical. This counterion exchange process changes the magnitude of the macroion-counterion interaction and, thus, is reflected in the dimension of the self-assembled {Mo(72)Fe(30)} blackberry supramolecular structures. The hydrophilic macroions exhibit a competitive recognition of various monovalent counterions in dilute solutions. A critical salt concentration (CSC) for each type of cation exists for the blackberry formation of {Mo(72)Fe(30)} macroions, above which the blackberry size increases significantly with the increasing total ionic strength in solution. The CSC values are much smaller for cations with higher valences and also decrease with the cations' hydrated size for various monovalent cations. The change of blackberry size corresponding to the change of ionic strength in solution is reversible.

The mechanism of CO2 hydration: a porous metal oxide nanocapsule catalyst can mimic the biological carbonic anhydrase role.

PubMed

Bandeira, Nuno A G; Garai, Somenath; Müller, Achim; Bo, Carles

2015-11-04

The mechanism for the hydration of CO2 within a Keplerate nanocapsule is presented. A network of hydrogen bonds across the water layers in the first metal coordination sphere facilitates the proton abstraction and nucleophilic addition of water. The highly acidic properties of the polyoxometalate cluster are crucial for explaining the catalysed hydration.

A little adjustment of synthetic strategy led to a new highly repeated heteropolyblue: Structure, characterizations and photocatalytic properties

NASA Astrophysics Data System (ADS)

Chen, Wu-Hua; Zhang, Zhu-Sen; Zhao, Jin-Hua; Qiu, Ze-Hai; Yuan, Qiu-Lan; Huang, Tian-Fu; Lin, Xue-Yu; Hu, Zhi-Biao

2017-06-01

Hydrothermal synthesis is known as the most efficient method to prepare novel structural polyoxometalate (POM)-based materials, but controlled synthesis of a structure-directing POM is always challenging task. The experimental repeatability is usually one of the key topics. To explore a reliable hydrothermal synthesis approach for new POMs will be a meaningful work. Our previous work, which we have hydrothermally synthesized the first Cr-complexes-capped Keggin-type POM, [Hdma]3[H2phen]{[Cr(phen)]2[MoV8MoVI4O36(PO4)]}·nH2O (n ≈ 2) (Chen et al., polyhedron, 2015, 85, 117), afford us some commendable synthetic experiences, arouse us some introspections as well for its tricky preparation conditions and low experimental repeatability. Based on the aforementioned work, a new high-repetition-rate and more steady heteropolyblue, [H3O]0.5(Hdma)2.5(dma)0.25{[Cr(phen)]2[MoV6MoVI6O8(PO4)]}·2H2O (1) (dma = dimethylamine (C2H7N), phen = 1,10-phenanthroline (C12H8N2)), has been successfully obtained by virtue of reasonably adjusting synthetic strategy. The adjustment of synthetic strategy includes controlling ratio of reactants and aging time, reasonably using redoxes and stepwise self-assembly plans. Compound 1 is the second POM with Keggin-type polyanion capped by Cr-complexes. Experiments demonstrate that compound 1 has good catalytic activity in the both degradation reactions of rhodamine B (RHB) and methyl orange (MO) under ultraviolet (UV)-light and oxidant H2O2 conditions. Detailed structural characterizations include single-crystal X-ray diffraction (XRD) analyses, energy-dispersive X-ray spectrometry (EDS) analyses, elemental analyses, cerate oxidimetry, powder XRD, fourier transform infrared (FT-IR) spectroscopy, ultraviolet-visible-near-infrared (UV-Vis-NIR) solid diffuse reflection spectrum and X-ray photoelectron spectroscopy (XPS) analyses. The electrochemical property (cyclic voltammetry (CV)) of compound 1 has also been studied.

Pico-level DNA sensing by hetero-polymetalate, Na10{Dy2W10O30(µ-S)6}·80H2O, cluster

NASA Astrophysics Data System (ADS)

Dutta, Taposhree; Ganguly, Jhuma; Sarkar, Sabyasachi

2018-04-01

The polyoxometalate dysprosium cluster, (Dy-S-W POM) , Na10[Dy2W10O30(µ-S)6]·80H2O, shows remarkable dsDNA denaturation property. In the presence of 0.22 µmol of this Dy-S-W POM, the melting temperature (Tm) of calf-thymus (CT) dsDNA is decreased to 62.35 °C. Dy-S-W POM shows bleaching of methylene blue (MB). Addition of CT-DNA in the MB bleached solution of Dy-S-W POM apparently intercalates MB. Such trapped MB by CT-DNA responds to its re-oxidation by elemental sulfur formed in the bleaching process involving Dy-S-W POM. This reduction-oxidation property of MB with Dy-S-W POM led to the detection of pico (13.20 pmol) level of DNA even by naked eye, which will be helpful for rapid trace DNA detection in forensic science and DNA-related diagnostics, complimenting time-consuming sophisticated methodology.

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

2011-11-07

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. © 2011 American Chemical Society

Synergistic influence of polyoxometalate surface corona towards enhancing the antibacterial performance of tyrosine-capped Ag nanoparticles.

PubMed

Daima, Hemant K; Selvakannan, P R; Kandjani, Ahmad E; Shukla, Ravi; Bhargava, Suresh K; Bansal, Vipul

2014-01-21

We illustrate a new strategy to improve the antibacterial potential of silver nanoparticles (AgNPs) by their surface modification with the surface corona of biologically active polyoxometalates (POMs). The stable POM surface corona was achieved by utilising zwitterionic tyrosine amino acid as a pH-switchable reducing and capping agent of AgNPs. The general applicability of this approach was demonstrated by developing surface coronas of phosphotungstic acid (PTA) and phosphomolybdic acid (PMA) around AgNPs. Our investigations on Gram negative bacterium Escherichia coli demonstrate that in conjugation with AgNPs, the surface corona of POMs enhances the physical damage to the bacterial cells due to synergistic antibacterial action of AgNPs and POMs, and the ability of tyrosine-reduced AgNPs (AgNPs(Y)) to act as an excellent carrier and stabiliser for the POMs. The further extension of this study towards Gram positive bacterium Staphylococcus albus showed a similar toxicity pattern, whereas these nanomaterials were found to be biocompatible for PC3 epithelial mammalian cells, suggesting the potential of these materials towards specific antimicrobial targeting for topical wound healing applications. The outcomes of this work show that facile tailorability of nanostructured surfaces may play a considerable role in controlling the biological activities of different nanomaterials.

Ultrastructural Analysis of In Vivo Hypoglycemiant Effect of Two Polyoxometalates in Rats with Streptozotocin-Induced Diabetes.

PubMed

Bâlici, Ştefana; Wankeu-Nya, Modeste; Rusu, Dan; Nicula, Gheorghe Z; Rusu, Mariana; Florea, Adrian; Matei, Horea

2015-10-01

Two polyoxometalates (POMs), synthesized through a self-assembling method, were used in the treatment of streptozotocin (STZ)-induced diabetic rats. One of these nanocompounds [tris(vanadyl)-substituted tungsto-antimonate(III)-anions—POM1] was previously described in the literature, whereas the second [tris-butyltin-21-tungsto-9-antimonate(III)-anions—POM2], was prepared by us based on our original formula. In rats with STZ-induced diabetes treated with POMs (up to a cumulative dose of 4 mg/kg bodyweight at the end of the treatments), statistically significant reduced levels of blood glucose were measured after 3 weeks, as compared with the diabetic control groups (DCGs). Ultrastructural analysis of pancreatic β-cells (including the mean diameter of secretory vesicles and of their insulin granules) in the treated diabetic rats proved the POMs contribute to limitation of cellular degeneration triggered by STZ, as well as to the presence of increased amounts of insulin-containing vesicles as compared with the DCG. The two POMs also showed hepatoprotective properties when ultrastructural aspects of hepatocytes in the experimental groups of rats were studied. Based on our in vivo studies, we concluded that the two POMs tested achieved hypoglycemiant effects by preventing STZ-triggered apoptosis of pancreatic β-cells and stimulation of insulin synthesis.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Synergistic influence of polyoxometalate surface corona towards enhancing the antibacterial performance of tyrosine-capped Ag nanoparticles

NASA Astrophysics Data System (ADS)

Daima, Hemant K.; Selvakannan, P. R.; Kandjani, Ahmad E.; Shukla, Ravi; Bhargava, Suresh K.; Bansal, Vipul

2013-12-01

We illustrate a new strategy to improve the antibacterial potential of silver nanoparticles (AgNPs) by their surface modification with the surface corona of biologically active polyoxometalates (POMs). The stable POM surface corona was achieved by utilising zwitterionic tyrosine amino acid as a pH-switchable reducing and capping agent of AgNPs. The general applicability of this approach was demonstrated by developing surface coronas of phosphotungstic acid (PTA) and phosphomolybdic acid (PMA) around AgNPs. Our investigations on Gram negative bacterium Escherichia coli demonstrate that in conjugation with AgNPs, the surface corona of POMs enhances the physical damage to the bacterial cells due to synergistic antibacterial action of AgNPs and POMs, and the ability of tyrosine-reduced AgNPs (AgNPsY) to act as an excellent carrier and stabiliser for the POMs. The further extension of this study towards Gram positive bacterium Staphylococcus albus showed a similar toxicity pattern, whereas these nanomaterials were found to be biocompatible for PC3 epithelial mammalian cells, suggesting the potential of these materials towards specific antimicrobial targeting for topical wound healing applications. The outcomes of this work show that facile tailorability of nanostructured surfaces may play a considerable role in controlling the biological activities of different nanomaterials.We illustrate a new strategy to improve the antibacterial potential of silver nanoparticles (AgNPs) by their surface modification with the surface corona of biologically active polyoxometalates (POMs). The stable POM surface corona was achieved by utilising zwitterionic tyrosine amino acid as a pH-switchable reducing and capping agent of AgNPs. The general applicability of this approach was demonstrated by developing surface coronas of phosphotungstic acid (PTA) and phosphomolybdic acid (PMA) around AgNPs. Our investigations on Gram negative bacterium Escherichia coli demonstrate that in conjugation

Polyoxometalates paneling through {Mo2O2S2} coordination: cation-directed conformations and chemistry of a supramolecular hexameric scaffold.

PubMed

Marrot, Jérôme; Pilette, Marie Anne; Haouas, Mohamed; Floquet, Sébastien; Taulelle, Francis; López, Xavier; Poblet, Josep M; Cadot, Emmanuel

2012-01-25

The chemical system based on the [Mo(2)O(2)S(2)(OH(2))(6)](2+) aqua cation (noted L) and the trivacant [AsW(9)O(33)](9-) polyoxometalate (noted POM) has been investigated. Depending upon the ionic strength and the nature of the alkali cations, these complementary components assemble to yield three different architectures derived as hexamer (1), tetramer (2), and dimer (3). This series of clusters displays the same stoichiometry {POM(6)L(9)}(36-), {POM(4)L(6)}(24-), and {POM(2)L(3)}(12-) for 1, 2, and 3, respectively, and their conditions of formation differ mainly by the nature and the concentration of the alkali cation (from Li to Cs). Structural characterizations of 1 reveal a large hexameric supramolecular scaffold (about 25 Å in diameter), which encloses a large internal hole (about 200 Å(3)) filled by water molecules and alkali cations (Na(+) or K(+)). The hexameric scaffold 1 exhibits a rare flexibility property evidenced in the solid state by two distinct conformations, either eclipsed (1a) or staggered-off (1b). Both conformations appear clearly separated by a large twist angle (~40°) and depend mainly on the composition of the internal hole. Structure of anion 2 shows a tetrahedral arrangement where the four POM units and the six connecting {Mo(2)O(2)S(2)} linkers are located at the corners and at the edges, respectively. The structure of anion 3 corresponds to the simplest arrangement, described as a dimeric association of two POM units linked by three {Mo(2)S(2)O(2)} pillars. Stability of the hexameric scaffold has been investigated in solution by (183)W and (39)K NMR and by UV-vis, showing that stability of 1 depends strongly on the proportion of potassium ions, which interfere through host-guest exchange. Density functional methodology (DFT) has been applied to compute the geometries and energies of dimer (3), tetramer (2) and hexamer (1) based on {AsW(9)O(33)} (POM) and {Mo(2)O(2)S(2)} (L) units. Calculations tend to show that internal cations act

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

PubMed

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

2006-04-03

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

Cluster-cluster clustering

NASA Technical Reports Server (NTRS)

Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C. S.

1985-01-01

The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales.

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

DOE PAGES

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 Mo 132-based SEPs are more polar than Mo 72V 30 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 Mo 132 and Mo 72V 30 SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is discussed.« less

Asymmetric Supercapacitors Based on Reduced Graphene Oxide with Different Polyoxometalates as Positive and Negative Electrodes.

PubMed

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

2017-07-10

Nanofabrication using a "bottom-up" approach of hybrid electrode materials into a well-defined architecture is essential for next-generation miniaturized energy storage devices. This paper describes the design and fabrication of reduced graphene oxide (rGO)/polyoxometalate (POM)-based hybrid electrode materials and their successful exploitation for asymmetric supercapacitors. First, redox active nanoclusters of POMs [phosphomolybdic acid (PMo 12 ) and phosphotungstic acid (PW 12 )] were uniformly decorated on the surface of rGO nanosheets to take full advantage of both charge-storing mechanisms (faradaic from POMs and electric double layer from rGO). The as-synthesized rGO-PMo 12 and rGO-PW 12 hybrid electrodes exhibited impressive electrochemical performances with specific capacitances of 299 (269 mF cm -2 ) and 370 F g -1 (369 mF cm -2 ) in 1 m H 2 SO 4 as electrolyte at 5 mA cm -2 . An asymmetric supercapacitor was then fabricated using rGO-PMo 12 as the positive and rGO-PW 12 as the negative electrode. This rGO-PMo 12 ∥rGO-PW 12 asymmetric cell could be successfully cycled in a wide voltage window up to 1.6 V and hence exhibited an excellent energy density of 39 Wh kg -1 (1.3 mWh cm -3 ) at a power density of 658 W kg -1 (23 mW cm -3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave-Assisted Preparation and Characterization of a Polyoxometalate-Based Inorganic 2D Framework Anode for Enhancing Lithium-Ion Battery Performance.

PubMed

Nie, Yan-Mei; Liang, Shuang; Yu, Wei-Dong; Yuan, Hao; Yan, Jun

2018-05-04

A pure inorganic 2D network molybdophosphate, [Mn 3 Mo 12 O 24 (OH) 6 (HPO 3 ) 8 (H 2 O) 6 ] 4- (1 a), synthesized through microwave irradiation with the existence of Mn 2+ and organic cations and isolated as [(CH 3 ) 2 NH 2 ] 3 Na[Mn 3 Mo 12 O 24 (OH) 6 (HPO 3 ) 8 (H 2 O) 6 ]⋅12 H 2 O (1), is found to possess highly enhanced performance in lithium-ion batteries' anode materials. The molecule shows multielectron redox properties suitable for producing anode materials with a specific capacity of 602 mA h g -1 at 100 mA g -1 after 50 cycles in lithium-ion batteries, although its specific capacity is the highest among all the reported pure inorganic 2D polyoxometalates to date, the cyclic stability is not that satisfactory. A hybrid nanocomposite of this 2D network and polypyrrole cations effectively reduces the capacity fading in initial cycles, and increases the stability and improves the electrochemical performance of lithium-ion batteries as well. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang Qun; Liu Shuxia, E-mail: liusx@nenu.edu.cn; Liang Dadong

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 movemore » 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.« less

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.

Cyclic oligomer of oxide clusters through a siloxane bond. Synthesis and structure of reaction products of alpha2-mono-lacunary Dawson polyoxometalate with tetrachlorosilane and tetraethoxysilane.

PubMed

Kurashina, Takayuki; Aoki, Shotaro; Hirasawa, Ryota; Hasegawa, Takeshi; Kasahara, Yuhki; Yoshida, Shoko; Yoza, Kenji; Nomiya, Kenji

2009-07-28

The title compound with the formula (Me2NH2)13H5[{alpha2-P2W17O61(Si2O)}3(micro-O)3].39H2O Me2NH(2)-1 was obtained in 12.8% (0.258 g scale) yield by a 1:2 molar ratio reaction of alpha2-mono-lacunary Dawson polyoxometalate (POM) [alpha2-P2W17O61]10- with SiCl4 in water and unequivocally characterized by complete elemental analysis, TG/DTA, FTIR, (solution and solid-state) 31P NMR, solid-state 29Si NMR and X-ray crystallography. [Note: the moieties of the polyoxoanions in Me2NH(2)-1 and Me2NH(2)-2 are abbreviated simply as 1 and 2, respectively.] X-Ray crystallography revealed that the molecular structure of polyoxoanion 1 was a cyclic trimer consisting of three alpha2-mono-lacunary Dawson POM subunits constituted through intra- and intermolecular siloxane bonds. The compound resulted in an approximate Cs symmetry, but not the idealized C3v symmetry, because one Dawson unit was unequivalently incorporated into the cyclic framework. This compound is the first example of a siloxane-bonding cyclic trimer of POMs and its formation suggests that the oxygen atoms in the lacunary site of POM are reactive just like the surface oxygen atoms of silica. The formation of the cyclic trimer was also clarified by two control experiments: (1) the reaction of [alpha2-P2W17O61]10- with Si(OEt)4 under acidic conditions (pH 1), and (2) oligomerization under 6 M aqueous HCl acidic conditions (pH approximately 0) of the reactive monomer units (RMUs: tentatively assigned as "[alpha2-P2W17O61{O(SiOH)2}]6-"), derived from the cleavage of Ph-Si bonds by the thermal degradation of [alpha2-P2W17O61{O(SiPh)2}]6-. On the other hand, the reactions of alpha2-mono-lacunary Dawson POMs with GeX4 (X=OEt, Cl) gave the monomeric species of mono-germanium-substituted Dawson POM (Me2NH2)7[alpha2-P2W17O61(GeOH)].5H2O Me2NH(2)-2, which was characterized by CHN analysis, TG/DTA, FTIR, X-ray crystallography, and (solid-state and solution) 31P NMR spectroscopy. X-ray crystallography revealed that compound Me2

High-Nuclearity Magnetic Clusters: Generalized Spin Hamiltonian and Its Use for the Calculation of the Energy Levels, Bulk Magnetic Properties, and Inelastic Neutron Scattering Spectra.

PubMed

Borrás-Almenar, J. J.; Clemente-Juan, J. M.; Coronado, E.; Tsukerblat, B. S.

1999-12-27

exchange interactions are involved. Finally this approach has been used to model the magnetic properties as well as the INS spectra of the polyoxometalate anion [Ni(9)(OH)(3)(H(2)O)(6)(HPO(4))(2)(PW(9)O(34))(3)](16)(-), which contains a central magnetic cluster formed by nine exchange-coupled Ni(II) ions surrounded by diamagnetic phosphotungstate ligands (PW(9)O(34))(9)(-).

Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

PubMed

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

2017-05-22

Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid Graphene-Polyoxometalates Nanofluids as Liquid Electrodes for Dual Energy Storage in Novel Flow Cells.

PubMed

Dubal, Deepak P; Rueda-Garcia, Daniel; Marchante, Carlos; Benages, Raul; Gomez-Romero, Pedro

2018-02-22

Solid Hybrid materials abound. But flowing versions of them are new actors in the materials science landscape and in particular for energy applications. This paper presents a new way to deliver nanostructured hybrid materials for energy storage, namely, in the form of nanofluids. We present here the first example of a hybrid electroactive nanofluid (HENFs) combining capacitive and faradaic energy storage mechanisms in a single fluid material. This liquid electrode is composed of reduced graphene oxide and polyoxometalates (rGO-POMs) forming a stable nanocomposite for electrochemical energy storage in novel Nanofluid Flow Cells. Two graphene based hybrid materials (rGO-phosphomolybdate, rGO-PMo 12 and rGO-phosphotungstate, rGO-PW 12 ) were synthesized and dispersed with the aid of a surfactant in 1 M H 2 SO 4 aqueous electrolyte to yield highly stable hybrid electroactive nanofluids (HENFs) of low viscosity which were tested in a home-made flow cell under static and continuous flowing conditions. Remarkably, even low concentration rGO-POMs HENFs (0.025 wt%) exhibited high specific capacitances of 273 F/g(rGO-PW 12 ) and 305 F/g(rGO-PMo 12 ) with high specific energy and specific power. Moreover, rGO-POM HENFs show excellent cycling stability (∼95 %) as well as Coulombic efficiency (∼77-79 %) after 2000 cycles. Thus, rGO-POM HENFs effectively behave as real liquid electrodes with excellent properties, demonstrating the possible future application of HENFs for dual energy storage in a new generation of Nanofluid Flow Cells. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intra-cluster Globular Clusters in a Simulated Galaxy Cluster

NASA Astrophysics Data System (ADS)

Ramos-Almendares, Felipe; Abadi, Mario; Muriel, Hernán; Coenda, Valeria

2018-01-01

Using a cosmological dark matter simulation of a galaxy-cluster halo, we follow the temporal evolution of its globular cluster population. To mimic the red and blue globular cluster populations, we select at high redshift (z∼ 1) two sets of particles from individual galactic halos constrained by the fact that, at redshift z = 0, they have density profiles similar to observed ones. At redshift z = 0, approximately 60% of our selected globular clusters were removed from their original halos building up the intra-cluster globular cluster population, while the remaining 40% are still gravitationally bound to their original galactic halos. As the blue population is more extended than the red one, the intra-cluster globular cluster population is dominated by blue globular clusters, with a relative fraction that grows from 60% at redshift z = 0 up to 83% for redshift z∼ 2. In agreement with observational results for the Virgo galaxy cluster, the blue intra-cluster globular cluster population is more spatially extended than the red one, pointing to a tidally disrupted origin.

Studies of cluster-assembled materials: From gas phase to condensed phase

NASA Astrophysics Data System (ADS)

Gao, Lin

. After being mass gated in a reflectron equipped time-of-flight mass spectrometer (TOF-MS) and deposited onto TEM grids, the resultant specimens can be loaded onto high-resolution TEM investigation via electron diffraction. In conclusion, soft-landing of mass selected clusters has been shown to be a successful approach to obtain structural information on Zr-Met-Car cluster-assembled materials collected from the gas phase. TEM images indicate the richness of the morphologies associated with these cluster crystals. However, passivation methods are expected to be examined further to overcome the limited stabilities of these novel clusters. From this initial study, it's shown the promising opportunity to study other Met-Cars species and more cluster-based materials. Experimental results of reactions run with a solvothermal synthesis method obtained while searching for new Zr-C cluster assembled materials, are reported. One unexpected product in single crystal form was isolated and tentatively identified by X-ray diffraction to be [Zr6i O(OH)O12·2(Bu)4], with space group P2 1/n and lattice parameters of a = 12.44 A, b = 22.06 A, c = 18.40 A, alpha = 90°, beta = 105°, gamma = 90°, V = 4875 A3 and R 1 = 3.15% for the total observed data (I ≥ 2 sigma I) and oR2 = 2.82%. This novel hexanuclear Zr(IV)-oxo-hydroxide cluster anion may be the first member in polyoxometalates class with metal atoms from the IVB group and having Oh symmetry. Alternatively, it may be the first member in {[(Zr6Z)X 12]X6}m- class with halides replaced by oxo- and hydroxyl groups and with an increased oxidation state of Zr. It is predicted to bear application potentials directed by both families. This work could suggest a direction in which the preparation of Zr-C cluster-assembled materials in a liquid environment may be eventually fulfilled. 1,3-Bis(diethylphosphino)propane (depp) protected small gold clusters are studied via multiple techniques, including Electrospray Ionization Mass Spectrometry

Fabrication and optical nonlinearities of composite films derived from the water-soluble Keplerate-type polyoxometalate and chloroform-soluble porphyrin.

PubMed

Shi, Zonghai; Zhou, Yunshan; Zhang, Lijuan; Yang, Di; Mu, Cuncun; Ren, Haizhou; Shehzad, Farooq Khurum; Li, Jiaqi

2015-03-07

Composite films derived from the water-soluble Keplerate-type polyoxometalate (NH4)42[Mo132O372(CH3COO)30(H2O)72]·ca. 300H2O·ca. 10CH3COONH4 (denoted (NH4)42{Mo132}) and chloroform-soluble tetraphenylporphyrin perchlorate [H2TPP](ClO4)2 are successfully fabricated by a layer-by-layer self-assembly method and characterized by UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS). The structure of the {Mo132} and [H2TPP](2+) in the films remain intact in light of the results of UV-vis spectroscopy and XPS. UV-vis spectra measurements reveal that the amounts of deposition of {Mo132} and [H2TPP](2+) remain constant in every adsorption cycle in the composite films assembly process. Nonlinear optical properties of the composite films have been investigated by using the Z-scan technique at a wavelength of 532 nm and pulse width of 7 ns. The results show that the composite films have notable nonlinear saturated absorption and self-defocusing effects. The combination of {Mo132} with [H2TPP](2+) can result in composite films with remarkably enhanced optical nonlinearities. The interfacial charge transfer induced by laser from porphyrin to POM in the films is thought to play a key role in the enhancement of NLO response. The third-order NLO susceptibility χ((3)) of the composite films increases with the increase of film thickness.

Ionothermal syntheses of three transition-metal-containing polyoxotungstate hybrids exhibiting the photocatalytic and electrocatalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, W.-L.; Chen, B.-W.; Tan, H.-Q.

2010-02-15

Employing the ionothermal synthesis approach, three new transition-metal-containing polyoxotungstate hybrids: [Dmim]{sub 2}Na{sub 3}[SiW{sub 11}O{sub 39}Fe(H{sub 2}O)].H{sub 2}O (Dmim=1,3-Dimethylimidazole) (1), [Emim]{sub 9}Na{sub 8}[(SiW{sub 9}O{sub 34}){sub 3}{l_brace}Fe{sub 3}(mu{sub 2}-OH){sub 2}(mu{sub 3}-O){r_brace}{sub 3}(WO{sub 4})].0.5H{sub 2}O (Emim=1-Ethyl-3-meth-ylimidazole) (2) and [Dmim]2[HMim]Na{sub 6}[(AsW{sub 9}O{sub 33}){sub 2}{l_brace}Mn{sup III}(H{sub 2}O){r_brace}{sub 3}].3H{sub 2}O (Dmim=1,3-Dimethylimidazole; Mim=1-Methylimidazole) (3) have been synthesized in 1-ethyl-3-methyl imidazolium bromide ([Emim]Br) ionic liquids (ILs). Compound 1 possesses a 3-D open framework constructed from the mono-iron{sup III}-substituted alpha-Keggin-type anion and the organic cations [Dmim]+ through the hydrogen bond interactions. Compound 2 contains a [{l_brace}Fe{sup III}{sub 3}(mu{sub 2}-OH){sub 2}(mu{sub 3}-O){r_brace}{sub 3}(mu{sub 4}-WO{sub 4})] cluster surrounded by three [SiW{submore » 9}O{sub 34}]{sup 10-} ligands, eight sodium cations and nine dissociative [Emim]{sup +} cations around the polyoxoanion. The polyoxoanion of 3 consists of a high-valent trinuclear-manganese (III)-substituted sandwiching polyoxoanion based on the [alpha-AsW{sub 9}O{sub 33}]{sup 9-} units. All the compounds are characterized by elemental analyses, IR, UV-vis spectra, TG-DTA and XRD analyses. The XPS and EPR spectra of Mn{sup III} in 3 were studied. The photocatalytic and electrocatalytic properties, as well as the stabilities of 1-3 were also investigated. - Graphical abstract: Three new transition-metal-containing polyoxotungstate hybrids were synthesized successfully under the ionothermal condition, which proves that the ionothermal synthesis is a suitable synthetic method for different kinds of polyoxometalates.« less

Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Musaev, Djamaladdin G; Hill, Craig L; Morokuma, Keiji

Abstract The central thrust of this integrated experimental and computational research program was to obtain an atomistic-level understanding of the structural and dynamic factors underlying the design of catalysts for water oxidation and selective reductant-free O2-based transformations. The focus was on oxidatively robust polyoxometalate (POM) complexes in which a catalytic active site interacts with proximal metal centers in a synergistic manner. Thirty five publications in high-impact journals arose from this grant. I. Developing an oxidatively and hydrolytically stable and fast water oxidation catalyst (WOC), a central need in the production of green fuels using water as a reductant, has provenmore » particularly challenging. During this grant period we have designed and investigated several carbon-free, molecular (homogenous), oxidatively and hydrolytically stable WOCs, including the Rb8K2[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]·25H2O (1) and [Co4(H2O)2(α-PW9O34)2]10- (2). Although complex 1 is fast, oxidatively and hydrolytically stable WOC, Ru is neither abundant nor inexpensive. Therefore, development of a stable and fast carbon-free homogenous WOC, based on earth-abundant elements became our highest priority. In 2010, we reported the first such catalyst, complex 2. This complex is substantially faster than 1 and stable under homogeneous conditions. Recently, we have extended our efforts and reported a V2-analog of the complex 2, i.e. [Co4(H2O)2(α-VW9O34)2]10- (3), which shows an even greater stability and reactivity. We succeeded in: (a) immobilizing catalysts 1 and 2 on the surface of various electrodes, and (b) elucidating the mechanism of O2 formation and release from complex 1, as well as the Mn4O4L6 “cubane” cluster. We have shown that the direct O-O bond formation is the most likely pathway for O2 formation during water oxidation catalyzed by 1. II. Oxo transfer catalysts that contain two proximal and synergistically interacting redox active

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

Effect of Heteroatoms on Field-Induced Slow Magnetic Relaxation of Mononuclear FeIII ( S = 5/2) Ions within Polyoxometalates.

PubMed

Minato, Takuo; Aravena, Daniel; Ruiz, Eliseo; Yamaguchi, Kazuya; Mizuno, Noritaka; Suzuki, Kosuke

2018-06-01

In this paper, the synthesis and magnetic properties of mononuclear Fe III -containing polyoxometalates (POMs) with different types of heteroatoms, TBA 7 H 10 [(A-α-XW 9 O 34 ) 2 Fe] (II X , X = Ge, Si; TBA = tetra- n-butylammonium), are reported. In these POMs, mononuclear highly distorted six-coordinate octahedral [FeO 6 ] 9- units are sandwiched by two trivacant lacunary units [A-α-XW 9 O 34 ] 10- (X = Ge, Si). These POMs exhibit field-induced slow magnetic relaxation based on the single high-spin Fe III magnetic center ( S = 5/2). Combining experiment and ab initio calculations, we investigated the effect of heteroatoms of the lacunary units on the field-induced slow magnetic relaxation of these POMs. By changing the heteroatoms from Si (II Si ) to Ge (II Ge ), the coordination geometry around the Fe III ion is mildly changed. Concretely, the axial Fe-O bond length in II Ge is shortened compared with that in II Si , and consequently the distortion of the [FeO 6 ] 9- unit in II Ge from the ideal octahedral coordination geometry becomes larger than that in II Si . The effective demagnetization barrier of II Ge (11.4 K) is slightly larger than that of II Si (9.2 K). Multireference ab initio calculations predict zero-field splitting parameters in good agreement with experiment. Although the differences in the coordination geometries and magnetic properties of II Ge and II Si are quite small, ab initio calculations indicate subtle changes in the magnetic anisotropy which are in line with the observed magnetic relaxation properties.

Capacity and recycling of polyoxometalate applied in As(III) oxidation by Fe(II)-Amended zero-valent aluminum.

PubMed

Hsu, Liang-Ching; Cho, Yen-Lin; Liu, Yu-Ting; Tzou, Yu-Min; Teah, Heng Yi

2018-06-01

Arsenic remediation is often initiated by oxidizing As(III) to As(V) to alleviate its toxicity and mobility. Due to the easy availability, zero-valent Al (ZVAl) like Al can was considered as potential alternatives to facilitate As(III) oxidation. This study determined the capability and recycling of polyoxometalate (POM) to catalyze As(III) oxidation in Fe(II)-amended ZVAl systems. POM acquired electrons from ZVAl more effectively at pH 1 than at pH 2. While 76% of the reduced POM [POM(e - )] reacted with O 2(g) to generate H 2 O 2 at pH 1, only 60% of POM(e - ) was used to produce H 2 O 2 at pH 2. The remaining POM(e - ) was oxidized by the generated H 2 O 2 . Such additional consumption of POM(e - ) and H 2 O 2 led to the incomplete As(III) oxidation in the system without residual ZVAl and emphasized the need for a continuous electron supply from ZVAl to compensate the depletion of POM(e - ). After the hydrolyzation at pH 6.0, the XANES data evidenced that not only As(V) but WO 4 released from the POM retained on surfaces of Al/Fe hydroxides. The competition for sorption sites on Al/Fe hydroxides between As(V) and WO 4 led to the incomplete As removal. Despite the loss of WO 4 , the POM re-polymerized at pH 1 still showed the comparable capability to catalyze As(III) oxidation with original POM. This study revealed electron transfer pathways from ZVAl to As(III) as catalyzed by POM and evidenced the effective POM recycling after As removal, which lowers the cost of POM application and turns the ZVAl/Fe(II)/POM/O 2 system into a practical strategy for As remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Document clustering methods, document cluster label disambiguation methods, document clustering apparatuses, and articles of manufacture

DOEpatents

Sanfilippo, Antonio [Richland, WA; Calapristi, Augustin J [West Richland, WA; Crow, Vernon L [Richland, WA; Hetzler, Elizabeth G [Kennewick, WA; Turner, Alan E [Kennewick, WA

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.

Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12Fe(III)30 (M = Mo(VI), W(VI)).

PubMed

Kuepper, Karsten; Derks, Christine; Taubitz, Christian; Prinz, Manuel; Joly, Loïc; Kappler, Jean-Paul; Postnikov, Andrei; Yang, Wanli; Kuznetsova, Tatyana V; Wiedwald, Ulf; Ziemann, Paul; Neumann, Manfred

2013-06-14

Giant Keplerate-type molecules with a {Mo72Fe30} core show a number of very interesting properties, making them particularly promising for various applications. So far, only limited data on the electronic structure of these molecules from X-ray spectra and electronic structure calculations have been available. Here we present a combined electronic and magnetic structure study of three Keplerate-type nanospheres--two with a {Mo72Fe30} core and one with a {W72Fe30} core by means of X-ray absorption spectroscopy, X-ray magnetic circular dichroism (XMCD), SQUID magnetometry, and complementary theoretical approaches. Furthermore, we present detailed studies of the Fe(3+)-to-Fe(2+) photoreduction process, which is induced under soft X-ray radiation in these molecules. We observe that the photoreduction rate greatly depends on the ligand structure surrounding the Fe ions, with negatively charged ligands leading to a dramatically reduced photoreduction rate. This opens the possibility of tailoring such polyoxometalates by X-ray spectroscopic studies and also for potential applications in the field of X-ray induced photochemistry.

Accuracy of embedded fragment calculation for evaluating electron interactions in mixed valence magnetic systems: study of 2e-reduced lindqvist polyoxometalates.

PubMed

Suaud, Nicolas; López, Xavier; Ben Amor, Nadia; Bandeira, Nuno A G; de Graaf, Coen; Poblet, Josep M

2015-02-10

Accurate quantum chemical calculations on real-world magnetic systems are challenging, the inclusion of electron correlation being the bottleneck of such task. One method proposed to overcome this difficulty is the embedded fragment approach. It tackles a chemical problem by dividing it into small fragments, which are treated in a highly accurate way, surrounded by an embedding included at an approximate level. For the vast family of medium-to-large sized polyoxometalates, two-electron-reduced systems are habitual and their magnetic properties are interesting. In this paper, we aim at assessing the quality of embedded fragment calculations by checking their ability to reproduce the electronic spectra of a complete system, here the mixed-metal series [MoxW6-xO19](4-) (x = 0-6). The microscopic parameters extracted from fragment calculations (electron hopping, intersite electrostatic repulsion, local orbital energy, etc.) have been used to reproduce the spectra through model Hamiltonian calculations. These energies are compared to the results of the highly accurate ab initio difference dedicated configuration interaction (DDCI) method on the complete system. In general, the model Hamiltonian calculations using parameters extracted from embedded fragments nearly exactly reproduce the DDCI spectra. This is quite an important result since it can be generalized to any inorganic magnetic system. Finally, the occurrence of singlet or triplet ground states in the series of molecules studied is rationalized upon the interplay of the parameters extracted.

Comprehensive cluster analysis with Transitivity Clustering.

PubMed

Wittkop, Tobias; Emig, Dorothea; Truss, Anke; Albrecht, Mario; Böcker, Sebastian; Baumbach, Jan

2011-03-01

Transitivity Clustering is a method for the partitioning of biological data into groups of similar objects, such as genes, for instance. It provides integrated access to various functions addressing each step of a typical cluster analysis. To facilitate this, Transitivity Clustering is accessible online and offers three user-friendly interfaces: a powerful stand-alone version, a web interface, and a collection of Cytoscape plug-ins. In this paper, we describe three major workflows: (i) protein (super)family detection with Cytoscape, (ii) protein homology detection with incomplete gold standards and (iii) clustering of gene expression data. This protocol guides the user through the most important features of Transitivity Clustering and takes ∼1 h to complete.

Cluster Physics with Merging Galaxy Clusters

NASA Astrophysics Data System (ADS)

Molnar, Sandor

Collisions between galaxy clusters provide a unique opportunity to study matter in a parameter space which cannot be explored in our laboratories on Earth. In the standard ΛCDM model, where the total density is dominated by the cosmological constant (Λ) and the matter density by cold dark matter (CDM), structure formation is hierarchical, and clusters grow mostly by merging. Mergers of two massive clusters are the most energetic events in the universe after the Big Bang, hence they provide a unique laboratory to study cluster physics. The two main mass components in clusters behave differently during collisions: the dark matter is nearly collisionless, responding only to gravity, while the gas is subject to pressure forces and dissipation, and shocks and turbulence are developed during collisions. In the present contribution we review the different methods used to derive the physical properties of merging clusters. Different physical processes leave their signatures on different wavelengths, thus our review is based on a multifrequency analysis. In principle, the best way to analyze multifrequency observations of merging clusters is to model them using N-body/HYDRO numerical simulations. We discuss the results of such detailed analyses. New high spatial and spectral resolution ground and space based telescopes will come online in the near future. Motivated by these new opportunities, we briefly discuss methods which will be feasible in the near future in studying merging clusters.

Cluster-cluster correlations and constraints on the correlation hierarchy

NASA Technical Reports Server (NTRS)

Hamilton, A. J. S.; Gott, J. R., III

1988-01-01

The hypothesis that galaxies cluster around clusters at least as strongly as they cluster around galaxies imposes constraints on the hierarchy of correlation amplitudes in hierachical clustering models. The distributions which saturate these constraints are the Rayleigh-Levy random walk fractals proposed by Mandelbrot; for these fractal distributions cluster-cluster correlations are all identically equal to galaxy-galaxy correlations. If correlation amplitudes exceed the constraints, as is observed, then cluster-cluster correlations must exceed galaxy-galaxy correlations, as is observed.

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

Convex clustering: an attractive alternative to hierarchical clustering.

PubMed

Chen, Gary K; Chi, Eric C; Ranola, John Michael O; Lange, Kenneth

2015-05-01

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/.

Cluster management.

PubMed

Katz, R

1992-11-01

Cluster management is a management model that fosters decentralization of management, develops leadership potential of staff, and creates ownership of unit-based goals. Unlike shared governance models, there is no formal structure created by committees and it is less threatening for managers. There are two parts to the cluster management model. One is the formation of cluster groups, consisting of all staff and facilitated by a cluster leader. The cluster groups function for communication and problem-solving. The second part of the cluster management model is the creation of task forces. These task forces are designed to work on short-term goals, usually in response to solving one of the unit's goals. Sometimes the task forces are used for quality improvement or system problems. Clusters are groups of not more than five or six staff members, facilitated by a cluster leader. A cluster is made up of individuals who work the same shift. For example, people with job titles who work days would be in a cluster. There would be registered nurses, licensed practical nurses, nursing assistants, and unit clerks in the cluster. The cluster leader is chosen by the manager based on certain criteria and is trained for this specialized role. The concept of cluster management, criteria for choosing leaders, training for leaders, using cluster groups to solve quality improvement issues, and the learning process necessary for manager support are described.

Clustering cancer gene expression data by projective clustering ensemble

PubMed Central

Yu, Xianxue; Yu, Guoxian

2017-01-01

Gene expression data analysis has paramount implications for gene treatments, cancer diagnosis and other domains. Clustering is an important and promising tool to analyze gene expression data. Gene expression data is often characterized by a large amount of genes but with limited samples, thus various projective clustering techniques and ensemble techniques have been suggested to combat with these challenges. However, it is rather challenging to synergy these two kinds of techniques together to avoid the curse of dimensionality problem and to boost the performance of gene expression data clustering. In this paper, we employ a projective clustering ensemble (PCE) to integrate the advantages of projective clustering and ensemble clustering, and to avoid the dilemma of combining multiple projective clusterings. Our experimental results on publicly available cancer gene expression data show PCE can improve the quality of clustering gene expression data by at least 4.5% (on average) than other related techniques, including dimensionality reduction based single clustering and ensemble approaches. The empirical study demonstrates that, to further boost the performance of clustering cancer gene expression data, it is necessary and promising to synergy projective clustering with ensemble clustering. PCE can serve as an effective alternative technique for clustering gene expression data. PMID:28234920

Seizure clustering.

PubMed

Haut, Sheryl R

2006-02-01

Seizure clusters, also known as repetitive or serial seizures, occur commonly in epilepsy. Clustering implies that the occurrence of one seizure may influence the probability of a subsequent seizure; thus, the investigation of the clustering phenomenon yields insights into both specific mechanisms of seizure clustering and more general concepts of seizure occurrence. Seizure clustering has been defined clinically as a number of seizures per unit time and, statistically, as a deviation from a random distribution, or interseizure interval dependence. This review explores the pathophysiology, epidemiology, and clinical implications of clustering, as well as other periodic patterns of seizure occurrence. Risk factors for experiencing clusters and potential precipitants of clustering are also addressed.

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

Globular clusters and environmental effects in galaxy clusters

NASA Astrophysics Data System (ADS)

Sales, Laura

2016-10-01

Globular clusters are old compact stellar systems orbiting around galaxies of all types. Tens of thousands of them can also be found populating the intra-cluster regions of nearby galaxy clusters like Virgo and Coma. Thanks to the HST Frontier Fields program, GCs are starting now to be detected also in intermediate redshift clusters. Yet, despite their ubiquity, a theoretical model for the formation and evolution of GCs is still missing, especially within the cosmological context.Here we propose to use cosmological hydrodynamical simulations of 18 galaxy clusters coupled to a post-processing GC formation model to explore the assembly of galaxies in clusters together with their expected GC population. The method, which has already been implemented and tested, will allow us to characterize for the first time the number, radial distribution and kinematics of GCs in clusters, with products directly comparable to observational maps. We will explore cluster-to-cluster variations and also characterize the build up of the intra-cluster component of GCs with time.As the method relies on a detailed study of the star-formation history of galaxies, we will jointly constrain the predicted quenching time-scales for satellites and the occurrence of starburst events associated to infall and orbital pericenters of galaxies in massive clusters. This will inform further studies on the distribution, velocity and properties of post-starburst galaxies in past, ongoing and future HST programs.

Uncertainties in the cluster-cluster correlation function

NASA Astrophysics Data System (ADS)

Ling, E. N.; Frenk, C. S.; Barrow, J. D.

1986-12-01

The bootstrap resampling technique is applied to estimate sampling errors and significance levels of the two-point correlation functions determined for a subset of the CfA redshift survey of galaxies and a redshift sample of 104 Abell clusters. The angular correlation function for a sample of 1664 Abell clusters is also calculated. The standard errors in xi(r) for the Abell data are found to be considerably larger than quoted 'Poisson errors'. The best estimate for the ratio of the correlation length of Abell clusters (richness class R greater than or equal to 1, distance class D less than or equal to 4) to that of CfA galaxies is 4.2 + 1.4 or - 1.0 (68 percentile error). The enhancement of cluster clustering over galaxy clustering is statistically significant in the presence of resampling errors. The uncertainties found do not include the effects of possible systematic biases in the galaxy and cluster catalogs and could be regarded as lower bounds on the true uncertainty range.

The cluster-cluster correlation function. [of galaxies

NASA Technical Reports Server (NTRS)

Postman, M.; Geller, M. J.; Huchra, J. P.

1986-01-01

The clustering properties of the Abell and Zwicky cluster catalogs are studied using the two-point angular and spatial correlation functions. The catalogs are divided into eight subsamples to determine the dependence of the correlation function on distance, richness, and the method of cluster identification. It is found that the Corona Borealis supercluster contributes significant power to the spatial correlation function to the Abell cluster sample with distance class of four or less. The distance-limited catalog of 152 Abell clusters, which is not greatly affected by a single system, has a spatial correlation function consistent with the power law Xi(r) = 300r exp -1.8. In both the distance class four or less and distance-limited samples the signal in the spatial correlation function is a power law detectable out to 60/h Mpc. The amplitude of Xi(r) for clusters of richness class two is about three times that for richness class one clusters. The two-point spatial correlation function is sensitive to the use of estimated redshifts.

Are clusters of dietary patterns and cluster membership stable over time? Results of a longitudinal cluster analysis study.

PubMed

Walthouwer, Michel Jean Louis; Oenema, Anke; Soetens, Katja; Lechner, Lilian; de Vries, Hein

2014-11-01

Developing nutrition education interventions based on clusters of dietary patterns can only be done adequately when it is clear if distinctive clusters of dietary patterns can be derived and reproduced over time, if cluster membership is stable, and if it is predictable which type of people belong to a certain cluster. Hence, this study aimed to: (1) identify clusters of dietary patterns among Dutch adults, (2) test the reproducibility of these clusters and stability of cluster membership over time, and (3) identify sociodemographic predictors of cluster membership and cluster transition. This study had a longitudinal design with online measurements at baseline (N=483) and 6 months follow-up (N=379). Dietary intake was assessed with a validated food frequency questionnaire. A hierarchical cluster analysis was performed, followed by a K-means cluster analysis. Multinomial logistic regression analyses were conducted to identify the sociodemographic predictors of cluster membership and cluster transition. At baseline and follow-up, a comparable three-cluster solution was derived, distinguishing a healthy, moderately healthy, and unhealthy dietary pattern. Male and lower educated participants were significantly more likely to have a less healthy dietary pattern. Further, 251 (66.2%) participants remained in the same cluster, 45 (11.9%) participants changed to an unhealthier cluster, and 83 (21.9%) participants shifted to a healthier cluster. Men and people living alone were significantly more likely to shift toward a less healthy dietary pattern. Distinctive clusters of dietary patterns can be derived. Yet, cluster membership is unstable and only few sociodemographic factors were associated with cluster membership and cluster transition. These findings imply that clusters based on dietary intake may not be suitable as a basis for nutrition education interventions. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

A Strategy to Enhance the Efficiency of Quantum Dot-Sensitized Solar Cells by Decreasing Electron Recombination with Polyoxometalate/TiO2 as the Electronic Interface Layer.

PubMed

Chen, Li; Chen, Weilin; Li, Jianping; Wang, Jiabo; Wang, Enbo

2017-07-21

Electron recombination occurring at the TiO 2 /quantum dot sensitizer/electrolyte interface is the key reason for hindering further efficiency improvements to quantum dot sensitized solar cells (QDSCs). Polyoxometalate (POM) can act as an electron-transfer medium to decrease electron recombination in a photoelectric device owing to its excellent oxidation/reduction properties and thermostability. A POM/TiO 2 electronic interface layer prepared by a simple layer-by-layer self-assembly method was added between fluorine-doped tin oxide (FTO) and mesoporous TiO 2 in the photoanode of QDSCs, and the effect on the photovoltaic performance was systematically investigated. Photovoltaic experimental results and the electron transmission mechanism show that the POM/TiO 2 electronic interface layer in the QDSCs can clearly suppress electron recombination, increase the electron lifetime, and result in smoother electron transmission. In summary, the best conversion efficiency of QDSCs with POM/TiO 2 electronic interface layers increases to 8.02 %, which is an improvement of 25.1 % compared with QDSCs without POM/TiO 2 . This work first builds an electron-transfer bridge between FTO and the quantum dot sensitizer and paves the way for further improved efficiency of QDSCs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fate of a giant {Mo72Fe30}-type polyoxometalate cluster in an aqueous solution at higher temperature: understanding related Keplerate chemistry, from molecule to material.

PubMed

Mekala, Raju; Supriya, Sabbani; Das, Samar K

2013-09-03

When the giant icosahedral {Mo72Fe30} cluster containing compound [Mo72Fe30O252(CH3COO)12{Mo2O7(H2O)}2{H2Mo2O8(H2O)}(H2O)91]·150H2O (1) is refluxed in water for 36 h, it results in the formation of nanoiron molybdate, Fe2(MoO4)3, in the form of a yellow precipitate; this simple approach not only generates nanoferric molybdate at a moderate temperature but also helps to understand the stability of {Mo72Fe30} in terms of the linker-pentagon complementary relationship.

Diametrical clustering for identifying anti-correlated gene clusters.

PubMed

Dhillon, Inderjit S; Marcotte, Edward M; Roshan, Usman

2003-09-01

Clustering genes based upon their expression patterns allows us to predict gene function. Most existing clustering algorithms cluster genes together when their expression patterns show high positive correlation. However, it has been observed that genes whose expression patterns are strongly anti-correlated can also be functionally similar. Biologically, this is not unintuitive-genes responding to the same stimuli, regardless of the nature of the response, are more likely to operate in the same pathways. We present a new diametrical clustering algorithm that explicitly identifies anti-correlated clusters of genes. Our algorithm proceeds by iteratively (i). re-partitioning the genes and (ii). computing the dominant singular vector of each gene cluster; each singular vector serving as the prototype of a 'diametric' cluster. We empirically show the effectiveness of the algorithm in identifying diametrical or anti-correlated clusters. Testing the algorithm on yeast cell cycle data, fibroblast gene expression data, and DNA microarray data from yeast mutants reveals that opposed cellular pathways can be discovered with this method. We present systems whose mRNA expression patterns, and likely their functions, oppose the yeast ribosome and proteosome, along with evidence for the inverse transcriptional regulation of a number of cellular systems.

The HectoMAP Cluster Survey. II. X-Ray Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sohn, Jubee; Chon, Gayoung; Bohringer, Hans

Here, we apply a friends-of-friends algorithm to the HectoMAP redshift survey and cross-identify associated X-ray emission in the ROSAT All-Sky Survey data (RASS). The resulting flux-limited catalog of X-ray cluster surveys is complete to a limiting flux of ~3 × 10 –13 erg s –1 cm –2 and includes 15 clusters (7 newly discovered) with redshifts z ≤ 0.4. HectoMAP is a dense survey (~1200 galaxies deg –2) that provides ~50 members (median) in each X-ray cluster. We provide redshifts for the 1036 cluster members. Subaru/Hyper Suprime-Cam imaging covers three of the X-ray systems and confirms that they are impressivemore » clusters. The HectoMAP X-ray clusters have an L X–σ cl scaling relation similar to that of known massive X-ray clusters. The HectoMAP X-ray cluster sample predicts ~12,000 ± 3000 detectable X-ray clusters in RASS to the limiting flux, comparable with previous estimates.« less

The HectoMAP Cluster Survey. II. X-Ray Clusters

DOE PAGES

Sohn, Jubee; Chon, Gayoung; Bohringer, Hans; ...

2018-03-10

Here, we apply a friends-of-friends algorithm to the HectoMAP redshift survey and cross-identify associated X-ray emission in the ROSAT All-Sky Survey data (RASS). The resulting flux-limited catalog of X-ray cluster surveys is complete to a limiting flux of ~3 × 10 –13 erg s –1 cm –2 and includes 15 clusters (7 newly discovered) with redshifts z ≤ 0.4. HectoMAP is a dense survey (~1200 galaxies deg –2) that provides ~50 members (median) in each X-ray cluster. We provide redshifts for the 1036 cluster members. Subaru/Hyper Suprime-Cam imaging covers three of the X-ray systems and confirms that they are impressivemore » clusters. The HectoMAP X-ray clusters have an L X–σ cl scaling relation similar to that of known massive X-ray clusters. The HectoMAP X-ray cluster sample predicts ~12,000 ± 3000 detectable X-ray clusters in RASS to the limiting flux, comparable with previous estimates.« less

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.

Synthesis, characterization and bioimaging of fluorescent labeled polyoxometalates.

PubMed

Geisberger, Georg; Gyenge, Emina Besic; Hinger, Doris; Bösiger, Peter; Maake, Caroline; Patzke, Greta R

2013-07-21

A fluorescent labeled Wells-Dawson type POM ({P2W17O61Fluo}) was newly synthesized and characterized by a wide range of analytical methods. {P2W17O61Fluo} was functionalized with fluorescein amine through a stable amide bond, and its long time stability was verified by UV/vis spectroscopic techniques at physiologically relevant pH values. No significant impact on the cell viability or morphology of HeLa cells was observed for POM concentrations up to 100 μg mL(-1). Cellular uptake of fluorescent {P2W17O61Fluo} was monitored by confocal laser scanning microscopy. POM uptake occurs mainly after prolonged incubation times of 24 h resulting in different intracellular patterns, i.e. randomly distributed over the entire cytoplasm, or aggregated in larger clusters. This direct monitoring strategy for the interaction of POMs with cells opens up new pathways for elucidating their unknown mode of action on the way to POM-based drug development.

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.

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

ClusterViz: A Cytoscape APP for Cluster Analysis of Biological Network.

PubMed

Wang, Jianxin; Zhong, Jiancheng; Chen, Gang; Li, Min; Wu, Fang-xiang; Pan, Yi

2015-01-01

Cluster analysis of biological networks is one of the most important approaches for identifying functional modules and predicting protein functions. Furthermore, visualization of clustering results is crucial to uncover the structure of biological networks. In this paper, ClusterViz, an APP of Cytoscape 3 for cluster analysis and visualization, has been developed. In order to reduce complexity and enable extendibility for ClusterViz, we designed the architecture of ClusterViz based on the framework of Open Services Gateway Initiative. According to the architecture, the implementation of ClusterViz is partitioned into three modules including interface of ClusterViz, clustering algorithms and visualization and export. ClusterViz fascinates the comparison of the results of different algorithms to do further related analysis. Three commonly used clustering algorithms, FAG-EC, EAGLE and MCODE, are included in the current version. Due to adopting the abstract interface of algorithms in module of the clustering algorithms, more clustering algorithms can be included for the future use. To illustrate usability of ClusterViz, we provided three examples with detailed steps from the important scientific articles, which show that our tool has helped several research teams do their research work on the mechanism of the biological networks.

GibbsCluster: unsupervised clustering and alignment of peptide sequences.

PubMed

Andreatta, Massimo; Alvarez, Bruno; Nielsen, Morten

2017-07-03

Receptor interactions with short linear peptide fragments (ligands) are at the base of many biological signaling processes. Conserved and information-rich amino acid patterns, commonly called sequence motifs, shape and regulate these interactions. Because of the properties of a receptor-ligand system or of the assay used to interrogate it, experimental data often contain multiple sequence motifs. GibbsCluster is a powerful tool for unsupervised motif discovery because it can simultaneously cluster and align peptide data. The GibbsCluster 2.0 presented here is an improved version incorporating insertion and deletions accounting for variations in motif length in the peptide input. In basic terms, the program takes as input a set of peptide sequences and clusters them into meaningful groups. It returns the optimal number of clusters it identified, together with the sequence alignment and sequence motif characterizing each cluster. Several parameters are available to customize cluster analysis, including adjustable penalties for small clusters and overlapping groups and a trash cluster to remove outliers. As an example application, we used the server to deconvolute multiple specificities in large-scale peptidome data generated by mass spectrometry. The server is available at http://www.cbs.dtu.dk/services/GibbsCluster-2.0. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Membership determination of open clusters based on a spectral clustering method

NASA Astrophysics Data System (ADS)

Gao, Xin-Hua

2018-06-01

We present a spectral clustering (SC) method aimed at segregating reliable members of open clusters in multi-dimensional space. The SC method is a non-parametric clustering technique that performs cluster division using eigenvectors of the similarity matrix; no prior knowledge of the clusters is required. This method is more flexible in dealing with multi-dimensional data compared to other methods of membership determination. We use this method to segregate the cluster members of five open clusters (Hyades, Coma Ber, Pleiades, Praesepe, and NGC 188) in five-dimensional space; fairly clean cluster members are obtained. We find that the SC method can capture a small number of cluster members (weak signal) from a large number of field stars (heavy noise). Based on these cluster members, we compute the mean proper motions and distances for the Hyades, Coma Ber, Pleiades, and Praesepe clusters, and our results are in general quite consistent with the results derived by other authors. The test results indicate that the SC method is highly suitable for segregating cluster members of open clusters based on high-precision multi-dimensional astrometric data such as Gaia data.

WordCluster: detecting clusters of DNA words and genomic elements

PubMed Central

2011-01-01

Background Many k-mers (or DNA words) and genomic elements are known to be spatially clustered in the genome. Well established examples are the genes, TFBSs, CpG dinucleotides, microRNA genes and ultra-conserved non-coding regions. Currently, no algorithm exists to find these clusters in a statistically comprehensible way. The detection of clustering often relies on densities and sliding-window approaches or arbitrarily chosen distance thresholds. Results We introduce here an algorithm to detect clusters of DNA words (k-mers), or any other genomic element, based on the distance between consecutive copies and an assigned statistical significance. We implemented the method into a web server connected to a MySQL backend, which also determines the co-localization with gene annotations. We demonstrate the usefulness of this approach by detecting the clusters of CAG/CTG (cytosine contexts that can be methylated in undifferentiated cells), showing that the degree of methylation vary drastically between inside and outside of the clusters. As another example, we used WordCluster to search for statistically significant clusters of olfactory receptor (OR) genes in the human genome. Conclusions WordCluster seems to predict biological meaningful clusters of DNA words (k-mers) and genomic entities. The implementation of the method into a web server is available at http://bioinfo2.ugr.es/wordCluster/wordCluster.php including additional features like the detection of co-localization with gene regions or the annotation enrichment tool for functional analysis of overlapped genes. PMID:21261981

Chemodynamical Clustering Applied to APOGEE Data: Rediscovering Globular Clusters

NASA Astrophysics Data System (ADS)

Chen, Boquan; D’Onghia, Elena; Pardy, Stephen A.; Pasquali, Anna; Bertelli Motta, Clio; Hanlon, Bret; Grebel, Eva K.

2018-06-01

We have developed a novel technique based on a clustering algorithm that searches for kinematically and chemically clustered stars in the APOGEE DR12 Cannon data. As compared to classical chemical tagging, the kinematic information included in our methodology allows us to identify stars that are members of known globular clusters with greater confidence. We apply our algorithm to the entire APOGEE catalog of 150,615 stars whose chemical abundances are derived by the Cannon. Our methodology found anticorrelations between the elements Al and Mg, Na and O, and C and N previously identified in the optical spectra in globular clusters, even though we omit these elements in our algorithm. Our algorithm identifies globular clusters without a priori knowledge of their locations in the sky. Thus, not only does this technique promise to discover new globular clusters, but it also allows us to identify candidate streams of kinematically and chemically clustered stars in the Milky Way.

Two supramolecular complexes based on polyoxometalates and Co-EDTA units via covalent connection or non-covalent interaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teng, Chunlin; Xiao, Hanxi; Cai, Qing

Two new 3D network organic-inorganic hybrid supramolecular complexes ([Na{sub 6}(CoEDTA){sub 2}(H{sub 2}O){sub 13}]·(H{sub 2}SiW{sub 12}O{sub 40})·xH{sub 2}O)n (1) and [CoH{sub 4}EDTA(H{sub 2}O)]{sub 2}(SiW{sub 12}O{sub 40})·15H{sub 2}O (2) (H{sub 4}EDTA=Ethylenediamine tetraacetic acid) have been successfully synthesized by solution method, and characterized by infrared spectrum (IR), thermogravimetric-differential thermal analysis (TG-DTA), cyclic voltammetry (CV) and single{sup −}crystal X-ray diffraction (XRD). Both of the complexes are the supramolecules, but with different liking mode, they are two representative models of supramolecule. complex (1) is a 3D infinite network supramolecular coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through coordinate-covalent bonds.more » While complex (2) is normal supramolecule, which linked by non-covalent interactions, such as H-bonding interaction, electrostatic interaction and van der waals force. Both of complex (1) and (2) exhibit good catalytic activities for catalytic oxidation of methanol, when the initial concentration of methanol is 3.0 g m{sup −3}, flow rate is 10 mL min{sup −1}, and the quality of catalyst is 0.2 g, for complex (1) and complex (2) the maximum elimination rates of methanol are 85% (150 °C) and 92% (120 °C), respectively. - Graphical abstract: Two new organic-inorganic hybrid supramolecular complexes based on Co-EDTA, and Keggin polyanions have been successfully synthesized with different pH value by solution method. They are attributed to two representative models of supramolecule. Complex(1) is an infinite coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through covalent bonds. Complex (2) is a normal supramolecule, which linked by non-covalent interactions of H-bonding interaction, electrostatic interaction and van der waals force. - Highlights: • Two

Primordial binary populations in low-density star clusters as seen by Chandra: globular clusters versus old open clusters

NASA Astrophysics Data System (ADS)

van den Berg, Maureen C.

2015-08-01

The binaries in the core of a star cluster are the energy source that prevents the cluster from experiencing core collapse. To model the dynamical evolution of a cluster, it is important to have constraints on the primordial binary content. X-ray observations of old star clusters are very efficient in detecting the close interacting binaries among the cluster members. The X-ray sources in star clusters are a mix of binaries that were dynamically formed and primordial binaries. In massive, dense star clusters, dynamical encounters play an important role in shaping the properties and numbers of the binaries. In contrast, in the low-density clusters the impact of dynamical encounters is presumed to be very small, and the close binaries detected in X-rays represent a primordial population. The lowest density globular clusters have current masses and central densities similar to those of the oldest open clusters in our Milky Way. I will discuss the results of studies with the Chandra X-ray Observatory that have nevertheless revealed a clear dichotomy: far fewer (if any at all) X-ray sources are detected in the central regions of the low-density globular clusters compared to the number of secure cluster members that have been detected in old open clusters (above a limiting X-ray luminosity of typically 4e30 erg/s). The low stellar encounter rates imply that dynamical destruction of binaries can be ignored at present, therefore an explanation must be sought elsewhere. I will discuss several factors that can shed light on the implied differences between the primordial close binary populations in the two types of star clusters.

Photochemical oxidation of water and reduction of polyoxometalate anions at interfaces of water with ionic liquids or diethylether

PubMed Central

Bernardini, Gianluca; Wedd, Anthony G.; Zhao, Chuan; Bond, Alan M.

2012-01-01

Photoreduction of [P2W18O62]6-, [S2Mo18O62]4-, and [S2W18O62]4- polyoxometalate anions (POMs) and oxidation of water occurs when water–ionic liquid and water–diethylether interfaces are irradiated with white light (275–750 nm) or sunlight. The ionic liquids (ILs) employed were aprotic ([Bmim]X; Bmim = (1-butyl-3-methylimidazolium,X = BF4,PF6) and protic (DEAS = diethanolamine hydrogen sulphate; DEAP = diethanolamine hydrogen phosphate). Photochemical formation of reduced POMs at both thermodynamically stable and unstable water–IL interfaces led to their initial diffusion into the aqueous phase and subsequent extraction into the IL phase. The mass transport was monitored visually by color change and by steady-state voltammetry at microelectrodes placed near the interface and in the bulk solution phases. However, no diffusion into the organic phase was observed when [P2W18O62]6- was photo-reduced at the water–diethylether interface. In all cases, water acted as the electron donor to give the overall process: 4POM + 2H2O + hν → 4POM- + 4H+ + O2. However, more highly reduced POM species are likely to be generated as intermediates. The rate of diffusion of photo-generated POM- was dependent on the initial concentration of oxidized POM and the viscosity of the IL (or mixed phase system produced in cases in which the interface is thermodynamically unstable). In the water-DEAS system, the evolution of dioxygen was monitored in situ in the aqueous phase by using a Clark-type oxygen sensor. Differences in the structures of bulk and interfacial water are implicated in the activation of water. An analogous series of reactions occurred upon irradiation of solid POM salts in the presence of water vapor. PMID:22753501

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.

Fast Constrained Spectral Clustering and Cluster Ensemble with Random Projection

PubMed Central

Liu, Wenfen

2017-01-01

Constrained spectral clustering (CSC) method can greatly improve the clustering accuracy with the incorporation of constraint information into spectral clustering and thus has been paid academic attention widely. In this paper, we propose a fast CSC algorithm via encoding landmark-based graph construction into a new CSC model and applying random sampling to decrease the data size after spectral embedding. Compared with the original model, the new algorithm has the similar results with the increase of its model size asymptotically; compared with the most efficient CSC algorithm known, the new algorithm runs faster and has a wider range of suitable data sets. Meanwhile, a scalable semisupervised cluster ensemble algorithm is also proposed via the combination of our fast CSC algorithm and dimensionality reduction with random projection in the process of spectral ensemble clustering. We demonstrate by presenting theoretical analysis and empirical results that the new cluster ensemble algorithm has advantages in terms of efficiency and effectiveness. Furthermore, the approximate preservation of random projection in clustering accuracy proved in the stage of consensus clustering is also suitable for the weighted k-means clustering and thus gives the theoretical guarantee to this special kind of k-means clustering where each point has its corresponding weight. PMID:29312447

Cluster Dynamical Mass from Magellan Multi-Object Spectroscopy for SGAS Clusters

NASA Astrophysics Data System (ADS)

Murray, Katherine; Sharon, Keren; Johnson, Traci; Gifford, Daniel; Gladders, Michael; Bayliss, Matthew; Florian, Michael; Rigby, Jane R.; Miller, Christopher J.

2016-01-01

Galaxy clusters are giant structures in space consisting of hundreds or thousands of galaxies, interstellar matter, and dark matter, all bound together by gravity. We analyze the spectra of the cluster members of several strong lensing clusters from a large program, the Sloan Giant Arcs Survey, to determine the total mass of the lensing clusters. From spectra obtained with the LDSS3 and IMACS cameras on the Magellan 6.5m telescopes, we measure the spectroscopic redshifts of about 50 galaxies in each cluster, and calculate the velocity distributions within the galaxy clusters, as well as their projected cluster-centric radii. From these two pieces of information, we measure the size and total dynamical mass of each cluster. We can combine this calculation with other measurements of mass of the same galaxy clusters (like measurements from strong lensing or X-ray) to determine the spatial distribution of luminous and dark matter out to the virial radius of the cluster.

Spitzer Clusters

NASA Astrophysics Data System (ADS)

Krick, Kessica

This proposal is a specific response to the strategic goal of NASA's research program to "discover how the universe works and explore how the universe evolved into its present form." Towards this goal, we propose to mine the Spitzer archive for all observations of galaxy groups and clusters for the purpose of studying galaxy evolution in clusters, contamination rates for Sunyaev Zeldovich cluster surveys, and to provide a database of Spitzer observed clusters to the broader community. Funding from this proposal will go towards two years of support for a Postdoc to do this work. After searching the Spitzer Heritage Archive, we have found 194 unique galaxy groups and clusters that have data from both the Infrared array camera (IRAC; Fazio et al. 2004) at 3.6 - 8 microns and the multiband imaging photometer for Spitzer (MIPS; Rieke et al. 2004) at 24microns. This large sample will add value beyond the individual datasets because it will be a larger sample of IR clusters than ever before and will have sufficient diversity in mass, redshift, and dynamical state to allow us to differentiate amongst the effects of these cluster properties. An infrared sample is important because it is unaffected by dust extinction while at the same time is an excellent measure of both stellar mass (IRAC wavelengths) and star formation rate (MIPS wavelengths). Additionally, IRAC can be used to differentiate star forming galaxies (SFG) from active galactic nuclei (AGN), due to their different spectral shapes in this wavelength regime. Specifically, we intend to identify SFG and AGN in galaxy groups and clusters. Groups and clusters differ from the field because the galaxy densities are higher, there is a large potential well due mainly to the mass of the dark matter, and there is hot X-ray gas (the intracluster medium; ICM). We will examine the impact of these differences in environment on galaxy formation by comparing cluster properties of AGN and SFG to those in the field. Also, we will

Evolutionary Metal Oxide Clusters for Novel Applications: Toward High-Density Data Storage in Nonvolatile Memories.

PubMed

Chen, Xiaoli; Zhou, Ye; Roy, Vellaisamy A L; Han, Su-Ting

2018-01-01

Because of current fabrication limitations, miniaturizing nonvolatile memory devices for managing the explosive increase in big data is challenging. Molecular memories constitute a promising candidate for next-generation memories because their properties can be readily modulated through chemical synthesis. Moreover, these memories can be fabricated through mild solution processing, which can be easily scaled up. Among the various materials, polyoxometalate (POM) molecules have attracted considerable attention for use as novel data-storage nodes for nonvolatile memories. Here, an overview of recent advances in the development of POMs for nonvolatile memories is presented. The general background knowledge of the structure and property diversity of POMs is also summarized. Finally, the challenges and perspectives in the application of POMs in memories are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Cluster Bootstrapping to Analyze Nested Data With a Few Clusters.

PubMed

Huang, Francis L

2018-04-01

Cluster randomized trials involving participants nested within intact treatment and control groups are commonly performed in various educational, psychological, and biomedical studies. However, recruiting and retaining intact groups present various practical, financial, and logistical challenges to evaluators and often, cluster randomized trials are performed with a low number of clusters (~20 groups). Although multilevel models are often used to analyze nested data, researchers may be concerned of potentially biased results due to having only a few groups under study. Cluster bootstrapping has been suggested as an alternative procedure when analyzing clustered data though it has seen very little use in educational and psychological studies. Using a Monte Carlo simulation that varied the number of clusters, average cluster size, and intraclass correlations, we compared standard errors using cluster bootstrapping with those derived using ordinary least squares regression and multilevel models. Results indicate that cluster bootstrapping, though more computationally demanding, can be used as an alternative procedure for the analysis of clustered data when treatment effects at the group level are of primary interest. Supplementary material showing how to perform cluster bootstrapped regressions using R is also provided.

Scientific Cluster Deployment and Recovery - Using puppet to simplify cluster management

NASA Astrophysics Data System (ADS)

Hendrix, Val; Benjamin, Doug; Yao, Yushu

2012-12-01

Deployment, maintenance and recovery of a scientific cluster, which has complex, specialized services, can be a time consuming task requiring the assistance of Linux system administrators, network engineers as well as domain experts. Universities and small institutions that have a part-time FTE with limited time for and knowledge of the administration of such clusters can be strained by such maintenance tasks. This current work is the result of an effort to maintain a data analysis cluster (DAC) with minimal effort by a local system administrator. The realized benefit is the scientist, who is the local system administrator, is able to focus on the data analysis instead of the intricacies of managing a cluster. Our work provides a cluster deployment and recovery process (CDRP) based on the puppet configuration engine allowing a part-time FTE to easily deploy and recover entire clusters with minimal effort. Puppet is a configuration management system (CMS) used widely in computing centers for the automatic management of resources. Domain experts use Puppet's declarative language to define reusable modules for service configuration and deployment. Our CDRP has three actors: domain experts, a cluster designer and a cluster manager. The domain experts first write the puppet modules for the cluster services. A cluster designer would then define a cluster. This includes the creation of cluster roles, mapping the services to those roles and determining the relationships between the services. Finally, a cluster manager would acquire the resources (machines, networking), enter the cluster input parameters (hostnames, IP addresses) and automatically generate deployment scripts used by puppet to configure it to act as a designated role. In the event of a machine failure, the originally generated deployment scripts along with puppet can be used to easily reconfigure a new machine. The cluster definition produced in our CDRP is an integral part of automating cluster deployment

Cluster-lensing: A Python Package for Galaxy Clusters and Miscentering

NASA Astrophysics Data System (ADS)

Ford, Jes; VanderPlas, Jake

2016-12-01

We describe a new open source package for calculating properties of galaxy clusters, including Navarro, Frenk, and White halo profiles with and without the effects of cluster miscentering. This pure-Python package, cluster-lensing, provides well-documented and easy-to-use classes and functions for calculating cluster scaling relations, including mass-richness and mass-concentration relations from the literature, as well as the surface mass density {{Σ }}(R) and differential surface mass density {{Δ }}{{Σ }}(R) profiles, probed by weak lensing magnification and shear. Galaxy cluster miscentering is especially a concern for stacked weak lensing shear studies of galaxy clusters, where offsets between the assumed and the true underlying matter distribution can lead to a significant bias in the mass estimates if not accounted for. This software has been developed and released in a public GitHub repository, and is licensed under the permissive MIT license. The cluster-lensing package is archived on Zenodo. Full documentation, source code, and installation instructions are available at http://jesford.github.io/cluster-lensing/.

Organic-inorganic hybrid resists for EUVL

NASA Astrophysics Data System (ADS)

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

2014-03-01

Herein, we describe preliminary results on organic-inorganic hybrid photoresists, capable of showing line patterns up to 16 nm under e-beam exposure studies, prepared by incorporating polyoxometalates (POMs) clusters into organic photoresist materials. Various Mo and W based clusters such as (TBA)2[Mo6O19], (TBA)5(H)[P2V3W15O62] and (TBA)4[P2Mo18O61] (where TBA = tetrabutyl ammonium counter ion) have been incorporated into PMMA matrix by mixing POM solutions and standard PMMA polymer in anisole (MW ~ 95000, MicroChem) in 1:33 w/v ratio. E-beam exposure followed by development with MIBK solutions showed that these new organic-inorganic hybrid photoresists show good line patterns upto 16 nm, which were not observed in the case of control experiments done on pure PMMA polymer resist. The observed enhancement of resist properties in the case of hybrid resists could possibly be due to a combination of features imparted to the resist by the POM clusters such as increased sensitivity, etch resistance and thermal stability.

Merging Clusters, Cluster Outskirts, and Large Scale Filaments

NASA Astrophysics Data System (ADS)

Randall, Scott; Alvarez, Gabriella; Bulbul, Esra; Jones, Christine; Forman, William; Su, Yuanyuan; Miller, Eric D.; Bourdin, Herve; Scott Randall

2018-01-01

Recent X-ray observations of the outskirts of clusters show that entropy profiles of the intracluster medium (ICM) generally flatten and lie below what is expected from purely gravitational structure formation near the cluster's virial radius. Possible explanations include electron/ion non-equilibrium, accretion shocks that weaken during cluster formation, and the presence of unresolved cool gas clumps. Some of these mechanisms are expected to correlate with large scale structure (LSS), such that the entropy is lower in regions where the ICM interfaces with LSS filaments and, presumably, the warm-hot intergalactic medium (WHIM). Major, binary cluster mergers are expected to take place at the intersection of LSS filaments, with the merger axis initially oriented along a filament. We present results from deep X-ray observations of the virialization regions of binary, early-stage merging clusters, including a possible detection of the dense end of the WHIM along a LSS filament.

Changing cluster composition in cluster randomised controlled trials: design and analysis considerations

PubMed Central

2014-01-01

Background There are many methodological challenges in the conduct and analysis of cluster randomised controlled trials, but one that has received little attention is that of post-randomisation changes to cluster composition. To illustrate this, we focus on the issue of cluster merging, considering the impact on the design, analysis and interpretation of trial outcomes. Methods We explored the effects of merging clusters on study power using standard methods of power calculation. We assessed the potential impacts on study findings of both homogeneous cluster merges (involving clusters randomised to the same arm of a trial) and heterogeneous merges (involving clusters randomised to different arms of a trial) by simulation. To determine the impact on bias and precision of treatment effect estimates, we applied standard methods of analysis to different populations under analysis. Results Cluster merging produced a systematic reduction in study power. This effect depended on the number of merges and was most pronounced when variability in cluster size was at its greatest. Simulations demonstrate that the impact on analysis was minimal when cluster merges were homogeneous, with impact on study power being balanced by a change in observed intracluster correlation coefficient (ICC). We found a decrease in study power when cluster merges were heterogeneous, and the estimate of treatment effect was attenuated. Conclusions Examples of cluster merges found in previously published reports of cluster randomised trials were typically homogeneous rather than heterogeneous. Simulations demonstrated that trial findings in such cases would be unbiased. However, simulations also showed that any heterogeneous cluster merges would introduce bias that would be hard to quantify, as well as having negative impacts on the precision of estimates obtained. Further methodological development is warranted to better determine how to analyse such trials appropriately. Interim recommendations

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.

Fuzzy Subspace Clustering

NASA Astrophysics Data System (ADS)

Borgelt, Christian

In clustering we often face the situation that only a subset of the available attributes is relevant for forming clusters, even though this may not be known beforehand. In such cases it is desirable to have a clustering algorithm that automatically weights attributes or even selects a proper subset. In this paper I study such an approach for fuzzy clustering, which is based on the idea to transfer an alternative to the fuzzifier (Klawonn and Höppner, What is fuzzy about fuzzy clustering? Understanding and improving the concept of the fuzzifier, In: Proc. 5th Int. Symp. on Intelligent Data Analysis, 254-264, Springer, Berlin, 2003) to attribute weighting fuzzy clustering (Keller and Klawonn, Int J Uncertain Fuzziness Knowl Based Syst 8:735-746, 2000). In addition, by reformulating Gustafson-Kessel fuzzy clustering, a scheme for weighting and selecting principal axes can be obtained. While in Borgelt (Feature weighting and feature selection in fuzzy clustering, In: Proc. 17th IEEE Int. Conf. on Fuzzy Systems, IEEE Press, Piscataway, NJ, 2008) I already presented such an approach for a global selection of attributes and principal axes, this paper extends it to a cluster-specific selection, thus arriving at a fuzzy subspace clustering algorithm (Parsons, Haque, and Liu, 2004).

About the Clusters Program

EPA Pesticide Factsheets

The Environmental Technology Innovation Clusters Program advises cluster organizations, encourages collaboration between clusters, tracks U.S. environmental technology clusters, and connects EPA programs to cluster needs.

Major cluster mergers and the location of the brightest cluster galaxy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martel, Hugo; Robichaud, Fidèle; Barai, Paramita, E-mail: Hugo.Martel@phy.ulaval.ca

Using a large N-body cosmological simulation combined with a subgrid treatment of galaxy formation, merging, and tidal destruction, we study the formation and evolution of the galaxy and cluster population in a comoving volume (100 Mpc){sup 3} in a ΛCDM universe. At z = 0, our computational volume contains 1788 clusters with mass M {sub cl} > 1.1 × 10{sup 12} M {sub ☉}, including 18 massive clusters with M {sub cl} > 10{sup 14} M {sub ☉}. It also contains 1, 088, 797 galaxies with mass M {sub gal} ≥ 2 × 10{sup 9} M {sub ☉} and luminositymore » L > 9.5 × 10{sup 5} L {sub ☉}. For each cluster, we identified the brightest cluster galaxy (BCG). We then computed two separate statistics: the fraction f {sub BNC} of clusters in which the BCG is not the closest galaxy to the center of the cluster in projection, and the ratio Δv/σ, where Δv is the difference in radial velocity between the BCG and the whole cluster and σ is the radial velocity dispersion of the cluster. We found that f {sub BNC} increases from 0.05 for low-mass clusters (M {sub cl} ∼ 10{sup 12} M {sub ☉}) to 0.5 for high-mass clusters (M {sub cl} > 10{sup 14} M {sub ☉}) with very little dependence on cluster redshift. Most of this result turns out to be a projection effect and when we consider three-dimensional distances instead of projected distances, f {sub BNC} increases only to 0.2 at high-cluster mass. The values of Δv/σ vary from 0 to 1.8, with median values in the range 0.03-0.15 when considering all clusters, and 0.12-0.31 when considering only massive clusters. These results are consistent with previous observational studies and indicate that the central galaxy paradigm, which states that the BCG should be at rest at the center of the cluster, is usually valid, but exceptions are too common to be ignored. We built merger trees for the 18 most massive clusters in the simulation. Analysis of these trees reveal that 16 of these clusters have experienced 1 or several major or

Dynamical evolution of globular-cluster systems in clusters of galaxies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muzzio, J.C.

1987-04-01

The dynamical processes that affect globular-cluster systems in clusters of galaxies are analyzed. Two-body and impulsive approximations are utilized to study dynamical friction, drag force, tidal stripping, tidal radii, globular-cluster swapping, tidal accretion, and galactic cannibalism. The evolution of galaxies and the collision of galaxies are simulated numerically; the steps involved in the simulation are described. The simulated data are compared with observations. Consideration is given to the number of galaxies, halo extension, location of the galaxies, distribution of the missing mass, nonequilibrium initial conditions, mass dependence, massive central galaxies, globular-cluster distribution, and lost globular clusters. 116 references.

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.

Locally Weighted Ensemble Clustering.

PubMed

Huang, Dong; Wang, Chang-Dong; Lai, Jian-Huang

2018-05-01

Due to its ability to combine multiple base clusterings into a probably better and more robust clustering, the ensemble clustering technique has been attracting increasing attention in recent years. Despite the significant success, one limitation to most of the existing ensemble clustering methods is that they generally treat all base clusterings equally regardless of their reliability, which makes them vulnerable to low-quality base clusterings. Although some efforts have been made to (globally) evaluate and weight the base clusterings, yet these methods tend to view each base clustering as an individual and neglect the local diversity of clusters inside the same base clustering. It remains an open problem how to evaluate the reliability of clusters and exploit the local diversity in the ensemble to enhance the consensus performance, especially, in the case when there is no access to data features or specific assumptions on data distribution. To address this, in this paper, we propose a novel ensemble clustering approach based on ensemble-driven cluster uncertainty estimation and local weighting strategy. In particular, the uncertainty of each cluster is estimated by considering the cluster labels in the entire ensemble via an entropic criterion. A novel ensemble-driven cluster validity measure is introduced, and a locally weighted co-association matrix is presented to serve as a summary for the ensemble of diverse clusters. With the local diversity in ensembles exploited, two novel consensus functions are further proposed. Extensive experiments on a variety of real-world datasets demonstrate the superiority of the proposed approach over the state-of-the-art.

Embedded Clusters

NASA Astrophysics Data System (ADS)

Ascenso, Joana

The past decade has seen an increase of star formation studies made at the molecular cloud scale, motivated mostly by the deployment of a wealth of sensitive infrared telescopes and instruments. Embedded clusters, long recognised as the basic units of coherent star formation in molecular clouds, are now seen to inhabit preferentially cluster complexes tens of parsecs across. This chapter gives an overview of some important properties of the embedded clusters in these complexes and of the complexes themselves, along with the implications of viewing star formation as a molecular-cloud scale process rather than an isolated process at the scale of clusters.

Multi-Optimisation Consensus Clustering

NASA Astrophysics Data System (ADS)

Li, Jian; Swift, Stephen; Liu, Xiaohui

Ensemble Clustering has been developed to provide an alternative way of obtaining more stable and accurate clustering results. It aims to avoid the biases of individual clustering algorithms. However, it is still a challenge to develop an efficient and robust method for Ensemble Clustering. Based on an existing ensemble clustering method, Consensus Clustering (CC), this paper introduces an advanced Consensus Clustering algorithm called Multi-Optimisation Consensus Clustering (MOCC), which utilises an optimised Agreement Separation criterion and a Multi-Optimisation framework to improve the performance of CC. Fifteen different data sets are used for evaluating the performance of MOCC. The results reveal that MOCC can generate more accurate clustering results than the original CC algorithm.

Review of methods for handling confounding by cluster and informative cluster size in clustered data

PubMed Central

Seaman, Shaun; Pavlou, Menelaos; Copas, Andrew

2014-01-01

Clustered data are common in medical research. Typically, one is interested in a regression model for the association between an outcome and covariates. Two complications that can arise when analysing clustered data are informative cluster size (ICS) and confounding by cluster (CBC). ICS and CBC mean that the outcome of a member given its covariates is associated with, respectively, the number of members in the cluster and the covariate values of other members in the cluster. Standard generalised linear mixed models for cluster-specific inference and standard generalised estimating equations for population-average inference assume, in general, the absence of ICS and CBC. Modifications of these approaches have been proposed to account for CBC or ICS. This article is a review of these methods. We express their assumptions in a common format, thus providing greater clarity about the assumptions that methods proposed for handling CBC make about ICS and vice versa, and about when different methods can be used in practice. We report relative efficiencies of methods where available, describe how methods are related, identify a previously unreported equivalence between two key methods, and propose some simple additional methods. Unnecessarily using a method that allows for ICS/CBC has an efficiency cost when ICS and CBC are absent. We review tools for identifying ICS/CBC. A strategy for analysis when CBC and ICS are suspected is demonstrated by examining the association between socio-economic deprivation and preterm neonatal death in Scotland. PMID:25087978

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…

THE SWIFT AGN AND CLUSTER SURVEY. II. CLUSTER CONFIRMATION WITH SDSS DATA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griffin, Rhiannon D.; Dai, Xinyu; Kochanek, Christopher S.

2016-01-15

We study 203 (of 442) Swift AGN and Cluster Survey extended X-ray sources located in the SDSS DR8 footprint to search for galaxy over-densities in three-dimensional space using SDSS galaxy photometric redshifts and positions near the Swift cluster candidates. We find 104 Swift clusters with a >3σ galaxy over-density. The remaining targets are potentially located at higher redshifts and require deeper optical follow-up observations for confirmation as galaxy clusters. We present a series of cluster properties including the redshift, brightest cluster galaxy (BCG) magnitude, BCG-to-X-ray center offset, optical richness, and X-ray luminosity. We also detect red sequences in ∼85% ofmore » the 104 confirmed clusters. The X-ray luminosity and optical richness for the SDSS confirmed Swift clusters are correlated and follow previously established relations. The distribution of the separations between the X-ray centroids and the most likely BCG is also consistent with expectation. We compare the observed redshift distribution of the sample with a theoretical model, and find that our sample is complete for z ≲ 0.3 and is still 80% complete up to z ≃ 0.4, consistent with the SDSS survey depth. These analysis results suggest that our Swift cluster selection algorithm has yielded a statistically well-defined cluster sample for further study of cluster evolution and cosmology. We also match our SDSS confirmed Swift clusters to existing cluster catalogs, and find 42, 23, and 1 matches in optical, X-ray, and Sunyaev–Zel’dovich catalogs, respectively, and so the majority of these clusters are new detections.« less

Microwave-assisted synthesis of HKUST-1 and functionalized HKUST-1-@H3PW12O40: selective adsorption of heavy metal ions in water analyzed with synchrotron radiation.

PubMed

Zou, Fang; Yu, Runhan; Li, Rongguan; Li, Wei

2013-08-26

A simple, rapid and efficient synthesis of the metal-organic framework (MOF) HKUST-1 [Cu3(1,3,5-benzene-tri-carboxilic-acid)2] by microwave irradiation is described, which afforded a homogeneous and highly selective material. The unusually short time to complete the synthesis by microwave irradiation is mainly attributable to rapid nucleation rather than to crystal growth rate. Using this method, HKUST-1-MW (MW=microwave) could be prepared within 20 min, whereas by hydrothermal synthesis, involving conventional heating, the preparation time is 8 h. Work efficiency was improved by the good performance of the obtained HKUST-1-MW which exhibited good selective adsorption of heavy metal ions, as well as a remarkably high adsorption affinity and adsorption capacity, but no adsorption of Hg(2+) under the same experimental conditions. Of particular importance is the preservation of the structure after metal-ion adsorption, which remained virtually intact, with only a few changes in X-ray diffraction intensity and a moderate decline in surface area. Synthesis of the polyoxometalate-containing HKUST-1-MW@H3PW12O40 afforded a MOF with enhanced stability in water, due to the introduced Keggin-type phosphotungstate, which systematically occluded in the cavities constituting the walls between the mesopores. Different Cu/W ratios were investigated according to the extrusion rate of cooper ions concentration, without significant structural changes after adsorption. The MOFs obtained feature particle sizes between 10-20 μm and their structures were determined using synchrotron-based X-ray diffraction. The results of this study can be considered important for potentially wider future applications of MOFs, especially to attend environmental issues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of Network Clustering Algorithms and Cluster Quality Metrics at Scale

PubMed Central

Kobourov, Stephen; Gallant, Mike; Börner, Katy

2016-01-01

Overview Notions of community quality underlie the clustering of networks. While studies surrounding network clustering are increasingly common, a precise understanding of the realtionship between different cluster quality metrics is unknown. In this paper, we examine the relationship between stand-alone cluster quality metrics and information recovery metrics through a rigorous analysis of four widely-used network clustering algorithms—Louvain, Infomap, label propagation, and smart local moving. We consider the stand-alone quality metrics of modularity, conductance, and coverage, and we consider the information recovery metrics of adjusted Rand score, normalized mutual information, and a variant of normalized mutual information used in previous work. Our study includes both synthetic graphs and empirical data sets of sizes varying from 1,000 to 1,000,000 nodes. Cluster Quality Metrics We find significant differences among the results of the different cluster quality metrics. For example, clustering algorithms can return a value of 0.4 out of 1 on modularity but score 0 out of 1 on information recovery. We find conductance, though imperfect, to be the stand-alone quality metric that best indicates performance on the information recovery metrics. Additionally, our study shows that the variant of normalized mutual information used in previous work cannot be assumed to differ only slightly from traditional normalized mutual information. Network Clustering Algorithms Smart local moving is the overall best performing algorithm in our study, but discrepancies between cluster evaluation metrics prevent us from declaring it an absolutely superior algorithm. Interestingly, Louvain performed better than Infomap in nearly all the tests in our study, contradicting the results of previous work in which Infomap was superior to Louvain. We find that although label propagation performs poorly when clusters are less clearly defined, it scales efficiently and accurately to large

Globular cluster formation with multiple stellar populations from hierarchical star cluster complexes

NASA Astrophysics Data System (ADS)

Bekki, Kenji

2017-05-01

Most old globular clusters (GCs) in the Galaxy are observed to have internal chemical abundance spreads in light elements. We discuss a new GC formation scenario based on hierarchical star formation within fractal molecular clouds. In the new scenario, a cluster of bound and unbound star clusters ('star cluster complex', SCC) that have a power-law cluster mass function with a slope (β) of 2 is first formed from a massive gas clump developed in a dwarf galaxy. Such cluster complexes and β = 2 are observed and expected from hierarchical star formation. The most massive star cluster ('main cluster'), which is the progenitor of a GC, can accrete gas ejected from asymptotic giant branch (AGB) stars initially in the cluster and other low-mass clusters before the clusters are tidally stripped or destroyed to become field stars in the dwarf. The SCC is initially embedded in a giant gas hole created by numerous supernovae of the SCC so that cold gas outside the hole can be accreted on to the main cluster later. New stars formed from the accreted gas have chemical abundances that are different from those of the original SCC. Using hydrodynamical simulations of GC formation based on this scenario, we show that the main cluster with the initial mass as large as [2-5] × 105 M⊙ can accrete more than 105 M⊙ gas from AGB stars of the SCC. We suggest that merging of hierarchical SSCs can play key roles in stellar halo formation around GCs and self-enrichment processes in the early phase of GC formation.

Relative efficiency and sample size for cluster randomized trials with variable cluster sizes.

PubMed

You, Zhiying; Williams, O Dale; Aban, Inmaculada; Kabagambe, Edmond Kato; Tiwari, Hemant K; Cutter, Gary

2011-02-01

The statistical power of cluster randomized trials depends on two sample size components, the number of clusters per group and the numbers of individuals within clusters (cluster size). Variable cluster sizes are common and this variation alone may have significant impact on study power. Previous approaches have taken this into account by either adjusting total sample size using a designated design effect or adjusting the number of clusters according to an assessment of the relative efficiency of unequal versus equal cluster sizes. This article defines a relative efficiency of unequal versus equal cluster sizes using noncentrality parameters, investigates properties of this measure, and proposes an approach for adjusting the required sample size accordingly. We focus on comparing two groups with normally distributed outcomes using t-test, and use the noncentrality parameter to define the relative efficiency of unequal versus equal cluster sizes and show that statistical power depends only on this parameter for a given number of clusters. We calculate the sample size required for an unequal cluster sizes trial to have the same power as one with equal cluster sizes. Relative efficiency based on the noncentrality parameter is straightforward to calculate and easy to interpret. It connects the required mean cluster size directly to the required sample size with equal cluster sizes. Consequently, our approach first determines the sample size requirements with equal cluster sizes for a pre-specified study power and then calculates the required mean cluster size while keeping the number of clusters unchanged. Our approach allows adjustment in mean cluster size alone or simultaneous adjustment in mean cluster size and number of clusters, and is a flexible alternative to and a useful complement to existing methods. Comparison indicated that we have defined a relative efficiency that is greater than the relative efficiency in the literature under some conditions. Our measure

Unequal cluster sizes in stepped-wedge cluster randomised trials: a systematic review.

PubMed

Kristunas, Caroline; Morris, Tom; Gray, Laura

2017-11-15

To investigate the extent to which cluster sizes vary in stepped-wedge cluster randomised trials (SW-CRT) and whether any variability is accounted for during the sample size calculation and analysis of these trials. Any, not limited to healthcare settings. Any taking part in an SW-CRT published up to March 2016. The primary outcome is the variability in cluster sizes, measured by the coefficient of variation (CV) in cluster size. Secondary outcomes include the difference between the cluster sizes assumed during the sample size calculation and those observed during the trial, any reported variability in cluster sizes and whether the methods of sample size calculation and methods of analysis accounted for any variability in cluster sizes. Of the 101 included SW-CRTs, 48% mentioned that the included clusters were known to vary in size, yet only 13% of these accounted for this during the calculation of the sample size. However, 69% of the trials did use a method of analysis appropriate for when clusters vary in size. Full trial reports were available for 53 trials. The CV was calculated for 23 of these: the median CV was 0.41 (IQR: 0.22-0.52). Actual cluster sizes could be compared with those assumed during the sample size calculation for 14 (26%) of the trial reports; the cluster sizes were between 29% and 480% of that which had been assumed. Cluster sizes often vary in SW-CRTs. Reporting of SW-CRTs also remains suboptimal. The effect of unequal cluster sizes on the statistical power of SW-CRTs needs further exploration and methods appropriate to studies with unequal cluster sizes need to be employed. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Unequal cluster sizes in stepped-wedge cluster randomised trials: a systematic review

PubMed Central

Morris, Tom; Gray, Laura

2017-01-01

Objectives To investigate the extent to which cluster sizes vary in stepped-wedge cluster randomised trials (SW-CRT) and whether any variability is accounted for during the sample size calculation and analysis of these trials. Setting Any, not limited to healthcare settings. Participants Any taking part in an SW-CRT published up to March 2016. Primary and secondary outcome measures The primary outcome is the variability in cluster sizes, measured by the coefficient of variation (CV) in cluster size. Secondary outcomes include the difference between the cluster sizes assumed during the sample size calculation and those observed during the trial, any reported variability in cluster sizes and whether the methods of sample size calculation and methods of analysis accounted for any variability in cluster sizes. Results Of the 101 included SW-CRTs, 48% mentioned that the included clusters were known to vary in size, yet only 13% of these accounted for this during the calculation of the sample size. However, 69% of the trials did use a method of analysis appropriate for when clusters vary in size. Full trial reports were available for 53 trials. The CV was calculated for 23 of these: the median CV was 0.41 (IQR: 0.22–0.52). Actual cluster sizes could be compared with those assumed during the sample size calculation for 14 (26%) of the trial reports; the cluster sizes were between 29% and 480% of that which had been assumed. Conclusions Cluster sizes often vary in SW-CRTs. Reporting of SW-CRTs also remains suboptimal. The effect of unequal cluster sizes on the statistical power of SW-CRTs needs further exploration and methods appropriate to studies with unequal cluster sizes need to be employed. PMID:29146637

Cluster synchronization induced by one-node clusters in networks with asymmetric negative couplings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jianbao; Ma, Zhongjun, E-mail: mzj1234402@163.com; Zhang, Gang

2013-12-15

This paper deals with the problem of cluster synchronization in networks with asymmetric negative couplings. By decomposing the coupling matrix into three matrices, and employing Lyapunov function method, sufficient conditions are derived for cluster synchronization. The conditions show that the couplings of multi-node clusters from one-node clusters have beneficial effects on cluster synchronization. Based on the effects of the one-node clusters, an effective and universal control scheme is put forward for the first time. The obtained results may help us better understand the relation between cluster synchronization and cluster structures of the networks. The validity of the control scheme ismore » confirmed through two numerical simulations, in a network with no cluster structure and in a scale-free network.« less

Cluster synchronization induced by one-node clusters in networks with asymmetric negative couplings

NASA Astrophysics Data System (ADS)

Zhang, Jianbao; Ma, Zhongjun; Zhang, Gang

2013-12-01

This paper deals with the problem of cluster synchronization in networks with asymmetric negative couplings. By decomposing the coupling matrix into three matrices, and employing Lyapunov function method, sufficient conditions are derived for cluster synchronization. The conditions show that the couplings of multi-node clusters from one-node clusters have beneficial effects on cluster synchronization. Based on the effects of the one-node clusters, an effective and universal control scheme is put forward for the first time. The obtained results may help us better understand the relation between cluster synchronization and cluster structures of the networks. The validity of the control scheme is confirmed through two numerical simulations, in a network with no cluster structure and in a scale-free network.

Semi-supervised clustering methods.

PubMed

Bair, Eric

2013-01-01

Cluster analysis methods seek to partition a data set into homogeneous subgroups. It is useful in a wide variety of applications, including document processing and modern genetics. Conventional clustering methods are unsupervised, meaning that there is no outcome variable nor is anything known about the relationship between the observations in the data set. In many situations, however, information about the clusters is available in addition to the values of the features. For example, the cluster labels of some observations may be known, or certain observations may be known to belong to the same cluster. In other cases, one may wish to identify clusters that are associated with a particular outcome variable. This review describes several clustering algorithms (known as "semi-supervised clustering" methods) that can be applied in these situations. The majority of these methods are modifications of the popular k-means clustering method, and several of them will be described in detail. A brief description of some other semi-supervised clustering algorithms is also provided.

Cluster assembly in nitrogenase.

PubMed

Sickerman, Nathaniel S; Rettberg, Lee A; Lee, Chi Chung; Hu, Yilin; Ribbe, Markus W

2017-05-09

The versatile enzyme system nitrogenase accomplishes the challenging reduction of N 2 and other substrates through the use of two main metalloclusters. For molybdenum nitrogenase, the catalytic component NifDK contains the [Fe 8 S 7 ]-core P-cluster and a [MoFe 7 S 9 C-homocitrate] cofactor called the M-cluster. These chemically unprecedented metalloclusters play a critical role in the reduction of N 2 , and both originate from [Fe 4 S 4 ] clusters produced by the actions of NifS and NifU. Maturation of P-cluster begins with a pair of these [Fe 4 S 4 ] clusters on NifDK called the P*-cluster. An accessory protein NifZ aids in P-cluster fusion, and reductive coupling is facilitated by NifH in a stepwise manner to form P-cluster on each half of NifDK. For M-cluster biosynthesis, two [Fe 4 S 4 ] clusters on NifB are coupled with a carbon atom in a radical-SAM dependent process, and concomitant addition of a 'ninth' sulfur atom generates the [Fe 8 S 9 C]-core L-cluster. On the scaffold protein NifEN, L-cluster is matured to M-cluster by the addition of Mo and homocitrate provided by NifH. Finally, matured M-cluster in NifEN is directly transferred to NifDK, where a conformational change locks the cofactor in place. Mechanistic insights into these fascinating biosynthetic processes are detailed in this chapter. © 2017 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

OPEN CLUSTERS AS PROBES OF THE GALACTIC MAGNETIC FIELD. I. CLUSTER PROPERTIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoq, Sadia; Clemens, D. P., E-mail: shoq@bu.edu, E-mail: clemens@bu.edu

2015-10-15

Stars in open clusters are powerful probes of the intervening Galactic magnetic field via background starlight polarimetry because they provide constraints on the magnetic field distances. We use 2MASS photometric data for a sample of 31 clusters in the outer Galaxy for which near-IR polarimetric data were obtained to determine the cluster distances, ages, and reddenings via fitting theoretical isochrones to cluster color–magnitude diagrams. The fitting approach uses an objective χ{sup 2} minimization technique to derive the cluster properties and their uncertainties. We found the ages, distances, and reddenings for 24 of the clusters, and the distances and reddenings formore » 6 additional clusters that were either sparse or faint in the near-IR. The derived ranges of log(age), distance, and E(B−V) were 7.25–9.63, ∼670–6160 pc, and 0.02–1.46 mag, respectively. The distance uncertainties ranged from ∼8% to 20%. The derived parameters were compared to previous studies, and most cluster parameters agree within our uncertainties. To test the accuracy of the fitting technique, synthetic clusters with 50, 100, or 200 cluster members and a wide range of ages were fit. These tests recovered the input parameters within their uncertainties for more than 90% of the individual synthetic cluster parameters. These results indicate that the fitting technique likely provides reliable estimates of cluster properties. The distances derived will be used in an upcoming study of the Galactic magnetic field in the outer Galaxy.« less

CytoCluster: A Cytoscape Plugin for Cluster Analysis and Visualization of Biological Networks.

PubMed

Li, Min; Li, Dongyan; Tang, Yu; Wu, Fangxiang; Wang, Jianxin

2017-08-31

Nowadays, cluster analysis of biological networks has become one of the most important approaches to identifying functional modules as well as predicting protein complexes and network biomarkers. Furthermore, the visualization of clustering results is crucial to display the structure of biological networks. Here we present CytoCluster, a cytoscape plugin integrating six clustering algorithms, HC-PIN (Hierarchical Clustering algorithm in Protein Interaction Networks), OH-PIN (identifying Overlapping and Hierarchical modules in Protein Interaction Networks), IPCA (Identifying Protein Complex Algorithm), ClusterONE (Clustering with Overlapping Neighborhood Expansion), DCU (Detecting Complexes based on Uncertain graph model), IPC-MCE (Identifying Protein Complexes based on Maximal Complex Extension), and BinGO (the Biological networks Gene Ontology) function. Users can select different clustering algorithms according to their requirements. The main function of these six clustering algorithms is to detect protein complexes or functional modules. In addition, BinGO is used to determine which Gene Ontology (GO) categories are statistically overrepresented in a set of genes or a subgraph of a biological network. CytoCluster can be easily expanded, so that more clustering algorithms and functions can be added to this plugin. Since it was created in July 2013, CytoCluster has been downloaded more than 9700 times in the Cytoscape App store and has already been applied to the analysis of different biological networks. CytoCluster is available from http://apps.cytoscape.org/apps/cytocluster.

Formation of Very Young Massive Clusters and Implications for Globular Clusters

NASA Astrophysics Data System (ADS)

Banerjee, Sambaran; Kroupa, Pavel

How Very Young Massive star Clusters (VYMCs; also known as "starburst" clusters), which typically are of ≳ 104 M ⊙ and are a few Myr old, form out of Giant Molecular Clouds is still largely an open question. Increasingly detailed observations of young star clusters and star-forming molecular clouds and computational studies provide clues about their formation scenarios and the underlying physical processes involved. This chapter is focused on reviewing the decade-long studies that attempt to computationally reproduce the well-observed nearby VYMCs, such as the Orion Nebula Cluster, R136 and NGC 3603 young cluster, thereby shedding light on birth conditions of massive star clusters, in general. On this regard, focus is given on direct N-body modelling of real-sized massive star clusters, with a monolithic structure and undergoing residual gas expulsion, which have consistently reproduced the observed characteristics of several VYMCs and also of young star clusters, in general. The connection of these relatively simplified model calculations with the structural richness of dense molecular clouds and the complexity of hydrodynamic calculations of star cluster formation is presented in detail. Furthermore, the connections of such VYMCs with globular clusters, which are nearly as old as our Universe, is discussed. The chapter is concluded by addressing long-term deeply gas-embedded (at least apparently) and substructured systems like W3 Main. While most of the results are quoted from existing and up-to-date literature, in an integrated fashion, several new insights and discussions are provided.

Discovery of gigantic molecular nanostructures using a flow reaction array as a search engine.

PubMed

Zang, Hong-Ying; de la Oliva, Andreu Ruiz; Miras, Haralampos N; Long, De-Liang; McBurney, Roy T; Cronin, Leroy

2014-04-28

The discovery of gigantic molecular nanostructures like coordination and polyoxometalate clusters is extremely time-consuming since a vast combinatorial space needs to be searched, and even a systematic and exhaustive exploration of the available synthetic parameters relies on a great deal of serendipity. Here we present a synthetic methodology that combines a flow reaction array and algorithmic control to give a chemical 'real-space' search engine leading to the discovery and isolation of a range of new molecular nanoclusters based on [Mo(2)O(2)S(2)](2+)-based building blocks with either fourfold (C4) or fivefold (C5) symmetry templates and linkers. This engine leads us to isolate six new nanoscale cluster compounds: 1, {Mo(10)(C5)}; 2, {Mo(14)(C4)4(C5)2}; 3, {Mo(60)(C4)10}; 4, {Mo(48)(C4)6}; 5, {Mo(34)(C4)4}; 6, {Mo(18)(C4)9}; in only 200 automated experiments from a parameter space spanning ~5 million possible combinations.

Open source clustering software.

PubMed

de Hoon, M J L; Imoto, S; Nolan, J; Miyano, S

2004-06-12

We have implemented k-means clustering, hierarchical clustering and self-organizing maps in a single multipurpose open-source library of C routines, callable from other C and C++ programs. Using this library, we have created an improved version of Michael Eisen's well-known Cluster program for Windows, Mac OS X and Linux/Unix. In addition, we generated a Python and a Perl interface to the C Clustering Library, thereby combining the flexibility of a scripting language with the speed of C. The C Clustering Library and the corresponding Python C extension module Pycluster were released under the Python License, while the Perl module Algorithm::Cluster was released under the Artistic License. The GUI code Cluster 3.0 for Windows, Macintosh and Linux/Unix, as well as the corresponding command-line program, were released under the same license as the original Cluster code. The complete source code is available at http://bonsai.ims.u-tokyo.ac.jp/mdehoon/software/cluster. Alternatively, Algorithm::Cluster can be downloaded from CPAN, while Pycluster is also available as part of the Biopython distribution.

CytoCluster: A Cytoscape Plugin for Cluster Analysis and Visualization of Biological Networks

PubMed Central

Li, Min; Li, Dongyan; Tang, Yu; Wang, Jianxin

2017-01-01

Nowadays, cluster analysis of biological networks has become one of the most important approaches to identifying functional modules as well as predicting protein complexes and network biomarkers. Furthermore, the visualization of clustering results is crucial to display the structure of biological networks. Here we present CytoCluster, a cytoscape plugin integrating six clustering algorithms, HC-PIN (Hierarchical Clustering algorithm in Protein Interaction Networks), OH-PIN (identifying Overlapping and Hierarchical modules in Protein Interaction Networks), IPCA (Identifying Protein Complex Algorithm), ClusterONE (Clustering with Overlapping Neighborhood Expansion), DCU (Detecting Complexes based on Uncertain graph model), IPC-MCE (Identifying Protein Complexes based on Maximal Complex Extension), and BinGO (the Biological networks Gene Ontology) function. Users can select different clustering algorithms according to their requirements. The main function of these six clustering algorithms is to detect protein complexes or functional modules. In addition, BinGO is used to determine which Gene Ontology (GO) categories are statistically overrepresented in a set of genes or a subgraph of a biological network. CytoCluster can be easily expanded, so that more clustering algorithms and functions can be added to this plugin. Since it was created in July 2013, CytoCluster has been downloaded more than 9700 times in the Cytoscape App store and has already been applied to the analysis of different biological networks. CytoCluster is available from http://apps.cytoscape.org/apps/cytocluster. PMID:28858211

The SAMI Galaxy Survey: the cluster redshift survey, target selection and cluster properties

NASA Astrophysics Data System (ADS)

Owers, M. S.; Allen, J. T.; Baldry, I.; Bryant, J. J.; Cecil, G. N.; Cortese, L.; Croom, S. M.; Driver, S. P.; Fogarty, L. M. R.; Green, A. W.; Helmich, E.; de Jong, J. T. A.; Kuijken, K.; Mahajan, S.; McFarland, J.; Pracy, M. B.; Robotham, A. G. S.; Sikkema, G.; Sweet, S.; Taylor, E. N.; Verdoes Kleijn, G.; Bauer, A. E.; Bland-Hawthorn, J.; Brough, S.; Colless, M.; Couch, W. J.; Davies, R. L.; Drinkwater, M. J.; Goodwin, M.; Hopkins, A. M.; Konstantopoulos, I. S.; Foster, C.; Lawrence, J. S.; Lorente, N. P. F.; Medling, A. M.; Metcalfe, N.; Richards, S. N.; van de Sande, J.; Scott, N.; Shanks, T.; Sharp, R.; Thomas, A. D.; Tonini, C.

2017-06-01

We describe the selection of galaxies targeted in eight low-redshift clusters (APMCC0917, A168, A4038, EDCC442, A3880, A2399, A119 and A85; 0.029 < z < 0.058) as part of the Sydney-AAO Multi-Object Integral field spectrograph Galaxy Survey (SAMI-GS). We have conducted a redshift survey of these clusters using the AAOmega multi-object spectrograph on the 3.9-m Anglo-Australian Telescope. The redshift survey is used to determine cluster membership and to characterize the dynamical properties of the clusters. In combination with existing data, the survey resulted in 21 257 reliable redshift measurements and 2899 confirmed cluster member galaxies. Our redshift catalogue has a high spectroscopic completeness (˜94 per cent) for rpetro ≤ 19.4 and cluster-centric distances R < 2R200. We use the confirmed cluster member positions and redshifts to determine cluster velocity dispersion, R200, virial and caustic masses, as well as cluster structure. The clusters have virial masses 14.25 ≤ log(M200/M⊙) ≤ 15.19. The cluster sample exhibits a range of dynamical states, from relatively relaxed-appearing systems, to clusters with strong indications of merger-related substructure. Aperture- and point spread function matched photometry are derived from Sloan Digital Sky Survey and VLT Survey Telescope/ATLAS imaging and used to estimate stellar masses. These estimates, in combination with the redshifts, are used to define the input target catalogue for the cluster portion of the SAMI-GS. The primary SAMI-GS cluster targets have R cluster regions.

Star cluster formation in cosmological simulations. I. Properties of young clusters

DOE PAGES

Li, Hui; Gnedin, Oleg Y.; Gnedin, Nickolay Y.; ...

2017-01-03

We present a new implementation of star formation in cosmological simulations by considering star clusters as a unit of star formation. Cluster particles grow in mass over several million years at the rate determined by local gas properties, with high time resolution. The particle growth is terminated by its own energy and momentum feedback on the interstellar medium. We test this implementation for Milky Way-sized galaxies at high redshift by comparing the properties of model clusters with observations of young star clusters. We find that the cluster initial mass function is best described by a Schechter function rather than a single power law. In agreement with observations, at low masses the logarithmic slope ismore » $$\\alpha \\approx 1.8\\mbox{–}2$$, while the cutoff at high mass scales with the star formation rate (SFR). A related trend is a positive correlation between the surface density of the SFR and fraction of stars contained in massive clusters. Both trends indicate that the formation of massive star clusters is preferred during bursts of star formation. These bursts are often associated with major-merger events. We also find that the median timescale for cluster formation ranges from 0.5 to 4 Myr and decreases systematically with increasing star formation efficiency. Local variations in the gas density and cluster accretion rate naturally lead to the scatter of the overall formation efficiency by an order of magnitude, even when the instantaneous efficiency is kept constant. As a result, comparison of the formation timescale with the observed age spread of young star clusters provides an additional important constraint on the modeling of star formation and feedback schemes.« less

Star cluster formation in cosmological simulations. I. Properties of young clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Hui; Gnedin, Oleg Y.; Gnedin, Nickolay Y.

We present a new implementation of star formation in cosmological simulations by considering star clusters as a unit of star formation. Cluster particles grow in mass over several million years at the rate determined by local gas properties, with high time resolution. The particle growth is terminated by its own energy and momentum feedback on the interstellar medium. We test this implementation for Milky Way-sized galaxies at high redshift by comparing the properties of model clusters with observations of young star clusters. We find that the cluster initial mass function is best described by a Schechter function rather than a single power law. In agreement with observations, at low masses the logarithmic slope ismore » $$\\alpha \\approx 1.8\\mbox{–}2$$, while the cutoff at high mass scales with the star formation rate (SFR). A related trend is a positive correlation between the surface density of the SFR and fraction of stars contained in massive clusters. Both trends indicate that the formation of massive star clusters is preferred during bursts of star formation. These bursts are often associated with major-merger events. We also find that the median timescale for cluster formation ranges from 0.5 to 4 Myr and decreases systematically with increasing star formation efficiency. Local variations in the gas density and cluster accretion rate naturally lead to the scatter of the overall formation efficiency by an order of magnitude, even when the instantaneous efficiency is kept constant. As a result, comparison of the formation timescale with the observed age spread of young star clusters provides an additional important constraint on the modeling of star formation and feedback schemes.« less

Star Cluster Formation in Cosmological Simulations. I. Properties of Young Clusters

NASA Astrophysics Data System (ADS)

Li, Hui; Gnedin, Oleg Y.; Gnedin, Nickolay Y.; Meng, Xi; Semenov, Vadim A.; Kravtsov, Andrey V.

2017-01-01

We present a new implementation of star formation in cosmological simulations by considering star clusters as a unit of star formation. Cluster particles grow in mass over several million years at the rate determined by local gas properties, with high time resolution. The particle growth is terminated by its own energy and momentum feedback on the interstellar medium. We test this implementation for Milky Way-sized galaxies at high redshift by comparing the properties of model clusters with observations of young star clusters. We find that the cluster initial mass function is best described by a Schechter function rather than a single power law. In agreement with observations, at low masses the logarithmic slope is α ≈ 1.8{--}2, while the cutoff at high mass scales with the star formation rate (SFR). A related trend is a positive correlation between the surface density of the SFR and fraction of stars contained in massive clusters. Both trends indicate that the formation of massive star clusters is preferred during bursts of star formation. These bursts are often associated with major-merger events. We also find that the median timescale for cluster formation ranges from 0.5 to 4 Myr and decreases systematically with increasing star formation efficiency. Local variations in the gas density and cluster accretion rate naturally lead to the scatter of the overall formation efficiency by an order of magnitude, even when the instantaneous efficiency is kept constant. Comparison of the formation timescale with the observed age spread of young star clusters provides an additional important constraint on the modeling of star formation and feedback schemes.

Clustering methods for the optimization of atomic cluster structure

NASA Astrophysics Data System (ADS)

Bagattini, Francesco; Schoen, Fabio; Tigli, Luca

2018-04-01

In this paper, we propose a revised global optimization method and apply it to large scale cluster conformation problems. In the 1990s, the so-called clustering methods were considered among the most efficient general purpose global optimization techniques; however, their usage has quickly declined in recent years, mainly due to the inherent difficulties of clustering approaches in large dimensional spaces. Inspired from the machine learning literature, we redesigned clustering methods in order to deal with molecular structures in a reduced feature space. Our aim is to show that by suitably choosing a good set of geometrical features coupled with a very efficient descent method, an effective optimization tool is obtained which is capable of finding, with a very high success rate, all known putative optima for medium size clusters without any prior information, both for Lennard-Jones and Morse potentials. The main result is that, beyond being a reliable approach, the proposed method, based on the idea of starting a computationally expensive deep local search only when it seems worth doing so, is capable of saving a huge amount of searches with respect to an analogous algorithm which does not employ a clustering phase. In this paper, we are not claiming the superiority of the proposed method compared to specific, refined, state-of-the-art procedures, but rather indicating a quite straightforward way to save local searches by means of a clustering scheme working in a reduced variable space, which might prove useful when included in many modern methods.

Subspace K-means clustering.

PubMed

Timmerman, Marieke E; Ceulemans, Eva; De Roover, Kim; Van Leeuwen, Karla

2013-12-01

To achieve an insightful clustering of multivariate data, we propose subspace K-means. Its central idea is to model the centroids and cluster residuals in reduced spaces, which allows for dealing with a wide range of cluster types and yields rich interpretations of the clusters. We review the existing related clustering methods, including deterministic, stochastic, and unsupervised learning approaches. To evaluate subspace K-means, we performed a comparative simulation study, in which we manipulated the overlap of subspaces, the between-cluster variance, and the error variance. The study shows that the subspace K-means algorithm is sensitive to local minima but that the problem can be reasonably dealt with by using partitions of various cluster procedures as a starting point for the algorithm. Subspace K-means performs very well in recovering the true clustering across all conditions considered and appears to be superior to its competitor methods: K-means, reduced K-means, factorial K-means, mixtures of factor analyzers (MFA), and MCLUST. The best competitor method, MFA, showed a performance similar to that of subspace K-means in easy conditions but deteriorated in more difficult ones. Using data from a study on parental behavior, we show that subspace K-means analysis provides a rich insight into the cluster characteristics, in terms of both the relative positions of the clusters (via the centroids) and the shape of the clusters (via the within-cluster residuals).

Clustering in analytical chemistry.

PubMed

Drab, Klaudia; Daszykowski, Michal

2014-01-01

Data clustering plays an important role in the exploratory analysis of analytical data, and the use of clustering methods has been acknowledged in different fields of science. In this paper, principles of data clustering are presented with a direct focus on clustering of analytical data. The role of the clustering process in the analytical workflow is underlined, and its potential impact on the analytical workflow is emphasized.

Adaptive Scaling of Cluster Boundaries for Large-Scale Social Media Data Clustering.

PubMed

Meng, Lei; Tan, Ah-Hwee; Wunsch, Donald C

2016-12-01

The large scale and complex nature of social media data raises the need to scale clustering techniques to big data and make them capable of automatically identifying data clusters with few empirical settings. In this paper, we present our investigation and three algorithms based on the fuzzy adaptive resonance theory (Fuzzy ART) that have linear computational complexity, use a single parameter, i.e., the vigilance parameter to identify data clusters, and are robust to modest parameter settings. The contribution of this paper lies in two aspects. First, we theoretically demonstrate how complement coding, commonly known as a normalization method, changes the clustering mechanism of Fuzzy ART, and discover the vigilance region (VR) that essentially determines how a cluster in the Fuzzy ART system recognizes similar patterns in the feature space. The VR gives an intrinsic interpretation of the clustering mechanism and limitations of Fuzzy ART. Second, we introduce the idea of allowing different clusters in the Fuzzy ART system to have different vigilance levels in order to meet the diverse nature of the pattern distribution of social media data. To this end, we propose three vigilance adaptation methods, namely, the activation maximization (AM) rule, the confliction minimization (CM) rule, and the hybrid integration (HI) rule. With an initial vigilance value, the resulting clustering algorithms, namely, the AM-ART, CM-ART, and HI-ART, can automatically adapt the vigilance values of all clusters during the learning epochs in order to produce better cluster boundaries. Experiments on four social media data sets show that AM-ART, CM-ART, and HI-ART are more robust than Fuzzy ART to the initial vigilance value, and they usually achieve better or comparable performance and much faster speed than the state-of-the-art clustering algorithms that also do not require a predefined number of clusters.

Optimized alumina coagulants for water treatment

DOEpatents

Nyman, May D [Albuquerque, NM; Stewart, Thomas A [Albuquerque, NM

2012-02-21

Substitution of a single Ga-atom or single Ge-atom (GaAl.sub.12 and GeAl.sub.12 respectively) into the center of an aluminum Keggin polycation (Al.sub.13) produces an optimal water-treatment product for neutralization and coagulation of anionic contaminants in water. GaAl.sub.12 consistently shows .about.1 order of magnitude increase in pathogen reduction, compared to Al.sub.13. At a concentration of 2 ppm, GaAl.sub.12 performs equivalently to 40 ppm alum, removing .about.90% of the dissolved organic material. The substituted GaAl.sub.12 product also offers extended shelf-life and consistent performance. We also synthesized a related polyaluminum chloride compound made of pre-hydrolyzed dissolved alumina clusters of [GaO.sub.4Al.sub.12(OH).sub.24(H.sub.2O).sub.12].sup.7+.

Hybrid fuzzy cluster ensemble framework for tumor clustering from biomolecular data.

PubMed

Yu, Zhiwen; Chen, Hantao; You, Jane; Han, Guoqiang; Li, Le

2013-01-01

Cancer class discovery using biomolecular data is one of the most important tasks for cancer diagnosis and treatment. Tumor clustering from gene expression data provides a new way to perform cancer class discovery. Most of the existing research works adopt single-clustering algorithms to perform tumor clustering is from biomolecular data that lack robustness, stability, and accuracy. To further improve the performance of tumor clustering from biomolecular data, we introduce the fuzzy theory into the cluster ensemble framework for tumor clustering from biomolecular data, and propose four kinds of hybrid fuzzy cluster ensemble frameworks (HFCEF), named as HFCEF-I, HFCEF-II, HFCEF-III, and HFCEF-IV, respectively, to identify samples that belong to different types of cancers. The difference between HFCEF-I and HFCEF-II is that they adopt different ensemble generator approaches to generate a set of fuzzy matrices in the ensemble. Specifically, HFCEF-I applies the affinity propagation algorithm (AP) to perform clustering on the sample dimension and generates a set of fuzzy matrices in the ensemble based on the fuzzy membership function and base samples selected by AP. HFCEF-II adopts AP to perform clustering on the attribute dimension, generates a set of subspaces, and obtains a set of fuzzy matrices in the ensemble by performing fuzzy c-means on subspaces. Compared with HFCEF-I and HFCEF-II, HFCEF-III and HFCEF-IV consider the characteristics of HFCEF-I and HFCEF-II. HFCEF-III combines HFCEF-I and HFCEF-II in a serial way, while HFCEF-IV integrates HFCEF-I and HFCEF-II in a concurrent way. HFCEFs adopt suitable consensus functions, such as the fuzzy c-means algorithm or the normalized cut algorithm (Ncut), to summarize generated fuzzy matrices, and obtain the final results. The experiments on real data sets from UCI machine learning repository and cancer gene expression profiles illustrate that 1) the proposed hybrid fuzzy cluster ensemble frameworks work well on real

Semi-supervised clustering methods

PubMed Central

Bair, Eric

2013-01-01

Cluster analysis methods seek to partition a data set into homogeneous subgroups. It is useful in a wide variety of applications, including document processing and modern genetics. Conventional clustering methods are unsupervised, meaning that there is no outcome variable nor is anything known about the relationship between the observations in the data set. In many situations, however, information about the clusters is available in addition to the values of the features. For example, the cluster labels of some observations may be known, or certain observations may be known to belong to the same cluster. In other cases, one may wish to identify clusters that are associated with a particular outcome variable. This review describes several clustering algorithms (known as “semi-supervised clustering” methods) that can be applied in these situations. The majority of these methods are modifications of the popular k-means clustering method, and several of them will be described in detail. A brief description of some other semi-supervised clustering algorithms is also provided. PMID:24729830

Cluster Correspondence Analysis.

PubMed

van de Velden, M; D'Enza, A Iodice; Palumbo, F

2017-03-01

A method is proposed that combines dimension reduction and cluster analysis for categorical data by simultaneously assigning individuals to clusters and optimal scaling values to categories in such a way that a single between variance maximization objective is achieved. In a unified framework, a brief review of alternative methods is provided and we show that the proposed method is equivalent to GROUPALS applied to categorical data. Performance of the methods is appraised by means of a simulation study. The results of the joint dimension reduction and clustering methods are compared with the so-called tandem approach, a sequential analysis of dimension reduction followed by cluster analysis. The tandem approach is conjectured to perform worse when variables are added that are unrelated to the cluster structure. Our simulation study confirms this conjecture. Moreover, the results of the simulation study indicate that the proposed method also consistently outperforms alternative joint dimension reduction and clustering methods.

Analysis of Network Clustering Algorithms and Cluster Quality Metrics at Scale.

PubMed

Emmons, Scott; Kobourov, Stephen; Gallant, Mike; Börner, Katy

2016-01-01

Notions of community quality underlie the clustering of networks. While studies surrounding network clustering are increasingly common, a precise understanding of the realtionship between different cluster quality metrics is unknown. In this paper, we examine the relationship between stand-alone cluster quality metrics and information recovery metrics through a rigorous analysis of four widely-used network clustering algorithms-Louvain, Infomap, label propagation, and smart local moving. We consider the stand-alone quality metrics of modularity, conductance, and coverage, and we consider the information recovery metrics of adjusted Rand score, normalized mutual information, and a variant of normalized mutual information used in previous work. Our study includes both synthetic graphs and empirical data sets of sizes varying from 1,000 to 1,000,000 nodes. We find significant differences among the results of the different cluster quality metrics. For example, clustering algorithms can return a value of 0.4 out of 1 on modularity but score 0 out of 1 on information recovery. We find conductance, though imperfect, to be the stand-alone quality metric that best indicates performance on the information recovery metrics. Additionally, our study shows that the variant of normalized mutual information used in previous work cannot be assumed to differ only slightly from traditional normalized mutual information. Smart local moving is the overall best performing algorithm in our study, but discrepancies between cluster evaluation metrics prevent us from declaring it an absolutely superior algorithm. Interestingly, Louvain performed better than Infomap in nearly all the tests in our study, contradicting the results of previous work in which Infomap was superior to Louvain. We find that although label propagation performs poorly when clusters are less clearly defined, it scales efficiently and accurately to large graphs with well-defined clusters.

Ultra-diffuse cluster galaxies as key to the MOND cluster conundrum

NASA Astrophysics Data System (ADS)

Milgrom, Mordehai

2015-12-01

Modified Newtonian Dynamics (MOND) reduces greatly the mass discrepancy in clusters of galaxies,but does leave a global discrepancy of about a factor of 2 (epitomized by the structure of the Bullet Cluster). It has been proposed, within the minimalist and purist MOND, that clusters harbour some indigenous, yet undetected, cluster baryonic (dark) matter (CBDM), whose total amount is comparable with that of the observed hot gas. Koda et al. have recently identified more than a thousand ultra-diffuse, galaxy-like objects (UDGs) in the Coma cluster. These, they argue, require, within Newtonian dynamics, that they are much more massive than their observed stellar component. Here, I propound that some of the CBDM is internal to UDGs, which endows them with robustness. The rest of the CBDM objects formed in now-disrupted kin of the UDGs, and is dispersed in the intracluster medium. The discovery of cluster UDGs is not in itself a resolution of the MOND cluster conundrum, but it lends greater plausibility to CBDM as its resolution. Alternatively, if the UDGs are only now falling into Coma, their large size and very low surface brightness could result from the inflation due to the MOND, variable external-field effect (EFE). I also consider briefly solutions to the conundrum that invoke more elaborate extensions of purist MOND, e.g. that in clusters, the MOND constant takes up larger than canonical values of the MOND constant. Whatever solves the cluster conundrum within MOND might also naturally account for UDGs.

Flare Clustering

NASA Astrophysics Data System (ADS)

Title, Alan; DeRosa, Marc

2016-10-01

The continuous full disk observations provided by the Atmospheric Imaging Assembly (AIA ) can give an observer the impression that many flare eruptions are causally related to one another. However, both detailed analyses of a number of events as well as several statistical studies have provided only rare examples or weak evidence of causal behavior. Since the mechanisms of flare triggering are not well understood, the lack of hard evidence is not surprising. For this study we looked instead for groups of flares (flare clusters) in which successive flares occur within a fixed time - the selection time. The data set used for the investigation is the flare waiting times provided by the X-ray flare detectors on the Geostationary Operational Environmental Satellites (GOES). We limited the study to flares of magnitude C5 and greater obtained during cycles 21, 22, 23, and 24. The GOES field of view includes the entire visible surface. While many flares in a cluster may come from the same active region, the larger clusters often have origins in multiple regions. The longest C5 cluster found with a linking window of 36 hours in cycles 21, 22, 23,and 24 was 54, 82, 42, and 18 days, respectively. X flares also cluster. A superposed epoch analyses demonstrates that there is a pronounced enhancement of number of C5 and and above flares that are centered on the X flare clusters. We suggest that this behavior implies that a component of the observed coordinated behavior originates from the MHD processes driven by the solar dynamo that in turn creates unstable states in the solar atmosphere. The relationship between flare clusters and magnetic centers of activity was explored as was the correlation between high flare rates and significant changes in the total solar magnetic flux,

Galaxy cluster luminosities and colours, and their dependence on cluster mass and merger state

NASA Astrophysics Data System (ADS)

Mulroy, Sarah L.; McGee, Sean L.; Gillman, Steven; Smith, Graham P.; Haines, Chris P.; Démoclès, Jessica; Okabe, Nobuhiro; Egami, Eiichi

2017-12-01

We study a sample of 19 galaxy clusters in the redshift range 0.15 < z < 0.30 with highly complete spectroscopic membership catalogues (to K < K*(z) + 1.5) from the Arizona Cluster Redshift Survey, individual weak-lensing masses and near-infrared data from the Local Cluster Substructure Survey, and optical photometry from the Sloan Digital Sky Survey. We fit the scaling relations between total cluster luminosity in each of six bandpasses (grizJK) and cluster mass, finding cluster luminosity to be a promising mass proxy with low intrinsic scatter σln L|M of only ∼10-20 per cent for all relations. At fixed overdensity radius, the intercept increases with wavelength, consistent with an old stellar population. The scatter and slope are consistent across all wavelengths, suggesting that cluster colour is not a function of mass. Comparing colour with indicators of the level of disturbance in the cluster, we find a narrower variety in the cluster colours of 'disturbed' clusters than of 'undisturbed' clusters. This trend is more pronounced with indicators sensitive to the initial stages of a cluster merger, e.g. the Dressler Schectman statistic. We interpret this as possible evidence that the total cluster star formation rate is 'standardized' in mergers, perhaps through a process such as a system-wide shock in the intracluster medium.

Ethical implications of excessive cluster sizes in cluster randomised trials.

PubMed

Hemming, Karla; Taljaard, Monica; Forbes, Gordon; Eldridge, Sandra M; Weijer, Charles

2018-02-20

The cluster randomised trial (CRT) is commonly used in healthcare research. It is the gold-standard study design for evaluating healthcare policy interventions. A key characteristic of this design is that as more participants are included, in a fixed number of clusters, the increase in achievable power will level off. CRTs with cluster sizes that exceed the point of levelling-off will have excessive numbers of participants, even if they do not achieve nominal levels of power. Excessively large cluster sizes may have ethical implications due to exposing trial participants unnecessarily to the burdens of both participating in the trial and the potential risks of harm associated with the intervention. We explore these issues through the use of two case studies. Where data are routinely collected, available at minimum cost and the intervention poses low risk, the ethical implications of excessively large cluster sizes are likely to be low (case study 1). However, to maximise the social benefit of the study, identification of excessive cluster sizes can allow for prespecified and fully powered secondary analyses. In the second case study, while there is no burden through trial participation (because the outcome data are routinely collected and non-identifiable), the intervention might be considered to pose some indirect risk to patients and risks to the healthcare workers. In this case study it is therefore important that the inclusion of excessively large cluster sizes is justifiable on other grounds (perhaps to show sustainability). In any randomised controlled trial, including evaluations of health policy interventions, it is important to minimise the burdens and risks to participants. Funders, researchers and research ethics committees should be aware of the ethical issues of excessively large cluster sizes in cluster trials. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is

3D-Printable Photochromic Molecular Materials for Reversible Information Storage.

PubMed

Wales, Dominic J; Cao, Qun; Kastner, Katharina; Karjalainen, Erno; Newton, Graham N; Sans, Victor

2018-06-01

The formulation of advanced molecular materials with bespoke polymeric ionic-liquid matrices that stabilize and solubilize hybrid organic-inorganic polyoxometalates and allow their processing by additive manufacturing, is effectively demonstrated. The unique photo and redox properties of nanostructured polyoxometalates are translated across the scales (from molecular design to functional materials) to yield macroscopic functional devices with reversible photochromism. These properties open a range of potential applications including reversible information storage based on controlled topological and temporal reduction/oxidation of pre-formed printed devices. This approach pushes the boundaries of 3D printing to the molecular limits, allowing the freedom of design enabled by 3D printing to be coupled with the molecular tuneability of polymerizable ionic liquids and the photoactivity and orbital engineering possible with hybrid polyoxometalates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Star Clusters within FIRE

NASA Astrophysics Data System (ADS)

Perez, Adrianna; Moreno, Jorge; Naiman, Jill; Ramirez-Ruiz, Enrico; Hopkins, Philip F.

2017-01-01

In this work, we analyze the environments surrounding star clusters of simulated merging galaxies. Our framework employs Feedback In Realistic Environments (FIRE) model (Hopkins et al., 2014). The FIRE project is a high resolution cosmological simulation that resolves star forming regions and incorporates stellar feedback in a physically realistic way. The project focuses on analyzing the properties of the star clusters formed in merging galaxies. The locations of these star clusters are identified with astrodendro.py, a publicly available dendrogram algorithm. Once star cluster properties are extracted, they will be used to create a sub-grid (smaller than the resolution scale of FIRE) of gas confinement in these clusters. Then, we can examine how the star clusters interact with these available gas reservoirs (either by accreting this mass or blowing it out via feedback), which will determine many properties of the cluster (star formation history, compact object accretion, etc). These simulations will further our understanding of star formation within stellar clusters during galaxy evolution. In the future, we aim to enhance sub-grid prescriptions for feedback specific to processes within star clusters; such as, interaction with stellar winds and gas accretion onto black holes and neutron stars.

Clustering by reordering of similarity and Laplacian matrices: Application to galaxy clusters

NASA Astrophysics Data System (ADS)

Mahmoud, E.; Shoukry, A.; Takey, A.

2018-04-01

Similarity metrics, kernels and similarity-based algorithms have gained much attention due to their increasing applications in information retrieval, data mining, pattern recognition and machine learning. Similarity Graphs are often adopted as the underlying representation of similarity matrices and are at the origin of known clustering algorithms such as spectral clustering. Similarity matrices offer the advantage of working in object-object (two-dimensional) space where visualization of clusters similarities is available instead of object-features (multi-dimensional) space. In this paper, sparse ɛ-similarity graphs are constructed and decomposed into strong components using appropriate methods such as Dulmage-Mendelsohn permutation (DMperm) and/or Reverse Cuthill-McKee (RCM) algorithms. The obtained strong components correspond to groups (clusters) in the input (feature) space. Parameter ɛi is estimated locally, at each data point i from a corresponding narrow range of the number of nearest neighbors. Although more advanced clustering techniques are available, our method has the advantages of simplicity, better complexity and direct visualization of the clusters similarities in a two-dimensional space. Also, no prior information about the number of clusters is needed. We conducted our experiments on two and three dimensional, low and high-sized synthetic datasets as well as on an astronomical real-dataset. The results are verified graphically and analyzed using gap statistics over a range of neighbors to verify the robustness of the algorithm and the stability of the results. Combining the proposed algorithm with gap statistics provides a promising tool for solving clustering problems. An astronomical application is conducted for confirming the existence of 45 galaxy clusters around the X-ray positions of galaxy clusters in the redshift range [0.1..0.8]. We re-estimate the photometric redshifts of the identified galaxy clusters and obtain acceptable values

Spatial suicide clusters in Australia between 2010 and 2012: a comparison of cluster and non-cluster among young people and adults.

PubMed

Robinson, Jo; Too, Lay San; Pirkis, Jane; Spittal, Matthew J

2016-11-22

A suicide cluster has been defined as a group of suicides that occur closer together in time and space than would normally be expected. We aimed to examine the extent to which suicide clusters exist among young people and adults in Australia and to determine whether differences exist between cluster and non-cluster suicides. Suicide data were obtained from the National Coronial Information System for the period 2010 and 2012. Data on date of death, postcode, age at the time of death, sex, suicide method, ICD-10 code for cause of death, marital status, employment status, and aboriginality were retrieved. We examined the presence of spatial clusters separately for youth suicides and adult suicides using the Scan statistic. Pearson's chi-square was used to compare the characteristics of cluster suicides with non-cluster suicides. We identified 12 spatial clusters between 2010 and 2012. Five occurred among young people (n = 53, representing 5.6% [53/940] of youth suicides) and seven occurred among adults (n = 137, representing 2.3% [137/5939] of adult suicides). Clusters ranged in size from three to 21 for youth and from three to 31 for adults. When compared to adults, suicides by young people were significantly more likely to occur as part of a cluster (difference = 3.3%, 95% confidence interval [CI] = 1.8 to 4.8, p < 0.0001). Suicides by people with an Indigenous background were also significantly more likely to occur in a cluster than suicide by non-Indigenous people and this was the case among both young people and adults. Suicide clusters have a significant negative impact on the communities in which they occur. As a result it is important to find effective ways of managing and containing suicide clusters. To date there is limited evidence for the effectiveness of those strategies typically employed, in particular in Indigenous settings, and developing this evidence base needs to be a future priority. Future research that examines in more depth

Photoionization of rare gas clusters

NASA Astrophysics Data System (ADS)

Zhang, Huaizhen

This thesis concentrates on the study of photoionization of van der Waals clusters with different cluster sizes. The goal of the experimental investigation is to understand the electronic structure of van der Waals clusters and the electronic dynamics. These studies are fundamental to understand the interaction between UV-X rays and clusters. The experiments were performed at the Advanced Light Source at Lawrence Berkeley National Laboratory. The experimental method employs angle-resolved time-of-flight photoelectron spectrometry, one of the most powerful methods for probing the electronic structure of atoms, molecules, clusters and solids. The van der Waals cluster photoionization studies are focused on probing the evolution of the photoelectron angular distribution parameter as a function of photon energy and cluster size. The angular distribution has been known to be a sensitive probe of the electronic structure in atoms and molecules. However, it has not been used in the case of van der Waals clusters. We carried out outer-valence levels, inner-valence levels and core-levels cluster photoionization experiments. Specifically, this work reports on the first quantitative measurements of the angular distribution parameters of rare gas clusters as a function of average cluster sizes. Our findings for xenon clusters is that the overall photon-energy-dependent behavior of the photoelectrons from the clusters is very similar to that of the corresponding free atoms. However, distinct differences in the angular distribution point at cluster-size-dependent effects were found. For krypton clusters, in the photon energy range where atomic photoelectrons have a high angular anisotropy, our measurements show considerably more isotropic angular distributions for the cluster photoelectrons, especially right above the 3d and 4p thresholds. For the valence electrons, a surprising difference between the two spin-orbit components was found. For argon clusters, we found that the

Applications of cluster analysis to the creation of perfectionism profiles: a comparison of two clustering approaches.

PubMed

Bolin, Jocelyn H; Edwards, Julianne M; Finch, W Holmes; Cassady, Jerrell C

2014-01-01

Although traditional clustering methods (e.g., K-means) have been shown to be useful in the social sciences it is often difficult for such methods to handle situations where clusters in the population overlap or are ambiguous. Fuzzy clustering, a method already recognized in many disciplines, provides a more flexible alternative to these traditional clustering methods. Fuzzy clustering differs from other traditional clustering methods in that it allows for a case to belong to multiple clusters simultaneously. Unfortunately, fuzzy clustering techniques remain relatively unused in the social and behavioral sciences. The purpose of this paper is to introduce fuzzy clustering to these audiences who are currently relatively unfamiliar with the technique. In order to demonstrate the advantages associated with this method, cluster solutions of a common perfectionism measure were created using both fuzzy clustering and K-means clustering, and the results compared. Results of these analyses reveal that different cluster solutions are found by the two methods, and the similarity between the different clustering solutions depends on the amount of cluster overlap allowed for in fuzzy clustering.

Applications of cluster analysis to the creation of perfectionism profiles: a comparison of two clustering approaches

PubMed Central

Bolin, Jocelyn H.; Edwards, Julianne M.; Finch, W. Holmes; Cassady, Jerrell C.

2014-01-01

Although traditional clustering methods (e.g., K-means) have been shown to be useful in the social sciences it is often difficult for such methods to handle situations where clusters in the population overlap or are ambiguous. Fuzzy clustering, a method already recognized in many disciplines, provides a more flexible alternative to these traditional clustering methods. Fuzzy clustering differs from other traditional clustering methods in that it allows for a case to belong to multiple clusters simultaneously. Unfortunately, fuzzy clustering techniques remain relatively unused in the social and behavioral sciences. The purpose of this paper is to introduce fuzzy clustering to these audiences who are currently relatively unfamiliar with the technique. In order to demonstrate the advantages associated with this method, cluster solutions of a common perfectionism measure were created using both fuzzy clustering and K-means clustering, and the results compared. Results of these analyses reveal that different cluster solutions are found by the two methods, and the similarity between the different clustering solutions depends on the amount of cluster overlap allowed for in fuzzy clustering. PMID:24795683

Defining objective clusters for rabies virus sequences using affinity propagation clustering

PubMed Central

Fischer, Susanne; Freuling, Conrad M.; Pfaff, Florian; Bodenhofer, Ulrich; Höper, Dirk; Fischer, Mareike; Marston, Denise A.; Fooks, Anthony R.; Mettenleiter, Thomas C.; Conraths, Franz J.; Homeier-Bachmann, Timo

2018-01-01

Rabies is caused by lyssaviruses, and is one of the oldest known zoonoses. In recent years, more than 21,000 nucleotide sequences of rabies viruses (RABV), from the prototype species rabies lyssavirus, have been deposited in public databases. Subsequent phylogenetic analyses in combination with metadata suggest geographic distributions of RABV. However, these analyses somewhat experience technical difficulties in defining verifiable criteria for cluster allocations in phylogenetic trees inviting for a more rational approach. Therefore, we applied a relatively new mathematical clustering algorythm named ‘affinity propagation clustering’ (AP) to propose a standardized sub-species classification utilizing full-genome RABV sequences. Because AP has the advantage that it is computationally fast and works for any meaningful measure of similarity between data samples, it has previously been applied successfully in bioinformatics, for analysis of microarray and gene expression data, however, cluster analysis of sequences is still in its infancy. Existing (516) and original (46) full genome RABV sequences were used to demonstrate the application of AP for RABV clustering. On a global scale, AP proposed four clusters, i.e. New World cluster, Arctic/Arctic-like, Cosmopolitan, and Asian as previously assigned by phylogenetic studies. By combining AP with established phylogenetic analyses, it is possible to resolve phylogenetic relationships between verifiably determined clusters and sequences. This workflow will be useful in confirming cluster distributions in a uniform transparent manner, not only for RABV, but also for other comparative sequence analyses. PMID:29357361

Robust continuous clustering

PubMed Central

Shah, Sohil Atul

2017-01-01

Clustering is a fundamental procedure in the analysis of scientific data. It is used ubiquitously across the sciences. Despite decades of research, existing clustering algorithms have limited effectiveness in high dimensions and often require tuning parameters for different domains and datasets. We present a clustering algorithm that achieves high accuracy across multiple domains and scales efficiently to high dimensions and large datasets. The presented algorithm optimizes a smooth continuous objective, which is based on robust statistics and allows heavily mixed clusters to be untangled. The continuous nature of the objective also allows clustering to be integrated as a module in end-to-end feature learning pipelines. We demonstrate this by extending the algorithm to perform joint clustering and dimensionality reduction by efficiently optimizing a continuous global objective. The presented approach is evaluated on large datasets of faces, hand-written digits, objects, newswire articles, sensor readings from the Space Shuttle, and protein expression levels. Our method achieves high accuracy across all datasets, outperforming the best prior algorithm by a factor of 3 in average rank. PMID:28851838

The HectoMAP Cluster Survey. I. redMaPPer Clusters

NASA Astrophysics Data System (ADS)

Sohn, Jubee; Geller, Margaret J.; Rines, Kenneth J.; Hwang, Ho Seong; Utsumi, Yousuke; Diaferio, Antonaldo

2018-04-01

We use the dense HectoMAP redshift survey to explore the properties of 104 redMaPPer cluster candidates. The redMaPPer systems in HectoMAP cover the full range of richness and redshift (0.08 < z < 0.60). Fifteen of the systems included in the Subaru/Hyper Suprime-Cam public data release are bona fide clusters. The median number of spectroscopic members per cluster is ∼20. We include redshifts of 3547 member candidates listed in the redMaPPer catalog whether they are cluster members or not. We evaluate the redMaPPer membership probability spectroscopically. The purity (number of real systems) in redMaPPer exceeds 90% even at the lowest richness. Three massive galaxy clusters (M ∼ 2 × 1013 M ⊙) associated with X-ray emission in the HectoMAP region are not included in the public redMaPPer catalog with λ rich > 20, because they lie outside the cuts for this catalog.

The HectoMAP Cluster Survey. I. redMaPPer Clusters

DOE PAGES

Sohn, Jubee; Geller, Margaret J.; Rines, Kenneth J.; ...

2018-04-05

We use the dense HectoMAP redshift survey to explore the properties of 104 redMaPPer cluster candidates. The redMaPPer systems in HectoMAP cover the full range of richness and redshift (0.08 < z < 0.60). Fifteen of the systems included in the Subaru/Hyper Suprime-Cam public data release are bona fide clusters. The median number of spectroscopic members per cluster is ~20. We include redshifts of 3547 member candidates listed in the redMaPPer catalog whether they are cluster members or not. Here, we evaluate the redMaPPer membership probability spectroscopically. The purity (number of real systems) in redMaPPer exceeds 90% even at themore » lowest richness. Three massive galaxy clusters (M ~ 2 × 10 13 M ⊙) associated with X-ray emission in the HectoMAP region are not included in the public redMaPPer catalog with λ rich > 20, because they lie outside the cuts for this catalog.« less

The HectoMAP Cluster Survey. I. redMaPPer Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sohn, Jubee; Geller, Margaret J.; Rines, Kenneth J.

We use the dense HectoMAP redshift survey to explore the properties of 104 redMaPPer cluster candidates. The redMaPPer systems in HectoMAP cover the full range of richness and redshift (0.08 < z < 0.60). Fifteen of the systems included in the Subaru/Hyper Suprime-Cam public data release are bona fide clusters. The median number of spectroscopic members per cluster is ~20. We include redshifts of 3547 member candidates listed in the redMaPPer catalog whether they are cluster members or not. Here, we evaluate the redMaPPer membership probability spectroscopically. The purity (number of real systems) in redMaPPer exceeds 90% even at themore » lowest richness. Three massive galaxy clusters (M ~ 2 × 10 13 M ⊙) associated with X-ray emission in the HectoMAP region are not included in the public redMaPPer catalog with λ rich > 20, because they lie outside the cuts for this catalog.« less

Stochastic coupled cluster theory: Efficient sampling of the coupled cluster expansion

NASA Astrophysics Data System (ADS)

Scott, Charles J. C.; Thom, Alex J. W.

2017-09-01

We consider the sampling of the coupled cluster expansion within stochastic coupled cluster theory. Observing the limitations of previous approaches due to the inherently non-linear behavior of a coupled cluster wavefunction representation, we propose new approaches based on an intuitive, well-defined condition for sampling weights and on sampling the expansion in cluster operators of different excitation levels. We term these modifications even and truncated selections, respectively. Utilising both approaches demonstrates dramatically improved calculation stability as well as reduced computational and memory costs. These modifications are particularly effective at higher truncation levels owing to the large number of terms within the cluster expansion that can be neglected, as demonstrated by the reduction of the number of terms to be sampled when truncating at triple excitations by 77% and hextuple excitations by 98%.

Cluster Organic Frameworks Constructed from Heterometallic Supertetrahedral Cluster Secondary Building Units.

PubMed

Lin, Li-Dan; Li, Xin-Xiong; Qi, Yan-Jie; Ma, Xiang; Zheng, Shou-Tian

2017-04-17

The two novel cluster organic frameworks based on heterometallic supertetrahedral cluster secondary building units (SBUs) [Cd 4 Cu 6 (L) 4 (Ac) 7 (H 2 O) 4 ](Ac)·7H 2 O (1) and [Mn 4 Cu 6 (L) 4 (Ac) 4.5 (H 2 O) 9 ]CuCN(Ac) 3.5 ·H 2 O (2), where H 3 L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol and Ac = CH 3 COO - , have been prepared under solvothermal conditions. 1 and 2 are the first cases of cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral cluster SBUs. Furthermore, 1 and 2 show an integration of magnetic properties and adsorption properties from both the heterometallic cluster secondary building units and the framework in a porous material.

Calibrating the Planck cluster mass scale with cluster velocity dispersions

NASA Astrophysics Data System (ADS)

Amodeo, S.; Mei, S.; Stanford, S. A.; Bartlett, J. G.; Lawrence, C. L.; Chary, R. R.; Shim, H.; Marleau, F.; Stern, D.

2017-12-01

The potential of galaxy clusters as cosmological probes critically depends on the capability to obtain accurate estimates of their mass. This will be a key measurement for the next generation of cosmological surveys, such as Euclid. The discrepancy between the cosmological parameters determined from anisotropies in the cosmic microwave background and those derived from cluster abundance measurements from the Planck satellite calls for careful evaluation of systematic biases in cluster mass estimates. For this purpose, it is crucial to use independent techniques, like analysis of the thermal emission of the intracluster medium (ICM), observed either in the X-rays or through the Sunyaev-Zeldovich (SZ) effect, dynamics of member galaxies or gravitational lensing. We discuss possible bias in the Planck SZ mass proxy, which is based on X-ray observations. Using optical spectroscopy from the Gemini Multi-Object Spectrograph of 17 Planck-selected clusters, we present new estimates of the cluster mass based on the velocity dispersion of the member galaxies and independently of the ICM properties. We show how the difference between the velocity dispersion of galaxy and dark matter particles in simulations is the primary factor limiting interpretation of dynamical cluster mass measurements at this time, and we give the first observational constraints on the velocity bias.

Diffuse Optical Light in Galaxy Clusters. II. Correlations with Cluster Properties

NASA Astrophysics Data System (ADS)

Krick, J. E.; Bernstein, R. A.

2007-08-01

We have measured the flux, profile, color, and substructure in the diffuse intracluster light (ICL) in a sample of 10 galaxy clusters with a range of mass, morphology, redshift, and density. Deep, wide-field observations for this project were made in two bands at the 1 m Swope and 2.5 m du Pont telescopes at Las Campanas Observatory. Careful attention in reduction and analysis was paid to the illumination correction, background subtraction, point-spread function determination, and galaxy subtraction. ICL flux is detected in both bands in all 10 clusters ranging from 7.6×1010 to 7.0×1011 h-170 Lsolar in r and 1.4×1010 to 1.2×1011 h-170 Lsolar in the B band. These fluxes account for 6%-22% of the total cluster light within one-quarter of the virial radius in r and 4%-21% in the B band. Average ICL B-r colors range from 1.5 to 2.8 mag when k- and evolution corrected to the present epoch. In several clusters we also detect ICL in group environments near the cluster center and up to 1 h-170 Mpc distant from the cluster center. Our sample, having been selected from the Abell sample, is incomplete in that it does not include high-redshift clusters with low density, low flux, or low mass, and it does not include low-redshift clusters with high flux, high mass, or high density. This bias makes it difficult to interpret correlations between ICL flux and cluster properties. Despite this selection bias, we do find that the presence of a cD galaxy corresponds to both centrally concentrated galaxy profiles and centrally concentrated ICL profiles. This is consistent with ICL either forming from galaxy interactions at the center or forming at earlier times in groups and later combining in the center.

Efficient Agent-Based Cluster Ensembles

NASA Technical Reports Server (NTRS)

Agogino, Adrian; Tumer, Kagan

2006-01-01

Numerous domains ranging from distributed data acquisition to knowledge reuse need to solve the cluster ensemble problem of combining multiple clusterings into a single unified clustering. Unfortunately current non-agent-based cluster combining methods do not work in a distributed environment, are not robust to corrupted clusterings and require centralized access to all original clusterings. Overcoming these issues will allow cluster ensembles to be used in fundamentally distributed and failure-prone domains such as data acquisition from satellite constellations, in addition to domains demanding confidentiality such as combining clusterings of user profiles. This paper proposes an efficient, distributed, agent-based clustering ensemble method that addresses these issues. In this approach each agent is assigned a small subset of the data and votes on which final cluster its data points should belong to. The final clustering is then evaluated by a global utility, computed in a distributed way. This clustering is also evaluated using an agent-specific utility that is shown to be easier for the agents to maximize. Results show that agents using the agent-specific utility can achieve better performance than traditional non-agent based methods and are effective even when up to 50% of the agents fail.

clusterProfiler: an R package for comparing biological themes among gene clusters.

PubMed

Yu, Guangchuang; Wang, Li-Gen; Han, Yanyan; He, Qing-Yu

2012-05-01

Increasing quantitative data generated from transcriptomics and proteomics require integrative strategies for analysis. Here, we present an R package, clusterProfiler that automates the process of biological-term classification and the enrichment analysis of gene clusters. The analysis module and visualization module were combined into a reusable workflow. Currently, clusterProfiler supports three species, including humans, mice, and yeast. Methods provided in this package can be easily extended to other species and ontologies. The clusterProfiler package is released under Artistic-2.0 License within Bioconductor project. The source code and vignette are freely available at http://bioconductor.org/packages/release/bioc/html/clusterProfiler.html.

Effects of cluster location and cluster distribution on performance on the traveling salesman problem.

PubMed

MacGregor, James N

2015-10-01

Research on human performance in solving traveling salesman problems typically uses point sets as stimuli, and most models have proposed a processing stage at which stimulus dots are clustered. However, few empirical studies have investigated the effects of clustering on performance. In one recent study, researchers compared the effects of clustered, random, and regular stimuli, and concluded that clustering facilitates performance (Dry, Preiss, & Wagemans, 2012). Another study suggested that these results may have been influenced by the location rather than the degree of clustering (MacGregor, 2013). Two experiments are reported that mark an attempt to disentangle these factors. The first experiment tested several combinations of degree of clustering and cluster location, and revealed mixed evidence that clustering influences performance. In a second experiment, both factors were varied independently, showing that they interact. The results are discussed in terms of the importance of clustering effects, in particular, and perceptual factors, in general, during performance of the traveling salesman problem.

Noble gas cluster ions

NASA Astrophysics Data System (ADS)

Kaya, Yunus; Kalkan, Yalçin; Veenhof, Rob

2018-02-01

In this work, a reaction mechanism of formation of noble gas (Ng) cluster ions has been theoretically investigated in detail. The kinetic studies of formation of Xe+Xe cluster in Xe, Ar+Ar cluster ions in Ar, and Ne+Ne cluster ions in Ne have been made as theoretically. The optimized structures in the ground state were calculated using the density functional theory (DFT) by the B3LYP method combined with the Stuttgart/Dresden effective core potential basis set (SDD). In addition, we calculated the rate constants of all cluster formations. The results are 1.15 × 10-31, 3.58 × 10-31, 0.23 × 10-31cm6/s, respectively for Neon, Argon, Xenon cluster ions.

Higher-order clustering in networks

NASA Astrophysics Data System (ADS)

Yin, Hao; Benson, Austin R.; Leskovec, Jure

2018-05-01

A fundamental property of complex networks is the tendency for edges to cluster. The extent of the clustering is typically quantified by the clustering coefficient, which is the probability that a length-2 path is closed, i.e., induces a triangle in the network. However, higher-order cliques beyond triangles are crucial to understanding complex networks, and the clustering behavior with respect to such higher-order network structures is not well understood. Here we introduce higher-order clustering coefficients that measure the closure probability of higher-order network cliques and provide a more comprehensive view of how the edges of complex networks cluster. Our higher-order clustering coefficients are a natural generalization of the traditional clustering coefficient. We derive several properties about higher-order clustering coefficients and analyze them under common random graph models. Finally, we use higher-order clustering coefficients to gain new insights into the structure of real-world networks from several domains.

Combining Mixture Components for Clustering*

PubMed Central

Baudry, Jean-Patrick; Raftery, Adrian E.; Celeux, Gilles; Lo, Kenneth; Gottardo, Raphaël

2010-01-01

Model-based clustering consists of fitting a mixture model to data and identifying each cluster with one of its components. Multivariate normal distributions are typically used. The number of clusters is usually determined from the data, often using BIC. In practice, however, individual clusters can be poorly fitted by Gaussian distributions, and in that case model-based clustering tends to represent one non-Gaussian cluster by a mixture of two or more Gaussian distributions. If the number of mixture components is interpreted as the number of clusters, this can lead to overestimation of the number of clusters. This is because BIC selects the number of mixture components needed to provide a good approximation to the density, rather than the number of clusters as such. We propose first selecting the total number of Gaussian mixture components, K, using BIC and then combining them hierarchically according to an entropy criterion. This yields a unique soft clustering for each number of clusters less than or equal to K. These clusterings can be compared on substantive grounds, and we also describe an automatic way of selecting the number of clusters via a piecewise linear regression fit to the rescaled entropy plot. We illustrate the method with simulated data and a flow cytometry dataset. Supplemental Materials are available on the journal Web site and described at the end of the paper. PMID:20953302

A revised moving cluster distance to the Pleiades open cluster

NASA Astrophysics Data System (ADS)

Galli, P. A. B.; Moraux, E.; Bouy, H.; Bouvier, J.; Olivares, J.; Teixeira, R.

2017-02-01

Context. The distance to the Pleiades open cluster has been extensively debated in the literature over several decades. Although different methods point to a discrepancy in the trigonometric parallaxes produced by the Hipparcos mission, the number of individual stars with known distances is still small compared to the number of cluster members to help solve this problem. Aims: We provide a new distance estimate for the Pleiades based on the moving cluster method, which will be useful to further discuss the so-called Pleiades distance controversy and compare it with the very precise parallaxes from the Gaia space mission. Methods: We apply a refurbished implementation of the convergent point search method to an updated census of Pleiades stars to calculate the convergent point position of the cluster from stellar proper motions. Then, we derive individual parallaxes for 64 cluster members using radial velocities compiled from the literature, and approximate parallaxes for another 1146 stars based on the spatial velocity of the cluster. This represents the largest sample of Pleiades stars with individual distances to date. Results: The parallaxes derived in this work are in good agreement with previous results obtained in different studies (excluding Hipparcos) for individual stars in the cluster. We report a mean parallax of 7.44 ± 0.08 mas and distance of pc that is consistent with the weighted mean of 135.0 ± 0.6 pc obtained from the non-Hipparcos results in the literature. Conclusions: Our result for the distance to the Pleiades open cluster is not consistent with the Hipparcos catalog, but favors the recent and more precise distance determination of 136.2 ± 1.2 pc obtained from Very Long Baseline Interferometry observations. It is also in good agreement with the mean distance of 133 ± 5 pc obtained from the first trigonometric parallaxes delivered by the Gaia satellite for the brightest cluster members in common with our sample. Full Table B.2 is only

Cluster Size Optimization in Sensor Networks with Decentralized Cluster-Based Protocols

PubMed Central

Amini, Navid; Vahdatpour, Alireza; Xu, Wenyao; Gerla, Mario; Sarrafzadeh, Majid

2011-01-01

Network lifetime and energy-efficiency are viewed as the dominating considerations in designing cluster-based communication protocols for wireless sensor networks. This paper analytically provides the optimal cluster size that minimizes the total energy expenditure in such networks, where all sensors communicate data through their elected cluster heads to the base station in a decentralized fashion. LEACH, LEACH-Coverage, and DBS comprise three cluster-based protocols investigated in this paper that do not require any centralized support from a certain node. The analytical outcomes are given in the form of closed-form expressions for various widely-used network configurations. Extensive simulations on different networks are used to confirm the expectations based on the analytical results. To obtain a thorough understanding of the results, cluster number variability problem is identified and inspected from the energy consumption point of view. PMID:22267882

Current rectification in a single molecule diode: the role of electrode coupling.

PubMed

Sherif, Siya; Rubio-Bollinger, Gabino; Pinilla-Cienfuegos, Elena; Coronado, Eugenio; Cuevas, Juan Carlos; Agraït, Nicolás

2015-07-24

We demonstrate large rectification ratios (> 100) in single-molecule junctions based on a metal-oxide cluster (polyoxometalate), using a scanning tunneling microscope (STM) both at ambient conditions and at low temperature. These rectification ratios are the largest ever observed in a single-molecule junction, and in addition these junctions sustain current densities larger than 10(5) A cm(-2). By following the variation of the I-V characteristics with tip-molecule separation we demonstrate unambiguously that rectification is due to asymmetric coupling to the electrodes of a molecule with an asymmetric level structure. This mechanism can be implemented in other type of molecular junctions using both organic and inorganic molecules and provides a simple strategy for the rational design of molecular diodes.

Current rectification in a single molecule diode: the role of electrode coupling

NASA Astrophysics Data System (ADS)

Sherif, Siya; Rubio-Bollinger, Gabino; Pinilla-Cienfuegos, Elena; Coronado, Eugenio; Cuevas, Juan Carlos; Agraït, Nicolás

2015-07-01

We demonstrate large rectification ratios (\\gt 100) in single-molecule junctions based on a metal-oxide cluster (polyoxometalate), using a scanning tunneling microscope (STM) both at ambient conditions and at low temperature. These rectification ratios are the largest ever observed in a single-molecule junction, and in addition these junctions sustain current densities larger than 105 A cm-2. By following the variation of the I-V characteristics with tip-molecule separation we demonstrate unambiguously that rectification is due to asymmetric coupling to the electrodes of a molecule with an asymmetric level structure. This mechanism can be implemented in other type of molecular junctions using both organic and inorganic molecules and provides a simple strategy for the rational design of molecular diodes.

Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters.

PubMed

Parnis, J Mark; Escobar-Cabrera, Eric; Thompson, Matthew G K; Jacula, J Paul; Lafleur, Rick D; Guevara-García, Alfredo; Martínez, Ana; Rayner, David M

2005-08-18

Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb8 and Nb10, for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C2H4, C2H2, or C2. With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb(n) cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of

Cluster dynamics and cluster size distributions in systems of self-propelled particles

NASA Astrophysics Data System (ADS)

Peruani, F.; Schimansky-Geier, L.; Bär, M.

2010-12-01

Systems of self-propelled particles (SPP) interacting by a velocity alignment mechanism in the presence of noise exhibit rich clustering dynamics. Often, clusters are responsible for the distribution of (local) information in these systems. Here, we investigate the properties of individual clusters in SPP systems, in particular the asymmetric spreading behavior of clusters with respect to their direction of motion. In addition, we formulate a Smoluchowski-type kinetic model to describe the evolution of the cluster size distribution (CSD). This model predicts the emergence of steady-state CSDs in SPP systems. We test our theoretical predictions in simulations of SPP with nematic interactions and find that our simple kinetic model reproduces qualitatively the transition to aggregation observed in simulations.

X-Ray Binaries and Star Clusters in the Antennae: Optical Cluster Counterparts

NASA Astrophysics Data System (ADS)

Rangelov, Blagoy; Chandar, Rupali; Prestwich, Andrea; Whitmore, Bradley C.

2012-10-01

We compare the locations of 82 X-ray binaries (XRBs) detected in the merging Antennae galaxies by Zezas et al., based on observations taken with the Chandra X-Ray Observatory, with a catalog of optically selected star clusters presented by Whitmore et al., based on observations taken with the Hubble Space Telescope. Within the 2σ positional uncertainty of ≈0farcs8, we find 22 XRBs are coincident with star clusters, where only two to three chance coincidences are expected. The ages of the clusters were estimated by comparing their UBVI, Hα colors with predictions from stellar evolutionary models. We find that 14 of the 22 coincident XRBs (64%) are hosted by star clusters with ages of ≈6 Myr or less. All of the very young host clusters are fairly massive and have M >~ 3 × 104 M ⊙, with many having masses M ≈ 105 M ⊙. Five of the XRBs are hosted by young clusters with ages τ ≈ 10-100 Myr, while three are hosted by intermediate-age clusters with τ ≈ 100-300 Myr. Based on the results from recent N-body simulations, which suggest that black holes are far more likely to be retained within their parent clusters than neutron stars, we suggest that our sample consists primarily of black hole binaries with different ages.

Nanothermodynamics of iron clusters: Small clusters, icosahedral and fcc-cuboctahedral structures

NASA Astrophysics Data System (ADS)

Angelié, C.; Soudan, J.-M.

2017-05-01

The study of the thermodynamics and structures of iron clusters has been carried on, focusing on small clusters and initial icosahedral and fcc-cuboctahedral structures. Two combined tools are used. First, energy intervals are explored by the Monte Carlo algorithm, called σ-mapping, detailed in the work of Soudan et al. [J. Chem. Phys. 135, 144109 (2011), Paper I]. In its flat histogram version, it provides the classical density of states, gp(Ep), in terms of the potential energy of the system. Second, the iron system is described by a potential which is called "corrected EAM" (cEAM), explained in the work of Basire et al. [J. Chem. Phys. 141, 104304 (2014), Paper II]. Small clusters from 3 to 12 atoms in their ground state have been compared first with published Density Functional Theory (DFT) calculations, giving a complete agreement of geometries. The series of 13, 55, 147, and 309 atom icosahedrons is shown to be the most stable form for the cEAM potential. However, the 147 atom cluster has a special behaviour, since decreasing the energy from the liquid zone leads to the irreversible trapping of the cluster in a reproducible amorphous state, 7.38 eV higher in energy than the icosahedron. This behaviour is not observed at the higher size of 309 atoms. The heat capacity of the 55, 147, and 309 atom clusters revealed a pronounced peak in the solid zone, related to a solid-solid transition, prior to the melting peak. The corresponding series of 13, 55, and 147 atom cuboctahedrons has been compared, underscoring the unstability towards the icosahedral structure. This unstability occurs clearly in several steps for the 147 atom cluster, with a sudden transformation at a transition state. This illustrates the concerted icosahedron-cuboctahedron transformation of Buckminster Fuller-Mackay, which is calculated for the cEAM potential. Two other clusters of initial fcc structures with 24 and 38 atoms have been studied, as well as a 302 atom cluster. Each one relaxes

A detection of wobbling brightest cluster galaxies within massive galaxy clusters

NASA Astrophysics Data System (ADS)

Harvey, David; Courbin, F.; Kneib, J. P.; McCarthy, Ian G.

2017-12-01

A striking signal of dark matter beyond the standard model is the existence of cores in the centre of galaxy clusters. Recent simulations predict that a brightest cluster galaxy (BCG) inside a cored galaxy cluster will exhibit residual wobbling due to previous major mergers, long after the relaxation of the overall cluster. This phenomenon is absent with standard cold dark matter where a cuspy density profile keeps a BCG tightly bound at the centre. We test this hypothesis using cosmological simulations and deep observations of 10 galaxy clusters acting as strong gravitational lenses. Modelling the BCG wobble as a simple harmonic oscillator, we measure the wobble amplitude, Aw, in the BAHAMAS suite of cosmological hydrodynamical simulations, finding an upper limit for the cold dark matter paradigm of Aw < 2 kpc at the 95 per cent confidence limit. We carry out the same test on the data finding a non-zero amplitude of A_w=11.82^{+7.3}_{-3.0} kpc, with the observations dis-favouring Aw = 0 at the 3σ confidence level. This detection of BCG wobbling is evidence for a dark matter core at the heart of galaxy clusters. It also shows that strong lensing models of clusters cannot assume that the BCG is exactly coincident with the large-scale halo. While our small sample of galaxy clusters already indicates a non-zero Aw, with larger surveys, e.g. Euclid, we will be able to not only confirm the effect but also to use it to determine whether or not the wobbling finds its origin in new fundamental physics or astrophysical process.

Effects of Cluster Environment on Chemical Abundances in Virgo Cluster Spirals

NASA Astrophysics Data System (ADS)

Kennicutt, R. C.; Skillman, E. D.; Shields, G. A.; Zaritsky, D.

1995-12-01

We have obtained new chemical abundance measurements of HII regions in Virgo cluster spiral galaxies, in order to test whether the cluster environment has significantly influenced the gas-phase abundances and chemical evolution of spiral disks. The sample of 9 Virgo spirals covers a narrow range of morphological type (Sbc - Sc) but shows broad ranges in HI deficiencies and radii in the cluster. This allows us to compare the Virgo sample as a whole to field spirals, using a large sample from Zaritsky, Kennicutt, & Huchra, and to test for systematic trends with HI content and location within the cluster. The Virgo spirals show a wide dispersion in mean disk abundances and abundance gradients. Strongly HI deficient spirals closest to the cluster core show anomalously high oxygen abundances (by 0.3 to 0.5 dex), while outlying spirals with normal HI content show abundances similar to those of field spirals. The most HI depleted spirals also show weaker abundance gradients on average, but the formal significance of this trend is marginal. We find a strong correlation between mean abundance and HI/optical diameter ratio that is quite distinct from the behavior seen in field galaxies. This suggests that dynamical processes associated with the cluster environment are more important than cluster membership in determining the evolution of chemical abundances and stellar populations in spiral galaxies. Simple chemical evolution models are calculated to predict the magnitude of the abundance enhancement expected if ram-pressure stripping or curtailment of infall is responsible for the gas deficiencies. The increased abundances of the spirals in the cluster core may have significant effects on their use as cosmological standard candles.

Clustering of Multivariate Geostatistical Data

NASA Astrophysics Data System (ADS)

Fouedjio, Francky

2017-04-01

Multivariate data indexed by geographical coordinates have become omnipresent in the geosciences and pose substantial analysis challenges. One of them is the grouping of data locations into spatially contiguous clusters so that data locations belonging to the same cluster have a certain degree of homogeneity while data locations in the different clusters have to be as different as possible. However, groups of data locations created through classical clustering techniques turn out to show poor spatial contiguity, a feature obviously inconvenient for many geoscience applications. In this work, we develop a clustering method that overcomes this problem by accounting the spatial dependence structure of data; thus reinforcing the spatial contiguity of resulting cluster. The capability of the proposed clustering method to provide spatially contiguous and meaningful clusters of data locations is assessed using both synthetic and real datasets. Keywords: clustering, geostatistics, spatial contiguity, spatial dependence.

SBA Innovation Clusters

DTIC Science & Technology

2012-03-02

Programs and services to help you start, grow and succeed www.sba.gov U.S. Small Business Administration Your Small Business Resource 1Approved for...Public Release SBA Innovation Clusters RADM Steven G. Smith USN (Ret) Advanced Defense Technology Cluster Coordinator U.S. Small Business ...UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) U.S. Small Business Administration ,Advanced Defense Technology Cluster,409 3rd St, SW

Seizure clusters: characteristics and treatment.

PubMed

Haut, Sheryl R

2015-04-01

Many patients with epilepsy experience 'clusters' or flurries of seizures, also termed acute repetitive seizures (ARS). Seizure clustering has a significant impact on health and quality of life. This review summarizes recent advances in the definition and neurophysiologic understanding of clustering, the epidemiology and risk factors for clustering and both inpatient and outpatient clinical implications. New treatments for seizure clustering/ARS are perhaps the area of greatest recent progress. Efforts have focused on creating a uniform definition of a seizure cluster. In neurophysiologic studies of refractory epilepsy, seizures within a cluster appear to be self-triggering. Clinical progress has been achieved towards a more precise prevalence of clustering, and consensus guidelines for epilepsy monitoring unit safety. The greatest recent advances are in the study of nonintravenous route of benzodiazepines as rescue medications for seizure clusters/ARS. Rectal benzodiazepines have been very effective but barriers to use exist. New data on buccal, intramuscular and intranasal preparations are anticipated to lead to a greater number of approved treatments. Progesterone may be effective for women who experience catamenial clusters. Seizure clustering is common, particularly in the setting of medically refractory epilepsy. Clustering worsens health and quality of life, and the field requires greater focus on clarifying of definition and clinical implications. Progress towards the development of nonintravenous routes of benzodiazepines has the potential to improve care in this area.

Constraining the mass–richness relationship of redMaPPer clusters with angular clustering

DOE PAGES

Baxter, Eric J.; Rozo, Eduardo; Jain, Bhuvnesh; ...

2016-08-04

The potential of using cluster clustering for calibrating the mass–richness relation of galaxy clusters has been recognized theoretically for over a decade. In this paper, we demonstrate the feasibility of this technique to achieve high-precision mass calibration using redMaPPer clusters in the Sloan Digital Sky Survey North Galactic Cap. By including cross-correlations between several richness bins in our analysis, we significantly improve the statistical precision of our mass constraints. The amplitude of the mass–richness relation is constrained to 7 per cent statistical precision by our analysis. However, the error budget is systematics dominated, reaching a 19 per cent total errormore » that is dominated by theoretical uncertainty in the bias–mass relation for dark matter haloes. We confirm the result from Miyatake et al. that the clustering amplitude of redMaPPer clusters depends on galaxy concentration as defined therein, and we provide additional evidence that this dependence cannot be sourced by mass dependences: some other effect must account for the observed variation in clustering amplitude with galaxy concentration. Assuming that the observed dependence of redMaPPer clustering on galaxy concentration is a form of assembly bias, we find that such effects introduce a systematic error on the amplitude of the mass–richness relation that is comparable to the error bar from statistical noise. Finally, the results presented here demonstrate the power of cluster clustering for mass calibration and cosmology provided the current theoretical systematics can be ameliorated.« less

Low-temperature cluster catalysis.

PubMed

Judai, Ken; Abbet, Stéphane; Wörz, Anke S; Heiz, Ulrich; Henry, Claude R

2004-03-10

Free and supported metal clusters reveal unique chemical and physical properties, which vary as a function of size as each cluster possesses a characteristic electron confinement. Several previous experimental results showed that the outcome of a given chemical reaction can be controlled by tuning the cluster size. However, none of the examples indicate that clusters prepared in the gas phase and then deposited on a support material are indeed catalytically active over several reaction cycles nor that their catalytic properties remain constant during such a catalytic process. In this work we report turn-over frequencies (TOF) for Pd(n) (n = 4, 8, 30) clusters using pulsed molecular beam experiments. The obtained results illustrate that the catalytic reactivity for the NO reduction by CO (CO + NO --> 1/2N(2) + CO(2)) is indeed a function of cluster size and that the measured TOF remain constant at a given temperature. More interestingly, the temperature of maximal reactivity is at least 100 K lower than observed for palladium nanoparticles or single crystals. One reason for this surprising observation is the character of the binding sites of these small clusters: N(2) forms already at relatively low temperatures (400 and 450 K) and therefore poisoning by adsorbed nitrogen adatoms is prevented. Thus, small clusters not only open the possibility of tuning a catalytic process by changing cluster size, but also of catalyzing chemical reactions at low temperatures.

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

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

PubMed

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic

Effective implementation of hierarchical clustering

NASA Astrophysics Data System (ADS)

Verma, Mudita; Vijayarajan, V.; Sivashanmugam, G.; Bessie Amali, D. Geraldine

2017-11-01

Hierarchical clustering is generally used for cluster analysis in which we build up a hierarchy of clusters. In order to find that which cluster should be split a large amount of observations are being carried out. Here the data set of US based personalities has been considered for clustering. After implementation of hierarchical clustering on the data set we group it in three different clusters one is of politician, sports person and musicians. Training set is the main parameter which decides the category which has to be assigned to the observations that are being collected. The category of these observations must be known. Recognition comes from the formulation of classification. Supervised learning has the main instance in the form of classification. While on the other hand Clustering is an instance of unsupervised procedure. Clustering consists of grouping of data that have similar properties which are either their own or are inherited from some other sources.

Global survey of star clusters in the Milky Way. VI. Age distribution and cluster formation history

NASA Astrophysics Data System (ADS)

Piskunov, A. E.; Just, A.; Kharchenko, N. V.; Berczik, P.; Scholz, R.-D.; Reffert, S.; Yen, S. X.

2018-06-01

Context. The all-sky Milky Way Star Clusters (MWSC) survey provides uniform and precise ages, along with other relevant parameters, for a wide variety of clusters in the extended solar neighbourhood. Aims: In this study we aim to construct the cluster age distribution, investigate its spatial variations, and discuss constraints on cluster formation scenarios of the Galactic disk during the last 5 Gyrs. Methods: Due to the spatial extent of the MWSC, we have considered spatial variations of the age distribution along galactocentric radius RG, and along Z-axis. For the analysis of the age distribution we used 2242 clusters, which all lie within roughly 2.5 kpc of the Sun. To connect the observed age distribution to the cluster formation history we built an analytical model based on simple assumptions on the cluster initial mass function and on the cluster mass-lifetime relation, fit it to the observations, and determined the parameters of the cluster formation law. Results: Comparison with the literature shows that earlier results strongly underestimated the number of evolved clusters with ages t ≳ 100 Myr. Recent studies based on all-sky catalogues agree better with our data, but still lack the oldest clusters with ages t ≳ 1 Gyr. We do not observe a strong variation in the age distribution along RG, though we find an enhanced fraction of older clusters (t > 1 Gyr) in the inner disk. In contrast, the distribution strongly varies along Z. The high altitude distribution practically does not contain clusters with t < 1 Gyr. With simple assumptions on the cluster formation history, the cluster initial mass function and the cluster lifetime we can reproduce the observations. The cluster formation rate and the cluster lifetime are strongly degenerate, which does not allow us to disentangle different formation scenarios. In all cases the cluster formation rate is strongly declining with time, and the cluster initial mass function is very shallow at the high mass end.

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.

X-RAY BINARIES AND STAR CLUSTERS IN THE ANTENNAE: OPTICAL CLUSTER COUNTERPARTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rangelov, Blagoy; Chandar, Rupali; Prestwich, Andrea

2012-10-20

We compare the locations of 82 X-ray binaries (XRBs) detected in the merging Antennae galaxies by Zezas et al., based on observations taken with the Chandra X-Ray Observatory, with a catalog of optically selected star clusters presented by Whitmore et al., based on observations taken with the Hubble Space Telescope. Within the 2{sigma} positional uncertainty of Almost-Equal-To 0.''8, we find 22 XRBs are coincident with star clusters, where only two to three chance coincidences are expected. The ages of the clusters were estimated by comparing their UBVI, H{alpha} colors with predictions from stellar evolutionary models. We find that 14 ofmore » the 22 coincident XRBs (64%) are hosted by star clusters with ages of Almost-Equal-To 6 Myr or less. All of the very young host clusters are fairly massive and have M {approx}> 3 Multiplication-Sign 10{sup 4} M {sub Sun }, with many having masses M Almost-Equal-To 10{sup 5} M {sub Sun }. Five of the XRBs are hosted by young clusters with ages {tau} Almost-Equal-To 10-100 Myr, while three are hosted by intermediate-age clusters with {tau} Almost-Equal-To 100-300 Myr. Based on the results from recent N-body simulations, which suggest that black holes are far more likely to be retained within their parent clusters than neutron stars, we suggest that our sample consists primarily of black hole binaries with different ages.« less

Integration K-Means Clustering Method and Elbow Method For Identification of The Best Customer Profile Cluster

NASA Astrophysics Data System (ADS)

Syakur, M. A.; Khotimah, B. K.; Rochman, E. M. S.; Satoto, B. D.

2018-04-01

Clustering is a data mining technique used to analyse data that has variations and the number of lots. Clustering was process of grouping data into a cluster, so they contained data that is as similar as possible and different from other cluster objects. SMEs Indonesia has a variety of customers, but SMEs do not have the mapping of these customers so they did not know which customers are loyal or otherwise. Customer mapping is a grouping of customer profiling to facilitate analysis and policy of SMEs in the production of goods, especially batik sales. Researchers will use a combination of K-Means method with elbow to improve efficient and effective k-means performance in processing large amounts of data. K-Means Clustering is a localized optimization method that is sensitive to the selection of the starting position from the midpoint of the cluster. So choosing the starting position from the midpoint of a bad cluster will result in K-Means Clustering algorithm resulting in high errors and poor cluster results. The K-means algorithm has problems in determining the best number of clusters. So Elbow looks for the best number of clusters on the K-means method. Based on the results obtained from the process in determining the best number of clusters with elbow method can produce the same number of clusters K on the amount of different data. The result of determining the best number of clusters with elbow method will be the default for characteristic process based on case study. Measurement of k-means value of k-means has resulted in the best clusters based on SSE values on 500 clusters of batik visitors. The result shows the cluster has a sharp decrease is at K = 3, so K as the cut-off point as the best cluster.

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.

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

fast_protein_cluster: parallel and optimized clustering of large-scale protein modeling data.

PubMed

Hung, Ling-Hong; Samudrala, Ram

2014-06-15

fast_protein_cluster is a fast, parallel and memory efficient package used to cluster 60 000 sets of protein models (with up to 550 000 models per set) generated by the Nutritious Rice for the World project. fast_protein_cluster is an optimized and extensible toolkit that supports Root Mean Square Deviation after optimal superposition (RMSD) and Template Modeling score (TM-score) as metrics. RMSD calculations using a laptop CPU are 60× faster than qcprot and 3× faster than current graphics processing unit (GPU) implementations. New GPU code further increases the speed of RMSD and TM-score calculations. fast_protein_cluster provides novel k-means and hierarchical clustering methods that are up to 250× and 2000× faster, respectively, than Clusco, and identify significantly more accurate models than Spicker and Clusco. fast_protein_cluster is written in C++ using OpenMP for multi-threading support. Custom streaming Single Instruction Multiple Data (SIMD) extensions and advanced vector extension intrinsics code accelerate CPU calculations, and OpenCL kernels support AMD and Nvidia GPUs. fast_protein_cluster is available under the M.I.T. license. (http://software.compbio.washington.edu/fast_protein_cluster) © The Author 2014. Published by Oxford University Press.

Strong Lens Models for Massive Galaxy Clusters in the Reionization Lensing Cluster Survey

NASA Astrophysics Data System (ADS)

Cerny, Catherine; Sharon, Keren; Coe, Dan A.; Paterno-Mahler, Rachel; Jones, Christine; Czakon, Nicole G.; Umetsu, Keiichi; Stark, Daniel; Bradley, Larry D.; Trenti, Michele; Johnson, Traci; Bradac, Marusa; Dawson, William; Rodney, Steven A.; Strolger, Louis-Gregory; RELICS Team

2017-01-01

We present strong lensing models for five galaxy clusters from the Planck SZ cluster catalog as a part of the Reionization Lensing Cluster Survey (RELICS), a program that seeks to constrain the galaxy luminosity function past z~9 by conducting a wide field survey of massive galaxy clusters with HST (GO-14096, PI: Coe). The strong gravitational lensing effects of these clusters significantly magnify background galaxies, which enhances our ability to discover the large numbers of high redshift galaxies at z~9-12 needed to create a representative sample. We use strong lensing models for these clusters to study their mass distribution and magnification, which allows us to quantify the lensing effect on the background galaxies. These models can then be utilized in the RELICS survey in order to identify high redshift galaxy candidates that may be lensed by the clusters. The intrinsic properties of these galaxy candidates can be derived by removing the lensing effect as predicted by our models, which will meet the science goals of the RELICS survey. We use HST WFC3 and ACS imaging to create lensing models for the clusters RXC J0142.9+4438, ACO-2537, ACO-2163, RXCJ2211.7-0349, and ACT-CLJ0102-49151.

Re-estimating sample size in cluster randomised trials with active recruitment within clusters.

PubMed

van Schie, S; Moerbeek, M

2014-08-30

Often only a limited number of clusters can be obtained in cluster randomised trials, although many potential participants can be recruited within each cluster. Thus, active recruitment is feasible within the clusters. To obtain an efficient sample size in a cluster randomised trial, the cluster level and individual level variance should be known before the study starts, but this is often not the case. We suggest using an internal pilot study design to address this problem of unknown variances. A pilot can be useful to re-estimate the variances and re-calculate the sample size during the trial. Using simulated data, it is shown that an initially low or high power can be adjusted using an internal pilot with the type I error rate remaining within an acceptable range. The intracluster correlation coefficient can be re-estimated with more precision, which has a positive effect on the sample size. We conclude that an internal pilot study design may be used if active recruitment is feasible within a limited number of clusters. Copyright © 2014 John Wiley & Sons, Ltd.

Information Theory and Voting Based Consensus Clustering for Combining Multiple Clusterings of Chemical Structures.

PubMed

Saeed, Faisal; Salim, Naomie; Abdo, Ammar

2013-07-01

Many consensus clustering methods have been applied in different areas such as pattern recognition, machine learning, information theory and bioinformatics. However, few methods have been used for chemical compounds clustering. In this paper, an information theory and voting based algorithm (Adaptive Cumulative Voting-based Aggregation Algorithm A-CVAA) was examined for combining multiple clusterings of chemical structures. The effectiveness of clusterings was evaluated based on the ability of the clustering method to separate active from inactive molecules in each cluster, and the results were compared with Ward's method. The chemical dataset MDL Drug Data Report (MDDR) and the Maximum Unbiased Validation (MUV) dataset were used. Experiments suggest that the adaptive cumulative voting-based consensus method can improve the effectiveness of combining multiple clusterings of chemical structures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Clustering-based classification of road traffic accidents using hierarchical clustering and artificial neural networks.

PubMed

Taamneh, Madhar; Taamneh, Salah; Alkheder, Sharaf

2017-09-01

Artificial neural networks (ANNs) have been widely used in predicting the severity of road traffic crashes. All available information about previously occurred accidents is typically used for building a single prediction model (i.e., classifier). Too little attention has been paid to the differences between these accidents, leading, in most cases, to build less accurate predictors. Hierarchical clustering is a well-known clustering method that seeks to group data by creating a hierarchy of clusters. Using hierarchical clustering and ANNs, a clustering-based classification approach for predicting the injury severity of road traffic accidents was proposed. About 6000 road accidents occurred over a six-year period from 2008 to 2013 in Abu Dhabi were used throughout this study. In order to reduce the amount of variation in data, hierarchical clustering was applied on the data set to organize it into six different forms, each with different number of clusters (i.e., clusters from 1 to 6). Two ANN models were subsequently built for each cluster of accidents in each generated form. The first model was built and validated using all accidents (training set), whereas only 66% of the accidents were used to build the second model, and the remaining 34% were used to test it (percentage split). Finally, the weighted average accuracy was computed for each type of models in each from of data. The results show that when testing the models using the training set, clustering prior to classification achieves (11%-16%) more accuracy than without using clustering, while the percentage split achieves (2%-5%) more accuracy. The results also suggest that partitioning the accidents into six clusters achieves the best accuracy if both types of models are taken into account.

Statistical Significance for Hierarchical Clustering

PubMed Central

Kimes, Patrick K.; Liu, Yufeng; Hayes, D. Neil; Marron, J. S.

2017-01-01

Summary Cluster analysis has proved to be an invaluable tool for the exploratory and unsupervised analysis of high dimensional datasets. Among methods for clustering, hierarchical approaches have enjoyed substantial popularity in genomics and other fields for their ability to simultaneously uncover multiple layers of clustering structure. A critical and challenging question in cluster analysis is whether the identified clusters represent important underlying structure or are artifacts of natural sampling variation. Few approaches have been proposed for addressing this problem in the context of hierarchical clustering, for which the problem is further complicated by the natural tree structure of the partition, and the multiplicity of tests required to parse the layers of nested clusters. In this paper, we propose a Monte Carlo based approach for testing statistical significance in hierarchical clustering which addresses these issues. The approach is implemented as a sequential testing procedure guaranteeing control of the family-wise error rate. Theoretical justification is provided for our approach, and its power to detect true clustering structure is illustrated through several simulation studies and applications to two cancer gene expression datasets. PMID:28099990

Star clusters in evolving galaxies

NASA Astrophysics Data System (ADS)

Renaud, Florent

2018-04-01

Their ubiquity and extreme densities make star clusters probes of prime importance of galaxy evolution. Old globular clusters keep imprints of the physical conditions of their assembly in the early Universe, and younger stellar objects, observationally resolved, tell us about the mechanisms at stake in their formation. Yet, we still do not understand the diversity involved: why is star cluster formation limited to 105M⊙ objects in the Milky Way, while some dwarf galaxies like NGC 1705 are able to produce clusters 10 times more massive? Why do dwarfs generally host a higher specific frequency of clusters than larger galaxies? How to connect the present-day, often resolved, stellar systems to the formation of globular clusters at high redshift? And how do these links depend on the galactic and cosmological environments of these clusters? In this review, I present recent advances on star cluster formation and evolution, in galactic and cosmological context. The emphasis is put on the theory, formation scenarios and the effects of the environment on the evolution of the global properties of clusters. A few open questions are identified.

Coma cluster of galaxies

NASA Technical Reports Server (NTRS)

1999-01-01

Atlas Image mosaic, covering 34' x 34' on the sky, of the Coma cluster, aka Abell 1656. This is a particularly rich cluster of individual galaxies (over 1000 members), most prominently the two giant ellipticals, NGC 4874 (right) and NGC 4889 (left). The remaining members are mostly smaller ellipticals, but spiral galaxies are also evident in the 2MASS image. The cluster is seen toward the constellation Coma Berenices, but is actually at a distance of about 100 Mpc (330 million light years, or a redshift of 0.023) from us. At this distance, the cluster is in what is known as the 'Hubble flow,' or the overall expansion of the Universe. As such, astronomers can measure the Hubble Constant, or the universal expansion rate, based on the distance to this cluster. Large, rich clusters, such as Coma, allow astronomers to measure the 'missing mass,' i.e., the matter in the cluster that we cannot see, since it gravitationally influences the motions of the member galaxies within the cluster. The near-infrared maps the overall luminous mass content of the member galaxies, since the light at these wavelengths is dominated by the more numerous older stellar populations. Galaxies, as seen by 2MASS, look fairly smooth and homogeneous, as can be seen from the Hubble 'tuning fork' diagram of near-infrared galaxy morphology. Image mosaic by S. Van Dyk (IPAC).

Estimating the concrete compressive strength using hard clustering and fuzzy clustering based regression techniques.

PubMed

Nagwani, Naresh Kumar; Deo, Shirish V

2014-01-01

Understanding of the compressive strength of concrete is important for activities like construction arrangement, prestressing operations, and proportioning new mixtures and for the quality assurance. Regression techniques are most widely used for prediction tasks where relationship between the independent variables and dependent (prediction) variable is identified. The accuracy of the regression techniques for prediction can be improved if clustering can be used along with regression. Clustering along with regression will ensure the more accurate curve fitting between the dependent and independent variables. In this work cluster regression technique is applied for estimating the compressive strength of the concrete and a novel state of the art is proposed for predicting the concrete compressive strength. The objective of this work is to demonstrate that clustering along with regression ensures less prediction errors for estimating the concrete compressive strength. The proposed technique consists of two major stages: in the first stage, clustering is used to group the similar characteristics concrete data and then in the second stage regression techniques are applied over these clusters (groups) to predict the compressive strength from individual clusters. It is found from experiments that clustering along with regression techniques gives minimum errors for predicting compressive strength of concrete; also fuzzy clustering algorithm C-means performs better than K-means algorithm.

Estimating the Concrete Compressive Strength Using Hard Clustering and Fuzzy Clustering Based Regression Techniques

PubMed Central

Nagwani, Naresh Kumar; Deo, Shirish V.

2014-01-01

Understanding of the compressive strength of concrete is important for activities like construction arrangement, prestressing operations, and proportioning new mixtures and for the quality assurance. Regression techniques are most widely used for prediction tasks where relationship between the independent variables and dependent (prediction) variable is identified. The accuracy of the regression techniques for prediction can be improved if clustering can be used along with regression. Clustering along with regression will ensure the more accurate curve fitting between the dependent and independent variables. In this work cluster regression technique is applied for estimating the compressive strength of the concrete and a novel state of the art is proposed for predicting the concrete compressive strength. The objective of this work is to demonstrate that clustering along with regression ensures less prediction errors for estimating the concrete compressive strength. The proposed technique consists of two major stages: in the first stage, clustering is used to group the similar characteristics concrete data and then in the second stage regression techniques are applied over these clusters (groups) to predict the compressive strength from individual clusters. It is found from experiments that clustering along with regression techniques gives minimum errors for predicting compressive strength of concrete; also fuzzy clustering algorithm C-means performs better than K-means algorithm. PMID:25374939

Studies of the Virgo cluster. VI - Morphological and kinematical structure of the Virgo cluster

NASA Technical Reports Server (NTRS)

Binggeli, Bruno; Tammann, G. A.; Sandage, Allan

1987-01-01

The structure of the Virgo cluster is analyzed on the basis of the positions, Hubble types, and radial velocities of 1277 Virgo cluster galaxies. The surface distribution of galaxies is considered according to type, and is discussed using maps, isopleths, strip counts, and radial-density distributions. It is found that the Virgo cluster shows pronounced double structure. The main concentration has a large velocity dispersion and is made up predominantly of early-type galaxies, while the secondary concentration has a much smaller velocity dispersion and contains late types. There is a strong spatial segregation of the Hubble types, the early-type galaxies being more concentrated toward the cluster center. There is significant substructure in the cluster core. The irregularity of the Virgo cluster in both configuration and velocity space shows that the core and the envelope are still forming, and hence that the cluster is young.

Star clusters in the Magellanic Clouds - I. Parametrization and classification of 1072 clusters in the LMC

NASA Astrophysics Data System (ADS)

Nayak, P. K.; Subramaniam, A.; Choudhury, S.; Indu, G.; Sagar, Ram

2016-12-01

We have introduced a semi-automated quantitative method to estimate the age and reddening of 1072 star clusters in the Large Magellanic Cloud (LMC) using the Optical Gravitational Lensing Experiment III survey data. This study brings out 308 newly parametrized clusters. In a first of its kind, the LMC clusters are classified into groups based on richness/mass as very poor, poor, moderate and rich clusters, similar to the classification scheme of open clusters in the Galaxy. A major cluster formation episode is found to happen at 125 ± 25 Myr in the inner LMC. The bar region of the LMC appears prominently in the age range 60-250 Myr and is found to have a relatively higher concentration of poor and moderate clusters. The eastern and the western ends of the bar are found to form clusters initially, which later propagates to the central part. We demonstrate that there is a significant difference in the distribution of clusters as a function of mass, using a movie based on the propagation (in space and time) of cluster formation in various groups. The importance of including the low-mass clusters in the cluster formation history is demonstrated. The catalogue with parameters, classification, and cleaned and isochrone fitted colour-magnitude diagrams of 1072 clusters, which are available as online material, can be further used to understand the hierarchical formation of clusters in selected regions of the LMC.

Cosmological Simulations of Galaxy Clusters

NASA Astrophysics Data System (ADS)

Borgani, Stefano; Kravtsov, Andrey

2011-02-01

We review recent progress in the description of the formation and evolution of galaxy clusters in a cosmological context by using state-of-art numerical simulations. We focus our presentation on the comparison between simulated and observed X-ray properties, while we will also discuss numerical predictions on properties of the galaxy population in clusters, as observed in the optical band. Many of the salient observed properties of clusters, such as scaling relations between X-ray observables and total mass, radial profiles of entropy and density of the intracluster gas, and radial distribution of galaxies are reproduced quite well. In particular, the outer regions of cluster at radii beyond about 10 per cent of the virial radius are quite regular and exhibit scaling with mass remarkably close to that expected in the simplest case in which only the action of gravity determines the evolution of the intra-cluster gas. However, simulations generally fail at reproducing the observed "cool core" structure of clusters: simulated clusters generally exhibit a significant excess of gas cooling in their central regions, which causes both an overestimate of the star formation in the cluster centers and incorrect temperature and entropy profiles. The total baryon fraction in clusters is below the mean universal value, by an amount which depends on the cluster-centric distance and the physics included in the simulations, with interesting tensions between observed stellar and gas fractions in clusters and predictions of simulations. Besides their important implications for the cosmological application of clusters, these puzzles also point towards the important role played by additional physical processes, beyond those already included in the simulations. We review the role played by these processes, along with the difficulty for their implementation, and discuss the outlook for the future progress in numerical modeling of clusters.

The impact of baryons on massive galaxy clusters: halo structure and cluster mass estimates

NASA Astrophysics Data System (ADS)

Henson, Monique A.; Barnes, David J.; Kay, Scott T.; McCarthy, Ian G.; Schaye, Joop

2017-03-01

We use the BAHAMAS (BAryons and HAloes of MAssive Systems) and MACSIS (MAssive ClusterS and Intercluster Structures) hydrodynamic simulations to quantify the impact of baryons on the mass distribution and dynamics of massive galaxy clusters, as well as the bias in X-ray and weak lensing mass estimates. These simulations use the subgrid physics models calibrated in the BAHAMAS project, which include feedback from both supernovae and active galactic nuclei. They form a cluster population covering almost two orders of magnitude in mass, with more than 3500 clusters with masses greater than 1014 M⊙ at z = 0. We start by characterizing the clusters in terms of their spin, shape and density profile, before considering the bias in both weak lensing and hydrostatic mass estimates. Whilst including baryonic effects leads to more spherical, centrally concentrated clusters, the median weak lensing mass bias is unaffected by the presence of baryons. In both the dark matter only and hydrodynamic simulations, the weak lensing measurements underestimate cluster masses by ≈10 per cent for clusters with M200 ≤ 1015 M⊙ and this bias tends to zero at higher masses. We also consider the hydrostatic bias when using both the true density and temperature profiles, and those derived from X-ray spectroscopy. When using spectroscopic temperatures and densities, the hydrostatic bias decreases as a function of mass, leading to a bias of ≈40 per cent for clusters with M500 ≥ 1015 M⊙. This is due to the presence of cooler gas in the cluster outskirts. Using mass weighted temperatures and the true density profile reduces this bias to 5-15 per cent.

Searching remote homology with spectral clustering with symmetry in neighborhood cluster kernels.

PubMed

Maulik, Ujjwal; Sarkar, Anasua

2013-01-01

Remote homology detection among proteins utilizing only the unlabelled sequences is a central problem in comparative genomics. The existing cluster kernel methods based on neighborhoods and profiles and the Markov clustering algorithms are currently the most popular methods for protein family recognition. The deviation from random walks with inflation or dependency on hard threshold in similarity measure in those methods requires an enhancement for homology detection among multi-domain proteins. We propose to combine spectral clustering with neighborhood kernels in Markov similarity for enhancing sensitivity in detecting homology independent of "recent" paralogs. The spectral clustering approach with new combined local alignment kernels more effectively exploits the unsupervised protein sequences globally reducing inter-cluster walks. When combined with the corrections based on modified symmetry based proximity norm deemphasizing outliers, the technique proposed in this article outperforms other state-of-the-art cluster kernels among all twelve implemented kernels. The comparison with the state-of-the-art string and mismatch kernels also show the superior performance scores provided by the proposed kernels. Similar performance improvement also is found over an existing large dataset. Therefore the proposed spectral clustering framework over combined local alignment kernels with modified symmetry based correction achieves superior performance for unsupervised remote homolog detection even in multi-domain and promiscuous domain proteins from Genolevures database families with better biological relevance. Source code available upon request. sarkar@labri.fr.

BioCluster: tool for identification and clustering of Enterobacteriaceae based on biochemical data.

PubMed

Abdullah, Ahmed; Sabbir Alam, S M; Sultana, Munawar; Hossain, M Anwar

2015-06-01

Presumptive identification of different Enterobacteriaceae species is routinely achieved based on biochemical properties. Traditional practice includes manual comparison of each biochemical property of the unknown sample with known reference samples and inference of its identity based on the maximum similarity pattern with the known samples. This process is labor-intensive, time-consuming, error-prone, and subjective. Therefore, automation of sorting and similarity in calculation would be advantageous. Here we present a MATLAB-based graphical user interface (GUI) tool named BioCluster. This tool was designed for automated clustering and identification of Enterobacteriaceae based on biochemical test results. In this tool, we used two types of algorithms, i.e., traditional hierarchical clustering (HC) and the Improved Hierarchical Clustering (IHC), a modified algorithm that was developed specifically for the clustering and identification of Enterobacteriaceae species. IHC takes into account the variability in result of 1-47 biochemical tests within this Enterobacteriaceae family. This tool also provides different options to optimize the clustering in a user-friendly way. Using computer-generated synthetic data and some real data, we have demonstrated that BioCluster has high accuracy in clustering and identifying enterobacterial species based on biochemical test data. This tool can be freely downloaded at http://microbialgen.du.ac.bd/biocluster/. Copyright © 2015 The Authors. Production and hosting by Elsevier Ltd.. All rights reserved.

Quantum annealing for combinatorial clustering

NASA Astrophysics Data System (ADS)

Kumar, Vaibhaw; Bass, Gideon; Tomlin, Casey; Dulny, Joseph

2018-02-01

Clustering is a powerful machine learning technique that groups "similar" data points based on their characteristics. Many clustering algorithms work by approximating the minimization of an objective function, namely the sum of within-the-cluster distances between points. The straightforward approach involves examining all the possible assignments of points to each of the clusters. This approach guarantees the solution will be a global minimum; however, the number of possible assignments scales quickly with the number of data points and becomes computationally intractable even for very small datasets. In order to circumvent this issue, cost function minima are found using popular local search-based heuristic approaches such as k-means and hierarchical clustering. Due to their greedy nature, such techniques do not guarantee that a global minimum will be found and can lead to sub-optimal clustering assignments. Other classes of global search-based techniques, such as simulated annealing, tabu search, and genetic algorithms, may offer better quality results but can be too time-consuming to implement. In this work, we describe how quantum annealing can be used to carry out clustering. We map the clustering objective to a quadratic binary optimization problem and discuss two clustering algorithms which are then implemented on commercially available quantum annealing hardware, as well as on a purely classical solver "qbsolv." The first algorithm assigns N data points to K clusters, and the second one can be used to perform binary clustering in a hierarchical manner. We present our results in the form of benchmarks against well-known k-means clustering and discuss the advantages and disadvantages of the proposed techniques.

Dynamics of cD Clusters of Galaxies. 4; Conclusion of a Survey of 25 Abell Clusters

NASA Technical Reports Server (NTRS)

Oegerle, William R.; Hill, John M.; Fisher, Richard R. (Technical Monitor)

2001-01-01

We present the final results of a spectroscopic study of a sample of cD galaxy clusters. The goal of this program has been to study the dynamics of the clusters, with emphasis on determining the nature and frequency of cD galaxies with peculiar velocities. Redshifts measured with the MX Spectrometer have been combined with those obtained from the literature to obtain typically 50 - 150 observed velocities in each of 25 galaxy clusters containing a central cD galaxy. We present a dynamical analysis of the final 11 clusters to be observed in this sample. All 25 clusters are analyzed in a uniform manner to test for the presence of substructure, and to determine peculiar velocities and their statistical significance for the central cD galaxy. These peculiar velocities were used to determine whether or not the central cD galaxy is at rest in the cluster potential well. We find that 30 - 50% of the clusters in our sample possess significant subclustering (depending on the cluster radius used in the analysis), which is in agreement with other studies of non-cD clusters. Hence, the dynamical state of cD clusters is not different than other present-day clusters. After careful study, four of the clusters appear to have a cD galaxy with a significant peculiar velocity. Dressler-Shectman tests indicate that three of these four clusters have statistically significant substructure within 1.5/h(sub 75) Mpc of the cluster center. The dispersion 75 of the cD peculiar velocities is 164 +41/-34 km/s around the mean cluster velocity. This represents a significant detection of peculiar cD velocities, but at a level which is far below the mean velocity dispersion for this sample of clusters. The picture that emerges is one in which cD galaxies are nearly at rest with respect to the cluster potential well, but have small residual velocities due to subcluster mergers.

Hierarchical Aligned Cluster Analysis for Temporal Clustering of Human Motion.

PubMed

Zhou, Feng; De la Torre, Fernando; Hodgins, Jessica K

2013-03-01

Temporal segmentation of human motion into plausible motion primitives is central to understanding and building computational models of human motion. Several issues contribute to the challenge of discovering motion primitives: the exponential nature of all possible movement combinations, the variability in the temporal scale of human actions, and the complexity of representing articulated motion. We pose the problem of learning motion primitives as one of temporal clustering, and derive an unsupervised hierarchical bottom-up framework called hierarchical aligned cluster analysis (HACA). HACA finds a partition of a given multidimensional time series into m disjoint segments such that each segment belongs to one of k clusters. HACA combines kernel k-means with the generalized dynamic time alignment kernel to cluster time series data. Moreover, it provides a natural framework to find a low-dimensional embedding for time series. HACA is efficiently optimized with a coordinate descent strategy and dynamic programming. Experimental results on motion capture and video data demonstrate the effectiveness of HACA for segmenting complex motions and as a visualization tool. We also compare the performance of HACA to state-of-the-art algorithms for temporal clustering on data of a honey bee dance. The HACA code is available online.

Alternative Parameterizations for Cluster Editing

NASA Astrophysics Data System (ADS)

Komusiewicz, Christian; Uhlmann, Johannes

Given an undirected graph G and a nonnegative integer k, the NP-hard Cluster Editing problem asks whether G can be transformed into a disjoint union of cliques by applying at most k edge modifications. In the field of parameterized algorithmics, Cluster Editing has almost exclusively been studied parameterized by the solution size k. Contrastingly, in many real-world instances it can be observed that the parameter k is not really small. This observation motivates our investigation of parameterizations of Cluster Editing different from the solution size k. Our results are as follows. Cluster Editing is fixed-parameter tractable with respect to the parameter "size of a minimum cluster vertex deletion set of G", a typically much smaller parameter than k. Cluster Editing remains NP-hard on graphs with maximum degree six. A restricted but practically relevant version of Cluster Editing is fixed-parameter tractable with respect to the combined parameter "number of clusters in the target graph" and "maximum number of modified edges incident to any vertex in G". Many of our results also transfer to the NP-hard Cluster Deletion problem, where only edge deletions are allowed.

A new method to prepare colloids of size-controlled clusters from a matrix assembly cluster source

NASA Astrophysics Data System (ADS)

Cai, Rongsheng; Jian, Nan; Murphy, Shane; Bauer, Karl; Palmer, Richard E.

2017-05-01

A new method for the production of colloidal suspensions of physically deposited clusters is demonstrated. A cluster source has been used to deposit size-controlled clusters onto water-soluble polymer films, which are then dissolved to produce colloidal suspensions of clusters encapsulated with polymer molecules. This process has been demonstrated using different cluster materials (Au and Ag) and polymers (polyvinylpyrrolidone, polyvinyl alcohol, and polyethylene glycol). Scanning transmission electron microscopy of the clusters before and after colloidal dispersion confirms that the polymers act as stabilizing agents. We propose that this method is suitable for the production of biocompatible colloids of ultraprecise clusters.

Intrinsic alignment of redMaPPer clusters: cluster shape-matter density correlation

NASA Astrophysics Data System (ADS)

van Uitert, Edo; Joachimi, Benjamin

2017-07-01

We measure the alignment of the shapes of galaxy clusters, as traced by their satellite distributions, with the matter density field using the public redMaPPer catalogue based on Sloan Digital Sky Survey-Data Release 8 (SDSS-DR8), which contains 26 111 clusters up to z ˜ 0.6. The clusters are split into nine redshift and richness samples; in each of them, we detect a positive alignment, showing that clusters point towards density peaks. We interpret the measurements within the tidal alignment paradigm, allowing for a richness and redshift dependence. The intrinsic alignment (IA) amplitude at the pivot redshift z = 0.3 and pivot richness λ = 30 is A_IA^gen=12.6_{-1.2}^{+1.5}. We obtain tentative evidence that the signal increases towards higher richness and lower redshift. Our measurements agree well with results of maxBCG clusters and with dark-matter-only simulations. Comparing our results to the IA measurements of luminous red galaxies, we find that the IA amplitude of galaxy clusters forms a smooth extension towards higher mass. This suggests that these systems share a common alignment mechanism, which can be exploited to improve our physical understanding of IA.

The smart cluster method. Adaptive earthquake cluster identification and analysis in strong seismic regions

NASA Astrophysics Data System (ADS)

Schaefer, Andreas M.; Daniell, James E.; Wenzel, Friedemann

2017-07-01

Earthquake clustering is an essential part of almost any statistical analysis of spatial and temporal properties of seismic activity. 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 for probabilistic seismic hazard assessment. This study introduces the Smart Cluster Method (SCM), a new methodology to identify earthquake clusters, which uses an adaptive point process for spatio-temporal cluster identification. It utilises the magnitude-dependent spatio-temporal earthquake density to adjust the search properties, subsequently analyses the identified clusters to determine directional variation 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 sequence, a reclassification procedure is applied to disassemble subsequent ruptures using near-field searches, nearest neighbour classification and temporal splitting. The method is capable of identifying and classifying earthquake clusters in space and time. It has been tested and validated using earthquake data from California and New Zealand. A total of more than 1500 clusters have been found in both regions since 1980 with M m i n = 2.0. Utilising the knowledge of cluster classification, the method has been adjusted to provide an earthquake declustering algorithm, which has been compared to existing methods. Its performance is comparable to established methodologies. The analysis of earthquake clustering statistics lead to various new and updated correlation functions, e.g. for ratios between mainshock and strongest aftershock and general aftershock activity metrics.

High–frequency cluster radio galaxies: Luminosity functions and implications for SZE–selected cluster samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Nikhel; Saro, A.; Mohr, J. J.

We study the overdensity of point sources in the direction of X-ray-selected galaxy clusters from the meta-catalogue of X-ray-detected clusters of galaxies (MCXC; < z > = 0.14) at South Pole Telescope (SPT) and Sydney University Molonglo Sky Survey (SUMSS) frequencies. Flux densities at 95, 150 and 220 GHz are extracted from the 2500 deg 2 SPT-SZ survey maps at the locations of SUMSS sources, producing a multifrequency catalogue of radio galaxies. In the direction of massive galaxy clusters, the radio galaxy flux densities at 95 and 150 GHz are biased low by the cluster Sunyaev–Zel’dovich Effect (SZE) signal, whichmore » is negative at these frequencies. We employ a cluster SZE model to remove the expected flux bias and then study these corrected source catalogues. We find that the high-frequency radio galaxies are centrally concentrated within the clusters and that their luminosity functions (LFs) exhibit amplitudes that are characteristically an order of magnitude lower than the cluster LF at 843 MHz. We use the 150 GHz LF to estimate the impact of cluster radio galaxies on an SPT-SZ like survey. The radio galaxy flux typically produces a small bias on the SZE signal and has negligible impact on the observed scatter in the SZE mass–observable relation. If we assume there is no redshift evolution in the radio galaxy LF then 1.8 ± 0.7 per cent of the clusters with detection significance ξ ≥ 4.5 would be lost from the sample. As a result, allowing for redshift evolution of the form (1 + z) 2.5 increases the incompleteness to 5.6 ± 1.0 per cent. Improved constraints on the evolution of the cluster radio galaxy LF require a larger cluster sample extending to higher redshift.« less

High–frequency cluster radio galaxies: Luminosity functions and implications for SZE–selected cluster samples

DOE PAGES

Gupta, Nikhel; Saro, A.; Mohr, J. J.; ...

2017-01-15

We study the overdensity of point sources in the direction of X-ray-selected galaxy clusters from the meta-catalogue of X-ray-detected clusters of galaxies (MCXC; < z > = 0.14) at South Pole Telescope (SPT) and Sydney University Molonglo Sky Survey (SUMSS) frequencies. Flux densities at 95, 150 and 220 GHz are extracted from the 2500 deg 2 SPT-SZ survey maps at the locations of SUMSS sources, producing a multifrequency catalogue of radio galaxies. In the direction of massive galaxy clusters, the radio galaxy flux densities at 95 and 150 GHz are biased low by the cluster Sunyaev–Zel’dovich Effect (SZE) signal, whichmore » is negative at these frequencies. We employ a cluster SZE model to remove the expected flux bias and then study these corrected source catalogues. We find that the high-frequency radio galaxies are centrally concentrated within the clusters and that their luminosity functions (LFs) exhibit amplitudes that are characteristically an order of magnitude lower than the cluster LF at 843 MHz. We use the 150 GHz LF to estimate the impact of cluster radio galaxies on an SPT-SZ like survey. The radio galaxy flux typically produces a small bias on the SZE signal and has negligible impact on the observed scatter in the SZE mass–observable relation. If we assume there is no redshift evolution in the radio galaxy LF then 1.8 ± 0.7 per cent of the clusters with detection significance ξ ≥ 4.5 would be lost from the sample. As a result, allowing for redshift evolution of the form (1 + z) 2.5 increases the incompleteness to 5.6 ± 1.0 per cent. Improved constraints on the evolution of the cluster radio galaxy LF require a larger cluster sample extending to higher redshift.« less

A proximity-based graph clustering method for the identification and application of transcription factor clusters.

PubMed

Spadafore, Maxwell; Najarian, Kayvan; Boyle, Alan P

2017-11-29

Transcription factors (TFs) form a complex regulatory network within the cell that is crucial to cell functioning and human health. While methods to establish where a TF binds to DNA are well established, these methods provide no information describing how TFs interact with one another when they do bind. TFs tend to bind the genome in clusters, and current methods to identify these clusters are either limited in scope, unable to detect relationships beyond motif similarity, or not applied to TF-TF interactions. Here, we present a proximity-based graph clustering approach to identify TF clusters using either ChIP-seq or motif search data. We use TF co-occurrence to construct a filtered, normalized adjacency matrix and use the Markov Clustering Algorithm to partition the graph while maintaining TF-cluster and cluster-cluster interactions. We then apply our graph structure beyond clustering, using it to increase the accuracy of motif-based TFBS searching for an example TF. We show that our method produces small, manageable clusters that encapsulate many known, experimentally validated transcription factor interactions and that our method is capable of capturing interactions that motif similarity methods might miss. Our graph structure is able to significantly increase the accuracy of motif TFBS searching, demonstrating that the TF-TF connections within the graph correlate with biological TF-TF interactions. The interactions identified by our method correspond to biological reality and allow for fast exploration of TF clustering and regulatory dynamics.

Enhanced water purification: a single atom makes a difference.

PubMed

Stewart, Tom A; Trudell, Daniel E; Alam, Todd M; Ohlin, C André; Lawler, Christian; Casey, William H; Jett, Stephen; Nyman, May

2009-07-15

The aluminum Keggin polycation (Al13) has been identified as an effective specie for neutralization and coagulation of anionic contaminants in water. In this study, we compare efficacy of the aluminum Keggin-ion to the analogues containing a single Ga-atom or single Ge-atom (GaAl12 and GeAl12, respectively) substituted into the center of the polycation in water-treatment studies. We investigated removal of bacteriophage (model viruses), Cryptosporidium, dissolved organic carbon (DOC), and turbidity. In every study, the order of contaminant removal efficacy trends GaAl12 > Al13 > GeAl12. By ESI MS (electrospray ionization mass spectrometry), we noted the GaAl12 deprotonates least of the three aluminum polycations, and thus probably carries the highest charge, and also optimal contaminant-neutralization ability. The ESI MS studies of the aluminum polycation solutions, as well as solid-state characterization of their resulting precipitates both reveal some conversion of Al13 to larger polycations, Al30 for instance. The GaAl12 does not show any evidence for this alteration that is responsible for poor shelf life of commercial prehydrolyzed aluminum coagulants such as polyaluminum chloride. Based on these studies, we conclude that substitution of a single Ga-atom in the center of the aluminum Keggin polycation produces an optimal water-treatment product due to enhanced shelf life and efficacy in neutralization of anionic contaminants.

Cluster-assembled metallic glasses

PubMed Central

2013-01-01

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. PMID:23899019

Al7CX (X=Li-Cs) clusters: Stability and the prospect for cluster materials

NASA Astrophysics Data System (ADS)

Ashman, C.; Khanna, S. N.; Pederson, M. R.; Kortus, J.

2000-12-01

Al7C clusters, recently found to have a high-electron affinity and exceptional stability, are shown to form ionic molecules when combined with alkali-metal atoms. Our studies, based on an ab initio gradient-corrected density-functional scheme, show that Al7CX (X=Li-Cs) clusters have a very low-electron affinity and a high-ionization potential. When combined, the two- and four-atom composite clusters of Al7CLi units leave the Al7C clusters almost intact. Preliminary studies indicate that Al7CLi may be suitable to form cluster-based materials.

Application of clustering methods: Regularized Markov clustering (R-MCL) for analyzing dengue virus similarity

NASA Astrophysics Data System (ADS)

Lestari, D.; Raharjo, D.; Bustamam, A.; Abdillah, B.; Widhianto, W.

2017-07-01

Dengue virus consists of 10 different constituent proteins and are classified into 4 major serotypes (DEN 1 - DEN 4). This study was designed to perform clustering against 30 protein sequences of dengue virus taken from Virus Pathogen Database and Analysis Resource (VIPR) using Regularized Markov Clustering (R-MCL) algorithm and then we analyze the result. By using Python program 3.4, R-MCL algorithm produces 8 clusters with more than one centroid in several clusters. The number of centroid shows the density level of interaction. Protein interactions that are connected in a tissue, form a complex protein that serves as a specific biological process unit. The analysis of result shows the R-MCL clustering produces clusters of dengue virus family based on the similarity role of their constituent protein, regardless of serotypes.

Deriving physical parameters of unresolved star clusters. V. M 31 PHAT star clusters

NASA Astrophysics Data System (ADS)

de Meulenaer, P.; Stonkutė, R.; Vansevičius, V.

2017-06-01

Context. This study is the fifth of a series that investigates the degeneracy and stochasticity problems present in the determination of physical parameters such as age, mass, extinction, and metallicity of partially resolved or unresolved star cluster populations in external galaxies when using HST broad-band photometry. Aims: In this work we aim to derive parameters of star clusters using models with fixed and free metallicity based on the HST WFC3+ACS photometric system. The method is applied to derive parameters of a subsample of 1363 star clusters in the Andromeda galaxy observed with the HST. Methods: Following Paper III, we derive the star cluster parameters using a large grid of stochastic models that are compared to the six observed integrated broad-band WFC3+ACS magnitudes of star clusters. Results: We show that the age, mass, and extinction of the M 31 star clusters, derived assuming fixed solar metallicity, are in agreement with previous studies. We also demonstrate the ability of the WFC3+ACS photometric system to derive metallicity of star clusters older than 1 Gyr. We show that the metallicity derived using broad-band photometry of 36 massive M 31 star clusters is in good agreement with the metallicity derived using spectroscopy. Table 1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/602/A112

Searching Remote Homology with Spectral Clustering with Symmetry in Neighborhood Cluster Kernels

PubMed Central

Maulik, Ujjwal; Sarkar, Anasua

2013-01-01

Remote homology detection among proteins utilizing only the unlabelled sequences is a central problem in comparative genomics. The existing cluster kernel methods based on neighborhoods and profiles and the Markov clustering algorithms are currently the most popular methods for protein family recognition. The deviation from random walks with inflation or dependency on hard threshold in similarity measure in those methods requires an enhancement for homology detection among multi-domain proteins. We propose to combine spectral clustering with neighborhood kernels in Markov similarity for enhancing sensitivity in detecting homology independent of “recent” paralogs. The spectral clustering approach with new combined local alignment kernels more effectively exploits the unsupervised protein sequences globally reducing inter-cluster walks. When combined with the corrections based on modified symmetry based proximity norm deemphasizing outliers, the technique proposed in this article outperforms other state-of-the-art cluster kernels among all twelve implemented kernels. The comparison with the state-of-the-art string and mismatch kernels also show the superior performance scores provided by the proposed kernels. Similar performance improvement also is found over an existing large dataset. Therefore the proposed spectral clustering framework over combined local alignment kernels with modified symmetry based correction achieves superior performance for unsupervised remote homolog detection even in multi-domain and promiscuous domain proteins from Genolevures database families with better biological relevance. Source code available upon request. Contact: sarkar@labri.fr. PMID:23457439

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.

Atomic cluster collisions

NASA Astrophysics Data System (ADS)

Korol, Andrey V.; Solov'yov, Andrey

2013-01-01

Atomic cluster collisions are a field of rapidly emerging research interest by both experimentalists and theorists. The international symposium on atomic cluster collisions (ISSAC) is the premier forum to present cutting-edge research in this field. It was established in 2003 and the most recent conference was held in Berlin, Germany in July of 2011. This Topical Issue presents original research results from some of the participants, who attended this conference. This issues specifically focuses on two research areas, namely Clusters and Fullerenes in External Fields and Nanoscale Insights in Radiation Biodamage.

Simulating star clusters with the AMUSE software framework. I. Dependence of cluster lifetimes on model assumptions and cluster dissolution modes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whitehead, Alfred J.; McMillan, Stephen L. W.; Vesperini, Enrico

2013-12-01

We perform a series of simulations of evolving star clusters using the Astrophysical Multipurpose Software Environment (AMUSE), a new community-based multi-physics simulation package, and compare our results to existing work. These simulations model a star cluster beginning with a King model distribution and a selection of power-law initial mass functions and contain a tidal cutoff. They are evolved using collisional stellar dynamics and include mass loss due to stellar evolution. After studying and understanding that the differences between AMUSE results and results from previous studies are understood, we explored the variation in cluster lifetimes due to the random realization noisemore » introduced by transforming a King model to specific initial conditions. This random realization noise can affect the lifetime of a simulated star cluster by up to 30%. Two modes of star cluster dissolution were identified: a mass evolution curve that contains a runaway cluster dissolution with a sudden loss of mass, and a dissolution mode that does not contain this feature. We refer to these dissolution modes as 'dynamical' and 'relaxation' dominated, respectively. For Salpeter-like initial mass functions, we determined the boundary between these two modes in terms of the dynamical and relaxation timescales.« less

Radio active galactic nuclei in galaxy clusters: Feedback, merger signatures, and cluster tracers

NASA Astrophysics Data System (ADS)

Paterno-Mahler, Rachel Beth

Galaxy clusters, the largest gravitationally-bound structures in the universe, are composed of 50-1000s of galaxies, hot X-ray emitting gas, and dark matter. They grow in size over time through cluster and group mergers. The merger history of a cluster can be imprinted on the hot gas, known as the intracluster medium (ICM). Merger signatures include shocks, cold fronts, and sloshing of the ICM, which can form spiral structures. Some clusters host double-lobed radio sources driven by active galactic nuclei (AGN). First, I will present a study of the galaxy cluster Abell 2029, which is very relaxed on large scales and has one of the largest continuous sloshing spirals yet observed in the X-ray, extending outward approximately 400 kpc. The sloshing gas interacts with the southern lobe of the radio galaxy, causing it to bend. Energy injection from the AGN is insufficient to offset cooling. The sloshing spiral may be an important additional mechanism in preventing large amounts of gas from cooling to very low temperatures. Next, I will present a study of Abell 98, a triple system currently undergoing a merger. I will discuss the merger history, and show that it is causing a shock. The central subcluster hosts a double-lobed AGN, which is evacuating a cavity in the ICM. Understanding the physical processes that affect the ICM is important for determining the mass of clusters, which in turn affects our calculations of cosmological parameters. To further constrain these parameters, as well as models of galaxy evolution, it is important to use a large sample of galaxy clusters over a range of masses and redshifts. Bent, double-lobed radio sources can potentially act as tracers of galaxy clusters over wide ranges of these parameters. I examine how efficient bent radio sources are at tracing high-redshift (z>0.7) clusters. Out of 646 sources in our high-redshift Clusters Occupied by Bent Radio AGN (COBRA) sample, 282 are candidate new, distant clusters of galaxies based on

Glutathione-complexed [2Fe-2S] clusters function in Fe-S cluster storage and trafficking.

PubMed

Fidai, Insiya; Wachnowsky, Christine; Cowan, J A

2016-10-01

Glutathione-coordinated [2Fe-2S] complex is a non-protein-bound [2Fe-2S] cluster that is capable of reconstituting the human iron-sulfur cluster scaffold protein IscU. This complex demonstrates physiologically relevant solution chemistry and is a viable substrate for iron-sulfur cluster transport by Atm1p exporter protein. Herein, we report on some of the possible functional and physiological roles for this novel [2Fe-2S](GS4) complex in iron-sulfur cluster biosynthesis and quantitatively characterize its role in the broader network of Fe-S cluster transfer reactions. UV-vis and circular dichroism spectroscopy have been used in kinetic studies to determine second-order rate constants for [2Fe-2S] cluster transfer from [2Fe-2S](GS4) complex to acceptor proteins, such as human IscU, Schizosaccharomyces pombe Isa1, human and yeast glutaredoxins (human Grx2 and Saccharomyces cerevisiae Grx3), and human ferredoxins. Second-order rate constants for cluster extraction from these holo proteins were also determined by varying the concentration of glutathione, and a likely common mechanism for cluster uptake was determined by kinetic analysis. The results indicate that the [2Fe-2S](GS4) complex is stable under physiological conditions, and demonstrates reversible cluster exchange with a wide range of Fe-S cluster proteins, thereby supporting a possible physiological role for such centers.

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.…

Cluster compression algorithm: A joint clustering/data compression concept

NASA Technical Reports Server (NTRS)

Hilbert, E. E.

1977-01-01

The Cluster Compression Algorithm (CCA), which was developed to reduce costs associated with transmitting, storing, distributing, and interpreting LANDSAT multispectral image data is described. The CCA is a preprocessing algorithm that uses feature extraction and data compression to more efficiently represent the information in the image data. The format of the preprocessed data enables simply a look-up table decoding and direct use of the extracted features to reduce user computation for either image reconstruction, or computer interpretation of the image data. Basically, the CCA uses spatially local clustering to extract features from the image data to describe spectral characteristics of the data set. In addition, the features may be used to form a sequence of scalar numbers that define each picture element in terms of the cluster features. This sequence, called the feature map, is then efficiently represented by using source encoding concepts. Various forms of the CCA are defined and experimental results are presented to show trade-offs and characteristics of the various implementations. Examples are provided that demonstrate the application of the cluster compression concept to multi-spectral images from LANDSAT and other sources.

Discovery of gigantic molecular nanostructures using a flow reaction array as a search engine

PubMed Central

Zang, Hong-Ying; de la Oliva, Andreu Ruiz; Miras, Haralampos N.; Long, De-Liang; McBurney, Roy T.; Cronin, Leroy

2014-01-01

The discovery of gigantic molecular nanostructures like coordination and polyoxometalate clusters is extremely time-consuming since a vast combinatorial space needs to be searched, and even a systematic and exhaustive exploration of the available synthetic parameters relies on a great deal of serendipity. Here we present a synthetic methodology that combines a flow reaction array and algorithmic control to give a chemical ‘real-space’ search engine leading to the discovery and isolation of a range of new molecular nanoclusters based on [Mo2O2S2]2+-based building blocks with either fourfold (C4) or fivefold (C5) symmetry templates and linkers. This engine leads us to isolate six new nanoscale cluster compounds: 1, {Mo10(C5)}; 2, {Mo14(C4)4(C5)2}; 3, {Mo60(C4)10}; 4, {Mo48(C4)6}; 5, {Mo34(C4)4}; 6, {Mo18(C4)9}; in only 200 automated experiments from a parameter space spanning ~5 million possible combinations. PMID:24770632

Electron exchange between r-keggin tungstoaluminates and a well-defined cluster-anion probe for studies in electron transfer

Treesearch

Yurii V. Geletii; Craig L. Hill; Alan J. Bailey; Kenneth I. Hardcastle; Rajai H. Atalla; Ira A. Weinstock

2005-01-01

Fully oxidized [alpha]-AlIIIW12O405-(1ox), and one-electron-reduced [alpha]-AlIIIW12O406-(1red), are well-behaved (stable and free of ion pairing) over a wide range of pH and ionic-strength values at room temperature in water. Having established this, 27Al NMR spectroscopy is used to measure rates of electron exchange between 1ox (27Al NMR: 72.2 ppm relative to Al(H2O)...

Galaxy Cluster Mass Reconstruction Project – III. The impact of dynamical substructure on cluster mass estimates

DOE PAGES

Old, L.; Wojtak, R.; Pearce, F. R.; ...

2017-12-20

With the advent of wide-field cosmological surveys, we are approaching samples of hundreds of thousands of galaxy clusters. While such large numbers will help reduce statistical uncertainties, the control of systematics in cluster masses is crucial. Here we examine the effects of an important source of systematic uncertainty in galaxy-based cluster mass estimation techniques: the presence of significant dynamical substructure. Dynamical substructure manifests as dynamically distinct subgroups in phase-space, indicating an ‘unrelaxed’ state. This issue affects around a quarter of clusters in a generally selected sample. We employ a set of mock clusters whose masses have been measured homogeneously withmore » commonly used galaxy-based mass estimation techniques (kinematic, richness, caustic, radial methods). We use these to study how the relation between observationally estimated and true cluster mass depends on the presence of substructure, as identified by various popular diagnostics. We find that the scatter for an ensemble of clusters does not increase dramatically for clusters with dynamical substructure. However, we find a systematic bias for all methods, such that clusters with significant substructure have higher measured masses than their relaxed counterparts. This bias depends on cluster mass: the most massive clusters are largely unaffected by the presence of significant substructure, but masses are significantly overestimated for lower mass clusters, by ~ 10 percent at 10 14 and ≳ 20 percent for ≲ 10 13.5. Finally, the use of cluster samples with different levels of substructure can therefore bias certain cosmological parameters up to a level comparable to the typical uncertainties in current cosmological studies.« less

Galaxy Cluster Mass Reconstruction Project – III. The impact of dynamical substructure on cluster mass estimates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Old, L.; Wojtak, R.; Pearce, F. R.

With the advent of wide-field cosmological surveys, we are approaching samples of hundreds of thousands of galaxy clusters. While such large numbers will help reduce statistical uncertainties, the control of systematics in cluster masses is crucial. Here we examine the effects of an important source of systematic uncertainty in galaxy-based cluster mass estimation techniques: the presence of significant dynamical substructure. Dynamical substructure manifests as dynamically distinct subgroups in phase-space, indicating an ‘unrelaxed’ state. This issue affects around a quarter of clusters in a generally selected sample. We employ a set of mock clusters whose masses have been measured homogeneously withmore » commonly used galaxy-based mass estimation techniques (kinematic, richness, caustic, radial methods). We use these to study how the relation between observationally estimated and true cluster mass depends on the presence of substructure, as identified by various popular diagnostics. We find that the scatter for an ensemble of clusters does not increase dramatically for clusters with dynamical substructure. However, we find a systematic bias for all methods, such that clusters with significant substructure have higher measured masses than their relaxed counterparts. This bias depends on cluster mass: the most massive clusters are largely unaffected by the presence of significant substructure, but masses are significantly overestimated for lower mass clusters, by ~ 10 percent at 10 14 and ≳ 20 percent for ≲ 10 13.5. Finally, the use of cluster samples with different levels of substructure can therefore bias certain cosmological parameters up to a level comparable to the typical uncertainties in current cosmological studies.« less

Gas Dynamics in Galaxy Clusters

NASA Astrophysics Data System (ADS)

McCourt, Michael Kingsley, Jr.

Galaxy clusters are the most massive structures in the universe and, in the hierarchical pattern of cosmological structure formation, the largest objects in the universe form last. Galaxy clusters are thus interesting objects for a number of reasons. Three examples relevant to this thesis are: 1. Constraining the properties of dark energy: Due to the hierarchical nature of structure formation, the largest objects in the universe form last. The cluster mass function is thus sensitive to the entire expansion history of the universe and can be used to constrain the properties of dark energy. This constraint complements others derived from the CMB or from Type Ia supernovae and provides an important, independent confirmation of such methods. In particular, clusters provide detailed information about the equation of state parameter w because they sample a large redshift range z ˜ 0 - 1. 2. Probing galaxy formation: Clusters contain the most massive galaxies in the uni- verse, and the most massive black holes; because clusters form so late, we can still witness the assembly of these objects in the nearby universe. Clusters thus provide a more detailed view of galaxy formation than is possible in studies of lower-mass ob- jects. An important example comes from x-ray studies of clusters, which unexpectedly found that star formation in massive galaxies in clusters is closely correlated with the properties of the hot, virialized gas in their halos. This correlation persists despite the enormous separation in temperature, in dynamical time-scales, and in length-scales between the virialized gas in the halo and the star-forming regions in the galaxy. This remains a challenge to interpret theoretically. 3. Developing our knowledge of dilute plasmas: The masses and sizes of galaxy clusters imply that the plasma which permeates them is both very hot (˜ 108 K) and very dilute (˜ 10 -2 cm-3). This plasma is collisional enough to be considered a fluid, but collisionless enough to

Robustness of cluster synchronous patterns in small-world networks with inter-cluster co-competition balance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jianbao; Ma, Zhongjun, E-mail: mzj1234402@163.com; Chen, Guanrong

All edges in the classical Watts and Strogatz's small-world network model are unweighted and cooperative (positive). By introducing competitive (negative) inter-cluster edges and assigning edge weights to mimic more realistic networks, this paper develops a modified model which possesses co-competitive weighted couplings and cluster structures while maintaining the common small-world network properties of small average shortest path lengths and large clustering coefficients. Based on theoretical analysis, it is proved that the new model with inter-cluster co-competition balance has an important dynamical property of robust cluster synchronous pattern formation. More precisely, clusters will neither merge nor split regardless of adding ormore » deleting nodes and edges, under the condition of inter-cluster co-competition balance. Numerical simulations demonstrate the robustness of the model against the increase of the coupling strength and several topological variations.« less

Robustness of cluster synchronous patterns in small-world networks with inter-cluster co-competition balance

NASA Astrophysics Data System (ADS)

Zhang, Jianbao; Ma, Zhongjun; Chen, Guanrong

2014-06-01

All edges in the classical Watts and Strogatz's small-world network model are unweighted and cooperative (positive). By introducing competitive (negative) inter-cluster edges and assigning edge weights to mimic more realistic networks, this paper develops a modified model which possesses co-competitive weighted couplings and cluster structures while maintaining the common small-world network properties of small average shortest path lengths and large clustering coefficients. Based on theoretical analysis, it is proved that the new model with inter-cluster co-competition balance has an important dynamical property of robust cluster synchronous pattern formation. More precisely, clusters will neither merge nor split regardless of adding or deleting nodes and edges, under the condition of inter-cluster co-competition balance. Numerical simulations demonstrate the robustness of the model against the increase of the coupling strength and several topological variations.

A populous intermediate-age open cluster and evidence of an embedded cluster among the FSR globular cluster candidates

NASA Astrophysics Data System (ADS)

Bica, E.; Bonatto, C.

2008-03-01

We study the nature of the globular cluster (GC) candidates FSR 1603 and FSR1755 selected from the catalogue of Froebrich, Scholz & Raftery. Their properties are investigated with Two-Micron All-Sky Survey field-star decontaminated photometry, which is used to build colour-magnitude diagrams (CMDs) and stellar radial density profiles. FSR1603 has the open cluster Ruprecht 101 as optical counterpart, and we show it to be a massive intermediate-age cluster. Relevant parameters of FSR1603 are the age ~1Gyr, distance from the Sun dsolar ~ 2.7kpc, Galactocentric distance RGC ~ 6.4kpc, core radius RC ~ 1.1pc, mass function slope χ ~ 1.8, observed stellar mass (for stars with mass in the range 1.27 <= m <= 2.03Msolar) Mobs ~ 500Msolar and a total (extrapolated to m = 0.08Msolar) stellar mass Mtot ~ 2300Msolar. FSR1755, on the other hand, is not a populous cluster. It may be a sparse young cluster embedded in the HII region Sh2-3, subject to an absorption AV ~ 4.1, located at dsolar ~ 1.3kpc. Important field-star contamination, spatially variable heavy dust obscuration, even in Ks, and gas emission characterize its field. A nearly vertical, sparse blue stellar sequence shows up in the CMDs.

Cluster-to-cluster transformation among Au6, Au8 and Au11 nanoclusters.

PubMed

Ren, Xiuqing; Fu, Junhong; Lin, Xinzhang; Fu, Xuemei; Yan, Jinghui; Wu, Ren'an; Liu, Chao; Huang, Jiahui

2018-05-22

We present the cluster-to-cluster transformations among three gold nanoclusters, [Au6(dppp)4]2+ (Au6), [Au8(dppp)4Cl2]2+ (Au8) and [Au11(dppp)5]3+ (Au11). The conversion process follows a rule that states that the transformation of a small cluster to a large cluster is achieved through an oxidation process with an oxidizing agent (H2O2) or with heating, while the conversion of a large cluster to a small one occurs through a reduction process with a reducing agent (NaBH4). All the reactions were monitored using UV-Vis spectroscopy and ESI-MS. This work may provide an alternative approach to the synthesis of novel gold nanoclusters and a further understanding of the structural transformation relationship of gold nanoclusters.

Massive Star Clusters in Ongoing Galaxy Interactions: Clues to Cluster Formation

NASA Astrophysics Data System (ADS)

Keel, William C.; Borne, Kirk D.

2003-09-01

We present HST WFPC2 observations, supplemented by ground-based Hα data, of the star-cluster populations in two pairs of interacting galaxies selected for being in very different kinds of encounters seen at different stages. Dynamical information and n-body simulations provide the details of encounter geometry, mass ratio, and timing. In NGC 5752/4 we are seeing a weak encounter, well past closest approach, after about 2.5×108 yr. The large spiral NGC 5754 has a normal population of disk clusters, while the fainter companion NGC 5752 exhibits a rich population of luminous clusters with a flatter luminosity function. The strong, ongoing encounter in NGC 6621/2, seen about 1.0×108 yr past closest approach between roughly equal-mass galaxies, has produced an extensive population of luminous clusters, particularly young and luminous in a small region between the two nuclei. This region is dynamically interesting, with such a strong perturbation in the velocity field that the rotation curve reverses sign. From these results, in comparison with other strongly interacting systems discussed in the literature, cluster formation requires a threshold level of perturbation, with stage of the interaction a less important factor. The location of the most active star formation in NGC 6621/2 draws attention to a possible role for the Toomre stability threshold in shaping star formation in interacting galaxies. The rich cluster populations in NGC 5752 and NGC 6621 show that direct contact between gas-rich galaxy disks is not a requirement to form luminous clusters and that they can be triggered by processes happening within a single galaxy disk (albeit triggered by external perturbations). 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.

Interacting star clusters in the Large Magellanic Cloud. Overmerging problem solved by cluster group formation

NASA Astrophysics Data System (ADS)

Leon, Stéphane; Bergond, Gilles; Vallenari, Antonella

1999-04-01

We present the tidal tail distributions of a sample of candidate binary clusters located in the bar of the Large Magellanic Cloud (LMC). One isolated cluster, SL 268, is presented in order to study the effect of the LMC tidal field. All the candidate binary clusters show tidal tails, confirming that the pairs are formed by physically linked objects. The stellar mass in the tails covers a large range, from 1.8x 10(3) to 3x 10(4) \\msun. We derive a total mass estimate for SL 268 and SL 356. At large radii, the projected density profiles of SL 268 and SL 356 fall off as r(-gamma ) , with gamma = 2.27 and gamma =3.44, respectively. Out of 4 pairs or multiple systems, 2 are older than the theoretical survival time of binary clusters (going from a few 10(6) years to 10(8) years). A pair shows too large age difference between the components to be consistent with classical theoretical models of binary cluster formation (Fujimoto & Kumai \\cite{fujimoto97}). We refer to this as the ``overmerging'' problem. A different scenario is proposed: the formation proceeds in large molecular complexes giving birth to groups of clusters over a few 10(7) years. In these groups the expected cluster encounter rate is larger, and tidal capture has higher probability. Cluster pairs are not born together through the splitting of the parent cloud, but formed later by tidal capture. For 3 pairs, we tentatively identify the star cluster group (SCG) memberships. The SCG formation, through the recent cluster starburst triggered by the LMC-SMC encounter, in contrast with the quiescent open cluster formation in the Milky Way can be an explanation to the paucity of binary clusters observed in our Galaxy. Based on observations collected at the European Southern Observatory, La Silla, Chile}

Hausdorff clustering

NASA Astrophysics Data System (ADS)

Basalto, Nicolas; Bellotti, Roberto; de Carlo, Francesco; Facchi, Paolo; Pantaleo, Ester; Pascazio, Saverio

2008-10-01

A clustering algorithm based on the Hausdorff distance is analyzed and compared to the single, complete, and average linkage algorithms. The four clustering procedures are applied to a toy example and to the time series of financial data. The dendrograms are scrutinized and their features compared. The Hausdorff linkage relies on firm mathematical grounds and turns out to be very effective when one has to discriminate among complex structures.

A Test for Cluster Bias: Detecting Violations of Measurement Invariance across Clusters in Multilevel Data

ERIC Educational Resources Information Center

Jak, Suzanne; Oort, Frans J.; Dolan, Conor V.

2013-01-01

We present a test for cluster bias, which can be used to detect violations of measurement invariance across clusters in 2-level data. We show how measurement invariance assumptions across clusters imply measurement invariance across levels in a 2-level factor model. Cluster bias is investigated by testing whether the within-level factor loadings…

Record-breaking ancient galaxy clusters

NASA Astrophysics Data System (ADS)

2003-12-01

A tale of two record-breaking clusters hi-res Size hi-res: 768 kb Credits: for RDCS1252: NASA, ESA, J.Blakeslee (Johns Hopkins Univ.), M.Postman (Space Telescope Science Inst.) and P.Rosati, Chris Lidman & Ricardo Demarco (European Southern Observ.) for TNJ1338: NASA, ESA, G.Miley (Leiden Observ.) and R.Overzier (Leiden Obs) A tale of two record-breaking clusters Looking back in time to when the universe was in its formative youth, the Advanced Camera for Surveys (ACS) aboard the NASA/ESA Hubble Space Telescope captured these revealing images of two galaxy clusters. The image at left, which is made with an additional infrared exposure taken with the European Southern Observatory’s Very Large Telescope, shows mature galaxies in a massive cluster that existed when the cosmos was 5000 million years old. The cluster, called RDCS1252.9-2927, is as massive as ‘300 trillion’ suns and is the most massive known cluster for its epoch. The image reveals the core of the cluster and is part of a much larger mosaic of the entire cluster. Dominating the core are a pair of large, reddish elliptical galaxies [near centre of image]. Their red colour indicates an older population of stars. Most of the stars are at least 1000 million years old. The two galaxies appear to be interacting and may eventually merge to form a larger galaxy that is comparable to the brightest galaxies seen in present-day clusters. The red galaxies surrounding the central pair are also cluster members. The cluster probably contains many thousands of galaxies, but only about 50 can be seen in this image. The full mosaic (heic0313d) reveals several hundred cluster members. Many of the other galaxies in the image, including several of the blue galaxies, are foreground or background galaxies. The colour-composite image was assembled from two observations (through i and z filters) taken between May and June 2002 by the ACS Wide Field Camera, and one image with the ISAAC instrument on the VLT taken in 2002

The Next Generation Virgo Cluster Survey. XX. RedGOLD Background Galaxy Cluster Detections

NASA Astrophysics Data System (ADS)

Licitra, Rossella; Mei, Simona; Raichoor, Anand; Erben, Thomas; Hildebrandt, Hendrik; Muñoz, Roberto P.; Van Waerbeke, Ludovic; Côté, Patrick; Cuillandre, Jean-Charles; Duc, Pierre-Alain; Ferrarese, Laura; Gwyn, Stephen D. J.; Huertas-Company, Marc; Lançon, Ariane; Parroni, Carolina; Puzia, Thomas H.

2016-09-01

We build a background cluster candidate catalog from the Next Generation Virgo Cluster Survey (NGVS) using our detection algorithm RedGOLD. The NGVS covers 104 deg2 of the Virgo cluster in the {u}* ,g,r,I,z-bandpasses to a depth of g ˜ 25.7 mag (5σ). Part of the survey was not covered or has shallow observations in the r band. We build two cluster catalogs: one using all bandpasses, for the fields with deep r-band observations (˜20 deg2), and the other using four bandpasses ({u}* ,g,I,z) for the entire NGVS area. Based on our previous Canada-France-Hawaii Telescope Legacy Survey W1 studies, we estimate that both of our catalogs are ˜100% (˜70%) complete and ˜80% pure, at z ≤ 0.6 (z ≲ 1), for galaxy clusters with masses of M ≳ 1014 M ⊙. We show that when using four bandpasses, though the photometric redshift accuracy is lower, RedGOLD detects massive galaxy clusters up to z ˜ 1 with completeness and purity similar to the five-band case. This is achieved when taking into account the bias in the richness estimation, which is ˜40% lower at 0.5 ≤ z < 0.6 and ˜20% higher at 0.6 < z < 0.8, with respect to the five-band case. RedGOLD recovers all the X-ray clusters in the area with mass M 500 > 1.4 × 1014 M ⊙ and 0.08 < z < 0.5. Because of our different cluster richness limits and the NGVS depth, our catalogs reach lower masses than the published redMaPPer cluster catalog over the area, and we recover ˜90%-100% of its detections.

Clustering Millions of Faces by Identity.

PubMed

Otto, Charles; Wang, Dayong; Jain, Anil K

2018-02-01

Given a large collection of unlabeled face images, we address the problem of clustering faces into an unknown number of identities. This problem is of interest in social media, law enforcement, and other applications, where the number of faces can be of the order of hundreds of million, while the number of identities (clusters) can range from a few thousand to millions. To address the challenges of run-time complexity and cluster quality, we present an approximate Rank-Order clustering algorithm that performs better than popular clustering algorithms (k-Means and Spectral). Our experiments include clustering up to 123 million face images into over 10 million clusters. Clustering results are analyzed in terms of external (known face labels) and internal (unknown face labels) quality measures, and run-time. Our algorithm achieves an F-measure of 0.87 on the LFW benchmark (13 K faces of 5,749 individuals), which drops to 0.27 on the largest dataset considered (13 K faces in LFW + 123M distractor images). Additionally, we show that frames in the YouTube benchmark can be clustered with an F-measure of 0.71. An internal per-cluster quality measure is developed to rank individual clusters for manual exploration of high quality clusters that are compact and isolated.

Mixture modelling for cluster analysis.

PubMed

McLachlan, G J; Chang, S U

2004-10-01

Cluster analysis via a finite mixture model approach is considered. With this approach to clustering, the data can be partitioned into a specified number of clusters g by first fitting a mixture model with g components. An outright clustering of the data is then obtained by assigning an observation to the component to which it has the highest estimated posterior probability of belonging; that is, the ith cluster consists of those observations assigned to the ith component (i = 1,..., g). The focus is on the use of mixtures of normal components for the cluster analysis of data that can be regarded as being continuous. But attention is also given to the case of mixed data, where the observations consist of both continuous and discrete variables.

The cluster galaxy circular velocity function

NASA Astrophysics Data System (ADS)

Desai, V.; Dalcanton, J. J.; Mayer, L.; Reed, D.; Quinn, T.; Governato, F.

2004-06-01

We present galaxy circular velocity functions (GCVFs) for 34 low-redshift (z<~ 0.15) clusters identified in the Sloan Digital Sky Survey (SDSS), for 15 clusters drawn from dark matter simulations of hierarchical structure growth in a ΛCDM cosmology, and for ~22 000 SDSS field galaxies. We find that the simulations successfully reproduce the shape, amplitude and scatter in the observed distribution of cluster galaxy circular velocities. The power-law slope of the observed cluster GCVF is ~-2.4, independent of cluster velocity dispersion. The average slope of the simulated GCVFs is somewhat steeper, although formally consistent given the errors. We find that the effects of baryons on galaxy rotation curves is to flatten the simulated cluster GCVF into better agreement with observations. The cumulative GCVFs of the simulated clusters are very similar across a wide range of cluster masses, provided individual subhalo circular velocities are scaled by the circular velocities of the parent cluster. The scatter is consistent with that measured in the cumulative, scaled observed cluster GCVF. Finally, the observed field GCVF deviates significantly from a power law, being flatter than the cluster GCVF at circular velocities less than 200 km s-1.

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

2014-02-03

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.

Data depth based clustering analysis

DOE PAGES

Jeong, Myeong -Hun; Cai, Yaping; Sullivan, Clair J.; ...

2016-01-01

Here, this paper proposes a new algorithm for identifying patterns within data, based on data depth. Such a clustering analysis has an enormous potential to discover previously unknown insights from existing data sets. Many clustering algorithms already exist for this purpose. However, most algorithms are not affine invariant. Therefore, they must operate with different parameters after the data sets are rotated, scaled, or translated. Further, most clustering algorithms, based on Euclidean distance, can be sensitive to noises because they have no global perspective. Parameter selection also significantly affects the clustering results of each algorithm. Unlike many existing clustering algorithms, themore » proposed algorithm, called data depth based clustering analysis (DBCA), is able to detect coherent clusters after the data sets are affine transformed without changing a parameter. It is also robust to noises because using data depth can measure centrality and outlyingness of the underlying data. Further, it can generate relatively stable clusters by varying the parameter. The experimental comparison with the leading state-of-the-art alternatives demonstrates that the proposed algorithm outperforms DBSCAN and HDBSCAN in terms of affine invariance, and exceeds or matches the ro-bustness to noises of DBSCAN or HDBSCAN. The robust-ness to parameter selection is also demonstrated through the case study of clustering twitter data.« less

Helium cluster isolation spectroscopy

NASA Astrophysics Data System (ADS)

Higgins, John Paul

Clusters of helium, each containing ~103- 104 atoms, are produced in a molecular beam and are doped with alkali metal atoms (Li, Na, and K) and large organic molecules. Electronic spectroscopy in the visible and UV regions of the spectrum is carried out on the dopant species. Since large helium clusters are liquid and attain an equilibrium internal temperature of 0.4 K, they interact weakly with atoms or molecules absorbed on their surface or resident inside the cluster. The spectra that are obtained are characterized by small frequency shifts from the positions of the gas phase transitions, narrow lines, and cold vibrational temperatures. Alkali atoms aggregate on the helium cluster surface to form dimers and trimers. The spectra of singlet alkali dimers exhibit the presence of elementary excitations in the superfluid helium cluster matrix. It is found that preparation of the alkali molecules on the surface of helium clusters leads to the preferential formation of high-spin, van der Waals bound, triplet dimers and quartet trimers. Four bound-bound and two bound-free transitions are observed in the triplet manifold of the alkali dimers. The quartet trimers serve as an ideal system for the study of a simple unimolecular reaction in the cold helium cluster environment. Analysis of the lowest quartet state provides valuable insight into three-body forces in a van der Waals trimer. The wide range of atomic and molecular systems studied in this thesis constitutes a preliminary step in the development of helium cluster isolation spectroscopy, a hybrid technique combining the advantages of high resolution spectroscopy with the synthetic, low temperature environment of matrices.

Flow over gravel beds with clusters

NASA Astrophysics Data System (ADS)

Little, M.; Venditti, J. G.

2014-12-01

The structure of a gravel bed has been shown to alter the entrainment threshold. Structures such as clusters, reticulate stone cells and other discrete structures lock grains together, making it more difficult for them to be mobilized. These structures also generate form drag, reducing the shear stress available for mobilization. Form drag over gravel beds is often assumed to be negligible, but this assumption is not well supported. Here, we explore how cluster density and arrangement affect flow resistance and the flow structure over a fixed gravel bed in a flume experiment. Cluster density was varied from 6 to 68.3 clusters per square meter which corresponds to areal bed coverages of 2 to 17%. We used regular, irregular and random arrangements of the clusters. Our results show that flow resistance over a planar gravel bed initially declines, then increases with flow depth. The addition of clusters increases flow resistance, but the effect is dependent on cluster density, flow depth and arrangement. At the highest density, clusters can increase flow resistance as by as much as 8 times when compared to flat planar bed with no grain-related form drag. Spatially resolved observations of flow over the clusters indicate that a well-defined wake forms in the lee of each cluster. At low cluster density, the wakes are isolated and weak. As cluster density increases, the wakes become stronger. At the highest density, the wakes interact and the within cluster flow field detaches from the overlying flow. This generates a distinct shear layer at the height of the clusters. In spite of this change in the flow field at high density, our results suggest that flow resistance simply increases with cluster density. Our results suggest that the form drag associated with a gravel bed can be substantial and that it depends on the arrangement of the grains on the bed.

Cluster bomb ocular injuries.

PubMed

Mansour, Ahmad M; Hamade, Haya; Ghaddar, Ayman; Mokadem, Ahmad Samih; El Hajj Ali, Mohamad; Awwad, Shady

2012-01-01

To present the visual outcomes and ocular sequelae of victims of cluster bombs. This retrospective, multicenter case series of ocular injury due to cluster bombs was conducted for 3 years after the war in South Lebanon (July 2006). Data were gathered from the reports to the Information Management System for Mine Action. There were 308 victims of clusters bombs; 36 individuals were killed, of which 2 received ocular lacerations and; 272 individuals were injured with 18 receiving ocular injury. These 18 surviving individuals were assessed by the authors. Ocular injury occurred in 6.5% (20/308) of cluster bomb victims. Trauma to multiple organs occurred in 12 of 18 cases (67%) with ocular injury. Ocular findings included corneal or scleral lacerations (16 eyes), corneal foreign bodies (9 eyes), corneal decompensation (2 eyes), ruptured cataract (6 eyes), and intravitreal foreign bodies (10 eyes). The corneas of one patient had extreme attenuation of the endothelium. Ocular injury occurred in 6.5% of cluster bomb victims and 67% of the patients with ocular injury sustained trauma to multiple organs. Visual morbidity in civilians is an additional reason for a global ban on the use of cluster bombs.

A Commodity Computing Cluster

NASA Astrophysics Data System (ADS)

Teuben, P. J.; Wolfire, M. G.; Pound, M. W.; Mundy, L. G.

We have assembled a cluster of Intel-Pentium based PCs running Linux to compute a large set of Photodissociation Region (PDR) and Dust Continuum models. For various reasons the cluster is heterogeneous, currently ranging from a single Pentium-II 333 MHz to dual Pentium-III 450 MHz CPU machines. Although this will be sufficient for our ``embarrassingly parallelizable problem'' it may present some challenges for as yet unplanned future use. In addition the cluster was used to construct a MIRIAD benchmark, and compared to equivalent Ultra-Sparc based workstations. Currently the cluster consists of 8 machines, 14 CPUs, 50GB of disk-space, and a total peak speed of 5.83 GHz, or about 1.5 Gflops. The total cost of this cluster has been about $12,000, including all cabling, networking equipment, rack, and a CD-R backup system. The URL for this project is http://dustem.astro.umd.edu.

Using Cluster Bootstrapping to Analyze Nested Data with a Few Clusters

ERIC Educational Resources Information Center

Huang, Francis L.

2018-01-01

Cluster randomized trials involving participants nested within intact treatment and control groups are commonly performed in various educational, psychological, and biomedical studies. However, recruiting and retaining intact groups present various practical, financial, and logistical challenges to evaluators and often, cluster randomized trials…

Ultraviolet studies of O and B stars in the LMC cluster NGC 2100, the SMC cluster NGC 330 and the Galactic cluster NGC 6530

NASA Technical Reports Server (NTRS)

Boehm-Vitense, E.; Hodge, P.

1984-01-01

High-resolution and low-resolution IUE spectra of O and B stars in the LMC cluster NGC 2100, the SMC cluster NGC 330, and the young Galactic cluster NGC 6530 are investigated. Temperatures and luminosities are determined. In the LMC and SMC clusters, the most luminous stars are evolved stars on the horizontal supergiant branch, while in NGC 6530 the stars are all still on the main sequence. Extinction laws were determined. They confirm the known differences between LMC and Galactic extinctions. No mass loss was detected for the evolved B stars in the LMC and SMC clusters, while the high-luminosity stars in NGC 6530 show P Cygni profiles.

Gravitational Lensing and Microlensing in Clusters: Clusters as Dark Matter Telescopes

NASA Astrophysics Data System (ADS)

Safonova, Margarita

2018-04-01

Gravitational lensing is brightening of background objects due to deflection of light by foreground sources. Rich clusters of galaxies are very effective lenses because they are centrally concentrated. Such natural Gravitational Telescopes provide us with strongly magnified galaxies at high redshifts otherwise too faint to be detected or analyzed. With a lensing boost, we can study galaxies shining at the end of the “Dark Ages”. We propose to exploit the opportunity provided by the large field of view and depth, to search for sources magnified by foreground clusters in the vicinity of the cluster critical curves, where enhancements can be of several tens in brightness. Another aspect is microlensing (ML), where we would like to continue our survey of a number of Galactic globular clusters over time-scales of weeks to years to search for ML events from planets to hypothesized central intermediate-mass black holes (IMBH).

Improving local clustering based top-L link prediction methods via asymmetric link clustering information

NASA Astrophysics Data System (ADS)

Wu, Zhihao; Lin, Youfang; Zhao, Yiji; Yan, Hongyan

2018-02-01

Networks can represent a wide range of complex systems, such as social, biological and technological systems. Link prediction is one of the most important problems in network analysis, and has attracted much research interest recently. Many link prediction methods have been proposed to solve this problem with various techniques. We can note that clustering information plays an important role in solving the link prediction problem. In previous literatures, we find node clustering coefficient appears frequently in many link prediction methods. However, node clustering coefficient is limited to describe the role of a common-neighbor in different local networks, because it cannot distinguish different clustering abilities of a node to different node pairs. In this paper, we shift our focus from nodes to links, and propose the concept of asymmetric link clustering (ALC) coefficient. Further, we improve three node clustering based link prediction methods via the concept of ALC. The experimental results demonstrate that ALC-based methods outperform node clustering based methods, especially achieving remarkable improvements on food web, hamster friendship and Internet networks. Besides, comparing with other methods, the performance of ALC-based methods are very stable in both globalized and personalized top-L link prediction tasks.

An agglomerative hierarchical clustering approach to visualisation in Bayesian clustering problems

PubMed Central

Dawson, Kevin J.; Belkhir, Khalid

2009-01-01

Clustering problems (including the clustering of individuals into outcrossing populations, hybrid generations, full-sib families and selfing lines) have recently received much attention in population genetics. In these clustering problems, the parameter of interest is a partition of the set of sampled individuals, - the sample partition. In a fully Bayesian approach to clustering problems of this type, our knowledge about the sample partition is represented by a probability distribution on the space of possible sample partitions. Since the number of possible partitions grows very rapidly with the sample size, we can not visualise this probability distribution in its entirety, unless the sample is very small. As a solution to this visualisation problem, we recommend using an agglomerative hierarchical clustering algorithm, which we call the exact linkage algorithm. This algorithm is a special case of the maximin clustering algorithm that we introduced previously. The exact linkage algorithm is now implemented in our software package Partition View. The exact linkage algorithm takes the posterior co-assignment probabilities as input, and yields as output a rooted binary tree, - or more generally, a forest of such trees. Each node of this forest defines a set of individuals, and the node height is the posterior co-assignment probability of this set. This provides a useful visual representation of the uncertainty associated with the assignment of individuals to categories. It is also a useful starting point for a more detailed exploration of the posterior distribution in terms of the co-assignment probabilities. PMID:19337306

THE M33 GLOBULAR CLUSTER SYSTEM WITH PAndAS DATA: THE LAST OUTER HALO CLUSTER?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cockcroft, Robert; Harris, William E.; Ferguson, Annette M. N., E-mail: cockcroft@physics.mcmaster.ca, E-mail: harris@physics.mcmaster.ca, E-mail: ferguson@roe.ac.uk

2011-04-01

We use CFHT/MegaCam data to search for outer halo star clusters in M33 as part of the Pan-Andromeda Archaeological Survey. This work extends previous studies out to a projected radius of 50 kpc and covers over 40 deg{sup 2}. We find only one new unambiguous star cluster in addition to the five previously known in the M33 outer halo (10 kpc {<=} r {<=} 50 kpc). Although we identify 2440 cluster candidates of various degrees of confidence from our objective image search procedure, almost all of these are likely background contaminants, mostly faint unresolved galaxies. We measure the luminosity, color,more » and structural parameters of the new cluster in addition to the five previously known outer halo clusters. At a projected radius of 22 kpc, the new cluster is slightly smaller, fainter, and redder than all but one of the other outer halo clusters, and has g' {approx} 19.9, (g' - i') {approx} 0.6, concentration parameter c {approx} 1.0, a core radius r{sub c} {approx} 3.5 pc, and a half-light radius r{sub h} {approx} 5.5 pc. For M33 to have so few outer halo clusters compared to M31 suggests either tidal stripping of M33's outer halo clusters by M31, or a very different, much calmer accretion history of M33.« less

The M33 Globular Cluster System with PAndAS Data: the Last Outer Halo Cluster?

NASA Astrophysics Data System (ADS)

Cockcroft, Robert; Harris, William E.; Ferguson, Annette M. N.; Huxor, Avon; Ibata, Rodrigo; Irwin, Mike J.; McConnachie, Alan W.; Woodley, Kristin A.; Chapman, Scott C.; Lewis, Geraint F.; Puzia, Thomas H.

2011-04-01

We use CFHT/MegaCam data to search for outer halo star clusters in M33 as part of the Pan-Andromeda Archaeological Survey. This work extends previous studies out to a projected radius of 50 kpc and covers over 40 deg2. We find only one new unambiguous star cluster in addition to the five previously known in the M33 outer halo (10 kpc <= r <= 50 kpc). Although we identify 2440 cluster candidates of various degrees of confidence from our objective image search procedure, almost all of these are likely background contaminants, mostly faint unresolved galaxies. We measure the luminosity, color, and structural parameters of the new cluster in addition to the five previously known outer halo clusters. At a projected radius of 22 kpc, the new cluster is slightly smaller, fainter, and redder than all but one of the other outer halo clusters, and has g' ≈ 19.9, (g' - i') ≈ 0.6, concentration parameter c ≈ 1.0, a core radius rc ≈ 3.5 pc, and a half-light radius rh ≈ 5.5 pc. For M33 to have so few outer halo clusters compared to M31 suggests either tidal stripping of M33's outer halo clusters by M31, or a very different, much calmer accretion history of M33.

Observing the clustering properties of galaxy clusters in dynamical dark-energy cosmologies

NASA Astrophysics Data System (ADS)

Fedeli, C.; Moscardini, L.; Bartelmann, M.

2009-06-01

We study the clustering properties of galaxy clusters expected to be observed by various forthcoming surveys both in the X-ray and sub-mm regimes by the thermal Sunyaev-Zel'dovich effect. Several different background cosmological models are assumed, including the concordance ΛCDM and various cosmologies with dynamical evolution of the dark energy. Particular attention is paid to models with a significant contribution of dark energy at early times which affects the process of structure formation. Past light cone and selection effects in cluster catalogs are carefully modeled by realistic scaling relations between cluster mass and observables and by properly taking into account the selection functions of the different instruments. The results show that early dark-energy models are expected to produce significantly lower values of effective bias and both spatial and angular correlation amplitudes with respect to the standard ΛCDM model. Among the cluster catalogs studied in this work, it turns out that those based on eRosita, Planck, and South Pole Telescope observations are the most promising for distinguishing between various dark-energy models.

The X-ray luminosity functions of Abell clusters from the Einstein Cluster Survey

NASA Technical Reports Server (NTRS)

Burg, R.; Giacconi, R.; Forman, W.; Jones, C.

1994-01-01

We have derived the present epoch X-ray luminosity function of northern Abell clusters using luminosities from the Einstein Cluster Survey. The sample is sufficiently large that we can determine the luminosity function for each richness class separately with sufficient precision to study and compare the different luminosity functions. We find that, within each richness class, the range of X-ray luminosity is quite large and spans nearly a factor of 25. Characterizing the luminosity function for each richness class with a Schechter function, we find that the characteristic X-ray luminosity, L(sub *), scales with richness class as (L(sub *) varies as N(sub*)(exp gamma), where N(sub *) is the corrected, mean number of galaxies in a richness class, and the best-fitting exponent is gamma = 1.3 +/- 0.4. Finally, our analysis suggests that there is a lower limit to the X-ray luminosity of clusters which is determined by the integrated emission of the cluster member galaxies, and this also scales with richness class. The present sample forms a baseline for testing cosmological evolution of Abell-like clusters when an appropriate high-redshift cluster sample becomes available.

ClusterControl: a web interface for distributing and monitoring bioinformatics applications on a Linux cluster.

PubMed

Stocker, Gernot; Rieder, Dietmar; Trajanoski, Zlatko

2004-03-22

ClusterControl is a web interface to simplify distributing and monitoring bioinformatics applications on Linux cluster systems. We have developed a modular concept that enables integration of command line oriented program into the application framework of ClusterControl. The systems facilitate integration of different applications accessed through one interface and executed on a distributed cluster system. The package is based on freely available technologies like Apache as web server, PHP as server-side scripting language and OpenPBS as queuing system and is available free of charge for academic and non-profit institutions. http://genome.tugraz.at/Software/ClusterControl

CORM: An R Package Implementing the Clustering of Regression Models Method for Gene Clustering

PubMed Central

Shi, Jiejun; Qin, Li-Xuan

2014-01-01

We report a new R package implementing the clustering of regression models (CORM) method for clustering genes using gene expression data and provide data examples illustrating each clustering function in the package. The CORM package is freely available at CRAN from http://cran.r-project.org. PMID:25452684

Cluster Interest Inventory.

ERIC Educational Resources Information Center

Herzog, Douglas